US20030040695A1 - Flushable tampon applicators - Google Patents
Flushable tampon applicators Download PDFInfo
- Publication number
- US20030040695A1 US20030040695A1 US09/944,672 US94467201A US2003040695A1 US 20030040695 A1 US20030040695 A1 US 20030040695A1 US 94467201 A US94467201 A US 94467201A US 2003040695 A1 US2003040695 A1 US 2003040695A1
- Authority
- US
- United States
- Prior art keywords
- thermoplastic
- blend
- polymers
- water
- peg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 190
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 180
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 151
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 147
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 72
- 239000000945 filler Substances 0.000 claims abstract description 64
- 229920002988 biodegradable polymer Polymers 0.000 claims abstract description 46
- 239000004621 biodegradable polymer Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims abstract description 26
- 239000000454 talc Substances 0.000 claims abstract description 22
- 229910052623 talc Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims description 316
- 239000004416 thermosoftening plastic Substances 0.000 claims description 99
- 229920000642 polymer Polymers 0.000 claims description 92
- -1 polyethylene Polymers 0.000 claims description 82
- 239000002131 composite material Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 51
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 48
- 125000001931 aliphatic group Chemical group 0.000 claims description 46
- 229920001577 copolymer Polymers 0.000 claims description 43
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 40
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 39
- 238000001746 injection moulding Methods 0.000 claims description 37
- 229920000728 polyester Polymers 0.000 claims description 36
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000314 lubricant Substances 0.000 claims description 20
- 229920001634 Copolyester Polymers 0.000 claims description 19
- 229920002472 Starch Polymers 0.000 claims description 19
- 239000008107 starch Substances 0.000 claims description 19
- 235000019698 starch Nutrition 0.000 claims description 19
- 239000004310 lactic acid Substances 0.000 claims description 18
- 235000014655 lactic acid Nutrition 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 239000004698 Polyethylene Substances 0.000 claims description 17
- 235000013312 flour Nutrition 0.000 claims description 17
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 17
- 150000002009 diols Chemical class 0.000 claims description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000001993 wax Substances 0.000 claims description 15
- 229920003232 aliphatic polyester Polymers 0.000 claims description 14
- 239000002023 wood Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 229920001519 homopolymer Polymers 0.000 claims description 12
- 239000004014 plasticizer Substances 0.000 claims description 12
- 229920001610 polycaprolactone Polymers 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 9
- 239000012766 organic filler Substances 0.000 claims description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 7
- 239000004632 polycaprolactone Substances 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 claims description 6
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 5
- 239000000344 soap Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 4
- RCGZRZBMXNWTFH-UHFFFAOYSA-N 2-[2-(2-octanoyloxyethoxy)ethoxy]ethyl decanoate Chemical compound CCCCCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCCC RCGZRZBMXNWTFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- 229920008262 Thermoplastic starch Polymers 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 229920003054 adipate polyester Polymers 0.000 claims description 4
- SCABKEBYDRTODC-UHFFFAOYSA-N bis[2-(2-butoxyethoxy)ethyl] hexanedioate Chemical compound CCCCOCCOCCOC(=O)CCCCC(=O)OCCOCCOCCCC SCABKEBYDRTODC-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 239000004628 starch-based polymer Substances 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- HERXOXLYNRDHGU-UHFFFAOYSA-N 5-methyl-2H-1,3-oxazol-2-id-4-one Chemical class CC1C(N=[C-]O1)=O HERXOXLYNRDHGU-UHFFFAOYSA-N 0.000 claims description 3
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- 229920002101 Chitin Polymers 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 claims description 3
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 3
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 3
- 229920006397 acrylic thermoplastic Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 229940031769 diisobutyl adipate Drugs 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 239000001087 glyceryl triacetate Substances 0.000 claims description 3
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012245 magnesium oxide Nutrition 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- 229920000765 poly(2-oxazolines) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229960002622 triacetin Drugs 0.000 claims description 3
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001069 triethyl citrate Substances 0.000 claims description 3
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000013769 triethyl citrate Nutrition 0.000 claims description 3
- TUUQISRYLMFKOG-UHFFFAOYSA-N trihexyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCOC(=O)CC(C(=O)OCCCCCC)(OC(C)=O)CC(=O)OCCCCCC TUUQISRYLMFKOG-UHFFFAOYSA-N 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000004386 Erythritol Substances 0.000 claims 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims 2
- 241000758789 Juglans Species 0.000 claims 2
- 229920002873 Polyethylenimine Polymers 0.000 claims 2
- 235000019414 erythritol Nutrition 0.000 claims 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims 2
- 229940009714 erythritol Drugs 0.000 claims 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 claims 2
- 239000012815 thermoplastic material Substances 0.000 abstract description 58
- 230000007613 environmental effect Effects 0.000 abstract description 10
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract 1
- 239000002202 Polyethylene glycol Substances 0.000 description 144
- 239000000463 material Substances 0.000 description 66
- 229920003023 plastic Polymers 0.000 description 42
- 239000004033 plastic Substances 0.000 description 42
- 230000000717 retained effect Effects 0.000 description 36
- 229920000747 poly(lactic acid) Polymers 0.000 description 35
- 239000007924 injection Substances 0.000 description 32
- 238000002347 injection Methods 0.000 description 32
- 239000000123 paper Substances 0.000 description 28
- 239000004615 ingredient Substances 0.000 description 27
- 239000004626 polylactic acid Substances 0.000 description 22
- 238000012545 processing Methods 0.000 description 20
- 101100457042 Dictyostelium discoideum mgst gene Proteins 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 238000001125 extrusion Methods 0.000 description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 16
- 238000010348 incorporation Methods 0.000 description 15
- 239000000178 monomer Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 description 14
- 235000010216 calcium carbonate Nutrition 0.000 description 14
- 239000008188 pellet Substances 0.000 description 14
- 239000010865 sewage Substances 0.000 description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 230000004580 weight loss Effects 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000002699 waste material Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 10
- CWEFIMQKSZFZNY-UHFFFAOYSA-N pentyl 2-[4-[[4-[4-[[4-[[4-(pentoxycarbonylamino)phenyl]methyl]phenyl]carbamoyloxy]butoxycarbonylamino]phenyl]methyl]phenyl]acetate Chemical compound C1=CC(CC(=O)OCCCCC)=CC=C1CC(C=C1)=CC=C1NC(=O)OCCCCOC(=O)NC(C=C1)=CC=C1CC1=CC=C(NC(=O)OCCCCC)C=C1 CWEFIMQKSZFZNY-UHFFFAOYSA-N 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- 229920002633 Kraton (polymer) Polymers 0.000 description 8
- 239000001361 adipic acid Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 8
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 8
- 239000004034 viscosity adjusting agent Substances 0.000 description 8
- 238000011010 flushing procedure Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 239000010802 sludge Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000006065 biodegradation reaction Methods 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000003780 insertion Methods 0.000 description 6
- 230000037431 insertion Effects 0.000 description 6
- 239000002667 nucleating agent Substances 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000003900 succinic acid esters Chemical class 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 5
- 150000008431 aliphatic amides Chemical class 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 235000019359 magnesium stearate Nutrition 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920002959 polymer blend Polymers 0.000 description 5
- 206010016825 Flushing Diseases 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000010128 melt processing Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 235000019271 petrolatum Nutrition 0.000 description 4
- 229920001281 polyalkylene Polymers 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008395 clarifying agent Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 229920002961 polybutylene succinate Polymers 0.000 description 3
- 239000004631 polybutylene succinate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000007655 standard test method Methods 0.000 description 3
- 229940070710 valerate Drugs 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N [H]CO Chemical compound [H]CO OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229960002684 aminocaproic acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920006187 aquazol Polymers 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 235000012243 magnesium silicates Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920002601 oligoester Polymers 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 150000003901 oxalic acid esters Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000012748 slip agent Substances 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 210000001215 vagina Anatomy 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 1
- JUQMLSGOTNKJKI-IZUQBHJASA-N (1s,4r)-2-(4-methylpiperazin-4-ium-1-carbonyl)-7-oxabicyclo[2.2.1]heptane-3-carboxylate Chemical compound C1C[NH+](C)CCN1C(=O)C1C(C([O-])=O)[C@H]2CC[C@@H]1O2 JUQMLSGOTNKJKI-IZUQBHJASA-N 0.000 description 1
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 description 1
- GZZLQUBMUXEOBE-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diol Chemical compound OCCC(C)CC(C)(C)CO GZZLQUBMUXEOBE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- CGYGETOMCSJHJU-UHFFFAOYSA-N 2-chloronaphthalene Chemical compound C1=CC=CC2=CC(Cl)=CC=C21 CGYGETOMCSJHJU-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 244000180278 Copernicia prunifera Species 0.000 description 1
- 235000010919 Copernicia prunifera Nutrition 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 241000870659 Crassula perfoliata var. minor Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- SRBFZHDQGSBBOR-ZRMNMSDTSA-N D-arabinopyranose Chemical compound O[C@@H]1COC(O)[C@@H](O)[C@@H]1O SRBFZHDQGSBBOR-ZRMNMSDTSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 241001553290 Euphorbia antisyphilitica Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 241001274658 Modulus modulus Species 0.000 description 1
- 235000009134 Myrica cerifera Nutrition 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 229920002534 Polyethylene Glycol 1450 Polymers 0.000 description 1
- 229920002562 Polyethylene Glycol 3350 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 229920002596 Polyethylene Glycol 900 Polymers 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000019915 STAR-DRI® Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 244000061457 Solanum nigrum Species 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- NRTLNQFZDQLUEY-UHFFFAOYSA-N [H]C(C)(OC(=O)C([H])(C)OC)C(C)=O Chemical compound [H]C(C)(OC(=O)C([H])(C)OC)C(C)=O NRTLNQFZDQLUEY-UHFFFAOYSA-N 0.000 description 1
- DLPGPGQJLPODMY-UHFFFAOYSA-N [H]C(C)(OC)C(C)=O Chemical compound [H]C(C)(OC)C(C)=O DLPGPGQJLPODMY-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001278 adipic acid derivatives Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 229940092738 beeswax Drugs 0.000 description 1
- HDLHSQWNJQGDLM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,5-dicarboxylic acid Chemical compound C1C2C(C(=O)O)CC1C(C(O)=O)C2 HDLHSQWNJQGDLM-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 description 1
- NZEWVJWONYBVFL-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1.CCCCOC(=O)C=C NZEWVJWONYBVFL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical class [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229920001887 crystalline plastic Polymers 0.000 description 1
- LNGJOYPCXLOTKL-UHFFFAOYSA-N cyclopentane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C1 LNGJOYPCXLOTKL-UHFFFAOYSA-N 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000008172 hydrogenated vegetable oil Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 150000002668 lysine derivatives Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical class [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001020 poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 102220235485 rs1131691363 Human genes 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 239000012176 shellac wax Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000012177 spermaceti Substances 0.000 description 1
- 229940084106 spermaceti Drugs 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000007056 transamidation reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/20—Tampons, e.g. catamenial tampons; Accessories therefor
- A61F13/26—Means for inserting tampons, i.e. applicators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S604/00—Surgery
- Y10S604/904—Tampons
Definitions
- the present invention relates to plastic tampon applicators which are readily disposed in a sewage system and/or by biodegradation.
- the present invention relates to flushable tampon applicators which are made from thermoplastic materials that are suitable for disposal in a toilet system.
- Feminine hygiene products such as tampons are commonly used by female consumers. Tampons can be described as a feminine hygiene article that has an absorbent device (i.e., pledget) withheld in a paper or plastic applicator.
- an absorbent device i.e., pledget
- Paper and plastic tampon applicators typically comprise an outer tubular member and a plunger for insertion of the pledget, whereby these components of the paper and plastic applicators are generally made from paper, paper coated, and plastic materials which retain their form during use and are shelf-stable under ambient conditions.
- paper tampon applicator components are suitable for disposal via a sewage system or by biodegradable waste disposal means. Therefore, paper tampon applicators are considered environmentally friendly in that these paper tampon applicators can readily disintegrate in a sewage system and/or can be disposed of through aerobic, anaerobic, and natural degradation processes.
- paper tampon articles are not very popular among females due to some tampon's pledget insertion difficulties associated with the use of a paper tampon applicator.
- plastic tampon applicators are made with a grip ring and petal-shaped forward end which facilitate ease of insertion of a tampon's pledget, although plastic tampon applicator components are not easily disposed of as compared to paper applicator components.
- Most plastic tampon applicators are made from polyethylene-based polymeric materials that are not biodegradable and that do not readily soften or break-up into smaller fragments for decomposition in a sewage system, resulting in increased environmental concerns for the disposal of plastic tampon applicators.
- plastic tampon applicators Many efforts to address the environmental concerns of the disposal of plastic tampon applicators include the manufacture of tampon applicators from thermoplastic materials other than polyethylene polymers. Such attempts include tampon applicators made from water-soluble materials, water-dispersible materials, biodegradable materials, photodegradable materials, ultraviolet light degradable materials, or combinations thereof. In particular, one attempt to address the disposal of plastic tampon applicators involves the use of plastic applicators made from biodegradable polymers such as polyvinyl alcohol polymers. It is known that tampon applicators made primarily from polyvinyl alcohol are water-dispersible and biodegradable, however, such applicators have been shown to suffer from issues involving moisture sensitivity, stability, odor, and stickiness.
- plastic tampon applicators made from other water-soluble materials such as polyethylene oxide polymers, thermoplastic starch, and hydroxypropyl cellulose; plastic tampon applicators made from combinations of water-soluble and water-insoluble/biodegradable materials such as combinations of polyvinyl alcohol and polycaprolactone, combinations of polyethylene oxide and polycaprolactone, combinations of polyethylene oxide and polyolefins such as polypropylene and polyethylene; and combinations of polyvinyl alcohol and polyethylene oxide polymers.
- plastic tampon applicator constructed from a combination of polyvinyl alcohol and polyethylene oxide is disclosed in U.S. Pat. No. 5,395,308.
- This plastic tampon applicator is described as being constructed to exhibit accelerated break-up and rapid disintegration in liquid such as water so that the plastic applicator can dissolve over an extended period of time without causing problems in sewage systems such as a waste treatment facility.
- the slow dissolution rate of these plastic tampon applicators can lead to the clogging of toilet systems and/or drain pipes because of the extended time required for these plastic applicators to initially come in contact with liquid such as toilet water and eventually reach waste disposal means at a waste treatment facility, especially if multiple plastic applicators are suited for disposal.
- plastic tampon applicators comprising polyvinyl alcohol have been known to become sticky when wet causing the applicator to stick to drain pipes which can result in repeated flushings to dispose of the applicator and to prevent clogging of toilet systems and/or the drain pipes.
- plastic tampon applicators made from thermoplastic materials that are flushable and can not only readily lose their structural integrity as for example breaking apart in unrecognizable pieces in a sewage system such as a toilet, but that can readily soften, disperse, disintegrate, and/or dissolve in a toilet for clear passage through the toilet to a municipal waste treatment facility.
- the tampon applicator components should also be anerobically and/or aerobically biodegradable, as well as provide for a flushable tampon applicator that is not slimy, sticky, or tacky to the touch before and during use.
- ingredients such as fillers, plasticizers, processing aids, dispersing agents, lubricants, resin modifiers, clarifying/nucleating agents, viscosity modifiers, and so forth are often included in the manufacturing of the applicator. These ingredients help in the process of the plastic tampon applicator as well as provide improved structural characteristics to the final applicator product form.
- plasticizers can increase flow and thermoplasticity of plastic materials by decreasing parameters such as the viscosity of polymer melts, the glass transition temperature, and the elasticity modulus of finished products to result in flushable plastic tampon applicators that have improved softness and flexibility.
- Lubricants are typically included as mold release agents and slip/anti-blocking agents to increase the overall rate of processing and to improve surface properties.
- Lubricants have been shown to improve product properties such as brightness, heat stability during processing, light stability, better additive dispersion, and improved optical and mechanical properties.
- Clarifying/nucleating agents are generally used to increase the crystallization rate, reduce the size of crystals, and improve transparency. Nucleating agents can also improve the meltflow and demolding behavior of partly crystalline plastic materials such as thermoplastic polyesters.
- fillers such as calcium carbonate and talc
- Filler materials are also important ingredients for use in the processing of the plastic applicators because they can assist in preventing the thermoplastics from sticking to the surface of processing equipment, reducing processing cycle time, acting as additional mold release and slip/anti-blocking agents, and increasing productivity.
- Another advantage of constructing flushable plastic tampon applicators with filler ingredients is the reduced cost to manufacture these applicators, especially when an acceptable flushable, plastic applicator can be constructed with low cost fillers to reduce the use of more costly thermoplastic material.
- the present invention is directed to flushable tampon applicators which comprise (a) from 0% to about 90% by weight of a water-dispersible polymer; (b) from about 10% to about 50% by weight of a biodegradable polymer, and (c) from 0% to about 50% by weight of a filler.
- the present invention is also directed to a method of making flushable tampon applicators wherein the method comprises (a) preparing a thermoplastic composite comprising (i) from 0% to about 90% by weight of a water-dispersible polymer; (ii) from about 10% to about 50% by weight of a biodegradable polymer; and (iii) from 0% to about 50% by weight of a filler; and (b) injection molding the thermoplastic composite into molded thermoplastic components used to construct the flushable tampon applicator.
- flushable tampon applicators can be made from a combination of thermoplastic materials, especially a blend of water-dispersible polymers such as high molecular weight polyethylene oxides and low molecular weight polyethylene glycols, and biodegradable polymers such as aliphatic/aromatic copolyesters, to result in flushable tampon applicators that readily disintegrate in a septic tank such as a toilet and are easily disposed of with minimal or no environmental issues.
- the flushable tampon applicators of the present invention comprise a combination of water-dispersible and biodegradable thermoplastic polymers which provide for improved disposal properties of the applicators. These applicators are capable of being flushed down a toilet or any other sewage system without causing drainage problems such as clogging, and are capable of biodegradation disposal using commonly employed biodegradation means.
- flushable tampon applicators have improved flushability and aesthetics when filler components are included in the construction of the applicators.
- the flushable tampon applicators are preferably constructed such that the filler is melt blended with the thermoplastic materials to form a composite mixture of filler particles and thermoplastic material, wherein the filler particles are uniformly dispersed throughout the applicator.
- the filler aids in the processing of the thermoplastic materials into final flushable plastic tampon applicator product forms that have improved flushability in addition to being nonsticky when wet, shelf stable, smooth, and soft to the touch.
- FIG. 1 is a perspective representation of a flushable tampon applicator ( 10 ) of the present invention made from a blend of thermoplastic materials.
- the flushable tampon applicator is comprised of a thermoplastic outer tubular member ( 11 ) and a thermoplastic inner tubular member or plunger ( 12 ).
- the outer tubular member ( 11 ) can be any known or otherwise effective thermoplastic, one-piece, hollow cylindrical body that has a plurality of flexible petal tips ( 13 ) extending from and disposed on the front end of the outer tube.
- the outer tubular member ( 11 ) functions to contain or house an absorbent device such as a pledget (not shown), and typically has a finger grip ring ( 14 ) formed on the opposite end of the outer tube wherein the finger grip ring has one or more ribs or protusions ( 15 ) on its exterior to provide a gripping surface to assist a user in holding the flushable tampon applicator ( 10 ).
- the finger grip portion of the outer tubular member ( 11 ) can be of other configurations such as gripping rings having score lines, ridges, dimples, one or more flat surfaces, a roughed surface, and so forth.
- the inner tubular member or plunger as referred to hereinafter ( 12 ) includes any known or otherwise effective thermoplastic plunger designed to be slidable and telescopically mounted within the finger grip ring ( 14 ) such that the plunger ( 12 ) can urge the pledget through the flexible petal tips ( 13 ) for insertion of the pledget into a woman's vagina.
- FIG. 2 is a cross-sectional view of a flushable tampon applicator of the present invention depicting a pledget absorbent device ( 16 ) positioned in the thermoplastic, cylindricallly shaped outer tubular member ( 11 ).
- a withdrawal string ( 17 ) is permanently attached to one end of the pledget ( 16 ) and provides a means of withdrawing the soiled tampon pledget ( 16 ) from a woman's vagina.
- FIG. 3 is a perspective view of a flushable tampon applicator ( 20 ) of the present invention having an outer tubular member ( 18 ) and a plunger ( 19 ), both of which are constructed from a composite of thermoplastic materials.
- the composite structure includes one or more units of water-dispersible thermoplastic polymers ( 21 ) affixed to one or more units of biodegradable polymers ( 22 ) such that the units are arranged in an alternating striped configuration.
- the composite structure can also be constructed such that the alternating units of water-dispersible and biodegradable polymers are arranged in a concentric ring configuration or a layered structure of composite materials.
- outer tubular members ( 11 ) and ( 18 ) are shown as having cylindrical shapes, the outer tubular members(II) and ( 18 ) can also be of square, elliptical, conical, or oval configurations.
- the plungers ( 12 ) and ( 19 ) which are typically of an oval configuration, can be configured in other shapes such as square, hemispherical, conical, and elliptical.
- the outer tubular members and plungers described herein can be constructed from clear, translucent, transparent, colored, or opaque thermoplastic materials, or combinations thereof.
- the flushable tampon applicators of the present invention comprise an outer tubular member and plunger made from water-dispersible and biodegradable materials that provide for tampon applicators that are readily disposed by flushing the applicator down a toilet, by biodegradable means, and/or by waste disposal means at a municipal waste treatment facility.
- flushable refers to materials which are capable of softening, dissolving, dispersing, disintegrating, and/or decomposing in a septic tank such as a toilet to provide clearance when flushed down the toilet without clogging the toilet or any other sewage drainage pipe.
- water-dispersible refers to materials that readily break apart in unrecognizable pieces upon contact with water as a result of dissolution, solubilization, dissipation, agitation, softening, or any other chemical or mechanical dispersion means.
- biodegradable refers to materials that when disposed of after use will physically and biologically decompose using known degradation procedures including aerobic, anaerobic, and microbial digestion processes.
- the biodegradable materials described herein include those degradable water-insoluble materials that will also physically and biologically decompose after disposal in a sewage system.
- ambient conditions refers to surrounding conditions at about one atmosphere of pressure, at about 50% relative humidity, at about 25° C.
- the water-dispersible and biodegradable thermoplastic polymers described herein can be generally defined according to their weight or number average molecular weight.
- the weight average molecular weight IMP) of a polymer is the summation of the weight fraction of each molecular species present multiplied by its molecular weight.
- the number average molecular weight (Mn) of a polymer is the summation of the mole fraction of each molecular species present multiplied by its molecular weight.
- the molecular weight of polymer materials can typically be determined by Size Exclusion Chromatography (SEC) or Gel Permeation Chromatography (GPC) techniques well known in the art.
- thermoplastic polymers described herein are used to construct the outer tubular member and plunger components of the flushable tampon applicators of the present invention.
- These outer tubular member and plunger components each have a density of greater than about 1.0 grams per cubic centimeter (g/cm 3 ) to about 3.0 g/cm 3 .
- Thermoplastic components having a density of greater than about 1.0 g/cm 3 will easily fall to the bottom of a septic tank such as a toilet, resulting in disposal of the thermoplastic components without the need of repeated flushings.
- the density of a given thermoplastic material and/or components made from the material will be dependent upon the degree of interaction of attractive forces between the polymer chains in the material, the degree of crystallinity of the thermoplastic material, and the presence of any additives, fillers or other optional components described herein. Therefore, if an individual thermoplastic material does not have a density of greater than about 1.0 g/cm 3 , the thermoplastic material can be combined with other thermoplastic materials and/or optional ingredients described herein to make suitable outer tubular members and plungers having a density of greater than about 1.0 g/cm 3 . Density values of the outer tubular and plunger components herein can be determined by any known or otherwise effective method for determining the density of thermoplastic materials and final products made from these materials.
- flushable tampon applicators of the present invention can comprise, consist of, or consist essentially of the elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, or limitations described herein.
- the flushable tampon applicators of the present invention typically comprise an outer tubular member and a plunger made from any known or otherwise effective thermoplastic materials that can readily soften and disintegrate upon contact with water such as toilet water.
- the thermoplastic materials are preferably combinations of water-dispersible and biodegradable polymers that are structurally stable before and during use while also being capable of rapid softening and disintegration in a toilet sewage system to provide disposal via the toilet to her enhance any additional disposal such as further disposal treatment of biodegradation and/or municipal waste disposal.
- the outer tubular member and plunger components of the flushable tampon applicator of the present invention can be constructed from the same or otherwise different water-dispersible and biodegradable materials.
- the outer tubular member and plunger both can be made from an individual or combination of water-dispersible materials; the outer tubular member and plunger both can be made from an individual or combination of biodegradable materials; the outer tubular member and plunger both can be made from a combination of water-dispersible and biodegradable materials; the outer tubular member can be made from water-dispersible materials and the plunger can be made from biodegradable materials; or the outer tubular member can be made from biodegradable materials and the plunger can be made from water-dispersible materials.
- outer tubular member and plunger components from the same or otherwise different combination of materials provide, for example, a flushable tampon applicator that has an outer tubular member with a lower stiffness or hardness relative to the plunger to increase insertion comfort.
- the outer tubular member and plunger may also be constructed from different combinations of materials to incorporate, for example, a flushability signal, such as a color change or effervescence, to the user.
- a flushability signal such as a color change or effervescence
- the flushable tampon applicators of the present invention comprise a total of from 0% to about 99%, preferably from about 5% to about 90%, more preferably from about 10% to about 80% of water-dispersible thermoplastic polymers by weight of the applicator.
- the water-dispersible thermoplastic polymers can be used individually or as a combination of polymers provided that the water-dispersible thermoplastic polymers can readily disintegrate in water, and can be combined with one or more biodegradable polymers described hereinafter.
- the water-dispersible thermoplastic polymers suitable for use herein include those water-dispersible compounds that can readily disintegrate in water such as toilet water while being structurally stable before contact with the water.
- the terms “structurally stable” and “structural stability” are used interchangeably herein to refer to materials that maintain their molded shape, form, and chemical composition before and during use, and that do not become sticky or slimy to the touch upon contact with moisture-laden air and/or moist human tissue.
- Nonlimiting examples of suitable water-dispersible thermoplastic polymers include high molecular weight polyethylene oxides, low molecular weight polyethylene glycols, polyethylene/polypropylene oxide copolymers, polyethylene/polybutylene oxide copolymers, polyethylene/polypropylene glycol copolymers, thermoplastic starch polymers, polyvinyl alcohols, partially hydrolyzed polyvinyl alcohols, modified polyvinyl alcohols, infrared treated polyvinyl alcohols, cross-linked polyvinyl alcohols such as a polyvinyl alcohol cross-linked with an aldehyde, alkali metal sulfonate thermoplastic polyesters, hydroxyethyl celluloses, hydroxypropyl celluloses, methylated hydroxypropyl celluloses, polyacrylic acids, polyaspartic acids, polymethacrylic acids, polysaccharides excluding sucrose polysaccharides suitable for use as a plasticizing agent herein, proteins, polyvinyl
- Preferred high molecular weight polyethylene oxides and low molecular weight polyethylene glycols suitable for use as water-dispersible thermoplastic polymers herein include those polyethylene oxides and polyethylene glycols which conform to the formula:
- n has an average value of from about 500 to about 180,000, preferably from about 650 to about 50,000, more preferably from about 800 to about 25,000, for high molecular weight polyethylene oxides; and an average value of from about 12 to about 465, preferably from about 12 to about 341, more preferably from about 13 to about 227, for low molecular weight polyethylene glycols.
- These materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, polyethylene glycols, and polymethoxyethylene glycols.
- preferred high molecular weight polyethylene oxides suitable for use as a water-dispersible thermoplastic polymer herein include, but are not limited to, polyethylene oxides having repeating alkylene oxide radicals in the ranges described hereinabove, and a weight average molecular weight of from about 65,000 daltons to about 8,000,000 daltons, preferably from about 80,000 daltons to about 2,000,000 daltons, more preferably from about 100,000 daltons to about 900,000 daltons.
- These polyethylene oxide polymers are prepared by methods known in the art for making high molecular weight copolymers and interpolymers of ethylene oxide.
- the high molecular weight copolymers of polyethylene oxide are prepared using ionic catalysts to react ethylene oxide with oxirane compounds such as styrene oxide, propylene oxide, butylene oxide, and the like.
- High molecular weight interpolymers of polyethylene oxide are prepared by co-polymerizing polyethylene oxide with one or more vinyl monomers such as N,N-dimethylaminoethyl methacrylate, styrene, methyl methacrylate, 2-methyl-5-vinyl pyridine, acrylonitrile, hydroxyethyl methacrylate, acrylic acid, acrylamide, and the like.
- Grafted or chemically modified high molecular weight polyethylene oxides are also suitable for use as a water-dispersible thermoplastic polymer herein.
- the weight average molecular weight (M w ) of the high molecular weight polyethylene oxides can be determined by measuring the intrinsic viscosity of a polyethylene oxide material in water at 30° C.
- Examples of commercially available high molecular weight polyethylene oxide polymers are the polyethylene oxides which are sold under the tradename POLYOX®, and which are available from the Dow Chemical Company located in Midland, Mich.. Specific examples of such polyethylene oxides include POLYOX® WSR-10 which has a M w of about 100,000; POLYOX® WSR-80 which has a M w of about 200,000; POLYOX® WSR-N-750 which has a M w of about 300,000; POLYOX® WSR-N-3000 which has a M w of about 400,000; POLYOX® WSR-3333 which has a M w of about 400,000; POLYOX® WSR-205 which has a M w of about 600,000; POLYOX® WSR-1105 which has a M w of about 900,000; POLYOX® WSR-N-K12 which has a M w of about 1,000,000; POLYOX® WSR-N-K60 which has a M
- preferred low molecular weight polyethylene glycols suitable for use as a water-dispersible thermoplastic polymer herein include, but are not limited to, polyethylene glycols having repeating alkylene oxide radicals in the ranges described hereinabove, and a number average molecular weight of from about 500 daltons to about 20,000 daltons, preferably from about 550 daltons to about 15,000 daltons, more preferably from about 600 daltons to about 10,000 daltons.
- the number average molecular weight (M n ) of the low molecular weight polyethylene glycols can be determined by known titration procedures used to determine the number of molecules having hydroxy-end groups wherein the M n is calculated based on the weight of a given polyethylene glycol divided by the number of hydroxy-end group-containing molecules within the polyethylene glycol polymer.
- Nonlimiting examples of the preferred low molecular weight polyethylene glycols include those polyethylene glycols (PEG) and polymethoxyethylene glycols (MPEG) that are commercially available from Dow Chemical, and sold as PEG-600 which has a M n of about 600; PEG-900 which has a M n of about 900; PEG-1000 which has a M n of about 1000; PEG-1450 which has a M n of about 1450; PEG-3350 which has a M n of about 3350; PEG-4000 which has a M n of about 4,000; PEG-4600 which has a M w of about 4600; PEG-8000 which has a M w of about 8,000; MPEG-550 which has a M n of about 550; MPEG-750 which has a M n of about 750; MPEG-2000 which has a M n of about 2,000; MPEG-5000 which has a M n of about 5,000; and mixtures thereof.
- PEG polyethylene glyco
- polyvinyl alcohols suitable for use as a water-dispersible thermoplastic polymer herein include, but are not limited to, those water-soluble thermoplastic polymers prepared by the partial or complete hydrolysis of polyvinyl acetate.
- the degree of hydrolysis of polyvinyl acetate results in polyvinyl alcohols having different residual acetyl groups and therefore different molecular weight and viscosity characteristics. Accordingly, the water solubility of the polyvinyl alcohol can be regulated by controlling the hydrolysis, molecular weight, and viscosity of the specific polyvinyl alcohol resin.
- Nonlimiting examples of such suitable polyvinyl alcohols include polyvinyl alcohols having a percent hydrolysis of from about 74% to about 98%, specific nonlimiting examples of which include polyvinyl alcohol 98% hydrolyzed ultra low viscosity resin having a viscosity of from about 3.2 centipoises (cps) to about 4.2 cps, and a weight average molecular weight of from about 13,000 daltons to about 23,000 daltons; polyvinyl alcohol 88% hydrolyzed ultra low viscosity resin having a viscosity of from about 3.0 cps to about 4.0 cps, and a weight average molecular weight of from about 13,000 daltons to about 23,000 daltons; polyvinyl alcohol 88% hydrolyzed low viscosity resin having a viscosity of from about 5.2 cps to about 6.2 cps, and a weight average molecular weight of from about 31,000 daltons to about 50,000 daltons; and mixture
- the viscosity of the polvinyl alcohols and any other suitable thermoplastic polymer and optional ingredient described herein are measured or determined under ambient conditions, unless otherwise specified, using suitable methods known in the art.
- suitable methods for measuring or determining viscosity include method DIN 53 015 which involves the use of a Hoppler falling-ball viscometer for measuring dynamic viscosity in units of Pascal-seconds (Pa-s), and methods DIN 53 562 and DIN 53 012 which involve the use of a Ubbelohde glass capillary viscometer to measure kinematic viscosity in units of square centimeters per second (cm 2 /sec).
- polyvinyl alcohols include, but are not limited to, water dispersible polyvinyl alcohol resins that have been modified to contain pendant alcohol groups. These modified polyvinyl alcohols can be produced by polymerizing a polyethylene oxide acrylate with vinyl acetate and then hydrolyzing the resultant polymer to produce pendant alcohol groups. Modified polyvinyl alcohols prepared by this procedure typically have viscosities ranging from about 500 poise to about 4,500 poise dependent upon the shear rate used to form the modified polyvinyl alcohol into a molded thermoplastic polymer.
- modified polyvinyl alcohols examples include those modified polyvinyl alcohol resins manufactured by Texas Polymer Services Incorporation (Houston, Tex.), and sold under the VINEX and AIRVOL tradenames.
- VINEX resins include, but are not limited to, VINEX 2019, VINEX 2025, VINEX 2034, and VINEX 2144.
- AIRVOL resins include, but are not limited to, AIRVOL 125 and AIRVOL 325.
- suitable polyvinyl alcohols include, but are not limited to, the polyvinyl alcohols that are commercially available from Clariant GmbH (Sulzbach, Germany) under the MOWIOL tradename.
- MOWIOL resins include MOWIOL 18-88, MOWIOL 26-88, and MOWIOL 30-92.
- Nonlimiting specific examples of alkali metal sulfonate polyesters suitable for use as a water-dispersible thermoplastic polymer herein include those water-dispersible, linear thermoplastic polyesters which contain carbonyloxy-linking groups in the linear, molecular structure.
- the alkali metal sulfonate polyesters are typically prepared by reacting at least one difunctional dicarboxylic acid, at least one diol, and at least one difunctional sulfomonomer containing at least one metal sulfonate group attached to an aromatic nucleus having the functional group carboxyl.
- the number average molecular weight of suitable alkali metal sulfonate polyesters ranges from about 13,000 daltons to about 19,000 daltons, based on the number of repeating sulfomonomer groups in the molecule. It is believed that the sulfomonomer substituent is primarily responsible for the water dispersibility of the thermoplastic polyester.
- Nonlimiting examples of commercially available water-dispersible, linear thermoplastic polyesters include the alkali metal sulfonates sold under the tradename Eastman AQ® polymer from Eastman Chemical Products, Incorporation located in Kingsport, Tenn., specific examples of which include Eastman AQ(D 1045, Eastman AQ® 1350, Eastman AQS 1950, Eastman AQ® 14,000, Eastman AQ® 29S, Eastman LB-100 AQ® 29S, Eastman AQ® 55S, Eastman AQ® 38S, Eastman AQ® 48, and mixtures thereof.
- Eastman AQ® polymer from Eastman Chemical Products, Incorporation located in Kingsport, Tenn.
- specific examples of which include Eastman AQ(D 1045, Eastman AQ® 1350, Eastman AQS 1950, Eastman AQ® 14,000, Eastman AQ® 29S, Eastman LB-100 AQ® 29S, Eastman AQ® 55S, Eastman AQ® 38S, Eastman AQ® 48
- the flushable tampon applicators of the present invention comprise a total of from about 1% to about 99%, preferably from about 5% to about 95%, more preferably from about 10% to about 90% of biodegradable thermoplastic polymers by weight of the applicator.
- the biodegradable thermoplastic polymers can be used individually or as a combination of polymers provided that the biodegradable thermoplastic polymers are degradable by biological and environmental means, and that they are compatible for combination with one or more water-dispersible polymers described hereinabove,
- the biodegradable polymers suitable for use herein are those biodegradable materials which are susceptible to being assimilated by microorganisms such as molds, fungi, and bacteria when the biodegradable material is buried in the ground or otherwise comes in contact with the microorganisms including contact under environmental conditions conducive to the growth of the microorganisms.
- Suitable biodegradable polymers also include those biodegradable materials which are environmentally degradable using aerobic or anerobic digestion procedures, or by virtue of being exposed to environmental elements such as sunlight, rain, moisture, wind, temperature, and the like.
- Nonlimiting examples of biodegradable thermoplastic polymers suitable for use in the flushable tampon applicators of the present invention include aliphatic polyesteramides; diacid/diol-based aliphatic polyesters; aromatic polyesters including modified polyethylene terephthalates; aliphatic/aromatic copolyesters; polycaprolactones; polycaprolactone copolymers; poly(3-hydroxyalkanoates) including poly(3-hydroxybutyrates), poly(3-hydroxyhexanoates), and poly(3-hydroxyvalerates); poly(3-hydroxyalkanoates) copolymers including poly(3-hydroxy) butyrate/valerate copolymers; polyesters and polyurethanes derived from aliphatic polyols (i.e., dialkanoyl polymers); polyvinyl acetates; polyethylene/vinyl alcohol copolymers; lactic acid polymers including lactic acid homopolymers and lactic acid copolymers;
- aliphatic polyesteramides suitable for use as a biodegradable thermoplastic polymer herein include, but are not limited to, aliphatic polyesteramides which are reaction products of a synthesis reaction of diols, dicarboxylic acids, and aminocarboxylic acids; aliphatic polyesteramides formed from reacting lactic acid with diamines and dicarboxylic acid dichlorides; aliphatic polyesteramides formed from caprolactone and caprolactam; aliphatic polyesteramides formed by reacting acid-terminated aliphatic ester prepolymers with aromatic diisocyanates; aliphatic polyesteramides formed by reacting aliphatic esters with aliphatic amides; and mixtures thereof. Aliphatic polyesteramides formed by reacting aliphatic esters with aliphatic amides are most preferred.
- Preferred aliphatic polyesteramides which are copolymers of aliphatic esters and aliphatic amides can be characterized in that these copolymers generally contain from about 30% to about 70%, preferably from about 40% to about 80% by weight of aliphatic esters, and from about 70% to about 30%, preferably from about 60% to about 20% by weight of aliphatic amides.
- the weight average molecular weight of these copolymers ranges from about 10,000 daltons to about 500,000 daltons, preferably from about 20,000 daltons to about 300,000 daltons as measured by known gel chromatography techniques used in the determination of molecular weight of polymers.
- the aliphatic ester and aliphatic amide copolymers of the preferred aliphatic polyesteramides are derived from monomers such as dialcohols including ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, and the like; dicarboxylic acids and dicarboxylhc acid esters including oxalic acid, succinic acid, adipic acid, oxalic acid esters, succinic acid esters, adipic acid esters, and the like; hydroxycarboxylic acid and lactones including caprolactone, and the like; aminoalcohols including ethanolamine, propanolamine, and the like; cyclic lactams including s-caprolactar, lauric lactam, and the like; (o-aminocarboxylic acids including aminocaproic acid, and the like; 1:1 salts of dicarboxylic acids including
- Hydroxy-terminated or acid-terminated polyesters such as acid terminated oligoesters can also be used as the ester-forming compound.
- the hydroxy-terminated or acid terminated polyesters typically have number average molecular weights of from about 200 daltons to about 10,000 daltons.
- the preferred aliphatic polyesteramides can be prepared by any suitable synthesis or stoichiometric technique known in the art for forming aliphatic polyesteramides having aliphatic ester and aliphatic amide monomers.
- a typical synthesis involves stoichiometrically mixing the starting monomers, optionally adding water to the reaction mixture, polymerizing the monomers at an elevated temperature of about 220° C., and subsequently removing the water and excess monomers by distillation using vacuum and elevated temperature, resulting in a final copolymer of an aliphatic polyesteramide.
- Other suitable techniques involve transesterification and transamidation reaction procedures.
- a catalyst can be used in the above-described synthesis reaction and transesterification or transaindation procedures, wherein suitable catalysts include phosphorous compounds, acid catalysts, magnesium acetates, zinc acetates, calcium acetates, lysine, lysine derivatives, and the like.
- the preferred aliphatic polyesteramides comprise copolymer combinations of adipic acid, 1,4-butanediol, and 6-aminocaproic acid with an ester portion of 45%; adipic acid, 1,4-butanediol, and ⁇ -caprolactam with an ester portion of 50%; adipic acid, 1,4-butanediol, and a 1:1 salt of adipic acid (“AH salt”) and 1,6-hexamethylenediamine; and an acid-terminated oligoester made from adipic acid, 1,4-butanediol, 1,6-hexamethylenediamine, and s-caprolactam.
- AH salt adipic acid
- s-caprolactam an acid-terminated oligoester made from adipic acid, 1,4-butanediol, 1,6-hexamethylenediamine, and s-caprolactam.
- polyesteramides have melting points of from about 115° C. to about 155° C. and relative viscosities (1 wt. % in m-cresol at 25° C.) of from about 2.0 to about 3.0, and are commercially available from Bayer Aktiengesellschaft located in Leverkusen, Germany under the BAK® tradename. Specific examples of such commercially available polyesteramides include BAK® 402, BAK® 403, and BAK® 404.
- preferred diacid/diol-based aliphatic polyesters suitable for use as a biodegradable thermoplastic polymer herein include, but are not limited to, aliphatic polyesters produced either from ring opening reactions or from the condensation polymerization of aliphatic diacids and aliphatic diols, wherein the number average molecular weight of these aliphatic polyesters typically range from about 30,000 daltons to about 300,000 daltons.
- the preferred diacid/diol-based aliphatic polyesters are reaction products of a C 2 -C 10 diol reacted with oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, copolymers thereof, or mixtures thereof.
- Nonlimting examples of preferred diacid/diol-based aliphatic polyesters include polyalkylene succinates such as polyethylene succinate, and polybutylene succinate; polyalkylene succinate copolymers such as polyethylene succinate/adipate copolymer, and polybutylene succinate/adipate copolymer; polypentamethyl succinates; polyhexamethyl succinates; polyheptamethyl succinates; polyoctamethyl succinates; polyalkylene oxalates such as polyethylene oxalate, and polybutylene oxalate; polyalkylene oxalate copolymers such as polybutylene oxalate/succinate copolymer and polybutylene oxalate/adipate copolymer; polybutylene oxalate/succinate/adipate terpolymers; and mixtures thereof.
- polyalkylene succinates such as polyethylene succinate, and polybutylene succ
- polyesters An example of suitable commercial diacid/diol-based aliphatic polyesters is the polybutylene succinate/adipate copolymers sold under the BIONOLLE 1000 and BIONOLLE 3000 tradenames from the Showa Highpolymer Company, Ltd. located in Tokyo, Japan.
- preferred poly(3-hydroxyalkanoates) suitable for use as a biodegradable thermoplastic polymer herein include, but are not limited to, the poly(3-hydroxyalkanoates commercially available under the Biomer 209H and Biomer 240H tradenames from the Biomer Company located in Krailling, Germany.
- Specific examples of preferred poly(3-hydroxyalkanoates) copolymers suitable for use as a biodegradable polymer herein include, but are not limited to the poly(3-hydroxy) butyrate/valerate copolymers disclosed in U.S. Pat. No. 5,391,423, issued to Wnuk et al. on Feb.
- poly(3-hydroxy) butyrate/valerate copolymers such as poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxydocosanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexadecanoate), poly(3-hydroxyvalerate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerateco-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerateco-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxydecanoate), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate-
- preferred aliphatic/aromatic copolyesters suitable for use as a biodegradable thermoplastic polymer herein include, but are not limited to, those aliphatic/aromatic copolyesters that are random copolymers formed from a condensation reaction of dicarboxylic acids or derivatives thereof and diols.
- Suitable dicarboxylic acids include, but are not limited to, malonic, succinic, glutaric, adipic, pimelic, azelaic, sebacic, fumaric, 2,2-dimethyl glutaric, suberic, 1,3-cyclopentanedicarboxylic, 1,4-cyclohexanedicarboxylic, 1,3-clohexanedicarboxylic, diglycolic, itaconic, maleic, 2,5-norbornanedicarboxylic, 1,4-terephthalic, 1,3-terephthalic, 2,6-naphthoic, 1,5-naphthoic, ester forming derivatives thereof, and combinations thereof.
- Suitable diols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and combinations thereof.
- Nonlimiting examples of such aliphatic/aromatic copolyesters include a 50/50 blend of poly(tetramethylene glutarate-co-terephthalate), a 60/40 blend of poly(tetramethylene glutarate-co-terephthalate), a 70/30 blend of poly(tetramethylene glutarate-co-terephthalate), an 85/15 blend of poly(tetramethylene glutarate-co-terephthalate), a 50/45/15 blend of poly(tetramethylene glutarate-co-terephthalate-co-diglycolate), a 70/30 blend of poly(ethylene glutarate-co-terephthalate), an 85/15 blend of poly(tetramethylene adipate-co-terephthalate), an 85/15 blend of poly(tetramethylene succinate-co-terephthalate), a 50/50 blend of poly(tetramethylene-co-ethylene glutarate-co-terephthalate), and a 70/30 blend of
- lactic acid polymers and lactide polymers suitable for use as a biodegradable thermoplastic polymer herein include, but are not limited to, those polylactic acid-based polymers and polylactide-based polymers that are generally referred to in the industry as “PLA”. Therefore, the terms “polylactic acid”, “polylactide” and “PLA” are used interchangeably to include homopolymers and copolymers of lactic acid and lactide based on polymer characterization of the polymers being formed from a specific monomer or the polymers being comprised of the smallest repeating monomer units.
- polylactide is a dimeric ester of lactic acid and can be formed to contain small repeating monomer units of lactic acid (actually residues of lactic acid) or be manufactured by polymerization of a lactide monomer, resulting in polylactide being referred to both as a lactic acid residue containing polymer and as a lactide residue containing polymer.
- polylactic acid polylactic acid
- polylactide and “PLA” are not intended to be limiting with respect to the manner in which the polymer is formed.
- the polylactic acid polymers generally have a lactic acid residue repeating monomer unit that conforms to the following formula:
- polylactide polymers generally having lactic acid residue repeating monomer units as described herein-above, or lactide residue repeating monomer units that conform to the following formula:
- polymerization of lactic acid and lactide will result in polymers comprising at least about 50% by weight of lactic acid residue repeating units, lactide residue repeating units, or combinations thereof.
- lactic acid and lactide polymers include homopolymers and copolymers such as random and/or block copolymers of lactic acid and/or lactide.
- the lactic acid residue repeating monomer units can be obtained from L-lactic acid and D-lactic acid.
- the lactide residue repeating monomer units can be obtained from L-lactide, D-lactide, and meso-lactide.
- Suitable lactic acid and lactide polymers include those homopolymers and copolymers of lactic acid and/or lactide which have a weight average molecular weight generally ranging from about 10,000 daltons to about 600,000 daltons.
- An example of commercially available polylactic acid polymers includes a variety of polylactic acids that are available from the Chronopol Incorporation located in Golden, Colorado.
- An example of commercially available polylactide polymers includes the polylactides sold under the tradename EcoPLA®.
- An example of commercially available “PLA” polymers includes PLA 44D and PLA 62-50, both of which are available from Cargill-Dow Polymers, LLC located in Minnetonka, Minn.
- polylactic acid polymers and copolymers include polylactic acid prepared by direct polycondensation of lactic acid (available from the Mitsui Chemical Incorporation under the tradename LACEA), and a block copolymer comprising a polylactic acid hard segment and a polyoxyalkylene dialkanoate soft segment (available from the Dainippon Ink and Chemicals Incorporation and the Shimadzu Corporation, both of which are located in Japan).
- biodegradable polymers include polycaprolactone polyesters having a number average molecular weight of from about 10,000 daltons to about 80,000 daltons.
- Commercially suitable polycaprolactone polymers are the polycaprolactones available from the Union Carbide Corporation sold under the TONE tradename, examples of which include Tone P-767, Tone P-787, and Tone P-303.
- Tone P-767 has a number average molecular weight of about 43,000 daltons.
- Tone P-787 has a number average molecular weight of about 80,000 daltons.
- Tone P-303 is an A-B-A block polymer of Tone P-767 polycaprolactone and polyethylene oxide, and has a number average molecular weight of from about 30,000 daltons to about 35,000 daltons.
- thermoplastic compositions containing these polymers will physically and biologically decompose using known degradation procedures such as aerobic, anaerobic, and microbial digestion processes.
- One such method of evaluating the decomposition of biodegradable materials includes an anaerobic disintegration procedure which involves measuring the percent weight loss of thermoplastic compositions containing biodegradable polymers.
- thermoplastic compositions containing biodegradable polymers are exposed to anaerobic sludge that can be obtained from a municipal wastewater treatment plant (e.g., sludge that has a pH of or between about 7 and 8, and about 1% total solids).
- the sludge-exposed thermoplastic compositions are allowed to disintegrate or decompose for 7, 14, and 28 days at 35° C. under controlled incubator conditions. After the 7, 14, or 28 day incubation period, the sludge-exposed thermoplastic compositions are evaluated for percent weight loss by recovering any undisintegrated portions of the compositions, drying these undisintegrtaed portions at 40° C. for at least 2 hours after a tap water rinsing, and determining the weight of the dried undisintegrated portions. The percent weight loss is calculated based on the weight of the thermoplastic compositions before and after exposure to sludge for a given time period.
- biodegradable polymer containing-thermoplastic compositions described herein lose their structural integrity by breaking apart into smaller pieces and/or by shrinking into smaller fragments after being exposed to sludge for only 7 days. Anaerobic biodegradation of these biodegradable polymer containing-thennoplastic compositions increased after the compositions were exposed to sludge for periods of 14 and 28 days.
- the flushable tampon applicators of the present invention preferably comprise one or more fillers which can aid in the applicators having an opaque appearance and provide for applicators that have a smooth, soft texture and improved water-dispersibility.
- the filler can be added by compounding the filler with the thermoplastic polymers and any optional ingredient described herein, and processing this compounded mixture according to the disclosed methods of constructing flushable tampon applicators of the present invention.
- the flushable tampon applicators are constructed such that the filler is melt blended with the thermoplastic polymers to form a composite of thermoplastic material and discrete filler particles that are uniformly dispersed throughout the composite, flushable tampon applicator structure.
- Suitable fillers include inorganic and organic filler materials.
- suitable inorganic fillers include clays, silica, mica, wollastonite, calcium hydroxide, calcium carbonate, sodium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, kaolin, calcium oxide, magnesium oxide, aluminum hydroxide, magnesium silicates including talc, titanium dioxide, and mixtures thereof.
- suitable organic fillers include wood flour, walnut shell flour, alpha cellulose floc, cellulose fibers, chitin, chitosan powders, organosilicone powders, nylon powders, polyester powders, polypropylene powders, starch granules, and mixtures thereof. Filler components such as calcium carbonate, talc, barium sulfate, starch granules, and wood flour are preferred.
- the fillers are typically included at total filler concentrations ranging from 0% to about 70%, preferably from about 5% to about 65%, more preferably from about 8% to about 60% by weight of the applicator.
- the inclusion of filler components within the defined concentration ranges have been found to provide the flushable tampon applicators with improved disintegration rate for spontaneous flushability in addition to the flushable tampon applicators being shelf stable, nonsticky when wet, nontacky when wet, and smooth to the touch.
- the filler components can be included in the construction of the flushable tampon applicators as an individual filler or a combination of filler components provided that the total filler concentration is within these defined concentration ranges.
- calcium carbonates suitable for use of a filler herein include but are not limited to, the calcium carbonates commercially available from Specialty Minerals (Bethlehem, Pa.) under the Vicron 15-15, Vicron 10-25, and Vicron 25-11 tradenames.
- magnesium silicates such as talc which are suitable for use as a filler herein include, but are not limited to, ABT 2500 talc and OPTIBLOC 10 talc, both of which are available from Specialty Minerals.
- starch granule materials suitable for use as a filler herein include, but are not limited to, the corn starch materials sold under the Staley STAR-DRI® 1 and Staley Pure Food Powdered tradenames, both of which are commercially available the A. E. Staley Manufacturing Company (Decatur, Ill.); Clinton 290 which is commercially available from ADM Corn Processing (Decatur, Ill.); and National Starch Melojel which is commercially available from National Starch & Chemical (Bridgewater, N.J.).
- wood flour materials suitable for use as a filler herein include, but are not limited to, Maple Wood Flour, Grade 10010 and Pine Wood Flour, Grade 10020, both of which are commercially available from American Wood Fibers (Columbia, Md.).
- a specific example of a nylon powder suitable for use as a filler herein is Morton Corvel White Nylon 11 powder which is commercially available from the Morton International Incorporation located in Chicago, Ill.
- a specific example of a polyester powder suitable for use as a filler herein is Morton Corvel H RF polyester powder which is commercially available from the Morton International Incorporation.
- Titanium Dioxide Grade R102 17145T-43 which is commercially available from Dupont White Pigment & Mineral Products located in Wilmington, Del.
- the flushable tampon applicators of the present invention preferably comprise a blend of water-dispersible and biodegradable materials, wherein this blend can be defined as a combination of one or more high molecular weight polyethylene oxides, one or more low molecular weight polyethylene glycols, and one or more aliphatic/aromatic copolyesters.
- this blend refers to a composition of thermoplastic materials that has been formed by melt processing two or more thermoplastic materials to result in a homogenous, heterogeneous, or mixture thereof, of these materials.
- thermoplastic blend comprising a combination of high molecular weight polyethylene oxides, low molecular weight polyethylene glycols, and aliphatic/aromatic copolyesters provides a flushable tampon applicator that readily disintegrates in water, that has improved aesthetics such as non-sticky, non-slimy, air-laden moisture resistance, softness, flexibility, and that is of little or no environmental concern for disposal.
- thermoplastic composition comprising a total of from about 1% to about 90% by weight of high molecular weight polyethylene oxides, a total of from about 1% to about 4 0% by weight of low molecular weight polyethylene glycols, and a total of from about 9% to about 59% by weight of aliphatic/aromatic copolyesters.
- thermoplastic compositions can comprise blended ratios of water-dispersible materials such as high 20 molecular weight polyethylene oxides and low molecular weight polyethylene glycols to biodegradable materials such as aliphatic/aromatic copolyesters of from about 10:1 to about 1:6, preferably of from about 4:1 to about 1:3.
- the ratio of water-dispersible materials such as a ratio of high molecular weight polyethylene oxide to low molecular weight polyethylene glycol, typically ranges from about 9:1 to about 1:4, preferably from about 3:1 to about 1:2.
- the flushable tampon applicators of the present invention can also comprise other blends of water-dispersible and biodegradable thermoplastic polymers, nonlimiting examples of which include a blend of one or more high molecular weight polyethylene oxides, one or more low molecular weight polyethylene glycols, and one or more diacid/diol-based aliphatic polyesters; a blend of one or more high molecular weight polyethylene oxides, one or more low molecular weight polyethylene glycols, and one or more aliphatic polyesteramides; and a blend of one or more high molecular weight polyethylene oxides, one or more low molecular weight polyethylene glycols, and one or more polylactic acid polymers.
- These blends as well as the above-described preferred thermoplastic polymer blend and any other blend or structure of thermoplastic materials are suitable for forming the outer tubular member and plunger components of the flushable tampon applicators of the present invention.
- the flushable tampon applicators of the present invention can also comprise a composite of thermoplastic materials.
- composite refers to a structure of thermoplastic polymeric materials that are intermingled together or joined such that each thermoplastic polymer forms at least one unit of the total composite structure.
- a thermoplastic composite can contain one or more units of water-dispersible polymers intermixed or joined with one or more units of biodegradable polymers such that within the overall composite structure the water-dispersible polymer units create structural discontinuities between the biodegradable polymer units.
- structural discontinuities refers to discrete or separate components that are joined or intermingled to provide adjacent or alternate units of individual components.
- thermoplastic composite is constructed such that it comprises less than about 99% of water-dispersible polymers and more than about 1% of biodegradable polymers, more preferably less than about 95% of water-dispersible polymers and more than about 5% of biodegradable polymers, even more preferably less than about 90% of water-dispersible polymers and more than about 10% of biodegradable polymers, by weight of the composite.
- the thermoplastic composites can be any composite combination of water-dispersible and biodegradable polymers described herein provided that the water-dispersible polymers allow for rapid dispersion of the biodegradable polymers into separate components so that the overall composite structure readily disintegrates upon contact with water.
- thermoplastic composite tampon applicators can be constructed using known procedures such as injection molding and co-injection molding which eliminate the need to assemble separate composite pieces for producing a final tampon applicator product.
- the thermoplastic composite tampon applicators can be constructed by molding separate composite pieces and assembling or joining the pieces into a final tampon applicator product, wherein means of assembling or joining the composite pieces include adhesive bonding, heat sealing, ultrasonic welding, solvent welding, dielectric sealing, and mechanical attachment.
- the flushable tampon applicators of the present invention made from thermoplastic composites have been found to be readily disposed of by flushing down a sewage system such as a toilet and by the disclosed biodegradation procedures.
- the composite tampon applicators can also be made from a composite structure of thermoplastic polymers combined with paper, cellulose, cellophane, rayon fiber, woven, nonwoven materials, or combinations thereof.
- flushable tampon applicators of the present invention can be constructed 30 in any other blend, composite, shape, or configuration using the water-dispersible and/or biodegradable thermoplastic polymers, and any other desired or optional ingredient described herein.
- Another nonlimiting preferred embodiment includes spiral shaped flushable tampon applicators made from spirally wound thermoplastic materials that are held together using water-soluble adhesives.
- the water-soluble adhesive materials may be any known or otherwise effective water-soluble adhesives, but preferably are polyethyloxazoline and methyl cellulose adhesives.
- the flushable tampon applicators of the present invention can also comprise a composite of thermoplastic material and a non-thermoplastic material wherein the non-thermoplastic material is selected from the group including paper, starch, cellulose, cellophane, rayon fiber, natural fiber fabrics either woven or nonwoven, and combinations thereof.
- the thermoplastic material may be combined with the non-thermoplastic material by various techniques such as overmolding or insert molding. In overmolding, the non-thermoplastic material, for example a paper tube, is placed into an injection mold cavity, the mold clamped shut, and a molten thermoplastic resin is injected into the cavity such that the non-thermoplastic material is encapsulated or partly encapsulated by the thermoplastic material.
- overmolding can provide, for example, a means of providing plastic-like features to a paper tube, or providing the look and feel of a plastic applicator to a paper tube, or providing a means of minimizing the amount of thermoplastic material needed to form the applicator components.
- Both inner and outer tube members may be fabricated from a composite of thermoplastic material and a non-thermoplastic material.
- the non-thermoplastic material is typically provided in a roll, unwound, and then trimmed or formed to a proper preform size and shape appropriate to insertion into the injection mold. The perform (or performs) is placed, along the wall of the mold cavity.
- insert molding can provide, for example, a means of attaching a thin, water-insoluble, biodegradable surface layer to a water-softenable or water-dispersable, or water-degradable, or water-soluble thermoplastic resin.
- flushable tampon applicators include a composite flushable tampon applicator made from a combination of water-dispersible thermoplastic polymers, biodegradable thermoplastic polymers, and filler. These composite applicator structures are less tacky when wet, non-sticky when wet, softer, and more flexible than plastic tampon applicators made without filler components.
- the filler-containing composite applicators also result in reduced manufacturing cost with improved processibility of the applicators.
- Any suitable inorganic and/or organic filler component can be included in the construction of the composite applicator, provided that during the processing of the applicator the filler does not melt and remain in its particle form.
- the processing temperatures are lower than the melting temperature and decomposition temperature of the fillers, and during processing the water-dispersible and biodegradable thermoplastic polymers are melted and the filler particles are uniformly dispersed in the matrix of polymer blends of the water-dispersible and biodegradable polymers to result in the formation of a composite structure.
- the fillers suitable for use herein generally are water insoluble which help to reduce the stickiness of the applicators upon contact of the applicators with water, and which help to increase the shelf stability of the applicators.
- the fillers are in the dispersed phase of the composite, they accelerate the disintegration rate when the matrix of polymer blends of water-dispersible and biodegradable polymers start to disintegrate after flushing into a sewage system such as a toilet.
- the flushable tampon applicators of the present invention be constructed from thermoplastic materials that are typically in the form of polymer films. It should be understood, however, that these thermoplastic materials are also suitable for use as fibrous materials in the construction of absorbent articles such as tampon pledgets or any other fibrous or nonwoven material.
- Thermoplastic compositions suitable for use in the manufacture of flushable tampon applicators of the present invention can be a blend or other configuration of polymeric materials which will result in the compositions exhibiting amorphous and crystalline properties that can be characterized in terms of compositional morphology. It has been found that a particular blend of water-dispersible and biodegradable polymers described herein results in a thermoplastic composition having a defined morphology which provides for individual components of the composition to have melt profiles that allows for the creation of crystalline structures in the form of separate regions or domains within the blended nmixture of thermoplastic materials.
- thermoplastic composition comprising a blend of high molecular weight polyethylene oxides, low molecular weight polyethylene glycols, and aliphatic polyesteramides or aliphatic/aromatic copolyesters exhibits a morphology such that the polyethylene oxides and polyethylene glycols form a homogenous blend of water-dispersible polymers that surrounds or encloses microdomains of the aliphatic polyesteramides or aliphatic/aromatic polyesters.
- microdomain refers to polymer crystalline structures that have particle sizes in the submicron to micron sized region.
- thermoplastic composition comprising a blend of water dispersible polymers such as high molecular weight polyethylene oxides and/or low molecular weight polyethylene glycols in combination with biodegradable polymers such as diacids/diols aliphatic polyesters forms a homogeneous one-phase polymer morphology.
- the two phase crystalline structure of a continuous phase of water-dispersible polymers and a discontinuous phase of biodegradable polymer microdomains are especially effective in forming thermoplastic compositions that can be melt processed into flushable tampon applicators of the present invention which are readily disposed of without creating any environmental concerns for their disposal.
- the two-phase crystalline structure has a morphology profile of water-dispersible and biodegradable polymers wherein in the liquid state (temperature above the melting point of the individual polymers), the polymers exhibit a heterogeneous phase morphology, but can be melt processed to result in a solid flushable tampon applicator exhibiting homogenous properties.
- the term “homogenous” refers to a uniform mixture of materials, whereas the term “heterogeneous” refers to a nonuniform mixture of materials.
- the phase morphology can be determined using optical and scanning electron microscopes, for example a convenient optical microscopy instrument that can be used to determine the phase morphology of the thermoplastic compositions described herein is the Zeiss Axioplan 2 Mot-Imaging Microscope that is equipped with a Linkham MDS-BCS-600 hot stage and that is available from the Carl Zeiss Incorporation located in Thornwood, N.Y.
- the phase morphology of the water-dispersible and biodegradable polymers defined herein can further be described in terms of the polymers glass transition temperatures (T g ).
- T g polymers glass transition temperatures
- the glass transition temperature of polymers or any other materials is typically identified as the area on the line where a distinct change in slope occurs, and can be determined using a thermal analysis instrument such as the 2980 Dynamic Mechanical Analyzer (DMA) in combination with Thermal Analyst Data Collection software program (Thermal Solutions version 2.5) and Data Analysis software program (Universal Analysis version 2.5H), all of which are available from T. A. Instruments Incorporation of New Castle, Delaware.
- DMA Dynamic Mechanical Analyzer
- thermoplastic compositions made from a composite or any other configuration of water dispersible and biodegradable polymers described herein.
- TABLE 1 Glass Transition Behavior of Water-Dispersible/Biodegradable Polymers and Polymer Blends Tg 1 Tg 2 Tg 3 Polymers (° C.) (° C.) (° C.) PEO 1 ⁇ 41 — — PEO 1 /PEG 2 -40/30 blend ⁇ 33 — — — aliphatic polyesteramide (BAK 404) 3 — ⁇ 7 — aliphatic-aromatic copolyester (Eastar 14776) 4 — ⁇ 25 — diacid-diol aliphatic polyester (Bionolle 3001) 5 — ⁇ 31 — PEO 1 /BAK 404 3 -75/25 blend ⁇ 43 8 — PEO 1 /Eastar 14776 4 -60/40 blend ⁇ 42 ⁇ 24 — PEO 1 /Bio
- the flushable tampon applicators of the present invention are made from thermoplastic compositions having physical properties of tensile strength at break, percent elongation at break, elastic modulus, and hardness.
- the thermoplastic compositions can include ingredients such as fillers, plasticizers, processing aids, dispersing agents, lubricants, resin modifiers, clarifying/nucleating agents, viscosity modifiers, and the like.
- Preferred thermoplastic compositions comprise water-dispersible thermoplastic polymers, biodegradable thermoplastic polymers, plasticizers, and/or lubricants, and/or fillers in various combinations.
- thermoplastic materials especially blends of thermoplastic materials
- ASTM D882-95a test method described in “Standard Test Method for Tensile Properties of Thin Plastic Sheeting”, pages 159-167. This procedure involves testing blends of thermoplastic materials for achieving desired properties of flexibility, elasticity, durability, unbrittleness, resilency, distensibility, tenacity, and so forth.
- blends of thermoplastic materials are injection molded to form “dogbone-shaped” test samples having dimensions of 1 ⁇ 2 inch length (L) ⁇ 1 ⁇ 8 inch width (W) ⁇ fraction (1/16) ⁇ inch height (H), then the “dogbone-shaped” test samples are evaluated for tensile strength at break, percent elongation at break, and elastic modulus using an Instron Tensile Tester (Model 1122 from Instron Corporation located in Canton, Mass.) equipped with a 50 pound load cell, grip separation of 1 inch, a gage length of 1 ⁇ 2 inches, 5 millimeter (mm) jaw gap, and a crosshead speed of 2 inches/minute.
- Instron Tensile Tester Model 1122 from Instron Corporation located in Canton, Mass.
- the “dogbone-shaped” test sample is stretched until breakage occurs, and a load-versus-extension plot is generated for determining the tensile strength at break, percent elongation at break, and elastic modulus properties.
- the tensile strength at break is the load at break divided by the cross-sectional area of the test sample, and is defined in units of mega-Pascal or MPa (newton/square meter).
- the percent elongation at break is determined by dividing the length of the extension at the point of rupture by the gage length, and then multiplying by 100.
- Elastic modulus is the slope of the initial linear portion of the load-extension curve, and is defined in units of MPa.
- thermoplastic compositions described herein preferably have a harness property such that the compositions exhibit a firm resistance to stress or strain, yet are not brittle or too soft for processing into flushable tampon applicators of the present invention.
- the hardness properties are determined according to ASTM D2240-97 test method described in “Standard Test Method for Rubber Property-Durometer Hardness, pages 388-391.
- thermoplastic materials are injected molded into bars that are stacked in groups of two bars per stack wherein each bar stack has a total thickness of 1 ⁇ 8 inches. The hardness value is measured at various points of the bar stack using a hardness instrument such as Model 307 L Shore D Durometer from PTC Instruments, and a mean hardness measurement is determined.
- thermoplastic compositions for constructing the flushable tampon applicators of the present invention have physical properties similar to or superior to physical properties of known thermoplastic materials that are used in the manufacture of tampon applicators.
- polyethylene-based thermoplastic polymers typically have elastic modulus properties of from about 80 MPa to about 200 MPa, wherein other thermoplastic polymers such as polypropylene-based polymers have elastic modulus of from about 1000 MPa to about 1500 MPa.
- thermoplastic compositions described herein exhibit desirable properties of an elastic modulus value of less than 1000 MPa, and this elastic modulus attribute in addition to the other described physical properties result in thermoplastic compositions having flexibility, elasticity, durability, resilency, distensibility, tenacity, and the like.
- the physical properties of the preferred thermoplastic compositions are exemplified hereinbelow in Table 2.
- thermoplastic compositions also have physical properties of dry and wet flexural modulus.
- the dry flexural modulus is determined according to ASTM D5943-96 test method described in “Standard Test Method for Determining Flexural Properties of Plastics”, pages 708-712. This procedure involves injection molding thermoplastic materials into “beams” of test samples having 5 inch L ⁇ 1 ⁇ 2 inch W ⁇ 1 ⁇ 8 inch H. Generally, the test samples are pre-loaded with 0.01 pounds of force, thereafter a force loading is applied at a rate of 0.1 inches per minute, and a stress-versus-strain curve is generated to determine the dry flexural modulus property.
- the dry flexural modulus is the slope of the stress-strain curve as calculated in the linear region of from about 0.05% to about 0.25% of the flexural strain.
- the wet flexural modulus is determined by submerging the dry “beams” of test samples in water at time intervals of 5 minutes, 15 minutes, and 60 minutes, and observing the softening of the test samples.
- the term “softening” refers to materials that readily lose their stiffness or undergo a decrease in flexural modulus property upon contact with water. It has been found that the preferred thermoplastic compositions described herein undergo a significant decrease in flexural modulus upon contact of the composition with water.
- thermoplastic compositions that are manufactured into flushable tampon applicators that readily lose their structural integrity in water for easy disposal down a sewage system such as a toilet. Dry and wet flexural modulus properties of preferred thermoplastic compositions are exemplified hereinbelow in Table 3. TABLE 3 Flexural Modulus Physical Properties Wet Wet Wet Dry Flexural Flexural Flexural Flexural Modulus Modulus Modulus Modulus (MPa) (MPa) Sample (MPa) at 5 min. at 15 min. at 60 min.
- PEO 1 /PEG 2 /Biomer 209H 6 (40/30/30 blend) 700 290 140 40 PEO 1 /PEG 2 /Bionolle 3001 5 (40/30/30 blend) 540 180 140 30 PEO 1 /PEG 2 /Bionolle 3001 5 (66/17/17 blend) 450 190 150 50 PEO 1 /PEG 2 /Eastar 14776 4 (40/30/30 blend) 610 180 120 20 PEO 1 /PEG 2 /BAK 404 3 (40/30/30 blend) 720 210 100 40 PEO 1 /PEG 2 /BAK 404 3 (40/40/20 blend) 840 450 300 60 PEO 1 /PEG 2 /BAK 3 /P-645 7 (36/27/27/10 blend) 360 230 150 30 PEO 1 /PEG 2 /BAK 3 /P-4141 8 (36/27/27/10 blend) 350 220 120 40 PEO 1 /PEG 2 /
- thermoplastic compositions also have physical properties of weight loss in water which can be determined by the percent weight loss of a dry specimen sample of a thermoplastic composition that has been submerged in water for time intervals of 5 minutes, 1 hour, 24 hours, and 1 week. For example, dry injection molded thermoplastic compositions having a thickness of about 1 ⁇ 8 inches are weighed to ascertain the dry specimens dry weight. The dry specimens are then soaked in water for a duration of 5 minutes, 1 hour, 24 hours, or 1 week, wherein dependent on the type of thermoplastic composition dissolution of the water-soaked specimen occurs. The water-soaked specimens are recovered for drying in a Blue M oven for 16 hours at 40° C. to obtain a final weight loss.
- the percent weight loss is calculated by subtracting the weight of dried water-soaked specimens minus the dry specimens initial weight, divided by the dry specimens initial weight, and multiplied by 100.
- the percent weight loss values of thermoplastic compositions described herein are exemplified hereinbelow in Table 4.
- a negative percent weight loss value is indicative of the thermoplastic composition being able to readily dissolve or disintegrate in water
- a positive percent weight loss value is indicative of the thermoplastic composition being able to maintain its structural integrity in water and not readily break apart into unrecognizable pieces.
- thermoplastic compositions described herein can be molded into flushable tampon applicators of the present invention that exhibit a weight loss in water such that after being submerged for a period of 5 minutes the tampon applicators are capable or readily breaking apart, an observation of such tampon applicators being suitable for disposal by flushing down a toilet. These flushable tampon applicators exhibited a significant weight loss in water over a time period of 24 hours.
- the flushable tampon applicators of the present invention are constructed of water-dispersible and biodegradable components to provide for applicators that readily lose their structural integrity and disintegrate in water, especially in water from a waste disposal system. It has been shown that the flushable tampon applicators of the present invention can soften and disintegrate into unrecognizable pieces in about an hour of exposure to wastewater. Prolonged exposure which is indicative of municipal waste disposal means results in further disintegration of these flushable tampon applicators.
- a flushable tampon applicator comprising thermoplastic materials
- the applicator is initially weighed to obtain an initial dry weight, and then the applicator is exposed to wastewater at time intervals of 1 hour, 6 hours, 24 hours, and 48 hours.
- Suitable wastewater that can be used in the disintegration test include influent wastewater that can be obtained from a municipal waste treatment plant.
- Thermoplastic tampon applicator products and control samples are each submerged in about one liter of wastewater and allowed to shake using any suitable rotary floor shaker capable of shaking the control/wastewater and applicator/wastewater test samples at a shaker rate of 150 revolutions per minute (rpm).
- Control samples which can be used for this disintegration test include about 3-5 grams of fluted or folded Whatman #41 filter paper (i.e., about 3-4 pieces of the filter paper for each control sample).
- the retained test sample from each sieve is transferred using forceps or commercial paint brushes to individual aluminum pans, and the aluminum pans are placed in a Blue M oven at 40° C. to dry overnight.
- tampon applicators of the present invention readily soften and disintegrate after being submerged in wastewater for one hour with substantially increased disintegration after only 6 hours of exposure.
- These tampon applicators are suitable for flushing in a sewage system such as a toilet due to their ability to readily break apart and dissolve in wastewater produced from toilet septic tanks.
- Data showing the disintegration rate of flushable tampon applicators of the present invention is exemplified hereinbelow.
- the flushable tampon applicators of the present invention can comprise optional ingredients in combination with the water-dispersible and biodegradable components wherein the optional ingredients provide benefits to the final product or to the thermoplastic materials used in making the final product.
- benefits include, but are not limited to, stability including oxidative stability, brightness, flexibility, resiliency, toughness, workability, odor control, improved strength, improved modulus, improved melt flow characteristics, and/or distensibility of the thermoplastic compositions.
- the flushable tampon applicators typically comprise from about 0.05% to about 25% of optional ingredients by weight of the applicator.
- the optional ingredients include plasticizing agents, antioxidants, slip agents, optical brighteners, crystallization accelerators or retarders, flow promoters, processing aids, pigments or colorants, mold release agents, nucleating agents, coating agents, gelling agents, antistatic agents, dispersing agents, compatibilizers, lubricants, surfactants, heat stabilizers including magnesium stearate, odor masking agents, opacifying agents such as aluminum oxide, dyes, viscosity modifiers, ester waxes, elastomers, and mixtures thereof.
- the optional plasticizing agents, coating agents, viscosity modifiers, and lubricants are described in detail hereinbelow.
- Kemamide E Ultra which is commercially available from the Crompton Corporation (Taft, Los Angeles).
- optional processing aids include, but are not limited to, the acrylic polymers commercially available from the ATOFINA Chemicals Incorporation (Philadelphia, Pa.) under the Metablen P-550, Metablen P-710 SD, and Metablen C-303 tradenames.
- optional nucleating agents include, but are not limited to, Licomont CaV 102 and Licomont NaV 101, both of which are commercially available from the Clariant Corporation (Coventry, R.I.); and Millad 3988 which is commercially available from Milliken Chemical (Inman, S.C.).
- a specific example of an optional heat stabilizer is Thermolite 890S which is commercially available from the ATOFINA Chemicals Incorporation.
- optional elastomers include, but are not limited to, Kraton L207, Kraton L1203, Kraton L2203, and Kraton G 1652, all of which are commercially available from Kraton Polymers (Houston, Tex.).
- thermoplastic polymers for making the flushable tampon applicators of the present invention
- the plasticizer is included at concentrations ranging from about 1% to 20 about 25% by weight of the applicator.
- plasticizing agent refers to any organic compound that, when added to a thermoplastic polymer, can provide modification to the polymer's morphology to result in increased ease of processing of the polymer and increased toughness and flexibility of the polymer after processing.
- optional plasticizing agents include glycerin, glycerin derivatives such as triacetin and glycerol monostearate, sorbitol, eritol, glucidol, mannitol, sucrose, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol caprate-caprylate, butylene glycol, pentamethylene glycol, hexamethylene glycol, diisobutyl adipate, oleic amide, erucic amide, pannitic amide, dimethyl acetamide, dimethyl sulfoxide, methyl pyrrolidone, tetramethylene sulfone, oxa monoacids, oxa diacids, polyoxa diacids, diglycolic acids, triethyl citrate, acetyl triethyl
- plasticizers examples include the adipate polyesters sold under the Plasthall P-645, Plasthall P-643, Plasthall HA7A, Paraplex G-54, and Paraplex G-50 tradenames; triethylene glycol caprate-caprylate sold under the Plasthall 4141 tradename; the polyesters sold under the Paraplex A-8200 and Paraplex A-8040 tradenames; the polyester glutarate sold under the Plasthall P-550 tradename; diisononyl phthalate sold under the Plasthall DINP tradename; dibutoxyethoxyethyl adipate sold under the Plasthall 226 tradename; and the Supermix Plasthall 226 and Supermix Paraplex G-50; all of which are available from the C. P. Hall Corporation (Chicago, Ill.).
- the flushable tampon applicators of the present invention preferably comprise from about 0.05% to about 10% of a coating agent by weight of the applicator.
- the coating agent provides stability to the final applicator product by serving as a moisture barrier, and is considered to be effective in reducing or eliminating the sticky or slippery film feel that can occur when the applicator comes in contact with air-laden or human moisture.
- the coating agent can be applied using any suitable coating technique known in the art for effectively applying a coating material on the outer or exterior surface of a thermoplastic material used to form a flushable tampon applicator. Some known effective coating methods can be typically described as tumbling coating, spray coating, brushing, dip coating, slot coating, gravure coating, extrusion coating, co-extrusion coating, and the like.
- the coating material can be applied directly to the outer or exterior surface of a thermoplastic material described herein, the coating material can also be applied as a coating solution.
- the coating solution comprises the coating solubilized in a volatile solvent, wherein suitable volatile solvents include saturated and unsaturated hydrocarbons such as heptane, cyclohexane, and toluene; halogenated hydrocarbons such as chlorobenzene, chloroform, and methylene chloride; hydrocarbon alcohol ethers; and mixtures thereof.
- Optional preferred coating agents suitable for use herein include waxes, hydrogenated vegetable oils, food grade shellac, epoxy resins, vinylidene chloride copolymer latexes, polysiloxanes, sucrose fatty acid esters, and mixtures thereof.
- a specific example of a vinylidene chloride copolymer latex is Daran SL 143 which is commercially available from the Hampshire Chemical Corporation.
- waxes suitable for use as an optional preferred coating agent include animal waxes (e.g., beeswax, spermaceti, lanolin, and shellac wax); vegetable waxes (e.g., carnauba, candelilla, bayberry, and sugar cane); mineral waxes (e.g., fossil or earth waxes such as ozokerite, ceresin, and montan, or petroleum waxes such as paraffin, microcrystalline, petrolatum, slack and scale wax); chlorinated naphthalenes (e.g., “Halowax”); and mixtures thereof.
- animal waxes e.g., beeswax, spermaceti, lanolin, and shellac wax
- vegetable waxes e.g., carnauba, candelilla, bayberry, and sugar cane
- mineral waxes e.g., fossil or earth waxes such as ozokerite, ceresin, and
- the flushable tampon applicators of the present invention can optionally comprise viscosity modifiers to increase the viscosity of the water-dispersible and biodegradable thermoplastic polymers described herein so that they can be molded using a preferred injection molding or any other molding technique described herein.
- viscosity modifiers are typically included at concentrations ranging from about 0.1% to about 5%, preferably from about 0.1% to about 2% by weight of the applicator.
- suitable viscosity modifiers include trifunctional alcohols such as trimethylolpropane, tetrafunctional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid, and the like.
- the flushable tampon applicators of the present invention can optionally comprise lubricants to increase the overall rate of processing and to improve surface properties. Therefore, lubricants are also referred to as mold release agents and slip/anti-blocking agents, and provide for improved product properties such as brightness, heat stability during processing, light stability, better dispersion of additives, and improved optical and mechanical properties). It is believed that the optional lubricants provide these processing and product surface properties due to the migration of the lubricants to the surface of the processed products where they resist adhesion to processing equipment.
- optional lubricants suitable for use herein include, but are not limited to, metal soaps (e.g., stearate soaps), hydrocarbon waxes including polyethylene wax, fatty acids, long-chain alcohols, fatty acid esters (e.g., ester waxes), fatty acid amides, silicones, fluorochemicals, acrylics, and mixtures thereof.
- metal soaps e.g., stearate soaps
- hydrocarbon waxes including polyethylene wax, fatty acids, long-chain alcohols, fatty acid esters (e.g., ester waxes), fatty acid amides, silicones, fluorochemicals, acrylics, and mixtures thereof.
- metal soaps suitable for use as an optional lubricant herein include, but are not limited to, calcium stearate commercially available from the Ferro Corporation (Cleveland, Ohio,) under the Synpro Calcium Stearate 392A tradename; magnesium stearate commercially available from the Aldrich Chemical Company (Milwaukee, Wis.); and the stearates commercially available from the Norac Incorporation (Helena, Ark.) such as calcium stearate commercially available under the COAD10 and COAD10LD tradenames, zinc stearate commercially available under the COAD21 and COAD23 tradenames, and magnesium stearate commercially available under the MATBHE magnesium stearate tradename.
- fatty acid esters suitable for use as an optional lubricant herein include, but are not limited to, the fatty acid esters commercially available from Cognis-Plastics Technology (Amber, Pa.) under the Loxiol G33, Loxiol G60, Loxiol G71S, and Loxiol HOB7111 tradenames; the ester waxes commercially available from the Clariant Corporation under the Licowax E, Licolub WE 4, and Licowax OP tradenames; and the ester waxes commercially available from the Fanning Corporation under the Natralube 120 and Natralube 125 tradenames.
- silicones suitable for use as an optional lubricant herein include, but are not limited to, the silicones commercially available from the Dow Corning Corporation (Midland, Mich.) under the Dow Corning MB50-002, Dow Corning MB50-010, Dow Corning 4-7051, and Dow Corning 9506 tradenames.
- fluorochemicals suitable for use as an optional lubricant herein include, but are not limited to, the fluoropolymers commercially available from the AG Fluoropolymers Incorporation (Downingtown, Pa.) under the Whitcon Tl-5 and Whitcon TL-155 tradenames; and the fluoropolymers commercially available from Dyneon LLC (Oakdale, Minn.) under the Dynamar FX 9613, Dynamar FX 5920A, Dynamar FX 5911X, Dynamar FX 5912X, Dynamar PPA 790, and Dynamar PPA 791 tradenames.
- a specific example of an acrylic suitable for use as an optional lubricant herein is the white powder acrylic commercially available from the ATOFINA Chemicals Incorporation under the Metablen L-1000SD tradename.
- the flushable tampon applicators of the present invention may be prepared by any known or otherwise effective technique for providing a disposable tampon applicator provided that the article is made to contain water-dispersible and biodegradable materials described herein, preferably a blend of water-dispersible and biodegradable materials.
- the flushable tampon applicators are molded in a desired shape or configuration using a variety of molding techniques to provide a thermoplastic applicator comprising an outer tubular member and a plunger.
- molding techniques include injection molding, extrusion molding, blow molding, compression molding, and cast film. These molding techniques can be used alone or in combination to make the flushable tampon applicators of the present invention.
- the outer tubular member and plunger components of the flushable tampon applicators herein can be made using an injection molding apparatus, or the outer tubular member and plunger can be made using an extrusion molding apparatus, or the outer tubular member can be made using injection molding and the plunger made using extrusion molding, or the outer tubular member made by extrusion molding and the plunger made by injection molding, or the outer tubular member and/or plunger are made using a combination of extrusion and injection molding.
- the process of making flushable tampon applicators of the present invention involves charging one or more high molecular weight polyethylene oxides, one or more low molecular weight polyethylene glycols, one or more aliphatic/aromatic copolyesters, and any other ingredients such as plasticizers and/or filler into an injection molding apparatus, and molding the melt blended mixture comprising uniformly dispersed filler into the desired flushable tampon applicator.
- a blend of the thermoplastic materials, optional plasticizer, and uniformly dispersed filler can be compounded into pellets by means of an extruder, and the pellets are then constructed into flushable tampon applicators using an injection molding apparatus.
- One example of a procedure of making flushable tampon applicators of the present invention involves mixing the thermoplastic polymers, optional plasticizer, and filler in a variable speed, high intensity blender, extruding the mixture at a temperature above the melting temperature of the thermoplastic polymers to form a rod, chopping the rod into pellets, and injection molding the pellets into the desired flushable tampon applicator form.
- the extruders which are commonly used to melt process thermoplastic compositions into compounded pellets are generally single-screw extruders, twin-screw extruders, and kneader extruders.
- Examples of commercially available extruders suitable for use herein include the Black-Clawson single-screw extruders, the Werner and Pfleiderer co-rotating twin-screw extruders, the HAAKE Polylab System counter-rotating twin screw extruders, and the Buss kneader extruders.
- a typical extrusion process can be described as compounding blended components using a twin-screw extruder having a screw diameter of 30 mm, a feed section, and a die tip.
- the blend is compounded at about 100 revolutions per minute (rpm) at a temperature ranging from about 60° C. at the feed section to about 130° C. at the die tip.
- the final product is a compounded rod that is chopped into pellets suitable for molding into desired flushable tampon applicators using an injection molding apparatus.
- General discussions of extrusion molding are disclosed in the Encyclopedia of Polymer Science and Engineering; Volume 6, pp. 571-631, 1986, and Volume 11, pp. 262-285, 1988; John Wiley and Sons, New York; which disclosures are incorporated by reference herein.
- Injection molding is the most commonly used process for constructing and configuring tampon applicators into a desired shape of form. This process is typically carried out under controlled temperature, time, speed and pressure, and involves melt processing pellets or blends of thermoplastic compositions wherein the melted thermoplastic composition is injected into a mold, cooled, and molded into a desired plastic object.
- An example of a suitable injection molding machine is the Engel Tiebarless ES 60 TL apparatus having a mold, a nozzle, and a barrel that is divided into zones wherein each zone is equipped with thermocouples and temperature-control units.
- the zones of the injection molding machine can be described as front, center, and rear zones whereby the pellets are introduced into the front zone under controlled temperature.
- the temperature of the nozzle, mold, and barrel components of the injection molding machine can vary according to the melt processing temperature of the pellets and the molds used, but will typically be in the following ranges: Component Temp (° C.) Nozzle 135-230 Front Zone 70-200 Center Zone 100-225 Rear Zone 120-225 Mold 20-50
- Other typical processing conditions include an injection pressure of from about 300 pounds per square inch (psi) to about 3000 psi (about 2 MPa to about 21MPa), a holding pressure of about 400 psi to about 2000 psi (about 3 Mpa to about 14MPa), a hold time of about 2 seconds to about 25 seconds, and an injection speed of from about 0.98 inches per second (in/sec) to about 8 in/sec.
- suitable injection molding apparatus are the injection molding machines made by Battenfeld, Brabender, Killion, Demag and Arburg, Windsor, Hesas, Boy, Van Dorn, Engel, and the Fischer companies. Specific examples of other suitable injection molding machines include the Van Dom Model 150-RS-8F, the Battenfeld Model 1600, and the Engel Model ES80. A general discussion of injection molding is disclosed in the Encyclopedia of Polymer Science and Engineering, Volume 8, pp. 102-138, John Wiley and Sons, New York, 1987, which disclosure is incorporated by reference herein.
- the flushable tampon applicators of the present invention are generally made using the extrusion and injection molding techniques described hereinabove. These techniques involve melt processing the thermoplastic polymers, filler, and any optional ingredients wherein the thermoplastic polymers, filler, and optional ingredients have melting temperatures typically ranging from about 25° C. to about 350° C., more typically from about 40° C. to about 300° C., even more typically from about 50° C. to about 200° C.
- thermoplastic polymers suitable for use in making the flushable tampon applicators of the present invention desirably have individual melt flow rates of from about 0.1 gram/10 minutes to about 600 grams/10 minutes, preferably from about 1 gram/10 minutes to about 400 grams/10 minutes, more preferably from about 5 grams/10 minutes to about 200 grams/10 minutes, even more preferably from about 10 grams/10 minutes to about 150 grams/10 minutes, as determined according to the ASTM Test Method D1238-E.
- the final products of flushable tampon applicators of the present invention are packaged in moisture-proof wrappers for storage prior to use.
- the moisture-proof wrappers prevents moisture from contacting the applicator or tampon pledget, and therefore aids in the assurance of shelf-stabilily for the tampon and provides an asethetically pleasing and acceptable tampon product prior to actual use.
- the flushable tampon applicators of the present invention can be packaged in any suitable wrapper provided that the wrapper is soil proof and disposable with dry waste.
- Preferred wrappers are those made from biodegradable materials which create minimal or no environmental concerns for their disposal. It is contemplated, however, that the tampon applicators of the present invention can be packaged in flushable wrappers made from paper, nonwoven, cellulose, thermoplastic, or any other suitable flushable material, or combinations of these materials.
- Flushable tampon applicators of the present invention are made by a melt extrusion process of blending water-dispersible polymers, biodegradable polymers, fillers, and any optional ingredient using a Werner Pfleiderer ZSK-30 co-rotating twin screw extruder having a screw diameter of 30 mm, six heating zones, a four hole die plate, two feeding hoppers, and a liquid pump which is connected to the extruder through a hole located between heating zones 3 and 4 .
- powder ingredients are dry blended together wherein the powder ingredients include water-dispersible polymers such as high molecular weight polyethylene oxide commercially available as POLYOX® WSR-80 and low molecular weight polyethylene glycol commercially available as PEG-8000; fillers such as calcium carbonate (commercially available as Vicron 15-15), talc (commercially available as ABT 2500), starch granule materials (commercially available as Staley Pure Food Powdered Starch and National Starch Melojel), and wood flours (commercially available as Pine Wood Flour Grade 10020); and optional ingredients such as ester wax (commercially available as Loxiol G33), magnesium stearate, and Kemamide E.
- water-dispersible polymers such as high molecular weight polyethylene oxide commercially available as POLYOX® WSR-80 and low molecular weight polyethylene glycol commercially available as PEG-8000
- fillers such as calcium carbonate (commercially available as Vicron 15-15), talc (commercially available as ABT 2500), star
- ingredients in pellet form are dry blended together such as a dry blend pellet mixture of biodegradable polymers.
- Any ingredients added in liquid form are mixed with other liquids prior to extrusion, for example, any liquid plasticizes and any other liquid optional ingredient are mixed together.
- the powder dry blend mixture is fed into the extruder through one feeding hopper while the pellet formed mixture is fed into the extruder through the other feeding hopper.
- the optional liquid mixture is pumped into the extruder through the liquid pump.
- the water-dispersible polymers, biodegradable polymers, optional plasticizers and any other optional ingredient form a melt-blended mixture.
- the fillers including inorganic and organic fillers are not melted and remain in their particle forms during the extrusion process and, therefore are uniformly dispersed throughout the melt blend mixture. Then, the melt blend mixture containing uniformly dispersed filler particles is extruded to the end of the extruder to the die to form four rods.
- the rods are carried on a conveyor, air cooled, and pelletized using a pelletizer for injection molding into a desired flushable tampon applicator.
- Compositions for forming flushable tampon applicators of the present invention and extrusion settings are further described hereinbelow in Table 5 and Table 6.
- Flushable tampon applicators of the present invention are made by dry blending a mixture of water-dispersible and biodegradable polymers, and then feeding this dry blended mixture of polymers into a HAAKE Polylab System counter-rotating twin screw extruder.
- the extruder is equipped with a single hole die plate for compounding the dry blended mixture into a single strand of molten plastic that is air-cooled and then chopped into small discs having a diameter of 20 mm and a thickness of 0.5 mm.
- the small discs are grounded using an IMS LP-288SC Grinder for injection molding into a desired flushable tampon applicator.
- An Engel Tiebarless ES 60 TL injection molding machine is suitable for manufacturing the final product of thermoplastic pellets of Examples 1 and 2 into flushable tampon applicators of the present invention.
- the injection molding process involves using a 25 mm screw and controlled processing conditions of controlled temperature, time, speed, and pressure, wherein the pellets are melt processed, injected into a mold, cooled, and then molded into the desired flushable tampon applicator.
- the Engel injection molding machine is also suitable for manufacturing composite paper flushable tampon applicators.
- spiral-wound paper is formed into paper tubes having a length of about 35 mm, inside diameter of about 10.8 mm, outside diameter of about 11.2 mm, and a weight of about 0.25 grams.
- the paper tube is positioned over a mold core pin, the mold is clamped shut, and a thermoplastic composition is injected into the mold.
- the paper tube is positioned over the mold core pin such that the thermoplastic composition is melt processed to flow over the entire length of the outer surface of the paper tube. Therefore, the resultant composite paper tampon applicator comprises a paper inner surface, thermoplastic resin outer surface, and thermoplastic petals and grip components.
- thermoplastic compositions and injection molding settings are described hereinbelow in Table 8 through Table 15.
- TABLE 8 Injection Molded Thermoplastic Compositions PEO 1 /PEG 2 / PEO 1 /PEG 2 / PEO 1 /PEG 2 / PEO/PEG/ Injection Molding BAK 404 3 BAK 404 3 Eastar 14776 4 Bionolle 3001 5 Settings (40/30/30 blend) (40/40/20 blend) (40/30/30 blend) (66/17/17 blend)
Abstract
Disclosed are flushable tampon applicators which comprise a combination of thermoplastic materials and filler such as calcium carbonate and talc, and which readily disintegrate in water such as toilet water for improved disposal and reduced environmental concerns regarding the destruction of these applicators. The flushable tampon applicators comprise a combination of high molecular weight polyethylene oxides, low molecular weight polyethylene glycols, biodegradable polymers, and filler, wherein this combination of water-dispersible thermoplastic polymers, biodegradable thermoplastic polymers, and filler provide flushable tampon applicators that are readily disposed of and that are smooth, soft, flexible, and non-sticky or non-slimy to the touch before and during use.
Description
- This is a continuation-in-part application of application Ser. No. 09/810,292, filed on Mar. 16, 2001, which is currently pending.
- The present invention relates to plastic tampon applicators which are readily disposed in a sewage system and/or by biodegradation. In particular, the present invention relates to flushable tampon applicators which are made from thermoplastic materials that are suitable for disposal in a toilet system.
- Feminine hygiene products such as tampons are commonly used by female consumers. Tampons can be described as a feminine hygiene article that has an absorbent device (i.e., pledget) withheld in a paper or plastic applicator.
- Paper and plastic tampon applicators typically comprise an outer tubular member and a plunger for insertion of the pledget, whereby these components of the paper and plastic applicators are generally made from paper, paper coated, and plastic materials which retain their form during use and are shelf-stable under ambient conditions.
- In addition to absorbent pledget devices, paper tampon applicator components are suitable for disposal via a sewage system or by biodegradable waste disposal means. Therefore, paper tampon applicators are considered environmentally friendly in that these paper tampon applicators can readily disintegrate in a sewage system and/or can be disposed of through aerobic, anaerobic, and natural degradation processes. However, paper tampon articles are not very popular among females due to some tampon's pledget insertion difficulties associated with the use of a paper tampon applicator.
- Certain female consumers prefer plastic tampon applicators because the plastic applicators are made with a grip ring and petal-shaped forward end which facilitate ease of insertion of a tampon's pledget, although plastic tampon applicator components are not easily disposed of as compared to paper applicator components. Most plastic tampon applicators are made from polyethylene-based polymeric materials that are not biodegradable and that do not readily soften or break-up into smaller fragments for decomposition in a sewage system, resulting in increased environmental concerns for the disposal of plastic tampon applicators.
- Many efforts to address the environmental concerns of the disposal of plastic tampon applicators include the manufacture of tampon applicators from thermoplastic materials other than polyethylene polymers. Such attempts include tampon applicators made from water-soluble materials, water-dispersible materials, biodegradable materials, photodegradable materials, ultraviolet light degradable materials, or combinations thereof. In particular, one attempt to address the disposal of plastic tampon applicators involves the use of plastic applicators made from biodegradable polymers such as polyvinyl alcohol polymers. It is known that tampon applicators made primarily from polyvinyl alcohol are water-dispersible and biodegradable, however, such applicators have been shown to suffer from issues involving moisture sensitivity, stability, odor, and stickiness.
- Other attempts in addressing the disposal of plastic tampon applicators include plastic tampon applicators made from other water-soluble materials such as polyethylene oxide polymers, thermoplastic starch, and hydroxypropyl cellulose; plastic tampon applicators made from combinations of water-soluble and water-insoluble/biodegradable materials such as combinations of polyvinyl alcohol and polycaprolactone, combinations of polyethylene oxide and polycaprolactone, combinations of polyethylene oxide and polyolefins such as polypropylene and polyethylene; and combinations of polyvinyl alcohol and polyethylene oxide polymers.
- An example of a plastic tampon applicator constructed from a combination of polyvinyl alcohol and polyethylene oxide is disclosed in U.S. Pat. No. 5,395,308. This plastic tampon applicator is described as being constructed to exhibit accelerated break-up and rapid disintegration in liquid such as water so that the plastic applicator can dissolve over an extended period of time without causing problems in sewage systems such as a waste treatment facility. The slow dissolution rate of these plastic tampon applicators can lead to the clogging of toilet systems and/or drain pipes because of the extended time required for these plastic applicators to initially come in contact with liquid such as toilet water and eventually reach waste disposal means at a waste treatment facility, especially if multiple plastic applicators are suited for disposal. Furthermore, plastic tampon applicators comprising polyvinyl alcohol have been known to become sticky when wet causing the applicator to stick to drain pipes which can result in repeated flushings to dispose of the applicator and to prevent clogging of toilet systems and/or the drain pipes.
- Therefore, the need exists for the manufacture of plastic tampon applicators made from thermoplastic materials that are flushable and can not only readily lose their structural integrity as for example breaking apart in unrecognizable pieces in a sewage system such as a toilet, but that can readily soften, disperse, disintegrate, and/or dissolve in a toilet for clear passage through the toilet to a municipal waste treatment facility. The tampon applicator components should also be anerobically and/or aerobically biodegradable, as well as provide for a flushable tampon applicator that is not slimy, sticky, or tacky to the touch before and during use.
- To increase the flushability of plastic tampon applicators and to improve the applicator aesthetics, ingredients such as fillers, plasticizers, processing aids, dispersing agents, lubricants, resin modifiers, clarifying/nucleating agents, viscosity modifiers, and so forth are often included in the manufacturing of the applicator. These ingredients help in the process of the plastic tampon applicator as well as provide improved structural characteristics to the final applicator product form. For example, plasticizers can increase flow and thermoplasticity of plastic materials by decreasing parameters such as the viscosity of polymer melts, the glass transition temperature, and the elasticity modulus of finished products to result in flushable plastic tampon applicators that have improved softness and flexibility. Lubricants are typically included as mold release agents and slip/anti-blocking agents to increase the overall rate of processing and to improve surface properties. Lubricants have been shown to improve product properties such as brightness, heat stability during processing, light stability, better additive dispersion, and improved optical and mechanical properties. Clarifying/nucleating agents are generally used to increase the crystallization rate, reduce the size of crystals, and improve transparency. Nucleating agents can also improve the meltflow and demolding behavior of partly crystalline plastic materials such as thermoplastic polyesters.
- It has been found, however, that fillers such as calcium carbonate and talc, are especially effective in providing for plastic applicators that are nonsticky when wet, shelf stable, have a smooth, soft texture and improved flushability. Filler materials are also important ingredients for use in the processing of the plastic applicators because they can assist in preventing the thermoplastics from sticking to the surface of processing equipment, reducing processing cycle time, acting as additional mold release and slip/anti-blocking agents, and increasing productivity. Another advantage of constructing flushable plastic tampon applicators with filler ingredients is the reduced cost to manufacture these applicators, especially when an acceptable flushable, plastic applicator can be constructed with low cost fillers to reduce the use of more costly thermoplastic material.
- Thus, not only does the need exist for plastic tampon applicators that are readily flushable, but there's also a need to provide flushable, plastic tampon applicators that meet consumer acceptability for their structural integrity and aesthetic characteristics of smoothness, flexibility, reduced stickiness, stability, and the like.
- The present invention is directed to flushable tampon applicators which comprise (a) from 0% to about 90% by weight of a water-dispersible polymer; (b) from about 10% to about 50% by weight of a biodegradable polymer, and (c) from 0% to about 50% by weight of a filler.
- The present invention is also directed to a method of making flushable tampon applicators wherein the method comprises (a) preparing a thermoplastic composite comprising (i) from 0% to about 90% by weight of a water-dispersible polymer; (ii) from about 10% to about 50% by weight of a biodegradable polymer; and (iii) from 0% to about 50% by weight of a filler; and (b) injection molding the thermoplastic composite into molded thermoplastic components used to construct the flushable tampon applicator.
- It has been found that flushable tampon applicators can be made from a combination of thermoplastic materials, especially a blend of water-dispersible polymers such as high molecular weight polyethylene oxides and low molecular weight polyethylene glycols, and biodegradable polymers such as aliphatic/aromatic copolyesters, to result in flushable tampon applicators that readily disintegrate in a septic tank such as a toilet and are easily disposed of with minimal or no environmental issues. The flushable tampon applicators of the present invention comprise a combination of water-dispersible and biodegradable thermoplastic polymers which provide for improved disposal properties of the applicators. These applicators are capable of being flushed down a toilet or any other sewage system without causing drainage problems such as clogging, and are capable of biodegradation disposal using commonly employed biodegradation means.
- It has also been found that flushable tampon applicators have improved flushability and aesthetics when filler components are included in the construction of the applicators. The flushable tampon applicators are preferably constructed such that the filler is melt blended with the thermoplastic materials to form a composite mixture of filler particles and thermoplastic material, wherein the filler particles are uniformly dispersed throughout the applicator. The filler aids in the processing of the thermoplastic materials into final flushable plastic tampon applicator product forms that have improved flushability in addition to being nonsticky when wet, shelf stable, smooth, and soft to the touch.
- While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter of the present invention, it is believed that the invention can be more readily understood from the following description taken in connection with the accompanying drawings, in which:
- FIG. 1 is a perspective representation of a flushable tampon applicator (10) of the present invention made from a blend of thermoplastic materials. The flushable tampon applicator is comprised of a thermoplastic outer tubular member (11) and a thermoplastic inner tubular member or plunger (12). The outer tubular member (11) can be any known or otherwise effective thermoplastic, one-piece, hollow cylindrical body that has a plurality of flexible petal tips (13) extending from and disposed on the front end of the outer tube. The outer tubular member (11) functions to contain or house an absorbent device such as a pledget (not shown), and typically has a finger grip ring (14) formed on the opposite end of the outer tube wherein the finger grip ring has one or more ribs or protusions (15) on its exterior to provide a gripping surface to assist a user in holding the flushable tampon applicator (10). The finger grip portion of the outer tubular member (11) can be of other configurations such as gripping rings having score lines, ridges, dimples, one or more flat surfaces, a roughed surface, and so forth.
- The inner tubular member or plunger as referred to hereinafter (12) includes any known or otherwise effective thermoplastic plunger designed to be slidable and telescopically mounted within the finger grip ring (14) such that the plunger (12) can urge the pledget through the flexible petal tips (13) for insertion of the pledget into a woman's vagina.
- FIG. 2 is a cross-sectional view of a flushable tampon applicator of the present invention depicting a pledget absorbent device (16) positioned in the thermoplastic, cylindricallly shaped outer tubular member (11). A withdrawal string (17) is permanently attached to one end of the pledget (16) and provides a means of withdrawing the soiled tampon pledget (16) from a woman's vagina.
- FIG. 3 is a perspective view of a flushable tampon applicator (20) of the present invention having an outer tubular member (18) and a plunger (19), both of which are constructed from a composite of thermoplastic materials. The composite structure includes one or more units of water-dispersible thermoplastic polymers (21) affixed to one or more units of biodegradable polymers (22) such that the units are arranged in an alternating striped configuration. The composite structure can also be constructed such that the alternating units of water-dispersible and biodegradable polymers are arranged in a concentric ring configuration or a layered structure of composite materials.
- It should be noted that although the outer tubular members (11) and (18) are shown as having cylindrical shapes, the outer tubular members(II) and (18) can also be of square, elliptical, conical, or oval configurations. Likewise, the plungers (12) and (19), which are typically of an oval configuration, can be configured in other shapes such as square, hemispherical, conical, and elliptical. The outer tubular members and plungers described herein can be constructed from clear, translucent, transparent, colored, or opaque thermoplastic materials, or combinations thereof.
- The flushable tampon applicators of the present invention comprise an outer tubular member and plunger made from water-dispersible and biodegradable materials that provide for tampon applicators that are readily disposed by flushing the applicator down a toilet, by biodegradable means, and/or by waste disposal means at a municipal waste treatment facility.
- The term “flushable” as used herein refers to materials which are capable of softening, dissolving, dispersing, disintegrating, and/or decomposing in a septic tank such as a toilet to provide clearance when flushed down the toilet without clogging the toilet or any other sewage drainage pipe.
- The term “water-dispersible” as used herein refers to materials that readily break apart in unrecognizable pieces upon contact with water as a result of dissolution, solubilization, dissipation, agitation, softening, or any other chemical or mechanical dispersion means.
- The term “biodegradable” as used herein refers to materials that when disposed of after use will physically and biologically decompose using known degradation procedures including aerobic, anaerobic, and microbial digestion processes. The biodegradable materials described herein include those degradable water-insoluble materials that will also physically and biologically decompose after disposal in a sewage system.
- The term “ambient conditions” as used herein refers to surrounding conditions at about one atmosphere of pressure, at about 50% relative humidity, at about 25° C.
- The water-dispersible and biodegradable thermoplastic polymers described herein can be generally defined according to their weight or number average molecular weight. The weight average molecular weight IMP) of a polymer is the summation of the weight fraction of each molecular species present multiplied by its molecular weight. The number average molecular weight (Mn) of a polymer is the summation of the mole fraction of each molecular species present multiplied by its molecular weight. The molecular weight of polymer materials can typically be determined by Size Exclusion Chromatography (SEC) or Gel Permeation Chromatography (GPC) techniques well known in the art.
- The thermoplastic polymers described herein are used to construct the outer tubular member and plunger components of the flushable tampon applicators of the present invention. These outer tubular member and plunger components each have a density of greater than about 1.0 grams per cubic centimeter (g/cm3) to about 3.0 g/cm3. Thermoplastic components having a density of greater than about 1.0 g/cm3 will easily fall to the bottom of a septic tank such as a toilet, resulting in disposal of the thermoplastic components without the need of repeated flushings. The density of a given thermoplastic material and/or components made from the material, will be dependent upon the degree of interaction of attractive forces between the polymer chains in the material, the degree of crystallinity of the thermoplastic material, and the presence of any additives, fillers or other optional components described herein. Therefore, if an individual thermoplastic material does not have a density of greater than about 1.0 g/cm3, the thermoplastic material can be combined with other thermoplastic materials and/or optional ingredients described herein to make suitable outer tubular members and plungers having a density of greater than about 1.0 g/cm3. Density values of the outer tubular and plunger components herein can be determined by any known or otherwise effective method for determining the density of thermoplastic materials and final products made from these materials.
- The flushable tampon applicators of the present invention can comprise, consist of, or consist essentially of the elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, or limitations described herein.
- All percentages, parts and ratios are by weight of the total applicator device, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the specific ingredient level and, therefore, do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.
- The flushable tampon applicators of the present invention typically comprise an outer tubular member and a plunger made from any known or otherwise effective thermoplastic materials that can readily soften and disintegrate upon contact with water such as toilet water. The thermoplastic materials are preferably combinations of water-dispersible and biodegradable polymers that are structurally stable before and during use while also being capable of rapid softening and disintegration in a toilet sewage system to provide disposal via the toilet to her enhance any additional disposal such as further disposal treatment of biodegradation and/or municipal waste disposal.
- The outer tubular member and plunger components of the flushable tampon applicator of the present invention can be constructed from the same or otherwise different water-dispersible and biodegradable materials. In other words, the outer tubular member and plunger both can be made from an individual or combination of water-dispersible materials; the outer tubular member and plunger both can be made from an individual or combination of biodegradable materials; the outer tubular member and plunger both can be made from a combination of water-dispersible and biodegradable materials; the outer tubular member can be made from water-dispersible materials and the plunger can be made from biodegradable materials; or the outer tubular member can be made from biodegradable materials and the plunger can be made from water-dispersible materials.
- Construction of the outer tubular member and plunger components from the same or otherwise different combination of materials provide, for example, a flushable tampon applicator that has an outer tubular member with a lower stiffness or hardness relative to the plunger to increase insertion comfort. The outer tubular member and plunger may also be constructed from different combinations of materials to incorporate, for example, a flushability signal, such as a color change or effervescence, to the user. The water-dispersible and biodegradable materials from which the outer tubular member and plunger can be made are described in detail hereinbelow.
- Water-Dispersible Components
- The flushable tampon applicators of the present invention comprise a total of from 0% to about 99%, preferably from about 5% to about 90%, more preferably from about 10% to about 80% of water-dispersible thermoplastic polymers by weight of the applicator. The water-dispersible thermoplastic polymers can be used individually or as a combination of polymers provided that the water-dispersible thermoplastic polymers can readily disintegrate in water, and can be combined with one or more biodegradable polymers described hereinafter.
- The water-dispersible thermoplastic polymers suitable for use herein include those water-dispersible compounds that can readily disintegrate in water such as toilet water while being structurally stable before contact with the water. The terms “structurally stable” and “structural stability” are used interchangeably herein to refer to materials that maintain their molded shape, form, and chemical composition before and during use, and that do not become sticky or slimy to the touch upon contact with moisture-laden air and/or moist human tissue.
- Nonlimiting examples of suitable water-dispersible thermoplastic polymers include high molecular weight polyethylene oxides, low molecular weight polyethylene glycols, polyethylene/polypropylene oxide copolymers, polyethylene/polybutylene oxide copolymers, polyethylene/polypropylene glycol copolymers, thermoplastic starch polymers, polyvinyl alcohols, partially hydrolyzed polyvinyl alcohols, modified polyvinyl alcohols, infrared treated polyvinyl alcohols, cross-linked polyvinyl alcohols such as a polyvinyl alcohol cross-linked with an aldehyde, alkali metal sulfonate thermoplastic polyesters, hydroxyethyl celluloses, hydroxypropyl celluloses, methylated hydroxypropyl celluloses, polyacrylic acids, polyaspartic acids, polymethacrylic acids, polysaccharides excluding sucrose polysaccharides suitable for use as a plasticizing agent herein, proteins, polyvinyl pyrrolidone homopolymers, polyvinyl pyrrolidone copolymers including polyvinyl pyrrolidonelvinyl acetate copolymers and polyvinyl pyrrolidone/acrylic acid copolymers, polyvinyl methyl ether homopolymers, polyoxazolines including polyethyloxazoline and poly(2-isopropyl-2-oxazoline), polyvinyl methyl oxazolidones, polyvinyl methyl oxazolidimones, polyethyleminines, polyacrylamides, polyvinyl methyl ether/maleic anhydride copolymers, water-dispersible polyurethanes, water-dispersible sulfonate polyesters, and mixtures thereof. Preferred water-dispersible thermoplastic polymers include high molecular weight polyethylene oxides and low molecular weight polyethylene glycols.
-
-
- wherein n has an average value of from about 500 to about 180,000, preferably from about 650 to about 50,000, more preferably from about 800 to about 25,000, for high molecular weight polyethylene oxides; and an average value of from about 12 to about 465, preferably from about 12 to about 341, more preferably from about 13 to about 227, for low molecular weight polyethylene glycols. These materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, polyethylene glycols, and polymethoxyethylene glycols.
- Specific examples of preferred high molecular weight polyethylene oxides suitable for use as a water-dispersible thermoplastic polymer herein include, but are not limited to, polyethylene oxides having repeating alkylene oxide radicals in the ranges described hereinabove, and a weight average molecular weight of from about 65,000 daltons to about 8,000,000 daltons, preferably from about 80,000 daltons to about 2,000,000 daltons, more preferably from about 100,000 daltons to about 900,000 daltons. These polyethylene oxide polymers are prepared by methods known in the art for making high molecular weight copolymers and interpolymers of ethylene oxide. For example, the high molecular weight copolymers of polyethylene oxide are prepared using ionic catalysts to react ethylene oxide with oxirane compounds such as styrene oxide, propylene oxide, butylene oxide, and the like. High molecular weight interpolymers of polyethylene oxide are prepared by co-polymerizing polyethylene oxide with one or more vinyl monomers such as N,N-dimethylaminoethyl methacrylate, styrene, methyl methacrylate, 2-methyl-5-vinyl pyridine, acrylonitrile, hydroxyethyl methacrylate, acrylic acid, acrylamide, and the like. Grafted or chemically modified high molecular weight polyethylene oxides are also suitable for use as a water-dispersible thermoplastic polymer herein.
- The weight average molecular weight (Mw) of the high molecular weight polyethylene oxides can be determined by measuring the intrinsic viscosity of a polyethylene oxide material in water at 30° C. The intrinsic viscosity, [η], is correlated to the Mw of polyethylene oxide materials, and can be expressed by the following equation: [η]=1.25×10−4Mw 0.78.
- Examples of commercially available high molecular weight polyethylene oxide polymers are the polyethylene oxides which are sold under the tradename POLYOX®, and which are available from the Dow Chemical Company located in Midland, Mich.. Specific examples of such polyethylene oxides include POLYOX® WSR-10 which has a Mw of about 100,000; POLYOX® WSR-80 which has a Mw of about 200,000; POLYOX® WSR-N-750 which has a Mw of about 300,000; POLYOX® WSR-N-3000 which has a Mw of about 400,000; POLYOX® WSR-3333 which has a Mw of about 400,000; POLYOX® WSR-205 which has a Mw of about 600,000; POLYOX® WSR-1105 which has a Mw of about 900,000; POLYOX® WSR-N-K12 which has a Mw of about 1,000,000; POLYOX® WSR-N-K60 which has a Mw of about 2,000,000; POLYOX® WSR-301 which has a Mw of about 4,000,000; POLYOX® WSR Coagulant which has a Mw of about 5,000,000; POLYOX® WSR-303 which has a Mw of about 7,000,000; POLYOX® WSR-308 which has a Mw of about 8,000,000; and mixtures thereof.
- Specific examples of preferred low molecular weight polyethylene glycols suitable for use as a water-dispersible thermoplastic polymer herein include, but are not limited to, polyethylene glycols having repeating alkylene oxide radicals in the ranges described hereinabove, and a number average molecular weight of from about 500 daltons to about 20,000 daltons, preferably from about 550 daltons to about 15,000 daltons, more preferably from about 600 daltons to about 10,000 daltons. The number average molecular weight (Mn) of the low molecular weight polyethylene glycols can be determined by known titration procedures used to determine the number of molecules having hydroxy-end groups wherein the Mn is calculated based on the weight of a given polyethylene glycol divided by the number of hydroxy-end group-containing molecules within the polyethylene glycol polymer.
- Nonlimiting examples of the preferred low molecular weight polyethylene glycols include those polyethylene glycols (PEG) and polymethoxyethylene glycols (MPEG) that are commercially available from Dow Chemical, and sold as PEG-600 which has a Mn of about 600; PEG-900 which has a Mn of about 900; PEG-1000 which has a Mn of about 1000; PEG-1450 which has a Mn of about 1450; PEG-3350 which has a Mn of about 3350; PEG-4000 which has a Mn of about 4,000; PEG-4600 which has a Mw of about 4600; PEG-8000 which has a Mw of about 8,000; MPEG-550 which has a Mn of about 550; MPEG-750 which has a Mn of about 750; MPEG-2000 which has a Mn of about 2,000; MPEG-5000 which has a Mn of about 5,000; and mixtures thereof.
- Specific examples of polyvinyl alcohols suitable for use as a water-dispersible thermoplastic polymer herein include, but are not limited to, those water-soluble thermoplastic polymers prepared by the partial or complete hydrolysis of polyvinyl acetate. The degree of hydrolysis of polyvinyl acetate results in polyvinyl alcohols having different residual acetyl groups and therefore different molecular weight and viscosity characteristics. Accordingly, the water solubility of the polyvinyl alcohol can be regulated by controlling the hydrolysis, molecular weight, and viscosity of the specific polyvinyl alcohol resin. Nonlimiting examples of such suitable polyvinyl alcohols include polyvinyl alcohols having a percent hydrolysis of from about 74% to about 98%, specific nonlimiting examples of which include polyvinyl alcohol 98% hydrolyzed ultra low viscosity resin having a viscosity of from about 3.2 centipoises (cps) to about 4.2 cps, and a weight average molecular weight of from about 13,000 daltons to about 23,000 daltons; polyvinyl alcohol 88% hydrolyzed ultra low viscosity resin having a viscosity of from about 3.0 cps to about 4.0 cps, and a weight average molecular weight of from about 13,000 daltons to about 23,000 daltons; polyvinyl alcohol 88% hydrolyzed low viscosity resin having a viscosity of from about 5.2 cps to about 6.2 cps, and a weight average molecular weight of from about 31,000 daltons to about 50,000 daltons; and mixtures thereof.
- The viscosity of the polvinyl alcohols and any other suitable thermoplastic polymer and optional ingredient described herein are measured or determined under ambient conditions, unless otherwise specified, using suitable methods known in the art. Examples of methods for measuring or determining viscosity include method DIN 53 015 which involves the use of a Hoppler falling-ball viscometer for measuring dynamic viscosity in units of Pascal-seconds (Pa-s), and methods DIN 53 562 and DIN 53 012 which involve the use of a Ubbelohde glass capillary viscometer to measure kinematic viscosity in units of square centimeters per second (cm2/sec).
- Other examples of suitable polyvinyl alcohols include, but are not limited to, water dispersible polyvinyl alcohol resins that have been modified to contain pendant alcohol groups. These modified polyvinyl alcohols can be produced by polymerizing a polyethylene oxide acrylate with vinyl acetate and then hydrolyzing the resultant polymer to produce pendant alcohol groups. Modified polyvinyl alcohols prepared by this procedure typically have viscosities ranging from about 500 poise to about 4,500 poise dependent upon the shear rate used to form the modified polyvinyl alcohol into a molded thermoplastic polymer. Examples of commercially available modified polyvinyl alcohols include those modified polyvinyl alcohol resins manufactured by Texas Polymer Services Incorporation (Houston, Tex.), and sold under the VINEX and AIRVOL tradenames. Specific examples of commercially available VINEX resins include, but are not limited to, VINEX 2019, VINEX 2025, VINEX 2034, and VINEX 2144. Specific examples of AIRVOL resins include, but are not limited to, AIRVOL 125 and AIRVOL 325.
- Other examples of suitable polyvinyl alcohols include, but are not limited to, the polyvinyl alcohols that are commercially available from Clariant GmbH (Sulzbach, Germany) under the MOWIOL tradename. Specific examples of MOWIOL resins include MOWIOL 18-88, MOWIOL 26-88, and MOWIOL 30-92.
- Nonlimiting specific examples of alkali metal sulfonate polyesters suitable for use as a water-dispersible thermoplastic polymer herein include those water-dispersible, linear thermoplastic polyesters which contain carbonyloxy-linking groups in the linear, molecular structure. The alkali metal sulfonate polyesters are typically prepared by reacting at least one difunctional dicarboxylic acid, at least one diol, and at least one difunctional sulfomonomer containing at least one metal sulfonate group attached to an aromatic nucleus having the functional group carboxyl. The number average molecular weight of suitable alkali metal sulfonate polyesters ranges from about 13,000 daltons to about 19,000 daltons, based on the number of repeating sulfomonomer groups in the molecule. It is believed that the sulfomonomer substituent is primarily responsible for the water dispersibility of the thermoplastic polyester. Nonlimiting examples of commercially available water-dispersible, linear thermoplastic polyesters include the alkali metal sulfonates sold under the tradename Eastman AQ® polymer from Eastman Chemical Products, Incorporation located in Kingsport, Tenn., specific examples of which include Eastman AQ(D 1045, Eastman AQ® 1350, Eastman AQS 1950, Eastman AQ® 14,000, Eastman AQ® 29S, Eastman LB-100 AQ® 29S, Eastman AQ® 55S, Eastman AQ® 38S, Eastman AQ® 48, and mixtures thereof.
- Biodegradable Components
- The flushable tampon applicators of the present invention comprise a total of from about 1% to about 99%, preferably from about 5% to about 95%, more preferably from about 10% to about 90% of biodegradable thermoplastic polymers by weight of the applicator. The biodegradable thermoplastic polymers can be used individually or as a combination of polymers provided that the biodegradable thermoplastic polymers are degradable by biological and environmental means, and that they are compatible for combination with one or more water-dispersible polymers described hereinabove, The biodegradable polymers suitable for use herein are those biodegradable materials which are susceptible to being assimilated by microorganisms such as molds, fungi, and bacteria when the biodegradable material is buried in the ground or otherwise comes in contact with the microorganisms including contact under environmental conditions conducive to the growth of the microorganisms.
- Suitable biodegradable polymers also include those biodegradable materials which are environmentally degradable using aerobic or anerobic digestion procedures, or by virtue of being exposed to environmental elements such as sunlight, rain, moisture, wind, temperature, and the like.
- Nonlimiting examples of biodegradable thermoplastic polymers suitable for use in the flushable tampon applicators of the present invention include aliphatic polyesteramides; diacid/diol-based aliphatic polyesters; aromatic polyesters including modified polyethylene terephthalates; aliphatic/aromatic copolyesters; polycaprolactones; polycaprolactone copolymers; poly(3-hydroxyalkanoates) including poly(3-hydroxybutyrates), poly(3-hydroxyhexanoates), and poly(3-hydroxyvalerates); poly(3-hydroxyalkanoates) copolymers including poly(3-hydroxy) butyrate/valerate copolymers; polyesters and polyurethanes derived from aliphatic polyols (i.e., dialkanoyl polymers); polyvinyl acetates; polyethylene/vinyl alcohol copolymers; lactic acid polymers including lactic acid homopolymers and lactic acid copolymers; lactide polymers including lactide homopolymers and lactide copolymers; glycolide polymers including glycolide homopolymers and glycolide copolymers; and mixtures thereof. Preferred are aliphatic polyesteramides, diacid/diol-based aliphatic polyesters, poly(3-hydroxyalkanoates), poly(3-hydroxyalkanoates) copolymers, aliphatic/aromatic copolyesters, lactic acid polymers, and lactide polymers.
- Specific examples of preferred aliphatic polyesteramides suitable for use as a biodegradable thermoplastic polymer herein include, but are not limited to, aliphatic polyesteramides which are reaction products of a synthesis reaction of diols, dicarboxylic acids, and aminocarboxylic acids; aliphatic polyesteramides formed from reacting lactic acid with diamines and dicarboxylic acid dichlorides; aliphatic polyesteramides formed from caprolactone and caprolactam; aliphatic polyesteramides formed by reacting acid-terminated aliphatic ester prepolymers with aromatic diisocyanates; aliphatic polyesteramides formed by reacting aliphatic esters with aliphatic amides; and mixtures thereof. Aliphatic polyesteramides formed by reacting aliphatic esters with aliphatic amides are most preferred.
- Preferred aliphatic polyesteramides which are copolymers of aliphatic esters and aliphatic amides can be characterized in that these copolymers generally contain from about 30% to about 70%, preferably from about 40% to about 80% by weight of aliphatic esters, and from about 70% to about 30%, preferably from about 60% to about 20% by weight of aliphatic amides. The weight average molecular weight of these copolymers ranges from about 10,000 daltons to about 500,000 daltons, preferably from about 20,000 daltons to about 300,000 daltons as measured by known gel chromatography techniques used in the determination of molecular weight of polymers.
- The aliphatic ester and aliphatic amide copolymers of the preferred aliphatic polyesteramides are derived from monomers such as dialcohols including ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, and the like; dicarboxylic acids and dicarboxylhc acid esters including oxalic acid, succinic acid, adipic acid, oxalic acid esters, succinic acid esters, adipic acid esters, and the like; hydroxycarboxylic acid and lactones including caprolactone, and the like; aminoalcohols including ethanolamine, propanolamine, and the like; cyclic lactams including s-caprolactar, lauric lactam, and the like; (o-aminocarboxylic acids including aminocaproic acid, and the like; 1:1 salts of dicarboxylic acids and diamines including 1:1 salt mixtures of dicarboxylic acids such as adipic acid, succinic acid, and the like, and diamines such as hexamethylenediamine, diaminobutane, and the like; and mixtures thereof. Hydroxy-terminated or acid-terminated polyesters such as acid terminated oligoesters can also be used as the ester-forming compound. The hydroxy-terminated or acid terminated polyesters typically have number average molecular weights of from about 200 daltons to about 10,000 daltons.
- The preferred aliphatic polyesteramides can be prepared by any suitable synthesis or stoichiometric technique known in the art for forming aliphatic polyesteramides having aliphatic ester and aliphatic amide monomers. A typical synthesis involves stoichiometrically mixing the starting monomers, optionally adding water to the reaction mixture, polymerizing the monomers at an elevated temperature of about 220° C., and subsequently removing the water and excess monomers by distillation using vacuum and elevated temperature, resulting in a final copolymer of an aliphatic polyesteramide. Other suitable techniques involve transesterification and transamidation reaction procedures. As apparent by those skilled in the art, a catalyst can be used in the above-described synthesis reaction and transesterification or transaindation procedures, wherein suitable catalysts include phosphorous compounds, acid catalysts, magnesium acetates, zinc acetates, calcium acetates, lysine, lysine derivatives, and the like.
- The preferred aliphatic polyesteramides comprise copolymer combinations of adipic acid, 1,4-butanediol, and 6-aminocaproic acid with an ester portion of 45%; adipic acid, 1,4-butanediol, and ε-caprolactam with an ester portion of 50%; adipic acid, 1,4-butanediol, and a 1:1 salt of adipic acid (“AH salt”) and 1,6-hexamethylenediamine; and an acid-terminated oligoester made from adipic acid, 1,4-butanediol, 1,6-hexamethylenediamine, and s-caprolactam. These preferred aliphatic polyesteramides have melting points of from about 115° C. to about 155° C. and relative viscosities (1 wt. % in m-cresol at 25° C.) of from about 2.0 to about 3.0, and are commercially available from Bayer Aktiengesellschaft located in Leverkusen, Germany under the BAK® tradename. Specific examples of such commercially available polyesteramides include BAK® 402, BAK® 403, and BAK® 404.
- Specific examples of preferred diacid/diol-based aliphatic polyesters suitable for use as a biodegradable thermoplastic polymer herein include, but are not limited to, aliphatic polyesters produced either from ring opening reactions or from the condensation polymerization of aliphatic diacids and aliphatic diols, wherein the number average molecular weight of these aliphatic polyesters typically range from about 30,000 daltons to about 300,000 daltons. The preferred diacid/diol-based aliphatic polyesters are reaction products of a C2-C10 diol reacted with oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, copolymers thereof, or mixtures thereof. Nonlimting examples of preferred diacid/diol-based aliphatic polyesters include polyalkylene succinates such as polyethylene succinate, and polybutylene succinate; polyalkylene succinate copolymers such as polyethylene succinate/adipate copolymer, and polybutylene succinate/adipate copolymer; polypentamethyl succinates; polyhexamethyl succinates; polyheptamethyl succinates; polyoctamethyl succinates; polyalkylene oxalates such as polyethylene oxalate, and polybutylene oxalate; polyalkylene oxalate copolymers such as polybutylene oxalate/succinate copolymer and polybutylene oxalate/adipate copolymer; polybutylene oxalate/succinate/adipate terpolymers; and mixtures thereof. An example of suitable commercial diacid/diol-based aliphatic polyesters is the polybutylene succinate/adipate copolymers sold under the BIONOLLE 1000 and BIONOLLE 3000 tradenames from the Showa Highpolymer Company, Ltd. located in Tokyo, Japan.
- Specific examples of preferred poly(3-hydroxyalkanoates) suitable for use as a biodegradable thermoplastic polymer herein include, but are not limited to, the poly(3-hydroxyalkanoates commercially available under the Biomer 209H and Biomer 240H tradenames from the Biomer Company located in Krailling, Germany. Specific examples of preferred poly(3-hydroxyalkanoates) copolymers suitable for use as a biodegradable polymer herein include, but are not limited to the poly(3-hydroxy) butyrate/valerate copolymers disclosed in U.S. Pat. No. 5,391,423, issued to Wnuk et al. on Feb. 21 1995, which disclosure is incorporated by reference herein; and the poly(3-hydroxy) butyrate/valerate copolymers such as poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxydocosanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexadecanoate), poly(3-hydroxyvalerate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerateco-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxydecanoate), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyoctanoate-co-3-hydroxydecanoate) disclosed in U.S. Pat, No. 5,489,470, issued to Noda on Feb. 6, 1996, which disclosure is incorporated by reference herein.
- Specific examples of preferred aliphatic/aromatic copolyesters suitable for use as a biodegradable thermoplastic polymer herein include, but are not limited to, those aliphatic/aromatic copolyesters that are random copolymers formed from a condensation reaction of dicarboxylic acids or derivatives thereof and diols. Suitable dicarboxylic acids include, but are not limited to, malonic, succinic, glutaric, adipic, pimelic, azelaic, sebacic, fumaric, 2,2-dimethyl glutaric, suberic, 1,3-cyclopentanedicarboxylic, 1,4-cyclohexanedicarboxylic, 1,3-clohexanedicarboxylic, diglycolic, itaconic, maleic, 2,5-norbornanedicarboxylic, 1,4-terephthalic, 1,3-terephthalic, 2,6-naphthoic, 1,5-naphthoic, ester forming derivatives thereof, and combinations thereof. Suitable diols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and combinations thereof. Nonlimiting examples of such aliphatic/aromatic copolyesters include a 50/50 blend of poly(tetramethylene glutarate-co-terephthalate), a 60/40 blend of poly(tetramethylene glutarate-co-terephthalate), a 70/30 blend of poly(tetramethylene glutarate-co-terephthalate), an 85/15 blend of poly(tetramethylene glutarate-co-terephthalate), a 50/45/15 blend of poly(tetramethylene glutarate-co-terephthalate-co-diglycolate), a 70/30 blend of poly(ethylene glutarate-co-terephthalate), an 85/15 blend of poly(tetramethylene adipate-co-terephthalate), an 85/15 blend of poly(tetramethylene succinate-co-terephthalate), a 50/50 blend of poly(tetramethylene-co-ethylene glutarate-co-terephthalate), and a 70/30 blend of poly(tetramethylene-co-ethylene glutarate-co-terephthalate). These aliphatic/aromatic copolyesters, in addition to other suitable aliphatic/aromatic polyesters, are further described in U.S. Pat. No. 5,292,783 issued to Buchanan et al. on Mar. 8, 1994, which descriptions are incorporated by reference herein. The poly(tetramethylene adipate-co-terephthalate) is a preferred aliphatic/aromatic copolyester that is commercially available from Eastman Chemical (Kingsport, Tenn.) under the Eastar Biodegradable Copolyester 14776 tradename.
- Specific examples of preferred lactic acid polymers and lactide polymers suitable for use as a biodegradable thermoplastic polymer herein include, but are not limited to, those polylactic acid-based polymers and polylactide-based polymers that are generally referred to in the industry as “PLA”. Therefore, the terms “polylactic acid”, “polylactide” and “PLA” are used interchangeably to include homopolymers and copolymers of lactic acid and lactide based on polymer characterization of the polymers being formed from a specific monomer or the polymers being comprised of the smallest repeating monomer units. In other words, polylactide is a dimeric ester of lactic acid and can be formed to contain small repeating monomer units of lactic acid (actually residues of lactic acid) or be manufactured by polymerization of a lactide monomer, resulting in polylactide being referred to both as a lactic acid residue containing polymer and as a lactide residue containing polymer. It should be understood, however, that the terms “polylactic acid”, “polylactide”, and “PLA” are not intended to be limiting with respect to the manner in which the polymer is formed.
-
-
- Typically, polymerization of lactic acid and lactide will result in polymers comprising at least about 50% by weight of lactic acid residue repeating units, lactide residue repeating units, or combinations thereof. These lactic acid and lactide polymers include homopolymers and copolymers such as random and/or block copolymers of lactic acid and/or lactide. The lactic acid residue repeating monomer units can be obtained from L-lactic acid and D-lactic acid. The lactide residue repeating monomer units can be obtained from L-lactide, D-lactide, and meso-lactide.
- Suitable lactic acid and lactide polymers include those homopolymers and copolymers of lactic acid and/or lactide which have a weight average molecular weight generally ranging from about 10,000 daltons to about 600,000 daltons. An example of commercially available polylactic acid polymers includes a variety of polylactic acids that are available from the Chronopol Incorporation located in Golden, Colorado. An example of commercially available polylactide polymers includes the polylactides sold under the tradename EcoPLA®. An example of commercially available “PLA” polymers includes PLA 44D and PLA 62-50, both of which are available from Cargill-Dow Polymers, LLC located in Minnetonka, Minn. Other suitable polylactic acid polymers and copolymers include polylactic acid prepared by direct polycondensation of lactic acid (available from the Mitsui Chemical Incorporation under the tradename LACEA), and a block copolymer comprising a polylactic acid hard segment and a polyoxyalkylene dialkanoate soft segment (available from the Dainippon Ink and Chemicals Incorporation and the Shimadzu Corporation, both of which are located in Japan).
- Specific examples of other suitable biodegradable polymers include polycaprolactone polyesters having a number average molecular weight of from about 10,000 daltons to about 80,000 daltons. Commercially suitable polycaprolactone polymers are the polycaprolactones available from the Union Carbide Corporation sold under the TONE tradename, examples of which include Tone P-767, Tone P-787, and Tone P-303. Tone P-767 has a number average molecular weight of about 43,000 daltons. Tone P-787 has a number average molecular weight of about 80,000 daltons. Tone P-303 is an A-B-A block polymer of Tone P-767 polycaprolactone and polyethylene oxide, and has a number average molecular weight of from about 30,000 daltons to about 35,000 daltons.
- The biodegradable polymers described herein, in addition to thermoplastic compositions containing these polymers, will physically and biologically decompose using known degradation procedures such as aerobic, anaerobic, and microbial digestion processes. One such method of evaluating the decomposition of biodegradable materials includes an anaerobic disintegration procedure which involves measuring the percent weight loss of thermoplastic compositions containing biodegradable polymers. Typically, thermoplastic compositions containing biodegradable polymers are exposed to anaerobic sludge that can be obtained from a municipal wastewater treatment plant (e.g., sludge that has a pH of or between about 7 and 8, and about 1% total solids). The sludge-exposed thermoplastic compositions are allowed to disintegrate or decompose for 7, 14, and 28 days at 35° C. under controlled incubator conditions. After the 7, 14, or 28 day incubation period, the sludge-exposed thermoplastic compositions are evaluated for percent weight loss by recovering any undisintegrated portions of the compositions, drying these undisintegrtaed portions at 40° C. for at least 2 hours after a tap water rinsing, and determining the weight of the dried undisintegrated portions. The percent weight loss is calculated based on the weight of the thermoplastic compositions before and after exposure to sludge for a given time period. It has been found that the biodegradable polymer containing-thermoplastic compositions described herein lose their structural integrity by breaking apart into smaller pieces and/or by shrinking into smaller fragments after being exposed to sludge for only 7 days. Anaerobic biodegradation of these biodegradable polymer containing-thennoplastic compositions increased after the compositions were exposed to sludge for periods of 14 and 28 days.
- Filler Components
- In addition to the water-dispersible and biodegradable thermoplastic materials, the flushable tampon applicators of the present invention preferably comprise one or more fillers which can aid in the applicators having an opaque appearance and provide for applicators that have a smooth, soft texture and improved water-dispersibility. The filler can be added by compounding the filler with the thermoplastic polymers and any optional ingredient described herein, and processing this compounded mixture according to the disclosed methods of constructing flushable tampon applicators of the present invention. Preferably, the flushable tampon applicators are constructed such that the filler is melt blended with the thermoplastic polymers to form a composite of thermoplastic material and discrete filler particles that are uniformly dispersed throughout the composite, flushable tampon applicator structure.
- Suitable fillers include inorganic and organic filler materials. Nonlimiting examples of suitable inorganic fillers include clays, silica, mica, wollastonite, calcium hydroxide, calcium carbonate, sodium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, kaolin, calcium oxide, magnesium oxide, aluminum hydroxide, magnesium silicates including talc, titanium dioxide, and mixtures thereof. Nonlimiting examples of suitable organic fillers include wood flour, walnut shell flour, alpha cellulose floc, cellulose fibers, chitin, chitosan powders, organosilicone powders, nylon powders, polyester powders, polypropylene powders, starch granules, and mixtures thereof. Filler components such as calcium carbonate, talc, barium sulfate, starch granules, and wood flour are preferred.
- The fillers are typically included at total filler concentrations ranging from 0% to about 70%, preferably from about 5% to about 65%, more preferably from about 8% to about 60% by weight of the applicator. The inclusion of filler components within the defined concentration ranges have been found to provide the flushable tampon applicators with improved disintegration rate for spontaneous flushability in addition to the flushable tampon applicators being shelf stable, nonsticky when wet, nontacky when wet, and smooth to the touch. The filler components can be included in the construction of the flushable tampon applicators as an individual filler or a combination of filler components provided that the total filler concentration is within these defined concentration ranges.
- Specific examples of calcium carbonates suitable for use of a filler herein, include but are not limited to, the calcium carbonates commercially available from Specialty Minerals (Bethlehem, Pa.) under the Vicron 15-15, Vicron 10-25, and Vicron 25-11 tradenames.
- Specific examples of magnesium silicates such as talc which are suitable for use as a filler herein include, but are not limited to, ABT 2500 talc and
OPTIBLOC 10 talc, both of which are available from Specialty Minerals. - Specific examples of starch granule materials suitable for use as a filler herein include, but are not limited to, the corn starch materials sold under the Staley STAR-DRI® 1 and Staley Pure Food Powdered tradenames, both of which are commercially available the A. E. Staley Manufacturing Company (Decatur, Ill.); Clinton 290 which is commercially available from ADM Corn Processing (Decatur, Ill.); and National Starch Melojel which is commercially available from National Starch & Chemical (Bridgewater, N.J.).
- Specific examples of wood flour materials suitable for use as a filler herein include, but are not limited to, Maple Wood Flour, Grade 10010 and Pine Wood Flour, Grade 10020, both of which are commercially available from American Wood Fibers (Columbia, Md.).
- A specific example of a nylon powder suitable for use as a filler herein is Morton Corvel White Nylon 11 powder which is commercially available from the Morton International Incorporation located in Chicago, Ill.
- A specific example of a polyester powder suitable for use as a filler herein is Morton Corvel H RF polyester powder which is commercially available from the Morton International Incorporation.
- A specific example of a titanium dioxide material suitable for use as a filler herein is Titanium Dioxide Grade R102 17145T-43 which is commercially available from Dupont White Pigment & Mineral Products located in Wilmington, Del.
- The flushable tampon applicators of the present invention preferably comprise a blend of water-dispersible and biodegradable materials, wherein this blend can be defined as a combination of one or more high molecular weight polyethylene oxides, one or more low molecular weight polyethylene glycols, and one or more aliphatic/aromatic copolyesters. In this context, the term “blend” refers to a composition of thermoplastic materials that has been formed by melt processing two or more thermoplastic materials to result in a homogenous, heterogeneous, or mixture thereof, of these materials. It has been found that a thermoplastic blend comprising a combination of high molecular weight polyethylene oxides, low molecular weight polyethylene glycols, and aliphatic/aromatic copolyesters provides a flushable tampon applicator that readily disintegrates in water, that has improved aesthetics such as non-sticky, non-slimy, air-laden moisture resistance, softness, flexibility, and that is of little or no environmental concern for disposal.
- The combination of the high molecular weight polyethylene oxides, low molecular weight polyethylene glycols, and aliphatic/aromatic copolyesters results in a thermoplastic composition comprising a total of from about 1% to about 90% by weight of high molecular weight polyethylene oxides, a total of from about 1% to about 4 0% by weight of low molecular weight polyethylene glycols, and a total of from about 9% to about 59% by weight of aliphatic/aromatic copolyesters. Therefore, the thermoplastic compositions can comprise blended ratios of water-dispersible materials such as high 20 molecular weight polyethylene oxides and low molecular weight polyethylene glycols to biodegradable materials such as aliphatic/aromatic copolyesters of from about 10:1 to about 1:6, preferably of from about 4:1 to about 1:3. The ratio of water-dispersible materials, such as a ratio of high molecular weight polyethylene oxide to low molecular weight polyethylene glycol, typically ranges from about 9:1 to about 1:4, preferably from about 3:1 to about 1:2.
- The flushable tampon applicators of the present invention can also comprise other blends of water-dispersible and biodegradable thermoplastic polymers, nonlimiting examples of which include a blend of one or more high molecular weight polyethylene oxides, one or more low molecular weight polyethylene glycols, and one or more diacid/diol-based aliphatic polyesters; a blend of one or more high molecular weight polyethylene oxides, one or more low molecular weight polyethylene glycols, and one or more aliphatic polyesteramides; and a blend of one or more high molecular weight polyethylene oxides, one or more low molecular weight polyethylene glycols, and one or more polylactic acid polymers. These blends as well as the above-described preferred thermoplastic polymer blend and any other blend or structure of thermoplastic materials are suitable for forming the outer tubular member and plunger components of the flushable tampon applicators of the present invention.
- The flushable tampon applicators of the present invention can also comprise a composite of thermoplastic materials. In this context, the term “composite” refers to a structure of thermoplastic polymeric materials that are intermingled together or joined such that each thermoplastic polymer forms at least one unit of the total composite structure. For example, a thermoplastic composite can contain one or more units of water-dispersible polymers intermixed or joined with one or more units of biodegradable polymers such that within the overall composite structure the water-dispersible polymer units create structural discontinuities between the biodegradable polymer units. In this context, the term “structural discontinuities” refers to discrete or separate components that are joined or intermingled to provide adjacent or alternate units of individual components. Preferably, a thermoplastic composite is constructed such that it comprises less than about 99% of water-dispersible polymers and more than about 1% of biodegradable polymers, more preferably less than about 95% of water-dispersible polymers and more than about 5% of biodegradable polymers, even more preferably less than about 90% of water-dispersible polymers and more than about 10% of biodegradable polymers, by weight of the composite. However, the thermoplastic composites can be any composite combination of water-dispersible and biodegradable polymers described herein provided that the water-dispersible polymers allow for rapid dispersion of the biodegradable polymers into separate components so that the overall composite structure readily disintegrates upon contact with water. The thermoplastic composite tampon applicators can be constructed using known procedures such as injection molding and co-injection molding which eliminate the need to assemble separate composite pieces for producing a final tampon applicator product. Alternatively, the thermoplastic composite tampon applicators can be constructed by molding separate composite pieces and assembling or joining the pieces into a final tampon applicator product, wherein means of assembling or joining the composite pieces include adhesive bonding, heat sealing, ultrasonic welding, solvent welding, dielectric sealing, and mechanical attachment. The flushable tampon applicators of the present invention made from thermoplastic composites have been found to be readily disposed of by flushing down a sewage system such as a toilet and by the disclosed biodegradation procedures. The composite tampon applicators can also be made from a composite structure of thermoplastic polymers combined with paper, cellulose, cellophane, rayon fiber, woven, nonwoven materials, or combinations thereof.
- It is contemplated that the flushable tampon applicators of the present invention can be constructed 30 in any other blend, composite, shape, or configuration using the water-dispersible and/or biodegradable thermoplastic polymers, and any other desired or optional ingredient described herein. Another nonlimiting preferred embodiment includes spiral shaped flushable tampon applicators made from spirally wound thermoplastic materials that are held together using water-soluble adhesives. The water-soluble adhesive materials may be any known or otherwise effective water-soluble adhesives, but preferably are polyethyloxazoline and methyl cellulose adhesives.
- The flushable tampon applicators of the present invention can also comprise a composite of thermoplastic material and a non-thermoplastic material wherein the non-thermoplastic material is selected from the group including paper, starch, cellulose, cellophane, rayon fiber, natural fiber fabrics either woven or nonwoven, and combinations thereof. The thermoplastic material may be combined with the non-thermoplastic material by various techniques such as overmolding or insert molding. In overmolding, the non-thermoplastic material, for example a paper tube, is placed into an injection mold cavity, the mold clamped shut, and a molten thermoplastic resin is injected into the cavity such that the non-thermoplastic material is encapsulated or partly encapsulated by the thermoplastic material. In a tampon applicator, overmolding can provide, for example, a means of providing plastic-like features to a paper tube, or providing the look and feel of a plastic applicator to a paper tube, or providing a means of minimizing the amount of thermoplastic material needed to form the applicator components. Both inner and outer tube members may be fabricated from a composite of thermoplastic material and a non-thermoplastic material. In insert molding, the non-thermoplastic material is typically provided in a roll, unwound, and then trimmed or formed to a proper preform size and shape appropriate to insertion into the injection mold. The perform (or performs) is placed, along the wall of the mold cavity. The mold is then clamped shut, and the thermoplastic material injected into the mold cavity. Heat and pressure conditions in the mold cavity bond the perform to the thermoplastic resin. Bonding between the thermoplastic material perform may occur through mechanical entanglement, adhesion, or via melt bonding or fusion if the surface of the non-thermoplastic material has been pre-treated with a meltable surface coating. The preform comprising the non-thermoplastic material, generally becomes the surface or part of the surface of the finished molded part. In a tampon applicator, insert molding can provide, for example, a means of attaching a thin, water-insoluble, biodegradable surface layer to a water-softenable or water-dispersable, or water-degradable, or water-soluble thermoplastic resin.
- Still yet another nonlimiting embodiment of flushable tampon applicators include a composite flushable tampon applicator made from a combination of water-dispersible thermoplastic polymers, biodegradable thermoplastic polymers, and filler. These composite applicator structures are less tacky when wet, non-sticky when wet, softer, and more flexible than plastic tampon applicators made without filler components. The filler-containing composite applicators also result in reduced manufacturing cost with improved processibility of the applicators. Any suitable inorganic and/or organic filler component can be included in the construction of the composite applicator, provided that during the processing of the applicator the filler does not melt and remain in its particle form. Typically, the processing temperatures are lower than the melting temperature and decomposition temperature of the fillers, and during processing the water-dispersible and biodegradable thermoplastic polymers are melted and the filler particles are uniformly dispersed in the matrix of polymer blends of the water-dispersible and biodegradable polymers to result in the formation of a composite structure. The fillers suitable for use herein generally are water insoluble which help to reduce the stickiness of the applicators upon contact of the applicators with water, and which help to increase the shelf stability of the applicators. Also, because the fillers are in the dispersed phase of the composite, they accelerate the disintegration rate when the matrix of polymer blends of water-dispersible and biodegradable polymers start to disintegrate after flushing into a sewage system such as a toilet.
- It is preferred that the flushable tampon applicators of the present invention be constructed from thermoplastic materials that are typically in the form of polymer films. It should be understood, however, that these thermoplastic materials are also suitable for use as fibrous materials in the construction of absorbent articles such as tampon pledgets or any other fibrous or nonwoven material.
- Thermoplastic compositions suitable for use in the manufacture of flushable tampon applicators of the present invention can be a blend or other configuration of polymeric materials which will result in the compositions exhibiting amorphous and crystalline properties that can be characterized in terms of compositional morphology. It has been found that a particular blend of water-dispersible and biodegradable polymers described herein results in a thermoplastic composition having a defined morphology which provides for individual components of the composition to have melt profiles that allows for the creation of crystalline structures in the form of separate regions or domains within the blended nmixture of thermoplastic materials. Specifically, it has been found that a thermoplastic composition comprising a blend of high molecular weight polyethylene oxides, low molecular weight polyethylene glycols, and aliphatic polyesteramides or aliphatic/aromatic copolyesters exhibits a morphology such that the polyethylene oxides and polyethylene glycols form a homogenous blend of water-dispersible polymers that surrounds or encloses microdomains of the aliphatic polyesteramides or aliphatic/aromatic polyesters. In this context the term “microdomain” refers to polymer crystalline structures that have particle sizes in the submicron to micron sized region. It has also been found that a thermoplastic composition comprising a blend of water dispersible polymers such as high molecular weight polyethylene oxides and/or low molecular weight polyethylene glycols in combination with biodegradable polymers such as diacids/diols aliphatic polyesters forms a homogeneous one-phase polymer morphology.
- The two phase crystalline structure of a continuous phase of water-dispersible polymers and a discontinuous phase of biodegradable polymer microdomains are especially effective in forming thermoplastic compositions that can be melt processed into flushable tampon applicators of the present invention which are readily disposed of without creating any environmental concerns for their disposal. The two-phase crystalline structure has a morphology profile of water-dispersible and biodegradable polymers wherein in the liquid state (temperature above the melting point of the individual polymers), the polymers exhibit a heterogeneous phase morphology, but can be melt processed to result in a solid flushable tampon applicator exhibiting homogenous properties. Therefore, as used herein the term “homogenous” refers to a uniform mixture of materials, whereas the term “heterogeneous” refers to a nonuniform mixture of materials. The phase morphology can be determined using optical and scanning electron microscopes, for example a convenient optical microscopy instrument that can be used to determine the phase morphology of the thermoplastic compositions described herein is the
Zeiss Axioplan 2 Mot-Imaging Microscope that is equipped with a Linkham MDS-BCS-600 hot stage and that is available from the Carl Zeiss Incorporation located in Thornwood, N.Y. - The phase morphology of the water-dispersible and biodegradable polymers defined herein can further be described in terms of the polymers glass transition temperatures (Tg). The glass transition temperature of polymers or any other materials is typically identified as the area on the line where a distinct change in slope occurs, and can be determined using a thermal analysis instrument such as the 2980 Dynamic Mechanical Analyzer (DMA) in combination with Thermal Analyst Data Collection software program (Thermal Solutions version 2.5) and Data Analysis software program (Universal Analysis version 2.5H), all of which are available from T. A. Instruments Incorporation of New Castle, Delaware. It has also been found that combinations of water-dispersible and biodegradable polymers exhibit one or two glass transition temperatures, providing further support of polymers having one- or two-phase morphology profiles. As exemplified in Table 1 hereinbelow, polymer blends of water-dispersible polymers and aliphatic polyesteramides exhibit two different glass transition temperatures indicative of a two-phase morphology wherein polymer blends of water-dispersible polymers and diacids/diols aliphatic polyesters exhibit one glass transition temperature indicative of a one-phase morphology.
- It is believed that these morphology properties will also be exhibited in thermoplastic compositions made from a composite or any other configuration of water dispersible and biodegradable polymers described herein.
TABLE 1 Glass Transition Behavior of Water-Dispersible/Biodegradable Polymers and Polymer Blends Tg1 Tg2 Tg3 Polymers (° C.) (° C.) (° C.) PEO1 −41 — — PEO1/PEG2-40/30 blend −33 — — aliphatic polyesteramide (BAK 404)3 — −7 — aliphatic-aromatic copolyester (Eastar 14776)4 — −25 — diacid-diol aliphatic polyester (Bionolle 3001)5 — −31 — PEO1/BAK 4043-75/25 blend −43 8 — PEO1/Eastar 147764-60/40 blend −42 −24 — PEO1/Bionolle 30015-70/30 blend — — −36 PEO1/Bionolle 30015-50/50 blend — — −28 PEO1/Bionolle 30015-15/85 blend — — −30 PEO1/PEG2/BAK 4043-40/30/30 blend −31 −10 — PEO1/PEG2/Eastar 147764-40/30/30 blend −41 −27 — PEO1/PEG2/Bionolle 30015-40/30/30 blend — — −31 - The flushable tampon applicators of the present invention are made from thermoplastic compositions having physical properties of tensile strength at break, percent elongation at break, elastic modulus, and hardness. The thermoplastic compositions can include ingredients such as fillers, plasticizers, processing aids, dispersing agents, lubricants, resin modifiers, clarifying/nucleating agents, viscosity modifiers, and the like. Preferred thermoplastic compositions comprise water-dispersible thermoplastic polymers, biodegradable thermoplastic polymers, plasticizers, and/or lubricants, and/or fillers in various combinations.
- The tensile strength at break, percent elongation at break, and elastic modulus of thermoplastic materials, especially blends of thermoplastic materials, are determined according to methods known in the art. One such method is the ASTM D882-95a test method described in “Standard Test Method for Tensile Properties of Thin Plastic Sheeting”, pages 159-167. This procedure involves testing blends of thermoplastic materials for achieving desired properties of flexibility, elasticity, durability, unbrittleness, resilency, distensibility, tenacity, and so forth. Typically, blends of thermoplastic materials are injection molded to form “dogbone-shaped” test samples having dimensions of ½ inch length (L)×⅛ inch width (W)×{fraction (1/16)} inch height (H), then the “dogbone-shaped” test samples are evaluated for tensile strength at break, percent elongation at break, and elastic modulus using an Instron Tensile Tester (Model 1122 from Instron Corporation located in Canton, Mass.) equipped with a 50 pound load cell, grip separation of 1 inch, a gage length of ½ inches, 5 millimeter (mm) jaw gap, and a crosshead speed of 2 inches/minute. For each analysis, the “dogbone-shaped” test sample is stretched until breakage occurs, and a load-versus-extension plot is generated for determining the tensile strength at break, percent elongation at break, and elastic modulus properties. The tensile strength at break is the load at break divided by the cross-sectional area of the test sample, and is defined in units of mega-Pascal or MPa (newton/square meter). The percent elongation at break is determined by dividing the length of the extension at the point of rupture by the gage length, and then multiplying by 100. Elastic modulus is the slope of the initial linear portion of the load-extension curve, and is defined in units of MPa.
- The thermoplastic compositions described herein preferably have a harness property such that the compositions exhibit a firm resistance to stress or strain, yet are not brittle or too soft for processing into flushable tampon applicators of the present invention. The hardness properties are determined according to ASTM D2240-97 test method described in “Standard Test Method for Rubber Property-Durometer Hardness, pages 388-391. Typically, thermoplastic materials are injected molded into bars that are stacked in groups of two bars per stack wherein each bar stack has a total thickness of ⅛ inches. The hardness value is measured at various points of the bar stack using a hardness instrument such as Model 307 L Shore D Durometer from PTC Instruments, and a mean hardness measurement is determined.
- The preferred thermoplastic compositions for constructing the flushable tampon applicators of the present invention have physical properties similar to or superior to physical properties of known thermoplastic materials that are used in the manufacture of tampon applicators. For example, polyethylene-based thermoplastic polymers typically have elastic modulus properties of from about 80 MPa to about 200 MPa, wherein other thermoplastic polymers such as polypropylene-based polymers have elastic modulus of from about 1000 MPa to about 1500 MPa. It has been found that the thermoplastic compositions described herein exhibit desirable properties of an elastic modulus value of less than 1000 MPa, and this elastic modulus attribute in addition to the other described physical properties result in thermoplastic compositions having flexibility, elasticity, durability, resilency, distensibility, tenacity, and the like. The physical properties of the preferred thermoplastic compositions are exemplified hereinbelow in Table 2.
TABLE 2 Thermoplastic Compositions Physical Properties Tensile Percent Strength Elongation Elastic at break at break Modulus Hardness Sample (MPa) (%) (MPa) (Shore D) PEO1/PEG2/Biomer 209H6 (40/30/30 blend) 6 20 310 58 PEO1/PEG2/Bionolle 30015 (40/30/30 blend) 8 460 220 51 PEO1/PEG2/Bionolle 30015 (66/17/17 blend) 5 80 270 52 PEO1/PEG2/Eastar 147764 (40/30/30 blend) 6 80 230 51 PEO1/PEG2/BAK 4043 (40/30/30 blend) 11 20 250 57 PEO1/PEG2/BAK 4043 (40/40/20 blend) 9 20 340 60 PEO1/PEG2/BAK3/P-6457 (36/27/27/10 blend) 8 46 190 51 PEO1/PEG2/BAK3/P-41418 (36/27/27/10 blend) 7 48 180 51 PEO1/PEG2/PLA 44D9 (40/30/30 blend) 19 13 530 67 PEO1/PEG2/PLA 62-50D9 (40/30/30 blend) 22 10 510 67 PEO1/PEG2/Eastar4/P-6457/CaCO3 10 (11/9/20/10/50 blend) 3 27 90 43 PEO1/PEG2/Eastar4/P-6457/CaCO3 10 (24/18/18/10/30 blend) 5 60 166 49 PEO1/PEG2/Eastar4/P-6457/CaCO3 10 (29/21/10/10/30 blend) 4 18 227 52 PEG2/PEG11/Eastar4/P-6457/CaCO3 10 (20/5/40/5/30 blend) 6 12 174 48 PEO1/PEG2/Eastar4/P-6457/CaCO3 10 (16/12/12/10/50 blend) 5 13 184 47 PEO1/PEG2/Eastar4/P-6457/Talc12 (17/13/10/10/50 blend) 5 16 173 43 PEO1/PEG2/Eastar4/P-6457/Talc12 (24/18/18/10/30 blend) 4 40 303 47 PEO1/PEG2/Eastar4/AB13/wood flour14/TiO2 15/Kemamide E16 17 5 640 61 (17/17/25/5/30/5/1 blend) PEO1/PEG2/Eastar4/Starch17/P-6457/Kemamide E16 2 22 98 34 (18/13/13/50/5/1 blend) PEO1/PEG2/Eastar4/Starch18/P-6457/Kemamide E16/MgSt19 4 180 160 46 (15/10/37/30/5/1/2 blend) PEO1/Eastar4/CaCO3 10/P-6457 (18/15/65/4 blend) 7 58 230 53 PEO1/PEG2/Eastar4/CaCO3 10/P-6457/Kemamide E16 6 95 180 49 (15/10/29/40/5/1 blend) PEO1/PEG2/Eastar4/CaCO3 10/P-6457/MgSt19/Loxiol G3320 5 310 160 43 (15/10/26/40/5/2/2 blend) PEO1/PEG2/Eastar4/CaCO3 10/P-6457/Kemamide E16 8 450 180 49 (15/10/39/30/5/1 blend) PEO1/PEG2/Eastar4/CaCO3 10/P-6457/Kemamide E16/Paraffin 5 340 140 42 wax21 (15/10/34/30/5/1/5 blend) PEO1/Eastar4/CaCO3 10/P-6457/Kemamide E16 10 640 83 44 (25/39/30/5/1 blend) PEG2/Eastar4/CaCO3 10/MgSt19 (17.5/64/17.5/1 blend) 6 650 150 46 PEG2/Eastar4/CaCO3 10/MgSt19/P-64322/DC4-705125 10 1040 68 37 (15/62/15/1/5/2 blend) PEO1/PEG2/Eastar4/CaCO3 10/P-6457/MgSt19/DC950623 5 130 150 44 (15/10/26/40/5/2/2 blend) PEO1/PEG2/Eastar4/CaCO310/P-6457/MgSt19/Loxiol 5 130 150 44 G3320/Kraton G 165224 (14.5/9.5/25.5/39.5/5/2/2/2 blend) - The thermoplastic compositions also have physical properties of dry and wet flexural modulus. The dry flexural modulus is determined according to ASTM D5943-96 test method described in “Standard Test Method for Determining Flexural Properties of Plastics”, pages 708-712. This procedure involves injection molding thermoplastic materials into “beams” of test samples having 5 inch L×½ inch W×⅛ inch H. Generally, the test samples are pre-loaded with 0.01 pounds of force, thereafter a force loading is applied at a rate of 0.1 inches per minute, and a stress-versus-strain curve is generated to determine the dry flexural modulus property. The dry flexural modulus is the slope of the stress-strain curve as calculated in the linear region of from about 0.05% to about 0.25% of the flexural strain. The wet flexural modulus is determined by submerging the dry “beams” of test samples in water at time intervals of 5 minutes, 15 minutes, and 60 minutes, and observing the softening of the test samples. As used herein, the term “softening” refers to materials that readily lose their stiffness or undergo a decrease in flexural modulus property upon contact with water. It has been found that the preferred thermoplastic compositions described herein undergo a significant decrease in flexural modulus upon contact of the composition with water. This decrease in flexural modulus property provides for thermoplastic compositions that are manufactured into flushable tampon applicators that readily lose their structural integrity in water for easy disposal down a sewage system such as a toilet. Dry and wet flexural modulus properties of preferred thermoplastic compositions are exemplified hereinbelow in Table 3.
TABLE 3 Flexural Modulus Physical Properties Wet Wet Wet Dry Flexural Flexural Flexural Flexural Modulus Modulus Modulus Modulus (MPa) (MPa) (MPa) Sample (MPa) at 5 min. at 15 min. at 60 min. PEO1/PEG2/Biomer 209H6 (40/30/30 blend) 700 290 140 40 PEO1/PEG2/Bionolle 30015 (40/30/30 blend) 540 180 140 30 PEO1/PEG2/Bionolle 30015 (66/17/17 blend) 450 190 150 50 PEO1/PEG2/Eastar 147764 (40/30/30 blend) 610 180 120 20 PEO1/PEG2/BAK 4043 (40/30/30 blend) 720 210 100 40 PEO1/PEG2/BAK 4043 (40/40/20 blend) 840 450 300 60 PEO1/PEG2/BAK3/P-6457 (36/27/27/10 blend) 360 230 150 30 PEO1/PEG2/BAK3/P-41418 (36/27/27/10 blend) 350 220 120 40 PEO1/PEG2/PLA 44D9 (40/30/30 blend) 1280 700 430 260 PEO1/PEG2/PLA 62-50D9 (40/30/30 blend) 1220 660 450 220 PEO1/PEG2/Eastar4/P-6457/CaCO310 (11/9/20/10/50 blend) 206 154 106 42 PEO1/PEG2/Eastar4/P-6457/CaCO310 (24/18/18/10/30 blend) 377 211 181 61 PEO1/PEG2/Eastar4/P-6457/CaCO310 (29/21/10/10/30 blend) 549 211 163 28 PEG2/PEG11/Eastar4/P-6457/CaCO310 (20/5/40/5/30 blend) 292 257 226 210 PEO1/PEG2/Eastar4/P-6457/CaCO310 (16/12/12/10/50 blend) 473 243 182 72 PEO1/PEG2/Eastar4/P-6457/Talc12 (17/13/10/10/50 blend) 554 280 246 77 PEO1/PEG2/Eastar4/P-6457/Talc12 (24/18/18/10/30 blend) 745 434 320 140 PEO1/PEG2/Eastar4/AB13/wood flour14/TiO2 15/Kemamide E16 2050 1120 — 260 (17/17/25/5/30/5/1 blend) PEO1/PEG2/Eastar4/Starch17/P-6457/Kemamide E16 330 130 — 12 (18/13/13/50/5/1 blend) PEO1/PEG2/Eastar4/Starch18/P-6457/Kemamide E16/MgSt19 360 308 211 120 (15/10/37/30/5/1/2 blend) PEO1/Eastar4/CaCO3 10/P-6457 (18/15/65/4 blend) 430 278 177 52 PEO1/PEG2/Eastar4/CaCO3 10/P-6457/Kemamide E16 390 270 206 83 (15/10/29/40/5/1 blend) PEO1/PEG2/Eastar4/CaCO3 10/P-6457/MgSt19/Loxiol G3320 410 271 203 81 (15/10/26/40/5/2/2 blend) PEO1/PEG2/Eastar4/CaCO3 10/P-6457/Kemamide E16 380 302 234 125 (15/10/39/30/5/1 blend) PEO1/Eastar4/CaCO3 10/P-6457/Kemamide E16 200 184 179 99 (25/39/30/5/1 blend) PEO1/PEG2/Eastar4/CaCO3 10/P-6457/Kemamide E16/Paraffin 300 205 187 94 wax21 (15/10/34/30/5/1/5 blend) PEG2/Eastar4/CaCO3 10/MgSt19 (17.5/64/17.1/1 blend) 320 263 245 228 PEG2/Eastar4/CaCO3 10/MgSt19/P-64322/DC4-705125 140 128 133 116 (15/62/15/1/5/2 blend) - The thermoplastic compositions also have physical properties of weight loss in water which can be determined by the percent weight loss of a dry specimen sample of a thermoplastic composition that has been submerged in water for time intervals of 5 minutes, 1 hour, 24 hours, and 1 week. For example, dry injection molded thermoplastic compositions having a thickness of about ⅛ inches are weighed to ascertain the dry specimens dry weight. The dry specimens are then soaked in water for a duration of 5 minutes, 1 hour, 24 hours, or 1 week, wherein dependent on the type of thermoplastic composition dissolution of the water-soaked specimen occurs. The water-soaked specimens are recovered for drying in a Blue M oven for 16 hours at 40° C. to obtain a final weight loss. The percent weight loss is calculated by subtracting the weight of dried water-soaked specimens minus the dry specimens initial weight, divided by the dry specimens initial weight, and multiplied by 100. The percent weight loss values of thermoplastic compositions described herein are exemplified hereinbelow in Table 4. A negative percent weight loss value is indicative of the thermoplastic composition being able to readily dissolve or disintegrate in water, and a positive percent weight loss value is indicative of the thermoplastic composition being able to maintain its structural integrity in water and not readily break apart into unrecognizable pieces. It has been found that the preferred thermoplastic compositions described herein can be molded into flushable tampon applicators of the present invention that exhibit a weight loss in water such that after being submerged for a period of 5 minutes the tampon applicators are capable or readily breaking apart, an observation of such tampon applicators being suitable for disposal by flushing down a toilet. These flushable tampon applicators exhibited a significant weight loss in water over a time period of 24 hours.
TABLE 4 % Weight (Wt.) Loss Physical Property % Wt. % Wt. % Wt. % Wt. loss loss loss loss (5 min, (1 hour (24 hours (1 week Sample soaking) soaking) soaking) soaking) PEO1/PEG2/Biomer 209H6 (40/30/30 blend) −4 −22 −69 −87 PEO1/PEG2/Bionolle 30015 (40/30/30 blend) −8 −16 −63 −67 PEO1/PEG2/Bionolle 30015 (66/17/17 blend) −4 −66 −76 −80 PEO1/PEG2/Eastar 147764 (40/30/30 blend) −3 −15 −69 −73 PEO1/PEG2/BAK 4043 (40/30/30 blend) −6 −19 −73 −77 PEO1/PEG2/BAK 4043 (40/40/20 blend) −12 −61 −100 −100 PEO1/PEG2/BAK3/P-6457 (36/27/27/10 blend) 6 −22 −61 −67 PEO1/PEG2/BAK3/P-41418 (36/27/27/10 blend) 1 −18 −60 −65 PEO1/PEG2/PLA 44D9 (40/30/30 blend) 3 −7 −51 −56 PEO1/PEG2/PLA 62-50D9 (40/30/30 blend) 1 −11 −52 −56 PEO1/PEG2/Eastar4/P-6457/CaCO3 10 (11/9/20/10/50 blend) −2 −8 −11 −21 PEO1/PEG2/Eastar4/P-6457/CaCO3 10 (24/18/18/10/30 blend) −1 −6 −37 −39 PEO1/PEG2/Eastar4/P-6457/CaCO3 10 (29/21/10/10/30 blend) −2 −22 — −77 PEG2/PEG11/Eastar4/P-6457/CaCO3 10 (20/5/40/5/30 blend) −3 −6 −18 −20 PEO1/PEG2/Eastar4/P-6457/CaCO3 10 (16/12/12/10/50 blend) −2 −10 −34 −35 PEO1/PEG2/Eastar4/P-6457/Talc12 (17/13/10/10/50 blend) −3 −8 −29 −30 PEO1/PEG2/Eastar4/P-6457/Talc12 (24/18/18/10/30 blend) 0 −5 −40 −41 - The flushable tampon applicators of the present invention are constructed of water-dispersible and biodegradable components to provide for applicators that readily lose their structural integrity and disintegrate in water, especially in water from a waste disposal system. It has been shown that the flushable tampon applicators of the present invention can soften and disintegrate into unrecognizable pieces in about an hour of exposure to wastewater. Prolonged exposure which is indicative of municipal waste disposal means results in further disintegration of these flushable tampon applicators.
- To test the disintegration rate of a flushable tampon applicator comprising thermoplastic materials, the applicator is initially weighed to obtain an initial dry weight, and then the applicator is exposed to wastewater at time intervals of 1 hour, 6 hours, 24 hours, and 48 hours. Suitable wastewater that can be used in the disintegration test include influent wastewater that can be obtained from a municipal waste treatment plant.
- Thermoplastic tampon applicator products and control samples are each submerged in about one liter of wastewater and allowed to shake using any suitable rotary floor shaker capable of shaking the control/wastewater and applicator/wastewater test samples at a shaker rate of 150 revolutions per minute (rpm). Control samples which can be used for this disintegration test include about 3-5 grams of fluted or folded Whatman #41 filter paper (i.e., about 3-4 pieces of the filter paper for each control sample).
- After a shaking period of one hour, visual observations of the test sample are recorded for any noticeable structural differences in the tampon applicator. After shaking periods of 6 hour, 24 hours, and 48 hours the test sample is filtered using sieves arranged from top to bottom in the following order: 8 millimeter (mn) sieve, 4 mm sieve, 2 mm sieve, 1 mm sieve, and a 0.5 mm sieve. The remaining solids of the test sample captured on the 8 mm sieve is then gently rinsed for 5 minutes using a hand-held showerhead spray nozzle while minimizing the passage of retained remaining solids to the next smaller sieve. The 8 mm sieve is removed, and the remaining solids on the next smaller sieve is rinsed for 5 minutes. The 5 minute rinsing cycle is performed on each sieve containing retained remaining solids.
- After rinsing, the retained test sample from each sieve is transferred using forceps or commercial paint brushes to individual aluminum pans, and the aluminum pans are placed in a Blue M oven at 40° C. to dry overnight. The dried test sample is weighed, and the retained fraction of each control and applicator product is determined using the following calculation:
- It has been found that the tampon applicators of the present invention readily soften and disintegrate after being submerged in wastewater for one hour with substantially increased disintegration after only 6 hours of exposure. These tampon applicators are suitable for flushing in a sewage system such as a toilet due to their ability to readily break apart and dissolve in wastewater produced from toilet septic tanks. Data showing the disintegration rate of flushable tampon applicators of the present invention is exemplified hereinbelow.
PEO1/PEG2/Eastar4 (40/30/30 blend) 8 mm 4 mm 2 mm 1 mm 0.5 mm Disintegration Rate sieve sieve sieve sieve sieve % Initial Fraction 100 — — — — 6 hour % Retained Fraction 40.79 0.00 0.00 0.03 0.08 24 hour % Retained Fraction 30.71 0.19 0.00 0.00 0.10 48 hour % Retained Fraction 32.31 0.00 0.03 0.03 0.07 -
PEO1/PEG2/BAK 4043 (40/30/30 blend) 8 mm 4 mm 2 mm 1 mm 0.5 mm Disintegration Rate sieve sieve sieve sieve sieve % Initial Fraction 100 — — — — 6 hour % Retained Fraction 10.61 3.89 0.25 0.08 2.33 24 hour % Retained Fraction 7.63 1.91 0.36 0.50 3.43 48 hour % Retained Fraction 4.48 2.09 0.89 0.91 2.62 -
PEO/PEG/Bionelle 30015 (40/30/30 blend) 8 mm 4 mm 2 mm 1 mm 0.5 mm Disintegration Rate sieve sieve sieve sieve sieve % Initial Fraction 100 — — — — 6 hour % Retained Fraction 56.35 0.00 0.00 0.00 0.00 24 hour % Retained Fraction 51.40 0.00 0.00 0.00 0.00 48 hour % Retained Fraction 42.46 0.00 0.00 0.00 0.11 -
PEO1/PEG2/PLA 44D9 (40/30/30 blend) 8 mm 4 mm 2 mm 1 mm 0.5 mm Disintegration Rate sieve sieve sieve sieve sieve % Initial Fraction 100 — — — — 6 hour % Retained Fraction 2.06 2.96 3.82 5.58 0.07 24 hour % Retained Fraction 1.39 3.58 2.25 3.93 5.06 48 hour % Retained Fraction 2.82 6.56 5.44 5.16 5.32 -
PEO1/PEG2/Biomer 209H6 (40/30/30 blend) 8 mm 4 mm 2 mm 1 mm 0.5 mm Disintegration Rate sieve sieve sieve sieve sieve % Initial Fraction 100 — — — — 6 hour % Retained Fraction 0.00 0.08 0.00 0.08 0.52 24 hour % Retained Fraction 0.00 0.10 0.04 0.25 0.66 48 hour % Retained Fraction 0.00 0.00 0.00 0.27 1.36 -
PEO1/PEG2/Eastar4/AB13/wood flour14/TiO2 15/Kemamide E16 (17/17/25/5/30/5/1 blend) 8 mm 4 mm 2 mm 1 mm 0.5 mm Disintegration Rate sieve sieve sieve sieve sieve % Initial Fraction 100 — — — — 6 hour % Retained Fraction 23.54 0.00 0.83 1.26 1.87 24 hour % Retained Fraction 6.31 2.39 3.34 3.11 3.31 48 hour % Retained Fraction 0.00 3.71 2.75 2.73 3.63 -
PEO1/PEG2/Eastar4/Starch17/P-6457/Kemamide E16 (18/13/13/50/5/1 blend) 8 mm 4 mm 2 mm 1 mm 0.5 mm Disintegration Rate sieve sieve sieve sieve sieve % Initial Fraction 100 — — — — 6 hour % Retained Fraction 4.36 1.56 7.65 4.77 4.53 24 hour % Retained Fraction 0.00 0.64 3.37 6.72 10.88 48 hour % Retained Fraction 0.00 0.00 2.18 5.36 9.14 -
PEO1/PEG2/Eastar4/P-6457/Talc12 (24/18/18/10/30 blend) 8 mm 4 mm 2 mm 1 mm 0.5 mm Disintegration Rate sieve sieve sieve sieve sieve % Initial Fraction 100 — — — — 6 hour % Retained Fraction 66.68 0.00 0.00 0.00 0.00 24 hour % Retained Fraction 57.24 0.00 1.17 0.47 0.30 48 hour % Retained Fraction 55.44 0.19 1.86 1.03 0.97 -
PEO1/PEG2/Eastar4/P-6457/CaCO3 10 (11/9/20/10/50 blend) 8 mm 4 mm 2 mm 1 mm 0.5 mm Disintegration Rate sieve sieve sieve sieve sieve % Initial Fraction 100 — — — — 6 hour % Retained Fraction 5.25 5.41 21.32 12.08 3.94 24 hour % Retained Fraction 2.73 2.51 7.09 16.71 10.51 48 hour % Retained Fraction 0.00 0.89 4.67 8.83 11.53 -
PEO1/PEG2/Eastar4/P-6457/CaCO3 10 (24/18/18/10/30 blend) 8 mm 4 mm 2 mm 1 mm 0.5 mm Disintegration Rate sieve sieve sieve sieve sieve % Initial Fraction 100 — — — — 6 hour % Retained Fraction 9.72 12.69 20.19 4.17 2.35 24 hour % Retained Fraction 2.17 3.90 16.02 12.87 3.53 48 hour % Retained Fraction 0.00 13.41 11.36 9.52 3.19 - The flushable tampon applicators of the present invention can comprise optional ingredients in combination with the water-dispersible and biodegradable components wherein the optional ingredients provide benefits to the final product or to the thermoplastic materials used in making the final product. Such benefits include, but are not limited to, stability including oxidative stability, brightness, flexibility, resiliency, toughness, workability, odor control, improved strength, improved modulus, improved melt flow characteristics, and/or distensibility of the thermoplastic compositions. The flushable tampon applicators typically comprise from about 0.05% to about 25% of optional ingredients by weight of the applicator. The optional ingredients include plasticizing agents, antioxidants, slip agents, optical brighteners, crystallization accelerators or retarders, flow promoters, processing aids, pigments or colorants, mold release agents, nucleating agents, coating agents, gelling agents, antistatic agents, dispersing agents, compatibilizers, lubricants, surfactants, heat stabilizers including magnesium stearate, odor masking agents, opacifying agents such as aluminum oxide, dyes, viscosity modifiers, ester waxes, elastomers, and mixtures thereof. The optional plasticizing agents, coating agents, viscosity modifiers, and lubricants, are described in detail hereinbelow.
- A specific example of a slip agent is Kemamide E Ultra which is commercially available from the Crompton Corporation (Taft, Los Angeles).
- pecific examples of optional processing aids include, but are not limited to, the acrylic polymers commercially available from the ATOFINA Chemicals Incorporation (Philadelphia, Pa.) under the Metablen P-550, Metablen P-710 SD, and Metablen C-303 tradenames.
- Specific examples of optional nucleating agents include, but are not limited to, Licomont CaV 102 and Licomont NaV 101, both of which are commercially available from the Clariant Corporation (Coventry, R.I.); and Millad 3988 which is commercially available from Milliken Chemical (Inman, S.C.).
- A specific example of an optional heat stabilizer is Thermolite 890S which is commercially available from the ATOFINA Chemicals Incorporation.
- Specific examples of optional elastomers include, but are not limited to, Kraton L207, Kraton L1203, Kraton L2203, and Kraton G 1652, all of which are commercially available from Kraton Polymers (Houston, Tex.).
- Optional Plasticizing Agent
- If a plasticizing agent is included with thermoplastic polymers for making the flushable tampon applicators of the present invention, the plasticizer is included at concentrations ranging from about 1% to 20 about 25% by weight of the applicator. In this context, the term “plasticizing agent” refers to any organic compound that, when added to a thermoplastic polymer, can provide modification to the polymer's morphology to result in increased ease of processing of the polymer and increased toughness and flexibility of the polymer after processing. Examples of optional plasticizing agents include glycerin, glycerin derivatives such as triacetin and glycerol monostearate, sorbitol, eritol, glucidol, mannitol, sucrose, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol caprate-caprylate, butylene glycol, pentamethylene glycol, hexamethylene glycol, diisobutyl adipate, oleic amide, erucic amide, pannitic amide, dimethyl acetamide, dimethyl sulfoxide, methyl pyrrolidone, tetramethylene sulfone, oxa monoacids, oxa diacids, polyoxa diacids, diglycolic acids, triethyl citrate, acetyl triethyl citrate, tri-n-butyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n-hexyl citrate, alkyl lactates, phthalate polyesters excluding the aromatic terephthalate polyesters suitable for use as a biodegradable polymer herein, adipate polyesters, glutate polyesters, diisononyl phthalate, diisodecyl phthalate, dihexyl phthalate, alkyl alylether diester adipate, dibutoxyethoxyethyl adipate, and mixtures thereof.
- Examples of commercially available plasticizers include the adipate polyesters sold under the Plasthall P-645, Plasthall P-643, Plasthall HA7A, Paraplex G-54, and Paraplex G-50 tradenames; triethylene glycol caprate-caprylate sold under the Plasthall 4141 tradename; the polyesters sold under the Paraplex A-8200 and Paraplex A-8040 tradenames; the polyester glutarate sold under the Plasthall P-550 tradename; diisononyl phthalate sold under the Plasthall DINP tradename; dibutoxyethoxyethyl adipate sold under the Plasthall 226 tradename; and the Supermix Plasthall 226 and Supermix Paraplex G-50; all of which are available from the C. P. Hall Corporation (Chicago, Ill.).
- Optional Coating Agent
- The flushable tampon applicators of the present invention preferably comprise from about 0.05% to about 10% of a coating agent by weight of the applicator. The coating agent provides stability to the final applicator product by serving as a moisture barrier, and is considered to be effective in reducing or eliminating the sticky or slippery film feel that can occur when the applicator comes in contact with air-laden or human moisture. The coating agent can be applied using any suitable coating technique known in the art for effectively applying a coating material on the outer or exterior surface of a thermoplastic material used to form a flushable tampon applicator. Some known effective coating methods can be typically described as tumbling coating, spray coating, brushing, dip coating, slot coating, gravure coating, extrusion coating, co-extrusion coating, and the like.
- While the coating material can be applied directly to the outer or exterior surface of a thermoplastic material described herein, the coating material can also be applied as a coating solution. The coating solution comprises the coating solubilized in a volatile solvent, wherein suitable volatile solvents include saturated and unsaturated hydrocarbons such as heptane, cyclohexane, and toluene; halogenated hydrocarbons such as chlorobenzene, chloroform, and methylene chloride; hydrocarbon alcohol ethers; and mixtures thereof.
- Optional preferred coating agents suitable for use herein include waxes, hydrogenated vegetable oils, food grade shellac, epoxy resins, vinylidene chloride copolymer latexes, polysiloxanes, sucrose fatty acid esters, and mixtures thereof. A specific example of a vinylidene chloride copolymer latex is Daran SL 143 which is commercially available from the Hampshire Chemical Corporation.
- Specific nonlimiting examples of waxes suitable for use as an optional preferred coating agent include animal waxes (e.g., beeswax, spermaceti, lanolin, and shellac wax); vegetable waxes (e.g., carnauba, candelilla, bayberry, and sugar cane); mineral waxes (e.g., fossil or earth waxes such as ozokerite, ceresin, and montan, or petroleum waxes such as paraffin, microcrystalline, petrolatum, slack and scale wax); chlorinated naphthalenes (e.g., “Halowax”); and mixtures thereof. A specific example of a paraffin wax is Paraflint H-1 which is commercially available from the Moore & Munger Incorporation located in Shelton, Conn.
- Optional Viscosity Modifiers
- The flushable tampon applicators of the present invention can optionally comprise viscosity modifiers to increase the viscosity of the water-dispersible and biodegradable thermoplastic polymers described herein so that they can be molded using a preferred injection molding or any other molding technique described herein. Such viscosity modifiers are typically included at concentrations ranging from about 0.1% to about 5%, preferably from about 0.1% to about 2% by weight of the applicator. Nonlimitng examples of suitable viscosity modifiers include trifunctional alcohols such as trimethylolpropane, tetrafunctional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid, and the like.
- Optional Lubricants
- The flushable tampon applicators of the present invention can optionally comprise lubricants to increase the overall rate of processing and to improve surface properties. Therefore, lubricants are also referred to as mold release agents and slip/anti-blocking agents, and provide for improved product properties such as brightness, heat stability during processing, light stability, better dispersion of additives, and improved optical and mechanical properties). It is believed that the optional lubricants provide these processing and product surface properties due to the migration of the lubricants to the surface of the processed products where they resist adhesion to processing equipment.
- Examples of optional lubricants suitable for use herein include, but are not limited to, metal soaps (e.g., stearate soaps), hydrocarbon waxes including polyethylene wax, fatty acids, long-chain alcohols, fatty acid esters (e.g., ester waxes), fatty acid amides, silicones, fluorochemicals, acrylics, and mixtures thereof.
- Specific examples of metal soaps suitable for use as an optional lubricant herein include, but are not limited to, calcium stearate commercially available from the Ferro Corporation (Cleveland, Ohio,) under the Synpro Calcium Stearate 392A tradename; magnesium stearate commercially available from the Aldrich Chemical Company (Milwaukee, Wis.); and the stearates commercially available from the Norac Incorporation (Helena, Ark.) such as calcium stearate commercially available under the COAD10 and COAD10LD tradenames, zinc stearate commercially available under the COAD21 and COAD23 tradenames, and magnesium stearate commercially available under the MATBHE magnesium stearate tradename.
- Specific examples of fatty acid esters suitable for use as an optional lubricant herein include, but are not limited to, the fatty acid esters commercially available from Cognis-Plastics Technology (Amber, Pa.) under the Loxiol G33, Loxiol G60, Loxiol G71S, and Loxiol HOB7111 tradenames; the ester waxes commercially available from the Clariant Corporation under the Licowax E, Licolub WE 4, and Licowax OP tradenames; and the ester waxes commercially available from the Fanning Corporation under the Natralube 120 and Natralube 125 tradenames.
- Specific examples of silicones suitable for use as an optional lubricant herein include, but are not limited to, the silicones commercially available from the Dow Corning Corporation (Midland, Mich.) under the Dow Corning MB50-002, Dow Corning MB50-010, Dow Corning 4-7051, and Dow Corning 9506 tradenames.
- Specific examples of fluorochemicals suitable for use as an optional lubricant herein include, but are not limited to, the fluoropolymers commercially available from the AG Fluoropolymers Incorporation (Downingtown, Pa.) under the Whitcon Tl-5 and Whitcon TL-155 tradenames; and the fluoropolymers commercially available from Dyneon LLC (Oakdale, Minn.) under the Dynamar FX 9613, Dynamar FX 5920A, Dynamar FX 5911X, Dynamar FX 5912X, Dynamar PPA 790, and Dynamar PPA 791 tradenames.
- A specific example of an acrylic suitable for use as an optional lubricant herein is the white powder acrylic commercially available from the ATOFINA Chemicals Incorporation under the Metablen L-1000SD tradename.
- Method of Manufacture
- The flushable tampon applicators of the present invention may be prepared by any known or otherwise effective technique for providing a disposable tampon applicator provided that the article is made to contain water-dispersible and biodegradable materials described herein, preferably a blend of water-dispersible and biodegradable materials. Typically, the flushable tampon applicators are molded in a desired shape or configuration using a variety of molding techniques to provide a thermoplastic applicator comprising an outer tubular member and a plunger. Such molding techniques include injection molding, extrusion molding, blow molding, compression molding, and cast film. These molding techniques can be used alone or in combination to make the flushable tampon applicators of the present invention. For example, the outer tubular member and plunger components of the flushable tampon applicators herein can be made using an injection molding apparatus, or the outer tubular member and plunger can be made using an extrusion molding apparatus, or the outer tubular member can be made using injection molding and the plunger made using extrusion molding, or the outer tubular member made by extrusion molding and the plunger made by injection molding, or the outer tubular member and/or plunger are made using a combination of extrusion and injection molding.
- Generally, the process of making flushable tampon applicators of the present invention involves charging one or more high molecular weight polyethylene oxides, one or more low molecular weight polyethylene glycols, one or more aliphatic/aromatic copolyesters, and any other ingredients such as plasticizers and/or filler into an injection molding apparatus, and molding the melt blended mixture comprising uniformly dispersed filler into the desired flushable tampon applicator. Alternatively, a blend of the thermoplastic materials, optional plasticizer, and uniformly dispersed filler can be compounded into pellets by means of an extruder, and the pellets are then constructed into flushable tampon applicators using an injection molding apparatus.
- One example of a procedure of making flushable tampon applicators of the present invention involves mixing the thermoplastic polymers, optional plasticizer, and filler in a variable speed, high intensity blender, extruding the mixture at a temperature above the melting temperature of the thermoplastic polymers to form a rod, chopping the rod into pellets, and injection molding the pellets into the desired flushable tampon applicator form.
- The extruders which are commonly used to melt process thermoplastic compositions into compounded pellets are generally single-screw extruders, twin-screw extruders, and kneader extruders. Examples of commercially available extruders suitable for use herein include the Black-Clawson single-screw extruders, the Werner and Pfleiderer co-rotating twin-screw extruders, the HAAKE Polylab System counter-rotating twin screw extruders, and the Buss kneader extruders. A typical extrusion process can be described as compounding blended components using a twin-screw extruder having a screw diameter of 30 mm, a feed section, and a die tip. The blend is compounded at about 100 revolutions per minute (rpm) at a temperature ranging from about 60° C. at the feed section to about 130° C. at the die tip. The final product is a compounded rod that is chopped into pellets suitable for molding into desired flushable tampon applicators using an injection molding apparatus. General discussions of extrusion molding are disclosed in the Encyclopedia of Polymer Science and Engineering; Volume 6, pp. 571-631, 1986, and Volume 11, pp. 262-285, 1988; John Wiley and Sons, New York; which disclosures are incorporated by reference herein.
- Injection molding is the most commonly used process for constructing and configuring tampon applicators into a desired shape of form. This process is typically carried out under controlled temperature, time, speed and pressure, and involves melt processing pellets or blends of thermoplastic compositions wherein the melted thermoplastic composition is injected into a mold, cooled, and molded into a desired plastic object.
- An example of a suitable injection molding machine is the Engel Tiebarless ES 60 TL apparatus having a mold, a nozzle, and a barrel that is divided into zones wherein each zone is equipped with thermocouples and temperature-control units. The zones of the injection molding machine can be described as front, center, and rear zones whereby the pellets are introduced into the front zone under controlled temperature. The temperature of the nozzle, mold, and barrel components of the injection molding machine can vary according to the melt processing temperature of the pellets and the molds used, but will typically be in the following ranges:
Component Temp (° C.) Nozzle 135-230 Front Zone 70-200 Center Zone 100-225 Rear Zone 120-225 Mold 20-50 - Other typical processing conditions include an injection pressure of from about 300 pounds per square inch (psi) to about 3000 psi (about 2 MPa to about 21MPa), a holding pressure of about 400 psi to about 2000 psi (about 3 Mpa to about 14MPa), a hold time of about 2 seconds to about 25 seconds, and an injection speed of from about 0.98 inches per second (in/sec) to about 8 in/sec.
- Other suitable injection molding apparatus are the injection molding machines made by Battenfeld, Brabender, Killion, Demag and Arburg, Windsor, Hesas, Boy, Van Dorn, Engel, and the Fischer companies. Specific examples of other suitable injection molding machines include the Van Dom Model 150-RS-8F, the Battenfeld Model 1600, and the Engel Model ES80. A general discussion of injection molding is disclosed in the Encyclopedia of Polymer Science and Engineering, Volume 8, pp. 102-138, John Wiley and Sons, New York, 1987, which disclosure is incorporated by reference herein.
- The flushable tampon applicators of the present invention are generally made using the extrusion and injection molding techniques described hereinabove. These techniques involve melt processing the thermoplastic polymers, filler, and any optional ingredients wherein the thermoplastic polymers, filler, and optional ingredients have melting temperatures typically ranging from about 25° C. to about 350° C., more typically from about 40° C. to about 300° C., even more typically from about 50° C. to about 200° C. Therefore, the thermoplastic polymers suitable for use in making the flushable tampon applicators of the present invention desirably have individual melt flow rates of from about 0.1 gram/10 minutes to about 600 grams/10 minutes, preferably from about 1 gram/10 minutes to about 400 grams/10 minutes, more preferably from about 5 grams/10 minutes to about 200 grams/10 minutes, even more preferably from about 10 grams/10 minutes to about 150 grams/10 minutes, as determined according to the ASTM Test Method D1238-E.
- The final products of flushable tampon applicators of the present invention are packaged in moisture-proof wrappers for storage prior to use. The moisture-proof wrappers prevents moisture from contacting the applicator or tampon pledget, and therefore aids in the assurance of shelf-stabilily for the tampon and provides an asethetically pleasing and acceptable tampon product prior to actual use. The flushable tampon applicators of the present invention can be packaged in any suitable wrapper provided that the wrapper is soil proof and disposable with dry waste. Preferred wrappers are those made from biodegradable materials which create minimal or no environmental concerns for their disposal. It is contemplated, however, that the tampon applicators of the present invention can be packaged in flushable wrappers made from paper, nonwoven, cellulose, thermoplastic, or any other suitable flushable material, or combinations of these materials.
- The following examples further describe and demonstrate embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention. All exemplified concentrations are weight-weight percents, unless otherwise specified.
- Flushable tampon applicators of the present invention are made by a melt extrusion process of blending water-dispersible polymers, biodegradable polymers, fillers, and any optional ingredient using a Werner Pfleiderer ZSK-30 co-rotating twin screw extruder having a screw diameter of 30 mm, six heating zones, a four hole die plate, two feeding hoppers, and a liquid pump which is connected to the extruder through a hole located between heating zones3 and 4. For example, powder ingredients are dry blended together wherein the powder ingredients include water-dispersible polymers such as high molecular weight polyethylene oxide commercially available as POLYOX® WSR-80 and low molecular weight polyethylene glycol commercially available as PEG-8000; fillers such as calcium carbonate (commercially available as Vicron 15-15), talc (commercially available as ABT 2500), starch granule materials (commercially available as Staley Pure Food Powdered Starch and National Starch Melojel), and wood flours (commercially available as Pine Wood Flour Grade 10020); and optional ingredients such as ester wax (commercially available as Loxiol G33), magnesium stearate, and Kemamide E. Likewise, ingredients in pellet form are dry blended together such as a dry blend pellet mixture of biodegradable polymers. Any ingredients added in liquid form are mixed with other liquids prior to extrusion, for example, any liquid plasticizes and any other liquid optional ingredient are mixed together. Next, the powder dry blend mixture is fed into the extruder through one feeding hopper while the pellet formed mixture is fed into the extruder through the other feeding hopper. The optional liquid mixture is pumped into the extruder through the liquid pump. During the extrusion process, the water-dispersible polymers, biodegradable polymers, optional plasticizers and any other optional ingredient form a melt-blended mixture. The fillers including inorganic and organic fillers are not melted and remain in their particle forms during the extrusion process and, therefore are uniformly dispersed throughout the melt blend mixture. Then, the melt blend mixture containing uniformly dispersed filler particles is extruded to the end of the extruder to the die to form four rods. The rods are carried on a conveyor, air cooled, and pelletized using a pelletizer for injection molding into a desired flushable tampon applicator. Compositions for forming flushable tampon applicators of the present invention and extrusion settings are further described hereinbelow in Table 5 and Table 6.
TABLE 5 Extrusion Molded Thermoplastic Compositions Zone 1 Zone 2 Zone 3 Zone 4 Zone 5 Zone 6 Die Screw Speed Composition (° C.) (° C.) (° C.) (° C.) (° C.) (° C.) (° C.) (rpm) PEO1/PEG2/BAK 4043 Off 80 101 128 141 114 120 100 (40/30/30 blend) PEO1/PEG2/BAK 4043 60 70 110 118 122 103 105 250 (40/40/20 blend) PEO1/PEG2/Eastar 147764 Off 80 99 130 140 115 120 100 (40/30/30 blend) PEO1/PEG2/Bionolle 30015 60 70 110 113 122 109 103 300 (66/17/17 blend) PEO1/PEG2/Bionolle 30015 Off 50 125 130 145 125 116 100 (40/30/30 blend) PEO1/PEG2/Biomer 209H6 75 85 98 146 161 148 130 300 (40/30/30 blend) PEO1/PEG2/BAK 4043/ Off 80 101 128 141 114 120 100 P-6457 (36/27/27/10 blend) PEO1/PEG2/BAK 4043/ Off 80 101 128 141 114 120 100 P-41418 (36/27/27/10 blend) PEO1/PEG2/Eastar4/ 75 80 96 148 164 113 91 275 P-6457/CaCO3 10 (11/9/20/10/50 blend) PEO1/PEG2/Eastar4/ 75 80 100 125 145 89 90 275 P-6457/CaCO3 10 (24/18/18/10/30 blend) PEO1/PEG2/Eastar4/ 75 80 100 125 145 100 95 275 P-6457/CaCO3 10 (29/21/10/10/30 blend) PEG2/PEG11/Eastar4/ 75 80 99 121 144 106 84 275 P-6457/CaCO3 10 (20/5/40/5/30 blend) PEO1/PEG2/Eastar4/ 75 80 100 125 144 100 93 275 P-6457/CaCO3 10 (16/12/12/10/50 blend) PEO1/PEG2/Eastar4/ 75 80 99 148 162 50 90 300 P-6457/Talc12 (17/13/10/10/50 blend) -
TABLE 6 Extrusion Molded Thermoplastic Compositions Zone 1 Zone 2 Zone 3 Zone 4 Zone 5 Zone 6 Die Screw Speed Composition (° C.) (° C.) (° C.) (° C.) (° C.) (° C.) (° C.) (rpm) PEG2/PEG11/Eastar4/ 75 80 99 121 144 106 84 275 P-6457/CaCO310 (20/5/40/5/30 blend) PEO1/PEG2/Eastar4/ 75 80 100 125 144 100 93 275 P-6457/CaCO310 (16/12/12/10/50 blend) PEO1/PEG2/Eastar4/ 75 80 99 148 162 50 90 300 P-6457/Talc12 (17/13/10/10/50 blend) PEO1/PEG2/Eastar4/ 75 80 100 125 145 90 91 275 P-6457/Talc12 (24/18/18/10/30 blend) PEO1/PEG2/Eastar4/AB13/ 70 70 90 115 135 135 95 60 wood flour14/TiO2 15/ Kemamide E16 (17/17/25/5/30/5/1 blend) PEO1/PEG2/Eastar4/ 70 75 90 115 135 110 100 150 Starch17/P-6457/Kemamide E16 (18/13/13/50/5/1 blend) PEO1/PEG2/Eastar4/ 50 70 102 122 134 110 92 260 Starch18/P-6457/Kemamide E16/MgSt19 (15/10/37/30/5/1/2 blend) PEO1/Eastar4CaCO3 10/ 50 70 115 137 153 91 114 250 P-6457 (18/15/65/4 blend) PEO1/PEG2/Eastar4/ 50 70 121 124 140 105 95 250 CaCO3 10/P-6457/Kemamide E16 (15/10/29/40/5/1 blend) PEO1/PEG2/Eastar4/ 50 70 110 133 137 115 105 250 CaCO3 10/P-6457/MgSt19/ Loxiol G3320 (15/10/26/40/5/2/2 blend) PEO1/PEG2/Eastar4/ 50 70 120 125 140 105 95 250 CaCO3 10/P-6457/Kemamide E16 (15/10/39/30/5/1 blend) PEO1/Eastar4/CaCO3 10/ 50 70 120 133 138 107 99 250 P-6457/Kemamide E16 (25/39/30/5/1 blend) PEO1/PEG2/Eastar4/ 50 70 115 128 141 112 95 250 CaCO3 10/P-6457/Kemamide E16/Paraffin wax21 (15/10/34/30/5/1/5 blend) PEG2/Eastar4/CaCO3 10/Mg 70 85 110 133 140 123 106 250 St19 (17.5/64/17.5/1 blend) PEG2/Eastar4/CaCO3 10/ 70 85 110 135 157 118 114 252 MgSt19/P-64322/ DC4-705125 (15/62/15/1/5/2 blend) PEO1/PEG2/Eastar4/ 50 70 110 134 139 121 105 250 CaCO3 10/P-6457/MgSt19/ DC950623 (15/10/26/40/5/2/2 blend) PEO1/PEG2/Eastar4/ 50 70 110 133 138 117 102 250 CaCO3 10/P-6457/MgSt19/ Loxiol G3320/Kraton G 165224 (14.5/9.5/25.5/39.5/5/2/2/2 blend) - Flushable tampon applicators of the present invention are made by dry blending a mixture of water-dispersible and biodegradable polymers, and then feeding this dry blended mixture of polymers into a HAAKE Polylab System counter-rotating twin screw extruder. The extruder is equipped with a single hole die plate for compounding the dry blended mixture into a single strand of molten plastic that is air-cooled and then chopped into small discs having a diameter of 20 mm and a thickness of 0.5 mm. The small discs are grounded using an IMS LP-288SC Grinder for injection molding into a desired flushable tampon applicator. The dry blended thermoplastic compositions of water-dispersible polymers and biodegradable polymers, in addition to the extrusion apparatus settings, are described hereinbelow in Table 7.
TABLE 7 Extrusion Molded Thermoplastic Compositions PEO1/PEG2/PLA 44D9 PEO1/PEG2/PLA 62-50D9 Extruder Settings (40/30/30 blend) (40/30/30 blend) Zone 1 (° C.) 80 80 Zone 2 (° C.) 200 200 Zone 3 (° C.) 210 210 Die (° C.) 130 120 Screw Speed 30 25 (rpm) - Injection Molding
- An Engel Tiebarless ES 60 TL injection molding machine is suitable for manufacturing the final product of thermoplastic pellets of Examples 1 and 2 into flushable tampon applicators of the present invention. The injection molding process involves using a 25 mm screw and controlled processing conditions of controlled temperature, time, speed, and pressure, wherein the pellets are melt processed, injected into a mold, cooled, and then molded into the desired flushable tampon applicator.
- The Engel injection molding machine is also suitable for manufacturing composite paper flushable tampon applicators. Typically, spiral-wound paper is formed into paper tubes having a length of about 35 mm, inside diameter of about 10.8 mm, outside diameter of about 11.2 mm, and a weight of about 0.25 grams. The paper tube is positioned over a mold core pin, the mold is clamped shut, and a thermoplastic composition is injected into the mold. The paper tube is positioned over the mold core pin such that the thermoplastic composition is melt processed to flow over the entire length of the outer surface of the paper tube. Therefore, the resultant composite paper tampon applicator comprises a paper inner surface, thermoplastic resin outer surface, and thermoplastic petals and grip components.
- Examples of thermoplastic compositions and injection molding settings are described hereinbelow in Table 8 through Table 15.
TABLE 8 Injection Molded Thermoplastic Compositions PEO1/PEG2/ PEO1/PEG2/ PEO1/PEG2/ PEO/PEG/ Injection Molding BAK 4043 BAK 4043 Eastar 147764 Bionolle 30015 Settings (40/30/30 blend) (40/40/20 blend) (40/30/30 blend) (66/17/17 blend) Nozzle (° C.) 177 163 149 135 Zone 1 (° C.) 149 107 127 74 Zone 2 (° C.) 160 135 138 107 Zone 3 (° C.) 168 149 143 121 Mold (° C.) 21 21 21 21 Screw Speed (rpm) 120 192 120 192 Injection Speed (in/sec) 4 4 4 4 Injection Pressure (psi) 843 418 1562 1302 Hold Time (sec) 4 12 8 5 Hold Pressure (psi) 500 800 650 1250 Cool Time (sec) 30 30 25 30 -
TABLE 9 Injection Molded Thermoplastic Compositions PEO1/PEG2/ PEO1/PEG2/ PEO1/PEG2/ PEO1/PEG2/ BAK 4043/P-6457 BAK 4043/P-41418 Injection Molding Bionolle 30015 Biomer 209H6 (36/27/27/10 (36/27/27/10 Settings (40/30/30 blend) (40/30/30 blend) blend) blend) Nozzle (° C.) 221 149 149 149 Zone 1 (° C.) 193 65 65 65 Zone 2 (° C.) 216 79 79 79 Zone 3 (° C.) 216 143 121 121 Mold (° C.) 21 21 21 21 Screw Speed (rpm) 120 192 192 192 Injection Speed (in/sec) 4 4 4 4 Injection Pressure (psi) 641 388 405 564 Hold Time (sec) 4 15 8 8 Hold Pressure (psi) 1100 500 500 500 Cool Time (sec) 35 60 40 40 -
TABLE 10 Injection Molded Thermoplastic Compositions PEO1/PEG2/ PEO1/PEG2/ PLA 44D9 PLA 62-50D9 Composite Paper Injection Molding (40/30/30 (40/30/30 with 40/30/30 blend of Settings blend) blend) PEO1/PEG2/BAK 4043 Nozzle (° C.) 199 199 163 Zone 1 (° C.) 149 149 121 Zone 2 (° C.) 149 149 140 Zone 3 (° C.) 177 177 152 Mold (° C.) 32 32 24 Screw Speed 120 120 160 (rpm) Injection Speed 4 4 3 (in/sec) Injection Pressure 348 315 400 (psi) Hold Time (sec) 5 5 5 Hold Pressure 800 800 300 (psi) Cool Time (sec) 30 30 4 -
TABLE 11 Injection Molded Thermoplastic Compositions PEO1/PEG2/ PEO1/PEG2/ PEO1/PEG2/ PEG2/PEG11/ Eastar4/P-6457/ Eastar4/P-6457/ Eastar4/P-6457/ Eastar4/P-6457/ CaCO3 10 CaCO3 10 CaCO3 10 CaCO3 10 Injection Molding (11/9/20/10/50 (24/18/18/10/30 (29/21/10/10/30 (20/5/40/5/30 Settings blend) blend) blend) blend) Nozzle (° C.) 163 163 163 163 Zone 1 (° C.) 121 121 121 121 Zone 2 (° C.) 135 135 135 135 Zone 3 (° C.) 149 149 149 149 Mold (° C.) 24 24 24 24 Screw Speed (rpm) 192 192 192 192 Injection Speed (in/sec) 4 4 4 4 Injection Pressure (psi) 700 510 576 410 Hold Time (sec) 7.5 5 5 7.5 Hold Pressure (psi) 500 500 500 500 Cool Time (sec) 45 45 45 45 -
TABLE 12 Injection Molded Thermoplastic Compositions PEG2/PEG11/ PEO1/PEG2/ PEO1/PEG2/ PEO1/PEG2/ Eastar4/AB13/wood Eastar4/P-6457 Eastar4/P-6457/ Eastar4/P-6457/ flour14/TiO2 15/ CaCO3 10 Talc12 Talc12 Kemamide E16 Injection Molding (16/12/12/10/50 17/13/10/10/50 24/18/18/10/30 17/17/25/5/30/5/1 Settings blend) blend) blend) blend) Nozzle (° C.) 163 163 163 174 Zone 1 (° C.) 121 121 121 149 Zone 2 (° C.) 135 135 135 168 Zone 3 (° C.) 149 149 149 171 Mold (° C.) 21 24 24 38 Screw Speed (rpm) 192 192 192 192 Injection Speed (in/sec) 4 4 4 2 Injection Pressure (psi) 744 410 451 1750 Hold Time (sec) 10 7.5 5 20 Hold Pressure (psi) 750 500 500 750 Cool Time (sec) 30 45 45 70 -
TABLE 13 Injection Molded Thermoplastic Compositions PEO1/PEG2/ PEO1/PEG2/ PEG2/PEG11/ Eastar4/Starch17/ PEO1/Eastar4/ Eastar4/CaCO3 10/ Eastar4/CaCO3 10/ P-6457/ CaCO3 10/ P-4657/ P-6457/ Kemamide E16 P-6457 Kemamide E16 Kemamide E16 Injection Molding (18/13/13/50/5/1 (18/15/65/4 (15/10/29/40/5/1 (15/10/39/30/5/1 Settings blend) blend) blend blend) Nozzle (° C.) 149 171 135 182 Zone 1 (° C.) 93 104 93 104 Zone 2 (° C.) 121 160 121 171 Zone 3 (° C.) 141 166 127 177 Mold (° C.) 22 19 21 24 Screw Speed (rpm) 192 240 240 360 Injection Speed (in/sec) 2 3 3 3 Injection Pressure (psi) 1880 2820 625 1530 Hold Time (sec) 20 15 5 15 Hold Pressure (psi) 750 2000 500 1000 Cool Time (sec) 60 40 30 30 -
TABLE 14 Injection Molded Thermoplastic Compositions PEO1/PEG2/ PEO1/Eastar4 Eastar4/CaCO3 10/ CaCO3 10/ P-6457/ PEG2/Eastar4/ P-6457/ Kemamide E16/ CaCO3 10/ Injection Kemamide E16 Paraffin wax21 MgSt19 Molding (25/39/30/5/1 (15/10/34/30/5/1/5 (17.5/64/17.5/1 Settings blend) blend) blend) Nozzle (° C.) 135 135 163 Zone 1 (° C.) 93 93 82 Zone 2 (° C.) 121 121 121 Zone 3 (° C.) 127 127 143 Mold (° C.) 24 18 18 Screw Speed 240 360 360 (rpm) Injection Speed 3 4 5 (in/sec) Injection Pressure 898 566 640 (psi) Hold Time (sec) 15 10 10 Hold Pressure 1500 500 1000 (psi) Cool Time (sec) 20 20 35 -
TABLE 15 Injection Molded Thermoplastic Compositions PEG2/Eastar4/ PEO1/PEG2/Eastar4/CaCO3 10/ CaCO3 10/MgSt19/ P-6457/MgSt19/Loxiol G3320/ Injection P-64322/DC4-705125 Kraton G 165224 Molding (15/62/15/1/5/2 (14.5/9.5/25.5/39.5/5/2/2/2 Settings blend) blend) Nozzle (° C.) 163 163 Zone 1 (° C.) 82 99 Zone 2 (° C.) 121 143 Zone 3 (° C.) 143 157 Mold (° C.) 18 18 Screw Speed 360 360 (rpm) Injection Speed 5 5 (in/sec) Injection Pressure 567 714 (psi) Hold Time (sec) 10 5 Hold Pressure 1000 500 (psi) Cool Time (sec) 35 45
Claims (20)
1. A flushable tampon applicator comprising:
(a) from 0% to about 90% by weight of a water-dispersible polymer;
(b) from about 10% to about 50% by weight of a biodegradable polymer; and
(c) from 0% to about 50% by weight of a filler.
2. The flushable tampon applicator of claim 1 wherein the water dispersible polymer is selected from the group consisting of high molecular weight polyethylene oxides, low molecular weight polyethylene glycols, polyethylene/polypropylene oxide copolymers, polyethylene/polybutylene oxide copolymers polyethylene/polypropylene glycol copolymers, thermoplastic starch polymers, polyvinyl alcohols, partially hydrolyzed polyvinyl alcohols, modified polyvinyl alcohols, infrared treated polyvinyl alcohols, cross-linked polyvinyl alcohols, alkali metal sulfonate thermoplastic polyesters, hydroxyethyl celluloses, hydroxypropyl celluloses, methylated hydroxypropyl celluloses, polyacrylic acids, polyaspartic acids, polymethacrylic acids, polysaccharides, proteins, polyvinyl pyrrolidone homopolymers, polyvinyl pyrrolidone copolymers, polyvinyl methyl ether homopolymers, polyoxazolines, polyvinyl methyl oxazolidones, polyvinyl methyl oxazolidimones, polyethylenimines, polyacrylamides, polyvinyl methyl ether/maleic anhydride copolymers, water-dispersible polyurethanes, water-dispersible sulfonate polyesters, and mixtures thereof.
3. The flushable tampon applicator of claim 2 wherein the water dispersible polymer is selected from the group consisting of high molecular weight polyethylene oxides having a weight average molecular weight of from about 65,000 daltons to about 8,000,000 daltons, low molecular weight polyethylene glycols having a number average molecular weight of from about 500 daltons to about 20,000 daltons, and mixtures thereof.
4. The flushable tampon applicator of claim 1 wherein the biodegradable polymer is selected from the group consisting of aliphatic polyesteramides, diacid/diol-based aliphatic polyesters, aromatic polyesters, aliphatic/aromatic copolyesters, polycaprolactones, polycaprolactone copolymers, poly(3-hydroxyalkanoates), poly(3-hydroxyalkanoates) copolymers, dialkanoyl polymers, polyvinyl acetates, polyethylene/vinyl alcohol copolymers, lactic acid polymers, lactide polymers, glycolide polymers, and mixtures thereof.
5. The flushable tampon applicator of claim 1 wherein the filler is selected from the group consisting of inorganic fillers, organic fillers, and mixtures thereof.
6. The flushable tampon applicator of claim 5 wherein the inorganic filler is selected from the group consisting of clays, silica, mica, wollastonite, calcium hydroxide, calcium carbonate, sodium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, kaolin, calcium oxide, magnesium oxide, aluminum hydroxide, talc, titanium dioxide, and mixtures thereof.
7. The flushable tampon applicator of claim 5 wherein the organic filler is selected from the group consisting of wood flour, walnut shell flour, alpha cellulose floc, cellulose fibers, chitin, chitosan powders, organosilicone powders, nylon powders, polyester powders, polypropylene powders, starch granules, and mixtures thereof.
8. The flushable tampon applicator of claim 1 wherein the applicator further comprises a lubricant selected from the group consisting of metal soaps, hydrocarbon waxes, fatty acids, long-chain alcohols, fatty acid esters, fatty acid amides, silicones, fluorochemicals, acrylics, and mixtures thereof.
9. The flushable tampon applicator of claim 1 wherein the applicator further comprises a plasticizer selected from the group consisting of glycerin, triacetin, glycerol, monostearate, sorbitol, erythritol, glucidol, mannitol, sucrose, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol caprate-caprylate, butylene glycol, pentamethylene glycol, hexamethylene glycol, diisobutyl adipate, oleic amide, erucic amide, palinitic amide, dimethyl acetamide, dimethyl sulfoxide, methyl pyrrolidone, tetramethylene sulfone, oxa monoacids, oxa diacids, polyoxa diacids, diglycolic acids, triethyl citrate, acetyl triethyl citrate, tri-n-butyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n-hexyl citrate, alkyl lactates, phthalate polyesters, adipate polyesters, glutate polyesters, diisononyl phthalate, diisodecyl phthalate, dihexyl phthalate, alkyl alylether diester adipate, dibutoxyethoxyethyl adipate, and mixtures thereof.
10. A thermoplastic composite comprising:
(a) from 0% to about 90% by weight of a water-dispersible polymer;
(b) from about 10% to about 50% by weight of a biodegradable polymer; and
(c) from 0% to about 50% by weight of a filler.
11. The thermoplastic composite of claim 10 wherein the water dispersible polymer is selected from the group consisting of high molecular weight polyethylene oxides, low molecular weight polyethylene glycols, polyethylene/polypropylene oxide copolymers, polyethylene/polybutylene oxide copolymers polyethylene/polypropylene glycol copolymers, thermoplastic starch polymers, polyvinyl alcohols, partially hydrolyzed polyvinyl alcohols, modified polyvinyl alcohols, infrared treated polyvinyl alcohols, cross-linked polyvinyl alcohols, alkali metal sulfonate thermoplastic polyesters, hydroxyethyl celluloses, hydroxypropyl celluloses, methylated hydroxypropyl celluloses, polyacrylic acids, polyaspartic acids, polymethacrylic acids, polysaccharides, proteins, polyvinyl pyrrolidone homopolymers, polyvinyl pyrrolidone copolymers, polyvinyl methyl ether homopolymers, polyoxazolines, polyvinyl methyl oxazolidones, polyvinyl methyl oxazolidimones, polyethylenimines, polyacrylamides, polyvinyl methyl ether/maleic anhydride copolymers, water-dispersible polyurethanes, water-dispersible sulfonate polyesters, and mixtures thereof.
12. The thermoplastic composite of claim 11 wherein the water dispersible polymer is selected from the group consisting of high molecular weight polyethylene oxides having a weight average molecular weight of from about 65,000 daltons to about 8,000,000 daltons, low molecular weight polyethylene glycols having a number average molecular weight of from about 500 daltons to about 20,000 daltons, and mixtures thereof.
13. The thermoplastic composite of claim 10 wherein the biodegradable polymer is selected from the group consisting of aliphatic polyesteramides, diacid/diol-based aliphatic polyesters, aromatic polyesters, aliphatic/aromatic copolyesters, polycaprolactones, polycaprolactone copolymers, poly(3-hydroxyalkanoates), poly(3-hydroxyalkanoates) copolymers, dialkanoyl polymers, polyvinyl acetates, polyethylene/vinyl alcohol copolymers, lactic acid polymers, lactide polymers, glycolide polymers, and mixtures thereof.
14. The thermoplastic composite of claim 10 wherein the filler is selected from the group consisting of inorganic fillers, organic fillers, and mixtures thereof.
15. The thermoplastic composite of claim 14 wherein the inorganic filler is selected from the group consisting of clays, silica, mica, wollastonite, calcium hydroxide, calcium carbonate, sodium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, kaolin, calcium oxide, magnesium oxide, aluminum hydroxide, talc, titanium dioxide, and mixtures thereof.
16. The thermoplastic composite of claim 14 wherein the organic filler is selected from the group consisting of wood flour, walnut shell flour, alpha cellulose floc, cellulose fibers, chitin, chitosan powders, organosilicone powders, nylon powders, polyester powders, polypropylene powders, starch granules, and mixtures thereof.
17. The thermoplastic composite of claim 10 wherein the composite further comprises a lubricant selected from the group consisting of metal soaps, hydrocarbon waxes, fatty acids, long-chain alcohols, fatty acid esters, fatty acid amides, silicones, fluorochemicals, acrylics, and mixtures thereof.
18. The thermoplastic composite of claim 10 wherein the composite further comprises a plasticizer selected from the group consisting of glycerin, triacetin, glycerol, monostearate, sorbitol, erythritol, glucidol, mannitol, sucrose, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol caprate-caprylate, butylene glycol, pentamethylene glycol, hexamethylene glycol, diisobutyl adipate, oleic amide, erucic amide, palmitic amide, dimethyl acetamide, dimethyl sulfoxide, methyl pyrrolidone, tetramethylene sulfone, oxa monoacids, oxa diacids, polyoxa diacids, diglycolic acids, triethyl citrate, acetyl triethyl citrate, tri-n-butyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n-hexyl citrate, alkyl lactates, phthalate polyesters, adipate polyesters, glutate polyesters, diisononyl phthalate, diisodecyl phthalate, dihexyl phthalate, alkyl alylether diester adipate, dibutoxyethoxyethyl adipate, and mixtures thereof.
19. A method of making a flushable tampon applicator wherein the method comprises the steps of:
(a) preparing a thermoplastic composite comprising:
(i) from 0% to about 90% by weight of a water-dispersible polymer;
(ii) from about 10% to about 50% by weight of a biodegradable polymer; and
(iii) from 0% to about 50% by weight of a filler; and
(b) injection molding the thermoplastic composite into molded thermoplastic components used to construct the flushable tampon applicator.
20. The method of claim 19 wherein the filler is selected from the group consisting of inorganic fillers, organic fillers, and mixtures thereof.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/944,672 US20030040695A1 (en) | 2001-03-16 | 2001-08-31 | Flushable tampon applicators |
AT02726639T ATE451128T1 (en) | 2001-03-16 | 2002-03-15 | FLUSHABLE TAMPON APPLICATOR |
DE60234682T DE60234682D1 (en) | 2001-03-16 | 2002-03-15 | REMOVABLE TAMPON APPLICATOR |
CA002437485A CA2437485A1 (en) | 2001-03-16 | 2002-03-15 | Flushable tampon applicators |
EP02726639A EP1368069B1 (en) | 2001-03-16 | 2002-03-15 | Flushable tampon applicators |
PCT/US2002/008052 WO2002074352A1 (en) | 2001-03-16 | 2002-03-15 | Flushable tampon applicators |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/810,292 US6730057B2 (en) | 2001-03-16 | 2001-03-16 | Flushable tampon applicators |
US09/944,672 US20030040695A1 (en) | 2001-03-16 | 2001-08-31 | Flushable tampon applicators |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/810,292 Continuation-In-Part US6730057B2 (en) | 2001-03-16 | 2001-03-16 | Flushable tampon applicators |
Publications (1)
Publication Number | Publication Date |
---|---|
US20030040695A1 true US20030040695A1 (en) | 2003-02-27 |
Family
ID=25203498
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/810,292 Expired - Lifetime US6730057B2 (en) | 2001-03-16 | 2001-03-16 | Flushable tampon applicators |
US09/944,672 Abandoned US20030040695A1 (en) | 2001-03-16 | 2001-08-31 | Flushable tampon applicators |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/810,292 Expired - Lifetime US6730057B2 (en) | 2001-03-16 | 2001-03-16 | Flushable tampon applicators |
Country Status (3)
Country | Link |
---|---|
US (2) | US6730057B2 (en) |
AT (1) | ATE451128T1 (en) |
DE (1) | DE60234682D1 (en) |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030176845A1 (en) * | 2002-03-18 | 2003-09-18 | The Procter & Gamble Company | Shaped tampon |
US20030181555A1 (en) * | 2002-03-20 | 2003-09-25 | Figuly Garret D. | Processing of polyhydroxyalkanoates using a nucleant and a plasticizer |
USD492033S1 (en) | 2003-04-04 | 2004-06-22 | Playtex Products, Inc. | Tampon applicator assembly |
US20040193285A1 (en) * | 2003-03-28 | 2004-09-30 | Roller Mark B. | Implantable medical devices and methods for making same |
US20040199100A1 (en) * | 2003-04-04 | 2004-10-07 | Playtex Products, Inc. | Tampon applicator assembly having an improved plunger and methods of making |
WO2004101644A1 (en) * | 2003-05-08 | 2004-11-25 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer compositions having short annealing cycle times |
US20040254639A1 (en) * | 2003-03-28 | 2004-12-16 | Zhigang Li | Reinforced implantable medical devices |
US20050070905A1 (en) * | 2003-09-29 | 2005-03-31 | Lisa Donnelly | Method of performing anterior cruciate ligament reconstruction using biodegradable interference screw |
US20050096617A1 (en) * | 2003-06-26 | 2005-05-05 | Playtex Products, Inc. | Coating composition and articles coated therewith |
US20050177091A1 (en) * | 2001-10-17 | 2005-08-11 | Playtex Products, Inc. | Tampon applicator |
US20060118258A1 (en) * | 2004-12-02 | 2006-06-08 | Chmielewski Harry J | Plasticizing formulation for fluff pulp and plasticized fluff pulp products made therefrom |
US20060217073A1 (en) * | 2003-11-17 | 2006-09-28 | Akihiro Saitou | Radio access point testing apparatus and method of testing radio access point |
US20070161942A1 (en) * | 2006-01-06 | 2007-07-12 | Pharmaphil Inc. | Biodegradable tampon applicator and method of making |
US20070184220A1 (en) * | 2006-02-06 | 2007-08-09 | Cleveland Christopher S | Biodegradable paper-based laminate with oxygen and moisture barrier properties and method for making biodegradable paper-based laminate |
US20070232982A1 (en) * | 2001-10-17 | 2007-10-04 | Playtex Products, Inc. | Tampon applicator |
US20100204636A1 (en) * | 2002-09-12 | 2010-08-12 | Playtex Products, Inc. | Ergonomic tampon applicator |
US8062245B2 (en) | 2007-02-08 | 2011-11-22 | The Procter & Gamble Company | Self-orienting applicator |
JP2014054367A (en) * | 2012-09-12 | 2014-03-27 | Uni Charm Corp | Applicator for tampon |
US20140289986A1 (en) * | 2011-06-24 | 2014-10-02 | Roweg Holding Ag | Cotton bud |
WO2015079336A1 (en) * | 2013-11-27 | 2015-06-04 | Kimberly-Clark Worldwide, Inc. | Water-dispersible thermoplastic injection molded composition |
WO2015079338A1 (en) * | 2013-11-27 | 2015-06-04 | Kimberly-Clark Worldwide, Inc. | Thermoplastic and water-dispersible injection moldable materials and articles |
WO2015079337A1 (en) * | 2013-11-27 | 2015-06-04 | Kimberly-Clark Worldwide, Inc. | Flushable tampon applicator |
US9192522B2 (en) | 2003-05-02 | 2015-11-24 | Eveready Battery Company, Inc. | Tampon assembly having shaped pledget |
US9820890B2 (en) | 2006-06-12 | 2017-11-21 | Edgewell Personal Care Brands, Llc. | Tampon assembly providing proper bodily placement of pledget |
WO2018081692A1 (en) * | 2016-10-31 | 2018-05-03 | Kimberly-Clark Worldwide, Inc. | Controlling surface dispersibility in thermoplastic injection molded and flushable materials |
WO2018102156A1 (en) * | 2016-11-30 | 2018-06-07 | Kimberly-Clark Worldwide, Inc. | Molding thermoplastic injection-molded and flushable materials |
CN109157679A (en) * | 2018-10-26 | 2019-01-08 | 广州润虹医药科技股份有限公司 | A kind of preparation method of nanometer hydroxyapatite-chitosan artificial bone |
US10821033B2 (en) | 2016-05-26 | 2020-11-03 | Edgewell Personal Care Brands, Llc | Composition for thin walled molded parts |
US11124641B2 (en) | 2016-11-30 | 2021-09-21 | Kimberly-Clark Worldwide, Inc. | Thermoplastic injection molded and flushable material |
US11123228B2 (en) | 2016-11-30 | 2021-09-21 | Kimberly-Clark Worldwide, Inc. | Thermoplastic injection molded and flushable tampon applicator |
US20220296434A1 (en) * | 2021-03-22 | 2022-09-22 | The Procter & Gamble Company | Tampon product including applicator having components molded of pulp-based composite |
US11643534B2 (en) * | 2021-09-30 | 2023-05-09 | Exxonmobil Chemical Patents Inc. | Polyethylene glycol-based polymer processing aid masterbatches |
WO2023149985A1 (en) | 2022-02-07 | 2023-08-10 | Exxonmobil Chemical Patents Inc. | Polyethylene glycol-based polymer processing aids |
WO2023154744A1 (en) | 2022-02-14 | 2023-08-17 | Exxonmobil Chemical Patents Inc. | Polyethylene glycol-based polymer processing aids |
Families Citing this family (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19909653A1 (en) | 1999-03-05 | 2000-09-07 | Stockhausen Chem Fab Gmbh | Powdery, crosslinked, aqueous liquids and blood-absorbing polymers, processes for their preparation and their use |
US20030065296A1 (en) * | 2001-02-26 | 2003-04-03 | Kaiser Thomas A. | Absorbent material of water absorbent polymer, thermoplastic polymer, and water and method for making same |
JP2004273154A (en) * | 2003-03-05 | 2004-09-30 | Yazaki Corp | Joint connector and terminal |
US7169843B2 (en) * | 2003-04-25 | 2007-01-30 | Stockhausen, Inc. | Superabsorbent polymer with high permeability |
US7098292B2 (en) * | 2003-05-08 | 2006-08-29 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer |
DE10334286B4 (en) | 2003-07-25 | 2006-01-05 | Stockhausen Gmbh | Powdered, water-absorbing polymers with fine particles bound by means of thermoplastic adhesives, process for their preparation and chemical products and compounds containing them |
EP1677964A1 (en) * | 2003-10-29 | 2006-07-12 | Prysmian Cavi e Sistemi Energia S.r.l. | Process for manufacturing a water-resistant telecommunication cable |
US7173086B2 (en) * | 2003-10-31 | 2007-02-06 | Stockhausen, Inc. | Superabsorbent polymer with high permeability |
US20050096621A1 (en) * | 2003-11-04 | 2005-05-05 | The Procter & Gamble Company | Substantially serpentine shaped tampon with varying density regions |
US7892218B2 (en) * | 2004-03-03 | 2011-02-22 | Rostam Ltd. | pH reducing formulation |
AU2005220860B2 (en) * | 2004-03-08 | 2011-03-03 | Playtex Products, Inc. | Tampon applicator and method for making same |
JP2008516016A (en) * | 2004-10-05 | 2008-05-15 | プランティック・テクノロジーズ・リミテッド | Moldable biodegradable polymer |
US8372028B2 (en) * | 2004-11-19 | 2013-02-12 | The Procter & Gamble Company | Tampon applicator |
US7812082B2 (en) * | 2005-12-12 | 2010-10-12 | Evonik Stockhausen, Llc | Thermoplastic coated superabsorbent polymer compositions |
RU2407497C2 (en) * | 2006-08-04 | 2010-12-27 | Плейтекс Продактс, Инк. | Applicator handle and tampon applicator (versions) |
GB2440842B (en) * | 2006-09-30 | 2008-08-20 | Funnelly Enough Ltd | Urine collection device |
US7715938B2 (en) * | 2006-12-08 | 2010-05-11 | The Procter & Gamble Company | Method and system for predictive modeling of articles, such as tampons |
US20080228128A1 (en) * | 2007-03-14 | 2008-09-18 | Nancy Karapasha | Applicator having an intermittent gripping structure |
US8075512B2 (en) * | 2007-04-13 | 2011-12-13 | The Procter & Gamble Company | Applicator having an enhanced gripping region |
US8088093B2 (en) * | 2008-08-07 | 2012-01-03 | Ottuso Patrick | Wound penetrating hemostatic device impregnated with coagulant, antibiotic and/or anesthetic |
GB2473206B (en) * | 2009-09-02 | 2014-12-17 | Welland Medical Ltd | A flushable ostomy bag having an outer protective and inner waste collecting pouch |
EP2627487A1 (en) * | 2010-10-15 | 2013-08-21 | The Gillette Company | A method of making a skin engaging member |
EP2710066A1 (en) | 2011-05-20 | 2014-03-26 | The Procter and Gamble Company | Molded articles of polymer-wax compositions |
WO2012162092A1 (en) | 2011-05-20 | 2012-11-29 | The Procter & Gamble Company | Molded articles of starch-polymer-wax-oil compositions |
EP2710060A1 (en) | 2011-05-20 | 2014-03-26 | The Procter and Gamble Company | Molded articles of polymer-oil compositions |
US9427361B2 (en) | 2012-06-25 | 2016-08-30 | Eveready Battery Company, Inc. | Package assembly for or with a tampon applicator |
US20140142234A1 (en) | 2012-11-20 | 2014-05-22 | The Procter & Gamble Company | Thermoplastic Polymer Compositions Comprising Hydrogenated Castor Oil, Methods of Making, and Non-Migrating Articles Made Therefrom |
RU2015119601A (en) | 2012-11-20 | 2017-01-10 | ИМФЛЮКС Инк. | Methods of forming from thermoplastic polymer compositions containing hydroxylated lipids |
CN104955887A (en) | 2012-11-20 | 2015-09-30 | 宝洁公司 | Polymer-soap compositions and methods of making and using the same |
US20140142225A1 (en) | 2012-11-20 | 2014-05-22 | The Procter & Gamble Company | Starch-Thermoplastic Polymer-Soap Compositions and Methods of Making and Using the Same |
WO2014081791A1 (en) | 2012-11-20 | 2014-05-30 | The Procter & Gamble Company | Starch-thermoplastic polymer-grease compositions and methods of making and using the same |
WO2014081751A1 (en) | 2012-11-20 | 2014-05-30 | The Procter & Gamble Company | Polymer-grease compositions and methods of making and using the same |
DE102013200002A1 (en) * | 2013-01-02 | 2014-07-03 | Erwin Pellkofer | Bag for disposing of tampons in the toilet |
WO2015066588A1 (en) | 2013-11-04 | 2015-05-07 | The Procter & Gamble Company | Thermoplastic polymer compositions having co-continuous plate-like morphology |
CA2933525C (en) * | 2013-12-12 | 2020-11-17 | Hollister Incorporated | Flushable catheters |
US20170246042A1 (en) | 2016-02-29 | 2017-08-31 | The Procter & Gamble Company | Masking applicator for feminine care product |
US20180000658A1 (en) | 2016-02-29 | 2018-01-04 | The Procter & Gamble Company | Applicator for feminine care product |
EP3534858B1 (en) | 2016-11-07 | 2021-03-24 | The Procter & Gamble Company | Tampon |
KR102405000B1 (en) * | 2016-11-30 | 2022-06-07 | 킴벌리-클라크 월드와이드, 인크. | Thermoplastic injection molded and flushable materials |
USD852360S1 (en) * | 2018-03-14 | 2019-06-25 | Lacey Lund | Self-lubricating tampon applicator |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6162890A (en) * | 1994-10-24 | 2000-12-19 | Eastman Chemical Company | Water-dispersible block copolyesters useful as low-odor adhesive raw materials |
US6432096B1 (en) * | 1997-06-16 | 2002-08-13 | The Procter & Gamble Company | Absorbent interlabial device having an integrally formed tab |
Family Cites Families (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3882869A (en) | 1970-03-19 | 1975-05-13 | Kimberly Clark Co | Water-dispersible plastic tampon insertion tubes and the like |
US3724462A (en) | 1971-11-01 | 1973-04-03 | Kimberly Clark Co | Water-dispersible insertion devices for tampons and the like |
US3882196A (en) | 1972-09-27 | 1975-05-06 | Kimberly Clark Co | Odor-free thermoformed heat-degraded polyvinyl alcohol |
US3911917A (en) | 1974-02-21 | 1975-10-14 | Kimberly Clark Co | Injector device for tampons or the like made from odor-free thermoformed heat-degraded polyvinyl alcohol |
US4233196A (en) * | 1979-04-30 | 1980-11-11 | Eastman Kodak Company | Polyester and polyesteramide compositions |
US4372311A (en) | 1980-09-12 | 1983-02-08 | Union Carbide Corporation | Disposable articles coated with degradable water insoluble polymers |
US4503098A (en) | 1980-09-12 | 1985-03-05 | Union Carbide Corporation | Disposable articles coated with degradable water insoluble polymers |
US4650459A (en) | 1985-10-21 | 1987-03-17 | Kimberly-Clark Corporation | Convolutely wound paper tampon tube |
US5310827A (en) * | 1987-01-22 | 1994-05-10 | Kuraray Co., Ltd. | Polyamide copolymers |
US4946932A (en) * | 1988-12-05 | 1990-08-07 | Eastman Kodak Company | Water-dispersible polyester blends |
US5002526A (en) | 1989-12-22 | 1991-03-26 | Kimberly-Clark Corporation | Tampon applicator |
US5087650A (en) * | 1990-12-05 | 1992-02-11 | Fully Compounded Plastics, Inc. | Biodegradable plastics |
CA2065966A1 (en) | 1991-04-23 | 1992-10-24 | Robert J. Petcavich | Disposable recyclable plastic articles and moldable synthetic resin blends for making the same |
EP0613672A1 (en) | 1993-03-01 | 1994-09-07 | Tambrands, Inc. | Water-soluble tampon applicator |
EP0635545A3 (en) | 1993-07-21 | 1995-07-12 | Air Prod & Chem | Injection molded articles from extrudable polyvinyl alcohol compositions. |
DE4327024A1 (en) | 1993-08-12 | 1995-02-16 | Bayer Ag | Thermoplastically processable and biodegradable aliphatic polyesteramides |
US5395308A (en) | 1993-09-24 | 1995-03-07 | Kimberly-Clark Corporation | Thermoplastic applicator exhibiting accelerated breakup when immersed in water |
CA2128483C (en) | 1993-12-16 | 2006-12-12 | Richard Swee-Chye Yeo | Flushable compositions |
CA2153818A1 (en) | 1994-08-03 | 1996-02-04 | Debra Hartley Durrance | Water-dispersible thermoplastic composition and articles thereof |
DE4437792A1 (en) | 1994-10-21 | 1996-04-25 | Inventa Ag | Molding compounds based on aliphatic polyesters |
US5496874A (en) | 1994-11-02 | 1996-03-05 | Kimberly-Clark Corporation | Moldable hydrodisintegratable material and products formed thereby |
US6103809A (en) | 1995-11-09 | 2000-08-15 | H.B. Fuller Licensing & Financing, Inc. | Thermoplastic compositions comprising crystalline water soluble polymers and amorphous water sensitive polymers |
US5954683A (en) | 1996-04-15 | 1999-09-21 | Playtex Products, Inc. | Composition and coating for a disposable tampon applicator and method of increasing applicator flexibility |
US5916969A (en) | 1996-11-22 | 1999-06-29 | Kimberly-Clark Corporation | Article and composition of matter made from polyolefins and PEO blend and method of making the same |
AU5522798A (en) | 1996-12-31 | 1998-07-31 | Kimberly-Clark Worldwide, Inc. | Water-responsive polymer compositions and method of making the same |
KR100568633B1 (en) | 1996-12-31 | 2006-04-07 | 킴벌리-클라크 월드와이드, 인크. | Thermoplastic Composition |
US5782794A (en) | 1997-01-28 | 1998-07-21 | Playtex Products, Inc. | Infrared treated tampon applicators |
IT1289966B1 (en) | 1997-02-25 | 1998-10-19 | Cedal Srl | THREE-STAGE PROCESS FOR THE PREPARATION OF SOLID THERMOPLASTIC COMPOSITIONS BASED ON POLYVINYL ALCOHOL AND PRINTABLE AND |
US5804653A (en) | 1997-03-07 | 1998-09-08 | Playtex Products, Inc. | Polyvinyl alcohol compound |
US6010971A (en) | 1997-11-21 | 2000-01-04 | Kimberly-Clark Worldwide, Inc. | Polyethylene oxide thermoplastic composition |
US6110849A (en) | 1997-12-19 | 2000-08-29 | Kimberly-Clark Worlwide, Inc. | Thermoplastic composition including polyethylene oxide |
US6172177B1 (en) | 1997-12-31 | 2001-01-09 | Kimberly-Clark Worldwide, Inc. | Grafted poly(ethylene oxide) compositions |
JPH11308105A (en) | 1998-04-24 | 1999-11-05 | Sony Corp | Pll frequency synthesizer |
US6020425A (en) | 1998-06-01 | 2000-02-01 | Kimberly-Clark Worldwide, Inc. | Unmodified polyvinyl alcohol films and fibers and methods of making the same |
US6228920B1 (en) | 1998-07-10 | 2001-05-08 | Kimberly-Clark Woldwide, Inc. | Compositions and process for making water soluble polyethylene oxide films with enhanced toughness and improved melt rheology and tear resistance |
GB2340835B (en) | 1998-08-26 | 2003-01-15 | Pvax Ploymers Ltd | PVA-containing compositions |
AR022140A1 (en) | 1998-12-31 | 2002-09-04 | Kimberly Clark Co | A COMPOSITION OF MATTER, A FILM AND AN ARTICLE THAT INCLUDE SUCH COMPOSITION AND THE PROCESS TO MAKE SUCH COMPOSITION |
AR022137A1 (en) | 1998-12-31 | 2002-09-04 | Kimberly Clark Co | A COMPOSITION OF MATTER, A FILM AND AN ARTICLE THAT INCLUDE SUCH COMPOSITION |
-
2001
- 2001-03-16 US US09/810,292 patent/US6730057B2/en not_active Expired - Lifetime
- 2001-08-31 US US09/944,672 patent/US20030040695A1/en not_active Abandoned
-
2002
- 2002-03-15 AT AT02726639T patent/ATE451128T1/en not_active IP Right Cessation
- 2002-03-15 DE DE60234682T patent/DE60234682D1/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6162890A (en) * | 1994-10-24 | 2000-12-19 | Eastman Chemical Company | Water-dispersible block copolyesters useful as low-odor adhesive raw materials |
US6432096B1 (en) * | 1997-06-16 | 2002-08-13 | The Procter & Gamble Company | Absorbent interlabial device having an integrally formed tab |
Cited By (73)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8756791B2 (en) * | 2001-10-17 | 2014-06-24 | Eveready Battery Company, Inc. | Tampon applicator |
US20070232982A1 (en) * | 2001-10-17 | 2007-10-04 | Playtex Products, Inc. | Tampon applicator |
US20050177091A1 (en) * | 2001-10-17 | 2005-08-11 | Playtex Products, Inc. | Tampon applicator |
US20030176845A1 (en) * | 2002-03-18 | 2003-09-18 | The Procter & Gamble Company | Shaped tampon |
US6932805B2 (en) * | 2002-03-18 | 2005-08-23 | The Procter & Gamble Company | Shaped tampon |
US20030181555A1 (en) * | 2002-03-20 | 2003-09-25 | Figuly Garret D. | Processing of polyhydroxyalkanoates using a nucleant and a plasticizer |
US6774158B2 (en) * | 2002-03-20 | 2004-08-10 | E. I. Du Pont De Nemours And Company | Processing of polyhydroxyalkanoates using a nucleant and a plasticizer |
US8337478B2 (en) | 2002-09-12 | 2012-12-25 | Playtex Products, Inc. | Ergonomic tampon applicator |
US20100204636A1 (en) * | 2002-09-12 | 2010-08-12 | Playtex Products, Inc. | Ergonomic tampon applicator |
US9421135B2 (en) | 2002-09-12 | 2016-08-23 | Edgewell Personal Care Brands, Llc. | Ergonomic tampon applicator |
US9662249B2 (en) | 2002-09-12 | 2017-05-30 | Edgewell Personal Care Brands, Llc. | Ergonomic tampon applicator |
US9737443B2 (en) | 2002-09-12 | 2017-08-22 | Edgewell Personal Care Brands, Llc | Ergonomic tampon applicator |
US7012106B2 (en) * | 2003-03-28 | 2006-03-14 | Ethicon, Inc. | Reinforced implantable medical devices |
US20040193285A1 (en) * | 2003-03-28 | 2004-09-30 | Roller Mark B. | Implantable medical devices and methods for making same |
US20040254639A1 (en) * | 2003-03-28 | 2004-12-16 | Zhigang Li | Reinforced implantable medical devices |
US7572298B2 (en) * | 2003-03-28 | 2009-08-11 | Ethicon, Inc. | Implantable medical devices and methods for making same |
USD492033S1 (en) | 2003-04-04 | 2004-06-22 | Playtex Products, Inc. | Tampon applicator assembly |
US7044928B2 (en) | 2003-04-04 | 2006-05-16 | Platex Products, Inc. | Tampon applicator assembly having an improved plunger and methods of making |
US20040199100A1 (en) * | 2003-04-04 | 2004-10-07 | Playtex Products, Inc. | Tampon applicator assembly having an improved plunger and methods of making |
US10105267B2 (en) | 2003-05-02 | 2018-10-23 | Edgewell Personal Care Brands, LLC> | Tampon assembly having a shaped pledget |
US10105266B2 (en) | 2003-05-02 | 2018-10-23 | Edgewell Personal Care Brands, Llc. | Tampon assembly having a shaped pledget |
US10383776B2 (en) | 2003-05-02 | 2019-08-20 | Edgewell Personal Care Brands, Llc | Tampon assembly having a shaped pledget |
US9192522B2 (en) | 2003-05-02 | 2015-11-24 | Eveready Battery Company, Inc. | Tampon assembly having shaped pledget |
WO2004101644A1 (en) * | 2003-05-08 | 2004-11-25 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer compositions having short annealing cycle times |
CN100577708C (en) * | 2003-05-08 | 2010-01-06 | 宝洁公司 | Molded or extruded articles comprising polyhydroxyalkanoate copolymer compositions having short annealing cycle times. |
US7887525B2 (en) | 2003-06-26 | 2011-02-15 | Playtex Products, Inc. | Coating composition with color and/or optical components and a tampon applicator coated therewith |
US20050096617A1 (en) * | 2003-06-26 | 2005-05-05 | Playtex Products, Inc. | Coating composition and articles coated therewith |
US9226816B2 (en) | 2003-09-29 | 2016-01-05 | Depuy Mitek, Llc | Method of performing anterior cruciate ligament reconstruction using biodegradable interference screw |
US8016865B2 (en) | 2003-09-29 | 2011-09-13 | Depuy Mitek, Inc. | Method of performing anterior cruciate ligament reconstruction using biodegradable interference screw |
US20070093895A1 (en) * | 2003-09-29 | 2007-04-26 | Lisa Donnelly | Method of performing anterior cruciate ligament reconstruction using biodegradable interference screw |
US9848978B2 (en) | 2003-09-29 | 2017-12-26 | Depuy Mitek, Llc | Method of performing anterior cruciate ligament reconstruction using biodegradable interference screw |
US8834538B2 (en) | 2003-09-29 | 2014-09-16 | Depuy Mitek, Llc | Method of performing anterior cruciate ligament reconstruction using biodegradable interference screw |
US20050070905A1 (en) * | 2003-09-29 | 2005-03-31 | Lisa Donnelly | Method of performing anterior cruciate ligament reconstruction using biodegradable interference screw |
US20060217073A1 (en) * | 2003-11-17 | 2006-09-28 | Akihiro Saitou | Radio access point testing apparatus and method of testing radio access point |
US20060118258A1 (en) * | 2004-12-02 | 2006-06-08 | Chmielewski Harry J | Plasticizing formulation for fluff pulp and plasticized fluff pulp products made therefrom |
US7854822B2 (en) * | 2004-12-02 | 2010-12-21 | Rayonier Trs Holdings Inc. | Plasticizing formulation for fluff pulp and plasticized fluff pulp products made therefrom |
US20070161942A1 (en) * | 2006-01-06 | 2007-07-12 | Pharmaphil Inc. | Biodegradable tampon applicator and method of making |
US20070184220A1 (en) * | 2006-02-06 | 2007-08-09 | Cleveland Christopher S | Biodegradable paper-based laminate with oxygen and moisture barrier properties and method for making biodegradable paper-based laminate |
US8637126B2 (en) | 2006-02-06 | 2014-01-28 | International Paper Co. | Biodegradable paper-based laminate with oxygen and moisture barrier properties and method for making biodegradable paper-based laminate |
US10575994B2 (en) | 2006-06-12 | 2020-03-03 | Edgewell Personal Care Brands, Llc | Tampon assembly providing proper bodily placement of pledget |
US11564850B2 (en) | 2006-06-12 | 2023-01-31 | Edgewell Personal Care Brands, Llc | Tampon assembly providing proper bodily placement of a pledget |
US9820890B2 (en) | 2006-06-12 | 2017-11-21 | Edgewell Personal Care Brands, Llc. | Tampon assembly providing proper bodily placement of pledget |
US8062245B2 (en) | 2007-02-08 | 2011-11-22 | The Procter & Gamble Company | Self-orienting applicator |
US20140289986A1 (en) * | 2011-06-24 | 2014-10-02 | Roweg Holding Ag | Cotton bud |
US9555153B2 (en) * | 2011-06-24 | 2017-01-31 | Roweg Holding Ag | Cotton bud |
TWI584790B (en) * | 2012-09-12 | 2017-06-01 | 優你 嬌美股份有限公司 | Tampons for sanitary napkins |
JP2014054367A (en) * | 2012-09-12 | 2014-03-27 | Uni Charm Corp | Applicator for tampon |
US9918882B2 (en) | 2012-09-12 | 2018-03-20 | Unicharm Corporation | Tampon applicator and sanitary tampon |
RU2648220C1 (en) * | 2013-11-27 | 2018-03-22 | Кимберли-Кларк Ворлдвайд, Инк. | Tampon applicator suitable for flushing into sewage |
WO2015079337A1 (en) * | 2013-11-27 | 2015-06-04 | Kimberly-Clark Worldwide, Inc. | Flushable tampon applicator |
US9456931B2 (en) | 2013-11-27 | 2016-10-04 | Kimberly-Clark Worldwide, Inc. | Thermoplastic and water-dispersible injection moldable materials and articles |
WO2015079336A1 (en) * | 2013-11-27 | 2015-06-04 | Kimberly-Clark Worldwide, Inc. | Water-dispersible thermoplastic injection molded composition |
RU2637322C1 (en) * | 2013-11-27 | 2017-12-04 | Кимберли-Кларк Ворлдвайд, Инк. | Water-dispersible thermoplastic composition moulded by casting under pressure |
US9339580B2 (en) | 2013-11-27 | 2016-05-17 | Kimberly-Clark Worldwide, Inc. | Flushable tampon applicator |
US9320656B2 (en) | 2013-11-27 | 2016-04-26 | Kimberly-Clark Worldwide, Inc. | Water-dispersible thermoplastic injection molded composition |
WO2015079338A1 (en) * | 2013-11-27 | 2015-06-04 | Kimberly-Clark Worldwide, Inc. | Thermoplastic and water-dispersible injection moldable materials and articles |
US10821033B2 (en) | 2016-05-26 | 2020-11-03 | Edgewell Personal Care Brands, Llc | Composition for thin walled molded parts |
US11826240B2 (en) | 2016-05-26 | 2023-11-28 | Edgewell Personal Care Brands, Llc | Composition for thin walled molded parts |
GB2570088A (en) * | 2016-10-31 | 2019-07-10 | Kimberly Clark Co | Controlling surface dispersibility in thermoplastic injection molded and flushable materials |
WO2018081692A1 (en) * | 2016-10-31 | 2018-05-03 | Kimberly-Clark Worldwide, Inc. | Controlling surface dispersibility in thermoplastic injection molded and flushable materials |
GB2570088B (en) * | 2016-10-31 | 2022-06-22 | Kimberly Clark Co | Controlling surface dispersibility in thermoplastic injection molded and flushable materials |
WO2018102156A1 (en) * | 2016-11-30 | 2018-06-07 | Kimberly-Clark Worldwide, Inc. | Molding thermoplastic injection-molded and flushable materials |
US11124641B2 (en) | 2016-11-30 | 2021-09-21 | Kimberly-Clark Worldwide, Inc. | Thermoplastic injection molded and flushable material |
US11123228B2 (en) | 2016-11-30 | 2021-09-21 | Kimberly-Clark Worldwide, Inc. | Thermoplastic injection molded and flushable tampon applicator |
GB2571875B (en) * | 2016-11-30 | 2021-10-13 | Kimberly Clark Co | Molding thermoplastic injection-molded and flushable materials |
GB2571875A (en) * | 2016-11-30 | 2019-09-11 | Kimberly Clark Co | Molding thermoplastic injection-molded and flushable materials |
CN109937026A (en) * | 2016-11-30 | 2019-06-25 | 金伯利-克拉克环球有限公司 | Molding thermoplastic injection-molded and the material that can be broken up |
CN109157679A (en) * | 2018-10-26 | 2019-01-08 | 广州润虹医药科技股份有限公司 | A kind of preparation method of nanometer hydroxyapatite-chitosan artificial bone |
US20220296434A1 (en) * | 2021-03-22 | 2022-09-22 | The Procter & Gamble Company | Tampon product including applicator having components molded of pulp-based composite |
US11643534B2 (en) * | 2021-09-30 | 2023-05-09 | Exxonmobil Chemical Patents Inc. | Polyethylene glycol-based polymer processing aid masterbatches |
WO2023149985A1 (en) | 2022-02-07 | 2023-08-10 | Exxonmobil Chemical Patents Inc. | Polyethylene glycol-based polymer processing aids |
WO2023149984A1 (en) | 2022-02-07 | 2023-08-10 | Exxonmobil Chemical Patents Inc. | Polyethylene glycol-based polymer processing aids |
WO2023154744A1 (en) | 2022-02-14 | 2023-08-17 | Exxonmobil Chemical Patents Inc. | Polyethylene glycol-based polymer processing aids |
Also Published As
Publication number | Publication date |
---|---|
US6730057B2 (en) | 2004-05-04 |
ATE451128T1 (en) | 2009-12-15 |
DE60234682D1 (en) | 2010-01-21 |
US20030036721A1 (en) | 2003-02-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6730057B2 (en) | Flushable tampon applicators | |
EP1368069B1 (en) | Flushable tampon applicators | |
US6664333B2 (en) | Cold-water flushable compositions comprising polylactic acid dispersed in polyvinyl alcohol | |
CA2523951C (en) | Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer | |
US5002526A (en) | Tampon applicator | |
JP3447299B2 (en) | Biodegradable polymer composition and product thereof | |
JP4181412B2 (en) | Fibers comprising polyhydroxyalkanoate copolymer / polylactic acid polymer or copolymer blend | |
JP4119260B2 (en) | Multicomponent fiber containing starch and biodegradable polymer | |
US6946506B2 (en) | Fibers comprising starch and biodegradable polymers | |
CN102695748B (en) | Biodegradability and Breathable films | |
US8907155B2 (en) | Biodegradable and flushable multi-layered film | |
CN1043736C (en) | Biodegradable, liquid impervious monolayer film compositions | |
JPH10511748A (en) | Dispersible compositions and dispersible articles and methods of disposing such compositions and articles | |
JPH08215246A (en) | Cotton swab of plastic material | |
JP2006102227A (en) | Biodegradable sanitary article | |
JP2021127454A (en) | Resin composition and method for producing the same, plasticized starch and method for producing the same | |
JP2002035037A (en) | Biodegradable hygienic article | |
JP2006296972A (en) | Sanitary article | |
JPH0578914A (en) | Bio-degradable staple fiber | |
JP4100516B2 (en) | High stretch multicomponent fiber containing starch and polymer | |
JPH0586250A (en) | Readily degradable property-providing agent and its composition | |
JP2002051939A (en) | Portable disposal bag | |
JP4098304B2 (en) | Bicomponent fiber with thermoplastic polymer surrounding a starch-rich core | |
JP4119431B2 (en) | High elongation, splittable multicomponent fiber containing starch and polymers | |
JPH0586226A (en) | Readily degradable composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: PROCTER & GAMBLE COMPANY, THE, OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZHAO, JEAN JIANQUN;GILBERTSON, GARY WAYNE;GARY, BRIAN FRANCIS;AND OTHERS;REEL/FRAME:012744/0009;SIGNING DATES FROM 20011022 TO 20011107 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |