CN100408646C - A modified binder polymer for coating compositions - Google Patents
A modified binder polymer for coating compositions Download PDFInfo
- Publication number
- CN100408646C CN100408646C CNB2004800153923A CN200480015392A CN100408646C CN 100408646 C CN100408646 C CN 100408646C CN B2004800153923 A CNB2004800153923 A CN B2004800153923A CN 200480015392 A CN200480015392 A CN 200480015392A CN 100408646 C CN100408646 C CN 100408646C
- Authority
- CN
- China
- Prior art keywords
- binder polymer
- mixture
- coating compositions
- polysaccharide
- plant gum
- 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.)
- Expired - Fee Related
Links
- 239000011230 binding agent Substances 0.000 title claims abstract description 91
- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- 239000008199 coating composition Substances 0.000 title claims abstract description 39
- 239000000835 fiber Substances 0.000 claims abstract description 47
- 241000196324 Embryophyta Species 0.000 claims abstract description 46
- 240000008042 Zea mays Species 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 229920001221 xylan Polymers 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 54
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 30
- 235000007244 Zea mays Nutrition 0.000 claims description 28
- 229920001282 polysaccharide Polymers 0.000 claims description 23
- 239000005017 polysaccharide Substances 0.000 claims description 23
- 150000004804 polysaccharides Chemical class 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 16
- 102000004169 proteins and genes Human genes 0.000 claims description 15
- 108090000623 proteins and genes Proteins 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 10
- 239000008107 starch Substances 0.000 claims description 10
- 235000019698 starch Nutrition 0.000 claims description 10
- 244000215068 Acacia senegal Species 0.000 claims description 6
- 235000006491 Acacia senegal Nutrition 0.000 claims description 6
- 235000013311 vegetables Nutrition 0.000 claims description 5
- 235000016068 Berberis vulgaris Nutrition 0.000 claims description 4
- 241000335053 Beta vulgaris Species 0.000 claims description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 4
- 235000007319 Avena orientalis Nutrition 0.000 claims description 2
- 235000007558 Avena sp Nutrition 0.000 claims description 2
- 240000005979 Hordeum vulgare Species 0.000 claims description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 241000209763 Avena sativa Species 0.000 claims 1
- 241000209140 Triticum Species 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 125000002348 vinylic group Chemical group 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 18
- 239000003973 paint Substances 0.000 abstract description 8
- 150000002243 furanoses Chemical class 0.000 abstract description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 abstract description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 abstract description 4
- 235000005822 corn Nutrition 0.000 abstract description 4
- 239000002966 varnish Substances 0.000 abstract description 3
- 239000004922 lacquer Substances 0.000 description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 239000000178 monomer Substances 0.000 description 31
- 239000006185 dispersion Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 25
- 229920001206 natural gum Polymers 0.000 description 22
- 239000007787 solid Substances 0.000 description 19
- 239000003999 initiator Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 16
- 230000004048 modification Effects 0.000 description 15
- 238000012986 modification Methods 0.000 description 15
- 239000000049 pigment Substances 0.000 description 15
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- 239000004615 ingredient Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000004581 coalescence Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 239000013543 active substance Substances 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- 239000004160 Ammonium persulphate Substances 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 9
- 235000019395 ammonium persulphate Nutrition 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 230000003115 biocidal effect Effects 0.000 description 8
- 239000003139 biocide Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000004606 Fillers/Extenders Substances 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 5
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 5
- SRBFZHDQGSBBOR-QMKXCQHVSA-N alpha-L-arabinopyranose Chemical compound O[C@H]1CO[C@@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-QMKXCQHVSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 229950006191 gluconic acid Drugs 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229960003487 xylose Drugs 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 150000003214 pyranose derivatives Chemical class 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- -1 rutile again Chemical compound 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000013011 aqueous formulation Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 240000002989 Euphorbia neriifolia Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical group CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- AHVOFPQVUVXHNL-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CCCCOC(=O)C=C AHVOFPQVUVXHNL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical class CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 1
- 210000000051 wattle Anatomy 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
A film-forming binder polymer for a coating composition such as a paint, varnish or woodstain where the polymer is modified by the presence of bonded moieties derived from plant gum, particularly plant fibre gum obtainable from plant fibre, especially corn fibre gum and more particularly moieties derived from proteo-xylans and/or furanose. The modified binder polymer minimises the need to use coalescing solvents without producing poor dried paint coatings which fail the scrub resistance tests also improves the opacity of the dried coating composition.
Description
The present invention relates to be used for the modification film-forming binder polymkeric substance of coating composition and contain this polymer-modified coating composition.This improved composition is specially adapted to architectural coating compositions such as lacquer, varnish or woodstain, and they can be applied under 0 to 30 ℃ envrionment temperature with buildings, furniture or in buildings or the relevant surface of device that exists around it by brush, roller or liner.For simplicity, all these architectural coating compositions are called " lacquer (paints) ".
All moisture building coatings comprise the film-forming binder polymkeric substance.Dry from the teeth outwards as the liquid coating lacquer, this film-forming binder polymkeric substance plays the effect that forms paint film (being dry coating), this paint film is bonded to the surface, and all nonvolatile elements of bonding lacquer of while are particularly including all opalizers, pigment and the extender that exist.
Can obtain various conventional film-forming binder polymkeric substance, but be generally used for moisture building coating most those obtain three kinds of broad types for belong to unsaturated monomer by monoene, be commonly referred to " acrylic acid or the like ", " vinyl-based " and " styrenic " in the spoken language." acrylic acid or the like " is generally the multipolymer (for example methyl methacrylate-butyl acrylate multipolymer) of at least two kinds of alkyl esters of one or more monoethylenically unsaturated carboxylic acids, and " vinyl-based " generally includes the mono-vinyl ester of unsaturated carboxylic acid and the multipolymer of at least a acrylic monomer or different mono-vinyl esters." styrenic " is the multipolymer that contains vinylbenzene (or similar monovinyl aromatic monomer) and be generally the copolymerisable monomer of acrylic acid or the like.
This film-forming binder polymkeric substance can be used as solution copolymerization thing or the dispersion copolymers production in carrier liq.The solution copolymerization thing is dissolved in the carrier liq basically, and dispersion copolymers is as the discrete particle manufacture in carrier liq.Particulate solvent borne or aqueous dispersion need stablizer, are sometimes referred to as emulsifying agent or tensio-active agent, to prevent particle flocculation and to form sediment, improve the storage and the shear stability of dispersion thus.Carrier liq can be organic solvent or water-bearing media.The carrier liq that typically is used to prepare the solution copolymerization thing is for being the liquid of good solvent to related copolymers, and this multipolymer is dissolved in wherein on substantially like this.When carrier liq was moisture, the liquid of 50wt% was water at least, and remaining is organic solvent or solvent mixture with water compatible.
This solution or the dispersion copolymers that can be used for the film-forming binder polymkeric substance, no matter it is solvent borne or water-based, all can be respectively by known solution polymerization or emulsion polymerisation process production.The lacquer that contains the aqueous dispersion of conventional film-forming binder polymer beads is particularly suitable for being higher than 10 ℃ be applied on the surface than under the warm temperature, but if they apply at low temperatures, then the dry coating of the lacquer of Xing Chenging is tending towards be full of cracks, and finally erasibility is bad.The reason that be full of cracks occurs is that low temperature obstruction binder polymer particle coalescence is a film.Coalescence can be improved by so-called organic " coalescence solvent " added in the lacquer batching, and the typical case of this organic solvent is ethylene glycol, propylene glycol, benzylalcohol and the dedicated solvent that is called " Texanol ", and it is a trimethylpentane glycol isobutyrate.At present, think that this type of solvent environment is unfriendly, another alternative method that therefore solves the be full of cracks problem has been used the binder polymer with lower glass transition temp (Tg), although there is known shortcoming in this low Tg.First shortcoming is to reduce erasibility.Second shortcoming is the relevant viscosity last much longer of dry coating with the lacquer of new coating.Glass transition temp Tg defines in European patent specification EP0425085A.
At present generally in architectural coating compositions, using binder polymer (this polymkeric substance can obtain from renewable resources) to have interest.For example, the binder polymer that contains mild oxidation starch is used in European patent specification EP0949307A suggestion, but it does not advise a kind of technology that is used to avoid using the coalescence solvent.British patent specification GB1038540A discloses in the application relevant with the paper coating technology with US Patent specification US5439964 both and has used protein and polysaccharide respectively, but the both does not have to solve the problem of avoiding using the coalescence solvent.
Opaque paint contains the titanium dioxide of granular pigments such as rutile form usually as permalba.Rutile particles is reduced to any trend that rutile is promoted photoinduction degraded with other oxide coatings minimum, rutile costliness like this.If rutile is used for coating with lacquer the erasibility that batching also reduces the dry coating of lacquer with high density.
Amount of pigment in the dried paint is a key character, because it can influence for example final color, opacity, hardness and the erasibility of dried lacquer.It is typically expressed as the volume of pigment contained in the dry film with respect to the dried lacquer cumulative volume of (comprising binding agent).This ratio is commonly referred to the pigment volume concentration (PVC) or the PVC of lacquer, and represents with per-cent.Other not film forming particulate material such as filler and extender (for example china clay) can be included in the calculating to obtain total PVC, be expressed as PVC (always) here, thus with itself and PVC (TiO
2) difference mutually, this PVC (TiO
2) only relate to the PVC that the content of titanium dioxide by lacquer obtains.
Opaque pigment such as titanium dioxide may be expensive and the performance of lacquer such as resistance to marring and weather resistance are had harmful effect.Any improvement of the opacity of lacquer can be developed by the expense or the improvement opacity that reduce lacquer, needs lacquer coating still less like this.This is a particularly important for soft colour and white, because such color has low opacity usually.
An object of the present invention is to provide a kind of architectural coating compositions that contains modification film-forming binder polymkeric substance, this polymkeric substance reduces at least to greatest extent and avoids coating composition need contain organic coalescence solvent usually, can not induce like this and induce the film be full of cracks or form bad resistance to marring and lasting adhesiveness in the dry coating of lacquer.Another purpose is to improve the opacity of coating composition.A purpose is the opaque and coloring effect that promotes titanium dioxide, particularly rutile again, it is needed seldom in prescription for obtaining given opacity like this.Another purpose of the present invention provides a kind of modification film-forming binder polymkeric substance that is used for architectural coating compositions.
Therefore, the invention provides a kind of architectural coating compositions that contains the film-forming binder polymkeric substance, wherein this binder polymer is modified in the presence of plant gum, described plant gum comprises the mixture that contains protein and polysaccharide, wherein this mixture closely mixes to this binder polymer or with this binder polymer in conjunction with (bonded), and wherein this mixture comprises starch less than 2wt%.
Preferably, be 0.1% to 15% based on the modification amount of the weight of modified binder, more preferably 1% to 10%.
Term comprises not only wherein that in conjunction with (bonded) plant gum part and film-forming binder polymkeric substance pass through for example chemically combined situation of covalent linkage, and comprises the situation that they exist with intimate mixture.The preferred Chemical bond of bound fraction, more preferably by covalent bonds to binder polymer.When modification film-forming binder polymkeric substance is dispersion, preferably most of particle, preferably all particles all partly are made up of binder polymer and plant gum basically, and no matter it is Chemical bond or is form of mixtures.These particles are further more preferably hud typed.
Find that the coating composition that contains modified binder polymer requires is minimum, be generally organic coalescence solvent of zero, yet can not run into tangible film be full of cracks, bad erasibility or too persistent viscosity in the dry coating of composition.Simultaneously, improved the opacity of coating composition.
Suitable plant gum comprises by plant, is generally to have those that the tree that damages bark oozes out.This suitable class natural gum is the Sudan Gum-arabic that is produced by wattle.Alternate and other suitable plant gum can be obtained by the vegetable fibre that forms the vegetable fibre part.Usually, pars fibrosa derives from shell or seed hulls but any sponge all can.The useful plant natural gum that contains the part that is fit to modified binder polymer can be obtained by various fibre of plant materials, and these plants comprise Zea mays, wheat, oat, barley, rice and beet.Can be called arabinan again by the plant gum that beet obtains.
For obtaining plant gum, fiber must be carried out chemical treatment by vegetable fibre.US Patent specification US6,147,206 (publication on November 14th, 2000), its content as with reference to introducing, has been described the method for extracting natural gum from the Zea mays fiber here, although comprising instruction also can be used for from other filamentary material, extracting plant gum.
US6, disclosed method is summarized as follows in 147,206.
Thick Zea mays fiber is being used for extracting the method for starch by the wet or zeistic byproduct acquisition of dry grinding.The starch that contains about 20% weight by the thick Zea mays fiber of Ginding process acquisition.This can remove by one of following two kinds of methods: with fiber in water with about 7wt% solids slurryization and be heated to 90 ℃, then with thermally-stabilised αDian Fenmei processing at least 1 hour.The enzyme of appropriate amount is about 1wt% on fibre solid.Subsequently, this fiber is filtered to remove dissolved starch and to use the fresh water rinsing to produce the destarching fiber by sieve or horizontal decantor.As other method, with fiber with the boiling several seconds in aqueous slurryization and the continuous steamer under being exposed to steam, so with starch solubilization.This fiber is filtered with the fresh water rinsing and with one group of sieve or horizontal decantor, produce the destarch fiber thus.Will be from the destarch fiber that contains 2% weight or lower starch now of each side's method slurryization and pH is risen to 11.5 in water once more with sodium hydroxide or calcium hydroxide.Preferred sodium hydroxide.Temperature is risen to 95 ℃ and add aqueous hydrogen peroxide solution (33%), by the about 10wt%'s of destarch fibre solid.Slurry temp remains on 95 ℃ and then it was filtered to remove Zea mays fiber resistates (present essentially no Zea mays fiber natural gum) by horizontal decantor under high pH in about 1 hour.This alkaline liquid comprises Zea mays fiber natural gum.With hydrochloric acid the pH of alkaline liquid is reduced to 4.5, form filtrate thus, it is filtered with the diatomaceous vacuum drums of coating.Abandon throw out and gained solution spraying drying be can be used for the dry Zea mays fiber natural gum of modification film-forming binder polymkeric substance with generation.
Suitable plant gum comprises the mixture that contains polysaccharide, protein and ash content (a kind of insoluble material).The relative quantity of these materials (by weight) is respectively 65 to 85: 0.5 to 35: 0 to 15, depends on the exact method that is used to obtain plant gum.Preferably, the amount of ash content be lower than 5% and protein be 2 to 15%, surplus is a polysaccharide.
The polysaccharide of finding in plant gum comprises that by various monose glucose, semi-lactosi, seminose, wood sugar, pectinose (1: 1 mixture of pyranose and furanose), rhamnosyl and glyconic acid (glucoronic acid) form.Yet, it is believed that some protein and polysaccharide covalent bonding form the protein-polysaccharide adducts that is called protein-xylan.These protein-xylans are effective tensio-active agent, and these tensio-active agents make the plant gum that contains them be specially adapted to provide the aqueous dispersion of binder polymer.Preferably at least some plant gums are protein-xylan, more preferably all are protein-xylan.
Zea mays fiber natural gum is known products, by people such as K B Hicks on June 2nd to 5,2002 at Kansas City, in paper ' middle description of Potential New Uses for Corn Fiber ' during Zea mays that USA holds utilizes and technical conference is collected (Proceedings of the Corn Utilization and Technology Conference), this paper is published by NationalCorn Growers Association and Corn Refiners Association, referring to the 122nd to 127 page.
Typical Zea mays fiber natural gum comprises polysaccharide, 5% protein and 15% ash content of about 80% weight, and polysaccharide fraction is made up of semi-lactosi, wood sugar, pectinose and glyconic acid.
Found to be specially adapted to provide the water dispersion of modified polymer granule, especially when these particles comprise binder polymer by plant gum, Sudan Gum-arabic and/or beet fiber that the Zea mays fiber obtains.Highly stable, the anti-sedimentation of these dispersions, and polymerization reactor produces few dirt during manufacture.It is believed that this may be owing to exist due to protein-xylan in these natural gum.
Preferably, the preferably modification by the existence of obtainable bound fraction of this binding agent is more preferably obtained by Zea mays fiber natural gum.Preferably, the consumption of this Zea mays fiber natural gum is 0.1wt%-10wt%, further more preferably 1wt% to 5wt%, and 2wt% to 4wt% most preferably is by total binder polymer.
Semi-lactosi and glyconic acid existed with weight ratio in about 2: 1.Pyranose and wood sugar only have at the different structural formula in carbon 4 positions, and wherein pyranose has hydroxyl on ring, and in the wood sugar ring hydroxyl below ring.Notice that the proton on the ring carbon atom is omitted for simplicity.
Furanose has structure given below, wherein there is very labile hydrogen atom, it is believed that chemical reaction takes place this hydrogen atom easily, be included in during the polymerization technique and conventional monomer bonding at carbon 4 places, during this polymerization technique, they form binder polymer.
The unstable of 4 hydrogen is described in Perkin Transactions (Volume2) of the Journal of the Chemical Society of 1998 by people such as Gilbert, in one piece of paper of p1565-1572.It is believed that ability that furanose participates in this type of reaction help with polysaccharide and or protein-xylan graft to binder polymer.
The suitable monoene that is used for conventional (promptly unmodified) polymkeric substance of preparation belongs to the binder polymer of the also suitable preparation of example of unsaturated monomer with the modification of Zea mays fiber natural gum.These monomers comprise that son also is fit to the binder polymer of preparation with the modification of Zea mays fiber natural gum.These monomers comprise a) " acrylic acid or the like " alkyl (particularly methyl, ethyl, ethylhexyl and normal-butyl) ester as unsaturated carboxylic acid such as acrylic or methacrylic acid or fumaric acid or maleic anhydride, and b) " vinyl-based " is as mono-vinyl ester (particularly vinyl-acetic ester or vinyl " t-carboxylic acid esters (Versatate) "
1), and c) " styrenic ", it typically is vinylbenzene, but also can be other conventional vinylidene aromatic such as Vinyl toluene or vinyl pyridine, and common and comonomer such as above-mentioned vinylformic acid ethyl or ethylhexyl or the copolymerization of butyl ester class.
Various monoethylenically unsaturated carboxylic acids or anhydride monomers can with the binding agent monomer copolymerization to improve the water-wet behavior of binder polymer in alkaline solution.This is particularly advantageous, because it plays the effect that improves aqueous dispersion stability.Yet these sour comonomers are no more than the 7mol% of total monomer usually, to such an extent as to otherwise binder polymer becomes too hydrophilic can not keep acceptable erasibility.
Suitable acid comprises unsaturated carboxylic acid, particularly acrylic or methacrylic acid, and unsaturated acid anhydride comprises maleic anhydride.Except by unsettled hydrogen and the furanose bonding, acid or its acid anhydrides can make binder polymer be bonded to other hydroxylic moiety in the Zea mays fiber natural gum by becoming ester moiety.
Need choose the monomeric combination of monomers that comprises that the space is huge, have Tg and be lower than 77 ℃, preferably be lower than 52 ℃ binder polymer to obtain chain portion wherein.This Tg is further more preferably-20 ℃ to 27 ℃, most preferably-10 ℃ to 10 ℃.Preferably " acrylic acid or the like " binding agent multipolymer comprise methyl methacrylate with as the huge monomeric butyl acrylate in space or 2-EHA and optionally with the multipolymer of 7mol% acrylic or methacrylic acid copolymerization at the most.Preferably " vinyl-based " binding agent multipolymer comprises that vinyl-acetic ester and huge monomer (being generally " tertiary carboxylic acid " vinyl acetate or above-mentioned huge acrylic monomer) add the multipolymer of identical non-essential sour comonomer.Preferably " styrenic " binding agent multipolymer comprises vinylbenzene and plays the butyl acrylate of huge monomer effect or the multipolymer of 2-EHA and the above-mentioned non-essential acid of 7mol% at the most comonomer.Tg be because of excessive crosslinked can not the rising with accepting, so the conjugated diene that does not add in binder polymer above 7wt% is necessary, and to avoid any this diolefine be very preferred.
Preferably, this film-forming binder polymkeric substance carries out in water-bearing media.Like this when using base
1The vinyl t-carboxylic acid esters is the vinyl acetate of so-called " tertiary carboxylic acid (Versatic acid) ", this tertiary carboxylic acid acid is the mixture that contains the mono carboxylic acid of aliphatic series of average 9,10 or 11 carbon atoms, and can be from Shell Chemical Company of Carrington, England is purchased.In the lacquer of binding agent, reduce organic solvent and be discharged in the environment, reduce disagreeable smell thus to greatest extent, particularly when in the space of sealing, painting.More preferably, it is the aqueous dispersion of polymer beads, and most preferably it is prepared by emulsion polymerization.
If the copolymerization under super-atmospheric pressure then can be turned down the wetting ability of binder polymer by comprise some monoolefines (being generally some ethene) in monomer in industrial tolerable.This will improve erasibility.
The plain mode of this production modified binder polymer is plant gum to be added formed in the polymerization reaction mixture of binder polymer by it.Preferably, plant gum can available from vegetable fibre, more preferably can be and most preferably available from the Zea mays fiber, plant gum comprises protein-xylan and/or furanose part.
A kind of modification film-forming binder polymkeric substance also is provided, promptly is used for the method for the binder polymer of coating composition, wherein with the plant gum of the above-mentioned type, preferred Zea mays fiber natural gum adds in the polyreaction of producing binder polymer.This polyreaction is undertaken by free radical or redox initiator usually.Carry out the polymeric temperature and depend on the boiling point of carrier liq of use and the free radical flux (radical flux) of the initiator chosen.When modified binder polymer prepared as the dispersion of polymer particles in water, temperature was preferably 20 to 98 ℃, and more preferably 30 to 95 ℃, most preferably 50 to 90 ℃.
Do not wishing to be subjected under this constraint, suspicious is that between polymerization period, plant gum such as Zea mays fiber natural gum composition chemically add in the multipolymer by for example capturing labile hydrogen by initiator from furanose.Preferably with 0.1 to 5wt% (more preferably 2 to 4wt%) plant gum, more preferably Zea mays fiber natural gum adds in the polymerization reaction mixture, wherein per-cent is based on the total monomer weight that is formed binder polymer by it.
A kind of coating composition also is provided, and wherein said composition comprises modified binder polymer described herein.Preferably, this coating composition further comprises component such as pigment, filler, extender, rheology modifier, dispersion agent, defoamer, flow promotor, linking agent and the biocide of finding usually in lacquer.Preferably, coating composition comprises pigment, and this pigment is titanium dioxide more preferably.This pigment is rutile titanium dioxide more preferably further.PVC (TiO2) is preferably 5 to 35%, and more preferably 10 to 35%, further more preferably 12to30%, most preferably 17 to 30%.This PVC (always) is preferably 8 to 75%, depends on the gloss or the honorable level of lacquer.
The aqueous dispersion of this modification film-forming binder multipolymer is converted into coating composition by it is mixed with all components (preferably except that any chelate structure reagent) of composition easily.If strong structurized composition is stirred into sequestrant wherein before then preferably in composition just will be packed into jar, to form gel structure in jar.
Most important other component is the organic polymer particles of opaque pigment such as rutile or anatase titania or spaceization.Typical filler and extender comprise chalkstone, Wingdale, kaolin and talcum.Silicon-dioxide also can be used as matting agent and exists.Although the present invention the most important thing is the preparation lacquer, also can save opacifying agent to produce varnish or woodstain.
This coating composition preferably has " Rotothinner " (low shearing) viscosity 0.15 and all measures in order to the 5.6cm diameter valve rod of 560rpm rotation in the time of 25 ℃ to 3.0Pa.sec.Strong structurizing thixotropic composition preferably has gel-strength 50g.cm at least when 1 week.
This coating composition is preferably solvent borne or water-based.Waterborne compositions is preferred, and the carrier liq of at least 50% weight is a water in the composition thus.These compositions discharge organic solvent still less in atmosphere, and also are preferred owing to having reduced smell to the user also.
The use of modified binder polymer has improved the opaqueness of coating composition in coating composition.Do not know to produce the mechanism of this phenomenon, although and do not wish fettered by this, it is believed that the opaque efficient of pigment such as titanium dioxide, particularly rutile improves 10 to 20%.The concentration that realizes bigger opaqueness or reduce rutile in addition like this, and therefore improve erasibility and cost.
Therefore, the present invention also provides a kind of by using a kind of modified binder polymer to improve the method for the opaqueness of coating composition as the binder polymer in the coating composition.This coating composition preferably comprises the non-film forming material of particle, and more preferably it is the titanium dioxide of titanium dioxide, especially rutile form.
By embodiment the present invention is described below, wherein embodiment A to E be comparative example.
The opaqueness of lacquer and erasibility are pressed following test:
Contrast gradient
Opaqueness is measured as follows with the contrast gradient method.To coat with lacquer with K-rod 6 and be coated on the Morest chart No.9, obtain the wet paint film of about 60 μ m.Should coat with lacquer in temperature to descend dry 2 to 3 hours for about 20 ℃.Half of this Morest chart dyed black, second half white colouring.The Spectroflash600PLUS spectrophotometer is used at first measuring reflected light at the black of the Morest chart dried lacquer on half, measures reflected light then at the dried lacquer of white on half.The amount that is reflected in the measuring light of black on half divided by the amount from the measuring light of white lateral reflection, and is expressed as the percentage ratio contrast gradient.Measure three times and it is average.
The erasibility test:
By the wet resistance to marring of following assessment: prepare the solid lacquer with 400 micron block coating instrument and film, be dried and in baking oven, wore out 7 days down at 40 ℃.With British Standard7719 test and the record weight loss of this aged lacquer according to 1994.Lacquer weight loss is lower than 2mg/cm
2Be acceptable (by).
List the component of using among the following embodiment below, they can be available from supplier or the method that provides.
Acrysol SCT275 nonionic associative thickener is available from Rohm and
Haas(UK)Ltd.
Aquaflow NHS300 polyethers thickening material is available from Hercules.
" Bentone " Ew POLARGEL NF is provided by Rheox Ltd of UK.
China clay Supreme china clay extender, available from ECC International,
UK
A kind of plant gum of Zea mays fiber natural gum, by US6,147,206 disclosed sides
Method obtains, and provides a kind of general in the description of its specification sheets
State: the group of the Zea mays fiber natural gum that obtains of method thus
Become (wt%): 80% polysaccharide, 5% protein and
15% ash content.Polysaccharide fraction comprise provide per-cent as
Following composition: 48.0% wood sugar, 39.4% pectinose,
8.4% semi-lactosi and 4.2% glyconic acid.
A kind of plant gum of Sudan Gum-arabic is available from Sigma-Aldrich of
Dorset，England。Its composition comprises (wt%)
97.9% polysaccharide and 2.1% protein.The polysaccharide fraction bag
Draw together the following composition that provides per-cent: 45.4% gala
Sugar, 24.7% pectinose, 13.4% rhamnosyl and
16.5% glyconic acid.
A kind of plant gum of araban is available from British Sugar.Its group
Become to comprise (wt%) 97.1% polysaccharide and 2.9% albumen
Matter.Polysaccharide fraction comprises the following one-tenth that provides per-cent
Part: 42.0% glucose, 8.4% semi-lactosi, 10.1%
Wood sugar, 35.3% pectinose and 4.2% rhamnosyl.
" Dispelair " CF246: a kind of tensio-active agent, available from Blackburn
Chemicals?Ltd?of?Blackburn，UK
" Disponil " A1580: a kind of tensio-active agent, available from Henkel
Performance?Chemicals?of?Germany
" Blanose " 7L2C: a kind of cellulose thickener, available from Hercules Inc of
USA
" Britomya " V: a kind of lime carbonate, available from OMYA UK Ltd of
Surrey，UK
" Dispex " N40: a kind of tensio-active agent, available from Allied Colloids of
UK
" Empimin " OT75: a kind of tensio-active agent, available from Albright ﹠amp; Wilson
of?UK
" Fordacal " 30: a kind of lime carbonate extender, available from by Foramin Co.
Ltd?of?UK.
" Lubrizol " 2405: a kind of tensio-active agent, available from Lubrizol UK LTD
of?UK
" Mergal " 711K6: a kind of biocide, available from Troy Chemicals
Europe?BV?of?the?Netherlands.
" Microdol " H 200: rhombspar, available from Omya of Cologne, Germany.
" Natrosol " 250MR: a kind of cellulose thickener, available from Hercules Inc of
USA
" Perlankrol " ESD60: a kind of tensio-active agent, available from Akzo Nobel
Chemicals?Ltd?of?the?Netherlands
" Rocima " V189: a kind of biocide, available from Thor Plastics UK,
New?Road，Newhaven，UK
" Rhodacal " A246L: a kind of tensio-active agent, available from Rhodia SA of
France
" Ropaque " ULTRA: a kind of space organic granular opacifying agent, available from Rohm
&?Haas?of?USA
Tioxide TR92: titanium dioxide, available from Huntsman Chemicals
" Tilcom " AT35: a kind of chelate structure reagent, available from Tioxide
Specialists?Ltd(Huntsman)of?Teeside，
UK
Embodiment 1
Produce the modified acrylic acid binder polymer: with component given below and according to the binder polymer aqueous dispersion of the prepared of describing with the modification of Zea mays fiber natural gum.
Plant gum ingredients by weight g
Water 578.35
Zea mays fiber natural gum 13.86
Sodium bicarbonate 1.32
Sodium-chlor (pure and vacuum drying) 1.12
Rhodacal?A246L 1.58
592.63
Seed monomer blends weight g
Vinyl-acetic ester 22.85
Vinyl " t-carboxylic acid esters " 4.04
“Empimin”OT?75 0.28
27.17
Seed initiator ingredients by weight g
Ammonium persulphate 0.78
Water 17.07
Lubrizol?2405 0.54
18.39
Acrylic monomer ingredients by weight g
Methyl methacrylate 252.01
“Disponil”A?1580 20.74
“Perlankrol”ESD60 3.15
2-EHA 241.58
517.48
Main initiator ingredients by weight g
Ammonium persulphate 0.76
Water 16.76
17.52
The initiator ingredients by weight of winding up g
Ammonium persulphate 0.18
Water 3.90
4.08
Biocide solution weight g
Rocima?V189 1.65
Water 4.40
6.05
Plant gum batching input is equipped with in the round-bottomed flask of agitator and nitrogen purging device.Should prepare burden by to wherein blasting nitrogen purging 5 minutes.Temperature is risen to 75 ℃ and kept 30 minutes.Then the seed monomer blends is added in the flask and at 75 ℃ and further kept 10 minutes down.Add the seed initiator batching then and temperature was risen to 90 ℃ in 30 minutes, during this period, form the aqueous dispersion of seed multipolymer, may be in conjunction with some parts from plant gum.
Acrylic monomer batching and main initiator batching were added dropwise in two hours in the seed multipolymer, simultaneously temperature are remained under 90 ℃.Form the aqueous dispersion of the seed multipolymer of methyl methacrylate and 2-EHA during this period, be combined with from the part of plant gum finish acrylic monomer reinforced after, add the initiator batching of winding up, and temperature kept 30 minutes down at 90 ℃, then this dispersion is cooled to 37 ℃.Then add biocide solution.
This dispersion comprises the multipolymer of methyl methacrylate/2-EHA/vinyl-acetic ester/tertiary carboxylic acid vinyl acetate, has solid content 46.0wt%.
Embodiment A contrasts unmodified binder polymer
Be prepared as follows the aqueous dispersion of unmodified binder polymer with following component.
Aqueous formulations weight g
Water 499.93
Blanose?7L2C 3.32
Disponil?A1580 2.58
Sodium bicarbonate 1.01
Sodium-chlor (pure and vacuum drying) 1.22
517.13
The component of aqueous formulations is under agitation added in the round bottom reactor.The temperature of content is risen to 75 ℃.
Between this heating period, preparation monomer feed mixture in another container.
The monomer feed mixture weight
Methyl methacrylate 302.74
Vinylformic acid (ice) 6.00
Disponil?A1580 23.81
Perlankrol?ESD60 3.61
2-EHA 290.76
626.92
Take out this mixture of 31.35g from container and add in the reactor.The temperature of reactor content kept under 75 ℃ 10 minutes again, prepared the initiator solution of being made up of the 1.87g ammonium persulphate in 41.16g water during this period.Taking-up 9.73g initiator solution also adds in the reactor.After 10 minutes, form seed polymer and temperature was risen to 90 ℃ in 30 minutes.Remaining 595.57g monomer feed mixture was added in 2 hours in the reactor, add during this period and also add the 28.01g initiator solution.At end during this period of time, remaining 5.29g initiator solution is joined in the reactor, and remain on 90 ℃ and reach 4 hours again to guarantee finishing of monomer polymerization.Add the reactor washing fluid of 15.38g water, then add the 6.64g biocide solution that comprises 1.80gRocima V 189 in the 4.80g water.
Solid content is 52.5wt%.
Embodiment 2, comparative example B and embodiment 3
Preparation and test acrylic acid or the like delustring lacquer
Embodiment 2
By being prepared as follows millbase.187.8g water just expected to add in 1 liter of decollator container, then adds 20.2g Orotan 731 and 1.5g Dispelair CF246.This mixture was stirred 5-6 minute under about 1000rpm with the high speed agitator that 7cm Cowles blade is housed.121.2g Microdol H200,101.3g china clay Supreme and 131.4g TioxideTR92 weighing are added in another container, join then in this 1 liter of container.Other 131.4g TioxideTR92 is joined in the decollator container.The speed of decollator is risen to 2000rpm gradually and kept this speed 5 to 10 minutes, and pigment and extender begin to disperse during this period.Add other 70.8g water, then add 1.5g Natrosol Plus Grade, the latter carefully is added to by being stirred on the vortex top that forms in the millbase.Along with disperseing to carry out, the viscosity of millbase raises, the speed of decollator is risen to about 3000rpm, with the good circulation that keeps millbase (at approximately halfway expand mixture in confirm by vortex), then add Natrosol PlusGrade, this millbase is disperseed to amount to 25 minutes, add 0.2g Rocima V189 then.
The lacquer preparation
In the 729.0g millbase, add in the 3.8g water and also under about 600rpm, stir with paddle stirrer.When the millbase of agitation and dilution, also add the aqueous dispersion of 220.9g according to the modified binder polymer of embodiment 1 preparation, then add the 0.4g ammonia soln, at last agitator speed is risen to 900rpm and add thickening material, this thickening material comprises 11.5g AcrysolSCT-275 and 4.8g Aquaflow NHS300.After adding thickening material, gained was coated with lacquer stir about 5 to 10 minutes and it was at room temperature placed 16 hours.
The essentially no coalescence solvent of this liquid lacquer composition.
This PVC (always) is 58.2%, PVC (TiO
2) be 25.8%.Recording contrast gradient is 98.1%.
According to the erasibility of British Standard7719 test drying solid lacquers in 1994, loss 0.77mg lacquer/cm
2(by).
Comparative example B
According to embodiment 2 preparation abrasives, just expect but use the solvent mixture of forming by 8.1g benzylalcohol and 20.2g Texanol to replace 28.3g water.
Adding 10.9g water in the 729.0g abrasive also stirs under about 600rpm with paddle agitator.Under agitation add 192.7g aqueous dispersion according to the preparation of comparative resin embodiment A.Remaining admixture and condition are identical with among the embodiment 2 those.
This liquid lacquer composition comprises 3% weight coalescence solvent.PVC (always) is 58.2%, PVC (TiO
2) be 25.8%.Contrast gradient is 94.1%.
According to the erasibility of British Standard7719 test drying solid lacquers in 1994, loss 0.76mg lacquer/cm
2(by).
Embodiment 3
Use the component of embodiment 2 and according to the method preparation lacquer of embodiment 2, different is the amount that reduces Tioxide TR92 pigment, to reach PVC (always) 55.2% and PVC (TiO
2) 20.9%.Recording contrast gradient is 94.5%.This can with use 25.8% obviously than high PVC (TiO
2) the contrast gradient of comparative example B compare, prove more effective use TiO 2 pigment.
According to the erasibility of British Standard7719 test drying solid lacquers in 1994, loss 0.74mg lacquer/cm
2(by).
Embodiment 4
With component given below and according to the aqueous dispersion of the method for embodiment 1 preparation with the binder polymer of Zea mays fiber natural gum modification.This binder polymer difference from Example 1 is that seed is based on acrylic monomer.
Plant gum ingredients by weight g
Water 522.03
Zea mays fiber tree 12.13
Sodium bicarbonate 1.23
Sodium-chlor (pure and vacuum drying) 1.05
Rhodacal?A246L 1.07
537.51
Seed monomer blends weight g
Methyl methacrylate 12.91
2-EHA 12.37
25.28
Seed initiator ingredients by weight g
Ammonium persulphate 0.73
Water 15.90
16.63
Acrylic monomer ingredients by weight g
Acetate 4.30
Methyl methacrylate 234.61
“Disponil”A?1580 19.31
“Perlankrol”ESD60 2.93
2-EHA 224.89
486.04
Main initiator ingredients by weight g
Ammonium persulphate 0.71
Water 15.59
16.30
The initiator ingredients by weight of winding up g
Ammonium persulphate 0.16
Water 16.76
16.92
Biocide solution weight g
Rocima?V189 1.54
Water 4.09
5.63
The solid content of water dispersion is 45.6wt%.
Embodiment 5
With component and the method preparation lacquer of embodiment 2, different is the modified binder polymer of the modified binder polymer replacement embodiment 1 of embodiment 4, by the solid weight meter based on the weight base, the PVC of embodiment 5 (always) and PVC (TiO
2) a little more than embodiment 2, as described below.
This liquid lacquer composition is substantially free of the coalescence solvent.
This PVC (always) is 60.5% and PVC (TiO
2) be 27.4%.Contrast gradient is 95.9%.
According to the erasibility of British Standard in 1994 7719 test drying solid lacquers, loss 1.72mg lacquer/cm
2(by).
Comparative example C
With contrast unmodified resin embodiment A preparation lacquer, all other components and amount are identical with Embodiment B, but PVC of Embodiment C (always) and PVC (TiO
2) a little higher than Embodiment B, as described below.
This liquid lacquer composition comprises 3% weight coalescence solvent.
This PVC (always) is 60.2% and PVC (TiO
2) be 27.2%.Contrast gradient is 91.7%.
According to the erasibility of British Standard7719 test drying solid lacquers in 1994, loss 0.72mg lacquer/cm
2(by).
Embodiment 6
With component given below and according to the binder polymer aqueous dispersion of the method preparation of describing among the embodiment 1 with the Sudan Gum-arabic modification.
Plant gum ingredients by weight g
Water 669.35
Sudan Gum-arabic 12.13
Sodium bicarbonate 1.23
Sodium-chlor (pure and vacuum drying) 1.05
Rhodacal?A246L 1.07
683.60
Seed monomer blends weight g
Vinyl-acetic ester 25.03
Empimin?OT75 0.25
25.28
Seed initiator ingredients by weight g
Ammonium persulphate 0.73
Water 15.90
16.63
Acrylic monomer ingredients by weight g
Methyl methacrylate 234.61
“Disponil”A1580 19.31
“Perlankrol”ESD60 2.93
2-EHA 224.89
481.74
Main initiator ingredients by weight g
Ammonium persulphate 0.87
Water 19.23
20.10
Reactor washing fluid weight g
(replacement wind up initiator batching)
Water 13.12
Biocide solution weight g
Rocima?V189 1.54
Water 4.09
5.63
The solid content of this aqueous dispersion is 42.9wt%.
Embodiment 7
With component and the method preparation lacquer of embodiment 2, different is the modified binder polymer of the modified binder polymer replacement embodiment 1 of embodiment 6, by the solid weight meter based on the weight base, the PVC of embodiment 7 (always) and PVC (TiO
2) a little more than embodiment 2, as described below.
This liquid lacquer composition is substantially free of the coalescence solvent.
This PVC (always) is 59.6% and PVC (TiO
2) be 26.4%.Contrast gradient is 96.3%.According to the erasibility of British Standard7719 test drying solid lacquers in 1994, loss 1.78mg/cm
2(by).
Embodiment 8
With the method identical with embodiment 6 and the component preparation aqueous dispersion with the binder polymer of araban modification, different is that the plant gum batching comprises the dry sodium-chlor of 605.55g water, 24.24g araban, 1.07g Rhodocol A246L and 1.05g pure vacuum.The solid content of this dispersion is 44.2wt%.
Embodiment 9
With component and the method preparation lacquer of embodiment 2, different is the modified binder polymer of the modified binder polymer replacement embodiment 1 of embodiment 8, by the solid weight meter based on the weight base.
This liquid lacquer composition comprises 0.8% coalescence solvent.
This PVC (always) is 59.0% and PVC (TiO
2) be 26.7%.Contrast gradient is 95.8%.
According to the erasibility of British Standard in 1994 7719 test drying solid lacquers, loss 1.38mg lacquer/cm
2(by).
Claims (12)
1. architectural coating compositions that contains the film-forming binder polymkeric substance, wherein this binder polymer is modified in the presence of plant gum, described plant gum comprises the mixture that contains protein and polysaccharide, wherein this mixture is attached to this binder polymer or closely mixes with this binder polymer, and wherein this mixture comprises starch less than 2wt%.
2. according to the architectural coating compositions of claim 1, wherein this mixture is by being covalently bound to this binder polymer.
3. according to the architectural coating compositions of claim 1, wherein this mixture comprises the proteinic adducts that is attached to polysaccharide.
4. according to the architectural coating compositions of claim 3, wherein this adducts is protein-xylan.
5. according to any one architectural coating compositions among the claim 1-4, wherein this mixture comprises the protein of 2-15wt%.
6. according to any one architectural coating compositions among the claim 1-4, wherein the mixture of protein and polysaccharide obtains from vegetable fibre.
7. according to the architectural coating compositions of claim 6, wherein the mixture of protein and polysaccharide is selected from fibre of plant acquisition at least a in Zea mays, wheat, oat, barley, rice, beet and the Sudan Gum-arabic by extraction.
8. according to any one architectural coating compositions among the claim 1-4, wherein binder polymer and plant gum form the particle with nucleocapsid structure, and wherein said plant gum comprises the mixture that contains protein and polysaccharide.
9. according to any one architectural coating compositions among the claim 1-4, wherein said composition also comprises rutile titanium dioxide.
10. film-forming binder polymkeric substance that is applicable to architectural coating compositions, wherein this binder polymer is modified in the presence of plant gum, described plant gum comprises the mixture that contains protein and polysaccharide, wherein this mixture is attached to this binder polymer or closely mixes with this binder polymer, and wherein this mixture comprises starch less than 2wt%.
11. according to the film-forming binder polymkeric substance of claim 10, wherein this polymkeric substance is selected from
A) acrylic polymers, it is the multipolymer of unsaturated carboxylic acid alkyl ester,
B) vinylic polymers, its be the mono-vinyl ester multipolymer and
C) styrenic polymer,
Wherein
D) this binder polymer is modified in the presence of plant gum, and described plant gum comprises the mixture that contains protein and polysaccharide,
E) wherein this mixture be attached to this binder polymer or closely mix with this binder polymer and
F) this mixture comprises the starch less than 2wt%.
12. according among the claim 1-9 any one coating composition at ambient temperature in relevant with buildings surface of coating or coating buildings furniture of existence around it or install in purposes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0312916A GB0312916D0 (en) | 2003-06-05 | 2003-06-05 | A modified binder polymer for coating compositions |
| GB0312916.0 | 2003-06-05 | ||
| GB0329415.4 | 2003-12-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1798814A CN1798814A (en) | 2006-07-05 |
| CN100408646C true CN100408646C (en) | 2008-08-06 |
Family
ID=9959371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800153923A Expired - Fee Related CN100408646C (en) | 2003-06-05 | 2004-05-26 | A modified binder polymer for coating compositions |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN100408646C (en) |
| AR (1) | AR044632A1 (en) |
| GB (2) | GB0312916D0 (en) |
| MY (1) | MY142753A (en) |
| PT (1) | PT1484374E (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102160611B (en) * | 2011-02-22 | 2014-04-09 | 上海交通大学 | Corn fiber gum composition thickener |
| TWI608063B (en) * | 2016-08-03 | 2017-12-11 | Vogue Long Ind Inc | Natural environment-friendly adhesive base material and manufacturing method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1039540A (en) * | 1963-11-25 | 1966-08-17 | Reed Paper Group Ltd | Improvements in or relating to coating methods |
| US3891580A (en) * | 1966-12-06 | 1975-06-24 | Freeport Minerals Co | Reaction of fine media miller strach or protein with a polymer or polymerizable monomer |
| US5439964A (en) * | 1992-08-19 | 1995-08-08 | Bayer Aktiengesellschaft | Thermoplastic molding compounds for the production of inorganic sintered moldings and a process for the production of inorganic sintered moldings |
| EP0949307A1 (en) * | 1998-04-08 | 1999-10-13 | Imperial Chemical Industries Plc | Environmentally friendly aqueous architectural coating compositions |
| US6090195A (en) * | 1992-08-11 | 2000-07-18 | E. Khashoggi Industries, Llc | Compositions used in manufacturing articles having an inorganically filled organic polymer matrix |
| CN1391596A (en) * | 1999-10-28 | 2003-01-15 | Ucb公司 | Water based polymer composition comprising biopolymer and polymer resin |
-
2003
- 2003-06-05 GB GB0312916A patent/GB0312916D0/en not_active Ceased
- 2003-12-19 GB GB0329415A patent/GB0329415D0/en not_active Ceased
-
2004
- 2004-05-26 PT PT04076544T patent/PT1484374E/en unknown
- 2004-05-26 CN CNB2004800153923A patent/CN100408646C/en not_active Expired - Fee Related
- 2004-06-02 MY MYPI20042109 patent/MY142753A/en unknown
- 2004-06-04 AR ARP040101963 patent/AR044632A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1039540A (en) * | 1963-11-25 | 1966-08-17 | Reed Paper Group Ltd | Improvements in or relating to coating methods |
| US3891580A (en) * | 1966-12-06 | 1975-06-24 | Freeport Minerals Co | Reaction of fine media miller strach or protein with a polymer or polymerizable monomer |
| US6090195A (en) * | 1992-08-11 | 2000-07-18 | E. Khashoggi Industries, Llc | Compositions used in manufacturing articles having an inorganically filled organic polymer matrix |
| US5439964A (en) * | 1992-08-19 | 1995-08-08 | Bayer Aktiengesellschaft | Thermoplastic molding compounds for the production of inorganic sintered moldings and a process for the production of inorganic sintered moldings |
| EP0949307A1 (en) * | 1998-04-08 | 1999-10-13 | Imperial Chemical Industries Plc | Environmentally friendly aqueous architectural coating compositions |
| CN1391596A (en) * | 1999-10-28 | 2003-01-15 | Ucb公司 | Water based polymer composition comprising biopolymer and polymer resin |
Also Published As
| Publication number | Publication date |
|---|---|
| PT1484374E (en) | 2007-10-31 |
| MY142753A (en) | 2010-12-31 |
| AR044632A1 (en) | 2005-09-21 |
| CN1798814A (en) | 2006-07-05 |
| GB0312916D0 (en) | 2003-07-09 |
| GB0329415D0 (en) | 2004-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1820028B (en) | Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions | |
| AU604352B2 (en) | Carboxymethyl hydrophobically modified hydroxyethyl cellulose and its use in protective coating compositions | |
| AU784198B2 (en) | Aqueous composition for wood stain | |
| US7026470B2 (en) | Use of carboxymethyl cellulose acetate butyrate as a precoat or size for cellulosic man-made fiber boards | |
| CN1039718C (en) | Waterborne coating compositions having improved metallic pigment orientation | |
| CA2326780C (en) | Environmentally friendly aqueous architectural coating compositions | |
| EP1686160B1 (en) | Improved coating composition | |
| US7716872B2 (en) | Removable protective coating | |
| US8329786B2 (en) | Modified binder polymer for coating compositions | |
| CN100408646C (en) | A modified binder polymer for coating compositions | |
| US5395436A (en) | Waterborne wiping stain for wood | |
| EP3548566B1 (en) | Process for the preparation of an aqueous binder composition, aqueous binder composition, and aqueous coating composition comprising such binder composition | |
| WO2001035719A2 (en) | Wood stain containing carboxymethyl cellulose acetate butyrate | |
| CN104292967A (en) | Excellent-weather-resistance printing ink for polypropylene material and preparation method thereof | |
| MXPA01010645A (en) | Pigmented compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: London, England, England Patentee after: Imperial Chemical Industries PLC Address before: London, England, England Patentee before: Imperial Chemical Industries PLC |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20160613 Address after: Holland Arnhem Patentee after: Akzo Nobel International Coatings Co.,Ltd. Address before: London, England, England Patentee before: Imperial Chemical Industries PLC |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080806 Termination date: 20180526 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |