WO2017133879A1 - Detergent liquid - Google Patents
Detergent liquid Download PDFInfo
- Publication number
- WO2017133879A1 WO2017133879A1 PCT/EP2017/050641 EP2017050641W WO2017133879A1 WO 2017133879 A1 WO2017133879 A1 WO 2017133879A1 EP 2017050641 W EP2017050641 W EP 2017050641W WO 2017133879 A1 WO2017133879 A1 WO 2017133879A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- detergent composition
- polymer
- surfactant
- liquid detergent
- total
- Prior art date
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 70
- 239000007788 liquid Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 188
- 229920000642 polymer Polymers 0.000 claims abstract description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000004094 surface-active agent Substances 0.000 claims abstract description 60
- 239000002689 soil Substances 0.000 claims abstract description 53
- 239000000975 dye Substances 0.000 claims abstract description 49
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000000344 soap Substances 0.000 claims abstract description 29
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 25
- 239000000194 fatty acid Substances 0.000 claims abstract description 25
- 229930195729 fatty acid Natural products 0.000 claims abstract description 25
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 22
- 102000004190 Enzymes Human genes 0.000 claims abstract description 17
- 108090000790 Enzymes Proteins 0.000 claims abstract description 17
- 239000004615 ingredient Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000004744 fabric Substances 0.000 claims abstract description 11
- 239000003752 hydrotrope Substances 0.000 claims abstract description 11
- 239000003205 fragrance Substances 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- 238000012546 transfer Methods 0.000 claims abstract description 6
- 238000007865 diluting Methods 0.000 claims abstract description 4
- 238000004900 laundering Methods 0.000 claims abstract description 4
- 238000010348 incorporation Methods 0.000 claims abstract description 3
- -1 polyethylene terephthalate Polymers 0.000 claims description 44
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- 229920002873 Polyethylenimine Polymers 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 15
- 238000010790 dilution Methods 0.000 claims description 14
- 239000012895 dilution Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 8
- 239000003352 sequestering agent Substances 0.000 claims description 8
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 239000007844 bleaching agent Substances 0.000 claims description 5
- 229940077388 benzenesulfonate Drugs 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 26
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 25
- 239000003795 chemical substances by application Substances 0.000 description 22
- 108010055059 beta-Mannosidase Proteins 0.000 description 19
- 102000004882 Lipase Human genes 0.000 description 18
- 108090001060 Lipase Proteins 0.000 description 18
- 229920005610 lignin Polymers 0.000 description 16
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 16
- 229920001732 Lignosulfonate Polymers 0.000 description 14
- 229940088598 enzyme Drugs 0.000 description 14
- 108010087558 pectate lyase Proteins 0.000 description 14
- 102100032487 Beta-mannosidase Human genes 0.000 description 13
- 239000002585 base Substances 0.000 description 13
- 239000002304 perfume Substances 0.000 description 13
- 239000004367 Lipase Substances 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- 235000019421 lipase Nutrition 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 11
- 125000000129 anionic group Chemical group 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 241000194110 Bacillus sp. (in: Bacteria) Species 0.000 description 8
- 230000001580 bacterial effect Effects 0.000 description 8
- 230000002538 fungal effect Effects 0.000 description 8
- 235000011187 glycerol Nutrition 0.000 description 8
- 108091005804 Peptidases Proteins 0.000 description 7
- 239000000982 direct dye Substances 0.000 description 7
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 6
- 108010065511 Amylases Proteins 0.000 description 6
- 102000013142 Amylases Human genes 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000004365 Protease Substances 0.000 description 6
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 6
- 239000000980 acid dye Substances 0.000 description 6
- 235000019418 amylase Nutrition 0.000 description 6
- 239000000981 basic dye Substances 0.000 description 6
- 229920001601 polyetherimide Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- 241000193830 Bacillus <bacterium> Species 0.000 description 5
- 108010084185 Cellulases Proteins 0.000 description 5
- 102000005575 Cellulases Human genes 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 241000223198 Humicola Species 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 102000003992 Peroxidases Human genes 0.000 description 5
- 108010064785 Phospholipases Proteins 0.000 description 5
- 102000015439 Phospholipases Human genes 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 108010005400 cutinase Proteins 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 4
- 108700020962 Peroxidase Proteins 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000000813 microbial effect Effects 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- ZIIUUSVHCHPIQD-UHFFFAOYSA-N 2,4,6-trimethyl-N-[3-(trifluoromethyl)phenyl]benzenesulfonamide Chemical compound CC1=CC(C)=CC(C)=C1S(=O)(=O)NC1=CC=CC(C(F)(F)F)=C1 ZIIUUSVHCHPIQD-UHFFFAOYSA-N 0.000 description 3
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000004382 Amylase Substances 0.000 description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- 235000014469 Bacillus subtilis Nutrition 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- 241000193385 Geobacillus stearothermophilus Species 0.000 description 3
- 241001480714 Humicola insolens Species 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 241000589516 Pseudomonas Species 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229940025131 amylases Drugs 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 239000001045 blue dye Substances 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003093 cationic surfactant Substances 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
- 239000000835 fiber Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000003904 phospholipids Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000002888 zwitterionic surfactant Substances 0.000 description 3
- KZYAYVSWIPZDKL-UHFFFAOYSA-N 1,4-diamino-2,3-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(Cl)C(Cl)=C2N KZYAYVSWIPZDKL-UHFFFAOYSA-N 0.000 description 2
- ZNQIAQXHADXXQI-UHFFFAOYSA-N 1-anilino-4-hydroxyanthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(O)=CC=C1NC1=CC=CC=C1 ZNQIAQXHADXXQI-UHFFFAOYSA-N 0.000 description 2
- CULIYQPRUGMRRT-UHFFFAOYSA-N 2-chloro-n-[2-[(2-cyano-4-nitrophenyl)diazenyl]-5-(diethylamino)phenyl]acetamide Chemical compound ClCC(=O)NC1=CC(N(CC)CC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1C#N CULIYQPRUGMRRT-UHFFFAOYSA-N 0.000 description 2
- NKVJCKOMRJVZLO-UHFFFAOYSA-N 3,6,7-trioxabicyclo[7.2.2]trideca-1(11),9,12-triene-2,8-dione Chemical compound O=C1OCCOOC(=O)C2=CC=C1C=C2 NKVJCKOMRJVZLO-UHFFFAOYSA-N 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- AOMZHDJXSYHPKS-DROYEMJCSA-L Amido Black 10B Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(\N=N\C=3C=CC=CC=3)C(O)=C2C(N)=C1\N=N\C1=CC=C(N(=O)=O)C=C1 AOMZHDJXSYHPKS-DROYEMJCSA-L 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000194108 Bacillus licheniformis Species 0.000 description 2
- 241000194103 Bacillus pumilus Species 0.000 description 2
- 244000063299 Bacillus subtilis Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 108010059892 Cellulase Proteins 0.000 description 2
- 241000207199 Citrus Species 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 102000011720 Lysophospholipase Human genes 0.000 description 2
- 108020002496 Lysophospholipase Proteins 0.000 description 2
- 102000004316 Oxidoreductases Human genes 0.000 description 2
- 108090000854 Oxidoreductases Proteins 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 241000223258 Thermomyces lanuginosus Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N aconitic acid Chemical compound OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229940106157 cellulase Drugs 0.000 description 2
- 235000020971 citrus fruits Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- QCWPZYSLMIXIHM-UHFFFAOYSA-L disodium 4-amino-5-hydroxy-3-[(3-nitrophenyl)diazenyl]-6-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Nc1c(N=Nc2cccc(c2)[N+]([O-])=O)c(cc2cc(c(N=Nc3ccccc3)c(O)c12)S([O-])(=O)=O)S([O-])(=O)=O QCWPZYSLMIXIHM-UHFFFAOYSA-L 0.000 description 2
- VDRKHPFIMDTBNX-UHFFFAOYSA-L disodium 7-amino-8-[[4-[4-[(2-amino-8-oxido-6-sulfonaphthalen-1-yl)diazenyl]phenyl]phenyl]diazenyl]-3-sulfonaphthalen-1-olate Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C=CC4=CC(=CC(=C43)[O-])S(=O)(=O)O)N)N=NC5=C(C=CC6=CC(=CC(=C65)[O-])S(=O)(=O)O)N.[Na+].[Na+] VDRKHPFIMDTBNX-UHFFFAOYSA-L 0.000 description 2
- NJPXFJXCALXJCX-UHFFFAOYSA-L disodium 7-anilino-3-[[4-[(2,4-dimethyl-6-sulfonatophenyl)diazenyl]-2,5-dimethylphenyl]diazenyl]-4-hydroxynaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Cc1cc(C)c(N=Nc2cc(C)c(cc2C)N=Nc2c(O)c3ccc(Nc4ccccc4)cc3cc2S([O-])(=O)=O)c(c1)S([O-])(=O)=O NJPXFJXCALXJCX-UHFFFAOYSA-L 0.000 description 2
- LARMRMCFZNGNNX-UHFFFAOYSA-L disodium 7-anilino-3-[[4-[(2,4-dimethyl-6-sulfonatophenyl)diazenyl]-2-methoxy-5-methylphenyl]diazenyl]-4-hydroxynaphthalene-2-sulfonate Chemical compound [Na+].[Na+].COc1cc(N=Nc2c(C)cc(C)cc2S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O LARMRMCFZNGNNX-UHFFFAOYSA-L 0.000 description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001924 fatty-acyl group Chemical group 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DMMDCPMHDXAIRV-UHFFFAOYSA-N n-[5-[bis(2-methoxyethyl)amino]-2-[(2-cyano-4-nitrophenyl)diazenyl]phenyl]acetamide Chemical compound CC(=O)NC1=CC(N(CCOC)CCOC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1C#N DMMDCPMHDXAIRV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001444 polymaleic acid Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920001290 polyvinyl ester Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- AXMCIYLNKNGNOT-UHFFFAOYSA-N sodium;3-[[4-[(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)-[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 AXMCIYLNKNGNOT-UHFFFAOYSA-N 0.000 description 2
- FJBHGWADYLMEJG-UHFFFAOYSA-M sodium;3-[[4-[[4-(diethylamino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC=1C=C(C=CC=1)S([O-])(=O)=O)=C(C=C1)C=CC1=[N+](CC)CC1=CC=CC(S([O-])(=O)=O)=C1 FJBHGWADYLMEJG-UHFFFAOYSA-M 0.000 description 2
- RBYJOOWYRXEJAM-UHFFFAOYSA-M sodium;5,9-dianilino-7-phenylbenzo[a]phenazin-7-ium-4,10-disulfonate Chemical compound [Na+].C=1C=CC=CC=1[N+]1=C2C=C(NC=3C=CC=CC=3)C(S(=O)(=O)[O-])=CC2=NC(C2=CC=CC(=C22)S([O-])(=O)=O)=C1C=C2NC1=CC=CC=C1 RBYJOOWYRXEJAM-UHFFFAOYSA-M 0.000 description 2
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- SCMDRBZEIUMBBQ-UHFFFAOYSA-N (1e)-1-[(8-amino-3,7-dimethyl-10-phenylphenazin-10-ium-2-yl)hydrazinylidene]naphthalen-2-one;chloride Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N\N=C\3C4=CC=CC=C4C=CC/3=O)C=C2[N+]=1C1=CC=CC=C1 SCMDRBZEIUMBBQ-UHFFFAOYSA-N 0.000 description 1
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- PORPENFLTBBHSG-MGBGTMOVSA-N 1,2-dihexadecanoyl-sn-glycerol-3-phosphate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(O)=O)OC(=O)CCCCCCCCCCCCCCC PORPENFLTBBHSG-MGBGTMOVSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- ZMLPKJYZRQZLDA-UHFFFAOYSA-N 1-(2-phenylethenyl)-4-[4-(2-phenylethenyl)phenyl]benzene Chemical group C=1C=CC=CC=1C=CC(C=C1)=CC=C1C(C=C1)=CC=C1C=CC1=CC=CC=C1 ZMLPKJYZRQZLDA-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- QTDIEDOANJISNP-UHFFFAOYSA-N 2-dodecoxyethyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOCCOS(O)(=O)=O QTDIEDOANJISNP-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 1
- UWOFGIXNNCPENM-UHFFFAOYSA-N 3,3-difluoropentan-2-one Chemical compound CCC(F)(F)C(C)=O UWOFGIXNNCPENM-UHFFFAOYSA-N 0.000 description 1
- POELEEGOWIJNBI-UHFFFAOYSA-N 3-[2-[[4-(diethylamino)phenyl]diazenyl]-6-ethoxy-1,3-benzothiazol-3-ium-3-yl]propanamide;chloride Chemical compound [Cl-].S1C2=CC(OCC)=CC=C2[N+](CCC(N)=O)=C1N=NC1=CC=C(N(CC)CC)C=C1 POELEEGOWIJNBI-UHFFFAOYSA-N 0.000 description 1
- VZOOHWGPNLPIHR-UHFFFAOYSA-N 3-[2-[[4-[bis(2-chloroethyl)amino]phenyl]diazenyl]-6-methoxy-1,3-benzothiazol-3-ium-3-yl]propanamide;chloride Chemical compound [Cl-].S1C2=CC(OC)=CC=C2[N+](CCC(N)=O)=C1N=NC1=CC=C(N(CCCl)CCCl)C=C1 VZOOHWGPNLPIHR-UHFFFAOYSA-N 0.000 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical compound CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- MXMWUQAFMKOTIQ-UHFFFAOYSA-N 4-(carboxymethoxy)-4-oxobutanoic acid Chemical class OC(=O)CCC(=O)OCC(O)=O MXMWUQAFMKOTIQ-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- 241001019659 Acremonium <Plectosphaerellaceae> Species 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 241000228215 Aspergillus aculeatus Species 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241000193744 Bacillus amyloliquefaciens Species 0.000 description 1
- 241001328122 Bacillus clausii Species 0.000 description 1
- 241000006382 Bacillus halodurans Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 241000589513 Burkholderia cepacia Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- 241000222511 Coprinus Species 0.000 description 1
- 244000251987 Coprinus macrorhizus Species 0.000 description 1
- BRDJPCFGLMKJRU-UHFFFAOYSA-N DDAO Chemical compound ClC1=C(O)C(Cl)=C2C(C)(C)C3=CC(=O)C=CC3=NC2=C1 BRDJPCFGLMKJRU-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 description 1
- 241000588698 Erwinia Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 241000223221 Fusarium oxysporum Species 0.000 description 1
- 101100448208 Human herpesvirus 6B (strain Z29) U69 gene Proteins 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 102100027612 Kallikrein-11 Human genes 0.000 description 1
- 241000588748 Klebsiella Species 0.000 description 1
- 239000004117 Lignosulphonate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 102000005741 Metalloproteases Human genes 0.000 description 1
- 108010006035 Metalloproteases Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- IZWSFJTYBVKZNK-UHFFFAOYSA-O N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonic acid Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCS(O)(=O)=O IZWSFJTYBVKZNK-UHFFFAOYSA-O 0.000 description 1
- 241000194105 Paenibacillus polymyxa Species 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 102000011420 Phospholipase D Human genes 0.000 description 1
- 108090000553 Phospholipase D Proteins 0.000 description 1
- 102000004861 Phosphoric Diester Hydrolases Human genes 0.000 description 1
- 108090001050 Phosphoric Diester Hydrolases Proteins 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000168225 Pseudomonas alcaligenes Species 0.000 description 1
- 241000589540 Pseudomonas fluorescens Species 0.000 description 1
- 241000589630 Pseudomonas pseudoalcaligenes Species 0.000 description 1
- 241000589774 Pseudomonas sp. Species 0.000 description 1
- 241000589614 Pseudomonas stutzeri Species 0.000 description 1
- 241000577556 Pseudomonas wisconsinensis Species 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 241001292348 Salipaludibacillus agaradhaerens Species 0.000 description 1
- 102000012479 Serine Proteases Human genes 0.000 description 1
- 108010022999 Serine Proteases Proteins 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 241000223257 Thermomyces Species 0.000 description 1
- 241001313536 Thermothelomyces thermophila Species 0.000 description 1
- 241001494489 Thielavia Species 0.000 description 1
- 241001495429 Thielavia terrestris Species 0.000 description 1
- 241000592342 Tracheophyta Species 0.000 description 1
- 241000223259 Trichoderma Species 0.000 description 1
- 101710152431 Trypsin-like protease Proteins 0.000 description 1
- 102000014384 Type C Phospholipases Human genes 0.000 description 1
- 108010079194 Type C Phospholipases Proteins 0.000 description 1
- 241000589634 Xanthomonas Species 0.000 description 1
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 description 1
- IURGIPVDZKDLIX-UHFFFAOYSA-M [7-(diethylamino)phenoxazin-3-ylidene]-diethylazanium;chloride Chemical compound [Cl-].C1=CC(=[N+](CC)CC)C=C2OC3=CC(N(CC)CC)=CC=C3N=C21 IURGIPVDZKDLIX-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005741 alkyl alkenyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 108090000637 alpha-Amylases Proteins 0.000 description 1
- 102000004139 alpha-Amylases Human genes 0.000 description 1
- 150000001413 amino acids Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229940071118 cumenesulfonate Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001982 diacylglycerols Chemical class 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- VUJGKADZTYCLIL-YHPRVSEPSA-L disodium;5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfonatophenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 VUJGKADZTYCLIL-YHPRVSEPSA-L 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229940059442 hemicellulase Drugs 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical class OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010412 laundry washing Methods 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IBOBFGGLRNWLIL-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)[O-] IBOBFGGLRNWLIL-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- QQBPIHBUCMDKFG-UHFFFAOYSA-N phenazopyridine hydrochloride Chemical group Cl.NC1=NC(N)=CC=C1N=NC1=CC=CC=C1 QQBPIHBUCMDKFG-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- KUIXZSYWBHSYCN-UHFFFAOYSA-L remazol brilliant blue r Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 KUIXZSYWBHSYCN-UHFFFAOYSA-L 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- SZINDZNWFLBXKV-UHFFFAOYSA-M sodium;2-(2-hydroxyethoxy)ethanesulfonate Chemical group [Na+].OCCOCCS([O-])(=O)=O SZINDZNWFLBXKV-UHFFFAOYSA-M 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C11D2111/12—
Definitions
- the present invention relates to improved laundry liquid compositions.
- the invention concerns concentrated detergent formulations which permit a reduction in dosage volume.
- a trend in detergent formulating is to reduce the amount of surfactant and to replace these petrochemical derived ingredients with highly weight efficient ingredients selected from cleaning and soil release polymers, sequestrants and enzyme cocktails.
- Typically some surfactant is retained in the composition and the work horse surfactant linear alkyl benzene sulphonate (LAS) is frequently a key part of the surfactant blend.
- LAS work horse surfactant linear alkyl benzene sulphonate
- the polymer ethoxylated polyethylene imine may be used as one of the weight efficient ingredients.
- Suitable compositions are taught, for example, in WO 09/153184. Example formulations are used at a dose of 35ml.
- WO00/50549 (Procter & Gamble Company) concerns cleaning compositions containing butoxy capped nonionic surfactants selected to improve dissolution of solid products and improve rates of mixing with water, while maintaining good physical attributes and good performance.
- the examples include an aqueous heavy duty liquid (HDL) laundry detergent composition which comprises a butoxy capped nonionic surfactant with an amide co-surfactant.
- Adjuvants may be added in the form of particulate material which ranges in size from about 0.1 to about 1500 microns, which are essentially insoluble in liquid phase.
- Fatty acids, such as Ci2-Ci8 monocarboxylic acids are generally not desired in the compositions.
- Composition pH's are typically in the range of about 7.5 to 1 1.
- Non aqueous liquid heavy duty liquid detergent compositions are provided in the form of a stable suspension as solid, substantially insoluble particulate material (in an amount of 0.2 to 30% by weight) dispersed throughout a structured surfactant-containing liquid phase.
- Laundry washing methods involve treatment of soiled laundry with from 40g to 300g of product dissolved in a wash solution of volume from 5 to 65 litres.
- WO2007/130567 is directed to a compact fluid laundry detergent in which the sum of water and non-amino functional solvent ranges from about 5% to about 45% by weight of the composition; a water content of 5 to 25% is proposed together with a fatty acid content of 10% to 25%.
- An example composition contains 10.5 wt% water in combination with 15.5 wt% fatty acids, 23.5 wt% of alkyl benzene sulfonic acid, 5 wt% of C12-14 alcohol 7 ethoxylate and 10.5 wt% of C12-14 alcohol 3 ethoxylate sulphate, sodium salt.
- WO2014/160820 (Procter & Gamble Company) concerns cleaning compositions that contain a polyether amine for stain removal at low wash temperatures of 30°C or lower, when 20 to 300g of product is dissolved or dispersed in the wash solution of volume from 5 litre to 65 litre.
- Example compositions contain an anionic surfactant blend of HFLAS, C14-15 alkyl ethoxy (2.5) sulphate, C14-15 alkyl ethoxy (3.0) sulphate and C24-9 nonionic surfactant (in a weight ratio of 65 : 35 anionic to nonionic) with 6 wt% coconut fatty acid and about 33 wt% solvent (made up of 1 ,2-propylene diol, glycerol and 12.4 wt% water).
- the compositions are used in an amount of 25.36g in water at 60°F (15°C).
- WO2014/160821 is directed to cleaning compositions containing a polyether amine, a soil release polymer and a carboxymethylcellulose, intended for cleaning in low wash temperatures of 30°C and below.
- Example compositions contain surfactant systems in which the weight ratio of anionic to nonionic surfactant is at least 2:1.
- the cleaning compositions are delivered in an amount of from 20g to 300g dispersed in 5 litre to 65 litre of water.
- Example compositions are included which contain about 30 wt% solvent (made up of water, dipropylene glycol,
- WO201 1/032138 (Procter & Gamble Company) concerns compact fluid detergent compositions which comprise a stabilization system against phase splitting which comprises (a) alkanolamine, (b) crystalline structurant and (c) coupling polymer.
- Example compositions contain 34wt% to 42wt% added water and employ anionic and nonionic surfactants in a ratio of about 72:28 by weight.
- WO2012/104159 (Unilever) proposes alkaline liquid detergent compositions which contain polyester substantive nonionic soil release polymers of the type E-M-L-E in which the end blocks E comprise capped oligomers of polyethylene glycol.
- compositions contain at least 27wt% water (for a 20ml dose) with 27wt% of non-soap surfactants.
- WO2013/092049 (Unilever) relates to isotropic liquid laundry detergent compositions that deliver lower than normal levels of surfactant to the wash. Examples contain 27wt% surfactant and 33wt% water.
- US6376446 B1 (Smadi et al) proposes concentrated liquid detergents which contain alkylamine ethoxylate surfactant in a surfactant pre-mixture which contains at least 20% water. Example detergent formulations contain at least about 40wt% water.
- laundry detergent compositions contain solvents and other adjuvants in order to provide a stable vehicle for storage and delivery of the functional materials in the wash.
- the present invention is directed to a liquid detergent composition in a concentrated form which permits low dosage volumes and which exhibits good dissolution characteristics.
- the present invention provides a pourable liquid detergent composition
- a pourable liquid detergent composition comprising
- solvents and hydrotropes are optionally non-amino functional solvents selected from one or more of glycerol, monopropylene glycol (MPG), and ethanol; more preferably MPG; and (g) additional ingredients up to 100% optionally including fragrance, enzymes, shading dyes, fluorescer and dye transfer inhibitor.
- compositions in accordance with the invention have been found to exhibit a combination of good physical
- the invention provides a method for the production of a pourable liquid detergent composition of the first aspect, which method comprises the incorporation of no more than 12wt% added water, and preferably no more than 10wt% added water, into a composition comprising (a), (b), (d), (e), (f) and (g).
- the invention provides a method of laundering fabric which comprises the steps of (A) providing a liquid detergent composition in accordance with the first aspect of the invention, (B) diluting a dose of the detergent composition in water by a factor of >500, preferably by a factor of 600 - 1200, so as to obtain a wash liquor which comprises 1 .3 to 0.2 g/l of non-soap surfactant, and (C) washing fabrics with the wash liquor so formed. In typical use conditions this would involve supplying the composition to a washing machine that may hold up to 15 litres of water for the dilution step.
- a dilution step preferably provides a wash liquor which comprises 3 to 20 g/ wash of non-soap surfactant.
- a preferred method provides at least 3.5 g/wash especially at least 4g/wash and more preferably at least 5 g/wash.
- Preferred methods also provide up to 19g/wash, especially up to 18g/wash, preferably using a detergent composition at a dose level of at least 13ml_ and preferably at least 14ml_.
- a dilution step also preferably provides a polymer system in an amount corresponding to 0.6 to 9 g/wash, preferably 0.8 to 4 and more preferably 1 to 3 g/wash.
- the polymer system is also preferably provided in an amount corresponding to 0.04 to 0.60g/L, preferably 0.05 to 0.3g/L, preferably 0.06 to 0.2g/L, calculated on the basis of a washing machine that can accommodate about 15 litres of water for the initial dilution step.
- the dilution step preferably provides a wash liquor which provides 3.6 to 20 g/ wash in total of functional ingredients comprising non-soap surfactant and polymer system, preferably 4 to 15 g/wash and especially 5 to 12g/wash.
- the dilution step provides 0.2 to 1.4g/l in total of functional ingredients made up of non-soap surfactant and polymer system, based on a dilution step with 15 litres of water.
- a pourable liquid detergent composition wherein the surfactant system (a) comprises nonionic and anionic surfactant in a ratio by weight in the range of 20:80 to 80:20, preferably in the range of 40:60 to 80:20, more preferably in the range of 40:60 to 70:30.
- LAS linear alkyl benzene sulfonate
- PAS primary alkyl sulfate
- AES alkyl ether sulfate
- a counter ion for the anionic surfactant is provided by an in
- a pourable liquid detergent composition wherein the polymer system (b) comprises particulate soil removal polymer (bi) and/ or antiredeposition polymer (bii), preferably provided in a total amount of between 1 to 18wt% of the composition, more preferably 2 to 15wt%, especially 3 to 10 wt% and most preferably 5 to 10wt%.
- a pourable liquid detergent composition wherein the polymer system (b) comprises a modified polyethyleneimine polymer EPEI as a particulate soil removal polymer (bi) and/or anti-redeposition polymer (bii), especially an ethoxylated polyethyleneimine such as PEI(600) 20 EO.
- a pourable liquid detergent composition wherein the polymer system (b) comprises soil release polymer (biii), preferably in an amount of from 1 to 12wt% of the composition, preferably from 2 to 12wt%, especially 2 to 8wt%.
- a pourable liquid detergent composition wherein the polymer system (b) comprises polyethylene terephthalate (PET) polyoxyethylene terephthalate (POET) polyester as a soil release polymer (biii) , especially SRN 100 or SRN 170 or SRN 240.
- a pourable liquid detergent composition wherein the polymer system (b) comprises at least two polymers selected from (bi), (bii) and (biii) and preferably comprises at least one of (bi) or (bii) with at least one of (biii), and further preferably provided in a total amount of at least 7wt% of the composition.
- a pourable liquid detergent composition wherein the weight ratio of polymer system (b) to surfactant system (a) is in the range of from 0.15:1 to 0.4 :1 , preferably 0.2:1 to 0.4:1 , and more preferably 0.2:1 to 0.3:1.
- a pourable liquid detergent composition which has a pH in a range of 5 to 9, preferably 6 to 8, more preferably 6 to 7, and especially 6.2 to 6.8 when measured on dilution of the liquid composition to 1 % using demineralised water.
- a pourable liquid detergent composition which contains less than 40wt% and preferably less than 35wt% , and more preferably less than 30wt% in total of added water (c) and solvents and hydrotropes (f).
- a pourable liquid detergent composition which contains less than 10wt %, preferably less than 8wt% of additional ingredients (g) including fragrance, enzymes, shading dyes, fluorescer and dye transfer inhibitor and optionally is substantially free of bleach and / or sequestrant.
- additional ingredients g
- a pourable liquid detergent composition which contains less than 0.5wt% of any additional inorganic builder materials and / or less than 0.5wt% of any additional organic builder materials.
- Preferred embodiments of the present invention may include one or more of the following features.
- compositions for use in the method of the invention comprise detersive surfactant.
- the non-soap detersive surfactant makes up at least 30 wt% in total of the liquid composition, preferably it makes up from 35 to 60 wt% and especially from 40 to 55 wt%.
- compositions are used in small doses that require them to be diluted in at least 500 or 600 times their own volume of water to form a main-wash liquor comprising up to 20g non-soap surfactant. Based on an initial dilution of 15L this corresponds to 1.3 g/l non-soap surfactant.
- compositions designed for front loading automatic washing machines which typically accommodate about 15L in a wash load and use about 50L of water in a wash cycle
- hand washing or top loading automatic washing machines In hand washing less water may be used and in top loading automatic washing machines a higher amount of water would normally be used than for a front loading automatic machine.
- the dose of detergent liquid could be adjusted accordingly to give appropriate wash liquor concentrations. Within this context it is preferred that the dose of liquid (especially if it is in unit dose form) is no more than 24.5ml.
- Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor.
- Anionic, or blends of anionic and nonionic, surfactants are a preferred feature of the present invention.
- the amount of anionic surfactant is preferably at least 5 wt% of the composition.
- anionic surfactants form at least 20wt% and/ or up to 60wt% of the non-soap surfactant (a).
- Preferred anionic surfactants have an anion selected from linear alkyl benzene sulfonate (LAS), primary alkyl sulfate (PAS), alkyl ether sulfate (AES) and mixtures thereof.
- LAS linear alkyl benzene sulfonate
- PAS primary alkyl sulfate
- AES alkyl ether sulfate
- alkyl sulphonates are alkylbenzene sulphonates, particularly linear
- alkylbenzene sulphonates having an alkyl chain length of Ce-Cis.
- the counter ion for anionic surfactants is generally an alkali metal (such sodium) or an ammoniacal counterion (such as MEA, TEA).
- Suitable anionic surfactant materials are available in the marketplace as the 'Genapol'TM range from Clariant.
- Preferred linear alkyl benzene sulphonate surfactants are Detal LAS with an alkyl chain length of from 8 to 15, more preferably 12 to 14. LAS is normally formulated into compositions in acid, i.e., HLAS form and then at least partially neutralized in-situ. Other common anionic surfactants are generally provided in pre-neutralised form.
- compositions also contain base (e) which may provide a counterion for any anionic surfactant, together with performing pH adjustment.
- base e
- a base provides a counterion selected from Na+, K+ and ammoniacal ions.
- bases include potassium hydroxide, sodium hydroxide, monoethanolamine, diethanolamine and triethanolammine. Most preferred bases include potassium hydroxide and
- the composition may optionally comprise an alkyl polyethoxylate sulphate anionic surfactant of the formula (I): where R is an alkyl chain having from 10 to 22 carbon atoms, especially 12 to 16 carbon atoms and is saturated or unsaturated, M is a cation which makes the compound water- soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15, especially 1 to 3.
- An example is the anionic surfactant sodium lauryl ether sulphate (SLES) which is the sodium salt of lauryl ether sulphonic acid in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3 moles of ethylene oxide per mole.
- the non-soap surfactant system (a) will contain less than 20wt% of any alkyl polyethoxylate sulfate anionic surfactants.
- alkyl sulphate surfactant may be used, especially the non-ethoxylated C12-15 primary and secondary alkyl sulphates.
- PES alkyl sulphate surfactant
- Nonionic surfactants include primary and secondary alcohol ethoxylates, especially Cs- C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used.
- the composition may contain from 0.2 wt% to 40 wt%, preferably 1 wt% to 35 wt%, more preferably 5 to 30 wt% of a nonionic surfactant, such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”).
- a nonionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”).
- Nonionic surfactants that may preferably be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the Clods primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Preferred surfactant systems (a) comprise nonionic and anionic surfactant in a weight ratio in the range of 40:60 to 80:20 and more preferably in a range of 40:60 to 70:30.
- the surfactant system of the composition may contain an amine oxide of the formula (2): R 1 N(0)(CH 2 R 2 ) 2 (2)
- R 1 is a long chain moiety and each CH2R 2 is a short chain moiety.
- R 2 is preferably selected from hydrogen, methyl and -CH 2 OH.
- R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety having chain length of from about 8 to about 18 and R 2 is H.
- These amine oxides are illustrated by Ci2-i4 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
- Example amine oxide materials are Lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO, commercially available from Hunstman under the trade name Empigen® OB. Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl
- compositions contain less than 10wt%, more preferably less than 5wt% amine oxide surfactant.
- zwitterionic surfactant such as sulphobetaine
- sulphobetaine a preferred zwitterionic material is a betaine available from Huntsman under the name Empigen® BB.
- compositions contain less than 10wt%, more preferably less than 5wt% zwitterionic surfactant.
- Cationic surfactants are preferably substantially absent.
- a particularly preferred surfactant system is provided by linear alkyl benzene sulfonate (LAS) and C10-C15 alcohol ethoxylated nonionic surfactant with 2 to 7 EO.
- LAS linear alkyl benzene sulfonate
- C10-C15 alcohol ethoxylated nonionic surfactant with 2 to 7 EO.
- compositions contain (b) 5 to 35wt% in total of a polymer system which comprises at least one of the following (bi) to (biii): (bi) one or more particulate soil removal polymer(s) and/or
- Example compositions may preferably contain up to 25wt%, more preferably up to 20wt% and especially up to 15wt% of the polymer system.
- the compositions contain at least 5wt%, preferably at least 6wt% and more preferably at least 7wt% of the polymer system.
- Preferred embodiments employ an ethoxylated polyethylene imine polymer (EPEI) which may assist with particulate soil removal and/or perform an anti-redeposition function.
- EPEI ethoxylated polyethylene imine polymer
- the EPEI is nonionic. That means it does not have any quaternary nitrogens, or nitrogen oxides or any ionic species other than possible pH affected protonation of nitrogens.
- Polyethylene imines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units.
- These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.
- a catalyst such as carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.
- Specific methods for preparing these polyamine backbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5, 1939; U.S. Pat. No.
- the EPEI comprises a polyethyleneimine backbone wherein the modification of the polyethyleneimine backbone is intended to leave the polymer without
- Such nonionic EPEI may be represented as PEI(X)YEO where X represents the molecular weight of the unmodified PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine backbone.
- the ethoxylation number Y may range from 9 to 40 ethoxy moieties per modification, preferably it is in the range of 16 to 26, most preferably 18 to 22.
- X is selected to be from about 300 to about 10000 weight average molecular weight and is preferably about 600.
- a preferred example EPEI is PEI (600) 20EO.
- the polymer (bi) and / or (bii), such as ethoxylated polyethyleneimine polymer (EPEI), may typically be included in the composition at a level of between 0.01 and 20 wt%, and preferably at a level of at least 1wt% and/or less than 18 wt%, more preferably at a level of from 2wt% and/or up to 15wt%.
- Particularly preferred compositions contain 3wt% to 10wt% and especially 5 to 10 wt% or 4 to 10wt% EPEI.
- a ratio of non-soap surfactant to EPEI may preferably be from 2:1 to 7:1 , preferably from 3:1 to 6:1 , or even to 3:1 to 5:1 .
- the polymer system of the composition preferably comprises at least some soil release polymer for oily soil removal, especially from polyester. Soil release polymers improve the main wash performance of the compositions when used in the low in wash surfactant process of the present invention.
- One preferred class of polymer is the fabric-substantive polymers comprising at least one of (i) saccharide or (ii) dicarboxylic acid and polyol monomer units. Typically these have soil release properties and while they can have a primary detergency effect they generally assist in subsequent cleaning. Preferably these should be present at a level of at least 2% wt preferably at least 3 wt% of the composition.
- the soil release polymer(s) (biii) will generally comprise up to 12.0 wt%, of the detergent composition, preferably up to 9 or 10 wt%. Preferably they are used in an amount of at least 1 or perhaps 2 wt%. Most preferably they are used in an amount of 1 to 9wt%, more preferably 2wt% to 9wt%, especially 2wt% to 8 wt%.
- the soil release polymers for polyester will comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols).
- the polymeric soil release agents useful herein especially include those soil release agents having:
- oxyethylene terephthalate C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C 4 -C6 alkylene or oxy C 4 -C6 alkylene segments, or mixtures therein,
- poly (vinyl ester) segments preferably polyvinyl acetate), having a degree of polymerization of at least 2, or
- Ci -C 4 alkyl ether or C 4 hydroxyalkyl ether substituents, or mixtures therein wherein said substituents are present in the form of Ci -C 4 alkyl ether or C 4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of Ci -C 4 alkyl ether and/or C 4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fibre surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fibre surface, to increase fibre surface hydrophilicity, or a combination of (a) and (b).
- the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
- Suitable oxy C 4 -C6 alkylene hydrophobic segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3 S(CH2)n OCH2 CH2 0-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Pat. No. 4,721 ,580, issued Jan. 26, 1988 to Gosselink.
- Soil release agents characterized by polyvinyl ester) hydrophobic segments include graft copolymers of polyvinyl ester), e.g., Ci -C6 vinyl esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
- polyvinyl ester e.g., Ci -C6 vinyl esters, preferably polyvinyl acetate
- soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
- One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
- the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975.
- Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10 to 15 wt% of ethylene terephthalate units together with 90 to 80 wt% weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
- this polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.
- Another preferred polymeric soil release agent is a sulphonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
- These soil release agents are described fully in U.S. Pat. No. 4,968,451 , issued Nov. 6, 1990 to J.J. Scheibel and E. P. Gosselink.
- Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Pat. No. 4,71 1 ,730, issued Dec. 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Pat. No. 4,721 ,580, issued Jan. 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.
- Preferred polymeric soil release agents also include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31 , 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
- Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propylene units.
- the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
- a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulphonate.
- Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline- reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
- a crystalline- reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
- Suitable soil release polymers are described in WO 2008095626 (Clariant); WO
- the most preferred soil release polymers are the water soluble/miscible or dispersible polyesters such as: linear polyesters sold under the Repel-O-Tex brand by Rhodia (Gerol), or the Texcare brand by Clariant, especially Texcare SRN100 and SRN170, and heavily branched polyesters such as those available from Sasol and described in US 71 19056.
- the polyesters are preferably nonionic and comprise a mid block of spaced apart terephthalate repeat units and at least one end block based on polyethylene glycol with a lower alkyl or hydrogen termination.
- Example soil release polymers may also be of the type E-M-L-E, where the ester midblock M is connected to generally hydrophilic end blocks E, each comprising capped oligomers of polyethylene glycol, the linking moiety L is of the form B-Ar-B, where B is a urethane, amide or ester moiety.
- Such soil release polymers are described in
- Particularly preferred polymer systems (bi), (bii) and (biii) are combinations of relatively high levels of EPEI, particularly greater than 2.5 wt% based on the composition, with soil release polymers, and preferably wherein the soil release polymer (biii) comprises a polyethylene terephthalate (PET) polyoxyethylene terephthalate (POET) polyester.
- PET polyethylene terephthalate
- POET polyoxyethylene terephthalate
- the polymer system (b) may typically be present in an amount such that the ratio of polymer system (b) to surfactant system (a) is in a range of 0.15:1 to 0.4:1 , preferably 0.2:1 to 0.4:1 and more preferably 0.2:1 to 0.3:1 .
- compositions are intended to be highly weight efficient and as such contain relatively low levels of water, namely up to (no more than)12wt% added water which is listed as component (c).
- Preferred embodiments contain up to 10wt% added water.
- the amount of water will vary in dependence upon the dose volume required.
- the present invention permits the use of very low dose volumes such as 25ml or lower, including 15 to 20ml. Dose volumes of 20ml and below preferably contain less than 10wt% added water.
- compositions may also contain water provided as a component of a raw material.
- the total water content of the composition is less than 20wt%, preferably less than 15wt% and more preferably less than 12wt%.
- compositions comprise (d) up to 10wt% total fatty acid and/or soap, preferably up to 8wt% and most preferably up to 5 or 6wt% fatty acid.
- a composition may contain at least 0.1wt% fatty acid and preferably at least 1wt%.
- Preferred example fatty acids contain 8 to 24 carbon atoms, preferably in a straight chain configuration, saturated or unsaturated. Particularly preferred fatty acids include those where the weighted average number of carbons in the alkyl/alkenyl chains is from 8 to 24, more preferably 10 to 22, most preferably from 12 to 18.
- Suitably fatty acids include linear and branched stearic, oleic, lauric, linoleic and tallow acids and mixtures thereof.
- Particularly preferred blends of fatty acids that are commercially available include:
- the fatty acid can act as a buffer in addition to preforming a builder and/or as an antifoam.
- Preferred fatty acids form part of a buffer system that provides buffering in a pH range of 5 to 9, preferably 6 to 8, more preferably 6 to 7 and especially 6.2 to 6.8.
- the present detergent compositions have a pH in those ranges when measured on dilution of the liquid composition to 1 % using demineralised water. The most preferred pH range will vary in dependence upon the polymer system; soil release polymers in particular can have reduced stability under certain conditions of pH. Base
- the compositions contain from 1 to 15wt%, preferably from 1 to 10wt% in total of base which may provide a counterion for any anionic surfactant and perform a pH adjustment function.
- Suitable bases include potassium hydroxide, sodium hydroxide, monoethanolamine, diethanolamine and triethanolammine. Most preferred bases include potassium hydroxide and monoethanolamine. Mixtures of bases may be employed.
- detergent compositions are intended to be highly weight efficient it is proposed that they contain less than 40wt%, preferably less than 35wt%, more preferably less than 30wt% and especially less than 20wt% of any solvents and hydrotropes.
- Solvents and hydrotropes may be substantially absent or, if present they may be included in an amount of at least 0.5wt%, optionally at least 1wt% and conveniently at least 5 wt%. Generally the solvents are "non-amino functional".
- non-amino functional solvent refers to any solvent that does not contain amino functional groups. It includes non-surfactant solvents such as C1-C5 alcohols (such as ethanol), C2-C6 diols (such as monopropylene glycol and dipropylene glycol) and C3-C9 triols (such as glycerol). In preferred embodiments the solvents are optionally selected from one or more of glycerol, monopropylene glycol (MPG) and ethanol.
- MPG monopropylene glycol
- a dose volume of 20ml (or lower) will preferably contain less than 35wt% and more preferably less than 30wt% of solvents and hydrotropes. Amino- functional materials are not included in the category of solvents as they would be classified by the skilled reader as a base for component (e).
- the combined total amount of added water and solvents is preferably less than 60wt%, preferably less than 55wt%, more preferably less than 50wt% and especially less than 45wt%.
- a dose volume of 20ml (or lower) may preferably contain less than 45wt% added water and solvents Additional ingredients up to 100%
- compositions may contain additional ingredients such a fragrance, enzymes, shading dyes, fluorescer, colorants, pearlisers and/or opacifiers, and dye transfer inhibitors.
- additional ingredients will be present in a total amount of less than 10wt%, more preferably less than 9wt% and especially less than 8wt%.
- Example additional ingredients may be as follows. Enzymes
- the detergent composition may comprise an effective amount of at least one enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase.
- at least one enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase.
- it comprises at least 2 of this group of enzymes, more advantageously at least 3 and most advantageously at least 4 of the enzymes from this group.
- proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included.
- the protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease.
- Preferred commercially available protease enzymes include AlcalaseTM, SavinaseTM, PrimaseTM, DuralaseTM, DyrazymTM, EsperaseTM,
- EverlaseTM, PolarzymeTM, and KannaseTM (Novozymes A S), MaxataseTM, MaxacalTM, MaxapemTM, ProperaseTM, PurafectTM, Purafect OxPTM, FN2TM, and FN3TM (Genencor International Inc.).
- Amylase Suitable amylases include those of bacterial or fungal origin.
- Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. lichen iform is, described in more detail in GB 1 ,296,839, or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060.
- Commercially available amylases are DuramylTM,
- TermamylTM Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
- Pectate lyases also called polygalacturonate lyases: Examples of pectate lyases include pectate lyases that have been cloned from different bacterial genera for example Erwinia, Pseudomonas, Klebsiella and Xanthomonas, as well as from Bacillus subtilis
- pectate lyase comprises the pectate lyase disclosed in Heffron et al., (1995) Mol. Plant-Microbe Interact.
- pectate lyases are disclosed in WO 99/27083 and WO 99/27084.
- Other specifically contemplated pectate lyases (derived from Bacillus licheniformis) are disclosed in US patent no. 6,284,524.
- pectate lyase variants are disclosed in WO 02/006442, especially the variants disclosed in the Examples in WO 02/006442.
- alkaline pectate lyases examples include BIOPREPTM and SCOURZYMETM L from Novozymes A/S, Denmark.
- Suitable examples of mannanases include mannanases of bacterial and fungal origin.
- the mannanase is derived from a strain of the filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus (WO 94/25576).
- WO 93/24622 discloses a mannanase isolated from
- Trichoderma reseei. Mannanases have also been isolated from several bacteria, including Bacillus organisms.
- Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 1 1 , pp. 3505-3510 (1990) describes a beta-mannanase derived from Bacillus stearothermophilus.
- Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551- 555 (1994) describes a beta-mannanase derived from Bacillus subtilis.
- JP-A-03047076 discloses a beta-mannanase derived from Bacillus sp.
- JP-A-63056289 describes the production of an alkaline, thermostable beta-mannanase.
- JP-A-63036775 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta- mannosidase.
- JP-A-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001 .
- a purified mannanase from Bacillus amyloliquefaciens is disclosed in WO 97/1 1 164.
- WO 91/18974 describes a hemicellulase for example a glucanase, xylanase or mannanase active. Contemplated are the alkaline family 5 and 26
- mannanases derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus halodurans, Bacillus clausii, Bacillus sp., and Humicola insolens disclosed in WO
- mannanases examples include MannawayTM available from Novozymes A/S Denmark.
- Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691 ,178, US 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307.
- cellulases include CelluzymeTM, CarezymeTM, EndolaseTM, RenozymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), and KAC-500(B)TM (Kao Corporation).
- Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin.
- peroxidases Chemically modified or protein engineered mutants are included.
- useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257.
- peroxidases include GuardzymeTM and NovozymTM 51004 (Novozymes A/S).
- Preferred lipase enzymes include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola, more preferably ones which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginose, most preferably strain DSM 4109. The amount in the composition is higher than typically found in liquid detergents. This can be seen by the ratio of non- soap surfactant to lipase enzyme, in particular. A particularly preferred lipase enzyme is available under the trademark LipocleanTM from Novozymes. Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola, more preferably ones which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginose, most preferably strain DSM 4109. The amount in
- Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO
- a Pseudomonas lipase e.g. from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1 ,372,034), P. fluorescens,
- Pseudomonas sp. strain SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a Bacillus lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1 131 , 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422).
- the preferred ones have a high degree of homology with the wild-type lipase derived from Humicola lanuginose.
- lipase variants for example those described in WO 92/05249, WO 94/01541 , EP 407 225, EP 260 105, WO 95/35381 , WO 96/00292,
- LipolaseTM Preferred commercially available lipase enzymes include LipolaseTM and Lipolase
- phospholipase is an enzyme which has activity towards phospholipids.
- Phospholipids for example lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1 ) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
- Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
- phospholipases Ai and A2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
- lysophospholipase or phospholipase B
- Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
- compositions may contain a cutinase. classified in EC 3.1.1.74.
- the cutinase used in the invention may be of any origin.
- Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
- Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol for example propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative for example 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
- stabilizing agents e.g., a polyol for example propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative for example 4-formylphenyl boronic acid
- a lignin compound may be used in the composition in an amount that can be optimised by trial and error.
- Lignin is a component of all vascular plants, found mostly between cellular structures but also within the cells and in the cell walls.
- the lignin compound comprises a lignin polymer and more preferably it is a modified lignin polymer.
- a modified lignin polymer as used herein is lignin that has been subjected to a chemical reaction to attach chemical moieties to the lignin covalently. The attached chemical moieties are preferably randomly substituted.
- Preferred modified lignin polymers are lignins that have been substituted with anionic, cationic or alkoxy groups, or mixtures thereof. Preferably the substitution occurs on the aliphatic portion of the lignin and is random.
- the modified lignin polymer is substituted with an anionic group, and preferably it is a sulfonate.
- a preferred cationic group is a quaternary amine.
- Preferred alkoxy groups are polyalkylene oxide chains having repeat units of alkoxy moieties in the range from 5 to 30, most preferably ethoxy.
- the modified lignin sulfonate is substituted with anionic or alkoxy groups.
- Modified lignin polymers are discussed in WO/2010/033743. Most preferably the modified lignin polymer is lignin sulfonate (lignosulfonate). Lignin sulfonate may be obtained by the Howard process. Exemplary lignin sulfonate may be obtained from a variety of sources including hardwoods, softwoods and recycling or effluent streams.
- the lignin sulfonate may be utilized in crude or pure forms, e.g., in an "as is" or whole liquor condition, or in a purified lignin sulfonate form from which or in which sugars and other saccharide constituents have been removed or destroyed, or from which or in which inorganic constituents have been partially or fully eliminated.
- the lignin sulfonate may be utilized in salt forms including calcium lignin sulfonate, sodium lignin sulfonate, ammonium lignin sulfonate, potassium lignin sulfonate, magnesium lignin sulfonate and mixtures or blends thereof.
- the lignin sulfonate preferably has a weight average molecular weight of from 2000 to 100000.
- Their basic structural unit is phenylpropane.
- the degree of sulphonation is preferably from 0.3 and 1 .0 sulfate groups per phenylpropane unit.
- Lignin sulfonates are available from a number of suppliers including Borregaard
- fluorescer in the compositions.
- these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
- the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.5 wt %.
- Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
- Di-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
- Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH
- Pyrazoline compounds e.g. Blankophor SN.
- Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1 ,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5-triazin-2- yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1 ,3,5- triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
- composition When the composition is used at very low levels of product dosage, it is advantageous to ensure that perfume is employed efficiently.
- a particularly preferred way of ensuring that perfume is employed efficiently is to use an encapsulated perfume.
- Use of a perfume that is encapsulated reduces the amount of perfume vapour that is produced by the composition before it is diluted. This is important when the perfume concentration is increased to allow the amount of perfume per wash to be kept at a reasonably high level.
- the perfume is not only encapsulated but also that the encapsulated perfume is provided with a deposition aid to increase the efficiency of perfume deposition and retention on fabrics.
- the deposition aid is preferably attached to the encapsulate by means of a covalent bond, entanglement or strong adsorption, preferably by a covalent bond or entanglement.
- Shading dye can be used to improve the performance of the compositions.
- Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics.
- a further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.
- Direct dyes are the class of water soluble dyes which have an affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
- bis-azo or tris-azo dyes are used.
- the direct dye is a direct violet of the following structures:
- ring D and E may be independently naphthyl or phenyl as shown;
- Ri is selected from: hydrogen and Ci-C4-alkyl, preferably hydrogen;
- R2 is selected from: hydrogen, Ci-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
- R 4 and R5 are independently selected from: hydrogen and Ci-C4-alkyl, preferably hydrogen or methyl;
- X and Y are independently selected from: hydrogen, Ci-C4-alkyl and Ci-C4-alkoxy;
- Preferred dyes are direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , and direct violet 99.
- Bis-azo copper containing dyes for example direct violet 66 may be used.
- the benzidene based dyes are less preferred.
- the direct dye is present at 0.000001 to 1 wt% more preferably 0.00001 wt% to 0.0010 wt% of the composition.
- the direct dye may be covalently linked to the photo-bleach, for example as described in WO2006/024612.
- Cotton substantive acid dyes give benefits to cotton containing garments.
- Preferred dyes and mixes of dyes are blue or violet.
- Preferred acid dyes are:
- R a , Rb, R c and Rd are selected from: H, a branched or linear C1 to C7-alkyl chain, benzyl a phenyl, and a naphthyl; the dye is substituted with at least one SO3 " or -COO " group;
- the B ring does not carry a negatively charged group or salt thereof; and the A ring may further substituted to form a naphthyl; the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, CI, Br, I , F, and N0 2 .
- Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
- non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
- the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
- Hydrophobic dyes :
- composition may comprise one or more hydrophobic dyes selected from
- Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
- Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
- the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
- Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International. Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71 , basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 .
- Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
- the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species for example a polymer, so as to the link the dye to this species.
- Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International. Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
- Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces. Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in WO2006/055787.
- Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , direct violet 99, acid blue 98, acid
- Shading dye can be used in the absence of fluorescer, but it is especially preferred to use a shading dye in combination with a fluorescer, for example in order to reduce yellowing due to chemical changes in adsorbed fluorescer. Bleaches
- Bleaching components such as halogen bleaches, peroxy acid bleaches and inorganic percompound bleaches, are preferably avoided in the present compositions on the grounds that the compositions preferably exhibit a pH in the range of 5 to 9 and more preferably 6 to 7.
- the compositions contain less than 0.5wt% of bleaching component, preferably less than 0.1 wt% and most preferably bleaching components are substantially absent from the compositions. Similarly bleach activators are not required.
- the detergent compositions preferably contain only low levels of organic detergent builder or sequestrant material.
- organic detergent builder or sequestrant material examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
- DEQUESTTM organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
- suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, for example those sold by BASF under the name SOKALANTM.
- the organic builder materials may comprise up to 2 wt%, preferably up to 1wt%, more preferably up to 0.5wt% of the composition.
- Example sequestrants are HEDP (1 -Hydroxyethylidene -1 ,1 ,-diphosphonic acid), for example sold as Dequest 2010, and (Diethylenetriamine penta(methylene phosphonic acid or Heptasodium DTPMP), Dequest® 2066.
- the compositions contain less than 1 wt%, more preferably less than 0.5wt% sequestrant.
- the compositions contain no more than 2 wt%, especially no more than 1 wt% and especially no more than 0.5 wt% of any inorganic builders.
- the fatty acid provides at least some buffering.
- compositions may have their rheology further modified by use of a material or materials that form a structuring network within the composition.
- Suitable structurants include hydrogenated castor oil, microfibrous cellulose and natural based structurants for example citrus pulp fibre. Citrus pulp fibre is particularly preferred especially if lipase enzyme is included in the composition.
- such external structurants are present in an amount of less than 2wt%, preferably less than 1wt%.
- compositions may comprise visual cues of solid material that is not dissolved in the composition.
- Preferred visual cues are lamellar cues formed from polymer film and possibly comprising functional ingredients that may not be as stable if exposed to the alkaline liquid. Enzymes and bleach catalysts are examples of such ingredients. Also perfume, particularly microencapsulated perfume. Packaging and dosing
- the liquids may supplied in multidose systems or in unit dose systems. In typical use conditions this would involve a dosage of 13ml to 25ml in to a washing machine that may hold 10 to 15 litres of water.
- a method of laundering fabric using the present compositions may involve diluting the dose of detergent composition by a factor of 600 to 1200 to obtain a wash liquor which comprises 1.3 to 0.2g/L of non-soap surfactant (based on a volume of water of 15L in the dilution step) and washing fabrics with the wash liquor so formed.
- a dilution step preferably provides a wash liquor which comprises 3 to 20 g/ wash of non-soap surfactant.
- a preferred method provides at least 3.5 g/wash especially at least 4g/wash and more preferably at least 5 g/wash.
- Preferred methods also provide up to 19g/wash, especially up to 18g/wash.
- Such g/wash calculations are typically based on a 15L wash volume, using a detergent composition at a dose level of at least 13ml_ and preferably at least 14ml_.
- dose volumes are up to 25ml, especially no more than 24.5ml.
- a dilution step also preferably provides a polymer system in an amount corresponding to 0.6 to 9 g/wash, preferably 0.8 to 4 and more preferably 1 to 3 g/wash.
- pourable means that the composition can be poured and as such it preferably has a shear viscosity (at 25 °C) of below 2 Pas at a shear rate of 21 s "1 .
- Preferred viscosities are in the range of 0.1 to 1.0 Pas.
- compositions are preferably isotropic and generally exhibit Newtonian flow characteristics.
- Example 1 to 4 and Comparative Examples 1 to 5 Concentrated laundry detergent compositions were prepared using relatively high levels of surfactant (at about 48 wt%) in combination with various levels of added water and various levels of a polymer system (containing EPEI and SRN 100 soil release polymer). The tables show the amounts by weight of active materials; water / solvent from raw materials will bring the totals to 100%.
- MPG is monopropylene glycol
- MEA is monoethanolamine
- Neodol 25_7 is a C12-C15 alcohol ethoxylate 7EO nonionic ex Shell Chemical
- LAS acid is C12-C14 linear alkylbenzene sulphonic acid
- Prifac 5908 is a saturated lauric fatty acid
- EPEI is an ethoxylated polyethylene imine polymer PEI(600)20EO
- Texcare SRN 100 is a soil release polymer
- Tinopal CBS-CL is a fluorescent agent
- the concentrated laundry detergent compositions illustrate potential 17ml dose formulations. All the examples and comparative examples contain less than 30wt% in total of added water and solvent/hydrotrope (MPG). Also all the examples and
- comparative examples provide about 8.2 g / wash non-soap surfactant.
- Examples 1 to 4 contain amounts of added water ranging from 0 wt% to 1 1.5 wt%.
- the comparative examples show amounts of added water ranging from 16.5 wt% to 26.3 wt%.
- compositions were tested to see if they were lamellar or isotropic by a visual assessment using a microscope. A lamellar sample was regarded as a "fail”.
- Comparative example 5 Failed The illustrative examples provide highly weight efficient low viscosity isotropic liquids which exhibit excellent dissolution in a wash liquor. In contrast, the comparative example compositions were either lamellar or showed poor dissolution characteristics.
- the illustrative examples thus provide concentrated detergent formulations containing high levels of active ingredients, in terms of surfactant and cleaning polymers, which are in a desirable product form of isotropic liquids. These formulations exhibit good dissolution characteristics without the need for high levels of solvent or water to be contained within them and, as a result, the formulations are highly weight efficient.
Abstract
A weight efficient, pourable liquid detergent composition comprising: (a) a non-soap surfactant system which comprises at least nonionic or anionic surfactant such that the total content of non-soap surfactant in the composition is at least 30wt%, preferably at least 35wt%; (b) a polymer system which comprises at least one of the following (bi) to (biii), such that the total content of (bi) to (biii) in the composition is in the range of 5 to 35wt%: (bi) one or more particulate soil removal polymer(s) and/or (bii) one or more anti-redeposition polymer(s) and/or (biii) one or more soil release polymer(s); (c) up to 12wt% total added water; (d) from 0.1wt% up to 10wt% total fatty acid/soap; (e) 1 to 15wt% in total of base, optionally providing one or more counterions for any anionic surfactant; (f) less than 40wt%, preferably less than 35wt%, in total of any solvents and hydrotropes, optionally selected from one or more of glycerol, MPG and ethanol; more preferably MPG; and (g) additional ingredients up to 100% optionally including fragrance, enzymes, shading dyes, fluorescer and dye transfer inhibitor. A method of producing the composition comprises the incorporation of no more than 12wt% added water into a composition comprising (a), (b), (d), (e) and (f). A method of laundering fabrics comprises diluting a dose of the detergent composition by a factor>500, especially by a factor of 600-1200, so as to obtain a wash liquor which comprises 3 to 20 g/wash of non-soap surfactant and washing fabric in the wash liquor.
Description
DETERGENT LIQUI D
The present invention relates to improved laundry liquid compositions. TECHNICAL FIELD
The invention concerns concentrated detergent formulations which permit a reduction in dosage volume. BACKGROUND
A trend in detergent formulating is to reduce the amount of surfactant and to replace these petrochemical derived ingredients with highly weight efficient ingredients selected from cleaning and soil release polymers, sequestrants and enzyme cocktails. Typically some surfactant is retained in the composition and the work horse surfactant linear alkyl benzene sulphonate (LAS) is frequently a key part of the surfactant blend. The polymer ethoxylated polyethylene imine may be used as one of the weight efficient ingredients. Suitable compositions are taught, for example, in WO 09/153184. Example formulations are used at a dose of 35ml.
It would be advantageous to provide more concentrated detergent formulations which would allow for a reduction in the dosage volume. This would result in various advantages such as a reduction in packaging and storage space for the detergents. However there are limits to the extent to which current detergent formulations can be concentrated by simply removing apparently non-functional solvent components. In particular, problems may occur with dispensing and delivery of products of high viscosity. Also, reductions in water or solvent content can lead to dissolution problems during the wash cycle.
Various concentrated formulations which contain low levels of added water have been described in the literature.
For example,WO00/50549 (Procter & Gamble Company) concerns cleaning compositions containing butoxy capped nonionic surfactants selected to improve dissolution of solid
products and improve rates of mixing with water, while maintaining good physical attributes and good performance. The examples include an aqueous heavy duty liquid (HDL) laundry detergent composition which comprises a butoxy capped nonionic surfactant with an amide co-surfactant. Adjuvants may be added in the form of particulate material which ranges in size from about 0.1 to about 1500 microns, which are essentially insoluble in liquid phase. Fatty acids, such as Ci2-Ci8 monocarboxylic acids are generally not desired in the compositions. Composition pH's are typically in the range of about 7.5 to 1 1. Non aqueous liquid heavy duty liquid detergent compositions are provided in the form of a stable suspension as solid, substantially insoluble particulate material (in an amount of 0.2 to 30% by weight) dispersed throughout a structured surfactant-containing liquid phase. Laundry washing methods involve treatment of soiled laundry with from 40g to 300g of product dissolved in a wash solution of volume from 5 to 65 litres.
WO2007/130567(Procter & Gamble Company) is directed to a compact fluid laundry detergent in which the sum of water and non-amino functional solvent ranges from about 5% to about 45% by weight of the composition; a water content of 5 to 25% is proposed together with a fatty acid content of 10% to 25%. An example composition contains 10.5 wt% water in combination with 15.5 wt% fatty acids, 23.5 wt% of alkyl benzene sulfonic acid, 5 wt% of C12-14 alcohol 7 ethoxylate and 10.5 wt% of C12-14 alcohol 3 ethoxylate sulphate, sodium salt.
WO2014/160820 (Procter & Gamble Company) concerns cleaning compositions that contain a polyether amine for stain removal at low wash temperatures of 30°C or lower, when 20 to 300g of product is dissolved or dispersed in the wash solution of volume from 5 litre to 65 litre. Example compositions contain an anionic surfactant blend of HFLAS, C14-15 alkyl ethoxy (2.5) sulphate, C14-15 alkyl ethoxy (3.0) sulphate and C24-9 nonionic surfactant (in a weight ratio of 65 : 35 anionic to nonionic) with 6 wt% coconut fatty acid and about 33 wt% solvent (made up of 1 ,2-propylene diol, glycerol and 12.4 wt% water). The compositions are used in an amount of 25.36g in water at 60°F (15°C).
WO2014/160821 (Procter & Gamble Company) is directed to cleaning compositions containing a polyether amine, a soil release polymer and a carboxymethylcellulose, intended for cleaning in low wash temperatures of 30°C and below. Example
compositions contain surfactant systems in which the weight ratio of anionic to nonionic surfactant is at least 2:1. The cleaning compositions are delivered in an amount of from 20g to 300g dispersed in 5 litre to 65 litre of water. Example compositions are included which contain about 30 wt% solvent (made up of water, dipropylene glycol,
monopropylene glycol and glycerine) in combination with C12-15 alkylethoxy (1.0) sulphate, C11-C12 alkylbenzene sulfonate and C12-15 alkyl ethoxylate in which the weight ratio of anionic surfactant to nonionic surfactant is about 9.
WO201 1/032138 (Procter & Gamble Company) concerns compact fluid detergent compositions which comprise a stabilization system against phase splitting which comprises (a) alkanolamine, (b) crystalline structurant and (c) coupling polymer. Example compositions contain 34wt% to 42wt% added water and employ anionic and nonionic surfactants in a ratio of about 72:28 by weight. WO2012/104159 (Unilever) proposes alkaline liquid detergent compositions which contain polyester substantive nonionic soil release polymers of the type E-M-L-E in which the end blocks E comprise capped oligomers of polyethylene glycol. Example
compositions contain at least 27wt% water (for a 20ml dose) with 27wt% of non-soap surfactants.
WO2013/092049 (Unilever) relates to isotropic liquid laundry detergent compositions that deliver lower than normal levels of surfactant to the wash. Examples contain 27wt% surfactant and 33wt% water. US6376446 B1 (Smadi et al) proposes concentrated liquid detergents which contain alkylamine ethoxylate surfactant in a surfactant pre-mixture which contains at least 20% water. Example detergent formulations contain at least about 40wt% water.
In addition to the surfactants, polymers and enzymes which perform a cleaning function, laundry detergent compositions contain solvents and other adjuvants in order to provide a stable vehicle for storage and delivery of the functional materials in the wash.
It would be desirable to provide a detergent composition which exhibits an enhanced combination of properties in terms of increased weight efficiency with good dissolution characteristics. Attempts to reduce the amount of added water and other solvents which
do not perform a cleaning function often result in compositions which show unsatisfactory dissolution in the wash.
The present invention is directed to a liquid detergent composition in a concentrated form which permits low dosage volumes and which exhibits good dissolution characteristics.
SUMMARY OF THE INVENTION
Accordingly, in a first aspect the present invention provides a pourable liquid detergent composition comprising
(a) at least 30wt%, preferably at least 35wt%, more preferably at least 40wt% in total of a non-soap surfactant system which comprises at least nonionic or anionic surfactant;
(b) 5 to 35wt%, preferably up to 30wt%, more preferably up to 25wt%, especially up to 20wt% and most preferably up to 15wt% and/or at least 6wt%, preferably at least 7wt% in total of a polymer system which comprises at least one of the following (bi) to (biii):
(bi) one or more particulate soil removal polymer(s) and/or (bii) one or more anti-redeposition polymer(s) and/or
(biii) one or more soil release polymer(s); (c) up to 12wt% and especially up to 10wt% total added water;
(d) from 0.1wt% up to 10wt%, preferably up to 8wt% in total of fatty acid or fatty acid soap; more preferably from 1wt% and/or up to 5wt% .especially from 3wt% and/or up to 5wt%;
(e) 1 to 15wt%, preferably 1 to 10wt% in total of base, optionally providing one or more counterions for any anionic surfactant;
(f) less than 40wt%, preferably less than 35wt%, more preferably less than 30wt% or 25wt% and especially less than 22wt% or less than 20wt% of any solvents and
hydrotropes, which solvents and hydrotropes are optionally non-amino functional solvents selected from one or more of glycerol, monopropylene glycol (MPG), and ethanol; more preferably MPG; and (g) additional ingredients up to 100% optionally including fragrance, enzymes, shading dyes, fluorescer and dye transfer inhibitor.
The present invention provides detergent compositions that are highly weight efficient and, as a result, are suitable for use in low dosage volumes. Compositions in accordance with the invention have been found to exhibit a combination of good physical
characteristics, as stable isotropic liquids, together with good dissolution characteristics.
In a second aspect the invention provides a method for the production of a pourable liquid detergent composition of the first aspect, which method comprises the incorporation of no more than 12wt% added water, and preferably no more than 10wt% added water, into a composition comprising (a), (b), (d), (e), (f) and (g).
In a further aspect the invention provides a method of laundering fabric which comprises the steps of (A) providing a liquid detergent composition in accordance with the first aspect of the invention, (B) diluting a dose of the detergent composition in water by a factor of >500, preferably by a factor of 600 - 1200, so as to obtain a wash liquor which comprises 1 .3 to 0.2 g/l of non-soap surfactant, and (C) washing fabrics with the wash liquor so formed. In typical use conditions this would involve supplying the composition to a washing machine that may hold up to 15 litres of water for the dilution step.
According to the method aspect, a dilution step preferably provides a wash liquor which comprises 3 to 20 g/ wash of non-soap surfactant. A preferred method provides at least 3.5 g/wash especially at least 4g/wash and more preferably at least 5 g/wash. Preferred methods also provide up to 19g/wash, especially up to 18g/wash, preferably using a detergent composition at a dose level of at least 13ml_ and preferably at least 14ml_.
Preferably dose volumes are up to 25ml, especially no more than 24.5ml. A dilution step also preferably provides a polymer system in an amount corresponding to 0.6 to 9 g/wash, preferably 0.8 to 4 and more preferably 1 to 3 g/wash.
The polymer system is also preferably provided in an amount corresponding to 0.04 to 0.60g/L, preferably 0.05 to 0.3g/L, preferably 0.06 to 0.2g/L, calculated on the basis of a washing machine that can accommodate about 15 litres of water for the initial dilution step.
Furthermore, the dilution step preferably provides a wash liquor which provides 3.6 to 20 g/ wash in total of functional ingredients comprising non-soap surfactant and polymer system, preferably 4 to 15 g/wash and especially 5 to 12g/wash. Conveniently the dilution step provides 0.2 to 1.4g/l in total of functional ingredients made up of non-soap surfactant and polymer system, based on a dilution step with 15 litres of water.
Preferred embodiments of the various aspects of the invention may include combinations of one or more of the following features. A pourable liquid detergent composition wherein the surfactant system (a) comprises nonionic and anionic surfactant in a ratio by weight in the range of 20:80 to 80:20, preferably in the range of 40:60 to 80:20, more preferably in the range of 40:60 to 70:30.
A pourable liquid detergent composition wherein the surfactant system (a) includes Cio- Ci5 alcohol ethoxylated nonionic surfactant with 2 to 7 EO.
A pourable liquid detergent composition wherein the surfactant system (a) includes less than 20wt % of any alkyl polyethoxylate sulphate anionic surfactant. A pourable liquid detergent composition wherein the surfactant system (a) includes anionic surfactant for which the anion is selected from linear alkyl benzene sulfonate (LAS), primary alkyl sulfate (PAS), alkyl ether sulfate (AES) and mixtures thereof, and is preferably LAS and wherein a counter ion for the anionic surfactant is provided by an inorganic and/or ammoniacal base (e) preferably selected from NaOH, KOH, MEA and TEA; more preferably KOH or MEA.
A pourable liquid detergent composition wherein the polymer system (b) comprises particulate soil removal polymer (bi) and/ or antiredeposition polymer (bii), preferably provided in a total amount of between 1 to 18wt% of the composition, more preferably 2 to 15wt%, especially 3 to 10 wt% and most preferably 5 to 10wt%.
A pourable liquid detergent composition wherein the polymer system (b) comprises a modified polyethyleneimine polymer EPEI as a particulate soil removal polymer (bi) and/or anti-redeposition polymer (bii), especially an ethoxylated polyethyleneimine such as PEI(600) 20 EO.
A pourable liquid detergent composition wherein the polymer system (b) comprises soil release polymer (biii), preferably in an amount of from 1 to 12wt% of the composition, preferably from 2 to 12wt%, especially 2 to 8wt%.
A pourable liquid detergent composition wherein the polymer system (b) comprises polyethylene terephthalate (PET) polyoxyethylene terephthalate (POET) polyester as a soil release polymer (biii) , especially SRN 100 or SRN 170 or SRN 240. A pourable liquid detergent composition wherein the polymer system (b) comprises at least two polymers selected from (bi), (bii) and (biii) and preferably comprises at least one of (bi) or (bii) with at least one of (biii), and further preferably provided in a total amount of at least 7wt% of the composition. A pourable liquid detergent composition wherein the weight ratio of polymer system (b) to surfactant system (a) is in the range of from 0.15:1 to 0.4 :1 , preferably 0.2:1 to 0.4:1 , and more preferably 0.2:1 to 0.3:1.
A pourable liquid detergent composition which has a pH in a range of 5 to 9, preferably 6 to 8, more preferably 6 to 7, and especially 6.2 to 6.8 when measured on dilution of the liquid composition to 1 % using demineralised water.
A pourable liquid detergent composition which contains less than 40wt% and preferably less than 35wt% , and more preferably less than 30wt% in total of added water (c) and solvents and hydrotropes (f).
A pourable liquid detergent composition which contains less than 10wt %, preferably less than 8wt% of additional ingredients (g) including fragrance, enzymes, shading dyes, fluorescer and dye transfer inhibitor and optionally is substantially free of bleach and / or sequestrant.
A pourable liquid detergent composition which contains less than 0.5wt% of any additional inorganic builder materials and / or less than 0.5wt% of any additional organic builder materials.
DETAILED DESCRIPTION OF THE INVENTION
Preferred embodiments of the present invention may include one or more of the following features.
The detergent liquids
The compositions for use in the method of the invention comprise detersive surfactant. The non-soap detersive surfactant makes up at least 30 wt% in total of the liquid composition, preferably it makes up from 35 to 60 wt% and especially from 40 to 55 wt%.
In the method the compositions are used in small doses that require them to be diluted in at least 500 or 600 times their own volume of water to form a main-wash liquor comprising up to 20g non-soap surfactant. Based on an initial dilution of 15L this corresponds to 1.3 g/l non-soap surfactant.
They may be concentrated compositions designed for front loading automatic washing machines (which typically accommodate about 15L in a wash load and use about 50L of water in a wash cycle), hand washing or top loading automatic washing machines. In hand washing less water may be used and in top loading automatic washing machines a higher amount of water would normally be used than for a front loading automatic machine. The dose of detergent liquid could be adjusted accordingly to give appropriate wash liquor concentrations. Within this context it is preferred that the dose of liquid (especially if it is in unit dose form) is no more than 24.5ml. Surfactants
Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor. Anionic, or blends of anionic and nonionic, surfactants are a preferred feature of the present invention. The amount of anionic surfactant is preferably at least 5 wt% of the composition. Preferably, anionic surfactants form at least 20wt% and/ or up to 60wt% of the non-soap surfactant (a).
Anionic Surfactants
Preferred anionic surfactants have an anion selected from linear alkyl benzene sulfonate (LAS), primary alkyl sulfate (PAS), alkyl ether sulfate (AES) and mixtures thereof.
Preferred alkyl sulphonates are alkylbenzene sulphonates, particularly linear
alkylbenzene sulphonates (LAS) having an alkyl chain length of Ce-Cis. The counter ion for anionic surfactants is generally an alkali metal (such sodium) or an ammoniacal counterion (such as MEA, TEA). Suitable anionic surfactant materials are available in the marketplace as the 'Genapol'™ range from Clariant. Preferred linear alkyl benzene sulphonate surfactants are Detal LAS with an alkyl chain length of from 8 to 15, more preferably 12 to 14. LAS is normally formulated into compositions in acid, i.e., HLAS form and then at least partially neutralized in-situ. Other common anionic surfactants are generally provided in pre-neutralised form.
The present compositions also contain base (e) which may provide a counterion for any anionic surfactant, together with performing pH adjustment. Typically a base provides a counterion selected from Na+, K+ and ammoniacal ions. Suitable bases include potassium hydroxide, sodium hydroxide, monoethanolamine, diethanolamine and triethanolammine. Most preferred bases include potassium hydroxide and
monoethanolamine. Mixtures of bases may be employed.
The composition may optionally comprise an alkyl polyethoxylate sulphate anionic surfactant of the formula (I):
where R is an alkyl chain having from 10 to 22 carbon atoms, especially 12 to 16 carbon atoms and is saturated or unsaturated, M is a cation which makes the compound water- soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15, especially 1 to 3. An example is the anionic surfactant sodium lauryl ether sulphate (SLES) which is the sodium salt of lauryl ether sulphonic acid in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3 moles of ethylene oxide per mole.
Typically the non-soap surfactant system (a) will contain less than 20wt% of any alkyl polyethoxylate sulfate anionic surfactants.
Some alkyl sulphate surfactant (PAS) may be used, especially the non-ethoxylated C12-15 primary and secondary alkyl sulphates. An example material, commercially available from Cognis, is Sulphopon 1214G.
Nonionic Surfactants
Nonionic surfactants include primary and secondary alcohol ethoxylates, especially Cs- C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used.
When included therein the composition may contain from 0.2 wt% to 40 wt%, preferably 1 wt% to 35 wt%, more preferably 5 to 30 wt% of a nonionic surfactant, such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("glucamides").
Nonionic surfactants that may preferably be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the Clods primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
Preferred surfactant systems (a) comprise nonionic and anionic surfactant in a weight ratio in the range of 40:60 to 80:20 and more preferably in a range of 40:60 to 70:30.
Such combinations of nonionic and anionic surfactant in particular have been found to be associated with good physical characteristics.
Amine Oxide Surfactants
The surfactant system of the composition may contain an amine oxide of the formula (2):
R1 N(0)(CH2 R2)2 (2)
In which R1 is a long chain moiety and each CH2R2 is a short chain moiety. R2 is preferably selected from hydrogen, methyl and -CH2OH. In general R1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R1 is a primary alkyl moiety having chain length of from about 8 to about 18 and R2 is H. These amine oxides are illustrated by Ci2-i4 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
Example amine oxide materials are Lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO, commercially available from Hunstman under the trade name Empigen® OB. Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl
Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
Preferably the compositions contain less than 10wt%, more preferably less than 5wt% amine oxide surfactant.
Zwitterionic Surfactants
Some zwitterionic surfactant, such as sulphobetaine, may be present. A preferred zwitterionic material is a betaine available from Huntsman under the name Empigen® BB.
Preferably the compositions contain less than 10wt%, more preferably less than 5wt% zwitterionic surfactant.
Cationic Surfactants
Cationic surfactants are preferably substantially absent.
A particularly preferred surfactant system is provided by linear alkyl benzene sulfonate (LAS) and C10-C15 alcohol ethoxylated nonionic surfactant with 2 to 7 EO.
The polymer system
The compositions contain (b) 5 to 35wt% in total of a polymer system which comprises at least one of the following (bi) to (biii): (bi) one or more particulate soil removal polymer(s) and/or
(bii) one or more anti-redeposition polymer(s) and/or
(biii) one or more soil release polymer(s).
The inclusion of such a polymer system results in enhanced weight efficiency for the compositions. In particular it has been found that such a polymer system contributes to the good dissolution characteristics of the compositions and allows for a reduction in the amount of other non-functional components and solvents required in order to achieve acceptable dissolution. Example compositions may preferably contain up to 25wt%, more preferably up to 20wt% and especially up to 15wt% of the polymer system. Preferably the compositions contain at least 5wt%, preferably at least 6wt% and more preferably at least 7wt% of the polymer system. Preferred embodiments employ an ethoxylated polyethylene imine polymer (EPEI) which may assist with particulate soil removal and/or perform an anti-redeposition function. Preferably the EPEI is nonionic. That means it does not have any quaternary nitrogens, or nitrogen oxides or any ionic species other than possible pH affected protonation of nitrogens.
Polyethylene imines (PEIs, especially modified PEIs) are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific methods for preparing these polyamine backbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5, 1939; U.S. Pat. No. 3,033,746, Mayle et al., issued May 8, 1962; U.S. Pat. No. 2,208,095, Esselmann et al., issued Jul. 16, 1940; U.S. Pat. No. 2,806,839, Crowther, issued Sep. 17, 1957; U.S. Pat. No. 2,553,696, Wilson, issued May 21 , 1951 and WO2006/086492 (BASF).
Preferably, the EPEI comprises a polyethyleneimine backbone wherein the modification of the polyethyleneimine backbone is intended to leave the polymer without
quaternisation. Such nonionic EPEI may be represented as PEI(X)YEO where X represents the molecular weight of the unmodified PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine backbone. The ethoxylation number Y may range from 9 to 40 ethoxy moieties per modification, preferably it is in the range of 16 to 26, most preferably 18 to 22. X is selected to be from about 300 to about 10000 weight average molecular weight and is preferably about 600.
A preferred example EPEI is PEI (600) 20EO.
If present, the polymer (bi) and / or (bii), such as ethoxylated polyethyleneimine polymer (EPEI), may typically be included in the composition at a level of between 0.01 and 20 wt%, and preferably at a level of at least 1wt% and/or less than 18 wt%, more preferably at a level of from 2wt% and/or up to 15wt%. Particularly preferred compositions contain 3wt% to 10wt% and especially 5 to 10 wt% or 4 to 10wt% EPEI. A ratio of non-soap surfactant to EPEI may preferably be from 2:1 to 7:1 , preferably from 3:1 to 6:1 , or even to 3:1 to 5:1 .
Soil Release Polymer
The polymer system of the composition preferably comprises at least some soil release polymer for oily soil removal, especially from polyester. Soil release polymers improve the main wash performance of the compositions when used in the low in wash surfactant process of the present invention.
One preferred class of polymer is the fabric-substantive polymers comprising at least one of (i) saccharide or (ii) dicarboxylic acid and polyol monomer units. Typically these have soil release properties and while they can have a primary detergency effect they generally assist in subsequent cleaning. Preferably these should be present at a level of at least 2% wt preferably at least 3 wt% of the composition.
If present, the soil release polymer(s) (biii) will generally comprise up to 12.0 wt%, of the detergent composition, preferably up to 9 or 10 wt%. Preferably they are used in an
amount of at least 1 or perhaps 2 wt%. Most preferably they are used in an amount of 1 to 9wt%, more preferably 2wt% to 9wt%, especially 2wt% to 8 wt%.
Generally the soil release polymers for polyester will comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols).
The polymeric soil release agents useful herein especially include those soil release agents having:
(a) one or more nonionic hydrophilic components consisting essentially of:
(i) polyoxyethylene segments with a degree of polymerization of at least 2, or
(ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophilic segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or
(iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophilic component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fibre surfaces upon deposit of the soil release agent on such surface, said hydrophilic segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or
(b) one or more hydrophobic components comprising:
(i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobic components also comprise oxyethylene terephthalate, the ratio of
oxyethylene terephthalate: C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4 -C6 alkylene or oxy C4 -C6 alkylene segments, or mixtures therein,
(iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) Ci -C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of Ci -C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose
derivatives are amphiphilic, whereby they have a sufficient level of Ci -C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fibre surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fibre surface, to increase fibre surface hydrophilicity, or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4 -C6 alkylene hydrophobic segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3 S(CH2)n OCH2 CH2 0-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Pat. No. 4,721 ,580, issued Jan. 26, 1988 to Gosselink.
Soil release agents characterized by polyvinyl ester) hydrophobic segments include graft copolymers of polyvinyl ester), e.g., Ci -C6 vinyl esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published Apr. 22, 1987 by Kud, et al.
Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975.
Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10 to 15 wt% of ethylene terephthalate units together with 90 to 80 wt% weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulphonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Pat. No. 4,968,451 , issued Nov. 6, 1990 to J.J. Scheibel and E. P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Pat. No. 4,71 1 ,730, issued Dec. 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Pat. No. 4,721 ,580, issued Jan. 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.
Preferred polymeric soil release agents also include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31 , 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulphonate. Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline- reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
Suitable soil release polymers are described in WO 2008095626 (Clariant); WO
2006133867 (Clariant); WO 2006133868 (Clariant); WO 2005097959 (Clariant); WO 9858044 (Clariant); WO 2000004120 (Rhodia Chimie); US 6242404 (Rhodia Inc); WO 2001023515 (Rhodia Inc); WO 9941346 (Rhodia Chim); WO 9815346 (Rhodia Inc); WO 9741 197 (BASF); EP 728795 (BASF); US 5008032 (BASF); WO 2002077063 (BASF); EP 483606 ( BASF); EP 442101 (BASF); WO 9820092 (Proctor & Gamble); EP 201 124 (Proctor & Gamble); EP 199403 (Proctor & Gamble); DE 2527793 (Proctor & Gamble); WO 9919429 (Proctor & Gamble); WO 9859030 (Proctor & Gamble); US 5834412 (Proctor & Gamble); WO 9742285 (Proctor & Gamble); WO 9703162 (Proctor & Gamble); WO 9502030 (Proctor & Gamble); WO 9502028 (Proctor & Gamble); EP 357280 (Proctor & Gamble); US 41 16885 (Proctor & Gamble); WO 9532232 (Henkel); WO 9532232 (Henkel); WO 9616150 (Henkel); WO 9518207 (Henkel); EP 1099748 (Henkel); FR
2619393 (Colgate Palmolive); DE 341 1941 (Colgate Palmolive); DE 3410810 (Colgate Palmolive); WO 2002018474 (RWE-DEA MINERALOEL & CHEM AG; SASOL
GERMANY GMBH); EP 743358 (Textil Color AG); PL 148326 (Instytut Ciezkiej Syntezy Organicznej "Blachownia", Pol.); JP 2001 181692 (Lion Corp); JP 1 1 193397 A (Lion Corp); RO 1 14357 (S.C. "Prod Cresus" S.A., Bacau, Rom.); and US 71 19056 (Sasol).
The most preferred soil release polymers are the water soluble/miscible or dispersible polyesters such as: linear polyesters sold under the Repel-O-Tex brand by Rhodia (Gerol), or the Texcare brand by Clariant, especially Texcare SRN100 and SRN170, and heavily branched polyesters such as those available from Sasol and described in US 71 19056. The polyesters are preferably nonionic and comprise a mid block of spaced apart terephthalate repeat units and at least one end block based on polyethylene glycol with a lower alkyl or hydrogen termination. Example soil release polymers may also be of the type E-M-L-E, where the ester midblock M is connected to generally hydrophilic end blocks E, each comprising capped oligomers of polyethylene glycol, the linking moiety L is of the form B-Ar-B, where B is a urethane, amide or ester moiety. Such soil release polymers are described in
WO2012/104159.
Particularly preferred polymer systems (bi), (bii) and (biii) are combinations of relatively high levels of EPEI, particularly greater than 2.5 wt% based on the composition, with soil release polymers, and preferably wherein the soil release polymer (biii) comprises a polyethylene terephthalate (PET) polyoxyethylene terephthalate (POET) polyester.
The polymer system (b) may typically be present in an amount such that the ratio of polymer system (b) to surfactant system (a) is in a range of 0.15:1 to 0.4:1 , preferably 0.2:1 to 0.4:1 and more preferably 0.2:1 to 0.3:1 . Water
The present compositions are intended to be highly weight efficient and as such contain relatively low levels of water, namely up to (no more than)12wt% added water which is listed as component (c). Preferred embodiments contain up to 10wt% added water. The amount of water will vary in dependence upon the dose volume required. The present
invention permits the use of very low dose volumes such as 25ml or lower, including 15 to 20ml. Dose volumes of 20ml and below preferably contain less than 10wt% added water.
The compositions may also contain water provided as a component of a raw material. Preferably the total water content of the composition (as provided by the raw materials and as added water) is less than 20wt%, preferably less than 15wt% and more preferably less than 12wt%.
Fatty acid/Soap
The compositions comprise (d) up to 10wt% total fatty acid and/or soap, preferably up to 8wt% and most preferably up to 5 or 6wt% fatty acid. Typically a composition may contain at least 0.1wt% fatty acid and preferably at least 1wt%.
Preferred example fatty acids contain 8 to 24 carbon atoms, preferably in a straight chain configuration, saturated or unsaturated. Particularly preferred fatty acids include those where the weighted average number of carbons in the alkyl/alkenyl chains is from 8 to 24, more preferably 10 to 22, most preferably from 12 to 18. Suitably fatty acids include linear and branched stearic, oleic, lauric, linoleic and tallow acids and mixtures thereof. Particularly preferred blends of fatty acids that are commercially available include:
hydrogenated topped palm kernel fatty acid, and coconut fatty acid saturated fatty acids are preferred. The fatty acid can act as a buffer in addition to preforming a builder and/or as an antifoam. Preferred fatty acids form part of a buffer system that provides buffering in a pH range of 5 to 9, preferably 6 to 8, more preferably 6 to 7 and especially 6.2 to 6.8. Preferably the present detergent compositions have a pH in those ranges when measured on dilution of the liquid composition to 1 % using demineralised water. The most preferred pH range will vary in dependence upon the polymer system; soil release polymers in particular can have reduced stability under certain conditions of pH. Base
As described above in relation to the anionic surfactant, the compositions contain from 1 to 15wt%, preferably from 1 to 10wt% in total of base which may provide a counterion for any anionic surfactant and perform a pH adjustment function. Suitable bases include potassium hydroxide, sodium hydroxide, monoethanolamine, diethanolamine and
triethanolammine. Most preferred bases include potassium hydroxide and monoethanolamine. Mixtures of bases may be employed.
Solvent and hydrotropes
As the present detergent compositions are intended to be highly weight efficient it is proposed that they contain less than 40wt%, preferably less than 35wt%, more preferably less than 30wt% and especially less than 20wt% of any solvents and hydrotropes.
Solvents and hydrotropes may be substantially absent or, if present they may be included in an amount of at least 0.5wt%, optionally at least 1wt% and conveniently at least 5 wt%. Generally the solvents are "non-amino functional".
In this context, "non-amino functional solvent" refers to any solvent that does not contain amino functional groups. It includes non-surfactant solvents such as C1-C5 alcohols (such as ethanol), C2-C6 diols (such as monopropylene glycol and dipropylene glycol) and C3-C9 triols (such as glycerol). In preferred embodiments the solvents are optionally selected from one or more of glycerol, monopropylene glycol (MPG) and ethanol.
The level of such solvents including non-amino functional solvents will vary in
dependence upon the dose volumes required. The present invention permits dose volumes of 20ml and lower. A dose volume of 20ml (or lower) will preferably contain less than 35wt% and more preferably less than 30wt% of solvents and hydrotropes. Amino- functional materials are not included in the category of solvents as they would be classified by the skilled reader as a base for component (e). In the present compositions the combined total amount of added water and solvents is preferably less than 60wt%, preferably less than 55wt%, more preferably less than 50wt% and especially less than 45wt%. For example a dose volume of 20ml (or lower) may preferably contain less than 45wt% added water and solvents Additional ingredients up to 100%
The compositions may contain additional ingredients such a fragrance, enzymes, shading dyes, fluorescer, colorants, pearlisers and/or opacifiers, and dye transfer inhibitors.
Typically such additional ingredients will be present in a total amount of less than 10wt%, more preferably less than 9wt% and especially less than 8wt%.
Example additional ingredients may be as follows. Enzymes
The detergent composition may comprise an effective amount of at least one enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase. Advantageously it comprises at least 2 of this group of enzymes, more advantageously at least 3 and most advantageously at least 4 of the enzymes from this group. Protease
Suitable proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included. The protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease. Preferred commercially available protease enzymes include Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™,
Everlase™, Polarzyme™, and Kannase™, (Novozymes A S), Maxatase™, Maxacal™, Maxapem™, Properase™, Purafect™, Purafect OxP™, FN2™, and FN3™ (Genencor International Inc.).
Amylase Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin.
Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. lichen iform is, described in more detail in GB 1 ,296,839, or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060. Commercially available amylases are Duramyl™,
Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™ and BAN™ (Novozymes A/S), Rapidase™ and Purastar™ (from Genencor International Inc.).
Pectate Lyase
Pectate lyases (also called polygalacturonate lyases): Examples of pectate lyases include pectate lyases that have been cloned from different bacterial genera for example Erwinia, Pseudomonas, Klebsiella and Xanthomonas, as well as from Bacillus subtilis
(Nasser et al. (1993) FEBS Letts. 335:319-326) and Bacillus sp. YA-14 (Kim et al. (1994) Biosci. Biotech. Biochem. 58:947-949). Purification of pectate lyases with maximum activity in the pH range of 8-10 produced by Bacillus pumilus (Dave and Vaughn (1971 ) J.
Bacteriol. 108:166-174), B. polymyxa (Nagel and Vaughn (1961 ) Arch. Biochem. Biophys. 93:344-352), B. stearothermophilus (Karbassi and Vaughn (1980) Can. J. Microbiol.
26:377-384), Bacillus sp. (Hasegawa and Nagel (1966) J. Food Sci. 31 :838-845) and Bacillus sp. RK9 (Kelly and Fogarty (1978) Can. J. Microbiol. 24:1 164-1 172) have also been described. Any of the above, as well as divalent cation-independent and/or thermostable pectate lyases, may be used in practicing the invention. In preferred embodiments, the pectate lyase comprises the pectate lyase disclosed in Heffron et al., (1995) Mol. Plant-Microbe Interact. 8: 331-334 and Henrissat et al., (1995) Plant Physiol. 107: 963-976. Specifically contemplated pectate lyases are disclosed in WO 99/27083 and WO 99/27084. Other specifically contemplated pectate lyases (derived from Bacillus licheniformis) are disclosed in US patent no. 6,284,524. Specifically contemplated pectate lyase variants are disclosed in WO 02/006442, especially the variants disclosed in the Examples in WO 02/006442.
Examples of commercially available alkaline pectate lyases include BIOPREP™ and SCOURZYME™ L from Novozymes A/S, Denmark.
Mannanase
Suitable examples of mannanases (EC 3.2.1.78) include mannanases of bacterial and fungal origin. In a specific embodiment the mannanase is derived from a strain of the filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus (WO 94/25576). WO 93/24622 discloses a mannanase isolated from
Trichoderma reseei. Mannanases have also been isolated from several bacteria, including Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 1 1 , pp. 3505-3510 (1990) describes a beta-mannanase derived from Bacillus stearothermophilus. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551- 555 (1994) describes a beta-mannanase derived from Bacillus subtilis. JP-A-03047076 discloses a beta-mannanase derived from Bacillus sp. JP-A-63056289 describes the production of an alkaline, thermostable beta-mannanase. JP-A-63036775 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta- mannosidase. JP-A-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001 . A purified mannanase from Bacillus amyloliquefaciens is disclosed in WO 97/1 1 164. WO 91/18974 describes a hemicellulase for example a glucanase, xylanase or mannanase active. Contemplated are the alkaline family 5 and 26
mannanases derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus
halodurans, Bacillus clausii, Bacillus sp., and Humicola insolens disclosed in WO
99/64619. Especially contemplated are the Bacillus sp. mannanases concerned in the Examples in WO 99/64619.
Examples of commercially available mannanases include Mannaway™ available from Novozymes A/S Denmark.
Cellulase
Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691 ,178, US 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307.
Commercially available cellulases include Celluzyme™, Carezyme™, Endolase™, Renozyme™ (Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation).
Peroxidase/oxidase
Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin.
Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257.
Commercially available peroxidases include Guardzyme™ and Novozym™ 51004 (Novozymes A/S).
Lipase
Preferred lipase enzymes include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola, more preferably ones which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginose, most preferably strain DSM 4109. The amount in the composition is higher than typically found in liquid detergents. This can be seen by the ratio of non- soap surfactant to lipase enzyme, in particular. A particularly preferred lipase enzyme is available under the trademark Lipoclean™ from Novozymes.
Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from
Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO
96/13580, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1 ,372,034), P. fluorescens,
Pseudomonas sp. strain SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a Bacillus lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1 131 , 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422). As noted above the preferred ones have a high degree of homology with the wild-type lipase derived from Humicola lanuginose.
Other examples are lipase variants for example those described in WO 92/05249, WO 94/01541 , EP 407 225, EP 260 105, WO 95/35381 , WO 96/00292,
WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202.
Preferred commercially available lipase enzymes include Lipolase™ and Lipolase
Ultra™, Lipex™ and Lipoclean™ (Novozymes A S).
Phospholipase
As used herein, the term phospholipase is an enzyme which has activity towards phospholipids. Phospholipids, for example lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1 ) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol. Phospholipases are enzymes which participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases Ai and A2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid respectively.
Cutinase
The compositions may contain a cutinase. classified in EC 3.1.1.74. The cutinase used in the invention may be of any origin. Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin. Enzyme Stabilizers:
Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol for example propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative for example 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
Lignin compounds:
When a lipase enzyme is included a lignin compound may be used in the composition in an amount that can be optimised by trial and error. Lignin is a component of all vascular plants, found mostly between cellular structures but also within the cells and in the cell walls.
Preferably the lignin compound comprises a lignin polymer and more preferably it is a modified lignin polymer. A modified lignin polymer as used herein is lignin that has been subjected to a chemical reaction to attach chemical moieties to the lignin covalently. The attached chemical moieties are preferably randomly substituted.
Preferred modified lignin polymers are lignins that have been substituted with anionic, cationic or alkoxy groups, or mixtures thereof. Preferably the substitution occurs on the aliphatic portion of the lignin and is random. Preferably the modified lignin polymer is substituted with an anionic group, and preferably it is a sulfonate. A preferred cationic group is a quaternary amine. Preferred alkoxy groups are polyalkylene oxide chains having repeat units of alkoxy moieties in the range from 5 to 30, most preferably ethoxy. Preferably the modified lignin sulfonate is substituted with anionic or alkoxy groups.
Modified lignin polymers are discussed in WO/2010/033743. Most preferably the modified lignin polymer is lignin sulfonate (lignosulfonate). Lignin sulfonate may be obtained by the Howard process.
Exemplary lignin sulfonate may be obtained from a variety of sources including hardwoods, softwoods and recycling or effluent streams. The lignin sulfonate may be utilized in crude or pure forms, e.g., in an "as is" or whole liquor condition, or in a purified lignin sulfonate form from which or in which sugars and other saccharide constituents have been removed or destroyed, or from which or in which inorganic constituents have been partially or fully eliminated. The lignin sulfonate may be utilized in salt forms including calcium lignin sulfonate, sodium lignin sulfonate, ammonium lignin sulfonate, potassium lignin sulfonate, magnesium lignin sulfonate and mixtures or blends thereof. The lignin sulfonate preferably has a weight average molecular weight of from 2000 to 100000. Their basic structural unit is phenylpropane. The degree of sulphonation is preferably from 0.3 and 1 .0 sulfate groups per phenylpropane unit.
Lignin sulfonates are available from a number of suppliers including Borregaard
LignoTech, Georgia-Pacific Corporation, Lenzing AG and Tembec Inc.
Lignin sulphonates are discussed in Lauten, R. A., Myrvold, B. O. and Gundersen, S. A. (2010) New Developments in the Commercial Utilization of Lignosulphonates, in
Surfactants from Renewable Resources (eds M. Kjellin and I. Johansson), John Wiley & Sons, Ltd, Chichester, UK.
Fluorescent Agents:
It may be advantageous to include fluorescer in the compositions. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.5 wt %.
Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1 ,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5-triazin-2- yl)]amino}stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1 ,3,5- triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
Perfume
When the composition is used at very low levels of product dosage, it is advantageous to ensure that perfume is employed efficiently.
A particularly preferred way of ensuring that perfume is employed efficiently is to use an encapsulated perfume. Use of a perfume that is encapsulated reduces the amount of perfume vapour that is produced by the composition before it is diluted. This is important when the perfume concentration is increased to allow the amount of perfume per wash to be kept at a reasonably high level.
It is even more preferable that the perfume is not only encapsulated but also that the encapsulated perfume is provided with a deposition aid to increase the efficiency of perfume deposition and retention on fabrics. The deposition aid is preferably attached to the encapsulate by means of a covalent bond, entanglement or strong adsorption, preferably by a covalent bond or entanglement.
Shading dyes
Shading dye can be used to improve the performance of the compositions. Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics. A further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.
Suitable and preferred classes of dyes are discussed below.
Direct Dyes:
Direct dyes (otherwise known as substantive dyes) are the class of water soluble dyes which have an affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
Preferably bis-azo or tris-azo dyes are used.
Most preferably, the direct dye is a direct violet of the following structures:
or
Ri is selected from: hydrogen and Ci-C4-alkyl, preferably hydrogen;
R2 is selected from: hydrogen, Ci-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
R4 and R5 are independently selected from: hydrogen and Ci-C4-alkyl, preferably hydrogen or methyl;
X and Y are independently selected from: hydrogen, Ci-C4-alkyl and Ci-C4-alkoxy;
preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.
Preferred dyes are direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , and direct violet 99. Bis-azo copper containing dyes for example direct violet 66 may be used. The benzidene based dyes are less preferred.
Preferably the direct dye is present at 0.000001 to 1 wt% more preferably 0.00001 wt% to 0.0010 wt% of the composition.
In another embodiment the direct dye may be covalently linked to the photo-bleach, for example as described in WO2006/024612.
Acid dyes:
Cotton substantive acid dyes give benefits to cotton containing garments. Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes are:
(i) azine dyes, wherein the dye is of the following core structure:
wherein Ra, Rb, Rc and Rd are selected from: H, a branched or linear C1 to C7-alkyl chain, benzyl a phenyl, and a naphthyl; the dye is substituted with at least one SO3" or -COO" group;
the B ring does not carry a negatively charged group or salt thereof; and the A ring may further substituted to form a naphthyl; the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, CI, Br, I , F, and N02.
Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
Preferably the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
Hydrophobic dyes:
The composition may comprise one or more hydrophobic dyes selected from
benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores. Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
Preferably the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
Basic dyes:
Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International. Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71 , basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 .
Reactive dyes:
Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton. Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species for example a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
Dye conjugates:
Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces. Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in WO2006/055787.
Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , direct violet 99, acid blue 98, acid
violet 50, acid blue 59, acid violet 17, acid black 1 , acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.
Shading dye can be used in the absence of fluorescer, but it is especially preferred to use a shading dye in combination with a fluorescer, for example in order to reduce yellowing due to chemical changes in adsorbed fluorescer. Bleaches
Bleaching components such as halogen bleaches, peroxy acid bleaches and inorganic percompound bleaches, are preferably avoided in the present compositions on the grounds that the compositions preferably exhibit a pH in the range of 5 to 9 and more preferably 6 to 7. Suitably the compositions contain less than 0.5wt% of bleaching component, preferably less than 0.1 wt% and most preferably bleaching components are substantially absent from the compositions. Similarly bleach activators are not required.
Builders and sequestrants
The detergent compositions preferably contain only low levels of organic detergent builder or sequestrant material. Examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other examples are DEQUEST™, organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, for example those sold by BASF under the name SOKALAN™.
If utilized, the organic builder materials may comprise up to 2 wt%, preferably up to 1wt%, more preferably up to 0.5wt% of the composition. Example sequestrants are HEDP (1 -Hydroxyethylidene -1 ,1 ,-diphosphonic acid), for example sold as Dequest 2010, and (Diethylenetriamine penta(methylene phosphonic acid or Heptasodium DTPMP), Dequest® 2066. Preferably the compositions contain less than 1 wt%, more preferably less than 0.5wt% sequestrant. Typically the compositions contain no more than 2 wt%, especially no more than 1 wt% and especially no more than 0.5 wt% of any inorganic builders.
Buffers
The presence of some buffer is preferred for pH control. In the present compositions the fatty acid provides at least some buffering.
External Structurants
The compositions may have their rheology further modified by use of a material or materials that form a structuring network within the composition. Suitable structurants include hydrogenated castor oil, microfibrous cellulose and natural based structurants for example citrus pulp fibre. Citrus pulp fibre is particularly preferred especially if lipase enzyme is included in the composition. Preferably, if utilised, such external structurants are present in an amount of less than 2wt%, preferably less than 1wt%. Visual Cues
The compositions may comprise visual cues of solid material that is not dissolved in the composition. Preferred visual cues are lamellar cues formed from polymer film and possibly comprising functional ingredients that may not be as stable if exposed to the alkaline liquid. Enzymes and bleach catalysts are examples of such ingredients. Also perfume, particularly microencapsulated perfume.
Packaging and dosing
The liquids may supplied in multidose systems or in unit dose systems. In typical use conditions this would involve a dosage of 13ml to 25ml in to a washing machine that may hold 10 to 15 litres of water.
A method of laundering fabric using the present compositions may involve diluting the dose of detergent composition by a factor of 600 to 1200 to obtain a wash liquor which comprises 1.3 to 0.2g/L of non-soap surfactant (based on a volume of water of 15L in the dilution step) and washing fabrics with the wash liquor so formed.
According to the method aspect, a dilution step preferably provides a wash liquor which comprises 3 to 20 g/ wash of non-soap surfactant. A preferred method provides at least 3.5 g/wash especially at least 4g/wash and more preferably at least 5 g/wash. Preferred methods also provide up to 19g/wash, especially up to 18g/wash. Such g/wash calculations are typically based on a 15L wash volume, using a detergent composition at a dose level of at least 13ml_ and preferably at least 14ml_.
Preferably dose volumes are up to 25ml, especially no more than 24.5ml. A dilution step also preferably provides a polymer system in an amount corresponding to 0.6 to 9 g/wash, preferably 0.8 to 4 and more preferably 1 to 3 g/wash.
In the context of the present invention, pourable means that the composition can be poured and as such it preferably has a shear viscosity (at 25 °C) of below 2 Pas at a shear rate of 21 s"1 . Preferred viscosities are in the range of 0.1 to 1.0 Pas.
The compositions are preferably isotropic and generally exhibit Newtonian flow characteristics. The invention will now be further described with reference to the following non-limiting examples.
EXAMPLES
Examples 1 to 4 and Comparative Examples 1 to 5
Concentrated laundry detergent compositions were prepared using relatively high levels of surfactant (at about 48 wt%) in combination with various levels of added water and various levels of a polymer system (containing EPEI and SRN 100 soil release polymer). The tables show the amounts by weight of active materials; water / solvent from raw materials will bring the totals to 100%.
MPG is monopropylene glycol,
MEA is monoethanolamine,
Neodol 25_7 is a C12-C15 alcohol ethoxylate 7EO nonionic ex Shell Chemical,
LAS acid is C12-C14 linear alkylbenzene sulphonic acid,
Prifac 5908 is a saturated lauric fatty acid,
EPEI is an ethoxylated polyethylene imine polymer PEI(600)20EO
Texcare SRN 100 is a soil release polymer
Tinopal CBS-CL is a fluorescent agent The concentrated laundry detergent compositions illustrate potential 17ml dose formulations. All the examples and comparative examples contain less than 30wt% in total of added water and solvent/hydrotrope (MPG). Also all the examples and
comparative examples provide about 8.2 g / wash non-soap surfactant. Examples 1 to 4 contain amounts of added water ranging from 0 wt% to 1 1.5 wt%. The comparative examples show amounts of added water ranging from 16.5 wt% to 26.3 wt%.
Table 1 Examples 1 - 4
Examples Ex 1 Ex 2 Ex 3 Ex 4
Water 1 1 .5 6.5 7.3 0.0
MPG 10.0 15.0 21 .5 21 .5
MEA 5.0 5.0 5.0 5.0
Neodol 25_7 24.1 24.1 24.1 24.1
LAS acid 24.1 24.1 24.1 24.1
Prifac 5908 4.3 4.3 4.3 4.3
EPEI 6.9 6.9 3.1 6.9
Texcare SRN 100 4.4 4.4 1 .9 4.4
Amylase 1 .3 1 .3 1 .3 1 .3
Protease 2.7 2.7 2.7 2.7
Fragrance 2.8 2.8 2.8 2.8
Table 2 Comparative examples 1 - 5
Tests and Results
The compositions were tested to see if they were lamellar or isotropic by a visual assessment using a microscope. A lamellar sample was regarded as a "fail".
A dissolution test was also performed on each sample in which 1 g was dropped in to 100ml of water to see if the sample dispersed. If it did not disperse it was also regarded as a "fail".
The results are provided in the table 3 below:
Table 3
Sample Number Status
Example 1 Passed
Example 2 Passed
Example 3 Passed
Example 4 Passed
Comparative example 1 Failed
Comparative example 2 Failed
Comparative example 3 Failed
Comparative example 4 Failed
Comparative example 5 Failed
The illustrative examples provide highly weight efficient low viscosity isotropic liquids which exhibit excellent dissolution in a wash liquor. In contrast, the comparative example compositions were either lamellar or showed poor dissolution characteristics. The illustrative examples thus provide concentrated detergent formulations containing high levels of active ingredients, in terms of surfactant and cleaning polymers, which are in a desirable product form of isotropic liquids. These formulations exhibit good dissolution characteristics without the need for high levels of solvent or water to be contained within them and, as a result, the formulations are highly weight efficient.
Claims
1. A pourable liquid detergent composition comprising:
(a) a non-soap surfactant system which comprises at least nonionic or anionic surfactant such that the total content of non-soap surfactant in the composition is at least 30wt%, preferably at least 35wt%;
(b) a polymer system which comprises at least one of the following (bi) to (biii) such that the total content of (bi), (bii) and (biii) in the composition is in the range of 5 to 35wt%:
(bi) one or more particulate soil removal polymer(s) and/or (bii) one or more anti-redeposition polymer(s) and/or
(biii) one or more soil release polymer(s);
(c) up to 12wt% total added water;
(d) from 0.1wt% up to 10wt% total fatty acid/soap;
(e) 1 to 15wt% in total of base, optionally providing one or more counterions for any anionic surfactant;
(f) less than 40wt% in total of any non-amino functional solvents and hydrotropes ; and
(g) additional ingredients up to 100% optionally including fragrance, enzymes, shading dyes, fluorescer and dye transfer inhibitor.
2. A pourable liquid detergent composition according to claim 1 wherein the
surfactant system (a) comprises nonionic and anionic surfactant in a weight ratio in the range of 40:60 to 80:20, more preferably in the range of 40:60 to 70:30.
3. A pourable liquid detergent composition according to any preceding claim wherein the polymer system (b) comprises an ethoxylated polyethyleneimine polymer
EPEI as a particulate soil removal polymer (bi) and/or anti-redeposition polymer (bii), provided in a total amount of between 1 to 18wt% of the composition.
4. A pourable liquid detergent composition according to any preceding claim wherein the polymer system (b) comprises a polyethylene terephthalate (PET) polyoxyethylene terephthalate (POET) polyester as a soil release polymer (biii), provided in a total amount of between 1 to 12wt% of the composition.
5. A pourable liquid detergent composition according to any preceding claim wherein the weight ratio of polymer system (b) to surfactant system (a) is in the range of from 0.15:1 to 0.4 :1 , preferably 0.2:1 to 0.4:1 , and more preferably 0.2:1 to 0.3:1.
6. A pourable liquid detergent composition according to any preceding claim which has a pH in a range of 5 to 9, preferably 6 to 8 when measured on dilution of the liquid composition to 1 % using demineralised water.
7. A pourable liquid detergent composition according to any preceding claim which contains less than 10wt % of additional ingredients (g) including fragrance, enzymes, shading dyes, fluorescer and dye transfer inhibitor and is substantially free of bleach and / or sequestrant.
8. A pourable liquid detergent composition according to any preceding claim which contains less than 0.5wt% of any additional organic builder materials and / or less than 0.5wt% of any additional inorganic builder materials.
9. A pourable liquid detergent composition according to any preceding claim which contains less than 40wt% and preferably less than 35wt% in total of added water (c) and solvents and hydrotropes (f).
10. A pourable liquid detergent composition according to any preceding claim
wherein the non-soap surfactant system (a) includes C10-C15 alcohol ethoxylated nonionic surfactant with 2 to 7 EO.
1 1 . A pourable liquid detergent composition according to any preceding claim
wherein the non-soap surfactant system (a) contains less than 20wt% of any alkylpolyethoxylate sulphate anionic surfactant.
12. A pourable liquid detergent composition according to any preceding claim
wherein the surfactant system (a) includes anionic surfactant for which the anion is selected from linear alkyl benzene sulfonate (LAS), primary alkyl sulfate (PAS), alkyl ether sulfate (AES) and mixtures thereof, and wherein a counter ion for the anionic surfactant is provided by an inorganic and/or ammoniacal base (e) selected from NaOH, KOH, MEA and TEA.
13. A method for the production of a pourable liquid detergent composition as claimed in any preceding claim which method comprises the incorporation of no more than 12wt% added water into a composition comprising (a), (b), (d), (e), (f) and (g).
14. A method of laundering fabric which comprises the steps of
(A) providing a liquid detergent composition as claimed in any one of claims 1 to 12,
(B) diluting a dose of the detergent composition in water by a factor of >500, and preferably by a factor of 600 - 1200, so as to obtain a wash liquor which comprises 3 to 20 g/wash of non-soap surfactant, and
(C) washing fabrics with the wash liquor so formed.
15. A method according to claim 14 which comprises providing less than 25ml, and preferably 15 to 20ml of the liquid detergent composition.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16154263.4 | 2016-02-04 | ||
EP16154263 | 2016-02-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017133879A1 true WO2017133879A1 (en) | 2017-08-10 |
Family
ID=55299396
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2017/050641 WO2017133879A1 (en) | 2016-02-04 | 2017-01-13 | Detergent liquid |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2017133879A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3517597A1 (en) * | 2018-01-25 | 2019-07-31 | The Procter & Gamble Company | Polymer composition |
EP3517596A1 (en) * | 2018-01-25 | 2019-07-31 | The Procter & Gamble Company | Method of making an opaque liquid detergent composition |
CN113481714A (en) * | 2021-06-14 | 2021-10-08 | 山东贝润防水材料有限公司 | Water seepage prevention polyester tire and preparation method thereof |
WO2022033884A1 (en) * | 2020-08-12 | 2022-02-17 | Unilever Ip Holdings B.V. | Laundry detergent composition |
EP3974505A1 (en) * | 2020-09-25 | 2022-03-30 | Henkel AG & Co. KGaA | Concentrated flowable detergent composition with improved properties |
Citations (115)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2182306A (en) | 1935-05-10 | 1939-12-05 | Ig Farbenindustrie Ag | Polymerization of ethylene imines |
US2208095A (en) | 1937-01-05 | 1940-07-16 | Ig Farbenindustrie Ag | Process of producing insoluble condensation products containing sulphur and nitrogen |
US2553696A (en) | 1944-01-12 | 1951-05-22 | Union Carbide & Carbon Corp | Method for making water-soluble polymers of lower alkylene imines |
US2806839A (en) | 1953-02-24 | 1957-09-17 | Arnold Hoffman & Co Inc | Preparation of polyimines from 2-oxazolidone |
US3033746A (en) | 1958-06-19 | 1962-05-08 | Dow Chemical Co | Polyalkyleneimine, phenol germicides |
GB1296839A (en) | 1969-05-29 | 1972-11-22 | ||
GB1372034A (en) | 1970-12-31 | 1974-10-30 | Unilever Ltd | Detergent compositions |
US3893929A (en) | 1971-10-28 | 1975-07-08 | Procter & Gamble | Compositions for imparting renewable soil release finish to polyester-containing fabrics |
DE2527793A1 (en) | 1974-06-25 | 1976-01-15 | Procter & Gamble | LIQUID DETERGENT PREPARATIONS WITH DIRT-REPELLENT PROPERTIES |
US3959230A (en) | 1974-06-25 | 1976-05-25 | The Procter & Gamble Company | Polyethylene oxide terephthalate polymers |
US4116885A (en) | 1977-09-23 | 1978-09-26 | The Procter & Gamble Company | Anionic surfactant-containing detergent compositions having soil-release properties |
US4435307A (en) | 1980-04-30 | 1984-03-06 | Novo Industri A/S | Detergent cellulase |
DE3411941A1 (en) | 1983-04-04 | 1984-10-04 | Colgate-Palmolive Co., New York, N.Y. | LIQUID DETERGENT |
DE3410810A1 (en) | 1983-03-29 | 1984-10-04 | Colgate-Palmolive Co., New York, N.Y. | PARTICULATE TEXTILE DETERGENT |
EP0199403A2 (en) | 1985-04-15 | 1986-10-29 | The Procter & Gamble Company | Stable liquid detergent compositions |
EP0201124A2 (en) | 1985-05-01 | 1986-11-12 | Procter & Gamble European Technical Center | Cleaning compositions |
EP0218272A1 (en) | 1985-08-09 | 1987-04-15 | Gist-Brocades N.V. | Novel lipolytic enzymes and their use in detergent compositions |
EP0219048A2 (en) | 1985-10-12 | 1987-04-22 | BASF Aktiengesellschaft | Use of graft copolymers of polyalkylenoxides and vinyl acetate as anti-redeposition agents in the washing and post-treatment of textiles containing synthetic fibres |
US4702857A (en) | 1984-12-21 | 1987-10-27 | The Procter & Gamble Company | Block polyesters and like compounds useful as soil release agents in detergent compositions |
US4711730A (en) | 1986-04-15 | 1987-12-08 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
US4721580A (en) | 1987-01-07 | 1988-01-26 | The Procter & Gamble Company | Anionic end-capped oligomeric esters as soil release agents in detergent compositions |
JPS6336775A (en) | 1986-07-31 | 1988-02-17 | Res Dev Corp Of Japan | Novel alkalophilic strain of bacillus genus capable of producing beta-mannanase and beta-mannosidase and use thereof |
EP0258068A2 (en) | 1986-08-29 | 1988-03-02 | Novo Nordisk A/S | Enzymatic detergent additive |
JPS6356289A (en) | 1986-07-30 | 1988-03-10 | Res Dev Corp Of Japan | Beta-mannanase and production thereof |
EP0260105A2 (en) | 1986-09-09 | 1988-03-16 | Genencor, Inc. | Preparation of enzymes having altered activity |
FR2619393A1 (en) | 1987-08-10 | 1989-02-17 | Colgate Palmolive Co | DETERGENT COMPOSITION BASED ON ETHOXYLATE AND A COPOLYMER OF TEREPHTHALATE FACILITATING SOIL DECOLUTION AND METHOD FOR USE THEREOF |
EP0305216A1 (en) | 1987-08-28 | 1989-03-01 | Novo Nordisk A/S | Recombinant Humicola lipase and process for the production of recombinant humicola lipases |
JPS6474992A (en) | 1987-09-16 | 1989-03-20 | Fuji Oil Co Ltd | Dna sequence, plasmid and production of lipase |
EP0331376A2 (en) | 1988-02-28 | 1989-09-06 | Amano Pharmaceutical Co., Ltd. | Recombinant DNA, bacterium of the genus pseudomonas containing it, and process for preparing lipase by using it |
WO1989009259A1 (en) | 1988-03-24 | 1989-10-05 | Novo-Nordisk A/S | A cellulase preparation |
US4877896A (en) | 1987-10-05 | 1989-10-31 | The Procter & Gamble Company | Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles |
PL148326B1 (en) | 1986-07-15 | 1989-10-31 | A softerner for teytile products | |
EP0357280A2 (en) | 1988-08-26 | 1990-03-07 | The Procter & Gamble Company | Soil release agents having allylderived sulfonated end caps |
US4968451A (en) | 1988-08-26 | 1990-11-06 | The Procter & Gamble Company | Soil release agents having allyl-derived sulfonated end caps |
EP0407225A1 (en) | 1989-07-07 | 1991-01-09 | Unilever Plc | Enzymes and enzymatic detergent compositions |
JPH0347076A (en) | 1989-08-25 | 1991-02-28 | Res Dev Corp Of Japan | Beta-mannase and production thereof |
US5008032A (en) | 1988-10-31 | 1991-04-16 | Basf Aktiengesellschaft | Use of partially esterified copolymers in liquid detergents |
EP0442101A1 (en) | 1990-01-19 | 1991-08-21 | BASF Aktiengesellschaft | Polyesters containing nonionic surfactants in a condensed form, their preparation and their use in detergents |
WO1991016422A1 (en) | 1990-04-14 | 1991-10-31 | Kali-Chemie Aktiengesellschaft | Alkaline bacillus lipases, coding dna sequences therefor and bacilli which produce these lipases |
WO1991018974A1 (en) | 1990-05-29 | 1991-12-12 | Chemgen Corporation | HEMICELLULASE ACTIVE AT EXTREMES OF pH AND TEMPERATURE AND THE MEANS FOR THE PRODUCTION THEREOF |
WO1992005249A1 (en) | 1990-09-13 | 1992-04-02 | Novo Nordisk A/S | Lipase variants |
EP0483606A2 (en) | 1990-10-29 | 1992-05-06 | BASF Aktiengesellschaft | Use of polyesters comprising condensed tartaric acid as detergent additive, process for production of the polyesters, and polyesters based upon tartaric acid and tetracarboxylic acids |
WO1992019708A1 (en) | 1991-04-30 | 1992-11-12 | The Procter & Gamble Company | Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme |
WO1992019709A1 (en) | 1991-04-30 | 1992-11-12 | The Procter & Gamble Company | Built liquid detergents with boric-polyol complex to inhibit proteolytic enzyme |
WO1993024622A1 (en) | 1992-05-22 | 1993-12-09 | Alko Ltd. | Mannanase enzymes, genes coding for them, methods for isolating the genes, and methods for bleaching lignocellulosic pulps |
WO1993024618A1 (en) | 1992-06-01 | 1993-12-09 | Novo Nordisk A/S | Peroxidase variants with improved hydrogen peroxide stability |
WO1994001541A1 (en) | 1992-07-06 | 1994-01-20 | Novo Nordisk A/S | C. antarctica lipase and lipase variants |
WO1994025578A1 (en) | 1993-04-27 | 1994-11-10 | Gist-Brocades N.V. | New lipase variants for use in detergent applications |
WO1994025576A1 (en) | 1993-04-30 | 1994-11-10 | Novo Nordisk A/S | An enzyme exhibiting mannanase activity |
WO1995002030A1 (en) | 1993-07-08 | 1995-01-19 | The Procter & Gamble Company | Detergent compositions comprising soil release agents |
WO1995002028A1 (en) | 1993-07-08 | 1995-01-19 | The Procter & Gamble Company | Detergent compositions comprising soil release agents |
WO1995006720A1 (en) | 1993-08-30 | 1995-03-09 | Showa Denko K.K. | Novel lipase, microorganism producing the lipase, process for producing the lipase, and use of the lipase |
WO1995010602A1 (en) | 1993-10-13 | 1995-04-20 | Novo Nordisk A/S | H2o2-stable peroxidase variants |
WO1995014783A1 (en) | 1993-11-24 | 1995-06-01 | Showa Denko K.K. | Lipase gene and variant lipase |
WO1995018207A1 (en) | 1993-12-24 | 1995-07-06 | Henkel Kommanditgesellschaft Auf Aktien | Liquid washing and cleaning agent |
WO1995022615A1 (en) | 1994-02-22 | 1995-08-24 | Novo Nordisk A/S | A method of preparing a variant of a lipolytic enzyme |
WO1995026397A1 (en) | 1994-03-29 | 1995-10-05 | Novo Nordisk A/S | Alkaline bacillus amylase |
WO1995030744A2 (en) | 1994-05-04 | 1995-11-16 | Genencor International Inc. | Lipases with improved surfactant resistance |
WO1995032232A1 (en) | 1994-05-20 | 1995-11-30 | Henkel Kommanditgesellschaft Auf Aktien | Soil release polyesters |
WO1995035381A1 (en) | 1994-06-20 | 1995-12-28 | Unilever N.V. | Modified pseudomonas lipases and their use |
WO1996000292A1 (en) | 1994-06-23 | 1996-01-04 | Unilever N.V. | Modified pseudomonas lipases and their use |
JPH0851975A (en) | 1991-10-09 | 1996-02-27 | Res Dev Corp Of Japan | New beta-mannanase and method for producing the same |
WO1996012012A1 (en) | 1994-10-14 | 1996-04-25 | Solvay S.A. | Lipase, microorganism producing same, method for preparing said lipase and uses thereof |
WO1996013580A1 (en) | 1994-10-26 | 1996-05-09 | Novo Nordisk A/S | An enzyme with lipolytic activity |
WO1996016150A1 (en) | 1994-11-17 | 1996-05-30 | Henkel Kommanditgesellschaft Auf Aktien | Soil-repellent detergent with specific combination of surfactants |
EP0728795A2 (en) | 1995-02-25 | 1996-08-28 | Basf Aktiengesellschaft | Process for preparing finely divided compositions of amphiphilic polymers and polycarboxylates and their use |
WO1996027002A1 (en) | 1995-02-27 | 1996-09-06 | Novo Nordisk A/S | Novel lipase gene and process for the production of lipase with the use of the same |
WO1996029397A1 (en) | 1995-03-17 | 1996-09-26 | Novo Nordisk A/S | Novel endoglucanases |
EP0743358A1 (en) | 1995-05-18 | 1996-11-20 | Textil Color Ag | Composition for washing and cleaning of textile materials |
WO1997003162A1 (en) | 1995-07-08 | 1997-01-30 | The Procter & Gamble Company | Detergent compositions |
WO1997004079A1 (en) | 1995-07-14 | 1997-02-06 | Novo Nordisk A/S | A modified enzyme with lipolytic activity |
WO1997007202A1 (en) | 1995-08-11 | 1997-02-27 | Novo Nordisk A/S | Novel lipolytic enzymes |
WO1997011164A1 (en) | 1995-09-20 | 1997-03-27 | Genencor International, Inc. | Purified mannanase from bacillus amyloliquefaciens and method of preparation |
US5648263A (en) | 1988-03-24 | 1997-07-15 | Novo Nordisk A/S | Methods for reducing the harshness of a cotton-containing fabric |
WO1997041197A1 (en) | 1996-04-25 | 1997-11-06 | Basf Aktiengesellschaft | Detergent components protected against exothermic decomposition by oxidation |
WO1997042285A1 (en) | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Cotton soil release polymers |
WO1998012307A1 (en) | 1996-09-17 | 1998-03-26 | Novo Nordisk A/S | Cellulase variants |
WO1998015346A1 (en) | 1996-10-04 | 1998-04-16 | Rhodia Inc. | Enhancement of soil release with gemini surfactants |
WO1998015257A1 (en) | 1996-10-08 | 1998-04-16 | Novo Nordisk A/S | Diaminobenzoic acid derivatives as dye precursors |
WO1998020092A2 (en) | 1996-11-01 | 1998-05-14 | The Procter & Gamble Company | Laundry detergent compositions comprising soil release polymer |
US5834412A (en) | 1995-12-21 | 1998-11-10 | The Procter & Gamble Company | Soil release polymers with fluorescent whitening properties |
WO1998058044A1 (en) | 1997-06-17 | 1998-12-23 | Clariant Gmbh | Detergent and cleaning agent |
WO1998059030A1 (en) | 1997-06-20 | 1998-12-30 | The Procter & Gamble Company | Soil release polymers with fluorescent whitening properties |
RO114357B1 (en) | 1998-02-26 | 1999-03-30 | Sc Prod Cresus Sa | Anti-soiling composition for textile materials |
WO1999019429A1 (en) | 1997-10-10 | 1999-04-22 | The Procter & Gamble Company | A detergent composition |
WO1999027083A1 (en) | 1997-11-24 | 1999-06-03 | Novo Nordisk A/S | PECTIN DEGRADING ENZYMES FROM $i(BACILLUS LICHENIFORMIS) |
WO1999027084A1 (en) | 1997-11-24 | 1999-06-03 | Novo Nordisk A/S | Novel pectate lyases |
JPH11193397A (en) | 1997-12-26 | 1999-07-21 | Lion Corp | Detergent particle composition and production thereof |
WO1999041346A1 (en) | 1998-02-11 | 1999-08-19 | Rhodia Chimie | Dirt removing detergent compositions |
WO1999064619A2 (en) | 1998-06-10 | 1999-12-16 | Novozymes A/S | Novel mannanases |
WO2000004120A1 (en) | 1998-07-15 | 2000-01-27 | Rhodia Chimie | Terephthalic polyester composition and its use as soil release agent |
WO2000050549A2 (en) | 1999-02-22 | 2000-08-31 | The Procter & Gamble Company | Cleaning compositions containing selected nonionic surfactants |
WO2000060060A2 (en) | 1999-03-31 | 2000-10-12 | Novozymes A/S | Polypeptides having alkaline alpha-amylase activity and nucleic acids encoding same |
WO2001023515A1 (en) | 1999-09-29 | 2001-04-05 | Rhodia Inc. | Novel polymer based cleaning compositions for use in hard surface cleaning and laundry applications |
EP1099748A2 (en) | 1999-11-13 | 2001-05-16 | Henkel Kommanditgesellschaft auf Aktien | Surfactant containing detergent compositions |
JP2001181692A (en) | 1999-12-27 | 2001-07-03 | Lion Corp | Liquid detergent composition for local washing |
US6284524B1 (en) | 1997-11-24 | 2001-09-04 | Novozymes A/S | Pectate lyases |
WO2002006442A2 (en) | 2000-07-19 | 2002-01-24 | Novozymes A/S | Cell-wall degrading enzyme variants |
WO2002018474A1 (en) | 2000-09-02 | 2002-03-07 | Sasol Germany Gmbh | Free-flowing, amphiphilic, non-ionic oligoesters |
US6376446B1 (en) | 1999-01-13 | 2002-04-23 | Melaleuca, Inc | Liquid detergent composition |
WO2002077063A1 (en) | 2001-03-28 | 2002-10-03 | Basf Aktiengesellschaft | Dirt-removing polyesters |
WO2005097959A1 (en) | 2004-04-08 | 2005-10-20 | Clariant Produkte (Deutschland) Gmbh | Detergent and cleaning agents containing dye fixatives and soil-release polymers |
WO2006024612A1 (en) | 2004-08-30 | 2006-03-09 | Ciba Specialty Chemicals Holding Inc. | Shading process |
WO2006055787A1 (en) | 2004-11-19 | 2006-05-26 | The Procter & Gamble Company | Whiteness perception compositions |
WO2006086492A1 (en) | 2005-02-08 | 2006-08-17 | Basf Aktiengesellschaft | Method of making an alkoxylated polyethylenimine product |
WO2006133867A1 (en) | 2005-06-15 | 2006-12-21 | Clariant Produkte (Deutschland) Gmbh | Dishwashing formulations comprising oligoesters |
WO2006133868A1 (en) | 2005-06-15 | 2006-12-21 | Clariant Produkte (Deutschland) Gmbh | Detergents for hard surfaces |
WO2007130567A2 (en) | 2006-05-05 | 2007-11-15 | The Procter & Gamble Company | Compact fluid laundry detergent composition |
WO2008095626A1 (en) | 2007-02-03 | 2008-08-14 | Clariant Finance (Bvi) Limited | Aqueous oligo- and polyester formulations |
WO2009153184A1 (en) | 2008-06-16 | 2009-12-23 | Unilever Plc | Improvements relating to fabric cleaning |
WO2010033743A1 (en) | 2008-09-19 | 2010-03-25 | The Procter & Gamble Company | Modified lignin biopolymer useful in cleaning compositions |
WO2011032138A2 (en) | 2009-09-14 | 2011-03-17 | The Procter & Gamble Company | Compact fluid laundry detergent composition |
WO2012104159A1 (en) | 2011-01-31 | 2012-08-09 | Unilever Plc | Alkaline liquid detergent compositions |
WO2013092049A1 (en) | 2011-12-20 | 2013-06-27 | Unilever Plc | Isotropic aqueous liquid laundry detergent comprising sequestrant |
WO2014160820A1 (en) | 2013-03-28 | 2014-10-02 | The Procter & Gamble Company | Cleaning compositions containing a polyetheramine |
-
2017
- 2017-01-13 WO PCT/EP2017/050641 patent/WO2017133879A1/en active Application Filing
Patent Citations (120)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2182306A (en) | 1935-05-10 | 1939-12-05 | Ig Farbenindustrie Ag | Polymerization of ethylene imines |
US2208095A (en) | 1937-01-05 | 1940-07-16 | Ig Farbenindustrie Ag | Process of producing insoluble condensation products containing sulphur and nitrogen |
US2553696A (en) | 1944-01-12 | 1951-05-22 | Union Carbide & Carbon Corp | Method for making water-soluble polymers of lower alkylene imines |
US2806839A (en) | 1953-02-24 | 1957-09-17 | Arnold Hoffman & Co Inc | Preparation of polyimines from 2-oxazolidone |
US3033746A (en) | 1958-06-19 | 1962-05-08 | Dow Chemical Co | Polyalkyleneimine, phenol germicides |
GB1296839A (en) | 1969-05-29 | 1972-11-22 | ||
GB1372034A (en) | 1970-12-31 | 1974-10-30 | Unilever Ltd | Detergent compositions |
US3893929A (en) | 1971-10-28 | 1975-07-08 | Procter & Gamble | Compositions for imparting renewable soil release finish to polyester-containing fabrics |
DE2527793A1 (en) | 1974-06-25 | 1976-01-15 | Procter & Gamble | LIQUID DETERGENT PREPARATIONS WITH DIRT-REPELLENT PROPERTIES |
US3959230A (en) | 1974-06-25 | 1976-05-25 | The Procter & Gamble Company | Polyethylene oxide terephthalate polymers |
US4116885A (en) | 1977-09-23 | 1978-09-26 | The Procter & Gamble Company | Anionic surfactant-containing detergent compositions having soil-release properties |
US4435307A (en) | 1980-04-30 | 1984-03-06 | Novo Industri A/S | Detergent cellulase |
DE3410810A1 (en) | 1983-03-29 | 1984-10-04 | Colgate-Palmolive Co., New York, N.Y. | PARTICULATE TEXTILE DETERGENT |
DE3411941A1 (en) | 1983-04-04 | 1984-10-04 | Colgate-Palmolive Co., New York, N.Y. | LIQUID DETERGENT |
US4702857A (en) | 1984-12-21 | 1987-10-27 | The Procter & Gamble Company | Block polyesters and like compounds useful as soil release agents in detergent compositions |
EP0199403A2 (en) | 1985-04-15 | 1986-10-29 | The Procter & Gamble Company | Stable liquid detergent compositions |
EP0201124A2 (en) | 1985-05-01 | 1986-11-12 | Procter & Gamble European Technical Center | Cleaning compositions |
EP0218272A1 (en) | 1985-08-09 | 1987-04-15 | Gist-Brocades N.V. | Novel lipolytic enzymes and their use in detergent compositions |
EP0219048A2 (en) | 1985-10-12 | 1987-04-22 | BASF Aktiengesellschaft | Use of graft copolymers of polyalkylenoxides and vinyl acetate as anti-redeposition agents in the washing and post-treatment of textiles containing synthetic fibres |
US4711730A (en) | 1986-04-15 | 1987-12-08 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
PL148326B1 (en) | 1986-07-15 | 1989-10-31 | A softerner for teytile products | |
JPS6356289A (en) | 1986-07-30 | 1988-03-10 | Res Dev Corp Of Japan | Beta-mannanase and production thereof |
JPS6336775A (en) | 1986-07-31 | 1988-02-17 | Res Dev Corp Of Japan | Novel alkalophilic strain of bacillus genus capable of producing beta-mannanase and beta-mannosidase and use thereof |
EP0258068A2 (en) | 1986-08-29 | 1988-03-02 | Novo Nordisk A/S | Enzymatic detergent additive |
EP0260105A2 (en) | 1986-09-09 | 1988-03-16 | Genencor, Inc. | Preparation of enzymes having altered activity |
US4721580A (en) | 1987-01-07 | 1988-01-26 | The Procter & Gamble Company | Anionic end-capped oligomeric esters as soil release agents in detergent compositions |
FR2619393A1 (en) | 1987-08-10 | 1989-02-17 | Colgate Palmolive Co | DETERGENT COMPOSITION BASED ON ETHOXYLATE AND A COPOLYMER OF TEREPHTHALATE FACILITATING SOIL DECOLUTION AND METHOD FOR USE THEREOF |
EP0305216A1 (en) | 1987-08-28 | 1989-03-01 | Novo Nordisk A/S | Recombinant Humicola lipase and process for the production of recombinant humicola lipases |
JPS6474992A (en) | 1987-09-16 | 1989-03-20 | Fuji Oil Co Ltd | Dna sequence, plasmid and production of lipase |
US4877896A (en) | 1987-10-05 | 1989-10-31 | The Procter & Gamble Company | Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles |
EP0331376A2 (en) | 1988-02-28 | 1989-09-06 | Amano Pharmaceutical Co., Ltd. | Recombinant DNA, bacterium of the genus pseudomonas containing it, and process for preparing lipase by using it |
US5691178A (en) | 1988-03-22 | 1997-11-25 | Novo Nordisk A/S | Fungal cellulase composition containing alkaline CMC-endoglucanase and essentially no cellobiohydrolase |
WO1989009259A1 (en) | 1988-03-24 | 1989-10-05 | Novo-Nordisk A/S | A cellulase preparation |
US5776757A (en) | 1988-03-24 | 1998-07-07 | Novo Nordisk A/S | Fungal cellulase composition containing alkaline CMC-endoglucanase and essentially no cellobiohydrolase and method of making thereof |
US5648263A (en) | 1988-03-24 | 1997-07-15 | Novo Nordisk A/S | Methods for reducing the harshness of a cotton-containing fabric |
EP0357280A2 (en) | 1988-08-26 | 1990-03-07 | The Procter & Gamble Company | Soil release agents having allylderived sulfonated end caps |
US4968451A (en) | 1988-08-26 | 1990-11-06 | The Procter & Gamble Company | Soil release agents having allyl-derived sulfonated end caps |
US5008032A (en) | 1988-10-31 | 1991-04-16 | Basf Aktiengesellschaft | Use of partially esterified copolymers in liquid detergents |
EP0407225A1 (en) | 1989-07-07 | 1991-01-09 | Unilever Plc | Enzymes and enzymatic detergent compositions |
JPH0347076A (en) | 1989-08-25 | 1991-02-28 | Res Dev Corp Of Japan | Beta-mannase and production thereof |
EP0442101A1 (en) | 1990-01-19 | 1991-08-21 | BASF Aktiengesellschaft | Polyesters containing nonionic surfactants in a condensed form, their preparation and their use in detergents |
WO1991016422A1 (en) | 1990-04-14 | 1991-10-31 | Kali-Chemie Aktiengesellschaft | Alkaline bacillus lipases, coding dna sequences therefor and bacilli which produce these lipases |
WO1991018974A1 (en) | 1990-05-29 | 1991-12-12 | Chemgen Corporation | HEMICELLULASE ACTIVE AT EXTREMES OF pH AND TEMPERATURE AND THE MEANS FOR THE PRODUCTION THEREOF |
WO1992005249A1 (en) | 1990-09-13 | 1992-04-02 | Novo Nordisk A/S | Lipase variants |
EP0483606A2 (en) | 1990-10-29 | 1992-05-06 | BASF Aktiengesellschaft | Use of polyesters comprising condensed tartaric acid as detergent additive, process for production of the polyesters, and polyesters based upon tartaric acid and tetracarboxylic acids |
WO1992019709A1 (en) | 1991-04-30 | 1992-11-12 | The Procter & Gamble Company | Built liquid detergents with boric-polyol complex to inhibit proteolytic enzyme |
WO1992019708A1 (en) | 1991-04-30 | 1992-11-12 | The Procter & Gamble Company | Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme |
JPH0851975A (en) | 1991-10-09 | 1996-02-27 | Res Dev Corp Of Japan | New beta-mannanase and method for producing the same |
WO1993024622A1 (en) | 1992-05-22 | 1993-12-09 | Alko Ltd. | Mannanase enzymes, genes coding for them, methods for isolating the genes, and methods for bleaching lignocellulosic pulps |
WO1993024618A1 (en) | 1992-06-01 | 1993-12-09 | Novo Nordisk A/S | Peroxidase variants with improved hydrogen peroxide stability |
WO1994001541A1 (en) | 1992-07-06 | 1994-01-20 | Novo Nordisk A/S | C. antarctica lipase and lipase variants |
WO1994025578A1 (en) | 1993-04-27 | 1994-11-10 | Gist-Brocades N.V. | New lipase variants for use in detergent applications |
WO1994025576A1 (en) | 1993-04-30 | 1994-11-10 | Novo Nordisk A/S | An enzyme exhibiting mannanase activity |
WO1995002028A1 (en) | 1993-07-08 | 1995-01-19 | The Procter & Gamble Company | Detergent compositions comprising soil release agents |
WO1995002030A1 (en) | 1993-07-08 | 1995-01-19 | The Procter & Gamble Company | Detergent compositions comprising soil release agents |
WO1995006720A1 (en) | 1993-08-30 | 1995-03-09 | Showa Denko K.K. | Novel lipase, microorganism producing the lipase, process for producing the lipase, and use of the lipase |
WO1995010602A1 (en) | 1993-10-13 | 1995-04-20 | Novo Nordisk A/S | H2o2-stable peroxidase variants |
WO1995014783A1 (en) | 1993-11-24 | 1995-06-01 | Showa Denko K.K. | Lipase gene and variant lipase |
WO1995018207A1 (en) | 1993-12-24 | 1995-07-06 | Henkel Kommanditgesellschaft Auf Aktien | Liquid washing and cleaning agent |
WO1995022615A1 (en) | 1994-02-22 | 1995-08-24 | Novo Nordisk A/S | A method of preparing a variant of a lipolytic enzyme |
WO1995026397A1 (en) | 1994-03-29 | 1995-10-05 | Novo Nordisk A/S | Alkaline bacillus amylase |
WO1995030744A2 (en) | 1994-05-04 | 1995-11-16 | Genencor International Inc. | Lipases with improved surfactant resistance |
WO1995032232A1 (en) | 1994-05-20 | 1995-11-30 | Henkel Kommanditgesellschaft Auf Aktien | Soil release polyesters |
WO1995035381A1 (en) | 1994-06-20 | 1995-12-28 | Unilever N.V. | Modified pseudomonas lipases and their use |
WO1996000292A1 (en) | 1994-06-23 | 1996-01-04 | Unilever N.V. | Modified pseudomonas lipases and their use |
WO1996012012A1 (en) | 1994-10-14 | 1996-04-25 | Solvay S.A. | Lipase, microorganism producing same, method for preparing said lipase and uses thereof |
WO1996013580A1 (en) | 1994-10-26 | 1996-05-09 | Novo Nordisk A/S | An enzyme with lipolytic activity |
WO1996016150A1 (en) | 1994-11-17 | 1996-05-30 | Henkel Kommanditgesellschaft Auf Aktien | Soil-repellent detergent with specific combination of surfactants |
EP0728795A2 (en) | 1995-02-25 | 1996-08-28 | Basf Aktiengesellschaft | Process for preparing finely divided compositions of amphiphilic polymers and polycarboxylates and their use |
WO1996027002A1 (en) | 1995-02-27 | 1996-09-06 | Novo Nordisk A/S | Novel lipase gene and process for the production of lipase with the use of the same |
WO1996029397A1 (en) | 1995-03-17 | 1996-09-26 | Novo Nordisk A/S | Novel endoglucanases |
EP0743358A1 (en) | 1995-05-18 | 1996-11-20 | Textil Color Ag | Composition for washing and cleaning of textile materials |
WO1997003162A1 (en) | 1995-07-08 | 1997-01-30 | The Procter & Gamble Company | Detergent compositions |
WO1997004079A1 (en) | 1995-07-14 | 1997-02-06 | Novo Nordisk A/S | A modified enzyme with lipolytic activity |
WO1997007202A1 (en) | 1995-08-11 | 1997-02-27 | Novo Nordisk A/S | Novel lipolytic enzymes |
WO1997011164A1 (en) | 1995-09-20 | 1997-03-27 | Genencor International, Inc. | Purified mannanase from bacillus amyloliquefaciens and method of preparation |
US5834412A (en) | 1995-12-21 | 1998-11-10 | The Procter & Gamble Company | Soil release polymers with fluorescent whitening properties |
WO1997041197A1 (en) | 1996-04-25 | 1997-11-06 | Basf Aktiengesellschaft | Detergent components protected against exothermic decomposition by oxidation |
WO1997042285A1 (en) | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Cotton soil release polymers |
WO1998012307A1 (en) | 1996-09-17 | 1998-03-26 | Novo Nordisk A/S | Cellulase variants |
US6242404B1 (en) | 1996-10-04 | 2001-06-05 | Rhodia Inc. | Enhanced soil release polymer compositions |
WO1998015346A1 (en) | 1996-10-04 | 1998-04-16 | Rhodia Inc. | Enhancement of soil release with gemini surfactants |
WO1998015257A1 (en) | 1996-10-08 | 1998-04-16 | Novo Nordisk A/S | Diaminobenzoic acid derivatives as dye precursors |
WO1998020092A2 (en) | 1996-11-01 | 1998-05-14 | The Procter & Gamble Company | Laundry detergent compositions comprising soil release polymer |
WO1998058044A1 (en) | 1997-06-17 | 1998-12-23 | Clariant Gmbh | Detergent and cleaning agent |
WO1998059030A1 (en) | 1997-06-20 | 1998-12-30 | The Procter & Gamble Company | Soil release polymers with fluorescent whitening properties |
WO1999019429A1 (en) | 1997-10-10 | 1999-04-22 | The Procter & Gamble Company | A detergent composition |
WO1999027084A1 (en) | 1997-11-24 | 1999-06-03 | Novo Nordisk A/S | Novel pectate lyases |
WO1999027083A1 (en) | 1997-11-24 | 1999-06-03 | Novo Nordisk A/S | PECTIN DEGRADING ENZYMES FROM $i(BACILLUS LICHENIFORMIS) |
US6284524B1 (en) | 1997-11-24 | 2001-09-04 | Novozymes A/S | Pectate lyases |
JPH11193397A (en) | 1997-12-26 | 1999-07-21 | Lion Corp | Detergent particle composition and production thereof |
WO1999041346A1 (en) | 1998-02-11 | 1999-08-19 | Rhodia Chimie | Dirt removing detergent compositions |
RO114357B1 (en) | 1998-02-26 | 1999-03-30 | Sc Prod Cresus Sa | Anti-soiling composition for textile materials |
WO1999064619A2 (en) | 1998-06-10 | 1999-12-16 | Novozymes A/S | Novel mannanases |
WO2000004120A1 (en) | 1998-07-15 | 2000-01-27 | Rhodia Chimie | Terephthalic polyester composition and its use as soil release agent |
US6376446B1 (en) | 1999-01-13 | 2002-04-23 | Melaleuca, Inc | Liquid detergent composition |
WO2000050549A2 (en) | 1999-02-22 | 2000-08-31 | The Procter & Gamble Company | Cleaning compositions containing selected nonionic surfactants |
WO2000060060A2 (en) | 1999-03-31 | 2000-10-12 | Novozymes A/S | Polypeptides having alkaline alpha-amylase activity and nucleic acids encoding same |
WO2001023515A1 (en) | 1999-09-29 | 2001-04-05 | Rhodia Inc. | Novel polymer based cleaning compositions for use in hard surface cleaning and laundry applications |
EP1099748A2 (en) | 1999-11-13 | 2001-05-16 | Henkel Kommanditgesellschaft auf Aktien | Surfactant containing detergent compositions |
JP2001181692A (en) | 1999-12-27 | 2001-07-03 | Lion Corp | Liquid detergent composition for local washing |
WO2002006442A2 (en) | 2000-07-19 | 2002-01-24 | Novozymes A/S | Cell-wall degrading enzyme variants |
WO2002018474A1 (en) | 2000-09-02 | 2002-03-07 | Sasol Germany Gmbh | Free-flowing, amphiphilic, non-ionic oligoesters |
US7119056B2 (en) | 2000-09-02 | 2006-10-10 | Sasol Germany Gmbh | Free-flowing, amphiphilic, non-ionic oligoesters |
WO2002077063A1 (en) | 2001-03-28 | 2002-10-03 | Basf Aktiengesellschaft | Dirt-removing polyesters |
WO2005097959A1 (en) | 2004-04-08 | 2005-10-20 | Clariant Produkte (Deutschland) Gmbh | Detergent and cleaning agents containing dye fixatives and soil-release polymers |
WO2006024612A1 (en) | 2004-08-30 | 2006-03-09 | Ciba Specialty Chemicals Holding Inc. | Shading process |
WO2006055787A1 (en) | 2004-11-19 | 2006-05-26 | The Procter & Gamble Company | Whiteness perception compositions |
WO2006086492A1 (en) | 2005-02-08 | 2006-08-17 | Basf Aktiengesellschaft | Method of making an alkoxylated polyethylenimine product |
WO2006133867A1 (en) | 2005-06-15 | 2006-12-21 | Clariant Produkte (Deutschland) Gmbh | Dishwashing formulations comprising oligoesters |
WO2006133868A1 (en) | 2005-06-15 | 2006-12-21 | Clariant Produkte (Deutschland) Gmbh | Detergents for hard surfaces |
WO2007130567A2 (en) | 2006-05-05 | 2007-11-15 | The Procter & Gamble Company | Compact fluid laundry detergent composition |
WO2008095626A1 (en) | 2007-02-03 | 2008-08-14 | Clariant Finance (Bvi) Limited | Aqueous oligo- and polyester formulations |
WO2009153184A1 (en) | 2008-06-16 | 2009-12-23 | Unilever Plc | Improvements relating to fabric cleaning |
WO2010033743A1 (en) | 2008-09-19 | 2010-03-25 | The Procter & Gamble Company | Modified lignin biopolymer useful in cleaning compositions |
WO2011032138A2 (en) | 2009-09-14 | 2011-03-17 | The Procter & Gamble Company | Compact fluid laundry detergent composition |
WO2012104159A1 (en) | 2011-01-31 | 2012-08-09 | Unilever Plc | Alkaline liquid detergent compositions |
WO2013092049A1 (en) | 2011-12-20 | 2013-06-27 | Unilever Plc | Isotropic aqueous liquid laundry detergent comprising sequestrant |
WO2014160820A1 (en) | 2013-03-28 | 2014-10-02 | The Procter & Gamble Company | Cleaning compositions containing a polyetheramine |
WO2014160821A1 (en) | 2013-03-28 | 2014-10-02 | The Procter & Gamble Company | Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose |
Non-Patent Citations (13)
Title |
---|
DARTOIS ET AL., BIOCHEMICA ET BIOPHYSICA ACTA, vol. 1131, 1993, pages 253 - 360 |
DAVE; VAUGHN, J. BACTERIOL., vol. 108, 1971, pages 166 - 174 |
HASEGAWA; NAGEL, J. FOOD SCI., vol. 31, 1966, pages 838 - 845 |
HEFFRON ET AL., MOL. PLANT-MICROBE INTERACT., vol. 8, 1995, pages 331 - 334 |
HENRISSAT ET AL., PLANT PHYSIOL., vol. 107, 1995, pages 963 - 976 |
KARBASSI; VAUGHN, CAN. J. MICROBIOL., vol. 26, 1980, pages 377 - 384 |
KELLY; FOGARTY, CAN. J. MICROBIOL., vol. 24, 1978, pages 1164 - 1172 |
KIM ET AL., BIOSCI. BIOTECH. BIOCHEM., vol. 58, 1994, pages 947 - 949 |
M. KJELLIN AND I. JOHANSSON: "Surfactants from Renewable Resources", 2010, JOHN WILEY & SONS, LTD, article LAUTEN, R. A.; MYRVOLD, B. O.; GUNDERSEN, S. A.: "New Developments in the Commercial Utilization of Lignosulphonates" |
MENDOZA ET AL., WORLD J. MICROBIOL. BIOTECH., vol. 10, no. 5, 1994, pages 551 - 555 |
NAGEL; VAUGHN, ARCH. BIOCHEM. BIOPHYS., vol. 93, 1961, pages 344 - 352 |
NASSER ET AL., FEBS LETTS, vol. 335, 1993, pages 319 - 326 |
TALBOT ET AL., APPL. ENVIRON. MICROBIOL., vol. 56, no. 11, 1990, pages 3505 - 3510 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3517597A1 (en) * | 2018-01-25 | 2019-07-31 | The Procter & Gamble Company | Polymer composition |
EP3517596A1 (en) * | 2018-01-25 | 2019-07-31 | The Procter & Gamble Company | Method of making an opaque liquid detergent composition |
US11066514B2 (en) | 2018-01-25 | 2021-07-20 | The Procter & Gamble Company | Soil release polymer composition comprising an anionic modified polyester |
WO2022033884A1 (en) * | 2020-08-12 | 2022-02-17 | Unilever Ip Holdings B.V. | Laundry detergent composition |
EP3974505A1 (en) * | 2020-09-25 | 2022-03-30 | Henkel AG & Co. KGaA | Concentrated flowable detergent composition with improved properties |
WO2022063466A1 (en) * | 2020-09-25 | 2022-03-31 | Henkel Ag & Co. Kgaa | Concentrated flowable detergent preparation having improved properties |
CN113481714A (en) * | 2021-06-14 | 2021-10-08 | 山东贝润防水材料有限公司 | Water seepage prevention polyester tire and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2009259498B2 (en) | Improvements relating to fabric cleaning | |
AU2012238950B2 (en) | Method of laundering fabric | |
US9150993B2 (en) | Methods and compositions for fabric cleaning | |
AU2012358647B2 (en) | Isotropic liquid detergents comprising soil release polymer | |
WO2016155993A1 (en) | Composition | |
CA2769440C (en) | Compact fluid laundry detergent composition | |
EP2707472B1 (en) | Aqueous concentrated laundry detergent compositions | |
CA3138778C (en) | Cleaning composition | |
EP2522714A1 (en) | Aqueous concentrated laundry detergent compositions | |
WO2017133879A1 (en) | Detergent liquid | |
EP2522715A1 (en) | Aqueous concentrated laundry detergent compositions | |
EP3298115A1 (en) | Method of making surfactant compositions and detergent compositions comprising alkoxylatep glycerine as a solvent | |
WO2012052306A1 (en) | Externally structured aqueous detergent liquid | |
EP3469048A1 (en) | Laundry products | |
EP3715444A1 (en) | Laundry detergent compositions with stain removal | |
WO2019038186A1 (en) | Improvements relating to fabric cleaning | |
WO2019038187A1 (en) | Improvements relating to fabric cleaning |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17700359 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17700359 Country of ref document: EP Kind code of ref document: A1 |