CN101473025B - 包含基于聚环氧烷和乙烯基酯的两亲性接枝聚合物的清洁组合物 - Google Patents
包含基于聚环氧烷和乙烯基酯的两亲性接枝聚合物的清洁组合物 Download PDFInfo
- Publication number
- CN101473025B CN101473025B CN2007800191524A CN200780019152A CN101473025B CN 101473025 B CN101473025 B CN 101473025B CN 2007800191524 A CN2007800191524 A CN 2007800191524A CN 200780019152 A CN200780019152 A CN 200780019152A CN 101473025 B CN101473025 B CN 101473025B
- Authority
- CN
- China
- Prior art keywords
- cleaning compositions
- weight
- composition
- graft polymers
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 26
- 229920001567 vinyl ester resin Polymers 0.000 title claims abstract description 22
- 229920000233 poly(alkylene oxides) Polymers 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 title claims description 119
- 238000004140 cleaning Methods 0.000 title claims description 66
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title 1
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 24
- 239000003599 detergent Substances 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 23
- 239000004064 cosurfactant Substances 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 17
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 239000013543 active substance Substances 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 150000003254 radicals Chemical group 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 241000282326 Felis catus Species 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 238000004851 dishwashing Methods 0.000 claims description 3
- 229920001290 polyvinyl ester Polymers 0.000 claims description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- -1 polyethylene Polymers 0.000 description 80
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 55
- 238000005502 peroxidation Methods 0.000 description 42
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 150000002148 esters Chemical group 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 235000013599 spices Nutrition 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- KVWOTUDBCFBGFJ-UHFFFAOYSA-N tert-butyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC(C)(C)C KVWOTUDBCFBGFJ-UHFFFAOYSA-N 0.000 description 4
- WLUUTGIJNRNHRF-UHFFFAOYSA-N tert-butyl heptanoate Chemical compound CCCCCCC(=O)OC(C)(C)C WLUUTGIJNRNHRF-UHFFFAOYSA-N 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical class CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 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
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002453 shampoo Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000002979 fabric softener Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 230000003165 hydrotropic effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical class CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical group CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical class CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- JCCIFDCPHCKATH-UHFFFAOYSA-N 2-methylbutan-2-yl acetate Chemical compound CCC(C)(C)OC(C)=O JCCIFDCPHCKATH-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 125000000242 4-chlorobenzoyl group Chemical group ClC1=CC=C(C(=O)*)C=C1 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- XSNXNRNMDLLTRG-UHFFFAOYSA-M C1(=CC=CC=C1)S(=O)(=O)[O-].C(CCCCCCCC)(=O)[O+] Chemical compound C1(=CC=CC=C1)S(=O)(=O)[O-].C(CCCCCCCC)(=O)[O+] XSNXNRNMDLLTRG-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 101000605014 Homo sapiens Putative L-type amino acid transporter 1-like protein MLAS Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- 102100038206 Putative L-type amino acid transporter 1-like protein MLAS Human genes 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- FRTNIYVUDIHXPG-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN FRTNIYVUDIHXPG-UHFFFAOYSA-N 0.000 description 1
- QTONSPKDOKVNBJ-UHFFFAOYSA-N acetic acid;n'-(2-aminoethyl)ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCN QTONSPKDOKVNBJ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DRZOELSSQWENBA-UHFFFAOYSA-N benzene-1,2-dicarboperoxoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(=O)OO DRZOELSSQWENBA-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- NSFKBZXCXCJZDQ-UHFFFAOYSA-N cumene;sodium Chemical compound [Na].CC(C)C1=CC=CC=C1 NSFKBZXCXCJZDQ-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying 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
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
- C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
-
- 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
-
- 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
- C11D3/3788—Graft polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Detergent Compositions (AREA)
- Graft Or Block Polymers (AREA)
- Polyethers (AREA)
- Steroid Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
包含两亲性接枝聚合物的衣物洗涤剂和清洁组合物,所述聚合物基于作为接枝基底的水溶性聚环氧烷(A)和经由乙烯基酯组分(B)聚合反应形成的侧链,所述聚合物每50个烯化氧单元具有平均≤1个接枝位点和3000至100,000的平均摩尔质量Mw。
Description
相关申请的交叉参考
此专利申请要求2006年5月31日提交的EP06114756的优先权。
发明领域
本发明涉及包含两亲性接枝聚合物的衣物洗涤组合物和清洁组合物,所述两亲性接枝聚合物基于作为接枝基底的水溶性聚环氧烷和乙烯基酯侧链。
发明概述
本发明涉及包含新的两亲性接枝聚合物的新型衣物洗涤剂和清洁组合物,所述两亲性接枝聚合物基于作为接枝基底的水溶性聚环氧烷(A)和经由乙烯基酯组分(B)聚合反应形成的侧链,所述聚合物每50个烯化氧单元具有平均≤1个接枝位点和3000至100,000的平均摩尔质量Mw。本发明还涉及这些两亲性接枝聚合物作为衣物洗涤剂和清洁组合物中促进污垢分离的添加剂的用途。
发明详述
除了表面活性剂以外,聚合物还可用作衣物洗涤剂和清洁组合物中的促进污垢分离的添加剂。例如,已知的聚合物非常适宜作为污垢颜料如粘土矿物或煤烟的分散剂以及作为阻止已被分离的污垢重新附着的添加剂。然而,此类分散剂尤其在低温下不能有效地从纺织物和硬质表面上移除疏水性污垢。
本发明的目的是提供适于用作洗涤和清洁组合物添加剂的聚合物,尤其是从纺织物和硬质表面上移除疏水性污垢。
因此,我们发现了两亲性接枝聚合物,所述两亲性接枝聚合物基于作为接枝基底的水溶性聚环氧烷(A)和经由乙烯基酯组分(B)聚合反应形 成的侧链,所述聚合物每50个烯化氧单元具有平均≤1个接枝位点和3000至100,000的平均摩尔质量Mw。
我们还发现了用于制备接枝聚合物的方法,所述方法包括在水溶性聚环氧烷(A)、自由基形成引发剂(C)和以组分(A)、(B)和(C)的总和为基准按重量计最多40%有机溶剂(D)(如果需要)的存在下,在所述引发剂(C)具有40至500分钟分解半衰期的平均聚合反应温度,以使反应混合物中未转化接枝单体(B)和引发剂(C)份数在数量上一直保持相对于聚环氧烷(A)不足的方式,使由乙酸乙烯酯和/或丙酸乙烯酯(B1)以及其它烯键式不饱和单体(B2)(如果需要)组成的乙烯基酯组分(B)聚合。
本发明接枝聚合物的特征在于它们的低支化度(接枝度)。以所获得的反应混合物为基准,它们每50个烯化氧单元平均具有不超过1个接枝位点,优选不超过0.6个接枝位点,更优选不超过0.5个接枝位点,并且最优选不超过0.4个接枝位点。以所获得的反应混合物为基准,它们每50个烯化氧单元平均包含优选至少0.05,具体地讲至少0.1个接枝位点。可经由例如 13C核磁共振光谱,由接枝位点与聚环氧烷-CH2-基团的信号积分来测定支化度。
根据它们的低支化度,本发明接枝聚合物中接枝与未接枝烯化氧单元的摩尔比为0.002至0.05,优选0.002至0.035,更优选0.003至0.025,并且最优选0.004至0.02。
本发明接枝聚合物的优选实施方案的特征在于具有窄摩尔质量分布,从而多分散度Mw/Mn一般≤3,优选≤2.5,并且更优选≤2.3。最优选地,它们的多分散度Mw/Mn在1.5至2.2的范围内。可经由例如采用窄分布聚甲基丙烯酸甲酯作为标准物的凝胶渗透色谱法来测定接枝聚合物的多分散度。
本发明接枝聚合物的平均重均分子量Mw为3000至100,000,优选6000至45,000,并且更优选8000至30,000。
由于它们的低支化度和它们的低多分散度,本发明接枝聚合物的两亲特性和嵌段聚合物结构尤其显著。
本发明接枝聚合物的其它优选实施方案还仅具有低含量的未接枝聚乙烯酯(B)。一般来讲,它们包含按重量计≤10%,优选按重量计≤7.5%,并且更优选按重量计≤5%的未接枝聚乙烯酯(B)。
由于低含量的未接枝聚乙烯酯以及组分(A)和(B)的平衡比率,本发明接枝聚合物可溶于水中或水/醇混合物中(例如按重量计25%的二甘醇单丁基醚水溶液)。它们具有显著低的浊点,对于可溶解于水中的接枝聚合物而言,其最多为50℃,一般≤95℃,优选≤85℃,并且更优选≤75℃,而对于在按重量计25%二甘醇单丁基醚中的其它接枝聚合物而言,其一般≤90℃,优选为45℃至85℃。
本发明的两亲性接枝聚合物优选具有
(A)按重量计20%至70%的作为接枝基底的水溶性聚环氧烷,和
(B)在(A)的存在下经由按重量计30%至80%乙烯基酯组分的自由基聚合反应形成的侧链,所述乙烯基酯组分包括
(B1)按重量计70%至100%的乙酸乙烯酯和/或丙酸乙烯酯,和
(B2)按重量计0至30%的其它烯键式不饱和单体。
更优选地,它们包含按重量计25%至60%的接枝基底(A)和按重量计40%至75%的聚乙烯酯组分(B)。
适于形成接枝基底(A)的水溶性聚环氧烷原则上为基于C2-C4-烯化氧的所有聚合物,所述聚合物包含按重量计至少50%,优选按重量计至少60%,更优选按重量计至少75%的共聚形式的环氧乙烷。
所述聚环氧烷(A)优选具有低多分散度Mw/Mn。它们的多分散度优选地≤1.5。
所述聚环氧烷(A)可以是游离形式的相应聚亚烷二醇,即具有OH端基,但是它们也可在一个或两个端基处被封端。适宜的端基是例如C1-C25-烷基、苯基和C1-C14-烷基苯基。
尤其适宜的聚环氧烷(A)的具体实例包括:
(A1)聚乙二醇,在一个或两个端基处所述聚乙二醇尤其可被C1-C25-烷基封端,但是优选未被醚化,并且具有优选1500至20,000,更优选2500至15,000的平均摩尔质量Mn;
(A2)环氧乙烷与环氧丙烷和/或环氧丁烷的共聚物,所述共聚物具有按重量计至少50%的环氧乙烷含量,其同样在一个或两个端基处尤其可被C1-C25-烷基封端,但是优选未被醚化,并且具有优选1500至20,000,更优选2500至15,000的平均摩尔质量Mn;
(A3)具体地讲平均摩尔质量为2500至20,000的扩链产物,所述产物可通过平均摩尔质量Mn为200至5000的聚乙二醇(A1)或平均摩尔质量Mn为200至5000的共聚物(A2)与C2-C12-二羧酸或二羧酸酯或C6-C18-二异氰酸酯的反应获得。
优选的接枝基底(A)为聚乙二醇(A1)。
本发明接枝聚合物的侧链可在接枝基底(A)的存在下经由乙烯基酯组分(B)的聚合反应生成。
所述乙烯基酯组分(B)可有利地由(B1)乙酸乙烯酯或丙酸乙烯酯或乙酸乙烯酯和丙酸乙烯酯的混合物组成,尤其优选乙酸乙烯酯作为乙烯基酯组分(B)。
然而,接枝聚合物的侧链还可经由乙酸乙烯酯和/或丙酸乙烯酯(B1)与其它烯键式不饱和单体(B2)的共聚反应生成。单体(B2)在乙烯基酯组分(B)中的份数按重量计可最多为30%,这相当于(B2)在接枝聚合物中按重量计24%的含量。
适宜的共聚单体(B2)是例如单烯键不饱和羧酸和二羧酸以及它们的衍生物,诸如酯、酰胺和酸酐以及苯乙烯。当然还可能使用不同共聚单体的混合物。
具体实例包括:(甲基)丙烯酸、(甲基)丙烯酸C1-C12-烷基酯和(甲基)丙烯酸羟基-C2-C12-烷基酯、(甲基)丙烯酰胺、N-C1-C12-烷基(甲基)丙烯酰胺、N,N-二(C1-C6-烷基)(甲基)丙烯酰胺、马来酸、马来酸酐和马来酸单(C1-C12-烷基)酯。
优选的单体(B2)是(甲基)丙烯酸C1-C8-烷基酯和丙烯酸羟基乙酯,尤其优选(甲基)丙烯酸C1-C4-烷基酯。
极其优选的单体(B2)是丙烯酸甲酯、丙烯酸乙酯,尤其是丙烯酸正丁酯。
当本发明接枝聚合物包含单体(B2)作为乙烯基酯组分(B)中的组分时,(B2)接枝聚合物的含量按重量计优选为0.5%至20%,按重量计更优选为1%至15%,并且按重量计最优选为2%至10%。
本发明接枝聚合物可有利地通过同样如本发明所述的方法获得,在水溶性聚环氧烷(A)、自由基形成引发剂(C)和以组分(A)、(B)和(C)的总和为基准按重量计最多40%有机溶剂(D)(如果需要)的存在下,在所述引发剂(C)具有40至500分钟分解半衰期的平均聚合反应温度,以使反应混合物中未转化接枝单体(B)和引发剂(C)份数在数量上一直保持相对于聚环氧烷(A)不足的方式,使由乙酸乙烯酯和/或丙酸乙烯酯(B1)以及其它烯键式不饱和单体(B2)(如果需要)组成的乙烯基酯组分(B)聚合。
在此方法中,优选使用按重量计30%至80%的乙烯基酯组分(B)和按重量计20%至70%的平均摩尔质量Mn为1500至20,000的水溶性聚环氧烷(A),所述乙烯基酯组分(B)包括
(B1)按重量计70%至100%的乙酸乙烯酯和/或丙酸乙烯酯,和
(B2)按重量计0%至30%的其它烯键式不饱和单体。
在每种情况下以组分(B)为基准,引发剂(C)的量按重量计优选地为0.2%至5%,具体地讲按重量计为0.5%至3.5%。
对于如本发明所述的方法,自由基在平均聚合反应温度时存在的稳态浓度基本上恒定的,并且接枝单体(B)始终仅以低浓度(例如按重量计不超过5%)存在于反应混合物中,这是必要的。这可使反应可控,并且以可控的方式制备具有所期望低支化度和所期望低多分散度的接枝聚合物。
此处术语“平均聚合反应温度”旨在表示,虽然所述方法是基本恒温的,但是由于反应放热,因此仍会有温度变化,优选将所述温度变化保持在±10℃的范围内,更优选在±5℃的范围内。
根据本发明,自由基形成引发剂(C)在平均聚合反应温度时应具有40至500分钟,优选50至400分钟,并且更优选60至300分钟的分解半衰期。
根据本发明,有利地以一定的方式加入引发剂(C)和接枝单体(B),以使得未分解引发剂和接枝单体(B)以低并且基本上恒定的浓度 存在于反应混合物中。以单体加入期间计量的引发剂总量为基准,未分解引发剂在整个反应混合物中的比例按重量计优选≤15%,具体地讲按重量计≤10%。
平均聚合反应温度大约在50℃至140℃,优选60℃至120℃,并且更优选65℃至110℃的范围内。
在50℃至140℃的范围内,其分解半衰期为20至500分钟的适宜引发剂(C)的实例是:
-叔-C4-C12-烷基氢过氧化物和叔-(C9-C12-芳烷基)氢过氧化物的O-C2-C12-酰化衍生物,诸如过氧乙酸叔丁酯、单过氧化马来酸叔丁酯、过氧化异丁酸叔丁酯、过氧化新戊酸叔丁酯、过氧化新庚酸叔丁酯、过氧化-2-乙基己酸叔丁酯、过氧化-3,5,5-三甲基己酸叔丁酯、过氧化新癸酸叔丁酯、过氧化新戊酸叔戊酯、过氧化-2-乙基己酸叔戊酯、过氧化新癸酸叔戊酯、过氧化新癸酸1,1,3,3-四甲基丁酯、过氧化新癸酸异丙苯酯、过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯和二过氧化邻苯二甲酸二叔丁酯;
-叔-C8-C14-亚烷基二过氧化物的二-O-C4-C12-酰化衍生物,诸如2,5-二甲基-2,5-二(2-乙基已酰过氧化)己烷、2,5-二甲基-2,5-二(苯甲酰过氧化)己烷和1,3-二(2-新癸酰过氧化异丙基)苯;二(C2-C12-烷酰基)过氧化物和二苯甲酰过氧化物,诸如二乙酰过氧化物、二丙酰过氧化物、二琥珀酰过氧化物、二辛酰过氧化物、二(3,5,5-三甲基己酰)过氧化物、二癸酰过氧化物、二月桂酰过氧化物、二苯甲酰过氧化物、二(4-甲基苯甲酰)过氧化物、二(4-氯苯甲酰)过氧化物和二(2,4-二氯苯甲酰)过氧化物;
-过氧化(C4-C12-烷基)碳酸叔-C4-C5-烷基酯,诸如过氧化(2-乙基己基)碳酸叔戊酯;
-过氧化二碳酸二(C2-C12-烷基酯),诸如过氧化二碳酸二(正丁酯)和
-过氧化二碳酸二(2-乙基己酯)。
根据平均聚合反应温度,尤其适宜的引发剂(C)实例是:
-在50℃至60℃的平均聚合反应温度:过氧化新庚酸叔丁酯、过氧化新癸酸叔丁酯、过氧化新戊酸叔戊酯、过氧化新癸酸叔戊酯、过氧化新癸酸1,1,3,3-四甲基丁酯、过氧化新癸酸异丙苯酯、1,3-二(2-新癸酰过氧化异丙基)苯、过氧化二碳酸二(正丁酯)和过氧化二碳酸二(2-乙基己酯);
-在60℃至70℃的平均聚合反应温度:过氧化新戊酸叔丁酯、过氧化新庚酸叔丁酯、过氧化新癸酸叔丁酯、过氧化新戊酸叔戊酯和二(2,4-二氯苯甲酰)过氧化物;
-在70℃至80℃的平均聚合反应温度:过氧化新戊酸叔丁酯、过氧化新庚酸叔丁酯、过氧化新戊酸叔戊酯、二丙酰过氧化物、二辛酰过氧化物、二癸酰过氧化物、二月桂酰过氧化物、二(2,4-二氯苯甲酰)过氧化物和2,5-二甲基-2,5-二(2-乙基己酰过氧化)己烷;
-在80℃至90℃的平均聚合反应温度:过氧化异丁酸叔丁酯、过氧化-2-乙基己酸叔丁酯、过氧化-2-乙基己酸叔戊酯、二丙酰过氧化物、二辛酰过氧化物、二癸酰过氧化物、二月桂酰过氧化物、二(3,5,5-三甲基己酰)过氧化物、二苯甲酰过氧化物和二(4-甲基苯甲酰)过氧化物;
-在90℃至100℃的平均聚合反应温度:过氧化异丁酸叔丁酯、过氧化-2-乙基己酸叔丁酯、单过氧化马来酸叔丁酯、过氧化-2-乙基己酸叔戊酯、二苯甲酰过氧化物和二(4-甲基苯甲酰)过氧化物;
-在100℃至110℃的平均聚合反应温度:单过氧化马来酸叔丁酯、过氧化异丁酸叔丁酯和过氧化(2-乙基己基)碳酸叔戊酯;
-在110℃至120℃的平均聚合反应温度:单过氧化马来酸叔丁酯、过氧化-3,5,5-三甲基己酸叔丁酯和过氧化(2-乙基己基)碳酸叔戊酯。
优选的引发剂(C)是叔-C4-C5-烷基氢过氧化物的O-C4-C12-酰化衍生物,尤其优选过氧化新戊酸叔丁酯和过氧化-2-乙基己酸叔丁酯。
通过精确调整引发剂(C)和聚合反应温度,可不费力气地确定尤其有利的聚合反应条件。例如,在使用过氧化新戊酸叔丁酯的情况下,优选的平均聚合反应温度为60℃至80℃,而在使用过氧化-2-乙基己酸叔丁酯的情况下,优选的平均聚合反应温度为80℃至100℃。
本发明的聚合反应可在少量有机溶剂(D)的存在下实施。当然还可能使用不同溶剂(D)的混合物。优选使用水溶性或水可混溶的溶剂。
当溶剂(D)用作稀释剂时,在每种情况下以组分(A)、(B)和(B)的总和为基准,其用量按重量计一般为1%至40%,按重量计优选1%至35%,按重量计更优选1.5%至30%,按重量计最优选2%至25%。
适宜溶剂(D)的实例包括:
-一元醇,优选C1-C16-脂族醇,更优选C2-C12-脂族醇,最优选C2-C4-醇,诸如乙醇、丙醇、异丙醇、丁醇、仲丁醇和叔丁醇;
-多元醇,优选C2-C10-二醇,更优选C2-C6-二醇,最优选C2-C4-烷撑二醇,诸如乙二醇和丙二醇;
-烷撑二醇醚,优选烷撑二醇一(C1-C12-烷基)醚和烷撑二醇二(C1-C6-烷基)醚,更优选烷撑二醇一-和二(C1-C2-烷基)醚,最优选烷撑二醇一(C1-C2-烷基)醚,诸如乙二醇一甲基醚和乙二醇一乙基醚,以及丙二醇一甲基醚和丙二醇一乙基醚;
-聚亚烷基二醇,优选具有2至20个C2-C4-烷撑二醇单元的聚(C2-C4-亚烷基)二醇,更优选具有2至20个乙二醇单元的聚乙二醇和具有2至10个丙二醇单元的聚丙二醇,最优选具有2至15个乙二醇单元的聚乙二醇和具有2至4个丙二醇单元的聚丙二醇,诸如二甘醇、三甘醇、二丙二醇和三丙二醇;
-聚亚烷基二醇单醚,优选具有2至20个烷撑二醇单元的聚(C2-C4-亚烷基)二醇单(C1-C25-烷基)醚,更优选具有2至20个烷撑二醇单元的聚(C2-C4-亚烷基)二醇单(C1-C20-烷基)醚,最优选具有3至20个烷撑二醇单元的聚(C2-C3-亚烷基)二醇单(C1-C16-烷基)醚;
-羧酸酯,优选C1-C6-羧酸的C1-C8-烷基酯,更优选C1-C3-羧酸的C1-C4-烷基酯,最优选C2-C3-羧酸的C2-C4-烷基酯,诸如乙酸乙酯和丙酸乙酯;
-优选具有3至10个碳原子的脂族酮,诸如丙酮、甲基乙基酮、二乙基酮和环己酮;
-环醚,具体地讲是四氢呋喃和二氧杂环己烷。
所述溶剂(D)有利地为还可用于配制(例如洗涤和清洁组合物中)所用本发明接枝聚合物从而保留在聚合反应产物中的那些溶剂。
这些溶剂的优选实例是具有2至15个乙二醇单元的聚乙二醇、具有2至6个丙二醇单元的聚丙二醇,尤其是C6-C8-醇的烷氧基化产物(烷撑二醇单烷基醚和聚亚烷基二醇单烷基醚)。
此处尤其优选具有高支化度的C8-C16-醇的烷氧基化产物,其能够制成在40℃至70℃可自由流动并且在较低粘度下具有极低聚合物含量的聚合物混合物。
支化可存在于醇的烷基链中和/或聚烷氧基化部分中(至少一种环氧丙烷、环氧丁烷或甲基环氧丙烷单元的共聚)。这些烷氧基化产物尤其适宜的实例是用1至15摩尔环氧乙烷烷氧基化的2-乙基己醇或2-丙基庚醇,用1至15摩尔环氧乙烷和1至3摩尔环氧丙烷烷氧基化的C13/C15含氧醇或C12/C14或C16/C18脂肪醇,优选用1至15摩尔环氧乙烷和1至3摩尔环氧丙烷烷氧基化的2-丙基庚醇。
在如本发明所述的方法中,在反应器中,将聚环氧烷(A)、接枝单体(B1)和(B2)(如果适宜的话)、引发剂(C)和溶剂(D)(如果适宜的话)加热至选定的平均聚合反应温度。
根据本发明,以使聚合物(聚环氧烷(A)以及所形成的接枝聚合物)一直过量存在于反应器中的方式来实施所述聚合反应。聚合物与未接枝单体和引发剂的定量比一般≥10:1,优选≥15:1,并且更优选≥20:1。
如本发明所述的聚合反应方法大体上可在各种类型反应器中实施。
所用反应器优选为搅拌槽,其中初始时完全或部分加入聚环氧烷(A)以及(如果适宜的话)一部分的一般按重量计占所述特定总量最多15%的接枝单体(B)、引发剂(C)和溶剂(D),并且加热至聚合反应 温度,并且优选分别定量加入剩余量的(B)、(C)和(如果适宜的话)(D)。优选在≥2小时,更优选≥4小时,并且最优选≥5小时的期间内,定量加入剩余量的(B)、(C)和(如果适宜的话)(D)。
在尤其优选基本上不含溶剂的工艺变型情况下,初始时以熔融物形式加入全部量的聚环氧烷(A),并且定量加入优选以按重量计10%至50%溶液形式存在于一种溶剂(D)中的接枝单体(B1)和(如果适宜的话)(B2)以及引发剂(C),控制温度,以使得聚合反应期间所选的平均聚合反应温度可尤其保持在±10℃的范围内,具体地讲在±5℃的范围内。
在其它尤其优选的少溶剂工艺变型中,所述步骤如上所述,不同的是在聚合反应期间定量加入溶剂(D)以限制反应混合物的粘度。还可以先进行聚合反应,紧接着开始定量加入溶剂,或者分批加入溶剂。
可在标准压力或低压或高压下实施所述聚合反应。如果在所选压力下超出了单体(B)或任何所用稀释剂(D)的沸点,则在回流冷凝下实施所述聚合反应。
由于它们显著的两亲特性,本发明接枝聚合物具有尤其良好的界面特性。它们可有利地用于洗涤和清洁组合物中,其中它们有助于表面活性剂从纺织物或硬质表面上移除疏水性污垢,从而改善了所述制剂的洗涤和清洁性能。此外,它们可致使所移除污垢更好地分散于洗涤或清洁液中,并且防止其再沉淀到所洗涤或所清洁物质的表面上。
衣物洗涤剂和清洁组合物
以具体总组成为基准,本发明的衣物洗涤剂和本发明的清洁组合物一般包含按重量计0.05%至10%,按重量计优选0.1%至5%,并且按重量计更优选0.25%至2.5%的本发明两亲性接枝聚合物。
此外,所述衣物洗涤剂和清洁组合物一般包含表面活性剂以及(如果适合的话)作为洗涤物质的其它聚合物、助洗剂和其它常规成分,例如共助洗剂、络合剂、漂白剂、标准化剂、泛灰抑制剂、染料转移抑制剂、酶和香料。
本发明的两亲性接枝聚合物可用于包含表面活性剂体系的衣物洗涤剂或清洁组合物中,所述表面活性剂体系包含C10-C15烷基苯磺酸盐(LAS) 和一种或多种辅助表面活性剂,所述辅助表面活性剂选自非离子辅助表面活性剂、阳离子辅助表面活性剂、阴离子辅助表面活性剂或它们的混合物。辅助表面活性剂的选择可取决于所期望的有益效果。在一个实施方案中,所述辅助表面活性剂选择为非离子表面活性剂,优选C12-C18烷基乙氧基化物。在另一个实施方案中,所述辅助表面活性剂可选为阴离子表面活性剂,优选C10-C18烷基烷氧基硫酸盐(AExS),其中x为1至30。在另一个实施方案中,所述辅助表面活性剂选择为阳离子表面活性剂,优选二甲基羟乙基月桂基氯化铵。如果所述表面活性剂体系包含C10-C15烷基苯磺酸盐(LAS),则LAS的用量按所述组合物的重量计在约9%至约25%,或约13%至约25%,或约15%至约23%的范围内。
所述表面活性剂体系可包含按所述组合物的重量计0%至约7%,或约0.1%至约5%,或约1%至约4%的辅助表面活性剂,所述辅助表面活性剂选自非离子辅助表面活性剂、阳离子辅助表面活性剂、阴离子辅助表面活性剂、以及它们的混合物。
非离子辅助表面活性剂的非限制性实例包括:C12-C18烷基乙氧基化物,诸如得自She11的非离子表面活性剂;C6-C12烷基酚烷氧基化物,其中所述烷氧基化物单元是乙烯氧基和丙烯氧基单元的混合物;C12-C18醇和C6-C12烷基酚与环氧乙烷/环氧丙烷嵌段烷基聚胺乙氧基化物的缩合物,诸如得自BASF的如US 6,150,322中所论述的C14-C22中链支化醇BA;如US 6,153,577、US 6,020,303和US 6,093,856中所论述的C14-C22中链支化的烷基烷氧基化物BAEX,其中x为1至30;如1986年1月26日公布的Llenado的U.S.4,565,647中所论述的烷基多糖;具体地讲,如US 4,483,780和US 4,483,779中所论述的烷基多苷;如US5,332,528中所论述的多羟基脂肪酸酰胺;以及如US6,482,994和WO01/42408中所论述的醚封端的聚(烷氧基化)醇表面活性剂。
半极性非离子辅助表面活性剂的非限制性实例包括:水溶性氧化胺,所述氧化胺包含一个具有约10至约18个碳原子的烷基部分和2个选自由下列组成的组的部分:包含约1至约3个碳原子的烷基部分和羟烷基部分;水溶性氧化膦,所述氧化膦包含一个具有约10至约18个碳原子的烷基部分和2个选自由下列组成的组的部分:包含约1至约3个碳原子的烷 基部分和羟烷基部分;和水溶性亚砜,所述亚砜包含一个具有约10至约18个碳原子的烷基部分和一个选自由下列组成的组的部分:具有约1至约3个碳原子的烷基部分和羟烷基部分。参见WO 01/32816、US 4,681,704和US 4,133,779。
阳离子辅助表面活性剂的非限制性实例包括:可具有最多26个碳原子的季铵表面活性剂,其包括:如US 6,136,769中所论述的烷氧基化季铵(AQA)表面活性剂;如6,004,922中所论述的二甲基羟乙基季铵;二甲基羟乙基月桂基氯化铵;如WO 98/35002、WO 98/35003、WO98/35004、WO 98/35005和WO 98/35006中所论述的多胺阳离子表面活性剂;如美国专利4,228,042、4,239,660、4,260,529和US 6,022,844中所论述的阳离子酯表面活性剂;以及如US 6,221,825和WO 00/47708中所论述的氨基表面活性剂,具体地讲为酰胺基丙基二甲胺(APA)。
可用于本发明的阴离子辅助表面活性剂的非限制性实例包括:C10-C20直链、支链和无规烷基硫酸盐(AS);C10-C18仲(2,3)烷基硫酸盐;C10-C18烷基烷氧基硫酸盐(AEXS),其中x为1至30;包含1至5个乙氧基单元的C10-C18烷基烷氧基羧酸盐;如US 6,020,303和US 6,060,443中所论述的中链支化的烷基硫酸盐;如US 6,008,181和US 6,020,303中所论述的中链支化的烷基烷氧基硫酸盐;如WO 99/05243、WO 99/05242和WO99/05244中所论述的改性烷基苯磺酸盐(MLAS);甲酯磺酸盐(MES);以及α-烯烃磺酸盐(AOS)。
本发明还涉及包含本发明两亲性接枝聚合物和表面活性剂体系的组合物,所述表面活性剂体系包含C8-C18直链烷基磺酸盐表面活性剂和辅助表面活性剂。所述组合物可为任何形式,即为以下形式:液体形式;固体形式,诸如粉末、颗粒、附聚物、糊剂、片剂、小袋、条状物、凝胶;乳液形式;以双隔室容器递送的类型;喷雾或泡沫洗涤剂形式;预润湿擦拭物形式(即,与无纺的材料相组合的清洁组合物,例如Mackey等人在US6,121,165中所述的那些);由消费者用水活化的干擦拭物(即,与无纺的材料相组合的清洁组合物,例如Fowl er等人在US 5,980,931中所述的那些),以及其它均匀或多相的消费者清洁产品形式。
在一个实施方案中,本发明的清洁组合物为液体或固体衣物洗涤剂组合物。在另一个实施方案中,本发明的清洁组合物为硬质表面清洁组合物,优选地其中所述硬质表面清洁组合物浸透无纺的基底。如本文所用,“浸透”是指所述硬质表面清洁组合物被置于与无纺的基底接触,使得所述硬质表面清洁组合物渗入至少一部分所述无纺的基底中。优选地,所述硬质表面清洁组合物将所述无纺的材料饱和。所述清洁组合物也可用于汽车护理组合物中,用于清洁各种表面如硬木、瓷砖、陶瓷、塑料、皮革、金属、玻璃。该清洁组合物也可设计用于个人护理和宠物护理组合物如洗发剂组合物、沐浴剂、液体或固体皂以及其它清洁组合物(其中,表面活性剂可与游离的硬度离子接触)中,以及用于所有需要耐硬度表面活性剂体系的组合物中,如石油钻探组合物。
在另一个实施方案中,所述清洁组合物为盘碟清洁组合物,如液体手洗盘碟洗涤组合物、固体自动盘碟洗涤组合物、液体自动盘碟洗涤组合物、以及自动盘碟洗涤组合物的片剂/单位剂型。
非常典型地,本文清洁组合物如衣物洗涤剂、衣物洗涤剂添加剂、硬质表面清洁剂、合成的和皂基洗涤条皂、织物软化剂和织物处理液体、织物处理固体以及各种多种处理制品将需要若干助剂,虽然某些简单配制的产品如漂白添加剂可能只需要例如氧漂白剂和本文所述的表面活性剂。适宜的洗涤或清洁辅助物质的详尽列表可见于WO 99/05242。
常见的清洁助剂包括助洗剂、酶、上文没有讨论的聚合物、漂白剂、漂白活化剂、催化物质等(不包括任何上文已经定义的物质)。本文其它的清洁助剂可包括促泡剂、抑泡剂(消泡剂)等、除上述那些以外的各种活性成分或专用物质如分散聚合物(例如,得自BASF Corp.或Rohm &Haas)、有色斑粒、银器保护剂、防锈和/或防蚀剂、染料、填充剂、杀菌剂、碱度来源、水溶助长剂、抗氧化剂、酶稳定剂、前香料、香料、增溶剂、载体、加工助剂、颜料,并且对于液体制剂,包括溶剂、螯合剂、染料转移抑制剂、分散剂、增白剂、抑泡剂、染料、结构弹性化剂、织物软化剂、抗磨蚀剂、水溶助长剂、加工助剂、以及其它织物护理剂、表面和皮肤护理剂。此类其它清洁助剂及用量的合适实例可见于美国专利5,576,282、6,306,812 B1和6,326,348 B1中。
使用方法
本发明包括清洁目标表面的方法。如本文所用,“目标表面”可包括这样的表面,诸如织物、盘碟、玻璃制品、以及其它烹饪表面、硬质表面、毛发或皮肤。如本文所用,“硬质表面”包括存在于典型家庭中的硬质表面,例如硬木、瓷砖、陶瓷、塑料、皮革、金属、玻璃。上述方法包括步骤:将包含改性的多羟基化合物的组合物(以纯物质形式或稀释在洗涤液体中)与至少一部分目标表面接触,然后任选地漂洗该目标表面。优选地,使所述目标表面在上述任选的漂洗步骤之前进行洗涤步骤。为了本发明的目的,洗涤包括但不限于擦洗、擦拭和机械搅拌。
如本领域的技术人员将意识到的,本发明的清洁组合物理想地适用于家用护理(硬质表面清洁组合物)和/或洗涤应用中。
在跨越大范围的pH,约5至约11中,选择所述组合物溶液的pH,以使其最适合要清洁的目标表面。对于个人护理如皮肤和毛发清洁,上述组合物的pH优选为约5至约8,对于衣物清洁组合物,pH为约8至约10。所述组合物优选以溶液中约200ppm至约10,000ppm的浓度使用。水温范围优选为约5℃至约100℃。
为用于衣物洗涤清洁组合物中,所述组合物在溶液(或洗涤液体)中优选的使用浓度为约200ppm至约10000ppm。水温优选在约5℃至约60℃的范围内。水与织物的比率优选为约1:1至约20:1。
所述方法包括使浸透的无纺的基底与本发明组合物实施方案相接触的步骤。如本文所用,“无纺的基底”可包括任何常规式样的无纺的薄片或网,所述无纺的薄片或网具有合适的基重、尺寸(厚度)、吸收性和强度特性。合适的市售无纺的基底的实施例包括DuPont以商品名和James River Corp.以商品名出售的那些。
如本领域技术人员认可的那样,本发明的洗涤剂组合物理想地适用于液体盘碟清洁组合物中。使用本发明液体盘碟清洁组合物的方法包括使脏污盘碟与有效量的(通常约0.5mL至约20mL)(每处理25个盘碟)水稀释的本发明液体盘碟清洁组合物相接触的步骤。
聚合物实例
本发明的两亲性接枝聚合物可如下制备。在23℃和按重量计1%的聚合物浓度下,在按重量计3%的NaCl水溶液中,测定K值。使用按重量计0.5%的LiBr二甲基乙酰胺溶液作为洗脱液并且以聚甲基丙烯酸甲酯(PMMA)作为标准物,通过凝胶渗透色谱法来测定平均摩尔质量和多分散度。可通过在氘代二甲基亚砜中,经由13C核磁共振光谱,由接枝位点和聚乙二醇-CH2-基团的信号积分来测定支化度。所报告的值涉及产物中存在的所有聚乙二醇,即包括未接枝的聚乙二醇,并且对应于每个聚乙二醇上存在的平均侧链数。
接枝聚合物1
起初,在氮气氛下向配备搅拌器和回流冷凝器的聚合反应容器中,充入480g聚乙二醇(Mn 12,000),并且在70℃下熔融。
在加入了16.0乙酸乙烯酯和0.2g溶解于0.9g二丙二醇中的过氧化新戊酸叔丁酯,并且再搅拌5分钟后,在70℃的内温和搅拌下,以恒定流量持续平行定量加入304g乙酸乙烯酯(在6小时内,供料1)和4.0g溶解于18g二丙二醇中的过氧化新戊酸叔丁酯(在7小时内,供料2)。
在供料2加完并且在70℃下将所述混合物再搅拌一小时后,在70℃下分三次加入4.8g溶解于9.0g二丙二醇中的过氧化新戊酸叔丁酯,每一次加入后均再搅拌两小时。此外,加入73g二丙二醇以降低粘度。
通过在70℃下真空蒸馏,除去残余量的乙酸乙烯酯。接着,通过加入水,使固体含量按重量计达到24.3%。
所得接枝聚合物具有28.4的K值,1.8的多分散度(重均分子量Mw为36,900,并且数均分子量Mn为21,000)和0.8%的支化度(相当于50个EO单元每0.15个接枝位点)。
接枝聚合物2
起初,在氮气氛下向配备搅拌器和回流冷凝器的聚合反应容器中,充入400g聚乙二醇(Mn 9000),并且在85℃下熔融。
在加入了20.0乙酸乙烯酯和0.25g溶解于0.9g二丙二醇中的过氧化-2-乙基己酸叔丁酯,并且再搅拌5分钟后,在85℃的内温和搅拌下,以恒定流量持续平行定量加入380g乙酸乙烯酯(在6小时内,供料1)和 5.0g溶解于18g二丙二醇中的过氧化-2-乙基己酸叔丁酯(在7小时内,供料2)。
在供料2加完并且在85℃下将所述混合物再搅拌一小时后,在85℃下分三次加入6.0g溶解于9.0g二丙二醇中的过氧化-2-乙基己酸叔丁酯,每一次加入后均再搅拌两小时。此外,加入73g二丙二醇以降低粘度。
通过在85℃下真空蒸馏,除去残余量的乙酸乙烯酯。接着,通过加入水,使固体含量按重量计达到23.2%。
所得接枝聚合物具有24.0的K值,1.9的多分散度(Mw为37000,Mn为19500)和0.8%的支化度(相当于0.20个接枝位点/50个EO单元)。
接枝聚合物3
起初,在氮气氛下向配备搅拌器和回流冷凝器的聚合反应容器中,充入1000g聚乙二醇(Mn 6000),并且在90℃下熔融。
然后,在90℃的内温和搅拌下,以恒定流量持续平行定量加入1500g乙酸乙烯酯(在6小时内,供料1)和14.5g溶解于60.5g三丙二醇中的过氧化-2-乙基己酸叔丁酯(在7小时内,供料2)。
在供料2加完并且在90℃下将所述混合物再搅拌一小时后,在90℃下分三次加入17.1g溶解于22.6g三丙二醇中的过氧化-2-乙基己酸叔丁酯,每一次加入后均再搅拌两小时。此外,加入73g二丙二醇以降低粘度。
通过在90℃下真空蒸馏,除去残余量的乙酸乙烯酯。接着,通过加入水,使固体含量按重量计达到22.8%。
所得接枝聚合物具有19.6的K值,1.9的多分散度(Mw为35,700,Mn为18,800)和0.9%的支化度(相当于0.33个接枝位点/50个EO单元)。
接枝聚合物4
起初,在氮气氛下向配备搅拌器和回流冷凝器的聚合反应容器中,充入480g聚乙二醇(Mn 12,000),并且在70℃下熔融。
在加入了14.0乙酸乙烯酯、1.6g丙烯酸丁酯和0.3g溶解于0.9g二丙二醇中的过氧化新戊酸叔丁酯,并且再搅拌5分钟后,在70℃的内温和搅拌下,以恒定流量持续平行定量加入274g乙酸乙烯酯(在6小时内,供料1)、30.4g丙烯酸丁酯(在6小时内,供料2)和6.0g溶解于18g二丙二醇中的过氧化新戊酸叔丁酯(在7小时内,供料3)。
在供料3加完并且在70℃下将所述混合物再搅拌一小时后,在70℃下分三次加入7.2g溶解于9.0g二丙二醇中的过氧化新戊酸叔丁酯,每一次加入后均再搅拌两小时。此外,加入73g二丙二醇以降低粘度。
通过在70℃下真空蒸馏,除去残余量的单体。接着,通过加入水,使固体含量按重量计达到19.8%。
所得接枝聚合物具有29.1的K值,1.9的多分散度(Mw为35,500,Mn为18,400)和0.7%的支化度(相当于0.13个接枝位点/50个EO单元)。
接枝聚合物5
起初,在氮气氛下向配备搅拌器和回流冷凝器的聚合反应容器中,充入1175g聚乙二醇(Mn 4000),并且在90℃下熔融。
在加入了88.0乙酸乙烯酯和0.85g溶解于3.5g三丙二醇中的过氧化-2-乙基己酸叔丁酯,并且再搅拌5分钟后,在90℃的内温和搅拌下,以恒定流量持续平行定量加入1674g乙酸乙烯酯(在6小时内,供料1)和17.0g溶解于71g三丙二醇中的过氧化-2-乙基己酸叔丁酯(在7小时内,供料2)。
在供料2加完并且在90℃下将所述混合物再搅拌一小时后,在70℃下分三次加入39.0g溶解于21.0g三丙二醇中的过氧化-2-乙基己酸叔丁酯,每一次加入后均再搅拌两小时。此外,加入73g二丙二醇以降低粘度。
通过在90℃下真空蒸馏,除去残余量的乙酸乙烯酯。接着,通过加入水,使固体含量按重量计达到23.4%。
所得接枝聚合物具有17.9的K值,2.3的多分散度(Mw为26,800,Mn为11,700)和0.6%的支化度(相当于0.33个接枝位点/50个EO单元)。
接枝聚合物6
起初,在氮气氛下向配备搅拌器和回流冷凝器的聚合反应容器中,充入444g聚乙二醇(Mn 6000),并且在90℃下熔融。
在加入了0.55g溶解于1.7g三丙二醇中的过氧化-2-乙基己酸叔丁酯,并且再搅拌15分钟后,在90℃的内温和搅拌下,以恒定流量持续平行定量加入666g乙酸乙烯酯(在6小时内,供料1)和7.22gg溶解于21.6g三丙二醇中的过氧化-2-乙基己酸叔丁酯(在6.5小时内,供料2),并且还在供料1开始加入3小时后,开始加入233g烷氧基化2-丙基庚醇(1摩尔PO和10摩尔EO/mol)(在3.5小时内,供料3)。
在供料2和3加完并且随后在90℃下再搅拌一小时后,在90℃下分三次加入6.1g溶解于18.25g三丙二醇中的过氧化-2-乙基己酸叔丁酯,每一次加入后均再搅拌两小时。
通过在90℃下真空蒸馏,除去残余量的乙酸乙烯酯。接着,通过加入水,使固体含量按重量计达到86.9%。
所得接枝聚合物具有17.6的K值,1.8的多分散度(Mw为35,700,Mn为20,000)和0.9%的支化度(相当于0.33个接枝位点/50个EO单元)。
组合物制剂
实施例7-颗粒状衣物洗涤剂
A | B | C | D | E | |
重量% | 重量% | 重量% | 重量% | 重量% | |
C11-12直链烷基苯磺酸盐 | 13-25 | 13-25 | 13-25 | 13-25 | 9-25 |
C12-18乙氧基化硫酸盐 | - | - | 0-3 | - | 0-1 |
C14-15烷基乙氧基化物(EO=7) | 0-3 | 0-3 | - | 0-5 | 0-3 |
二甲基羟乙基月桂基氯化铵 | - | - | 0-2 | 0-2 | 0-2 |
三聚磷酸钠 | 20-40 | - | 18-33 | 12-22 | 0-15 |
沸石 | 0-10 | 20-40 | 0-3 | - | - |
硅酸盐助洗剂 | 0-10 | 0-10 | 0-10 | 0-10 | 0-10 |
碳酸盐 | 0-30 | 0-30 | 0-30 | 5-25 | 0-20 |
二亚乙基三胺五乙酸盐 | 0-1 | 0-1 | 0-1 | 0-1 | 0-1 |
聚丙烯酸酯 | 0-3 | 0-3 | 0-3 | 0-3 | 0-3 |
羧甲基纤维素 | 0.2-0.8 | 0.2-0.8 | 0.2-0.8 | 0.2-0.8 | 0.2-0.8 |
聚合物1 | 0.05-10 | 0.05-10 | 5.0 | 2.5 | 1.0 |
过碳酸盐 | 0-10 | 0-10 | 0-10 | 0-10 | 0-10 |
壬酰氧苯磺酸盐 | - | - | 0-2 | 0-2 | 0-2 |
四乙酰基乙二胺 | - | - | 0至-0.6 | 0-0.6 | 0-0.6 |
四磺酸酞菁锌 | - | - | 0-0.005 | 0-0.005 | 0-0.005 |
增白剂 | 0.05-0.2 | 0.05-0.2 | 0.05-0.2 | 0.05-0.2 | 0.05-0.2 |
MgSO4 | - | - | 0至-0.5 | 0-0.5 | 0-0.5 |
酶 | 0-0.5 | 0-0.5 | 0-0.5 | 0-0.5 | 0-0.5 |
微量组分(香料、染料、泡沫稳定剂) | 余量 | 余量 | 余量 | 余量 | 余量 |
1如实施例1、2、3、4、5或6中任一项所述的两亲性接枝聚合物或任何聚合物混合物。
实施例8-颗粒状衣物洗涤剂
含水浆液组合物。
组分 | 占含水浆液的重量百分比(%) |
具有以下通用结构的化合物:二((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3)-二((C2H5O)(C2H4O)n),其中n=20至30,并且x=3至8,或者它们的硫酸化或磺酸化变体 | 1.23 |
乙二胺二琥珀酸 | 0.35 |
增白剂 | 0.12 |
硫酸镁 | 0.72 |
丙烯酸酯/马来酸酯共聚物 | 6.45 |
聚合物1 | 1.60 |
直链烷基苯磺酸盐 | 11.92 |
羟乙烷二(亚甲基膦酸) | 0.32 |
碳酸钠 | 4.32 |
硫酸钠 | 47.49 |
皂 | 0.78 |
水 | 24.29 |
杂项 | 0.42 |
总份数 | 100.00 |
1如实施例1、2、3、4、5或6中任一项所述的两亲性接枝聚合物或任何聚合物混合物。
喷雾干燥粉末的制备。
制备含有上述组合物的含水浆液,其含水量为25.89%。将所述含水浆液加热至72℃,然后在高压(5.5x106Nm-2至6.0x106Nm-2)下泵吸至空气进口温度为270℃至300℃的逆流喷雾干燥塔中。使所述含水浆液雾化,然后使雾化后的浆液干燥以制得固体混合物,然后将其冷却并筛分,以除去特大的物料(>1.8mm),形成自由流动的喷雾干燥粉末。细小的物料(<0.15mm)用喷雾干燥塔中的废气淘洗,然后收集在塔后的防泄漏体系中。所述喷雾干燥粉末的含水量为1.0%重量,堆积体积密度为427g/L,而粒径分布使得95.2%重量的喷雾干燥粉末的粒径为150至710微米。下面给出该喷雾干燥粉末的组成。
喷雾干燥粉末组合物。
组分 | 占喷雾干燥粉末的重量百分比(%) |
具有以下通用结构的化合物:二((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3)-二((C2H5O)(C2H4O)n),其中n=20至30,并且x=3至8,或者它们的硫酸化或磺酸化变体 | 1.65 |
乙二胺二琥珀酸 | 0.47 |
增白剂 | 0.16 |
硫酸镁 | 0.96 |
丙烯酸酯/马来酸酯共聚物 | 8.62 |
直链烷基苯磺酸盐 | 15.92 |
羟乙烷二(亚甲基膦酸) | 0.43 |
碳酸钠 | 5.77 |
硫酸钠 | 63.43 |
皂 | 1.04 |
水 | 1.00 |
杂项 | 0.55 |
总份数 | 100.00 |
阴离子表面活性剂颗粒1的制备
使用Tilt-A-Pin,随后使用Tilt-A-Plow搅拌器(均由Procesall制造),以520g的批量标准,制备阴离子去污表面活性剂颗粒1。将所提供的108g硫酸钠连同244g碳酸钠一起,加入到Tilt-A-Pin搅拌器中。将168g具有70%活性的C25E3S糊剂(基于C12/15醇和环氧乙烷的乙氧基硫 酸钠)加入到Tilt-A-Pin搅拌器中。然后在1200rpm下将所述组分搅拌10秒。然后将所得粉末转移到Tilt-A-Plow搅拌器中,并以200rpm的速度搅拌2分钟,以形成颗粒。然后使所述颗粒以2500升/分钟的速度在120℃的流化床烘干机中干燥,直至所述颗粒的平衡相对湿度小于15%。然后将干燥的颗粒进行筛分,并且将通过1180μm并留在250μm的部分保留下来。阴离子去污表面活性剂颗粒1的组成如下所示:
25.0% 重量的C25E3S乙氧基硫酸钠
18.0% 重量的硫酸钠
57.0% 重量的碳酸钠
阳离子去污表面活性剂颗粒1的制备
在Morton FM-50 Loedige搅拌器上,以14.6kg的批量标准,制备阳离子表面活性剂颗粒1。在Morton FM-50 Loedige搅拌器中,将4.5kg微粉化的硫酸钠和4.5kg微粉化的碳酸钠预混合。将4.6kg具有40%活性的一-C12-14烷基一羟乙基二甲基季铵氯化物(阳离子表面活性剂)水溶液加入到Morton FM-50 Loedige搅拌器中,同时运行主传动器和断路器。在搅拌约2分钟后,将1.0kg微粉化硫酸钠与微粉化碳酸钠重量比率为1:1的混合物加入到搅拌器中。收集所得的附聚物,并使用流化床烘干机以2500升/分钟空气为基准于100℃至140℃干燥30分钟。将所得粉末筛分,收集通过1400μm的部分,以作为阳离子表面活性剂颗粒1。阳离子表面活性剂颗粒1的组成如下所示:
15% 重量的一C12-14烷基一羟乙基二甲基季铵氯化物
40.76% 重量的碳酸钠
40.76% 重量的硫酸钠
3.48% 重量的水分和杂项
颗粒状衣物洗涤剂组合物的制备
将10.84kg的实施例1中的喷雾干燥粉末、4.76kg的阴离子去污表面活性剂颗粒1、1.57kg的阳离子去污表面活性剂颗粒1和7.83kg(总量)的其它单独给料的干燥添加物质,加入到直径1m的以24rpm的速度运作的混凝土间歇式搅拌器中。当所有物质均被加入到搅拌器中后,将所述 混合物搅拌5分钟,以形成颗粒状衣物洗涤剂组合物。颗粒状衣物洗涤剂组合物的配方如下所述:
颗粒状衣物洗涤剂组合物
实施例9-液体衣物洗涤剂
成分 | A | B | C | D | E | F3 |
重量% | 重量% | 重量% | 重量% | 重量% | 重量% | |
烷基醚硫酸钠 | 14.4% | 14.4% | 9.2% | 5.4% | ||
直链烷基苯磺酸 | 4.4% | 4.4% | 12.2% | 5.7% | 1.3 | |
烷基乙氧基化物 | 2.2% | 2.2% | 8.8% | 8.1% | 3.4% | |
氧化胺 | 0.7% | 0.7% | 1.5% | |||
柠檬酸 | 2.0% | 2.0% | 3.4% | 1.9% | 1.0% | 1.6% |
脂肪酸 | 3.0% | 3.0% | 8.3% | 16.0% | ||
蛋白酶 | 1.0% | 1.0% | 0.7% | 1.0% | 2.5% | |
淀粉酶 | 0.2% | 0.2% | 0.2% | 0.3% | ||
脂肪酶 | 0.2% |
硼砂 | 1.5% | 1.5% | 2.4% | 2.9% | ||
甲酸钙和甲酸钠 | 0.2% | 0.2% | ||||
甲酸 | 1.1 | |||||
聚合物1 | 1.8% | 1.8% | 2.1% | 3.2% | ||
聚丙烯酸钠 | 0.2% | |||||
聚丙烯酸钠共聚物 | 0.6% | |||||
DTP A2 | 0.1% | 0.1% | 0.9% | |||
DTPMP3 | 0.3% | |||||
乙二胺四乙酸4 | 0.1% | |||||
荧光增白剂 | 0.15% | 0.15% | 0.2% | 0.12% | 0.12% | 0.2% |
乙醇 | 2.5% | 2.5% | 1.4% | 1.5% | ||
丙二醇 | 6.6% | 6.6% | 4.9% | 4.0% | 15.7% | |
山梨醇 | 4.0% | |||||
乙醇胺 | 1.5% | 1.5% | 0.8% | 0.1% | 11.0% | |
氢氧化钠 | 3.0% | 3.0% | 4.9% | 1.9% | 1.0% | |
异丙基苯磺酸钠 | 2.0% | |||||
硅氧烷抑泡剂 | 0.01% | |||||
香料 | 0.3% | 0.3% | 0.7% | 0.3% | 0.4% | 0.6% |
遮光剂5 | 0.30% | 0.20% | 0.50% | |||
水 | 余量 | 余量 | 余量 | 余量 | 余量 | 余量 |
100.0% | 100.0% | 100.0% | 100.0% | 100.0% | 100.0% |
1如实施例1、2、3、4、5或6中任一项所述的两亲性接枝聚合物或任何聚合物混合物。
2二亚乙基三胺五醋酸,钠盐
3二亚乙基三胺五甲叉膦酸,钠盐
4乙二胺四乙酸,钠盐
5Acusol OP 301
实施例10-液体手洗盘碟洗涤剂
1如实施例1、2、3、4、5或6中任一项所述的两亲性接枝聚合物或任何聚合物混合物。
2非离子物可以是任一个包含9个乙氧基的C11烷基乙氧基化表面活性剂。
31,3BAC是1,3-二(甲胺)环己烷。
4(N,N-二甲基氨基)甲基丙烯酸乙酯均聚物
实施例11-自动盘碟洗涤剂
1 如实施例1、2、3、4、5或6中任一项所述的两亲性接枝聚合物或任何聚合物混合物。
3 诸如得自Ol in Corporat ion的SLF-18 PLY TERGENT。
除非另外指明,所有组分或组合物含量均是关于该组分或组合物的活性物质含量,不包括可能存在于可商购获得的来源中的杂质,例如残余溶剂或副产品。
除非另外指明,所有百分比和比率均按重量计算。除非另外指明,所有百分比和比率均基于总组合物计算。
应当理解,在整个说明书中给出的每一最大数值限度包括每一较低数值限度,就像这样的较低数值限度在本文中是明确地写出一样。在整个说明书中给出的每一最小数值限度包括每一较高数值限度,就像这样的较高数值限度在本文中是明确地写出一样。在整个说明书中给出的每一数值范围包括落在该较宽数值范围内的每一较窄数值范围,就像这样的较窄数值范围在本文中是明确地写出一样。
在发明详述中引用的所有文件都在相关部分中以引用方式并入本文中。对于任何文件的引用不应当解释为承认其是有关本发明的现有技术。
虽然已经举例说明和描述了本发明的具体实施方案,但是对于本领域技术人员来说显而易见的是,在不背离本发明实质和范围的情况下可以做出多个其他改变和变型。因此,权利要求书意欲包括在本发明范围内的所有这样的改变和变型。
Claims (14)
1.一种清洁组合物,所述清洁组合物包含两亲性接枝聚合物,所述聚合物基于作为接枝基底的水溶性聚环氧烷(A)和经由乙烯基酯组分(B)聚合反应形成的侧链,所述聚合物每50个烯化氧单元具有平均≤1个接枝位点,且所述聚合物具有3000至100000的平均摩尔质量Mw。
2.如权利要求1所述的清洁组合物,其中所述清洁组合物是衣物洗涤剂。
3.如权利要求1所述的清洁组合物,其中所述清洁组合物选自由下列组成的组:液体衣物洗涤剂组合物、固体衣物洗涤剂组合物、硬质表面清洁组合物、液体手动餐具洗涤组合物、固体自动盘碟洗涤组合物、液体自动盘碟洗涤组合物、以及片剂/单位剂型的自动盘碟洗涤组合物。
4.如权利要求1或权利要求3所述的清洁组合物,其中所述清洁组合物包含按所述清洁组合物的重量计0.05%至10%的两亲性接枝聚合物。
5.如权利要求1所述的清洁组合物,其中所述两亲性接枝聚合物具有小于或等于3的多分散度。
6.如权利要求1所述的清洁组合物,其中所述两亲性接枝聚合物包含按所述聚合物的重量计小于或等于10%的未接枝形式的聚乙烯基酯。
7.如权利要求1所述的清洁组合物,其中所述两亲性接枝聚合物具有
(A)按重量计20%至70%的作为接枝基底的水溶性聚环氧烷,和
(B)在(A)的存在下经由按重量计30%至80%乙烯基酯组分的自由基聚合反应形成的侧链,所述乙烯基酯组分由下述物质组成:
(B1)按重量计70%至100%的乙酸乙烯酯和/或丙酸乙烯酯,和
(B2)按重量计0%至30%的其它烯键式不饱和单体。
8.如权利要求1或权利要求3所述的清洁组合物,其中所述两亲性接枝聚合物可通过使(B)按重量计30%至80%的乙烯基酯组分在
(A)按重量计20%至70%的平均摩尔质量Mn为1500至20000的水溶性聚环氧烷,
(C)以组分(B)为基准,按重量计0.25%至5%的自由基形成引发剂,和
(D)以组分(A)、(B)和(C)的总和为基准,按重量计0%至40%的有机溶剂存在下,
在所述引发剂(C)具有40至500分钟分解半衰期的平均聚合反应温度,以使所述反应混合物中未转化的接枝单体(B)和引发剂(C)份数在数量上一直保持相对于所述聚环氧烷(A)不足的方式发生自由基聚合反应获得,所述乙烯基酯组分由(B1)按重量计70%至100%的乙酸乙烯酯和/或丙酸乙烯酯、和(B2)按重量计0%至30%的其它烯键式不饱和单体组成。
9.如权利要求1所述的清洁组合物,其中所述组合物还包含表面活性剂体系。
10.如权利要求9所述的清洁组合物,其中所述表面活性剂体系包含C10-C15烷基苯磺酸盐。
11.如权利要求9所述的清洁组合物,其中所述表面活性剂体系包含C8-C18直链烷基磺酸盐表面活性剂。
12.如权利要求10或权利要求11所述的清洁组合物,其中所述表面活性剂体系还包含一种或多种辅助表面活性剂,所述辅助表面活性剂选自由下列组成的组:非离子表面活性剂、阳离子表面活性剂、阴离子表面活性剂以及它们的混合物。
13.如权利要求1所述的清洁组合物,其中所述组合物还包含清洁辅助添加剂。
14.一种清洁工具,所述清洁工具包括无纺的基底和如前述任一项权利要求所述的清洁组合物。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06114756.7 | 2006-05-31 | ||
EP06114756 | 2006-05-31 | ||
PCT/EP2007/055198 WO2007138054A1 (en) | 2006-05-31 | 2007-05-29 | Cleaning compositions with amphiphilic graft polymers based on polyalkylene oxides and vinyl esters |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101473025A CN101473025A (zh) | 2009-07-01 |
CN101473025B true CN101473025B (zh) | 2011-06-15 |
Family
ID=38377210
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2007800191524A Active CN101473025B (zh) | 2006-05-31 | 2007-05-29 | 包含基于聚环氧烷和乙烯基酯的两亲性接枝聚合物的清洁组合物 |
CN2007800198078A Active CN101454364B (zh) | 2006-05-31 | 2007-05-29 | 基于聚氧化烯和乙烯基酯的两亲性接枝聚合物 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2007800198078A Active CN101454364B (zh) | 2006-05-31 | 2007-05-29 | 基于聚氧化烯和乙烯基酯的两亲性接枝聚合物 |
Country Status (15)
Country | Link |
---|---|
US (2) | US8519060B2 (zh) |
EP (2) | EP2029645B1 (zh) |
JP (2) | JP2009538946A (zh) |
KR (1) | KR20090023374A (zh) |
CN (2) | CN101473025B (zh) |
AT (2) | ATE474906T1 (zh) |
BR (2) | BRPI0712159B1 (zh) |
CA (2) | CA2653880C (zh) |
DE (2) | DE602007007945D1 (zh) |
EG (1) | EG25183A (zh) |
ES (2) | ES2349236T3 (zh) |
MX (2) | MX2008014819A (zh) |
RU (1) | RU2413756C2 (zh) |
WO (2) | WO2007138053A1 (zh) |
ZA (1) | ZA200808921B (zh) |
Families Citing this family (325)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2349236T3 (es) | 2006-05-31 | 2010-12-29 | Basf Se | Polímeros anfifílicos de injerto con base en óxidos de polialquileno y ésteres de vinil. |
EP2014755B1 (en) * | 2007-05-29 | 2012-03-21 | The Procter & Gamble Company | Method of cleaning dishware |
AR067365A1 (es) * | 2007-06-29 | 2009-10-07 | Procter & Gamble | Composiciones detergentes para lavanderia que comprenden polimeros anfifilicos injertados basados en oxidos de polialquileno y vinilesteres |
MX306402B (es) * | 2007-11-09 | 2013-01-04 | Basf Se | Polialcanolaminas alcoxiladas. |
PL2209837T3 (pl) * | 2007-11-09 | 2020-02-28 | Basf Se | Amfifilowe rozpuszczalne w wodzie alkoksylowane polialkilenoiminy zawierające wewnętrzny blok poli(tlenku etylenu) i zewnętrzny blok poli(tlenku propylenu) |
WO2009087523A2 (en) | 2008-01-04 | 2009-07-16 | The Procter & Gamble Company | A laundry detergent composition comprising glycosyl hydrolase |
HUE042847T2 (hu) | 2008-06-06 | 2019-07-29 | Procter & Gamble | A 44 xiloglukanáz család egyik variánsát tartalmazó felületaktív készítmény |
EP2138568A1 (en) | 2008-06-25 | 2009-12-30 | The Procter and Gamble Company | Neutralisation process for producing a laundry detergent composition comprising anionic detersive surfactant and polymeric material |
EP2321395A4 (en) * | 2008-09-01 | 2012-12-19 | Procter & Gamble | COMPOSITION WITH POLYOXYALKYLENEBASE POLYMER COMPOUND |
EP2328999A1 (en) * | 2008-09-30 | 2011-06-08 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
EP2328998A1 (en) * | 2008-09-30 | 2011-06-08 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
WO2010039572A1 (en) | 2008-09-30 | 2010-04-08 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
EP2216392B1 (en) | 2009-02-02 | 2013-11-13 | The Procter and Gamble Company | Liquid hand dishwashing detergent composition |
ES2488117T3 (es) | 2009-02-02 | 2014-08-26 | The Procter & Gamble Company | Composición detergente líquida para lavado de vajillas a mano |
EP2216391A1 (en) | 2009-02-02 | 2010-08-11 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
EP3023483A1 (en) | 2009-02-02 | 2016-05-25 | The Procter and Gamble Company | Liquid hand diswashing detergent composition |
EP2216390B1 (en) | 2009-02-02 | 2013-11-27 | The Procter and Gamble Company | Hand dishwashing method |
EP2213713B1 (en) | 2009-02-02 | 2014-03-12 | The Procter and Gamble Company | Liquid hand dishwashing detergent composition |
US7973004B2 (en) | 2009-02-12 | 2011-07-05 | Hercules Incorporated | Rheology modifier for aqueous surfactant-based formulations |
US8153574B2 (en) | 2009-03-18 | 2012-04-10 | The Procter & Gamble Company | Structured fluid detergent compositions comprising dibenzylidene polyol acetal derivatives and detersive enzymes |
US8293697B2 (en) | 2009-03-18 | 2012-10-23 | The Procter & Gamble Company | Structured fluid detergent compositions comprising dibenzylidene sorbitol acetal derivatives |
EP2264138B2 (en) | 2009-06-19 | 2023-03-08 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
ES2412684T3 (es) | 2009-06-19 | 2013-07-12 | The Procter & Gamble Company | Composición detergente de lavado de vajillas a mano líquida |
PL2295530T3 (pl) * | 2009-09-14 | 2012-04-30 | Procter & Gamble | Kompozycja detergentu |
JP5133460B2 (ja) | 2009-09-15 | 2013-01-30 | ザ プロクター アンド ギャンブル カンパニー | キレート剤の混合物を含む洗剤組成物 |
EP2302026A1 (en) * | 2009-09-15 | 2011-03-30 | The Procter & Gamble Company | Detergent composition comprising surfactant boosting polymers |
US20110150817A1 (en) | 2009-12-17 | 2011-06-23 | Ricky Ah-Man Woo | Freshening compositions comprising malodor binding polymers and malodor control components |
JP5574678B2 (ja) * | 2009-11-17 | 2014-08-20 | 株式会社日本触媒 | 新規重合体およびその製造方法 |
JP5637678B2 (ja) * | 2009-11-17 | 2014-12-10 | 株式会社日本触媒 | 新規重合体およびその製造方法 |
US8334250B2 (en) * | 2009-12-18 | 2012-12-18 | The Procter & Gamble Company | Method of making granular detergent compositions comprising amphiphilic graft copolymers |
US20110152161A1 (en) * | 2009-12-18 | 2011-06-23 | Rohan Govind Murkunde | Granular detergent compositions comprising amphiphilic graft copolymers |
CA2785479C (en) * | 2009-12-22 | 2015-06-16 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
ES2444618T3 (es) * | 2009-12-22 | 2014-02-26 | The Procter & Gamble Company | Composición limpiadora y/o de lavado líquida |
EP2338961A1 (en) | 2009-12-22 | 2011-06-29 | The Procter & Gamble Company | An alkaline liquid hand dish washing detergent composition |
EP2501792A2 (en) | 2009-12-29 | 2012-09-26 | Novozymes A/S | Gh61 polypeptides having detergency enhancing effect |
SG173230A1 (en) * | 2010-01-25 | 2011-08-29 | Rohm & Haas | Laundry detergent bar composition |
US8865637B2 (en) | 2010-02-25 | 2014-10-21 | Novozymes Als | Variants of a lysozyme and polynucleotides encoding same |
DK2365055T3 (en) * | 2010-03-01 | 2018-03-05 | Procter & Gamble | COMPOSITION INCLUDING SUBSTITUTED CELLULOSE POLYMES AND AMYLASE |
EP2365059A1 (en) * | 2010-03-01 | 2011-09-14 | The Procter & Gamble Company | Solid laundry detergent composition comprising C.I. fluorescent brightener 260 in alpha-crystalline form |
CA2791485A1 (en) * | 2010-03-08 | 2011-09-15 | Basf Se | Composition comprising an active substance and a polyalkyleneoxide vinylester graft polymer |
EP2380956A1 (en) | 2010-04-19 | 2011-10-26 | The Procter & Gamble Company | Process for making a detergent |
EP2561056A1 (en) | 2010-04-21 | 2013-02-27 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
JP5847177B2 (ja) | 2010-07-22 | 2016-01-20 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 保護コロイドで安定化したエマルション重合体を有する減音材 |
US8623463B2 (en) | 2010-07-22 | 2014-01-07 | Basf Se | Sound deadener composition with emulsion polymer stabilized by protective colloids |
US8685171B2 (en) | 2010-07-29 | 2014-04-01 | The Procter & Gamble Company | Liquid detergent composition |
EP2412792A1 (en) | 2010-07-29 | 2012-02-01 | The Procter & Gamble Company | Liquid detergent composition |
ES2659402T3 (es) | 2010-08-17 | 2018-03-15 | The Procter & Gamble Company | Método para lavado de vajillas a mano que tiene jabonaduras duraderas |
EP2420558B1 (en) | 2010-08-17 | 2017-08-02 | The Procter & Gamble Company | Stable sustainable hand dish-washing detergents |
US8629093B2 (en) | 2010-09-01 | 2014-01-14 | The Procter & Gamble Company | Detergent composition comprising mixture of chelants |
WO2012035103A1 (en) | 2010-09-16 | 2012-03-22 | Novozymes A/S | Lysozymes |
EP2431455A1 (en) | 2010-09-21 | 2012-03-21 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
EP2431451A1 (en) | 2010-09-21 | 2012-03-21 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
JP5702469B2 (ja) | 2010-09-21 | 2015-04-15 | ザ プロクター アンド ギャンブルカンパニー | 液体洗浄組成物 |
WO2012040142A1 (en) | 2010-09-21 | 2012-03-29 | The Procter & Gamble Company | Liquid cleaning composition |
EP2431452B1 (en) | 2010-09-21 | 2015-07-08 | The Procter & Gamble Company | Liquid cleaning composition |
CN103476916A (zh) | 2011-02-16 | 2013-12-25 | 诺维信公司 | 包含m7或m35金属蛋白酶的去污剂组合物 |
JP2014508830A (ja) | 2011-02-16 | 2014-04-10 | ノボザイムス アクティーゼルスカブ | 金属プロテアーゼを含む洗剤組成物 |
US20140038270A1 (en) | 2011-02-16 | 2014-02-06 | Novozymes A/S | Detergent Compositions Comprising Metalloproteases |
JP2014511415A (ja) | 2011-03-03 | 2014-05-15 | ザ プロクター アンド ギャンブル カンパニー | 食器洗浄方法 |
EP2537917A1 (en) | 2011-06-20 | 2012-12-26 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
US8852643B2 (en) | 2011-06-20 | 2014-10-07 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
RU2575931C2 (ru) | 2011-06-20 | 2016-02-27 | Дзе Проктер Энд Гэмбл Компани | Жидкий состав для чистки и/или глубокой очистки |
RU2566750C2 (ru) | 2011-06-20 | 2015-10-27 | Дзе Проктер Энд Гэмбл Компани | Жидкий состав для чистки и/или глубокой очистки |
US8828920B2 (en) | 2011-06-23 | 2014-09-09 | The Procter & Gamble Company | Product for pre-treatment and laundering of stained fabric |
CN103620029B (zh) | 2011-06-24 | 2017-06-09 | 诺维信公司 | 具有蛋白酶活性的多肽和编码它们的多核苷酸 |
HUE058093T2 (hu) | 2011-06-30 | 2022-06-28 | Novozymes As | Eljárás alfa-amilázok szkrínelésére |
EP2737040A1 (en) | 2011-07-27 | 2014-06-04 | The Procter and Gamble Company | Multiphase liquid detergent composition |
JP2014531895A (ja) | 2011-08-15 | 2014-12-04 | ノボザイムス アクティーゼルスカブ | セルラーゼ活性を有するポリペプチドおよびそれをコードするポリヌクレオチド |
EP2573156A1 (en) | 2011-09-20 | 2013-03-27 | The Procter & Gamble Company | Liquid cleaning composition |
CN104204200B (zh) | 2011-09-22 | 2017-06-09 | 诺维信公司 | 具有蛋白酶活性的多肽和编码它们的多核苷酸 |
BR112014012170A2 (pt) | 2011-11-25 | 2020-06-23 | Novozymes A/S | polipetídeo isolado, composição, aditivo de ração animal, uso de um polipetídeo, métodos de isolamento de dna de bastérias, e de produção de um poliptídeo, polinucleotídeo isolado, constructo de ácido nucleico ou vetor de expressão, célula hospedeira recombinante, e, planta, parte de planta ou célula de planta |
MX2014006205A (es) | 2011-11-25 | 2014-07-14 | Novozymes As | Variantes de subtilasa y polinucleotidos que las codifican. |
US20130150276A1 (en) * | 2011-12-09 | 2013-06-13 | The Procter & Gamble Company | Method of providing fast drying and/or delivering shine on hard surfaces |
US8840731B2 (en) * | 2011-12-09 | 2014-09-23 | Basf Se | Preparations, their production and use |
BR112014011576A2 (pt) * | 2011-12-09 | 2017-05-09 | Basf Se | usos de uma preparação e de um copolímero, e, método para a lavagem de louças a máquina |
US20140335596A1 (en) | 2011-12-20 | 2014-11-13 | Novozymes A/S | Subtilase Variants and Polynucleotides Encoding Same |
ES2680145T3 (es) | 2011-12-29 | 2018-09-04 | Novozymes A/S | Composiciones detergentes con variantes de lipasa |
EP2807254B1 (en) | 2012-01-26 | 2017-08-02 | Novozymes A/S | Use of polypeptides having protease activity in animal feed and detergents |
WO2013120948A1 (en) | 2012-02-17 | 2013-08-22 | Novozymes A/S | Subtilisin variants and polynucleotides encoding same |
EP2631286A1 (en) | 2012-02-23 | 2013-08-28 | The Procter & Gamble Company | Liquid cleaning composition |
CN104704102A (zh) | 2012-03-07 | 2015-06-10 | 诺维信公司 | 洗涤剂组合物和洗涤剂组合物中光增亮剂的取代 |
US9068023B2 (en) | 2012-03-09 | 2015-06-30 | Basf Se | Continuous process for the synthesis of graft polymers based on polyethers |
WO2013132042A1 (en) | 2012-03-09 | 2013-09-12 | Basf Se | Continuous process for the synthesis of graft polymers based on polyethers |
CA2865507A1 (en) * | 2012-03-09 | 2013-09-12 | The Procter & Gamble Company | Detergent compositions comprising graft polymers having broad polarity distributions |
CN117904080A (zh) | 2012-05-07 | 2024-04-19 | 诺维信公司 | 具有黄原胶降解活性的多肽以及编码其的核苷酸 |
US9068147B2 (en) | 2012-05-11 | 2015-06-30 | Basf Se | Quaternized polyethylenimines with a high quaternization degree |
WO2013189802A1 (en) | 2012-06-19 | 2013-12-27 | Novozymes A/S | Enzymatic reduction of hydroperoxides |
CN104394708A (zh) | 2012-06-20 | 2015-03-04 | 诺维信公司 | 具有蛋白酶活性的多肽在动物饲料和洗涤剂中的用途 |
EP2880074B1 (en) | 2012-07-31 | 2016-06-29 | Unilever Plc. | Alkaline liquid laundry detergent compositions comprising polyesters |
EP2692842B1 (en) | 2012-07-31 | 2014-07-30 | Unilever PLC | Concentrated liquid detergent compositions |
CN104603266B (zh) | 2012-08-22 | 2017-11-10 | 诺维信公司 | 来自脂环酸芽孢杆菌属的金属蛋白酶 |
BR112015003726A2 (pt) | 2012-08-22 | 2019-09-24 | Novozymes As | composição detergente, uso de uma composição e de um polipeptídeo, e, método para remoção de uma nódoa de uma superfície. |
MX2015002211A (es) | 2012-08-22 | 2015-05-08 | Novozymes As | Metaloproteasa de exiguobacterium. |
EP2719752B1 (en) | 2012-10-15 | 2016-03-16 | The Procter and Gamble Company | Liquid detergent composition with abrasive particles |
WO2014090940A1 (en) | 2012-12-14 | 2014-06-19 | Novozymes A/S | Removal of skin-derived body soils |
MX363360B (es) | 2012-12-21 | 2019-03-21 | Novozymes As | Polipéptidos que poseen actividad proteasa y polinucleótidos que los codifican. |
US9902946B2 (en) | 2013-01-03 | 2018-02-27 | Novozymes A/S | Alpha-amylase variants and polynucleotides encoding same |
US9873854B2 (en) * | 2013-01-16 | 2018-01-23 | Jelmar, Llc | Stain removing solution |
EP2970830B1 (en) | 2013-03-14 | 2017-12-13 | Novozymes A/S | Enzyme and inhibitor contained in water-soluble films |
CN105164244B (zh) | 2013-05-03 | 2019-08-20 | 诺维信公司 | 洗涤剂酶的微囊化 |
ITMI20130782A1 (it) | 2013-05-13 | 2014-11-14 | Fra Ber S R L | Prodotti per autolavaggi a base enzimatica |
WO2014183921A1 (en) | 2013-05-17 | 2014-11-20 | Novozymes A/S | Polypeptides having alpha amylase activity |
CN105264058B (zh) | 2013-06-06 | 2022-03-29 | 诺维信公司 | α-淀粉酶变体以及对其进行编码的多核苷酸 |
EP3013956B1 (en) | 2013-06-27 | 2023-03-01 | Novozymes A/S | Subtilase variants and polynucleotides encoding same |
EP3013955A1 (en) | 2013-06-27 | 2016-05-04 | Novozymes A/S | Subtilase variants and polynucleotides encoding same |
RU2015156280A (ru) | 2013-07-04 | 2017-08-09 | Новозимс А/С | Полипептиды, обладающие эффектом против переосаждения, и полинуклеотиды, кодирующие их |
CN105358684A (zh) | 2013-07-29 | 2016-02-24 | 诺维信公司 | 蛋白酶变体以及对其进行编码的多核苷酸 |
US10150957B2 (en) | 2013-07-29 | 2018-12-11 | Novozymes A/S | Protease variants and polynucleotides encoding same |
EP2832843B1 (en) * | 2013-07-30 | 2019-08-21 | The Procter & Gamble Company | Method of making granular detergent compositions comprising polymers |
EP2832842B1 (en) | 2013-07-30 | 2018-12-19 | The Procter & Gamble Company | Method of making granular detergent compositions comprising surfactants |
EP2832841B1 (en) * | 2013-07-30 | 2016-08-31 | The Procter & Gamble Company | Method of making detergent compositions comprising polymers |
EP2832844A1 (en) * | 2013-07-30 | 2015-02-04 | The Procter & Gamble Company | Method of making detergent compositions comprising polymers |
WO2015049370A1 (en) | 2013-10-03 | 2015-04-09 | Novozymes A/S | Detergent composition and use of detergent composition |
EP3453757B1 (en) | 2013-12-20 | 2020-06-17 | Novozymes A/S | Polypeptides having protease activity and polynucleotides encoding same |
EP2899259A1 (en) | 2014-01-22 | 2015-07-29 | The Procter and Gamble Company | Detergent compositions |
US20160333292A1 (en) | 2014-03-05 | 2016-11-17 | Novozymes A/S | Compositions and Methods for Improving Properties of Cellulosic Textile Materials with Xyloglucan Endotransglycosylase |
CN106062270A (zh) | 2014-03-05 | 2016-10-26 | 诺维信公司 | 使用木葡聚糖内糖基转移酶改进非纤维素纺织材料的性质的组合物和方法 |
DE102014206064A1 (de) | 2014-03-31 | 2015-10-01 | Henkel Ag & Co. Kgaa | Flüssigwaschmittel enthaltend Polymere zur Verstärkung der Duftstoffleistung |
CN106103708A (zh) | 2014-04-01 | 2016-11-09 | 诺维信公司 | 具有α淀粉酶活性的多肽 |
RU2737535C2 (ru) | 2014-04-11 | 2020-12-01 | Новозимс А/С | Моющая композиция |
US20170121695A1 (en) | 2014-06-12 | 2017-05-04 | Novozymes A/S | Alpha-amylase variants and polynucleotides encoding same |
US20170121646A1 (en) | 2014-07-03 | 2017-05-04 | Novozymes A/S | Improved Stabilization of Non-Protease Enzyme |
CN106661566A (zh) | 2014-07-04 | 2017-05-10 | 诺维信公司 | 枯草杆菌酶变体以及编码它们的多核苷酸 |
EP3164486B1 (en) | 2014-07-04 | 2020-05-13 | Novozymes A/S | Subtilase variants and polynucleotides encoding same |
EP3143114B1 (en) * | 2014-07-11 | 2023-12-13 | The Procter & Gamble Company | Structured particles comprising amphiphilic graft copolymer, and granular laundry detergent comprising thereof |
EP2980198A1 (en) * | 2014-07-31 | 2016-02-03 | The Procter and Gamble Company | Composition comprising amphiphilic graft polymer |
EP2980197A1 (en) * | 2014-07-31 | 2016-02-03 | The Procter and Gamble Company | Liquid laundry detergent composition |
WO2016075179A1 (en) | 2014-11-11 | 2016-05-19 | Clariant International Ltd | Laundry detergents containing soil release polymers |
MX2017006151A (es) | 2014-11-11 | 2017-11-20 | Clariant Int Ltd | Detergentes de lavanderia que contienen polimeros de liberacion de suciedad. |
EP3221447A1 (en) | 2014-11-20 | 2017-09-27 | Novozymes A/S | Alicyclobacillus variants and polynucleotides encoding same |
EP3227444B1 (en) | 2014-12-04 | 2020-02-12 | Novozymes A/S | Subtilase variants and polynucleotides encoding same |
CN116286218A (zh) | 2014-12-04 | 2023-06-23 | 诺维信公司 | 包括蛋白酶变体的液体清洁组合物 |
WO2016096714A1 (en) | 2014-12-15 | 2016-06-23 | Henkel Ag & Co. Kgaa | Detergent composition comprising subtilase variants |
CN107002049A (zh) | 2014-12-16 | 2017-08-01 | 诺维信公司 | 具有n‑乙酰基葡萄糖胺氧化酶活性的多肽 |
EP3741848A3 (en) | 2014-12-19 | 2021-02-17 | Novozymes A/S | Protease variants and polynucleotides encoding same |
CN107002061A (zh) | 2014-12-19 | 2017-08-01 | 诺维信公司 | 蛋白酶变体以及对其进行编码的多核苷酸 |
EP3280791A1 (en) | 2015-04-10 | 2018-02-14 | Novozymes A/S | Laundry method, use of dnase and detergent composition |
CN108012544A (zh) | 2015-06-18 | 2018-05-08 | 诺维信公司 | 枯草杆菌酶变体以及编码它们的多核苷酸 |
EP3106508B1 (en) | 2015-06-18 | 2019-11-20 | Henkel AG & Co. KGaA | Detergent composition comprising subtilase variants |
CN107922896A (zh) | 2015-06-30 | 2018-04-17 | 诺维信公司 | 衣物洗涤剂组合物、用于洗涤的方法和组合物的用途 |
WO2017046260A1 (en) | 2015-09-17 | 2017-03-23 | Novozymes A/S | Polypeptides having xanthan degrading activity and polynucleotides encoding same |
US10844360B2 (en) | 2015-10-07 | 2020-11-24 | Novozymes A/S | Polypeptides |
EP3362556A1 (en) | 2015-10-14 | 2018-08-22 | Novozymes A/S | Polypeptide variants |
CN108291215A (zh) | 2015-10-14 | 2018-07-17 | 诺维信公司 | 具有蛋白酶活性的多肽以及编码它们的多核苷酸 |
MX2018004683A (es) | 2015-10-28 | 2018-07-06 | Novozymes As | Composicion detergente que comprende variantes de amilasa y proteasa. |
EP3380608A1 (en) | 2015-11-24 | 2018-10-03 | Novozymes A/S | Polypeptides having protease activity and polynucleotides encoding same |
JP2018537099A (ja) | 2015-12-07 | 2018-12-20 | ノボザイムス アクティーゼルスカブ | ベータ−グルカナーゼ活性を有するポリペプチド、これをコードするポリヌクレオチド、ならびにクリーニング組成物中でのおよび洗剤組成物中でのこの使用 |
EP3408386A1 (en) | 2016-01-29 | 2018-12-05 | Novozymes A/S | Beta-glucanase variants and polynucleotides encoding same |
EP3205393A1 (en) | 2016-02-12 | 2017-08-16 | Basf Se | Process for preparation of microcapsules |
EP3433347B1 (en) | 2016-03-23 | 2020-05-06 | Novozymes A/S | Use of polypeptide having dnase activity for treating fabrics |
CN114480035A (zh) | 2016-04-08 | 2022-05-13 | 诺维信公司 | 洗涤剂组合物及其用途 |
MX2018013139A (es) | 2016-04-29 | 2019-02-13 | Novozymes As | Composiciones detergentes y sus usos. |
CN109563450A (zh) | 2016-05-31 | 2019-04-02 | 诺维信公司 | 稳定的液体过氧化物组合物 |
CN109715792A (zh) | 2016-06-03 | 2019-05-03 | 诺维信公司 | 枯草杆菌酶变体和对其进行编码的多核苷酸 |
CN109640659B (zh) | 2016-06-29 | 2021-08-31 | 科莱恩国际有限公司 | 用于抑制微生物的组合物 |
WO2018001959A1 (en) | 2016-06-30 | 2018-01-04 | Novozymes A/S | Lipase variants and compositions comprising surfactant and lipase variant |
WO2018002261A1 (en) | 2016-07-01 | 2018-01-04 | Novozymes A/S | Detergent compositions |
EP3481949B1 (en) | 2016-07-05 | 2021-06-09 | Novozymes A/S | Pectate lyase variants and polynucleotides encoding same |
WO2018007573A1 (en) | 2016-07-08 | 2018-01-11 | Novozymes A/S | Detergent compositions with galactanase |
CA3027272C (en) | 2016-07-13 | 2022-06-21 | The Procter & Gamble Company | Bacillus cibi dnase variants and uses thereof |
CN109563498A (zh) | 2016-08-24 | 2019-04-02 | 汉高股份有限及两合公司 | 包含黄原胶裂解酶变体i的洗涤剂组合物 |
EP3504329A1 (en) | 2016-08-24 | 2019-07-03 | Novozymes A/S | Xanthan lyase variants and polynucleotides encoding same |
EP3504330A1 (en) | 2016-08-24 | 2019-07-03 | Novozymes A/S | Gh9 endoglucanase variants and polynucleotides encoding same |
EP3504313A1 (en) | 2016-08-24 | 2019-07-03 | Henkel AG & Co. KGaA | Detergent composition comprising gh9 endoglucanase variants i |
WO2018052993A1 (en) | 2016-09-13 | 2018-03-22 | The Procter & Gamble Company | Process for making a composition comprising benefit agent delivery particles |
US20190284647A1 (en) | 2016-09-29 | 2019-09-19 | Novozymes A/S | Spore Containing Granule |
EP3532592A1 (en) | 2016-10-25 | 2019-09-04 | Novozymes A/S | Detergent compositions |
EP3535377B1 (en) | 2016-11-01 | 2022-02-09 | Novozymes A/S | Multi-core granules |
DE102016223584A1 (de) | 2016-11-28 | 2018-05-30 | Clariant International Ltd | Copolymer enthaltende waschmittelzusammensetzungen |
DE102016223588A1 (de) | 2016-11-28 | 2018-05-30 | Clariant International Ltd | Copolymere und deren verwendung in reinigungsmittel-zusammensetzungen |
DE102016223586A1 (de) | 2016-11-28 | 2018-05-30 | Clariant International Ltd | Copolymere und deren verwendung in reinigungsmittel-zusammensetzungen |
DE102016223590A1 (de) | 2016-11-28 | 2018-05-30 | Clariant International Ltd | Copolymer enthaltende reinigungsmittelzusammensetzungen |
DE102016223585A1 (de) | 2016-11-28 | 2018-05-30 | Clariant International Ltd | Copolymere und deren verwendung in waschmittel-zusammensetzungen |
EP3330345A1 (en) * | 2016-11-30 | 2018-06-06 | The Procter & Gamble Company | Use of an amphiphilic graft polymer as a dye transfer inhibitor |
EP3551740B1 (en) | 2016-12-12 | 2021-08-11 | Novozymes A/S | Use of polypeptides |
CN110099566A (zh) * | 2016-12-23 | 2019-08-06 | 巴斯夫欧洲公司 | 使用分散组分稳定涂覆有非两性、可季化和水溶性聚合物的颗粒 |
WO2018178061A1 (en) | 2017-03-31 | 2018-10-04 | Novozymes A/S | Polypeptides having rnase activity |
EP3601549A1 (en) | 2017-03-31 | 2020-02-05 | Novozymes A/S | Polypeptides having dnase activity |
US11208639B2 (en) | 2017-03-31 | 2021-12-28 | Novozymes A/S | Polypeptides having DNase activity |
US20200109354A1 (en) | 2017-04-04 | 2020-04-09 | Novozymes A/S | Polypeptides |
US20200109352A1 (en) | 2017-04-04 | 2020-04-09 | Novozymes A/S | Polypeptide compositions and uses thereof |
CN110651029B (zh) | 2017-04-04 | 2022-02-15 | 诺维信公司 | 糖基水解酶 |
EP3385361B1 (en) | 2017-04-05 | 2019-03-27 | Henkel AG & Co. KGaA | Detergent compositions comprising bacterial mannanases |
EP3385362A1 (en) | 2017-04-05 | 2018-10-10 | Henkel AG & Co. KGaA | Detergent compositions comprising fungal mannanases |
MX2019011764A (es) | 2017-04-06 | 2019-11-28 | Novozymes As | Composiciones limpiadoras y usos de las mismas. |
EP3607042A1 (en) | 2017-04-06 | 2020-02-12 | Novozymes A/S | Cleaning compositions and uses thereof |
EP3626809A1 (en) | 2017-04-06 | 2020-03-25 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2018184818A1 (en) | 2017-04-06 | 2018-10-11 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2018184816A1 (en) | 2017-04-06 | 2018-10-11 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2018185285A1 (en) | 2017-04-06 | 2018-10-11 | Novozymes A/S | Cleaning compositions and uses thereof |
EP3607043A1 (en) | 2017-04-06 | 2020-02-12 | Novozymes A/S | Cleaning compositions and uses thereof |
MX2019011653A (es) | 2017-04-06 | 2020-02-20 | Novozymes As | Composiciones detergentes y sus usos. |
EP3401385A1 (en) | 2017-05-08 | 2018-11-14 | Henkel AG & Co. KGaA | Detergent composition comprising polypeptide comprising carbohydrate-binding domain |
WO2018206535A1 (en) | 2017-05-08 | 2018-11-15 | Novozymes A/S | Carbohydrate-binding domain and polynucleotides encoding the same |
WO2018224544A1 (en) | 2017-06-08 | 2018-12-13 | Novozymes A/S | Compositions comprising polypeptides having cellulase activity and amylase activity, and uses thereof in cleaning and detergent compositions |
CN111108183A (zh) | 2017-06-30 | 2020-05-05 | 诺维信公司 | 酶浆液组合物 |
US11359188B2 (en) | 2017-08-24 | 2022-06-14 | Novozymes A/S | Xanthan lyase variants and polynucleotides encoding same |
US20210130744A1 (en) | 2017-08-24 | 2021-05-06 | Henkel Ag & Co. Kgaa | Detergent composition comprising xanthan lyase variants ii |
WO2019038059A1 (en) | 2017-08-24 | 2019-02-28 | Henkel Ag & Co. Kgaa | DETERGENT COMPOSITIONS COMPRISING GH9 ENDOGLUCANASE VARIANTS II |
CA3070749A1 (en) | 2017-08-24 | 2019-02-28 | Novozymes A/S | Gh9 endoglucanase variants and polynucleotides encoding same |
WO2019057902A1 (en) | 2017-09-22 | 2019-03-28 | Novozymes A/S | NEW POLYPEPTIDES |
CA3072932C (en) | 2017-09-27 | 2023-09-26 | The Procter & Gamble Company | Detergent compositions comprising lipases |
CN111417725A (zh) | 2017-10-02 | 2020-07-14 | 诺维信公司 | 具有甘露聚糖酶活性的多肽和编码它们的多核苷酸 |
BR112020006621A2 (pt) | 2017-10-02 | 2020-10-06 | Novozymes A/S | polipeptídeos com atividade de mananase e polinucleotídeos codificando os mesmos |
CN111448302A (zh) | 2017-10-16 | 2020-07-24 | 诺维信公司 | 低粉化颗粒 |
US20200318037A1 (en) | 2017-10-16 | 2020-10-08 | Novozymes A/S | Low dusting granules |
WO2019076800A1 (en) | 2017-10-16 | 2019-04-25 | Novozymes A/S | CLEANING COMPOSITIONS AND USES THEREOF |
EP3701001A1 (en) | 2017-10-24 | 2020-09-02 | Novozymes A/S | Compositions comprising polypeptides having mannanase activity |
ES2910120T3 (es) | 2017-10-27 | 2022-05-11 | Procter & Gamble | Composiciones detergentes que comprenden variantes polipeptídicas |
MX2020004145A (es) | 2017-10-27 | 2020-08-03 | Novozymes As | Variantes de desoxirribonucleasa (dnasa). |
DE102017125559A1 (de) | 2017-11-01 | 2019-05-02 | Henkel Ag & Co. Kgaa | Reinigungszusammensetzungen, die dispersine ii enthalten |
BR112020008737A2 (pt) | 2017-11-01 | 2020-10-13 | Novozymes A/S | polipeptídeos e composições que compreendam tais polipeptídeos |
CN111479919A (zh) | 2017-11-01 | 2020-07-31 | 诺维信公司 | 多肽以及包含此类多肽的组合物 |
DE102017125558A1 (de) | 2017-11-01 | 2019-05-02 | Henkel Ag & Co. Kgaa | Reinigungszusammensetzungen, die dispersine i enthalten |
EP3704220A1 (en) | 2017-11-01 | 2020-09-09 | Novozymes A/S | Methods for cleaning medical devices |
DE102017125560A1 (de) | 2017-11-01 | 2019-05-02 | Henkel Ag & Co. Kgaa | Reinigungszusammensetzungen, die dispersine iii enthalten |
EP3489340A1 (en) | 2017-11-28 | 2019-05-29 | Clariant International Ltd | Renewably sourced soil release polyesters |
EP3489338A1 (en) | 2017-11-28 | 2019-05-29 | Clariant International Ltd | Detergent compositions containing renewably sourced soil release polyesters |
WO2019115478A1 (en) | 2017-12-11 | 2019-06-20 | Clariant International Ltd | Composition for inhibiting micro-organisms |
WO2019162000A1 (en) | 2018-02-23 | 2019-08-29 | Henkel Ag & Co. Kgaa | Detergent composition comprising xanthan lyase and endoglucanase variants |
EP3765185B1 (en) | 2018-03-13 | 2023-07-19 | Novozymes A/S | Microencapsulation using amino sugar oligomers |
WO2019180111A1 (en) | 2018-03-23 | 2019-09-26 | Novozymes A/S | Subtilase variants and compositions comprising same |
EP3781660A1 (en) | 2018-04-17 | 2021-02-24 | Novozymes A/S | Polypeptides comprising carbohydrate binding activity in detergent compositions and their use in reducing wrinkles in textile or fabric |
WO2019201785A1 (en) | 2018-04-19 | 2019-10-24 | Novozymes A/S | Stabilized cellulase variants |
CN112272701B (zh) | 2018-04-19 | 2024-05-14 | 诺维信公司 | 稳定化的纤维素酶变体 |
WO2019224030A1 (en) | 2018-05-24 | 2019-11-28 | Clariant International Ltd | Soil release polyesters for use in detergent compositions |
US11326129B2 (en) | 2018-06-26 | 2022-05-10 | The Procter & Gamble Company | Fabric care compositions that include a graft copolymer and related methods |
US20210071115A1 (en) | 2018-06-28 | 2021-03-11 | Novozymes A/S | Detergent Compositions and Uses Thereof |
WO2020005879A1 (en) | 2018-06-28 | 2020-01-02 | The Procter & Gamble Company | Fabric treatment compositions with polymer system and related processes |
EP3814489A1 (en) | 2018-06-29 | 2021-05-05 | Novozymes A/S | Subtilase variants and compositions comprising same |
EP3814473A1 (en) | 2018-06-29 | 2021-05-05 | Novozymes A/S | Detergent compositions and uses thereof |
US20210189296A1 (en) | 2018-07-02 | 2021-06-24 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2020007875A1 (en) | 2018-07-03 | 2020-01-09 | Novozymes A/S | Cleaning compositions and uses thereof |
EP3818140A1 (en) | 2018-07-06 | 2021-05-12 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2020008024A1 (en) | 2018-07-06 | 2020-01-09 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2020070063A2 (en) | 2018-10-01 | 2020-04-09 | Novozymes A/S | Detergent compositions and uses thereof |
WO2020070209A1 (en) | 2018-10-02 | 2020-04-09 | Novozymes A/S | Cleaning composition |
WO2020070014A1 (en) | 2018-10-02 | 2020-04-09 | Novozymes A/S | Cleaning composition comprising anionic surfactant and a polypeptide having rnase activity |
US20230287306A1 (en) | 2018-10-02 | 2023-09-14 | Novozymes A/S | Cleaning Composition |
WO2020070249A1 (en) | 2018-10-03 | 2020-04-09 | Novozymes A/S | Cleaning compositions |
US11993762B2 (en) | 2018-10-03 | 2024-05-28 | Novozymes A/S | Polypeptides having alpha-mannan degrading activity and polynucleotides encoding same |
EP3864122A1 (en) | 2018-10-09 | 2021-08-18 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2020074499A1 (en) | 2018-10-09 | 2020-04-16 | Novozymes A/S | Cleaning compositions and uses thereof |
EP3864124A1 (en) | 2018-10-11 | 2021-08-18 | Novozymes A/S | Cleaning compositions and uses thereof |
EP3647398B1 (en) | 2018-10-31 | 2024-05-15 | Henkel AG & Co. KGaA | Cleaning compositions containing dispersins v |
EP3647397A1 (en) | 2018-10-31 | 2020-05-06 | Henkel AG & Co. KGaA | Cleaning compositions containing dispersins iv |
CN113302270A (zh) | 2018-12-03 | 2021-08-24 | 诺维信公司 | 低pH粉末洗涤剂组合物 |
CN113302295A (zh) | 2018-12-03 | 2021-08-24 | 诺维信公司 | 粉末洗涤剂组合物 |
EP3898962A2 (en) | 2018-12-21 | 2021-10-27 | Novozymes A/S | Polypeptides having peptidoglycan degrading activity and polynucleotides encoding same |
EP3898919A1 (en) | 2018-12-21 | 2021-10-27 | Novozymes A/S | Detergent pouch comprising metalloproteases |
EP3702452A1 (en) | 2019-03-01 | 2020-09-02 | Novozymes A/S | Detergent compositions comprising two proteases |
AU2020242303A1 (en) | 2019-03-21 | 2021-06-24 | Novozymes A/S | Alpha-amylase variants and polynucleotides encoding same |
US20220169953A1 (en) | 2019-04-03 | 2022-06-02 | Novozymes A/S | Polypeptides having beta-glucanase activity, polynucleotides encoding same and uses thereof in cleaning and detergent compositions |
WO2020207944A1 (en) | 2019-04-10 | 2020-10-15 | Novozymes A/S | Polypeptide variants |
MX2021012289A (es) | 2019-04-12 | 2021-11-12 | Novozymes As | Variantes de glucosido hidrolasa estabilizadas. |
WO2021009067A1 (en) | 2019-07-12 | 2021-01-21 | Novozymes A/S | Enzymatic emulsions for detergents |
US20220325204A1 (en) | 2019-08-27 | 2022-10-13 | Novozymes A/S | Detergent composition |
US20220315866A1 (en) | 2019-09-19 | 2022-10-06 | Novozymes A/S | Detergent Composition |
US20210095229A1 (en) | 2019-09-30 | 2021-04-01 | The Procter & Gamble Company | Fabric care compositions that include a copolymer and related methods |
WO2021064068A1 (en) | 2019-10-03 | 2021-04-08 | Novozymes A/S | Polypeptides comprising at least two carbohydrate binding domains |
WO2021122117A1 (en) | 2019-12-20 | 2021-06-24 | Henkel Ag & Co. Kgaa | Cleaning composition coprising a dispersin and a carbohydrase |
CN114929848A (zh) | 2019-12-20 | 2022-08-19 | 诺维信公司 | 稳定的液体无硼酶组合物 |
CA3154794A1 (en) * | 2019-12-20 | 2021-06-24 | Renae Dianna Fossum | Particulate fabric care composition |
US20230048546A1 (en) | 2019-12-20 | 2023-02-16 | Henkel Ag & Co. Kgaa | Cleaning compositions comprising dispersins vi |
WO2021123307A2 (en) | 2019-12-20 | 2021-06-24 | Novozymes A/S | Polypeptides having proteolytic activity and use thereof |
CN114846128A (zh) | 2019-12-20 | 2022-08-02 | 汉高股份有限及两合公司 | 包含分散蛋白viii的清洁组合物 |
WO2021122121A1 (en) | 2019-12-20 | 2021-06-24 | Henkel Ag & Co. Kgaa | Cleaning compositions comprising dispersins ix |
WO2021130167A1 (en) | 2019-12-23 | 2021-07-01 | Novozymes A/S | Enzyme compositions and uses thereof |
US20230159861A1 (en) | 2020-01-23 | 2023-05-25 | Novozymes A/S | Enzyme compositions and uses thereof |
EP4097226A1 (en) | 2020-01-31 | 2022-12-07 | Novozymes A/S | Mannanase variants and polynucleotides encoding same |
JP2023511739A (ja) | 2020-01-31 | 2023-03-22 | ノボザイムス アクティーゼルスカブ | マンナナーゼバリアント及びそれをコードするポリヌクレオチド |
JP7439275B2 (ja) | 2020-02-14 | 2024-02-27 | ビーエーエスエフ ソシエタス・ヨーロピア | 生分解性グラフトポリマー |
EP3892708A1 (en) | 2020-04-06 | 2021-10-13 | Henkel AG & Co. KGaA | Cleaning compositions comprising dispersin variants |
JP2023520312A (ja) | 2020-04-08 | 2023-05-17 | ノボザイムス アクティーゼルスカブ | 炭水化物結合モジュールバリアント |
WO2021214059A1 (en) | 2020-04-21 | 2021-10-28 | Novozymes A/S | Cleaning compositions comprising polypeptides having fructan degrading activity |
WO2021233987A1 (en) | 2020-05-20 | 2021-11-25 | Clariant International Ltd | Soil release polyesters for use in detergent compositions |
US20230212548A1 (en) | 2020-05-26 | 2023-07-06 | Novozymes A/S | Subtilase variants and compositions comprising same |
EP3936593A1 (en) | 2020-07-08 | 2022-01-12 | Henkel AG & Co. KGaA | Cleaning compositions and uses thereof |
CN116056571A (zh) | 2020-08-07 | 2023-05-02 | 巴斯夫欧洲公司 | 农业化学配制剂 |
CN111961165B (zh) * | 2020-08-12 | 2021-09-28 | 四川大学 | 用于二氧化碳驱油过程防气窜的热/二氧化碳双重刺激增黏聚合物及其制备方法 |
MX2023001888A (es) | 2020-08-25 | 2023-03-10 | Novozymes As | Variantes de una xiloglucanasa de la familia 44. |
EP4204548A1 (en) | 2020-08-28 | 2023-07-05 | Novozymes A/S | Polyester degrading protease variants |
CN116507725A (zh) | 2020-10-07 | 2023-07-28 | 诺维信公司 | α-淀粉酶变体 |
WO2022084303A2 (en) | 2020-10-20 | 2022-04-28 | Novozymes A/S | Use of polypeptides having dnase activity |
US20230399588A1 (en) | 2020-10-28 | 2023-12-14 | Novozymes A/S | Use of lipoxygenase |
EP4001388A1 (en) * | 2020-11-17 | 2022-05-25 | The Procter & Gamble Company | Automatic dishwashing method with amphiphilic graft polymer in the rinse |
US20220169952A1 (en) * | 2020-11-17 | 2022-06-02 | The Procter & Gamble Company | Automatic dishwashing composition comprising amphiphilic graft polymer |
WO2022106400A1 (en) | 2020-11-18 | 2022-05-27 | Novozymes A/S | Combination of immunochemically different proteases |
WO2022106404A1 (en) | 2020-11-18 | 2022-05-27 | Novozymes A/S | Combination of proteases |
EP4032966A1 (en) | 2021-01-22 | 2022-07-27 | Novozymes A/S | Liquid enzyme composition with sulfite scavenger |
US20240124805A1 (en) | 2021-01-28 | 2024-04-18 | Novozymes A/S | Lipase with low malodor generation |
EP4039806A1 (en) | 2021-02-04 | 2022-08-10 | Henkel AG & Co. KGaA | Detergent composition comprising xanthan lyase and endoglucanase variants with im-proved stability |
CN117015592A (zh) | 2021-02-12 | 2023-11-07 | 诺维信公司 | 稳定的生物洗涤剂 |
WO2022171780A2 (en) | 2021-02-12 | 2022-08-18 | Novozymes A/S | Alpha-amylase variants |
JP2024512291A (ja) | 2021-03-02 | 2024-03-19 | クラリアント・インターナシヨナル・リミテツド | 抗微生物組成物 |
EP4305146A1 (en) | 2021-03-12 | 2024-01-17 | Novozymes A/S | Polypeptide variants |
US20240060061A1 (en) | 2021-03-15 | 2024-02-22 | Novozymes A/S | Dnase variants |
EP4060036A1 (en) | 2021-03-15 | 2022-09-21 | Novozymes A/S | Polypeptide variants |
EP4314222A1 (en) | 2021-03-26 | 2024-02-07 | Novozymes A/S | Detergent composition with reduced polymer content |
CA3213769A1 (en) | 2021-04-01 | 2022-10-06 | Sterilex, Llc | Quat-free powdered disinfectant/sanitizer |
WO2022263354A1 (en) | 2021-06-18 | 2022-12-22 | Basf Se | Biodegradable graft polymers |
WO2022268885A1 (en) | 2021-06-23 | 2022-12-29 | Novozymes A/S | Alpha-amylase polypeptides |
EP4363401A1 (en) | 2021-06-30 | 2024-05-08 | Clariant International Ltd | Bio-based isethionate compounds |
WO2023017062A1 (en) | 2021-08-12 | 2023-02-16 | Basf Se | Biodegradable graft polymers |
WO2023017064A1 (en) | 2021-08-12 | 2023-02-16 | Basf Se | Biodegradable graft polymers |
EP4134420A1 (en) | 2021-08-12 | 2023-02-15 | The Procter & Gamble Company | Detergent composition comprising detersive surfactant and biodegradable graft polymers |
EP4134421A1 (en) | 2021-08-12 | 2023-02-15 | The Procter & Gamble Company | Detergent composition comprising detersive surfactant and graft polymer |
WO2023017061A1 (en) | 2021-08-12 | 2023-02-16 | Basf Se | Biodegradable graft polymers for dye transfer inhibition |
EP4159038A1 (en) | 2021-10-01 | 2023-04-05 | Clariant International Ltd | Composition for inhibiting microorganisms |
WO2023052616A1 (en) | 2021-10-01 | 2023-04-06 | Clariant International Ltd | Sugar amides and mixtures thereof |
WO2023061928A1 (en) | 2021-10-12 | 2023-04-20 | Novozymes A/S | Endoglucanase with improved stability |
EP4206309A1 (en) | 2021-12-30 | 2023-07-05 | Novozymes A/S | Protein particles with improved whiteness |
WO2023165507A1 (en) | 2022-03-02 | 2023-09-07 | Novozymes A/S | Use of xyloglucanase for improvement of sustainability of detergents |
WO2023165950A1 (en) | 2022-03-04 | 2023-09-07 | Novozymes A/S | Dnase variants and compositions |
WO2023194204A1 (en) | 2022-04-08 | 2023-10-12 | Novozymes A/S | Hexosaminidase variants and compositions |
WO2023247348A1 (en) | 2022-06-21 | 2023-12-28 | Novozymes A/S | Mannanase variants and polynucleotides encoding same |
WO2023227802A1 (en) | 2022-07-20 | 2023-11-30 | Clariant International Ltd | Antimicrobial combinations |
WO2024017797A1 (en) | 2022-07-21 | 2024-01-25 | Basf Se | Biodegradable graft polymers useful for dye transfer inhibition |
EP4321604A1 (en) | 2022-08-08 | 2024-02-14 | The Procter & Gamble Company | A fabric and home care composition comprising surfactant and a polyester |
EP4349806A1 (en) | 2022-10-07 | 2024-04-10 | Clariant International Ltd | Bio-based antimicrobial compounds |
WO2024083819A1 (en) | 2022-10-20 | 2024-04-25 | Novozymes A/S | Lipid removal in detergents |
WO2024094800A1 (en) | 2022-11-04 | 2024-05-10 | The Procter & Gamble Company | Fabric and home care composition |
WO2024094802A1 (en) | 2022-11-04 | 2024-05-10 | The Procter & Gamble Company | Fabric and home care composition |
WO2024094803A1 (en) | 2022-11-04 | 2024-05-10 | The Procter & Gamble Company | Fabric and home care composition |
WO2023247803A2 (en) | 2022-12-20 | 2023-12-28 | Clariant International Ltd | Antimicrobial combinations |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1145094A (zh) * | 1994-03-30 | 1997-03-12 | 普罗格特-甘布尔公司 | 含有织物柔软粘土和纤维素酶的洗衣用洗涤剂条 |
CN1183115A (zh) * | 1995-04-28 | 1998-05-27 | 尤尼利弗公司 | 洗涤剂条 |
CN1721515A (zh) * | 2004-06-18 | 2006-01-18 | 福吉米株式会社 | 清洗组合物及清洗和制造硅片的方法 |
Family Cites Families (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1222944A (fr) * | 1958-04-15 | 1960-06-14 | Hoechst Ag | Polymères greffés et leur procédé de préparation |
DE1077430B (de) | 1958-04-15 | 1960-03-10 | Hoechst Ag | Verfahren zur Herstellung von Pfropfpolymerisaten von Polyvinylestern |
FR2436213A1 (fr) | 1978-09-13 | 1980-04-11 | Oreal | Composition de traitement des matieres fibreuses a base de polymeres cationiques et anioniques |
DE3536530A1 (de) * | 1985-10-12 | 1987-04-23 | Basf Ag | Verwendung von pfropfcopolymerisaten aus polyalkylenoxiden und vinylacetat als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut |
IT1200217B (it) * | 1986-09-30 | 1989-01-05 | Valducci Roberto | Membrana per uso farmaceutico ed industriale |
DE3711298A1 (de) | 1987-04-03 | 1988-10-13 | Basf Ag | Verwendung von propfpolymerisaten auf basis von polyalkylenoxiden als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut |
DE3711319A1 (de) | 1987-04-03 | 1988-10-20 | Basf Ag | Verwendung von pfropfpolymerisaten auf basis von polyalkylenoxiden als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut |
DE3711318A1 (de) * | 1987-04-03 | 1988-10-20 | Basf Ag | Verwendung von pfropfpolymerisaten auf basis von polyalkylenoxiden als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut |
GB8821035D0 (en) | 1988-09-07 | 1988-10-05 | Unilever Plc | Detergent compositions |
GB8821034D0 (en) | 1988-09-07 | 1988-10-05 | Unilever Plc | Detergent compositions |
GB8821032D0 (en) | 1988-09-07 | 1988-10-05 | Unilever Plc | Detergent compositions |
US5049302A (en) * | 1988-10-06 | 1991-09-17 | Basf Corporation | Stable liquid detergent compositions with enchanced clay soil detergency and anti-redeposition properties |
US5082585A (en) * | 1989-02-02 | 1992-01-21 | Lever Brothers Company, Division Of Conopco, Inc. | Enzymatic liquid detergent compositions containing nonionic copolymeric stabilizing agents for included lipolytic enzymes |
US4908150A (en) † | 1989-02-02 | 1990-03-13 | Lever Brothers Company | Stabilized lipolytic enzyme-containing liquid detergent composition |
CA2029631A1 (en) * | 1989-11-22 | 1991-05-23 | Kathleen A. Hughes | Graft polymers as biodegradable detergent additives |
GB9300311D0 (en) | 1993-01-08 | 1993-03-03 | Unilever Plc | Detergent powders and process for preparing them |
GB9403155D0 (en) | 1994-02-18 | 1994-04-06 | Unilever Plc | Detergent compositions |
DE4410921C2 (de) * | 1994-03-29 | 1996-12-19 | Atochem Elf Deutschland | Polymermischung und deren Verwendung |
US5733856A (en) * | 1994-04-08 | 1998-03-31 | Basf Corporation | Detergency boosting polymer blends as additives for laundry formulations |
DE4424818A1 (de) * | 1994-07-14 | 1996-01-18 | Basf Ag | Niederviskose Mischungen aus amphiphilen nicht-ionischen Pfropfcopolymeren und viskositätserniedrigenden Zusätzen |
EP0754712B1 (en) * | 1995-02-03 | 2002-01-16 | Nippon Shokubai Co., Ltd. | Water-soluble polymer, process for producing the same, and detergent composition comprising water-soluble polymer |
GB2304726A (en) | 1995-09-04 | 1997-03-26 | Unilever Plc | Granular adjuncts containing soil release polymers, and particulate detergent compositions containing them |
US5576282A (en) * | 1995-09-11 | 1996-11-19 | The Procter & Gamble Company | Color-safe bleach boosters, compositions and laundry methods employing same |
DE69729815T2 (de) | 1996-01-25 | 2004-12-02 | Unilever N.V. | Vorbehandlungszusammensetzungen in Stickform |
MA24137A1 (fr) * | 1996-04-16 | 1997-12-31 | Procter & Gamble | Fabrication d'agents de surface ramifies . |
ES2188911T3 (es) * | 1996-10-25 | 2003-07-01 | Procter & Gamble | Productos de limpieza. |
CN1241965A (zh) * | 1996-10-29 | 2000-01-19 | 克里奥瓦克公司 | 可射频热合枕形袋 |
US5756444A (en) † | 1996-11-01 | 1998-05-26 | The Procter & Gamble Company | Granular laundry detergent compositions which are substantially free of phosphate and aluminosilicate builders |
CA2282466C (en) * | 1997-03-07 | 2005-09-20 | The Procter & Gamble Company | Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids |
AU737736B2 (en) | 1997-07-21 | 2001-08-30 | Procter & Gamble Company, The | Improved alkylbenzenesulfonate surfactants |
BR9811718A (pt) * | 1997-07-31 | 2000-08-15 | Procter & Gamble | Artigo de limpeza com carga úmida |
DE10015468A1 (de) * | 2000-03-29 | 2001-10-11 | Basf Ag | Hartkapseln, enthaltend Polymerisate und Vinylestern und Polyethern, deren Verwendung und Herstellung |
US6315835B1 (en) * | 2000-04-27 | 2001-11-13 | Basf Corporation | Anti-spotting and anti-filming hard surface cleaning formulations and methods |
CA2345283A1 (en) * | 2000-05-01 | 2001-11-01 | Kmc Exim Corp. | Pre-glued ornamental fingernail accessory |
US6391973B1 (en) | 2000-07-24 | 2002-05-21 | Basf Corporation | Curable coating composition with improved stability |
DE10041220A1 (de) | 2000-08-22 | 2002-03-07 | Basf Ag | Hautkosmetische Formulierungen |
JP4601880B2 (ja) * | 2000-10-18 | 2010-12-22 | 株式会社クラレ | エチレン−酢酸ビニル共重合体の製造方法と、この方法により得た共重合体のけん化物およびこれを含む成形物 |
GB0030671D0 (en) | 2000-12-15 | 2001-01-31 | Unilever Plc | Detergent compositions |
ES2305496T5 (es) * | 2002-09-12 | 2012-03-05 | The Procter & Gamble Company | Sistemas de pol�?meros y composiciones limpiadoras que los comprenden. |
ES2318201T3 (es) | 2002-11-04 | 2009-05-01 | Unilever N.V. | Composicion detergente para lavado de ropa. |
DE602004015081D1 (de) * | 2003-02-21 | 2008-08-28 | Dow Global Technologies Inc | Verfahren zur rückgewinnung eines addukts eines bis(4-hydroxyaryl)alkans und einer phenolischen verbindung |
DE10347043A1 (de) | 2003-10-07 | 2005-05-25 | Henkel Kgaa | Erhöhung der Wasseraufnahmefähigkeit von Textilien |
BRPI0611337A2 (pt) | 2005-05-31 | 2010-08-31 | Procter & Gamble | composicões detergentes contendo polìmero, e uso das mesmas |
MX2007015067A (es) | 2005-05-31 | 2008-01-24 | Procter & Gamble | Composicion detergente. |
US20080015135A1 (en) * | 2006-05-05 | 2008-01-17 | De Buzzaccarini Francesco | Compact fluid laundry detergent composition |
US7465701B2 (en) * | 2006-05-31 | 2008-12-16 | The Procter & Gamble Company | Detergent composition |
ES2349236T3 (es) | 2006-05-31 | 2010-12-29 | Basf Se | Polímeros anfifílicos de injerto con base en óxidos de polialquileno y ésteres de vinil. |
AR067365A1 (es) * | 2007-06-29 | 2009-10-07 | Procter & Gamble | Composiciones detergentes para lavanderia que comprenden polimeros anfifilicos injertados basados en oxidos de polialquileno y vinilesteres |
-
2007
- 2007-05-29 ES ES07729619T patent/ES2349236T3/es active Active
- 2007-05-29 MX MX2008014819A patent/MX2008014819A/es active IP Right Grant
- 2007-05-29 CA CA2653880A patent/CA2653880C/en not_active Expired - Fee Related
- 2007-05-29 DE DE602007007945T patent/DE602007007945D1/de active Active
- 2007-05-29 CN CN2007800191524A patent/CN101473025B/zh active Active
- 2007-05-29 KR KR1020087030071A patent/KR20090023374A/ko not_active Application Discontinuation
- 2007-05-29 EP EP07729619A patent/EP2029645B1/en active Active
- 2007-05-29 DE DE602007007940T patent/DE602007007940D1/de active Active
- 2007-05-29 WO PCT/EP2007/055197 patent/WO2007138053A1/en active Application Filing
- 2007-05-29 RU RU2008142866/04A patent/RU2413756C2/ru active
- 2007-05-29 US US12/302,386 patent/US8519060B2/en active Active
- 2007-05-29 EP EP07729620.0A patent/EP2024479B2/en active Active
- 2007-05-29 WO PCT/EP2007/055198 patent/WO2007138054A1/en active Application Filing
- 2007-05-29 BR BRPI0712159-8A patent/BRPI0712159B1/pt active IP Right Grant
- 2007-05-29 AT AT07729620T patent/ATE474906T1/de not_active IP Right Cessation
- 2007-05-29 CN CN2007800198078A patent/CN101454364B/zh active Active
- 2007-05-29 US US12/226,185 patent/US8143209B2/en active Active
- 2007-05-29 JP JP2009512580A patent/JP2009538946A/ja active Pending
- 2007-05-29 ES ES07729620.0T patent/ES2349321T5/es active Active
- 2007-05-29 CA CA2650067A patent/CA2650067C/en active Active
- 2007-05-29 BR BRPI0711719-1 patent/BRPI0711719B1/pt active IP Right Grant
- 2007-05-29 MX MX2008015367A patent/MX2008015367A/es active IP Right Grant
- 2007-05-29 AT AT07729619T patent/ATE474868T1/de active
- 2007-05-29 JP JP2009512581A patent/JP5542434B2/ja active Active
-
2008
- 2008-10-17 ZA ZA200808921A patent/ZA200808921B/xx unknown
- 2008-11-26 EG EG2008111919A patent/EG25183A/xx active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1145094A (zh) * | 1994-03-30 | 1997-03-12 | 普罗格特-甘布尔公司 | 含有织物柔软粘土和纤维素酶的洗衣用洗涤剂条 |
CN1183115A (zh) * | 1995-04-28 | 1998-05-27 | 尤尼利弗公司 | 洗涤剂条 |
CN1721515A (zh) * | 2004-06-18 | 2006-01-18 | 福吉米株式会社 | 清洗组合物及清洗和制造硅片的方法 |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101473025B (zh) | 包含基于聚环氧烷和乙烯基酯的两亲性接枝聚合物的清洁组合物 | |
CN102197125B (zh) | 包含聚氧化烯系聚合物组合物的组合物 | |
CN102197127A (zh) | 含磺酸根基团的共聚物及其制备方法 | |
CN102439126A (zh) | 聚合物组合物及其制备方法 | |
CN101848984A (zh) | 具有包含内层聚环氧乙烷嵌段和外层聚环氧丙烷嵌段的两亲水溶性聚亚烷基亚胺的清洁组合物 | |
JPH04505630A (ja) | ポリアルキレンオキシドブロック含有のモノマーを重合導入して含有するコポリマー、その製造およびその使用 | |
CN115103862A (zh) | 可生物降解的接枝聚合物 | |
US8859484B2 (en) | Detergent compositions comprising graft polymers having broad polarity distributions | |
CA2407757A1 (en) | Use of 2-methyl-1,3-propanediol and polycarboxylate builders in laundry detergents | |
CN102197126B (zh) | 包含疏水性基团的共聚物及其制备方法 | |
CN102197126A (zh) | 包含疏水性基团的共聚物及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |