CN113330103B - 洗衣洗涤剂 - Google Patents
洗衣洗涤剂 Download PDFInfo
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- CN113330103B CN113330103B CN202080010557.7A CN202080010557A CN113330103B CN 113330103 B CN113330103 B CN 113330103B CN 202080010557 A CN202080010557 A CN 202080010557A CN 113330103 B CN113330103 B CN 113330103B
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- 229940024171 alpha-amylase Drugs 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 238000006149 azo coupling reaction Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 108010055059 beta-Mannosidase Proteins 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000010500 citrus oil Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 150000001982 diacylglycerols Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XSNQECSCDATQEL-UHFFFAOYSA-N dihydromyrcenol Chemical compound C=CC(C)CCCC(C)(C)O XSNQECSCDATQEL-UHFFFAOYSA-N 0.000 description 1
- 229930008394 dihydromyrcenol Natural products 0.000 description 1
- PMPJQLCPEQFEJW-HPKCLRQXSA-L disodium;2-[(e)-2-[4-[4-[(e)-2-(2-sulfonatophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonate Chemical group [Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC=C1\C=C\C1=CC=C(C=2C=CC(\C=C\C=3C(=CC=CC=3)S([O-])(=O)=O)=CC=2)C=C1 PMPJQLCPEQFEJW-HPKCLRQXSA-L 0.000 description 1
- VUJGKADZTYCLIL-YHPRVSEPSA-L disodium;5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfonatophenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 VUJGKADZTYCLIL-YHPRVSEPSA-L 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000005562 fading Methods 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
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- 230000003179 granulation Effects 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N n-hexan-3-ol Natural products CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 108010087558 pectate lyase Proteins 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 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
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ABHHITAVUODQNA-UHFFFAOYSA-M potassium;benzenesulfonate Chemical class [K+].[O-]S(=O)(=O)C1=CC=CC=C1 ABHHITAVUODQNA-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229930007790 rose oxide Natural products 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RYMZZMVNJRMUDD-HGQWONQESA-N simvastatin Chemical compound C([C@H]1[C@@H](C)C=CC2=C[C@H](C)C[C@@H]([C@H]12)OC(=O)C(C)(C)CC)C[C@@H]1C[C@@H](O)CC(=O)O1 RYMZZMVNJRMUDD-HGQWONQESA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
- C09B29/0033—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom containing a five-membered heterocyclic ring with one nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0808—Amino benzenes free of acid groups characterised by the amino group unsubstituted amino group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
- C09B31/02—Disazo dyes
- C09B31/10—Disazo dyes from a coupling component "C" containing reactive methylene groups
- C09B31/105—Disazo dyes from a coupling component "C" containing reactive methylene groups containing acid groups, e.g. -CO2H, -SO3H, -PO3H2, -OSO3H, -OPO2H2; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
- C09B62/006—Azodyes
- C09B62/008—Monoazo dyes
- C09B62/0086—Monoazo dyes with coupling component containing a reactive methylene group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C11D2111/12—
Abstract
一种洗衣洗涤剂组合物,其包含:2至70重量%的表面活性剂;和0.00001至0.1重量%的调色染料,其共价结合至少一个烷氧基‑CH=CH2或‑CH=CH2封端的聚烷氧基。
Description
技术领域
本发明涉及包含pH稳定性调色染料(shading dye)的洗衣洗涤剂组合物。本发明还涉及使用包含所述调色染料的洗衣洗涤剂组合物处理织物的家用方法。
背景技术
需要保持织物的白色外观,使得尽可能长地保持美学价值。许多织物是白色的,但是在这些织物的寿命期间,白色褪色或变黄,降低了织物的美学价值。为了抵消这点,洗衣洗涤剂制造商可以将调色染料引入他们的产品中。调色染料的目的是沉积到织物上,由此通常通过向经洗衣的织物提供优选蓝紫色调来抵消织物的褪色和变黄。调色染料需要能够在家用洗衣过程期间从包含表面活性剂的洗衣洗液沉积到织物上,同时以相对低的量存在。
包含烯烃基团的调色染料提供了允许染料的进一步化学反应(例如通过自由基加成反应)而不破坏发色团的优点。WO2012/166768(Procter and Gamble)公开了共价结合到含有烯基的基于烷氧基/烷基的侧链的单偶氮噻吩调色染料。发现这种染料在pH 4-10范围内对水解敏感。洗衣洗涤剂组合物中通常存在碱性条件。
本发明的一个目的是提供包含用烯烃基团官能化的调色染料的洗衣洗涤剂组合物,所述调色染料在酸性和碱性条件下并且优选在碱性条件下对水解具有降低的敏感性。特别地,该目的是提供用烯烃基团官能化的调色染料,当与如WO2012/166768中公开的染料相比时,所述调色染料对pH 4至10范围内的水解具有降低的敏感性和/或对自由基加成更具反应性。
发明内容
在第一方面,本发明提供一种洗衣洗涤剂组合物,其包含:
(i)2至70重量%的表面活性剂;和
(ii)0.00001至0.1重量%的调色染料,其共价结合至少一个烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基。
至少一个基团共价结合所述调色染料。可以存在连接基团。如果存在连接基团,则其是芳族连接基团。更优选地,不存在连接基团。(聚)烷氧基链优选没有被进一步取代。
烷氧基的实例包括衍生自环氧丁烷、缩水甘油氧化物(glycidol oxide)、环氧乙烷和/或环氧丙烷的那些。
在第二方面,本发明提供一种处理织物的家用方法,所述方法包括以下步骤:
a.用0.5至20g/L,更优选1至10g/L的根据本发明的第一方面的洗衣洗涤剂组合物的水溶液处理织物;
b.优选地,漂洗和干燥所述织物。
通过使用根据本发明的调色染料可以提供以下益处:
·改善在pH 4-10范围内的抗水解性;和/或
·改善对自由基加成的反应性;和/或
·在家用洗涤方法期间,改善基于纤维素和/或合成物的织物上的直接性(substantivity);和/或
·在家用洗涤方法期间,在纤维素和一种或多种合成纤维类型如尼龙和聚酯和/或基于它们的织物上更平衡的沉积。
在第三方面,本发明涉及调色染料,其共价结合至少一个烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基,如所要求保护的。
具体实施方式
定义
除非另行指出,否则重量百分比(重量%)是基于洗衣洗涤剂组合物的总重量。应当理解,成分的总重量的量不超过100重量%。每当本文定量了组分的量或浓度时,除非另行指出,否则所定量的量或定量的浓度指所述组分本身,即使按惯例可能以溶液形式或与一种或多种其它成分的共混物的形式添加这样的组分。此外,应理解动词“包含”及其动词词形变化以其非限制性含义用于指包括该词语之后的项,但是没有排除未明确提及的项。最后,通过不定冠词“一个/种(a/an)”所指的要素并未排除超过一个/种所述要素存在的可能性,除非上下文清楚地要求存在一个/种所述要素且仅存在一个/种所述要素。因此,不定冠词“一个/种”通常意思是“至少一个/种”。除非另行指出,否则所有的测量都是在标准条件下进行。每当参数如浓度或比率被认为小于某一上限时,应当理解在不存在指定的下限时,所述参数的下限为0。
染料
在Industrial Dyes(K.Hunger ed,Wiley VCH 2003)和Color Chemistry(H.Zollinger,第3版,Wiley VCH 2003)中描述了染料。在colour index(Society ofDyers and Colourists and American Association of Textile Chemists andColorists)中列出了许多染料。在WO2018/085315(Procter and Gamble)中描述了隐色染料(Leuco dye)。
染料是在范围400-700nm,优选540-640nm的任何波长下,吸收系数大于4000,优选大于10 000mol-1L cm-1的有机分子。摩尔吸收系数优选地是在有机溶剂(优选丙-2醇)中使用1、5或10cm池测量的。
隐色染料
隐色染料是有机分子,其在暴露于特定化学或物理触发剂,如氧化、还原、质子化或去质子化时,显示出从无色或轻微着色状态到染料的变化。色深的变化可被人眼视觉感知。触发的隐色染料颜色变化导致摩尔消光系数在400-750nm范围内变化。当触发时摩尔消光系数的增加应大于50%,优选大于200%,并且甚至更优选大于500%。这样的隐色染料描述在现有技术中,如WO2018/085300、WO2018/085301、WO2018/085302、WO2018/085303、WO2018/085304、WO2018/085305、WO2018/085306、WO2018/085308、WO2018/085309、WO2018/085310、WO2018/085311、WO2018/085312、WO2018/085313、WO2018/085314、WO2018/085315。
优选的隐色调色染料是根据WO2018/085300的权利要求5,更优选根据WO2018/085302的权利要求6到12,其中更优选的隐色调色染料是具有权利要求6至权利要求12的递增的权利要求编号。WO2018/085302的权利要求12的隐色调色染料从而代表最优选的隐色调色染料。WO2018/085302的这些权利要求的主题在关于指定的隐色染料方面被认为在本文中重复。
除非另行指出,否则如在本说明书中使用的术语调色染料包括隐色染料。然而,优选地,在本发明中使用的调色染料是非隐色调色染料(non-leuco shading dye)。
调色染料
本发明中使用的调色染料(隐色或非隐色调色染料)向白色织物提供色调,并且优选向白色织物提供蓝色或紫色色调。在这方面,调色染料赋予白布蓝色或紫色,具有的色调角为240至330,更优选260至320,最优选265至300。使用的白布是漂白的非丝光处理的编织棉片。优选地,在室温下,在2g/L的基础洗涤剂(10重量%的直链烷基苯磺酸盐,5重量%的伯醇乙氧基化物(C12-15,具有7摩尔的乙氧基),pH=8)的水溶液(6°法国硬水,液体298K:布为30:1)中搅拌一片10cm×10cm白色漂白的非丝光处理的编织棉布30分钟。取出布,漂洗并滚筒干燥。在加入和不加入调色染料的情况下重复该实验。使用反射计测定布的颜色,并将其表示为CIE L*a*b*值。在制剂中加入0.001重量%的染料,重复该实验。
添加到布上的总颜色计算为ΔE值,使得
ΔE=(ΔL2+Δa2+Δb2)0.5
其中ΔL=L(对照)-L(染料);Δa=a(对照)-a(染料);Δb=b(对照)-b(染料)
布的实际颜色计算为色调角,当前颜色范围的色调角由下式给出:
色调角=270+180/π×atan(-Δa/Δb)
360/0的色调角为红色,270为蓝色,180为绿色。
根据本发明的染料是调色染料,这意味着其能够在家用洗涤条件期间在含有表面活性剂的洗涤液的存在下沉积在织物上。这可以使用上述测试进行评价,其中调色染料将给出非零ΔE值。
调色染料共价结合至少一个烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基。调色染料可以共价结合多个相同类型的这样的基团或不同的这样的基团的混合物。
优选地,本发明中使用的调色染料共价结合一个或两个-烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基,并且更优选地共价结合一个烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基。
最优选的基团是符合下式的那些:-([CH2]mO)nCH=CH2,其中n为1-20,且其中m为2-4。优选m为2或3,更优选m为2。优选n为1-10,更优选n为2-5。
优选地,调色染料结合至少一个-(CH2CH2O)nCH=CH2基团,其中n为1-20。在这种意义上,(聚)烷氧基部分如果存在,则其优选为(聚)乙氧基部分。有利地,n为1-10,更优选为2-5。
在不同(聚)烷氧基化物长度的混合物的情况下,“n”指摩尔平均烷氧基化物长度。
优选地,调色染料经由杂原子共价结合至少一个烷氧基-CH=CH2或–CH=CH2封端的聚烷氧基,其中所述杂原子更优选为O或N,并且其中所述杂原子甚至更优选为N。
非隐色调色染料优选含有选自以下发色团类别的发色团:蒽醌、偶氮、噁嗪、吖嗪、三苯二噁嗪、三苯甲烷、呫吨和酞菁,更优选偶氮和蒽醌,最优选单偶氮的或双偶氮的。
优选地,非隐色调色染料发色团是单偶氮或双偶氮染料,并且甚至更优选单偶氮染料。
一种高度优选的非隐色单偶氮染料具有结构(I):
其中D表示芳香族基团或杂芳香族基团。优选地,D选自:偶氮噻吩、偶氮苯并噻唑和偶氮吡啶酮。芳香族环可以被进一步取代,例如和优选被甲基取代。最优选地,染料是偶氮噻吩。
更优选,非隐色单偶氮染料具有结构(II):
在结构(I)和(II)中,R1和R2中的至少一个表示烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基。在结构(I)和(II)中,优选地,R1和R2中的一个表示烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基;并且,R1和R2中的剩余一个表示-H、-烷氧基或-聚烷氧基,更优选地表示-乙氧基或-聚乙氧基。
甚至进一步优选的非隐色单偶氮染料具有结构(III):
其中r+q为1-10,优选2-5,并且甚至更优选地,r=1且q=1。r为至少1。
优选的非隐色双偶氮染料具有结构(IV):
其中:
R1和R2独立地为H、烷基、烷氧基、亚烷氧基、烷基封端的亚烷氧基,聚亚烷氧基、烷基封端的聚亚烷氧基、脲、酰氨基或乙酰氨基;
Z为氧、氮或磺酰氨基(sulfonamido),其进一步被至少一个且优选一个烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基取代;
Y为取代的或未取代的氨基。
更优选的非隐色双偶氮染料具有结构(V):
其中n为1-10。
结构(IV)和(V)描述双偶氮染料结构,其中偶氮基团之一被描述为腙形式。这些结构应被解释为也涵盖其中两个偶氮基团均处于-N=N-形式的双偶氮染料。优选地,偶氮基团之一是腙形式,而一个当溶解在水中时是偶氮形式。P.F.Gordon和P.Gregory的OrganicChemistry in Colour(Springer-Verlag 1983)中讨论了偶氮-腙互变异构现象。染料直接紫9的偶氮和腙形式如下所示:
非隐色双偶氮染料可以作为碱金属、碱土金属或季胺的盐存在,最优选地,抗衡离子为钠盐。结构(IV)和(V)也被解释为包括这样的盐形式和游离酸形式。
蓝色或紫色偶氮染料的制备
优选的双偶氮染料可以经由公知的偶氮偶合反应合成,例如
WO2012/054058中描述了具有至少一个被-CH=CH2基团封端的聚烷氧基链的多种双偶氮染料的合成,尽管这样的染料还包含另外的-COOH基团。
单偶氮噻吩染料的合成描述在US4912203和WO2011/017719中。主要偶合反应是:
其中R1和R2中的至少一个表示烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基基团。
-CH=CH2部分可以通过使相应乙氧基化材料脱水而获得,如下所示:
和
末端醇基团的脱水可以通过在强酸如硫酸或磷酸的存在下加热,然后纯化来实现。
本发明调色染料的另外的优点是双键对自由基加成更有活性,并且染料对织物具有更好的沉积特性。
表面活性剂
本发明的洗衣洗涤剂组合物包含2至70重量%的表面活性剂,最优选10至30重量%。一般而言,表面活性剂体系中的非离子和阴离子表面活性剂可以选自“SurfaceActive Agents”,第1卷,Schwartz&Perry,Interscience 1949;第2卷,Schwartz,Perry&Berch,Interscience 1958,Manufacturing Confectioners Company出版的当前版本"McCutcheon's Emulsifiers and Detergents"或"Tenside-Taschenbuch",H.Stache,第2版,Carl Hauser Verlag,1981中描述的表面活性剂。优选地,所使用的表面活性剂是饱和的。
合适的非离子表面活性剂可以包括,特别是,具有疏水基团和反应性氢原子的化合物(例如脂肪醇、酸、酰胺)与环氧烷(特别是环氧乙烷单独或与环氧丙烷一起)的反应产物。具体的非离子表面活性剂是脂肪族C8至C18直链或支链伯或仲醇与环氧乙烷的缩合产物,通常为5至40EO,优选为7EO至9EO。
可以使用的合适的阴离子表面活性剂通常是具有含约8至约22个碳原子的烷基的有机硫酸和磺酸的水溶性碱金属盐,术语烷基用于包括高级酰基的烷基部分。合适的合成阴离子表面活性剂的实例是烷基硫酸钠和烷基硫酸钾,特别是通过使例如从牛油或椰子油产生的高级C8至C18醇硫酸盐化而获得的那些;烷基C9至C20苯磺酸钠和钾,特别是直链仲烷基C10至C15苯磺酸钠;和烷基甘油醚硫酸钠,特别是衍生自牛油或椰子油的高级醇和衍生自石油的合成醇的那些醚。优选的阴离子表面活性剂是C11至C15烷基苯磺酸钠和C12至C18烷基硫酸钠。高度优选的是阴离子烷基苯磺酸盐,其更有利地是直链烷基苯磺酸盐。还适用的是例如EP-A-328 177(Unilever)中描述的那些表面活性剂,其显示耐盐析,EP-A-070 074中描述的烷基多糖苷表面活性剂,以及烷基单糖苷。
优选的表面活性剂体系是阴离子与非离子表面活性剂的混合物,特别是在EP-A-346 995(Unilever)中指出的阴离子和非离子表面活性剂的组和实例。特别优选的是作为C16至C18伯醇硫酸的碱金属盐与C12至C15伯醇3至7EO乙氧基化物一起的混合物的表面活性剂体系。非离子表面活性剂优选以基于表面活性剂体系的总重量小于50重量%,最优选小于20重量%的量存在。阴离子表面活性剂可以例如以基于表面活性剂体系的总重量约50%至100重量%范围的量存在。因此,基于表面活性剂的总重量,高度有利的表面活性剂包含50-100重量%的直链烷基苯磺酸盐。
助洗剂或络合剂
助洗剂材料可以选自1)钙螯合剂材料,2)沉淀材料,3)钙离子交换材料,及4)其混合物。
钙螯合剂助洗剂材料的实例包括碱金属聚磷酸盐,如三聚磷酸钠,和有机螯合剂,如乙二胺四乙酸。
沉淀助洗剂材料的实例包括正磷酸钠和碳酸钠。
钙离子交换助洗剂材料的实例包括各种类型的水不溶性晶体或无定形铝硅酸盐,其中沸石是最有名的代表,例如沸石A、沸石B(也称为沸石P)、沸石C、沸石X、沸石Y以及在EP-A-0,384,070中描述的沸石P型。
本发明的洗衣洗涤剂组合物还可以含有0-65重量%的助洗剂或络合剂,如乙二胺四乙酸、二亚乙基三胺五乙酸、烷基或烯基琥珀酸、次氮基三乙酸,或下文所述的其他助洗剂。许多助洗剂因其络合金属离子的能力而同样是漂白稳定剂。
沸石和碳酸盐(碳酸盐(包括碳酸氢盐和倍半碳酸盐))是优选的助洗剂,其中碳酸盐是更优选的。
组合物可以含有晶体铝硅酸盐,优选碱金属铝硅酸盐,更优选铝硅酸钠作为助洗剂。这通常以小于15重量%的水平存在。铝硅酸盐是具有以下通式的材料:
0.8-1.5M2O·Al2O3·0.8-6SiO2
其中M是一价阳离子,优选钠。这些材料含有一些结合水并需要具有至少50mgCaO/g的钙离子交换容量。优选的铝硅酸钠在上式中含有1.5-3.5个SiO2单元。它们可以通过硅酸钠与铝酸钠之间的反应容易地制备,如文献中所充分描述的。表面活性剂与铝硅酸盐(存在时)的比率优选大于5:2,更优选大于3:1。
替代性地,或除铝硅酸盐助洗剂以外地,可以使用磷酸盐助洗剂。在本领域中术语“磷酸盐”包括二磷酸盐、三磷酸盐和膦酸盐种类。助洗剂的其他形式包括硅酸盐,例如可溶性硅酸盐、偏硅酸盐、层状硅酸盐(例如来自Hoechst的SKS-6)。
优选地,洗衣洗涤剂制剂是非磷酸盐助洗的洗衣洗涤剂制剂,即含有少于1重量%的磷酸盐。优选地,洗衣洗涤剂制剂是碳酸盐助洗的。
荧光剂
本发明的洗衣洗涤剂组合物优选包含荧光剂(光学增亮剂)。荧光剂是众所周知的,并且许多这样的荧光剂是可商购的。通常,这些荧光剂以其碱金属盐,例如钠盐的形式供应和使用。本发明的洗衣洗涤剂组合物中使用的一种或多种荧光剂的总量通常为0.005至2重量%,更优选0.01至0.1重量%。优选的荧光剂类别是:二苯乙烯基联苯化合物,如Tinopal(商标)CBS-X;二胺二苯乙烯二磺酸化合物,如Tinopal DMS pure Xtra和Blankophor(商标)HRH;以及吡唑啉化合物,例如Blankophor SN。优选的荧光剂是:2(4-苯乙烯基-3-磺苯基)-2H-萘酚[1,2-d]三唑钠、4,4'-双{[(4-苯胺基-6-(N甲基-N-2羟乙基)氨基1,3,5-三嗪-2-基)]氨基}二苯乙烯-2,2'二磺酸二钠、4,4'-双{[(4-苯胺基-6-吗啉基-1,3,5-三嗪-2-基)]氨基}二苯乙烯-2-2'二磺酸二钠,和4,4'-双(2-磺苯乙烯基)联苯二钠。
优选的是根据本发明的洗衣洗涤剂组合物包含荧光剂。类似地,优选的是用于处理织物的家用方法的水溶液包含荧光剂。当荧光剂存在于所述水溶液中时,其优选在0.0001g/l至0.1g/l,更优选0.001至0.02g/l的范围内。
洗衣洗涤剂组合物可包含根据本发明的不同调色染料的混合物以及根据本发明的调色染料和其它不是根据本发明的调色染料的混合物。
香料
优选地,洗衣洗涤剂组合物包含香料。香料优选地在0.001至3重量%,最优选0.1至1重量%的范围内。香料的许多合适的实例在由CFTA Publication出版的CTFA(Cosmetic,Toiletry and Fragrance Association)1992International Buyers Guide和由Schnell Publishing Co.出版的OPD 1993Chemicals Buyers Directory 80th AnnualEdition中提供。
在洗衣制剂中存在多种香料组分是常见的。在本发明的洗衣洗涤剂组合物中,设想将存在四种或更多种,优选五种或更多种,更优选六种或更多种或甚至七种或更多种不同的香料组分。在香料混合物中,优选15至25重量%是头香。头香由Poucher定义(Journalofthe Society of Cosmetic Chemists 6(2):80[1955])。优选的头香选自柑橘油,里哪醇,乙酸里哪酯,薰衣草,二氢月桂烯醇,玫瑰醚(rose oxide)和顺式-3-己醇。香料和头香有利地用于提示本发明的洗衣洗涤剂组合物提供的白色益处。
优选的是本发明的洗衣洗涤剂组合物不含过氧漂白剂,例如过碳酸钠、过硼酸钠和过酸。
聚合物
本发明的洗衣洗涤剂组合物可包含一种或多种另外的聚合物。实例为羧甲基纤维素、聚(乙二醇)、聚(乙烯醇)、聚羧酸酯类如聚丙烯酸酯类、马来/丙烯酸共聚物和甲基丙烯酸月桂酯/丙烯酸共聚物。
存在以阻止染料沉积的聚合物,例如聚(乙烯基吡咯烷酮)、聚(乙烯基吡啶-N-氧化物)和聚(乙烯基咪唑),优选不存在于制剂中。
酶
在本发明的洗衣洗涤剂组合物中和当实施本发明的方法时优选存在一种或多种酶。优选地,每种酶在本发明的洗衣洗涤剂组合物中的水平为0.0001重量%至0.1重量%蛋白质。
特别设想的酶包括蛋白酶、α-淀粉酶、纤维素酶、脂肪酶、过氧化物酶/氧化酶、果胶酸裂解酶和甘露聚糖酶或其混合物。
合适的脂肪酶包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的脂肪酶的实例包括来自以下的脂肪酶:腐质霉(Humicola)(同义词嗜热真菌(Thermomyces)),例如来自EP 258 068和EP 305 216中所述的H.lanuginosa(T.lanuginosus)或来自WO 96/13580中所述的H.insolens;假单胞菌脂肪酶,例如来自产碱假单胞菌(P.alcaligenes)或假产碱假单胞菌(P.pseudoalcaligenes)(EP 218 272)、洋葱假单胞菌(P.cepacia)(EP 331 376)、施氏假单胞菌(P.stutzeri)(GB 1,372,034)、荧光假单胞菌(P.fluorescens),假单胞菌菌株SD 705(WO 95/06720和WO 96/27002)、P.wisconsinensis(WO 96/12012);芽孢杆菌脂肪酶,例如来自枯草芽孢杆菌(B.subtilis)(Dartois等(1993),Biochemica et Biophysica Acta,1131,253-360)、嗜热脂肪芽孢杆菌(B.stearothermophilus)(JP 64/744992)或短小芽孢杆菌(B.pumilus)(WO 91/16422)。
其他实例是脂肪酶变体,例如在WO 92/05249、WO 94/01541、EP 407225、EP260105、WO 95/35381、WO 96/00292、WO 95/30744、WO 94/25578、WO 95/14783、WO 95/22615、WO 97/04079和WO 97/07202、WO 00/60063中描述的那些。
优选的可商购脂肪酶包括LipolaseTM和Lipolase UltraTM、LipexTM和lipocleanTM(Novozymes A/S)。
优选的磷脂酶分类为EC 3.1.1.4和/或EC 3.1.1.32。如在本文中所使用的术语磷脂酶是对磷脂具有活性的酶。
磷脂,例如卵磷脂或磷脂酰胆碱,由在外部(sn-1)和中间(sn-2)位置被两个脂肪酸酯化,并在第三位置被磷酸酯化的甘油组成;磷酸反过来可以被酯化成氨基醇。磷脂酶是参与磷脂水解的酶。可以区分磷脂酶活性的多种类型,包括磷脂酶A1和A2,其水解一个脂肪酰基(分别在sn-1和sn-2位置)以形成溶血磷脂;和溶血磷脂酶(或磷脂酶B),其可以水解溶血磷脂中剩余的脂肪酰基。磷脂酶C和磷脂酶D(磷酸二酯酶)分别释放二酰基甘油或磷脂酸。
酶和光漂白剂可以显示出一些相互作用,并且应选择为使得这种相互作用不是负面的。通过在产品内包封一种或另一种酶或光漂白剂和/或其他隔离,可以避免某些负面相互作用。
合适的蛋白酶包括具有动物、植物或微生物来源的那些。微生物来源是优选的。包括化学修饰的或蛋白质工程化的突变体。蛋白酶可以是丝氨酸蛋白酶或金属蛋白酶,优选碱性微生物蛋白酶或胰蛋白酶样蛋白酶。优选的可商购蛋白酶包括AlcalaseTM、SavinaseTM、PrimaseTM、DuralaseTM、DyrazymTM、EsperaseTM、EverlaseTM、PolarzymeTM、andKannaseTM、(Novozymes A/S)、MaxataseTM、MaxacalTM、MaxapemTM、ProperaseTM、PurafectTM、Purafect OxPTM、FN2TM和FN3TM(Genencor International Inc.)。
优选的角质酶分类为EC 3.1.1.74。角质酶可以具有任何来源。
优选地,角质酶具有微生物来源,特别是细菌、真菌或酵母来源。
合适的淀粉酶(α和/或β)包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。淀粉酶包括例如获自芽孢杆菌,如在GB 1,296,839中更详细描述的地衣芽孢杆菌的特殊菌株,或在WO 95/026397或WO 00/060060中公开的芽孢杆菌菌株的α-淀粉酶。可商购的淀粉酶是DuramylTM、TermamylTM、Termamyl UltraTM、NatalaseTM、StainzymeTM、FungamylTM和BANTM(Novozymes A/S),RapidaseTM和PurastarTM(fromGenencor International Inc.)。
合适的纤维素酶包括具有细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。合适的纤维素酶包括来自以下的纤维素酶:芽孢杆菌属、假单胞菌属、腐质霉属、镰刀菌属、梭孢壳属、支顶孢属,例如从公开在US 4,435,307、US 5,648,263、US 5,691,178、US 5,776,757、WO 89/09259、WO 96/029397和WO 98/012307的特异腐质霉、太瑞斯梭孢壳霉、嗜热毁丝霉和尖孢镰刀菌产生的真菌纤维素酶。可商购的纤维素酶包括CelluzymeTM、CarezymeTM、Celluclean TM、EndolaseTM、RenozymeTM(Novozymes A/S)、ClazinaseTM和Puradax HATM(Genencor International Inc.)和KAC-500(B)TM(KaoCorporation)。
合适的过氧化物酶/氧化酶包括具有植物、细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的过氧化物酶的实例包括来自鬼伞属,例如来自灰盖鬼伞的过氧化物酶,及其变体,如在WO 93/24618、WO 95/10602和WO 98/15257中所述的那些。可商购的过氧化物酶包括GuardzymeTM和NovozymTM 51004(Novozymes A/S)。
另外的适用的酶在WO2009/087524、WO2009/090576、WO2009/107091、WO2009/111258和WO2009/148983中讨论。
优选的酶为蛋白酶、脂肪酶、淀粉酶和纤维素酶,最有利地,丝氨酸蛋白酶被本发明的洗衣洗涤剂组合物包含。
酶稳定剂
存在于组合物中的任何酶可以使用常规的稳定剂稳定化,例如多元醇,如丙二醇或甘油;糖或糖醇;乳酸;硼酸或硼酸衍生物,例如芳族硼酸酯,或苯基硼酸衍生物,如4-甲酰基苯基硼酸,并且组合物可以如例如WO 92/19709和WO 92/19708中所述配制。
当烷基足够长以形成支链或环状链时,烷基包括支链的、环状的和直链的烷基链。烷基优选为直链或支链的,最优选为直链的。
洗衣洗涤剂组合物的形式
本发明的洗衣洗涤剂组合物可以是液体或粉末。
为减少粉末作为整体被调色染料着色,本发明的调色染料有利地存在于包含低于5重量%的调色染料的后定量加料颗粒(post-dosed granules)中。还发现将本发明的调色染料在后定量加料染料颗粒中的量限制为至多5重量%,减少了在产品的纯净施用(neatapplication)后的染渍(例如,作为湿织物上的粉末)。优选地,在后定量加料颗粒中加入另外的非调色染料,以赋予颗粒以蓝色。
优选地,基于后定量加料染料颗粒的总重量,后定量加料染料颗粒包含的调色染料的总量为0.1至2重量%。
调色染料可以与水溶性盐(例如硫酸钠)预混合,以形成后定量加料染料颗粒。后定量加料染料颗粒可通过本领域已知的技术制备,例如制粒、流化床凝聚等。本发明的后定量加料染料颗粒可以随后与基础洗涤剂颗粒混合。
后定量加料染料颗粒的尺寸可以在50至3000μm的范围内。最优选的是,颗粒的颗粒尺寸在100至2000μm的范围内,最优选180μm至1000μm。给出的尺寸是颗粒在任何一个方向上的最大长度,使得颗粒通过所需尺寸的标准筛。
在洗衣洗涤剂组合物是粉末的情况下,该组合物优选包含直链烷基苯磺酸盐、碳酸盐和硫酸钠的组合以及后定量加料染料颗粒,其中后定量加料染料颗粒包含根据本发明的调色染料。
在洗衣洗涤剂组合物是瓶装液体洗涤剂产品的形式的情况下,瓶子优选为具有可再密封的(resealable)螺旋盖的1至5L瓶子,瓶子的倾倒颈部的最大维度比瓶子的最大维度小至少3倍。在首次销售时,按重量计,瓶子应当灌注到大于瓶子容量的95%。令人惊奇地是,这减少了制剂中的本发明使用的调色染料在储存期间的氧化。在洗衣洗涤剂组合物为单位剂量的情况下,优选地,其为液体单位剂量产品。有利地,单位剂量洗衣洗涤剂产品包含在可再封闭的塑料箱中。所述可再封闭的塑料箱是高度有利的防儿童拆开包装(childresistance packaging)。对于防儿童拆开包装的要求在ISO 8317中给出。令人惊奇地,提供液体单位剂量形式的根据本发明的洗衣洗涤剂组合物,特别是当包含在符合防儿童拆开包装要求的可再封闭的塑料箱中时,可以减少制剂中的调色染料在储存期间的氧化。
除非另行指出,否则本发明的一个方面(例如洗衣洗涤剂组合物)的上下文中的优选方面也可适用于其他方面之一的上下文中的优选方面,(例如,如在处理织物的家用方面中使用的洗衣洗涤剂组合物),加以必要的变更。
现通过以下非限制性实施例阐述本发明。
实施例
实施例1
可以制备具有下述配方的液体洗衣洗涤剂:
该液体洗衣洗涤剂包含0.001重量%的根据以下结构的调色染料(实施例1,根据本发明):
其中r=1且q为1(即,r+q=2)(实施例1)。作为比较例(不是根据本发明),可以使用0.001重量%的具有以下结构的调色染料:
(比较例A,不是根据本发明)。作为参比,使用该液体洗衣洗涤剂组合物,但不含任何加入的调色染料(参比液体)。
洗涤液是通过将4g/L的洗衣洗涤剂粉末定量加料到Tergotometer罐中的13°FH水中制备的,并加入一片10×10cm的纺织棉、针织棉、65/35聚棉、微纤维聚酯或80/20尼龙-弹性织物,使得洗涤液与织物的比率为100:1。将洗涤溶液在室温下以200rpm搅拌1小时,将织物在13°FH水中漂洗并干燥。
使用反射计测量织物的颜色,并表示为CIE L*a*b*。相对于使用参比液体洗涤的织物的颜色变化,表示使用根据实施例1或根据比较例A的洗衣洗涤剂粉末洗涤的织物的颜色变化。使用以下表述:Δb=b(参比)-b(染料)。因此,可以比较根据实施例1或根据比较例A的染料的相对沉积。
实施例2
可以制备具有以下配方的粉末洗衣洗涤剂制剂:
成分 | 重量% |
直链烷基苯磺酸盐 | 14.5 |
碳酸钠 | 20.0 |
硫酸钠 | 50.0 |
硅酸钠 | 6.0 |
沸石 | 2.5 |
盐斑颗粒(蓝色和红色) | 1.8 |
香料 | 0.3 |
羧甲基纤维素钠 | 0.1 |
Sokalan CP5(来自BASF) | 0.1 |
调色染料颗粒 | 0.3 |
次要成分(包括荧光剂)和水分 | 至100% |
调色染料颗粒为如WO2006/053598中描述的,所述制剂含有0.0004重量%的调色染料。调色染料是根据以下结构的(即实施例2,根据本发明)。
其中r=1且q为1(即,r+q=2)(实施例2)。作为比较例(不是根据本发明),可以使用0.001重量%的以下结构的调色染料:
(比较例B,不是根据本发明)。作为参比,使用粉末洗衣洗涤剂组合物,但不含任何加入的调色染料(参比粉末)。
洗涤液是通过将4g/L的洗衣洗涤剂粉末定量加料到Tergotometer罐中的13°FH水中制备的,并加入一片10×10cm的纺织棉、针织棉、65/35聚棉、微纤维聚酯或80/20尼龙-弹性织物,使得洗涤液与织物的比率为100:1。将洗涤溶液在室温下以200rpm搅拌1小时,将织物在13°FH水中漂洗并干燥。
使用反射计测量织物的颜色,并表示为CIE L*a*b*。相对于使用参比粉末洗涤的织物的颜色变化,表示使用根据实施例2或根据比较例B的洗衣洗涤剂粉末洗涤的织物的颜色变化。使用以下表述:Δb=b(参比)-b(染料)。因此,可以比较根据实施例2或根据比较例B的染料的相对沉积。
实施例3
通过将约2×10-5mol L-1的染料溶解在水中,然后将pH从9.6改变到1.9,并观察UV-VIS光谱在570nm处的变化,测量参比染料的pKa值(酸解常数)。该变化对2个-COOH基团的双pKa进行的拟合,给出了表中所示的值。该pKa值高于预期游离-COOH基团会有的3-4,这归因于烷基链的作用。本发明的染料在类似条件下不溶解,因此计算潜在的pKa值(Chemalize,Chemazon),没有发现在4至10范围内的pKa值(最强的酸性pKa=15.1,最强的碱性pKa=1.0)。
k(甲基)值是甲基基团对双键的溶液加成速率常数,根据Fischer H.,and Radom,L.Angew.Chem.Int.Ed 2001,40.1340-1371计算。将[(CH2=CH(OCH2CH3)与E-(CH3)HC=CH(CH3)]进行比较。
本发明的化合物在pH 4-10范围内抗水解,并且比参比化合物对自由基加成更有反应性。
Claims (27)
1.一种洗衣洗涤剂组合物,其包含:
(i)2至70重量%的表面活性剂;和
(ii)0.00001至0.1重量%的调色染料,其共价结合至少一个烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基基团。
2.根据权利要求1所述的洗衣洗涤剂组合物,其中所述调色染料向白色织物提供蓝色或紫色色调。
3.根据权利要求1或2所述的洗衣洗涤剂组合物,其中所述调色染料共价结合一个或两个烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基基团。
4.根据权利要求1或2所述的洗衣洗涤剂组合物,其中所述调色染料共价结合一个烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基基团。
5.根据权利要求1或2所述的洗衣洗涤剂组合物,其中所述至少一个烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基基团是根据下式:
-([CH2]mO)nCH=CH2,
其中n为1-20并且其中m为2-4。
6.根据权利要求5所述的洗衣洗涤剂组合物,其中m为2-3。
7.根据权利要求5所述的洗衣洗涤剂组合物,其中m为2。
8.根据权利要求5所述的洗衣洗涤剂组合物,其中n为1-10。
9.根据权利要求5所述的洗衣洗涤剂组合物,其中n为2-5。
10.根据权利要求1或2所述的洗衣洗涤剂组合物,其中所述调色染料经由杂原子结合所述基团。
11.根据权利要求10所述的洗衣洗涤剂组合物,其中所述杂原子为O或N。
12.根据权利要求10所述的洗衣洗涤剂组合物,其中所述杂原子为N。
13.根据权利要求1或2所述的洗衣洗涤剂组合物,其中所述调色染料为非隐色蓝色或非隐色紫色调色染料。
14.根据权利要求1或2所述的洗衣洗涤剂组合物,其中所述调色染料发色团是单偶氮或双偶氮的。
15.根据权利要求1或2所述的洗衣洗涤剂组合物,其中所述调色染料发色团是单偶氮的。
18.根据权利要求17所述的洗衣洗涤剂组合物,其中R1和R2中的一个表示烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基;并且R1和R2中的剩下一个表示-H、-烷氧基或-聚烷氧基。
19.根据权利要求17所述的洗衣洗涤剂组合物,其中R1和R2中的一个表示烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基;并且R1和R2中的剩下一个表示-乙氧基或-聚乙氧基。
20.一种处理织物的家用方法,所述方法包括以下步骤:
a.用0.5至20g/L的根据权利要求1-19中任一项所述的洗衣洗涤剂组合物的水溶液处理织物;
b.任选地漂洗和干燥所述织物。
21.根据权利要求20所述的方法,其中在步骤a中,用1至10g/L的根据权利要求1-19中任一项所述的洗衣洗涤剂组合物的水溶液处理织物。
23.根据权利要求22所述的蓝色或紫色非隐色调色染料,其中R1和R2中的一个表示烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基;并且R1和R2中的剩余一个表示-H、-烷氧基或-聚烷氧基。
24.根据权利要求22所述的蓝色或紫色非隐色调色染料,其中其中R1和R2中的一个表示烷氧基-CH=CH2或-CH=CH2封端的聚烷氧基;并且R1和R2中的剩余一个表示-乙氧基或-聚乙氧基。
26.根据权利要求25所述的蓝色或紫色非隐色调色染料,其中r+q为2-5。
27.根据权利要求25所述的蓝色或紫色非隐色调色染料,其中r=1且q=1。
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2020
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- 2020-01-09 US US17/424,151 patent/US20220098525A1/en active Pending
- 2020-01-09 BR BR112021014332-7A patent/BR112021014332A2/pt unknown
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CN113330103A (zh) | 2021-08-31 |
EP3752589B1 (en) | 2023-08-30 |
US20220098525A1 (en) | 2022-03-31 |
EP3752589A1 (en) | 2020-12-23 |
BR112021014332A2 (pt) | 2021-09-28 |
WO2020151959A1 (en) | 2020-07-30 |
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