CN106471111A - 洗衣液组合物 - Google Patents
洗衣液组合物 Download PDFInfo
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- CN106471111A CN106471111A CN201580036837.4A CN201580036837A CN106471111A CN 106471111 A CN106471111 A CN 106471111A CN 201580036837 A CN201580036837 A CN 201580036837A CN 106471111 A CN106471111 A CN 106471111A
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- 239000000203 mixture Substances 0.000 title claims abstract description 114
- 239000007788 liquid Substances 0.000 title claims abstract description 14
- 229920000728 polyester Polymers 0.000 claims abstract description 56
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 8
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 229960004063 propylene glycol Drugs 0.000 claims abstract description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical class CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 5
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical class CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims abstract description 3
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 229940083957 1,2-butanediol Drugs 0.000 claims description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
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- 150000001450 anions Chemical class 0.000 claims 1
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- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000004744 fabric Substances 0.000 abstract description 8
- 239000002689 soil Substances 0.000 abstract description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 polyol compound Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000005202 decontamination Methods 0.000 description 4
- 230000003588 decontaminative effect Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229920002601 oligoester Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WYVVKGNFXHOCQV-UHFFFAOYSA-N 3-iodoprop-2-yn-1-yl butylcarbamate Chemical compound CCCCNC(=O)OCC#CI WYVVKGNFXHOCQV-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000003165 hydrotropic effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000003381 stabilizer Substances 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
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 230000002255 enzymatic effect Effects 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
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
本申请公开了包含去污聚合物的储存稳定的组合物。所述组合物包含A)45‑55重量%的一种或多种根据下式(I)的聚酯,其中R1和R2彼此独立地为X‑(OC2H4)n‑(OC3H6)m,其中X为C1‑4烷基,‑(OC2H4)基团和‑(OC3H6)基团分段布置且由‑(OC3H6)基团组成的段键合到COO基团或者其是HO‑(C3H6),n基于摩尔平均为12‑120的数,m基于摩尔平均为1‑10的数,和a基于摩尔平均为4‑9的数,和B)10‑30重量%的一种或多种醇,其选自乙二醇、1,2‑丙二醇、1,3‑丙二醇、1,2‑丁二醇、1,3‑丁二醇、1,4‑丁二醇和丁基乙二醇和C)24‑42重量%的水;每种情况下的量基于所述组合物的总重量。所述组合物可有利地用于洗衣洗涤剂和织物护理产品。本申请公开了用于制备包含所述活性共混物的洗衣液组合物的方法。
Description
本发明涉及包含聚酯的洗衣液组合物及制备包含聚酯的组合物的方法。
DE 10 2007 013 217 A1和WO 2007/079850 A1公开了可在洗涤和清洁组合物中用作去污组分的阴离子聚酯。
DE 10 2007 005 532 A1描述了具有低粘度的去污低聚酯和聚酯的水性制剂。
EP 0 964 015 A1公开了去污低聚酯,其可用作洗涤剂中的去污聚合物,且其使用包含3至6个羟基基团的多元醇制备。
EP 1 661 933 A1涉及在室温下可流动的、两性的和非离子低聚酯,其通过使二羧酸化合物、多元醇化合物和水溶性环氧烷加合物反应进行制备,以及它们作为洗涤和清洁组合物中的添加剂的用途。
因此,并在第一方面,提供了碱性洗衣液组合物,其包含至少1重量%的三乙醇胺、至少5%的非皂表面活性剂和至少0.5%的聚酯,所述聚酯作为包含以下组分的活性共混物提供:
A)所述活性共混物的45-55重量%的一种或多种根据下式(I)的聚酯
其中
R1和R2彼此独立地为X-(OC2H4)n-(OC3H6)m,其中X为C1-4烷基并优选甲基,-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团或是HO-(C3H6),且优选地彼此独立地是X-(OC2H4)n-(OC3H6)m,
n基于摩尔平均为12-120且优选40-50的数,
m基于摩尔平均为1-10且优选1-7的数,和
a基于摩尔平均为4-9的数,和
B)活性共混物的10-30重量%的一种或多种醇,其选自乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇和丁基乙二醇和
C)活性共混物的24-42重量%的水。
活性共混物意思是其预形成并添加到洗衣液组合物的其余物中,或者添加到最终形成洗衣液组合物的组分中。
优选地,丁基乙二醇具有下面的结构:CH3(CH2)3OCH2CH2OH。
令人惊讶地,活性共混物基于水和基于不易燃的溶剂。
聚酯的水性溶液或水性-醇溶液当储存在5℃时往往具有相对良好的稳定性。但是,在运输或储存期间可发生的在25℃下储存较长时间段且甚至更快地在30-50℃的升高温度下,非本发明的聚酯组合物在储存期间首先显示混浊,其后来导致大量的沉淀。这些沉淀在80℃下不能溶解,表明各产物不可认为是储存稳定的,且它们的性质通过在升高温度下储存而被不可逆地改变。
所述活性共混物在升高的温度下也是充分地储存稳定。
所述活性共混物组合物优选在25℃下是溶液。
在组分A)的聚酯中,基团“X”是C1-4烷基并优选是甲基。
在本发明的优选实施方式中,本发明组合物的组分A)的聚酯是根据下式(I)
其中
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团或是HO-(C3H6),且优选地彼此独立地是H3C-(OC2H4)n-(OC3H6)m,
n基于摩尔平均为40-50的数,
m基于摩尔平均为1-7的数,和
a基于摩尔平均为4-9的数。
在本发明组合物的组分A)的聚酯中,变量“a”基于摩尔平均优选为5-8的数且更优选为6-7的数。
在本发明组合物的组分A)的聚酯中,变量“m”基于摩尔平均优选为2-5的数
在本发明组合物的组分A)的聚酯中,变量“n”基于摩尔平均优选为43-47的数、且更优选为44-46的数且甚至更优选为45。
在本发明的一个特别优选的实施方式中,本发明组合物的组分A)的聚酯是根据下式(I)
其中
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团,
n基于摩尔平均为44-46的数,
m基于摩尔平均为2,和
a基于摩尔平均为5-8的数。
在这些聚酯中,根据式(I)的聚酯是尤其优选的:
其中
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团,
n基于摩尔平均为45,
m基于摩尔平均为2,和
a基于摩尔平均为6-7的数。
在本发明的另一个特别优选的实施方式中,本发明组合物的组分A)的聚酯是根据下式(I)
其中
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团,
n基于摩尔平均为44-46的数,
m基于摩尔平均为5,和
a基于摩尔平均为5-8的数。
在这些聚酯中,根据式(I)的聚酯是尤其优选的:
其中
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团,
n基于摩尔平均为45,
m基于摩尔平均为5,和
a基于摩尔平均为6-7的数。
在结构单元“X-(OC2H4)n-(OC3H6)m”或“H3C-(OC2H4)n-(OC3H6)m”中的基团-O-C2H4-具有式-O-CH2-CH2-。
在用“a”标示的结构单元中、在结构单元“X-(OC2H4)n-(OC3H6)m”或“H3C-(OC2H4)n-(OC3H6)m”中和在结构单元HO-(C3H6)中的基团-O-C3H6-具有式-O-CH(CH3)-CH2-或-O-CH2-CH(CH3)-,即具有式
REM:组合物
活性共混物组合物可有利地用于洗衣洗涤剂和织物护理产品中并特别用于液体洗衣洗涤剂和织物护理产品中。这些洗衣洗涤剂和织物护理产物可包含一种或多种任选的组分,例如它们可包含常用于洗衣洗涤剂和织物护理产品中的常规成分。任选成分的实例包括但不限于助洗剂、表面活性剂、漂白剂、漂白活性化合物、漂白活化剂、漂白催化剂、光漂白剂、染料转移抑制剂、颜色保护剂、抗再沉积剂、分散剂、织物柔软和抗静电剂、荧光增白剂、酶、酶稳定剂、泡沫调节剂、消泡剂、臭味降低剂、防腐剂、消毒剂、水溶助长剂、纤维润滑剂、抗皱剂、缓冲剂、香料、加工助剂、着色剂、染料、颜料、抗腐蚀剂、填料、稳定剂和用于洗衣洗涤剂和织物护理产品中的其他常规成分。
活性共混物组合物在碱性环境中具有有利的稳定性,具有有益的溶解性并有利地明显可溶于碱性组合物例如重负荷洗涤液中并还具有有利的去污性质。在洗衣洗涤剂或织物护理产品中,它们产生有益的洗涤性质,特别是在储存之后。而且,它们在升高的温度下储存稳定,即它们在升高的温度下还在长时间的储存之后是清亮的溶液。在洗衣液组合物的情况下,活性共混物提供了:
·易于添加&潜在地更短的批循环时间
·由于在较低温度下添加而更好的香料、防腐&酶性质
·改善的聚合物递送。
活性共混物组合物的聚酯组分A)可有利地通过这样的方法制备,所述方法包括首先在大气压力下,在添加催化剂的情况下加热对苯二甲酸二甲酯(DMT)、1,2-丙二醇(PG)和X-(OC2H4)n-(OC3H6)m-OH(其中X为C1-4烷基并优选甲基,-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到-OH,且n和m如对于本发明组合物的组分A)的聚酯的定义)至160-220℃的温度,并然后在160-240℃的温度下在降低的压力下继续反应。
降低的压力优选地表示0.1-900毫巴的压力且更优选0.5-500毫巴的压力。
优选地,本发明组合物的组分A)的聚酯的制备方法的特征在于
a)将对苯二甲酸二甲酯、1,2-丙二醇、X-(OC2H4)n-(OC3H6)m-OH(其中X为C1-4烷基并优选甲基)和催化剂加入反应容器,在惰性气体优选氮气下加热至160-220℃的温度以除去甲醇并然后将压力降低到低于大气压力,优选至200-900毫巴的压力且更优选400-600毫巴的压力下,以完成酯交换,和
b)在第二步中,反应在210-240℃的温度下和在0.1-10毫巴并优选0.5-5毫巴的压力下继续进行以形成聚酯。
乙酸钠(NaOAc)和原钛酸四异丙酯(IPT)优选用作本发明组合物的组分A)的聚酯的制备中的催化剂体系。
活性共混物组合物的组分A)的聚酯的制备例如描述在WO 2013/019658 A1中。
优选地,本发明组合物的组分B)中的所述一种或多种醇选自1,2丙二醇、1,3-丙二醇和丁基乙二醇。
更优选地,本发明组合物的组分B)中的醇是1,2-丙二醇。
活性共混物组合物优选地包含
-45-55重量%的组分A)的所述一种或多种聚酯,
-15-25重量%的组分B)的所述一种或多种醇,和
-24-40重量%的组分C)的水。
每种情况下的量基于活性共混物的总重量。
活性共混物可优选地包含0-10重量%、更优选0-5重量%的通常可用于洗涤剂应用中的一种或多种添加剂。可使用的添加剂为例如螯合剂、络合剂、与本发明组合物的组分A)中的所述一种或多种聚酯不同的聚合物、和表面活性剂。
优选地,活性共混物优选地包含一种或多种添加剂(组分D)),且在该情况下,组分C)中水的量优选为24-39.95重量%,在每种情况下,所述量基于活性共混物的总重量。
活性共混物的组分D)中的所述一种或多种添加剂优选地选自螯合剂、络合剂、与本发明组合物的组分A)中的所述一种或多种聚酯不同的聚合物、和表面活性剂。
合适的螯合剂例如为聚丙烯酸或丙烯酸/马来酸共聚物(例如Sokalan CP 12S,BASF)
合适的络合剂例如为EDTA(乙二胺四乙酸),二亚乙基三胺五乙酸、次氮基三乙酸盐或亚氨基二琥珀酸盐。
与本发明组合物的组分A)中的所述一种或多种聚酯不同的合适的聚合物为例如染料转移抑制剂,例如乙烯基吡咯烷酮。
合适的表面活性剂可为阴离子表面活性剂例如月桂基硫酸盐、月桂基醚硫酸盐、烷烃磺酸盐、直链烷基苯磺酸盐、甲基酯磺酸盐、胺氧化物或甜菜碱表面活性剂。
优选地,组分D)中的所述一种或多种添加剂在活性共混物组合物中的存在量高达10重量%,且在这种情况下,活性共混物组合物中组分C)的水的量优选为24-39.95重量%,在每种情况下,所述量基于活性共混物的总重量。
更优选地,组分D)中的所述一种或多种添加剂在活性共混物组合物中的存在量为0.1-10重量%,且在这种情况下,活性共混物组合物中组分C)的水的量优选为24-39.9重量%,在每种情况下,所述量基于活性共混物的总重量。
甚至更优选地,组分D)中的所述一种或多种添加剂在活性共混物组合物中的存在量为0.5-5重量%,且在这种情况下,活性共混物组合物中组分C)的水的量优选为24-39.5重量%,在每种情况下,所述量基于活性共混物的总重量。
在进一步优选的实施方式中,活性共混物由组分A)的所述一种或多种聚酯、组分B)的所述一种或多种醇,和组分C)的水组成。
优选地,活性共混物组合物的粘度在25℃下测量为200-5000mPa·s。
更优选地,活性共混物组合物的粘度在25℃下测量为500-2000mPa·s。
使用DV II型Brookfield粘度计和锭子组RV的锭子,在20转/分钟和25℃下对活性共混物组合物本身测量粘度。1号锭子用于最高500mPa·s的粘度,2号锭子用于最高1000mPa·s的粘度,3号锭子用于最高5000mPa·s的粘度,4号锭子用于最高10000mPa·s的粘度,5号锭子用于最高20000mPa·s的粘度,6号锭子用于最高50000mPa·s的粘度且7号锭子用于最高20000mPa·s的粘度。
在第二方面,提供了制备洗衣液组合物的方法,其包括将上述活性共混物添加到包含选自阴离子表面活性剂和非离子表面活性剂的清洁表面活性剂的组合物中。优选地,所述方法包括在添加香料、芳香物或防腐剂之前添加本文所述的活性共混物并混合。优选地,将活性共混物添加到其中的表面活性剂的混合物的温度不超过50℃且优选为10-40℃。
优选的防腐剂包括BIT(1,2-苯并异噻唑啉-3-酮);MIT(甲基异噻唑啉酮);苯氧基乙醇,IPBC及其混合物。
优选的防腐剂体系包括BIT(1,2-苯并异噻唑啉-3-酮),BIT(1,2-苯并异噻唑啉-3-酮)和MIT(甲基异噻唑啉酮);和苯氧基乙醇和BIT;苯氧基乙醇和IPBC。
在第三方面,提供了通过根据第二方面的方法可获得的洗衣液组合物。
下面的实施例旨在详细说明本发明,但是不对其进行限制。除非另有清楚的指示,给出的所有百分比为重量百分比(重量%或wt.%)。
制备聚酯的一般程序
聚酯合成通过使用乙酸钠(NaOAc)和原钛酸四异丙酯(IPT)作为催化剂体系使对苯二甲酸二甲酯(DMT)、1,2-丙二醇(PG)和甲基聚亚烷基二醇反应来进行。合成为两步程序。第一步为酯交换和第二步为缩聚。
酯交换
将对苯二甲酸二甲酯(DMT)、1,2-丙二醇(PG)、甲基聚亚烷基二醇、乙酸钠(无水)(NaOAc)和原钛酸四异丙酯(IPT)在室温下称重装入反应容器中。
为了熔融过程和均匀化,混合物在氮气流喷射下加热到170℃保持1小时,并然后加热到210℃再保持1小时。在酯交换过程中,甲醇从反应释放并蒸馏出体系(蒸馏温度<55℃)。在2小时后,在210℃下关掉氮气且压力在3小时内降低到400毫巴。
缩聚
混合物加热到高达230℃。在230℃下,压力在160分钟内降低到1毫巴。一旦缩聚反应开始,就将1,2-丙二醇蒸馏出体系。混合物在230℃下和1毫巴压力下搅拌4小时。将反应混合物冷却到140-150℃。在氮气下释放真空并将熔融聚合物转移到玻璃瓶中。
实施例I
获得根据式(I)的聚酯,其中
R1和R2为H3C-(OC2H4)n-(OC3H6)m,其中-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团,
n基于摩尔平均为45,
m基于摩尔平均其为5,和
a基于摩尔平均其为6-7的数。
实施例II
获得根据式(I)的聚酯,其中
R1和R2为H3C-(OC2H4)n-(OC3H6)m,其中-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团,
n基于摩尔平均为45,
m基于摩尔平均其为2,和
a基于摩尔平均其为6-7的数。
稳定性测试
根据下表的组成的溶液已经通过将聚酯溶解在水和醇溶剂的各自的混合物中进行制备。添加剂Sokalan CP 12S被溶解在最终混合物中。研究混合物在储存室中的稳定性(+=澄清溶液,o=混浊,-=显著混浊/沉淀)。新鲜制备的样品为澄清溶液。
实施例I(Ex.I)的聚酯已经用于稳定性测试。
Sokalan CP 12S(丙烯酸/马来酸共聚物,BASF)已经用作添加剂。
从表中可以看出,去污聚酯在水中的溶液(实施例1-4)在45℃下在两星期储存之后已经变浑浊。包含1,2-丙二醇或丁基乙二醇的本发明组合物在45℃下储存4星期后仍澄清。
实施例III
用于制备洗衣液组合物的方法
将光学增亮剂、盐、酸、碱剂以及水溶助长剂加入水中,然后以以下顺序加入表面活性剂:非离子的、LAS然后脂肪酸。然后使用磨机在线注入SLES。一旦SLES被分散,就然后加入来自Clariant的Texcare SRN UL 50(聚酯活性共混物)。在另外的容器中,制备染料&水的预混物,其然后加入主混合器中。在该点之后,加入次要物质(防腐剂&香料&酶,如果适用的话)。
Claims (26)
1.碱性洗衣液组合物,其包含所述组合物的至少1重量%的三乙醇胺、所述组合物的至少5%的非皂表面活性剂和所述组合物的至少0.5%的聚酯,其特征在于所述聚酯作为包含以下组分的活性共混物提供:
A)所述活性共混物的45-55重量%的一种或多种根据下式(I)的聚酯
其中
R1和R2彼此独立地为X-(OC2H4)n-(OC3H6)m,其中X为C1-4烷基并优选甲基,-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的所述段键合到COO基团或者其是HO-(C3H6),且优选地彼此独立地是X-(OC2H4)n-(OC3H6)m,
n基于摩尔平均为12-120且优选40-50的数,
m基于摩尔平均为1-10且优选1-7的数,和
a基于摩尔平均为4-9的数,和
B)所述活性共混物的10-30重量%的一种或多种醇,其选自乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇和丁基乙二醇和
C)所述活性共混物的24-42重量%的水。
2.根据权利要求1的组合物,其特征在于在组分A)的所述一种或多种聚酯中:
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团或者其是HO-(C3H6),且优选地彼此独立地是H3C-(OC2H4)n-(OC3H6)m,
n基于摩尔平均为40-50的数,
m基于摩尔平均为1-7的数,和
a基于摩尔平均为4-9的数。
3.根据权利要求1或2所述的组合物,其特征在于在组分A)的所述一种或多种聚酯中,a基于摩尔平均为5-8的数。
4.根据权利要求3所述的组合物,其特征在于在组分A)的所述一种或多种聚酯中,a基于摩尔平均为6-7的数。
5.根据权利要求1-4中一项或多项所述的组合物,其特征在于在组分A)的所述一种或多种聚酯中,m基于摩尔平均为2-5的数。
6.根据权利要求1-5中一项或多项所述的组合物,其特征在于在组分A)的所述一种或多种聚酯中,n基于摩尔平均为43-47的数。
7.根据权利要求1-6中一项或多项所述的组合物,其特征在于在组分A)的所述一种或多种聚酯中,n基于摩尔平均为44-46的数。
8.根据权利要求7所述的组合物,其特征在于在组分A)的所述一种或多种聚酯中,n基于摩尔平均为45。
9.根据权利要求1-3和5-7中一项或多项所述的组合物,其特征在于在组分A)的所述一种或多种聚酯中
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团,
n基于摩尔平均为44-46的数,
m基于摩尔平均为2,和
a基于摩尔平均为5-8的数。
10.根据权利要求9所述的组合物,其特征在于在组分A)的所述一种或多种聚酯中,n基于摩尔平均为45,且a基于摩尔平均为6-7的数。
11.根据权利要求1-3和5-7中一项或多项所述的组合物,其特征在于在组分A)的所述一种或多种聚酯中
R1和R2彼此独立地为H3C-(OC2H4)n-(OC3H6)m,其中-(OC2H4)基团和-(OC3H6)基团分段布置且由-(OC3H6)基团组成的段键合到COO基团,
n基于摩尔平均为44-46的数,
m基于摩尔平均为5,和
a基于摩尔平均为5-8的数。
12.根据权利要求11所述的组合物,其特征在于在组分A)的所述一种或多种聚酯中,n基于摩尔平均为45,且a基于摩尔平均为6-7的数。
13.根据权利要求1-12中一项或多项所述的组合物,其特征在于组分B)中的所述一种或多种醇选自1,2-丙二醇、1,3-丙二醇和丁基乙二醇。
14.根据权利要求13所述的组合物,其特征在于组分B)中的所述醇为1,2-丙二醇。
15.根据权利要求1-14中一项或多项所述的组合物,其特征在于其包含
-所述活性共混物的45-55重量%的组分A)中的所述一种或多种聚酯,
-所述活性共混物的15-25重量%的组分B)中的所述一种或多种醇,和
-所述活性共混物的24-40重量%的组分C)的水。
16.根据权利要求1-15中一项或多项所述的组合物,其特征在于其包含一种或多种添加剂(组分D)),且在该情况下,水的量优选为所述活性共混物的24-39.95重量%。
17.根据权利要求16所述的组合物,其特征在于组分D)的所述一种或多种添加剂选自螯合剂、络合剂、与组分A)的所述一种或多种聚酯不同的聚合物,和表面活性剂。
18.根据权利要求16或17所述的组合物,其特征在于组分D)的所述一种或多种添加剂以所述活性共混物的最高10重量%的量存在于所述组合物中,且在这种情况下,水的量优选为所述活性共混物的24-39.95重量%。
19.根据权利要求16-18中一项或多项所述的组合物,其特征在于组分D)的所述一种或多种添加剂在所述组合物中的存在量为0.1-10重量%,且在这种情况下,水的量优选为24-39.9重量%,在每种情况下,所述量基于所述活性共混物的总重量。
20.根据权利要求16-19中一项或多项所述的组合物,其特征在于组分D)的所述一种或多种添加剂在所述组合物中的存在量为0.5-5重量%,且在这种情况下,水的量优选为24-39.5重量%,在每种情况下,所述量基于所述活性共混物的总重量。
21.根据权利要求1-15中一项或多项所述的组合物,其特征在于其由组分A)的所述一种或多种聚酯、组分B)的所述一种或多种醇、和水组成。
22.根据权利要求1-21中一项或多项所述的组合物,其特征在于所述活性共混物的粘度在25℃下测量为200-5000mPa·s。
23.根据权利要求22所述的组合物,其特征在于所述活性共混物的粘度在25℃下测量为500-2000mPa·s。
24.用于制备洗衣液组合物的方法,其包括将上述活性共混物添加到包含选自阴离子表面活性剂和非离子表面活性剂的清洁表面活性剂的组合物中。
25.根据权利要求24所述的方法,其中所述方法包括在添加香料、芳香物或防腐剂之前添加本文所述的活性共混物并混合。
26.根据权利要求24或25所述的方法,其中将所述活性共混物添加到其中的表面活性剂的混合物的温度不超过50℃且优选10-40℃。
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