CN1133060A - 含钙离子及二磺酸盐表面活性剂的浓缩液体或凝胶洗碗洗涤剂组合物 - Google Patents
含钙离子及二磺酸盐表面活性剂的浓缩液体或凝胶洗碗洗涤剂组合物 Download PDFInfo
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- CN1133060A CN1133060A CN94193810.7A CN94193810A CN1133060A CN 1133060 A CN1133060 A CN 1133060A CN 94193810 A CN94193810 A CN 94193810A CN 1133060 A CN1133060 A CN 1133060A
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- alkyl
- surfactants
- disulfonate
- sugar
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- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 19
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- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 5
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
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- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
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- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
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- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000003841 chloride salts Chemical group 0.000 claims description 4
- 125000001165 hydrophobic group Chemical group 0.000 claims description 4
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- 229940071104 xylenesulfonate Drugs 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
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- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 2
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 2
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- JCQLYHFGKNRPGE-FCVZTGTOSA-N lactulose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 JCQLYHFGKNRPGE-FCVZTGTOSA-N 0.000 claims description 2
- 229960000511 lactulose Drugs 0.000 claims description 2
- PFCRQPBOOFTZGQ-UHFFFAOYSA-N lactulose keto form Natural products OCC(=O)C(O)C(C(O)CO)OC1OC(CO)C(O)C(O)C1O PFCRQPBOOFTZGQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims 5
- 235000010290 biphenyl Nutrition 0.000 claims 3
- 239000004305 biphenyl Substances 0.000 claims 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 3
- 150000005215 alkyl ethers Chemical class 0.000 claims 2
- 229950006191 gluconic acid Drugs 0.000 claims 2
- 125000000185 sucrose group Chemical group 0.000 claims 2
- 241000282326 Felis catus Species 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims 1
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 claims 1
- 230000021523 carboxylation Effects 0.000 claims 1
- 238000006473 carboxylation reaction Methods 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 229940071089 sarcosinate Drugs 0.000 claims 1
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 claims 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- GDJZZWYLFXAGFH-UHFFFAOYSA-M xylenesulfonate group Chemical group C1(C(C=CC=C1)C)(C)S(=O)(=O)[O-] GDJZZWYLFXAGFH-UHFFFAOYSA-M 0.000 claims 1
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- 239000004519 grease Substances 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 2
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- 125000000217 alkyl group Chemical group 0.000 description 47
- 125000004432 carbon atom Chemical group C* 0.000 description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000002253 acid Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
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- 239000011575 calcium Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000002280 amphoteric surfactant Substances 0.000 description 6
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- 229910052791 calcium Inorganic materials 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
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- 150000001408 amides Chemical class 0.000 description 5
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- 239000001257 hydrogen Substances 0.000 description 5
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- 239000011591 potassium Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
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- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 description 3
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- 150000007513 acids Chemical class 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
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- 125000002947 alkylene group Chemical group 0.000 description 3
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
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- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 3
- 239000002888 zwitterionic surfactant Substances 0.000 description 3
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
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- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
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- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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Abstract
公开了含高活性表面活性剂、钙离子和二磺酸盐表面活性剂的浓缩液体或凝胶洗碗洗涤剂组合物。这些组合物除提供好的清洁能力和去除油脂能力外,还显示出改善的稳定性。特别优选的组合物还含有单糖类。
Description
技术领域
本发明涉及含有高活性洗涤剂表面活性剂、钙离子及二磺酸盐表面活性剂的稳定浓缩液体或凝胶洗碗洗涤剂组合物。
发明背景
典型的轻役型液体或凝胶洗碗洗涤剂含约15%至约30%的阴离子表面活性剂。配制浓缩洗涤剂组合物越来越普遍,尤其在洗衣和自动洗碗洗涤剂组合物中更是如此。这些浓缩组合物通过减少所需的和/或使用的包装及产品物质量而解决环境问题,另外,用户也非常需要去除油脂能力好的轻役型液体或凝胶洗碗洗涤剂。钙离子和镁离子已加入某些液体或凝胶洗涤剂组合物中以改善油脂清除效果。但是常常难于配制含有源自典型的离子源如氯化钙和/或甲酸钙的钙离子的稳定的浓缩液体或凝胶洗碗洗涤剂组合物。
令人惊讶的是已经发现通过加入约0.1%至约40%的二磺酸盐表面活性剂,能够配成稳定的含钙浓缩液体或凝胶洗涤剂组合物。二磺酸盐表面活性剂不但改进了产品的稳定性,而且增强了油脂清洁能力,用作水溶助长剂,并在酸性及过氧化氢环境中高度稳定。
发明概要
液体或凝胶洗碗洗涤剂组合物按重量计包括:
(a)约20%至约95%的选自阴离子表面活性剂、非离子表面活性剂、两性表面活性剂及其混合物的表面活性剂;
(b)约0.01%至约4.0%的钙离子;
(c)约0.1%至约40%的二磺酸盐表面活性剂;以及
(d)约5%至约45%的水;其中所述组合物在20℃10%水溶液中的pH值为约7至约10。
特别优选的实施方案还包括约0.1%至约5.0%(重量)的单糖。
发明的详细说明
本发明的浓缩液体或凝胶、优选是液体洗碗洗涤剂组合物含一种表面活性剂、一种钙离子源及二磺酸盐表面活性剂。此组合物还可含有一种单糖以进一步增加稳定性。在液体或凝胶洗碗组合物中常有的这些或其它任选成分说明如下。
在此使用的术语“轻役型洗碗洗涤剂组合物”是指那些用于人工(即手)洗碗的组合物。
在此使用的术语“浓缩”是指含至少40%总表面活性剂的洗涤剂组合物。
术语“糖”是指单糖或双糖或其衍生物,或水溶性降解淀粉、或水溶性化学改性的降解淀粉。表面活性剂
本发明的组合物含有阳离子表面活性剂、非离子表面活性剂、两性表面活性剂及其混合物,其含量按重量计为约20%至约95%,优选约30%至约75%,更优选约40%至约70%。这些表面活性剂对组合物发泡、去污力及/或柔和性起贡献作用。
在这类中包括数种常用于液体或凝胶洗碗洗涤剂的阴离子表面活性剂。与这些阴离子表面活性剂结合的阳离子可以是碱金属、铵、单、双及三乙醇铵,优选钠、钾、铵及其混合物。可用于本发明的阴离子辅助表面活性剂有如下类别:
(1)烷基苯磺酸盐,其中烷基基团含9-15个碳原子,优选11到14个碳原子,为直链或支链构型。特别优选含约12个碳原子的线性烷基苯磺酸盐。美国专利U.S.Pat.Nos,2,220,099和2,477,383详细描述了这些表面活性剂。
(2)硫酸化含8到22个碳原子,优选12到16个碳原子的醇得到的烷基硫酸盐。烷基硫酸盐具有式ROSO3 -M+,其中R是C8-22烷基,且M是一个单价和/或双价阳离子。
(3)烷基部分含有8到22个碳原子,优选12到16个碳原子的链烷烃磺酸盐。这些表面活性剂可购自Hoechst Celanese,品名为Hostapur SAS。
(4)具有8到22个碳原子,优选12到16个碳原子的烯烃磺酸盐。美国专利U.S.Pat.Nos,3,332,880包含了合适的烯烃磺酸盐的说明。
(5)醇经乙氧基化衍生得到的烷基醚硫酸盐,含有8到22个碳原子,优选12到16个碳原子,少于30摩尔、优选少于12摩尔的氧化乙烯。烷基醚硫酸盐具有式:
RO(C2H4O)xSO3 -M+其中R是C8-22烷基,x为1-30,M是一个单价或二价阳离子。
(6)烷基甘油基醚磺酸盐,其中烷基部分具有8至22个碳原子,优选12至16个碳原子。
(7)下式的脂肪酸酯磺酸盐:
R1-CH(SO3M+)CO2R2其中R1是约C8至C18,优选C12到C16的直链或支链烷基,R2是约C1至C5,优选主要是C1的直链或支链烷基,且M+代表一个单价或二价阳离子。
(8)6到18个碳原子,优选8到16个碳原子的仲醇硫酸盐。
(9)下面的通式说明本发明中应用的一些特殊皂类(或它们的前体酸)。
A.此处应用的非常优选的一类皂包括式R3CH(R4)COON的C10-C16二代羧基物(secondary carboxy material),其中R3是CH3(CH2)x,R4是CH3(CH2)y,其中y可以是0或1至6的整数,x是6至12的整数,且x+y之和是6-12,优选为7-11,最优选为8-9。
B.此处可用的另一类特定皂类包括那些羧基化合物,其中羧基取代基在一个环烃基单元上,即式R5-R6-COOM的二级皂(secondary soap),其中R5是C7-C10,优选C8-C9的烷基或烯基,R6是环结构,如苯、环戊烷、环己烷等等。(注:R5可以是环上羧基的邻位、对位和间位)。
C.再一类皂包括式R7CH(R8)COOM的C10-C18一代羧基(primary carboxyl)和二代羧基化合物,其中R7和R8的碳原子数之和是8-16,R7具有CH3-(CHR9)x的形式且R8是H-(CHR9)y的形式,其中x和y是在0-15范围的整数,R9是H或C1-4的直链或支链烷基。在单个-(CHR9)x.y基团之内R9可以是H和C1-4直链或支链烷基基团的任意组合,但这一类中每个分子必须至少含一个不是H的R9基团。这类分子可由数种方法制得,如通过支链烯烃的羰基化和氧化、支链烯烃的羟基羧基化(hydoxylcarboxylation)、包括支链羰基合成醇的格尔伯特反应产物的氧化。支链烯烃可由短链烯烃如丁烯、异丁烯、支链己烯、丙烯及戊烯的低聚化衍生得到。
D.再一类皂包括如新酸(neo-acid)等式R10CR11(R12)COOM的C10-C18三代羧基(tertiary carboxyl)化合物,其中R10、R11和R12中碳原子数之和是8-16,R10、R11和R12具有CH3-(CHR13)x的形式,其中x是在0-13范围内的整数,且R13是H或C1-4的直链或支链烷基基团。注意在单个的-(CHR13)x基团中,R13可以是H和C1-4直链或支链烷基的任意组合。这类分子来源于羧基加成到支链烯烃上的过程,例如由科赫反应(Kochreaction)得到。市售实例包括Exxon生产的新癸酸以及Shell生产的VersaticTM酸。
在以上A、B、C和D每种式中,M可以是任一合适的反离子,特别是水溶性反离子,例如H、碱金属、碱土金属、铵、醇铵、二和三醇铵、C1-C5烷基取代的铵等。钠及二乙醇铵离子是方便的反离子。
此处优选采用的二级皂(secondary soap)类选自2-甲基-1-十一烷酸、2-乙基-1-癸酸、2-丙基-1-壬酸、2-丁基-1-辛酸;2-戊基-1-庚酸、2-甲基-1-十二烷酸;2-乙基-1-十一烷酸;2-丙基-1-癸酸;2-丁基-1-壬酸;2-戊基-1-辛酸及其混合物的水溶性盐。
(10)它们的混合物
上述阴离子表面活性剂都可购得。必须注意,虽然二烷基磺基琥珀酸酯及脂肪酸酯磺酸盐在中性至微碱性pH条件下都很好地起作用,它们在pH值大大超过约8.5的组合物中的化学稳定性不好。同样必须指出,由于烷基硫酸盐、烷基醚硫酸盐水解或由硫酸化或磺酸化过程捕集的SO3与水反应,故可能存在有硫酸盐杂质。硫酸盐污染物可能对产品的稳定性起有害的作用。所以,在这一具体实施方案中重要的一点是所用的阴离子表面活性剂含非常少量(即按重量计小于1%,优选0至约0.6%,更优选0至约0.3%)(如果有话)硫酸盐离子杂质。
合适的非离子洗涤剂表面活性剂由Laughlin等1975年12月30日公布的美国专利U.S.Patent 3,929,678的13栏第14行到16栏第6行作一般性公开。此处引入作为参考。下面列出示例的非限制性的一类适用非离子表面活性剂。
1.烷基酚的聚环氧乙烷、聚环氧丙烷及聚环氧丁烷缩合物。一般优选聚环氧乙烷缩合物。这些化合物包括带含有6到12个碳原子的直链或支链烷基的烷基酚与烯化氧的缩合产物。这类市售的非离子表面活性剂包括由GAF公司销售的IgepalTMCO-630;Rohm&Haas公司销售的TritonTM X-45、X-114、X-100和X-102。
2.脂肪醇与约1到约25摩尔环氧乙烷的缩合产物。脂肪醇的烷基链可以是直链或支链的伯醇或仲醇,一般含8至22个碳原子。特别优选带含约10至20个碳原子的烷基的醇与对于每摩尔醇约2至约10摩尔环氧乙烷的缩合产物。
3.环氧乙烷和由环氧丙烷与丙二醇缩合形成的疏水基的缩合产品。这些化合物的疏水部分优选具有约1500至约1800的分子量并显示水不溶性。
4.环氧乙烷与由环氧丙烷和乙二胺反应生成的产物的缩合产品。
5.1986年1月21日公布的Llenado的美国专利U.S.Patent4,565,647公开的烷基多糖,具有含约6至约30个碳原子的疏水基团,优选地含约10到约16碳原子的疏水基团和含约1.3至约10,优选约1.3至约3,最优选约1.3至约2.7个糖单元的一种多糖亲水基团,例如聚糖苷亲水基团。美国专利U.S.Patent Nos.4,373,203和4,732,704也描述了可接受的表面活性剂,在此引入作为参考。
这些表面活性剂典型的存在浓度(重量)为约1%至约15%,优选约2%至约10%。
6.本发明的烷基乙氧基羧酸盐有通式RO(CH2CH2O)xCH2COO-M+,其中R是C12至C16的烷基,x的范围为0到约10,并且乙氧基化物按重量计其分布为:x为零的物质量小于约20%,优选小于约15%,最优选小于约10%,而x大于7的物质的量小于约25%,优选小于约15%,最优选小于约10%,当平均R是C13或小于C13时,x平均值为约2至4,而当平均R大于C13时,x平均值为约3到6,并且M是阳离子,优选选自碱金属、铵、单、双及三乙醇铵,最优选选自钠、钾、铵及其与镁离子的混合物。优选的烷基乙氧基羧酸盐为其中R为C12到C14烷基的化合物。制备烷基乙氧基羧酸盐的合适方法公开于美国专利U.S.Patent No.5,233,087中,此处引入作为参考。
其它表面活性剂包括下式的脂肪酸酰胺表面活性剂:其中R6是烷基基团,含有7到21个碳原子,优选9到17个碳原子,并且每一个R7选自氢、C1-C4烷基、C1-C4羟烷基及-(C2H4O)xH,其中x为约1至约3。
本组合物还可含下述结构式的多羟基脂肪酸酰胺:其中,R1是H、C1-C4烃基、2-羟乙基、2-羟基丙基或其混合物,优选C1-C4烷基、更优选C1或C2烷基,最优选C1烷基(即甲基);R2是C5-C31烃基,优选直链C7-C19烷基或链烯基、更优选直链C9-C17烷基或链烯基,最优选直链C11-C17烷基或链烯基,或其混合物;z是多羟基烃基,它带有直链烃基链,并且有至少3个羟基直接连到链上,或它的烷氧基化(优选乙氧基化或丙氧基化)衍生物。Z优选衍生自还原胺化反应中的还原糖,更优选Z是糖醇基(glycityl)。合适的还原糖包括葡萄糖、果糖、麦芽糖、乳糖、半乳糖、甘露糖、木糖。除上述各种糖外,还可用高右旋糖玉米糖浆、高果糖玉米糖浆、高麦芽糖玉米糖浆作为原料。这些玉米糖浆可以产生用作Z的糖组分混合体。应当理解这并不意味着要排除其它合适的原料。Z优选选自-CH2-(CHOH)n-CH2OH、-CH(CH2OH)-(CHOH)n-1-CH2OH、-CH2-(CHOH)2(CHOR1)(CHOH)-CH2OH,其中n是3至5的整数,包括3和5,且R1是H或环状或脂族单糖及其烷氧基化衍生物。最优选其中n是4的糖醇基,特别是-CH2-(CHOH)4-CH2OH。
在式(I)中,R1可以是例如N-甲基、N-乙基、N-丙基、N-异丙基、N-丁基、N-2-羟乙基或N-2-羟丙基。
R2-CO-N<可以是如柯卡酰胺(cocamide)、硬脂酰胺、油酰胺、月桂酰胺、肉豆蔻酰胺、癸酰胺、棕榈酸酰胺、牛脂酰胺(tallowamide)等。
Z可以是1-脱氧糖醇基、2-脱氧果糖醇基(deoxyfructityl)、1-脱氧麦芽糖醇基(deoxylmaltityl)、1-脱氧乳糖醇基(deoxylactityl)、1-脱氧半乳糖醇基(deoxygalactityl)、1-脱氧甘露糖醇基(deoxylmannityl)、2-脱氧麦芽三糖醇基(deoxylmaltotriotityl)等。
在本技术领域制造多羟基脂肪酸酰胺的方法是已知的。一般它们可以在还原胺化反应中由烷基胺与还原糖反应,生成对应的N-烷基多羟基胺,然后将N-烷基多羟基胺和脂肪族酯或甘油三酯在缩合/酰胺化步骤中反应生成N-烷基、N-多羟基脂肪酸酰胺产品。制造含多羟基脂肪酸酰胺组合物的方法公开于例如1959年2月18日公开的Thomas Hedley & Co.,Ltd.的英国专利G.B.PatentSpecification 809,060、1960年12月20日公开的E.R.Wilson的美国专利2,965,576以及美国专利U.S.2,703,798(AnthonyM.Schwartz,公开日期1955年3月8日)、U.S.Patent 1,985,424(Piggott,1934年12月25日公开),每一专利在此都作为参考。
在生产N-烷基或N-羟烷基、N-脱氧糖醇基脂肪酸酰胺的优选方法中(其中糖醇基组分衍生自葡萄糖,并且N-烷基或N-羟烷基官能团是N-甲基、N-乙基、N-丙基、N-丁基、N-羟乙基或N-羟丙基),产品是由N-烷基或N-羟烷基葡糖胺和选自脂肪甲酯、脂肪乙酯或脂肪甘油三酯的一种脂肪酯在催化剂存在下反应得到,催化剂选自磷酸三锂、磷酸三钠、磷酸三钾、焦磷酸四钠、三聚磷酸五钾、氢氧化锂、氢氧化钠、氢氧化钾、氢氧化钙、碳酸锂、碳酸钠、碳酸钾、酒石酸二钠、酒石酸二钾、酒石酸钠钾、柠檬酸三钢、柠檬酸三钾、碱式硅酸钠、碱式硅酸钾、碱式硅铝酸钠、碱式硅铝酸钾及其混合物。催化剂量以N-烷基或N-羟烷基葡糖胺摩尔量为基准,优选为约0.5摩尔%至约50摩尔%,更优选约2.0摩尔%至约10摩尔%。反应优选在约138℃到约170℃,进行一般约20到约90分钟。当甘油三酯作为脂肪酯源用于反应混合物时,反应还优选使用反应混合物总重量的约1%到约10%的相转移剂进行,相转移剂选自饱和脂肪醇聚乙氧基化物、烷基多苷、线性糖酰胺(glycamide)表面活性利及其混合物。
这一过程最好如下进行:
(a)预热脂肪酯到约138℃至约170℃;
(b)将N-烷基或N-羟烷基葡糖胺加入到热的脂肪酸酯中,并混合到形成二相溶液混合物的必要程度;
(c)将催化剂混入反应混合物中;并
(d)搅拌规定的反应时间。
如果脂肪酯是甘油三酯,则还优选占反应物总量约2%至约20%的预先生成的线性N-烷基/N-羟烷基、N-线性葡糖基脂肪酰胺产物作为相转移剂加入反应混合物中。这样可以给反应接晶,从而加速反应速率。
这些多羟基“脂肪酸”酰胺物质也给洗涤剂配制者提供了好处,因为它们可以全部或主要地从天然、可循环的非石油化工原料得到,并且可降解。它们也只表现出对水中生物的低毒性。
必须承认除式(I)的多羟基脂肪酸酰胺外,用于生产它们的方法还常常产生一定量的非挥发性副产品,如酯酰胺及环状多羟基脂肪酸酰胺。这些副产品的含量将随具体的反应物及反应条件而变化。优选加入到本洗涤剂组合物中的多羟基脂肪酸酰胺将以这样一种形式供给,即加入到洗涤剂中的含多羟基脂肪酸酰胺的组合物含少于约10%、优选小于约4%的环状多羟基脂肪酸酰胺。上述的优选方法是有利的,因为它们能产生相当低含量的包括这类环状酰胺副产物在内的副产品。
其它的两性表面活性剂也可加入本洗涤剂组合物中。这些表面活性剂可以广泛地描述为仲胺或叔胺的脂族衍生物、或杂环仲胺或叔胺的脂族衍生物,其中脂族基团可以是直链-支链。脂族取代基之一含至少8个碳原子、一般8至18个碳原子,并且至少有一个取代基含阴离子水溶性基团,如羧基、磺酸根、硫酸根。有用的两性表面活性剂实例可参见Laughlin等的1975年12月30日公开的U.S.PatentNo.3,929,678第19栏18-35行(此处引入作为参考)。
可加入下式的烷基两性羧酸(amphocarboxylic acid):其中R是C8-C18烷基,且R1具有下式:其中R1是(CH2)xCOOM或CH2CH2OH,x是1或2,M选自碱金属、碱土金属、铵、单、双及三乙醇铵,最优选钠、钾、铵及其与镁离子的混合物。优选的R烷基链长为C10到C14烷基。
在优选实施方案中,两性羧酸是产自脂肪咪唑啉的两性二羧酸,其中两性羧酸的二羧酸官能团是二乙酸和/或二丙酸。此处可应用的烷基两性羧酸实例是Miranol,Inc,Dayton,NJ,制造的两性表面活性剂MiranolC2M Conc.,具有下述通式:其中R是C8至C18烷基,x是1或2,M是阳离子。
两性离子表面活性剂同样可加入本洗涤剂组合物中。这些表面活性剂可以广泛描述为仲胺和叔胺的衍生物、杂环仲胺和权胺的衍生物、或季铵、季鏻或叔铳化合物的衍生物。作为有用的两性离子表面活性剂实例可参见Laughlin等,1975年12月30日公开的美国专利U.S.Patent No.3,929,678第19栏38行到第22栏48行(此处引入作为参考)。
这类两性或两性离子表面活性剂一般和一种或多种阴离子和/或非离子表面活性剂结合使用。
如果包括在本发明的组合物中,这些种类表面活性剂以组合物重量的约1%至约15%,优选约2%至约10%的浓度存在。钙离子
钙离子的存在极大改善了本发明组合物去除油脂污垢的能力,特别是当这一组合物用于含较少二价离子的软水中时更是如此。
钙离子可以以氯化物、乙酸盐、二甲苯磺酸盐、甲酸盐或硝酸盐的形式加入到组合物中,优选氯化物盐、二甲苯磺酸盐和/或甲酸盐。
本发明组合物中存在的钙离子含量为组合物重量的约0.01%至4.0%,优选约0.05%至3.5%,更优选约0.1%至约2.0%。
本发明组合物中钙离子的存在量取决于阴离子和/或非离子表面活性剂的总量。当本发明组合物中存在钙离子和阴离子和/或非离子表面活性剂时,则组合物中钙离子与总的阴离子和/或非离子表面活性剂的摩尔比为约1∶15至约1∶2。二磺酸盐
在本发明中,二磺酸盐表面活性剂含量可为约0.1%至约40%,优选约0.5%至约25%,更优选约1%至约10%。
适用的二磺酸盐表面活性剂包括下式的烷基二苯基氧二磺酸盐表面活性剂:R=C10-C18,可以是支链或直链;R1=H或R;M=Na+、K+、NH4 +、Ca++或Mg++ R=C10-C18,可以是支链或直链:R1=H或R;M1=Ca++或Mg++
合适的市售二磺酸盐表面活性剂是Dow Chemical(Dowfax 2A1,3B2,8290)的DOWFAX系列和Olin Corp的POLY-TERGENT系列。水
本组合物一般地含水最多约45%,优选约5%至约45%,最优选约20%至约40%。组合物的pH值
本发明的组合物在20℃10%水溶液中的pH值为约7至约10,更优选约7至约9。
本发明的洗碗组合物在投入使用时,即稀释并用于带污垢的碗碟时,将受食物污垢产生的酸性作用。如果pH值大于7的组合物要最有效地改进性能那么在组合物和在溶液,即约0.1%至约0.4%(重量)的水溶液中必须含有一种能够维持碱性pH值的缓冲剂。
缓冲剂的PKa值应该低于组合物所需pH值(如上所确定)0.5到1.0个pH单位。优选的缓冲剂PKa值应当在约7至约9.5。在这些条件下,即使使用最少量的缓冲剂也可以最有效地控制pH值。
缓冲剂本身可以是活性洗涤剂,或是用于保持碱性pH值的低分子量有机物或无机物。本发明组合物优选的缓冲剂是含氮物质。氨基酸或低级醇胺如单、二和三乙醇胺是一些实例。其它的优选含氮缓冲剂是2-氨基-2-乙基-1,3-丙二醇、2-氨基-2-甲基-丙醇、2-氨基-2-甲基-1,3-丙二醇、三(羟甲基)-氨基甲烷(a.k.a.tris)及谷氨酸二钠。N-甲基二乙醇胺、1,3-二氨基-2-丙醇、N,N’-四甲基-1,3-二氨基-2-丙醇、N,N-双(2-羟乙基)甘氨酸(a.k.a.bicine)及N-三(羟甲基)甲基甘氨酸(a.k.a.tricine)同样也是优选的。以上任意物质的混合物也是可以接受的。本发明组合物中的缓冲剂存在量为组合物重量的约0.1%至约15%,优选为约1%至约10%,最优选约2%至约8%。糖类
本发明包括约0.1%至约5.0%、优选约0.5%至约4.0%的单糖或二糖。糖重复单元只要保证水溶性,可以有少至5个碳原子,或多至50个碳原子。糖衍生物可以是糖的醇或酸,“水溶性”在本文中指糖在室温下在蒸馏水可形成浓度为0.01g/l的透明溶液或稳定的胶体分散体。
可用于本发明中的糖中,有蔗糖(最优选,原因是便宜易得)、纤维素二糖、山莴苣糖(lactulose)、麦芽糖及乳糖,这些糖是二糖。适用的单糖衍生物包括葡糖酸、葡萄糖、果糖、半乳糖、木糖、阿戊糖和核糖。泡沫增强剂(suds booster)
可包括在本发明组合物中的另一组分是泡沫稳定表面活性剂(泡沫增强剂),其含量以组合物重量计为小于约15%,优选约0.5%到12%,更优选约1%至约10%。可在本发明组合物中实用的任选泡沫稳定表面活性剂为:磺基内铵盐(sultaine)、复合内铵盐、内铵盐、环氧乙烷缩合物、脂肪酸酰胺、氧化胺半极性非离子及阳离子表面活性剂。
本发明组合物可含有下式的内铵盐表面活性剂:
R-N(+)(R1)2-R2COO(-)其中R是疏水基团,选自含约10至约22个碳原子的烷基,优选含约12至约18个碳原子的烷基,含类似碳原子数的烷基芳基及芳基烷基,其中苯环接等价于约2个碳原子数计算,以及由酰氨基或醚键所隔断的类似结构;每一个R1是含约1至3个碳原子的烷基;R2是含1至约6个碳原子的亚烷基。
优选的内铵盐实例是十二烷基二甲基内铵盐、十六烷基二甲基内铵盐、十二烷基酰氨基丙基二甲基内铵盐、十四烷基二甲基内铵盐、十四烷基酰氨基丙基二甲基内铵盐和十二烷基二甲基铵己酸盐。
其它合适的酰氨基烷基内铵盐公开于U.S.Patent.Nos.3,950,417;4,137,191及4,375,421;以及British Patent GB NO.2,103,236,全部在此引入作为参考。
必须承认,以上内铵盐表面活性剂的烷基(及酰基)基团可以衍生自天然物质或合成物质;例如它们可衍生自天然脂肪酸,由Ziegler或Oxo过程制备的烯烃;或裂化的或未裂化的石油中分离的烯烃。
可用于本发明的磺基内铵盐为具有下式的那些:R(R1)2N+R2SO3 -,其中R是C6-C18烃基,优选C10-C16烷基,更优选为C12-C13烷基,每一个R1一般为C1-C3烷基,优选甲基,R2是C1-C6烃基,优选C1-C3亚烷基,或优选羟基亚烷基。合适的磺基内铵盐的实例包括C12-C14二甲基氨基(ammonio)-2-羟丙基磺酸盐、C12-C14酰氨基丙基氨基(ammonio)-2-羟丙基磺酸盐、C12-C14二羟乙基氨基(ammonio)丙烷磺酸盐,以及C16-18二甲基氨基(ammonio)己烷磺酸盐,其中优选C12-C14酰氨基丙基氨基(ammonio)-2-羟丙基磺基内铵盐。
此处应用的复合内铵盐具有下式:其中R是具有7到22个碳原子的烃基,A是(C(O)基团,n是0或1,R1是氢或低级烷基,x是2或3,y是0至4的整数,Q是-R2COOM基团,其中R2是亚烷基,它具有1到6个碳原子,M是氢或选自碱金属、碱土金属、铵及取代铵的离子,B是氢或如所定义的Q基团。
这一范畴的实例是烷基两性多羧基甘氨酸盐,其式为:
环氧乙烷缩合物广泛地定义为由环氧乙烷基团(亲水性质)与有机疏水化合物缩合产生的化合物,疏水化合物可以是脂族的或烷基芳族的化合物。与任何具体的疏水基团缩合的亲水基团或聚氧化烯基团的长度可以容易地调节以生成具有所需亲水亲油平衡值的水溶性化合物。
可用作泡沫稳定剂的合适环氧乙烷缩合物的实例是脂肪醇与环氧乙烷的缩合产品。脂肪醇的烷基链可以是直链也可以是支链,一般含有约8至约18个碳原子,优选约8至约14个碳原子,以获得最好的泡沫稳定剂性能,其中环氧乙烷的存在量对每摩尔醇为约8摩尔至约30摩尔,优选约8至14摩尔。
可用于此的酰胺表面活性剂实例包括脂肪酸的氨、单乙醇酰胺及二乙醇酰胺,其中酰基部分含约8至约18个碳原子,并用下式表示:
R1-CO-N(H)m-1(R2OH)3-m其中R是饱和或不饱和的脂族烃基,它具有约7至21个碳原子,优选约11至17个碳原子;R2代表亚甲基或亚乙基;m是1、2或3,优选为1。上述酰胺的特定实例是单乙醇胺椰子脂肪酸酰胺及二乙醇胺十二烷基脂肪酸酰胺。这些酰基部分可以衍生自天然甘油酯,如椰油、棕榈油、豆油和动物脂,也可合成得到,例如通过氧化石油或经Fisher Tropsch过程氢化一氧化碳反应得到。优选C12-C14脂肪酸的单乙醇酰胺或二乙醇酰胺。
氧化胺半极性非离子表面活性剂含有下式的化合物及其混合物:其中R1是烷基、2-羟烷基、3-羟烷基或3-烷氧基-2-羟丙基,其中烷基和烷氧基分别含约8至约18个碳原子,R2和R3各自是甲基、乙基、丙基、异丙基、2-羟乙基、2-羟丙基或3-羟丙基,并且n从0到约10。特别优选下式的氧化胺:其中R1是C12-C15烷基,并且R2和R3是甲基或乙基。上述环氧乙烷缩合物、酰胺及氧化胺在U.S.Pat.No.4,316,824(Puncheri)中有更充分的描述,在此引入作为参考。
本发明的组合物还可含有某些下式的阳离子季铵盐表面活性剂:
[R1(OR2)y][R3(OR2)y]2R4N+X-或下式的胺表面活性剂:
[R1(OR2)y][R3(OR2)y]R4N其中R1是烷基链上有约6至约16个碳原子的烷基或烷基苄基;每一个R2选自-CH2CH2-、-CH2CH(CH3)-、-CH2CH(CH2OH)-、-CH2CH2CH2-及其混合物:当y不是0时,每一个R3选自C1-C4烷基、C1-C4羟烷基、苄基和氢;R4和R3相同,或是烷基链,其中R1和R4碳原子总数为约8至约16;每一个y为0至约10,y值之和为0至约15;x是任意的相容阴离子。
当R4选自与R3相同的基团时,上述优选的是烷基季铵盐表面活性剂,特别是上式的单长链烷基表面活性剂,最优选的季铵盐表面活性剂是C8-C16烷基三甲基铵的盐酸、氢溴酸和甲基硫酸盐、C8-C16烷基二(羟乙基)甲基铵盐、C8-C16烷基羟乙基二甲基铵盐、C8-C16烷氧基丙基三甲基铵盐及C8-C16烷氧基丙基二羟乙基甲基铵盐。上述化合物中,优选C10-14烷基三甲基铵盐,如十二烷基三甲基甲基硫酸铵、月桂基三甲基氯化铵、十四烷基三甲基溴化铵及椰子三甲基铵的盐酸及甲基硫酸盐。
本发明组合物中应用的泡沫增强剂可以含上述泡沫增强剂的任何一种或其混合物。其他任选成分
除了前述成分外,本发明组合物可包括适用于液体或凝胶洗碗组合物中的其它常规成分。
镁离子可加入到组合物中,其用量为0.01%至约4%,优选为约0.1%至约3%,并以氯化物、乙酸盐、甲酸盐、硝酸盐形式加入,优选氯化物盐或甲酸盐。
任选成分包括促进排污的乙氧基化的非离子表面活性剂,这一类见Pancheri(1982年2月23日)公开的U.S.Pat.No.4,316,824,在此引入作为参考。
醇类,如C1-C4单羟基醇,优选乙醇及丙二醇,可以用来获得所需的产品相稳定性和粘度。醇类如乙醇和丙二醇含量为组合物重量的0%至约15%,更优选约0.1%至约10%,对本发明的液体组合物而言非常适用。
本发明的凝胶组合物一般不含醇。这些凝胶组合物可以以含有组合物重量约10%至约30%的尿素及常规增稠剂作为胶凝剂。
其它必要的成分包括稀释剂和溶剂。稀释剂可以是无机盐,如氯化铵、氯化钠、氯化钾等,溶剂包括水、低分子量醇,如乙醇、异丙醇等。配制
一般来讲,任何常规方法都可用于配制本发明的组合物。但是,二磺酸盐表面活性剂的加入次序对配制本发明的稳定浓缩轻役型液体洗碗洗涤剂组合物十分重要。已经发现二磺酸盐表面活性剂应当加入到组合物的表面活性剂糊料中。方法方面
在本发明的方法方面,带污垢碗与有效量、一般约0.5毫升至20毫升(每次处理25个碗)、优选约3至10毫升的本发明洗涤剂组合物接触。液体洗涤剂组合物的实际用量取决于使用者的判断,一般取决于诸如包括活性成分浓度在内的组合物的特定产品组成、要清洗的带污垢碗的数量、碗污垢的程度等因素。特定的产品组成本身又取决于许多因素,如组合物产品的意向市场(即美国、欧洲、日本等)。下面是本发明的洗涤剂组合物用于洗碗的一般方法的实例。这些实例的目的只在于说明而非限制。
在典型的美国应用中,将约3毫升至约15毫升、优选约5毫升至约10毫升的液体洗涤剂组合物和约1,000毫升至约10,000毫升、更一般约3,000毫升至约5,000毫升水在池中混合,池体积容量为约5,000毫升至约20,000毫升,更典型为约10,000毫升至约15,000毫升。洗涤剂组合物中表面活性剂混合物浓度以重量计为约21%至约44%、优选约25%至约40%。带污垢的碗浸在含洗涤剂组合物和水的池中,在池中用布、海绵或类似物品接触碗的表面的污垢,以清洁碗。在和碗表面接触以前,布、海绵或类似物品可以浸在洗涤剂组合物和水的混合物中,并且和碗表面接触约1至约10秒,当然实际时间将依每次使用及使用者而不同。布、海绵或类似物品在与碗表面接触的同时最好同时擦洗碗表面。
在典型的欧洲市场应用中,将约3毫升至约15毫升、优选约3至约10毫升的液体洗涤剂组合物与约1,000毫升至约10,000毫升水、更常常约3,000毫升至约5,000毫升水在池中混合,池容积为约5,000毫升至约20,000毫升,更常常为约10,000毫升至约15,000毫升。洗涤剂组合物中表面活性剂混合物浓度以重量计为约20%至约50%、优选约30%至约40%。将带污垢的碗浸在含洗涤剂组合物和水的池中,在池中用布、海绵或类似物品接触碗的污垢表面,清洁碗。布、海绵或类似物品可以预先浸入洗涤剂组合物和水的混合物中,然后和碗表面接触,并和碗表面接触一般约1秒至约10秒,当然实际时随每次使用及使用者而不同。布、海绵或类似物品与碗表面接触的同时,最好同时擦洗碗的表面。
在典型的拉丁美洲和日本市场应用中,将约1毫升至约50毫升、优选约2毫升至约10毫升的洗涤剂组合物和约50毫升至约2,000毫升水,更典型地为约100毫升至约1,000毫升水在盆中混合,盆的容积为约500毫升至约5,000毫升,更典型为约500毫升至约2,000毫升。洗涤剂组合物具有的表面活性剂混合物重量浓度为约5%至约40%,优选约10%至约30%。带污垢的碗可通过用布、海绵或类似物品接触碗的污垢表面而清洗。在和碗表面接触之前,布、海绵或类似物品可先浸在洗涤剂组合物和水的混合物中,并和碗表面通常接触约1秒至约10秒,当然实际时间将依每次使用及使用者而变化。布、海绵或类似物品与碗表面接触的同时最好伴随擦洗碗表面。
另一使用方法包括将带污垢的碗浸到不含任何液体洗碗洗涤剂的水浴中。一种吸收液体洗碗洗涤剂的器具如海绵直接放到一份单独量的未稀释液体洗碗洗涤剂中约1至约5秒钟。将吸收洗涤剂的器具,以及未稀释的液体洗碗洗涤剂组合物然后逐个和每个带污垢的碗表面接触以除去所述污垢。吸收器具通常与每个碗表面接触约1秒至约10秒钟,当然实际使用时间将随诸如碗的污垢程度等因素而变。吸收器具与碗表面的接触最好同时伴随有擦洗。
除非另有说明,本文中所用的所有百分数、部分和比值都以重量计。
下列各实施例说明本发明并帮助理解本发明。
实施例1
下面的浓缩轻役型液体组合物制备如下
表1
重量百分数
成分 A B C二甲苯磺酸钠 3.00 3.00 0.00二亚乙基三胺五乙酸 0.06 0.06 0.06乙醇 8.06 8.06 8.06丙二醇 1.60 1.60 1.60氯化镁 3.21 3.21 3.21烷基乙氧基(1.0)硫酸钠 9.00 9.00 9.00烷基乙氧基(3.0)硫酸钠 19.80 19.80 19.80多羟基脂肪酸酰胺 9.00 9.00 9.00氧化胺 3.00 3.00 3.00NEODOL1-91 3.15 3.15 3.15香料 0.09 0.09 0.09DOWFAX 2A1 0.00 0.00 1.35甲酸钙 0.00 1.33 0.00二水氯化钙 1.51 0.00 1.51水 ………余额………
1 C11E9非离子表面活性剂
将产品放置在120°F环境下一周,评价稳定性。结果如下:
表2稳定性 A B C120°F/1月 沉淀 沉淀 透明
组合物C含二磺酸盐表面活性剂(DOWFAX2A1)和不含这一表面活性剂的浓缩组合物相比,在苛刻的环境条件下仍然是稳定的。
实施例II
下面所列轻役型液体组合物如下配制:
表3
重量%
成分 D E F G二甲苯磺酸钠 2.30 2.30 1.15 0.00二亚乙基三胺五乙酸 0.06 0.06 0.06 0.06乙醇 9.15 9.15 9.15 9.15氢氧化镁 2.18 2.18 2.18 2.18蔗糖 1.50 1.50 1.50 1.50烷基乙氧基(1.0)硫酸盐 34.14 34.14 34.14 34.14氢氧化钠 1.13 1.13 1.13 1.13多羟基脂肪酸酰胺 6.50 6.50 6.50 6.50氧化铵 3.00 3.00 3.00 3.00椰酰氨基丙基内铵盐 2.00 2.00 2.00 2.00香料 0.23 0.23 0.23 0.23DOWFAX 2Al 0.00 0.00 0.00 0.00二甲苯磺酸钙 0.00 0.00 3.59 3.58DOWFAX 3B2 0.00 0.00 1.15 1.15甲酸钙 0.00 1.14 0.00 0.00二水氯化钙 1.28 0.00 0.00 0.00水 ………余额………
重量%
成分 H I二甲苯磺酸钠 0.00 0.00二亚乙基三胺五乙酸 0.06 0.06乙醇 9.15 9.15氢氧化镁 2.18 2.18蔗糖 1.50 1.50烷基乙氧基(1.0)硫酸盐 34.14 34.14氢氧化钠 1.13 1.13多羟基脂肪酸酰胺 6.50 6.50氧化铵 3.00 3.00椰酰氨基丙基内铵盐 2.00 2.00香料 0.23 0.23DOWFAX 2Al 1.04 2.30二甲苯磺酸钙 0.00 0.00DOWFAX 3B2 0.00 0.00甲酸钙 0.00 1.14二水氯化钙 1.28 0.00水 ………余额………
将产品在120°F环境下放置一周,检查稳定性并目测外观,结果如下。
表4稳定性 D E F G120°F/1周 沉淀 沉淀 透明 透明稳定性 H I120°F/1周 透明 透明
含二磺酸盐表面活性剂的组合物(组合物F和G DOWFAX 3B2,组合物H和I,DOWFAX 2A1)与只含二甲苯磺酸钠的组合物(组合物D和E)相比在苛刻的温度下更稳定。
实施例III
下述各轻役型液体组合物制备如下:
表5
重量%
成分 H I烷基二甲基内铵盐 2.00 0.00椰酰氨基丙基内铵盐 0.00 2.00二亚乙基三胺五乙酸 0.06 0.06乙醇 7.00 10.00烷基乙氧基(1.0)硫酸钠 15.00 20.00氯化镁(2.6)HOH 2.35 4.91烷基乙氧基(3.5)羧酸盐 3.79 0.00烷基乙氧基(3.0)硫酸钠 6.00 6.00多羟基脂肪酸酰胺 6.00 6.00氧化铵 1.00 1.50NEODOL1-91 10.00 10.00异丙基苯磺酸钠 2.00 2.002-丁基-1-癸酸 4.00 5.00烷基二苯基氧二磺酸盐2 4.00 4.00香料 0.15 0.18Tetronic 0.00 0.10氯化氢 0.00 0.18水和微调剂 ……余额……pH 8.3 8.3
1C9E11非离子表面活性剂
2DOWFAX 2A1
Claims (10)
1.一种液体或凝胶洗涤剂组合物,按组合物重量计包括:(a)20%至95%的选自阴离子表面活性剂、非离子表面活性剂、两性表面活性剂及其混合物的表面活性剂;(b)0.01%至4.0%的钙离子,所述钙离子优选以选自氯化物盐、乙酸盐、硝酸盐、甲酸盐、二甲苯磺酸盐及其混合物的盐的形式加到所述组合物中;(c)0.5%至40%的二磺酸盐表面活性剂;(d)5.0%至45%的水;其中所述组合物在20℃10%水溶液中的pH值为7至10之间。
2.按权利要求1的组合物,含有30%至75%的选自烷基硫酸盐、烷基醚硫酸盐、聚醚羧酸盐、仲烯(secondary olefin)磺酸盐、肌氨酸盐、甲酯磺酸盐、烷基甘油醚磺酸盐、烷基酚的聚环氧乙烷、聚环氧丙烷及聚环氧丁烷的缩合物;脂族醇与环氧乙烷的烷基乙氧基化物缩合产物、由环氧丙烷与丙二醇缩合生成的疏水基与环氧乙烷的缩合产物、环氧乙烷与乙二胺的缩合产物、烷基多糖、脂肪酸酰胺、烷基乙氧基羧酸盐、特殊皂类、多羟基脂肪酸酰胺及其混合物的表面活性剂。
3.按权利要求1或2的组合物,还含有0.1%至5%的糖,所述糖选自蔗糖、麦芽糖、纤维素二糖、山莴苣糖(lactulose)、乳糖、葡糖酸、葡萄糖、果糖、半乳糖、木糖、核糖及其混合物。
5.按前述任一权利要求的组合物,含0.1%至2%的钙离子。
6.按前述任一权利要求的组合物,还含少于15%的泡沫增强剂,选自内铵盐、磺基内铵盐(sultaine)、复合内铵盐、环氧乙烷缩合物、脂肪酸酰胺、氧化胺半极性非离子表面活性剂、阳离子表面活性剂及其混合物
7.按前述任一权利要求的组合物,含0.05%至4.0%的糖。
8.轻役型液体洗碗洗涤剂组合物,以重量计含有:a)40%至70%的表面活性剂,选自阴离子表面活性剂、非离子表面活性剂、两性表面活性剂及其混合物;b)0.1%至2.0%以盐形式加入的钙离子,所述盐选自二甲苯磺酸盐、甲酸盐、氯化物盐及其混合物;c)0.5%至25%的烷基二苯基氧二磺酸盐;d)0.5%至4.0%的糖,选自蔗糖、麦芽糖、乳糖、葡糖酸、葡萄糖、果糖及其混合物;e)0.1%至3%以盐的形式加入的镁,所述盐选自氯化物盐、甲酸盐及其混合物;及f)0.5%至12%的泡沫增强剂,选自内铵盐、脂肪酸酰胺、氧化胺半极性非离子物质及其混合物;其中所述组合物在20℃10%水溶液中的pH值为7至9.0之间。
9.按前述任一权利要求的组合物,其中所述表面活性剂选自烷基乙氧基羧酸盐、多羟基脂肪酸酰胺、烷基醚硫酸盐及其混合物。
10.用于形成稳定浓缩组合物的方法,包括向一种或多种阴离子表面活性剂、非离子表面活性剂、两性表面活性剂或它们的混合物中加入二磺酸盐表面活性剂和钙离子,其中所述二磺酸盐表面活性和是一种烷基二苯基氧表面活性剂。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US08/113,495 US5417893A (en) | 1993-08-27 | 1993-08-27 | Concentrated liquid or gel light duty dishwashing detergent compositions containing calcium ions and disulfonate surfactants |
US08/113,495 | 1993-08-27 |
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Publication Number | Publication Date |
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CN1133060A true CN1133060A (zh) | 1996-10-09 |
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CN94193810.7A Pending CN1133060A (zh) | 1993-08-27 | 1994-08-09 | 含钙离子及二磺酸盐表面活性剂的浓缩液体或凝胶洗碗洗涤剂组合物 |
Country Status (9)
Country | Link |
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US (1) | US5417893A (zh) |
EP (1) | EP0715650B1 (zh) |
JP (1) | JPH09501969A (zh) |
CN (1) | CN1133060A (zh) |
AT (1) | ATE151458T1 (zh) |
AU (1) | AU7452494A (zh) |
DE (1) | DE69402558T2 (zh) |
ES (1) | ES2102240T3 (zh) |
WO (1) | WO1995006106A1 (zh) |
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-
1993
- 1993-08-27 US US08/113,495 patent/US5417893A/en not_active Expired - Fee Related
-
1994
- 1994-08-09 WO PCT/US1994/008947 patent/WO1995006106A1/en active IP Right Grant
- 1994-08-09 ES ES94924141T patent/ES2102240T3/es not_active Expired - Lifetime
- 1994-08-09 JP JP7507608A patent/JPH09501969A/ja active Pending
- 1994-08-09 CN CN94193810.7A patent/CN1133060A/zh active Pending
- 1994-08-09 DE DE69402558T patent/DE69402558T2/de not_active Expired - Fee Related
- 1994-08-09 AU AU74524/94A patent/AU7452494A/en not_active Abandoned
- 1994-08-09 AT AT94924141T patent/ATE151458T1/de not_active IP Right Cessation
- 1994-08-09 EP EP94924141A patent/EP0715650B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0715650A1 (en) | 1996-06-12 |
US5417893A (en) | 1995-05-23 |
DE69402558D1 (de) | 1997-05-15 |
EP0715650B1 (en) | 1997-04-09 |
ES2102240T3 (es) | 1997-07-16 |
DE69402558T2 (de) | 1997-11-06 |
WO1995006106A1 (en) | 1995-03-02 |
JPH09501969A (ja) | 1997-02-25 |
AU7452494A (en) | 1995-03-21 |
ATE151458T1 (de) | 1997-04-15 |
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