CN1201486A - 颜色安全的漂白增效剂、组合物和使用它们的洗涤方法 - Google Patents
颜色安全的漂白增效剂、组合物和使用它们的洗涤方法 Download PDFInfo
- Publication number
- CN1201486A CN1201486A CN96197991A CN96197991A CN1201486A CN 1201486 A CN1201486 A CN 1201486A CN 96197991 A CN96197991 A CN 96197991A CN 96197991 A CN96197991 A CN 96197991A CN 1201486 A CN1201486 A CN 1201486A
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- Prior art keywords
- composition
- acid
- bleaching composition
- detergent
- salt
- Prior art date
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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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
- C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
- C07D217/10—Quaternary compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
Abstract
本发明公开了含有两性离子亚胺和阴离子亚胺多离子的漂白增效剂。漂白增效剂增加了在较低温度溶液中的漂白效果,显示杰出的颜色安全性能。漂白增效剂理想地适合包含于包括含有洗涤剂表面活性剂和酶的漂白组合物中。本发明还提供洗涤添加剂产物,其含有作为漂白增效剂的两性离子亚胺、带有净负电荷的阴离子亚胺多离子。本发明还公开了采用本发明的漂白增效剂洗涤织物的方法。
Description
发明领域
本发明涉及颜色安全的漂白增效剂、组合物和使用颜色安全的漂白增效剂的洗涤方法。更具体地说,本发明涉及两性离子和阴离子亚胺漂白增效剂、组合物和使用两性离子和阴离子亚胺漂白增效剂的洗涤方法。
发明背景
近年来,氧漂白剂在家庭和个人护理产品中越来越普及,以有助于除去污渍和污垢。漂白剂的去除污渍、肮脏织物清洁、增白和消毒性质是尤其合乎需要的。在洗涤产物如洗涤剂,在自动餐具洗涤产物和在硬表面清洁剂中氧漂白剂被发现是尤其适用的。然而,氧漂白剂的有效性有某种限制。一些通常遇到的缺点包括织物的颜色损害和对洗涤用具的损害,尤其是其中包括了橡胶管的用具。此外,氧漂白剂趋向于极端的温度速率依赖性。因此,其使用的溶液温度越低,漂白作用的效果越差。对于氧漂白剂在溶液中的效果,通常需要超过60℃的温度。
为解决上述温度速率依赖性,开发了一类称为“漂白活化剂”的化合物。漂白活化剂,通常是带有离去基团的可过水解的酰基化合物如苯酚磺酸盐,其与通常为过氧化氢或它的阴离子的活性氧基反应以形成更有效的过氧酸氧化剂。正是过氧酸化合物然后氧化沾污或弄脏的携污体物质。然而,漂白活化剂也稍稍是依赖温度的。漂白活化剂在温度为约40℃至约60℃的温水下更有效的。在低于约40℃的水温下,过氧酸化合物损失其部分漂白效果。
已尝试开发一种在较低温度水条件下有效的漂白体系。Madison等人的US5360568、Madison等人的US5360569和Madison等人的US5370826均涉及带正电荷的季亚胺盐,其作为过氧化合物转移活性氧的催化剂,因而被认为在一水温范围内,包括在较低的温度下增加了过氧化合物的活性。然而,这些带正电荷的季亚胺盐在洗涤漂白应用中不是完全令人满意的。尤其当在这些参考文献中公开的带正电荷的季亚胺盐与过氧化合物结合时,导致织物的不可接受程度的颜色损害。
因此,仍需要一种有效的漂白增效剂和含有漂白增效剂的组合物,该组合物提供了在较低水温下有效的漂白作用,并提供了改善的颜色安全性质。
发明概述
本发明提供了颜色安全的漂白增效剂,满足了该需求。本发明的漂白增效剂在较低水温下提供杰出的漂白效果以及杰出的颜色安全性质。根据本发明的第一实施方案,提供了漂白组合物。组合物含有过氧源和选自两性离子亚胺、带有约-1至约-3的净负电荷的阴离子亚胺多离子和它们的混合物的漂白增效剂。漂白增效剂优选占漂白组合物重量的约0.01%至约10%,过氧源占漂白组合物重量的约0.01%至约60%。
过氧源包括预先形成的过酸化合物,其选自过羧酸及其盐、过碳酸及其盐、过亚氨酸及其盐、过氧单硫酸及其盐和它们的混合物。另外,过氧源可含有过氧化氢或与漂白活化剂结合的过氧化氢。过氧化氢源可选自过硼酸盐化合物、过碳酸盐化合物、过磷酸盐化合物和它们的混合物。漂白活化剂可选自四乙酰基乙二胺、辛酰氧基苯磺酸钠、壬酰氧基苯磺酸钠、癸酰氧基苯磺酸钠、(6-辛酰氨基己酰基)氧苯磺酸盐、(6-壬酰氨基己酰基)氧苯磺酸盐、(6-癸酰氨基己酰基)氧苯磺酸盐和它们的混合物。
漂白增效剂优选选自芳基亚铵两性离子、带有-1至-3净负电荷的芳基亚铵多离子和它们的混合物。通常优选的增效剂具有下式:其中R1-R3是有约0至约-1总电荷的基团;R1和R2形成共同环的部分;T选自:-(CH2)b-,其中b是约1至约8,-(CH(R5))-,其中R5是C1-C8烷基-、CH2(C6H4)-、和-(CH2)d(E)(CH2)f-,其中d是2-8,f是1-3,E是-C(O)O-或-C(O)NR6,其中R6是H或C1-C4烷基;Z与T共价连接,Z选自-CO2 -、-SO3 -和-OSO3 -,a是1或2。R1和R2可一起形成不带电基团:
漂白增效剂更优选是芳基亚铵两性离子和R3是H,T是-(CH2)b-或-CH2(C6H4)-,Z是-SO3 -,a是1和b是2-4。芳基亚铵两性离子可具有下式:
本发明的漂白增效剂还含有带有净负电荷的芳基亚铵多离子,和R3是H,T是-(CH2)b-或-CH2(C6H4)-,Z是-SO3 -,a是2和b是2-4。芳基亚铵多离子优选可具有下式:或是这些化合物的水溶性盐。漂白组合物还可含有至少一种洗涤剂表面活性剂、至少一种螯合剂、至少一种洗涤剂酶,且漂白组合物的1%溶液优选具有约8至约10的pH。
在另一个本发明的实施方案中,提供了两性离子洗涤漂白增效剂。两性离子洗涤漂白增效剂选自:
根据本发明的另一方面,其提供了洗涤织物的方法。该方法包括使需洗涤的织物与洗涤溶液接触。洗涤溶液包括过氧源和漂白增效剂。漂白增效剂选自两性离子亚胺、带有约-1至约-3净负电荷的阴离子亚胺多离子和它们的混合物。
洗涤溶液还可含有至少一种洗涤剂表面活性剂、至少一种螯合剂和至少一种洗涤剂酶。洗涤溶液的pH优选为约8至约10。过氧源可含有过氧化氢源或与漂白活化剂结合的过氧化氢源。过氧化氢源可选自过硼酸盐化合物、过碳酸盐化合物、过磷酸盐化合物和它们的混合物。漂白活化剂可选自四乙酰基乙二胺、辛酰氧基苯磺酸钠、壬酰氧基苯磺酸钠、癸酰氧基苯磺酸钠、(6-辛酰氨基己酰基)氧苯磺酸盐、(6-壬酰氨基己酰基)氧苯磺酸盐、(6-癸酰氨基己酰基)氧苯磺酸盐和它们的混合物。漂白增效剂优选选自芳基亚铵两性离子、带有约-1至约-3的负净电荷的芳基亚铵多离子和它们的混合物。
在本发明的另一实施方案中,提供了洗涤添加剂产物。洗涤添加剂产物含有洗涤添加剂。洗涤添加剂包括选自两性离子亚胺、带有约-1至约-3净负电荷的阴离子亚胺多离子和它们的混合物的漂白增效剂。添加剂以剂量形式用于添加到洗涤溶液中。
添加剂还包括过氧化氢源,其选自过硼酸盐化合物、过碳酸盐化合物、过磷酸盐化合物和它们的混合物。此外,添加剂可包括漂白活化剂,其选自四乙酰基乙二胺、辛酰氧基苯磺酸钠、壬酰氧基苯磺酸钠、癸酰氧基苯磺酸钠、(6-辛酰氨基己酰基)氧苯磺酸盐、(6-壬酰氨基己酰基)氧苯磺酸盐、(6-癸酰氨基己酰基)氧苯磺酸盐和它们的混合物。漂白增效剂优选选自芳基亚铵两性离子、带有约-1至约-3的负净电荷的芳基亚铵多离子和它们的混合物。剂量形式可包括丸剂、片剂、caplet、胶囊(gelcap)或其它单一剂量形式。合适的载体也可以包括在添加剂中。
因此,本发明的一个目的是提供漂白组合物,其在较低温度溶液中显示改善的性能,和杰出的对织物的颜色安全性。本发明的一项特征是提供漂白组合物,其含有漂白增效剂,该漂白增效剂两性离子亚胺、带有约-1至约-3净负电荷的阴离子亚胺多离子和它们的混合物。本发明的另一目的是提供采用两性离子亚胺、带有约-1至约-3净负电荷的阴离子亚胺多离子和它们的混合物的漂白增效剂洗涤织物的方法。本发明的另一特征是提供洗涤添加剂产物,其含有两性离子亚胺、带有约-1至约-3净负电荷的阴离子亚胺多离子和它们的混合物的漂白增效剂。本发明的这些和其它的目的,特征和优点通过如下的描述和所附的权利要求书被本领域其它技术人员所认识。
除非另外说明,所有百分数、比率和比例为重量基准。所有引用的文献在此引入作为参考。
发明详述
本发明公开了新的非常有用的颜色安全的漂白增效化合物和组合物,和使用该新漂白增效化合物的方法。本发明的漂白增效剂提供了在较低温度应用中增加的漂白效果,同时得到杰出的织物颜色安全性能。本发明的漂白增效剂与常规过氧漂白源结合起作用提供上述增加的漂白效果和杰出的颜色安全性能。
本发明的漂白增效剂含有两性离子亚胺、带有约-1至约-3净负电荷的阴离子亚胺多离子和它们的混合物。本发明的这些亚胺漂白增效剂包括如下一般结构的那些漂白增效剂:其中R1-R4可以是氢或未取代或取代的基团,其选自苯基、芳基、杂环基、烷基和环烷基基团,只是至少R1-R4中之一含有带阴离子电荷的基团。
R1-R3是总电荷为约0至约-1的基团;
R1-R3可以是氢或未取代或取代的基团,其选自苯基、芳基、杂环基、烷基和环烷基基团;
T选自:-(CH2)b-,其中b是约1至约8,-(CH(R5))-,其中R5是C1-C8烷基、-CH2(C6H4)-、和-(CH2)d(E)(CH2)f-,其中d是2-8,f是1-3,和E是-C(O)O-、-C(O)NR6-或其中R6是H或C1-C4烷基;
Z与T共价连接,Z选自-CO2 -、-SO3 -和-OSO3 -,a是至少1。因此,当Z与T共价连接时(当R1-R3总电荷是0时),当a是1时,亚胺是两性离子或当a大于1时,亚胺是带有净负电荷的多离子。优选a是1或2,和漂白增效剂是两性离子或净负电荷为-1的多离子。
在更优选的实施方案中,本发明的漂白增效剂是芳基亚铵两性离子、带有约-1至约-3的净负荷的芳基亚铵多离子。在该优选实施方案中,R1和R2一起形成共同环的部分。R1和R2尤其可一起形成一个或多个五元、六元或七元环。最优选的芳基亚铵由如下不带电荷的基团得到:
因此,优选的芳基亚铵两性离子包括R1和R2一起形成的不带电荷的基团(III),T选自:-(CH2)b-,其中b是约1至约6,-(CH(R5))-,其中R5是甲基,-CH2(C6H4)-、其中a是1和Z选自-CO2 -和-SO3 -。本发明更优选的芳基亚铵两性离子包括R1和R2一起形成的不带电荷的基团(III),T是-(CH2)b-或-CH2(C6H4)-,其中a是1和Z是-SO3 -,b是2-4。本发明最优选的芳基亚铵两性离子由下式表示:分别为3-(3,4-二氢异喹啉鎓)丙磺酸盐和4-(3,4-二氢异喹啉鎓)丁磺酸盐。
本发明优选的芳基亚铵多离子包括R1和R2一起形成的不带电荷的基团(III),T选自:和-(CH2)d(E)(CH2)f-,其中d是2-8,f是1-3,和E是:a至少为2,Z选自-CO2 -和-SO3 -。本发明更优选的芳基亚铵多离子包括R1和R2一起形成的不带电荷的基团(III),T选自:和-(CH2)d(E)(CH2)f-,其中d是2-6,f是1,和E是:a是2,Z是-SO3 -。本发明最优选的多离子由下式表示:
本发明亚胺漂白增效剂与过氧源结合起作用以提供更有效的漂白体系。过氧源在现有技术中是众所周知的,在本发明中使用的过氧源包括任何这些众所周知的源体,包括过氧化合物以及在消费者使用条件下就地提供有效量过氧的化合物。过氧源可包括过氧化氢源、通过过氧化氢源和漂白活化剂的反应就地形成过酸阴离子、预先形成的过酸化合物或合适过氧源的混合物。当然,本领域的普通技术人员将认识到可采用其它过氧源而不会脱离本发明的范围。
本发明使用的预先形成的过酸化合物是任何在消费者使用条件下提供有效量的过酸阴离子的常规化合物。合适的非限定性实例包括过羧酸和其盐、过碳酸和其盐、过亚氨酸和其盐、过氧单硫酸和其盐和它们的混合物。过羧酸和其盐的适合的实例包括单过氧邻苯二甲酸镁六水合物,间氯过苯甲酸镁,4-壬基氨基-4-氧代过氧丁酸镁和二过氧十二烷二酸镁。这些漂白剂公开在1984年11月20日授权的Hartman的美国专利4483781,Burns等人的美国专利4634551,1985年2月20日公开的Banks等人的欧洲专利申请0133354和1983年11月1日授权的Chung等人的美国专利4412934中。源体还包括在1987年1月6日授权给Burns等人的美国专利4634551中描述的6-壬基氨基-6-氧代过氧己酸。过硫酸盐化合物如商业上由德国Wilmington的E.I.DuPont de Nemours生产的OXONE也可用作过氧单硫酸的合适源体。
本发明所用的过氧化氢源是在消费者使用条件下提供有效量的过氧化氢的任何常规化合物或混合物。其含量可广泛变化,通常为按漂白组合物重量计约0.5%至约70%,更一般地为约0.5%至约25%。本发明中使用的过氧化氢源可以是任何常规来源,包括过氧化氢本身。例如,过硼酸盐如过硼酸钠(任何水合物,但优选单或四水合物)、碳酸钠过氧水合物或当量过碳酸盐、焦磷酸钠过氧水合物、脲过氧水合物或过氧化钠可用于本发明中。也可以使用任何常规过氧化氢源的混合物。
优选的过碳酸盐漂白剂包含平均颗粒尺寸为约500微米至约1000微米的干颗粒,其中按重量计不超过约10%的所述颗粒小于约200微米,按重量计不超过约10%的所述颗粒大于约1250微米。过碳酸盐可任选地用硅酸盐、硼酸盐或水溶性表面活性剂涂覆。过碳酸盐由不同的商业来源如FMC、Solvay和Tokai Denka得到。
本发明中使用的漂白活化剂是任何与过氧化氢源结合使用时引起就地产生相应于漂白活化剂的过酸的化合物。活化剂的非限定性实例公开在1990年4月10日授权给Mao等人的US4915854和US4412934中。壬酰氧基苯磺酸盐(NOBS)和四乙酰基乙二胺(TAED)活化剂是典型的,它们的混合物也可以使用。对于其它的用于本发明的漂白剂和活化剂也可见US4634551。
高度优选的酰氨基衍生的漂白活化剂具有下式:
R1N(R5)C(O)-R2C(O)L或R1C(O)N(R5)R2C(O)L,其中这些化合物所用的R1是含有约6至约12个碳原子的烷基,R2是含有1至约6个碳原子的亚烷基,R5是氢或含有约1至约10个碳原子的烷基、芳基或烷芳基和L是任何适当的离去基团。离去基团是任何由于过氧化氢阴离子亲核进攻漂白活化剂而从漂白活化剂上离去的基团。优选的离去基团是苯酚磺酸盐。
上式的漂白活化剂的优选实例包括如US4634551中描述的(6-辛酰氨基己酰基)氧基苯磺酸盐、(6-壬酰氨基己酰基)氧基苯磺酸盐、(6-癸酰氨基己酰基)氧基苯磺酸盐和它们的混合物,引入本文作为参考。
另一类漂白活化剂包括在1990年10月30日授权的Hodge等人的US4966723中公开的苯并噁嗪型活化剂,列入本文作为参考。高度优选的苯并噁嗪型活化剂是:
另一类优选漂白活化剂包括酰基内酰胺活化剂,尤其是下式的酰基己内酰胺和酰基戊内酰胺:在这些化合物中使用的R6是H或含有1至约12碳原子的烷基、芳基、烷氧基芳基或烷芳基。高度优选的内酰胺活化剂的实例包括苯甲酰基己内酰胺、辛酰基己内酰胺、3,5,5-三甲基己酰基己内酰胺、壬酰基己内酰胺、癸酰基己内酰胺、十一碳烯酰基己内酰胺、苯甲酰基戊内酰胺、辛酰基戊内酰胺、癸酰基戊内酰胺、十一碳烯酰基戊内酰胺、壬酰基戊内酰胺、3,5,5-三甲基己酰基戊内酰胺和它们的混合物。还参见1985年10月8日授权给Sanderson的US4545784,引入本文作为参考,其公开了酰基己内酰胺,包括吸附在过硼酸钠中的苯甲酰基己内酰胺。
本发明的亚胺漂白增效剂与过氧源结合起作用以增加漂白效果。漂白增效剂与过氧源反应以形成更活性的漂白物质,氧杂亚铵(oxaziridinium)化合物。形成的氧杂亚铵化合物是与亚胺漂白增效剂相同的带有净负电荷的两性离子或多离子。氧杂亚铵化合物在较低的温度下有相对于过氧化合物增加的活性。氧杂亚铵化合物由下式表示:并且可由本发明的亚胺通过如下反应制备:因此,由式(IV)表示的本发明的优选漂白增效剂产生由下式表示的活性氧杂亚铵漂白剂物质:
在漂白组合物中本发明的漂白增效剂可与过氧源结合使用。在组合物中,过氧源可以按组合物重量计约0.1%至约60%,优选按组合物重量计约1%至约40%的含量存在。在组合物中,漂白增效剂以按组合物重量计约0.01%至约10%,优选按组合物重量计约0.05%至约5%的含量存在。
本发明的漂白组合物可有利地用于洗涤应用、硬表面清洁、自动餐具洗涤应用以及美容应用,例如假牙、牙齿、头发和皮肤。然而,由于在较低温度溶液中独特的增加效果和杰出的颜色安全性能的优点,本发明的漂白增效剂理想地适用于洗涤应用,例如通过使用含有漂白剂的洗涤剂或洗涤漂白剂添加剂漂白织物。此外,本发明的漂白增效剂可用于颗粒和液体组合物中。
因此,本发明的漂白组合物可包括各种添加组分,它们在洗涤应用中是需要的。这种组分包括洗涤剂表面活性剂、漂白催化剂、助洗剂、螯合剂、酶、聚合去污剂、增白剂和各种其它组分。包括任何各种添加组分的组合物在1%漂白组合物溶液中优选具有约8至约10的pH。洗涤剂表面活性剂-本发明的漂白组合物可含有洗涤剂表面活性剂。包括在本发明提供的全配制组合物中的洗涤剂表面活性剂根据所用的具体表面活性剂和所需的效果,占组合物重量的至少1%,优选约1%-约99.8%。在高度优选的实施方案中,洗涤剂表面活性剂占组合物重量的约5%-约80%。
洗涤剂表面活性剂可以是非离子、阴离子、两性、两性离子或阳离子表面活性剂。也可以使用这些表面活性剂的混合物。优选的洗涤剂组合物包含阴离子洗涤剂表面活性剂或阴离子表面活性剂与其它表面活性剂,尤其是非离子表面活性剂的混合物。
本文中使用的表面活性剂的非限定性实例包括常规的C11-C18烷基苯磺酸盐和伯、仲无规烷基硫酸盐、C10-C18烷基烷氧基硫酸盐、C10-C18烷基多苷和其相应的硫酸化多苷、C12-C18α-磺化的脂肪酸脂、C12-C18烷基和烷基酚烷氧基化物(尤其是乙氧基化物和混合的乙氧基/丙氧基化物)、C12-C18甜菜碱和磺基甜菜碱(“磺基甜菜碱”)、C10-C18氧化胺等。其它可用的常规表面活性剂列在标准文献中。
尤其适用于本发明的漂白组合物中的一类非离子表面活性剂是环氧乙烷与疏水基团的缩合物,以提供平均亲水亲油平衡值(HLB)为5-17,优选6-14,最优选7-12的表面活性剂。疏水(亲油)基团性质上可以是脂族或芳族的。与任何具体的疏水基团缩合的聚氧乙烯基的长度可容易地调节以得到具有所需亲水和疏水部分之间平衡程度的水溶性化合物。
这种类型的尤其优选的非离子表面活性剂是每摩尔醇含有3-8摩尔环氧乙烷的C9-C15伯醇乙氧基化物,尤其是每摩尔醇含有6-8摩尔环氧乙烷的C14-C15伯醇、每摩尔醇含有3-5摩尔环氧乙烷的C12-C15伯醇和它们的混合物。
另一合适类别的非离子表面活性剂包括下式的多羟基脂肪酸酰胺:
R2C(O)N(R1)Z其中,R1为氢,C1-C8烃基,2-羟乙基,2-羟丙基,或它们的混合物,优选C1-C4烷基,更优选C1或C2烷基,最优选C1烷基(即甲基);R2为C5-C32烃基部分,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-C19烷基或链烯基或其混合物;Z为具有直接连在链上的至少二个羟基(在甘油醛的情况下)或至少三个羟基(在其它还原糖的情况下)的线性烃基链的多羟基烃基部分或其烷氧基化衍生物(优选乙氧基化或丙氧基化)。Z优选在还原胺化反应中由还原糖得到,更优选Z为糖基部分。适宜的还原糖包括葡萄糖,果糖,麦芽糖,乳糖,半乳糖,甘露糖和木糖及甘油醛。作为原料,和以上所列的单个糖一样,可以使用高葡萄糖玉米糖浆,高果糖玉米糖浆和高麦芽糖玉米糖浆。由这些玉米糖浆可得到糖组分Z的混合物。应当认识到这里并没有打算排除其它适宜的原料。Z优选选自-CH2(CHOH)n-CH2OH、-CH(CH2OH)(CHOH)n-1-CH2OH、-CH2-(CHOH)2(CHOR′)(CHOH)-CH2OH,其中,n为1至5的整数,包括1和5,R′是H或环状的单糖或多糖和其烷氧基化衍生物。最优选其中n为4的糖基,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-异丁基、N-2-羟基乙基或N-2-羟基丙基。为得到最好的起泡性,R1优选为甲基或羟基烷基。如果需要低起泡性,R1优选为C2-C8烷基,尤其是正丙基,异丙基,正丁基,异丁基,戊基,己基和2-乙基己基。
R2-CO-N<可以是例如椰子酰胺、硬脂酰胺、油酰胺、月桂酰胺、肉豆蔻酰胺、癸酰胺、棕榈酰胺、牛脂酰胺等。常规洗涤剂添加剂-尽管对本发明而言不是必需的,但若干下文描述的常规添加剂适用于本发明的组合物,并可加入本发明的优选实施方案中,例如以有助于或改善洗涤性能、用于处理所洗涤的携污体或在香料、颜料、染料等的情况下改善漂白组合物的美观。这些附加组分的确切性质和加入的含量将取决于组合物的物理形式和所用的洗涤操作的性质。除非另有说明,本发明的漂白组合物可配制成例如颗粒或粉末形式全用途或“重垢”洗涤剂,尤其是所谓的重垢液体类型;液体轻洗织物洗涤剂;手工餐具洗涤剂或轻垢餐具洗涤剂,尤其是高泡型的;机洗餐具洗涤剂,包括用于家庭和公开场所用途的各种片剂、颗粒、液体和漂清助剂型;液体洗涤和消毒剂,包括杀菌洗手型、洗衣皂条、漱口剂、假牙洗净剂、汽车或地毯香波、浴室清洁剂;洗发香波和护发素;淋浴凝胶和泡沫浴和金属清洁剂;以及洗涤辅助剂,例如漂白添加剂和“顽固污垢”或预处理型。漂白催化剂-如果需要的话,本发明的漂白组合物可通过锰化合物催化。这类化合物在现有技术中是众所周知的,其包括,例如在US5246621、US5244594、US5194416、US5114606和欧洲专利申请公开号549271A1、549272A1、544440A2和544490A1中公开的锰基催化剂。这些催化剂的优选实例包括MnIV 2(u-O)3(1,4,7-三甲基-1,4,7-三氮杂环壬烷)2-(PF6)2、MnIII 2(u-O)1(u-OAc)2(1,4,7-三甲基-1,4,7-三氮杂环壬烷)2(ClO4)2、MnIV 4(u-O)6(1,4,7-三氮杂环壬烷)4(ClO4)4、MnIII-MnIV 4-(u-O)1(u-OAc)2-(1,4,7-三甲基-1,4,7-三氮杂环壬烷)2(ClO4)3、MnIV-(1,4,7-三甲基-1,4,7-三氮杂环壬烷)-(OCH3)3(PF6)和它们的混合物。其它金属基的漂白剂催化剂包括在US4430243和US5114611中公开的那些。具有各种复杂配位体以提高漂白作用的锰的应用在如下美国专利中也有报导:4728455;5284944;5246612;5256779;5280117;5274147;5153161和5227084。
所述锰可与乙二胺二琥珀酸盐预配合,或者例如作为硫酸盐单独地与乙二胺二琥珀酸盐一起加入。在所述含有过渡金属的漂白剂催化剂中的其它优选的过渡金属包括铁或铜。
事实上,但不是为了限制,可调节本发明的漂白组合物和方法以提供在含水洗涤母液中大约每千万至少一份活性漂白剂催化剂物质,优选在洗涤母液中提供约0.1ppm至约700ppm,更优选约1ppm至约50ppm催化剂物质。助洗剂-洗涤剂助洗剂可任选地包含在本发明的组合物中以有助于控制矿物硬度。可以使用无机和有机助洗剂。助洗剂一般用于织物洗涤组合物中以有助于除去颗粒污垢。
助洗剂的含量根据组合物的最终用途和其所需的物理形式可以在宽范围内变化。当使用助洗剂时,组合物中一般含有至少约1%的助洗剂。液体配方通常含有按重量计约5%至约50%,更常见的为约5%至约30%的洗涤剂助洗剂。颗粒配方一般包含按重量计约10%至约80%,更典型约15%至约50%的助洗剂。但是,这并不意味着排除更低或者更高的助洗剂含量。
无机或含磷洗涤助洗剂包括,但不局限于此,聚磷酸盐(例如三聚磷酸盐,焦磷酸盐,和玻璃状聚合的偏磷酸盐),膦酸盐,肌醇六磷酸,硅酸盐,碳酸盐(包括碳酸氢盐和倍半碳酸盐),硫酸盐和硅铝酸盐的碱金属,铵和烷醇铵盐。然而在某些地方需要非磷酸盐助洗剂。重要的是本发明组合物甚至在有所谓的"弱"助洗剂(与磷酸盐比较)如柠檬酸盐、或在用沸石或层状硅酸盐助洗剂所产生的所谓的"欠复配"环境中具有意想不到的好效果。
硅酸盐助洗剂的实例为碱金属硅酸盐,特别是SiO2∶Na2O的比率在1.6∶1至3.2∶1范围内的硅酸盐,和层状硅酸盐,如在1987年5月12日授权给H.P.Rieck的美国专利4664839中描述的层状硅酸钠。NaSKS-6是由Hoechst销售的层状结晶硅酸盐的商标(在本文中通常缩写为"SKS-6")。不象沸石助洗剂,NaSkS-6硅酸盐助洗剂不含铝。NaSkS-6是具有δ-Na2SiO5形态学构形的层状硅酸盐。其可以通过如在DE-A-3417649和DE-A-3742043中描述的方法制备。SKS-6是本文中使用的高度优选的层状硅酸盐,但可以使用其它的层状硅酸盐,如具有通式NaMSixO2x+1·yH2O,其中M为钠或氢,x为1.9至4的数值,优选为2,y为0至20的数值,优选为0的层状硅酸盐。从Hoechst购得的各种其它层状硅酸盐包括NaSkS-5,NaSkS-7,和NaSkS-11,为α、β和γ形式。δ-Na2SiO5(NaSkS-6形式)是本文中最优选使用的。其它的硅酸盐也是有用的,例如硅酸镁,其可作为颗粒配方中的松脆剂,氧漂白剂的稳定剂和控泡体系的组分。
碳酸盐助洗剂的实例是在1973年11月15日公开的德国专利申请号2321001中的碱土金属和碱金属碳酸盐。
硅铝酸盐助洗剂在本发明中是有用的。硅铝酸盐助洗剂在最流行的市售重垢粒状洗涤剂组合物中最重要,也可以是液体洗涤剂配方中重要的助洗剂组分。硅铝酸盐助洗剂包括具有以下经验式的助洗剂:
Mz(zAlO2)y]·xH2O其中z和y为至少是6的整数,z与y的摩尔比在1.0至约0.5的范围内,x是约15至约264的整数。
有用的硅铝酸盐离子交换材料是商业上可购买的。这些硅铝酸盐可以是结晶或无定形结构,并且可以是天然存在的硅铝酸盐或合成得到的。制备硅铝酸盐离子交换材料的方法公开在1976年10月12日授权的Krummel等的美国专利3985669中。用于本文的优选合成结晶硅铝酸盐离子交换材料是按名称沸石A、沸石P(B)、沸石MAP和沸石X购买的。在特别优选的实施方案中,结晶硅铝酸盐离子交换材料具有下式:
Na12[(AlO2)12(SiO2)12]·xH2O其中x为约20至约30,尤其是约为27。该物质称为沸石A。在本发明中也可使用脱水沸石(x=0-10)。优选的硅铝酸盐具有直径为约0.1-10微米的颗粒尺寸。
适合本发明用途的有机助洗剂包括,但不局限于此,各种多羧酸盐化合物。本文中所用的“多羧酸盐”指的是具有多个羧酸盐基团、优选至少3个羧酸盐基团的化合物。多羧酸盐助洗剂通常可以以酸形式加入组合物中,但也可以中和盐的形式加入。当以盐的形式使用时,碱金属,如钠、钾和锂或烷醇铵盐是优选的。
在多羧酸盐助洗剂中包括的是多种类型的有用物质。重要的一类多羧酸盐助洗剂包括醚多羧酸盐,包括氧联二琥珀酸盐,如在1964年4月7日授权的Berg的美国专利3128287,和1972年1月18日授权的Lamberti等的美国专利3635830中公开的。也参见1987年5月5日授权给Bush等的美国专利4663071中的"TMS/TDS"助洗剂。适合的醚多羧酸盐也包括环状化合物,特别是脂环族化合物,如在美国专利3923679;3835163;4158635;4120874和4102903中描述的那些化合物。
其他有用的洗涤助洗剂包括醚羟基多羧酸盐,马来酸酐与乙烯或乙烯基甲基醚的共聚物,1,3,5-三羟基苯-2,4,6-三磺酸和羧甲基氧联琥珀酸,各种多乙酸,如乙二胺四乙酸和次氮基三乙酸的碱金属,铵和取代铵盐,以及多羧酸盐如苯六甲酸,琥珀酸,氧联二琥珀酸,聚马来酸,苯-1,3,5-三羧酸,羧甲基氧联琥珀酸和其水溶性盐。
柠檬酸盐助洗剂,例如,柠檬酸和其水溶性盐(特别是钠盐)是重垢液体洗涤剂配方中特别重要的多羧酸盐助洗剂,原因是它们可由可再生资源得到和它们的生物可降解性。柠檬酸盐也可以用于颗粒组合物中,尤其是可以与沸石和/或层状硅酸盐助洗剂结合使用。氧联二琥珀酸盐在这些组合物和混合物中也是特别有用的。
适合在本发明洗涤剂组合物中使用的还有在1986年1月28日授权的Bush等的美国专利4566984中公开的3,3-二羧基-4-氧杂-1,6-己二酸盐和其相关的化合物。有用的琥珀酸助洗剂包括C5-C20烷基和链烯基琥珀酸和其盐。这种类型中特别优选的化合物为十二碳烯基琥珀酸。琥珀酸盐助洗剂的具体实例包括:月桂基琥珀酸盐,肉豆寇基琥珀酸盐、棕榈基琥珀酸盐、2-十二碳烯基琥珀酸盐(优选),2-十五碳烯基琥珀酸盐等。月桂基琥珀酸盐是该组中优选的助洗剂,并被描述在1986年11月5日公开的欧洲专利申请86200690.5/0200263中。
其他适合的多羧酸盐公开在1979年3月13日授权的Crutchfield等的美国专利4144226中和在1967年3月7日授权的Diehl的美国专利3308067中。也参见Diehl的美国专利3723322。
脂肪酸,例如C12-18单羧酸也可以单独掺入组合物中,或与前述的助洗剂,尤其是柠檬酸盐和/或琥珀酸盐助洗剂结合掺入组合物中以提供附加的助洗剂活性。如此使用脂肪酸一般会导致降低起泡性,这是配方师应当考虑的。
在可以使用磷基助洗剂的情况下,特别是在用于手洗操作的皂条配方中,可以使用各种碱金属磷酸盐,如众所周知的三聚磷酸钠,焦磷酸钠,和正磷酸钠。膦酸盐助洗剂如乙烷-1-羟基-1,1-二膦酸盐和其它已知的膦酸盐(参见,例如US3159581;3213030;3422021;3400148和3422137)也可使用。酶-为了多种织物洗涤目的,包括例如去除蛋白质基的,碳水化合物基的或三甘油酯基的污渍,以及为了避免脱落的染料迁移和为了织物的复原,在本发明洗涤剂配方中可包括酶。可掺入的酶包括蛋白酶、淀粉酶、脂肪酶、纤维素酶和过氧化物酶,以及其混合物。也可以包括其它类型的酶,它们可以来自任何适宜的来源,如植物、动物、细菌、霉菌和酵母源。然而,它们的选择由几个因素决定,如pH活性和/或稳定性最佳点、热稳定性、对活性洗涤剂和助洗剂的稳定性等。在该方面,细菌或霉菌是优选的,如细菌淀粉酶和蛋白酶,以及霉菌纤维素酶。
酶通常被掺入足够的量以提供每克组合物中多达约5毫克(重量),一般为约0.01-约3毫克的活性酶。另外说明的是,本文中的组合物一般包括约0.001%-约5%,优选0.01%-1%(重量)商业酶制品。蛋白酶通常在这种商业制品中的存在量足以提供每克组合物0.005-0.1Anson单位(AU)活度。
适宜的蛋白酶的例子为枯草杆菌蛋白酶,其是由枯草芽孢杆菌和地衣型芽孢杆菌的特殊菌株得到的。另一种适宜的蛋白酶是由芽孢杆菌属菌株得到的,其在pH8-12范围内具有最大活性,是由Novo Industries A/S开发和销售的,注册的商品名称为ESPERASE。这种酶和类似酶的制备描述在Novo的英国专利说明书号1243784中。商业上可买到的适宜除去蛋白质基污渍的蛋白水解酶包括由Novo Industries A/S(丹麦)销售的商品名为ALCALASE和SAVINASE的蛋白酶,和由International Bio-Synthetics,Inc.(荷兰)销售的商品名为MAXA TASE的蛋白酶。其它蛋白酶包括蛋白酶A(参见欧洲专利申请130756,1985.01.09公开)和蛋白酶B(参见欧洲专利申请系列NO.87303761.8,1987.04.28申请,和Bott等的1985.01.09公开的欧洲专利申请130756)。
淀粉酶包括例如在GB1296839(Novo)中描述的α-淀粉酶,RAPIDASE(International Bio-Synthetics,Inc.)和TERMAMYL(NovoIndustries)。
可用于本发明中的纤维素酶包括细菌和霉菌纤维素酶。优选它们具有最佳pH范围5-9.5。适宜的纤维素酶公开在Barbesgoard等的1984年3月6日授权的美国专利4435307中,其公开了由Humicola insolens和腐殖霉菌株DSM1800产生的霉菌纤维素酶或者属于气单胞菌属的产生纤维素酶212的霉菌,和由海生软体动物(Dolabella Auricula Solander)的肝胰腺中提取的纤维素酶。适宜的纤维素酶也公开在GB-A-2075028;GB-A-2095275和DE-OS-2247832中。CAREZYME(Novo)是尤其有用的。
洗涤剂可使用的适宜脂肪酶包括由假单胞菌属族中的微生物,如司徒茨氏假单胞菌ATCC 19.154产生的那些脂肪酶,如英国专利1372034所公开。也参见在1978年2月24日公开提供公众审查的日本专利申请53-20487中的脂肪酶。这种脂肪酶可由Amano PharmaceuticalCo.Ltd.,Nagoya,Japan买到,商品名为脂肪酶P“Amano”,下文称之为“Amano-P”。其它的商业脂肪酶包括Amano-CES,来自Chromobacter viscosum的脂酶,例如,Chromobacter viscosum var.lipolyticum NRRLB 3673,在商业上可由Toyo Jozo Co.,Tagata,Japan买到;和其它Chromobacter viscosum脂酶,由U.S.BiochemicalCorp.(USA)和Disoynth Co.(荷兰)买到,和来自唐菖蒲假单胞菌(Pseudomonas gladioli)的脂酶。由胎毛腐殖菌(Humicola lanuginosa)得到的并且在商业上可由Novo(同样参见EPO 341947)买到的LIPOLASE酶是用于本文中的优选脂酶。
过氧化物酶是与氧源,例如过碳酸盐、过硼酸盐、过硫酸盐、过氧化氢等结合使用。它们用于“溶液漂白”,即抑制在洗涤过程中从基物中脱落的染料或颜料迁移至洗涤溶液中的其它基物上。过氧化物酶在本领域中是已知的,并且包括如辣根过氧化物酶、木质素酶,和卤代过氧化物酶,如氯代和溴代过氧化物酶。含有过氧化物酶的洗涤剂组合物公开在例如1989年10月19日公开的由O.Kirk转让给Novo Industries A/S的PCT国际申请WO89/099813中。
各种的酶物质和将它们掺入合成洗涤剂组合物中的方法也公开在1971年1月5日授权给的McCarty等的美国专利3553139中。一些酶还公开在1978年7月18日授权的Place等人的美国专利4101457,和1985年3月26日授权的Hughes的美国专利4507219中。用于液体洗涤剂配方的酶物质,和它们掺入到这些配方中的方法公开在1981年4月14日授权的Hora等的美国专利4261868中。用于洗涤剂中的酶可用各种技术使其稳定化。酶稳定化技术公开并举例说明在1971年8月17日授权给Gedge等的美国专利3600319,和欧洲专利申请公开号0199405,申请号86200586.5,1986年10月29日公开,Venegas。酶稳定化体系也描述在例如US3519570中。酶稳定剂-本文中所使用的酶可由在最终组合物中的水溶性钙和/或镁离子源(其给酶提供该离子)存在下被稳定。(钙离子通常比镁离子更有效,并且在如果仅使用一种类型的阳离子时钙离子优选用于本发明中)。另外的稳定性可通过在各种其它现有技术公开的稳定剂,尤其是硼酸盐类存在下获得,参见Severson的U.S.4537706。一般洗涤剂,尤其是液体,包括按每升最终组合物计约1至约30,优选约2至约20,更优选约5至约15,最优选约8至约12毫摩尔的钙离子。其根据存在的酶的量和酶对钙离子或镁离子的响应度可略有变化。应当这样选择钙或镁离子的量,使得其在与组合物中的助洗剂、脂肪酸等络合之后,对于酶来说总是存在有效的最小量。任何水溶性钙或镁盐都可作为钙或镁离子物源,其包括,但不限于,氯化钙、硫酸钙、苹果酸钙、马来酸钙、氢氧化钙、甲酸钙和乙酸钙,和相应的镁盐。由于酶浆液和配方水中的钙,少量的钙离子,一般约0.05至约0.4毫摩尔/每升也常存在于组合物中。在本发明的固体洗涤剂组合物中,配方可包括足够量的水溶性钙离子物源以提供在洗衣液中所需的量。另一方面,天然水的硬度可能是足够的。
应认识到,前述钙和/或镁离子的量足以提供酶稳定性。可将更多的钙和/或镁离子加入组合物中以提供实现对油脂去除的辅助手段。因此,总之,本发明的组合物一般包括约0.05%至约2%(重量)水溶性钙或镁离子物源,或者包括二者。当然该量可随组合物中所使用的酶的量和类型而变化。
本发明组合物也可任选地,但优选含有各种另外的稳定剂,尤其是硼酸盐型的稳定剂。一般地,这种稳定剂在组合物中的用量按组合物中的硼酸或其它能形成硼酸的硼酸盐化合物计算(基于硼酸计算的)为约0.25%至约10%,优选约0.5%至约5%,更优选约0.75%至约3%(重量)。虽然,其它化合物,如氧化硼、硼砂和其它碱金属硼酸盐(例如原硼酸钠、偏硼酸钠和焦硼酸钠和戊硼酸钠)是适宜的。取代的硼酸(例如,苯基硼酸、丁烷硼酸和对溴苯基硼酸)也可以代替硼酸使用。聚合去污剂-已知的聚合去污剂,下文称为“SRA”,可任选地用于本发明的洗涤剂组合物中。如果使用,SRA通常为按重量计占组合物的0.01%-10.0%,通常为0.1%-5%,优选0.2%-3.0%。
SRA优选一般含有使疏水纤维如聚酯和尼龙的表面亲水化的亲水片段;SRA还含有疏水部分以沉积在疏水纤维上并且在整个洗涤、漂洗循环中始终附着在纤维表面上,因此对亲水部分起固定作用。这使得经SRA处理后存在的污渍在以后的洗涤过程中更容易清洗。
SRA可包括各种带电荷的单体单元,例如阴离子或甚至阳离子物质,参见1990年9月11日授权给Gosselink等的US4956447,以及不带电荷的单体单元,它们的结构可以是直链、支链或甚至是星形的。它们可包括封端基团,它在控制分子量或改变物理或表面活性性质方面是尤其有效的。对于应用于不同的纤维或纺织类型和不同的洗涤剂或洗涤剂添加剂产物可改变结构和电荷分布。
优选的SRA包括齐聚对苯二甲酸酯,其通常通过包括至少一种酯基转移作用/齐聚作用的方法来制备,通常使用金属催化剂,例如烷醇钛(IV)。该酯可使用能够通过一个、二个、三个、四个或多个位置加入酯结构,而不形成紧密交联的整体结构的附加的单体制备。
合适的SRA包括基本上直链的酯齐聚物的磺化产物,它由对苯二甲酰基和氧化烯氧基重复单元的齐聚酯骨架和共价连接于骨架的烯丙基衍生的磺化端基组成,例如如1990年11月6日的J.J.Scheibel和E.P.Gosselink的US4968451所述。该酯齐聚物可通过如下方法制备:(a)乙氧基化烯丙基醇;(b)使(a)的产物与对苯二甲酸二甲酯(“DMT”)和1,2-丙二醇(“PG”)在两级酯基转移作用/齐聚过程中反应;和(c)使(b)的产物与偏亚硫酸氢钠在水中反应。其它SRA包括1987年12月8日的Gosselink等的US4711730的非离子封端的1,2-丙二醇/聚氧乙烯对苯二甲酸酯聚酯,它由例如聚(乙二醇)甲基醚、DMT、PG和聚(乙二醇)(“PEG”)的酯基转移作用/齐聚作用制备。SRA的其它实例包括1988年1月26日的Gosselink的US4721580的部分和全部阴离子封端的齐聚酯,例如由乙二醇(“EG”)、PG、DMT和3,6-二氧杂-8-羟基辛磺酸钠得到的齐聚物;1987年10月27日的Gosselink的非离子封端的嵌段聚酯齐聚化合物,例如由DMT、甲基(Me)封端的PEG和EG和/或PG,或DMT、EG和/或PG、Me封端的PEG和5-磺基间苯二甲酸二甲酯钠制备;和1989年10月31日的Maldonado,Gosselink等的US4877896的阴离子,尤其是磺基芳酰基封端的对苯二甲酸酯,后者是用于洗涤和织物调理产物的SRA类型,其实例是由间磺基苯甲酸单钠盐、PG和DMT制备的酯组合物,任选地,但优选还含有加入的PEG,例如PEG3400。
SRA还包括亚乙基对苯二甲酸酯或亚丙基对苯二甲酸酯与聚环氧乙烷或聚环氧丙烷对苯二甲酸酯的简单共聚物嵌段,参见1976年5月25日的Hays的US3959230和1975年7月18日的Basadur的US3893929;纤维素衍生物,例如由Dow得到的名称内METHOCEL的羟基醚纤维素聚合物;C1-4烷基纤维素和C4羟烷基纤维素;参见1976年12月28日的Nicol等的美国专利4000093;和每脱水葡萄糖单元的平均取代(甲基)程度为约1.6至约2.3和作为2%水溶液在20℃下测定的溶液粘度为约80至约120厘泊的甲基纤维素醚。该物质作为METOLOSE SM100和METOLOSESM200得到,它们是由Shin-etsu Kagaku Kogyo KK制备的甲基纤维素醚的商品名。
聚(乙烯基酯)疏水片段为特征的合适SRA包括聚(乙烯基酯)如,C1-6乙烯基酯的接枝共聚物,优选接枝于聚烯化氧骨架上的聚(乙酸乙烯酯)。参见1987年4月22日公开的Kud等的欧洲专利申请0219048。市售的这类聚合去污剂例子包括SOKALAN SRN,例如SOKALAN HP-22,由BASF(德国)得到。其它SRA是带有重复单元的聚酯,其中重复单元含有10-15%(重量)的亚乙基对苯二甲酸酯和80%-90%(重量)的聚氧乙烯对苯二甲酸酯,其从平均分子量为300-5000的聚氧乙二醇得到。商业实例包括由Dupont得到的ZELCON 5126和由ICI得到的MILEASE T。
另一类优选的SRA是经验式为(CAP)2(EG/PG)5(T)5(SIP)1的齐聚物,其含有对苯二甲酰基(T)、磺基间苯二甲酰基(SIP)、氧化乙烯氧基和氧基-1,2-丙烯(EG/PG)单元,它优选由端基(CAP)封端,端基优选是改性的羟乙磺酸盐,例如,含有一个磺基间苯二甲酰基单元、5个对苯二甲酰基单元、限定比率的氧化乙烯氧基和氧基-1,2-丙烯氧基单元,优选约0.5∶1至约10∶1,和两个由2-(2-羟基乙氧基)-乙磺酸钠得到的端基单元的齐聚物。所述SRA优选还含有按齐聚物重量计0.5%至20%的结晶度降低稳定剂,例如阴离子表面活性剂,如直链十二烷基苯磺酸钠或选自二甲苯-、枯烯-和甲苯-磺酸盐或它们的混合物的物质,这些稳定剂或改性剂被加入合成容器中,所有这些在1995年5月16日授权的Gosselink,Pan,Kellett和Hall的US5415807中有描述。合适的用于上述SRA的单体包括2-(2-羟基乙氧基)-乙磺酸钠、DMT、5-磺基间苯二甲酸二甲酯钠、EG和PG。
另一类优选的SRA是齐聚物酯,其含有:(1)骨架,其含有(a)至少一种选自如下的单元:二羟基磺酸酯、多羟基磺酸酯、至少三官能团从而形成的酯键产生支链齐聚物骨架的单元和它们的组合;(b)至少一种为对苯二甲酰基基团的单元;和(c)至少一种为1,2-氧化烯氧基基团的未磺化单元;和(2)一种或多种封端单元,其选自非离子封端单元、阴离子封端单元如烷氧基化,优选乙氧基化羟乙磺酸盐、烷氧基化丙磺酸盐、烷氧基化丙磺酸盐、烷氧基化丙二磺酸盐、烷氧基化苯酚磺酸盐、磺基芳酰基衍生物和它们的混合物。优选如下经验式的酯:
{(CAP)x(EG/PG)y’(DEG)y”(PEG)y(T)z(SIP)z’(SEG)q(B)m}其中CAP、EG/PG、PEG、T和SIP是如上定义的,(DEG)表示二(氧化乙烯)氧基单元,(SEG)表示由甘油磺基乙基醚和相关的基团单元得到的单元,(B)表示支化单元,它是至少三个官能团的,从而形成的酯键产生支链齐聚物骨架,x是约1至约12,y’是约0.5至约25,y”是0至约12,y是0至约10,y”+y”+y总数为约0.5至约25,z是约1.5至约25,z’是0至约12,z+z’总数为约1.5至约25,q是约0.05至约12;m是约0.01至约10,和x、y’、y”、y、z、z’、q和m表示每摩尔所述酯相应单元的平均摩尔数,所述酯具有约500至约5000的分子量。
上述酯的优选SEG和CAP单体包括2-(2-,3-二羟基丙氧基)乙磺酸钠(“SEG”)、2-{2-(2-羟基乙氧基)乙氧基}乙磺酸钠(“SE3”)和它的同系物和它们的混合物以及乙氧基化以及磺化烯丙基醇的产物。这类中优选的SRA酯包括2-{2-(2-羟基乙氧基)乙氧基}乙磺酸钠和/或2-[2-{2-(2-羟基乙氧基)乙氧基}乙氧基]乙磺酸钠、DMT、2-(2,3-二羟基丙氧基)乙磺酸钠、EG和PG的使用合适的Ti(IV)催化剂的酯基转移和齐聚产物,可称为(CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13,其中CAP是(Na+-O3S[CH2-CH2O]3.5)-,和B是由甘油得到的单元,EG/PG摩尔比是约1.7∶1,在完全水解后由常规气相色谱法测定。
另外类别的SRA包括:(I)使用二异氰酸酯偶合剂以连接至聚酯结构上的非离子对苯二甲酸酯,参见Violland等的US4201824和Lagasse等的US4240918;和(II)通过将偏苯三酸酐加成到已知SRA中将末端羟基转化成偏苯三酸酯制备的带有羧酸酯端基的SRA。通过合适地选择催化剂,偏苯三酸酐通过偏苯三酸酐的单独的羧酸酯与聚合物的末端成键,而不是通过打开酐键成键。非离子或阴离子SRA均可用作起始物料,只要它们具有可被酯化的羟基端基。参见Tung等的US4525524。其他类别包括:(III)尿烷连接种类的阴离子对苯二甲酸盐基的SRA,参见Violland等的US4201824;(IV)聚(乙烯基己内酰胺)和具有单体如乙烯基吡咯烷酮和/或甲基丙烯酸二甲基氨基乙基酯的相关共聚物,既包括非离子又包括阳离子聚合物,参见Ruppert等的US4579681;(V)除了由BASF得到的SOKALAN类型之外,参见在磺化聚酯上接枝丙烯酸单体制备的接枝共聚物。这些SRA无疑具有类似于已知纤维素醚的去污活性和抗再沉积活性:参见1988年的Rhone-Poulenc Chemie的EP279134A。其他的类别还包括:(VI)乙烯基单体如丙烯酸和乙酸乙烯酯在蛋白质,例如酪蛋白上的接枝物,参见BASF的EP457205A(1991);和(VII)通过缩合己二酸、己内酰胺和聚乙二醇制备的聚酯-聚酰胺SRA,尤其适用于处理聚酰胺织物,参见Bevan等的DE2335044(Unilever N.V.,1974)。其它有用的SRA在US4240918、4787989和4525524中有描述。螯合剂-本发明的组合物还可以任选地含有一种或多种铁和/或锰螯合剂。这类螯合剂可选自氨基羧酸盐,氨基膦酸盐,多官能取代的芳族螯合剂及其混合物,所有的螯合剂如在下文中定义。尽管不打算受理论的限制,但人们认为这些物质的优点部分在于它们具有通过形成可溶性螯合物从洗涤溶液中除去铁和锰的优异性能。
可用作任选的螯合剂的氨基羧酸盐包括乙二胺四乙酸盐,N-羟乙基乙二胺三乙酸盐,次氮基三乙酸盐,乙二胺四丙酸盐,三亚乙基四胺六乙酸盐,二亚乙基三胺五乙酸盐和乙醇二甘氨酸,它们的碱金属盐,铵盐和取代铵盐以及它们的混合物。
当在本发明洗涤剂组合物中允许存在至少低的总磷含量时,氨基膦酸盐也适合用作本发明的螯合剂,其包括:乙二胺四(亚甲基膦酸盐),DEQUEST。这些氨基膦酸盐优选不含超过约六个碳原子的烷基或链烯基基团。
在本发明组合物中还可以使用多官能取代的芳族螯合剂。参见1974年5月21日授权给Connor等的US3812044。这类酸形式的优选化合物是二羟基二磺基二苯,例如1,2-二羟基-3,5-二磺基苯。
优选用于本发明中的可生物降解的螯合剂是乙二胺二琥珀酸盐("EDDS"),尤其是[S,S]异构体,如1987年11月3日的Hartman和Perkins的US4704233。
如果使用螯合剂,则其用量为本发明洗涤剂组合物重量的约0.1%-约10%。如果使用,更优选的螯合剂用量是该组合物重量的约0.1%-约3.0%。粘土污垢去除剂/抗再沉积剂
本发明的组合物还可以任选地含有具有去除粘土污垢和抗再沉积性能的水溶性乙氧基化胺。含有这些化合物的颗粒洗涤剂组合物一般含有按重量计约0.01%-约10.0%的水溶性乙氧基化胺;液体洗涤剂组合物通常含有约0.01%至约5%。
最优选的去污剂和抗再沉积剂是乙氧基化四亚乙基五胺。乙氧基化胺的实例在1986年7月1日授权的VanderMeer的US4597898中描述。另一类优选的粘土污垢去除剂/抗再沉积剂是1984年6月27日公开的Oh和Gosselink的欧洲专利申请111965中公开的阳离子化合物。可以使用的其他粘土污垢去除剂/抗再沉积剂包括1984年6月27日公开的Gosselink的欧洲专利申请111984中公开的乙氧基化胺聚合物;1984年7月4日公开的Gosselink的欧洲专利申请112592中公开的两性离子聚合物;和1985年10月22日授权的Connor的US4548744中公开的氧化胺。本领域中已知的其他粘土污垢去除剂/抗再沉积剂也可以用在本发明的组合物中。另一类优选的抗再沉积剂包括羧甲基纤维素(CMC)物质。这些物质是本领域众所周知的。聚合分散剂-聚合分散剂可以有利地以按重量计约0.1%-约7%的含量用于本发明组合物中,尤其是在沸石和/或层状硅酸盐助洗剂存在时。适合的聚合分散剂包括聚合的多羧酸盐和聚乙二醇,虽然本领域其他已知聚合分散剂也可以使用。尽管不希望为理论所限制,但是可以确信当聚合分散剂与其他助洗剂(包括低分子量的多羧酸盐)一起使用时,通过晶体生长抑制作用,尤其是解脱污垢的胶溶作用和抗再沉积作用,可以提高洗涤助洗剂的总体性能。
通过使适合的不饱和单体,优选是酸形式的不饱和单体聚合或共聚可以制备聚合多羧酸盐物质。可以经聚合形成适合的聚合多羧酸盐的不饱和单体酸包括丙烯酸,马来酸(或马来酸酐),富马酸,衣康酸,乌头酸,中康酸,柠康酸和亚甲基丙二酸。在本发明的聚合多羧酸盐中,含有不带有羧酸盐基团如乙烯基甲基醚,苯乙烯,乙烯等的单体片段是适合的,只要这种片段不超过按重量计约40%。
尤其适合的聚合多羧酸盐可以从丙烯酸得到。本发明中使用的这种丙烯酸基的聚合物是聚合丙烯酸的水溶性盐。以酸形式存在的这种聚合物的平均分子量优选为约2000-10000,更优选为约4000-7000,最优选为约4000-5000。这种丙烯酸聚合物的水溶性盐的实例包括例如碱金属盐,铵盐和取代铵盐。该类可溶的聚合物是已知的物质。例如,1967年3月7日授权的Diehl的US3308067中公开了该类聚丙烯酸盐在洗涤剂组合物中的应用。
以丙烯酸/马来酸为携污体的共聚物也可以用作分散/抗再沉积剂的优选组分。这类物质包括丙烯酸和马来酸共聚物的水溶性盐。以酸形式存在的这种共聚物的平均分子量优选为约2000-100000,更优选为约5000-75000,最优选为约7000-65000。在这种共聚物中丙烯酸盐部分与马来酸盐部分的比率一般为约30∶1至约1∶1,更优选约10∶1至2∶1。这种丙烯酸/马来酸共聚物的水溶性盐可以包括,例如,碱金属盐,铵盐和取代铵盐。这类可溶性丙烯酸盐/马来酸盐共聚物是已知的物质,其描述在1982年12月15日公开的欧洲专利申请号66915中,以及描述在1986年9月3日公开的EP193360中,它还描述了含有丙烯酸羟基丙基酯的这种聚合物。其它有用的分散剂还包括马来酸/丙烯酸/乙烯醇的三元共聚物。该物质还公开在EP193360中,其包括例如马来酸/丙烯酸/乙烯醇的45/45/10三元共聚物。
另一类可以被包括的聚合物是聚乙二醇(PEG)。PEG可显示出分散剂的性能以及作为粘土污垢去除剂/抗再沉积剂。作为该用途的聚乙二醇的分子量一般为约500-约100000,优选为约1000-约50000,更优选为约1500-约10000。
也可以使用聚天冬氨酸盐和聚谷氨酸盐分散剂,尤其是与沸石助洗剂结合使用。分散剂,例如聚天冬氨酸盐优选具有约10000的分子量(平均)。增白剂-本领域已知的任何荧光增白剂或其他增亮剂或增白剂一般可以按重量计约0.01%-约1.2%的含量掺入本发明洗涤剂组合物中。可以用于本发明的市售荧光增白剂可以被分为下列小组,其包括,但不必受此限制,芪衍生物,吡唑啉,香豆素,羧酸,次甲基菁,二苯并噻吩-5,5-二氧化物,吡咯,5-和6-元环的杂环物质,以及其他微量试剂。这些增白剂的实例公开在“荧光增白剂的制备和应用”中,M.Zahradnik,由John Wiley & Sons,New York(1982)出版。
在本发明组合物中使用的荧光增白剂的具体实例与1988年12月13日授权给Wixon的US4790856中公开的相同。这些增白剂包括Verona的PHOR WHITE增白剂系列。在该参考文献中公开的其他增白剂包括:Ciba-Geigy的Tinopal UNPA,Tinopal CBS和Tinopal 5BM;ArticWhite CC和Artic White CWD;2-(4-苯乙烯基苯基)-2H-萘并[1,2-d]三唑;4,4′-双(1,2,3-三唑-2-基)芪;4,4′-双(苯乙烯基)联苯和氨基香豆素。这些增白剂的具体实例包括:4-甲基-7-二乙基氨基香豆素;1,2-双(苯并咪唑-2-基)乙烯;1,3-二苯基吡唑啉;2,5-双(苯并噁唑-2-基)噻吩;2-苯乙烯基-萘并[1,2-d]噁唑和2-(芪-4-基)-2H-萘并[1,2-d]三唑。还可见1972年2月29日授权给Hamilton的US3646015。抑泡剂-可以在本发明组合物中掺入用于降低或抑制泡沫形成的化合物。泡沫的抑制在US4489455和4489574中描述的所谓“高浓度洗涤方法”和在欧洲前装式洗衣机情况下尤为重要。
可以使用各种物质作为抑泡剂,抑泡剂是本领域技术人员众所周知的。参见,例如,Kirk Othmer《化学工艺百科全书》,第3版,第7卷,第430-447页(John Wiley & Sons,Inc.,1979)。一类特别重要的抑泡剂包括单羧酸基脂肪酸和其可溶性盐。参见1960年9月27日授权给Wayne St.John的美国专利2954347。用作抑泡剂的单羧酸基脂肪酸及其盐一般具有含10-约24个碳原子,优选12-18个碳原子的烃基链。适合的盐包括碱金属盐,例如钠盐,钾盐和锂盐;铵盐和链烷醇铵盐。
本发明的洗涤剂组合物还可以含有非表面活性剂的抑泡剂。这类抑泡剂包括例如:高分子量烃,例如石蜡,脂肪酸酯(如甘油三脂肪酸酯),一元醇的脂肪酸酯,脂族C18-40酮(如硬脂酮)等。其他抑泡剂包括N-烷基化的氨基三嗪,例如三至六-烷基蜜胺或二至四烷基二胺氯代三嗪,它们是氰脲酰氯与2或3摩尔含有1-24个碳原子的伯或仲胺,环氧丙烷,和单硬脂烷基磷酸酯盐,如单硬脂烷醇磷酸酯和单硬脂烷基二碱金属(如K,Na,和Li)磷酸盐和磷酸酯的产物。烃如石蜡和卤代石蜡可以以液体形式使用。该液体烃在室温和大气压下应该为液态,并应具有约-40℃-约50℃的倾点,最低沸点不低于约110℃(大气压)。使用含蜡烃也是已知的,优选其具有不低于约100℃的熔点。该类烃是洗涤剂组合物的一类优选的抑泡剂。例如在1981年5月5日授权给Gandolfo等的US4265779中描述了烃抑泡剂。因此,该烃包括含有约12至约70个碳原子的脂族,脂环族,芳族和杂环饱和或不饱和烃。在有关抑泡剂的讨论中使用的术语"石蜡"包括真正的石蜡和环烃的混合物。
另一类优选的非表面活性剂的抑泡剂包括聚硅氧烷抑泡剂。该类别包括使用聚硅氧烷油,例如聚二甲基硅氧烷,聚硅氧烷油或树脂的分散体或乳状液,以及聚硅氧烷与二氧化硅颗粒的混合物,其中的聚硅氧烷被化学吸附或熔合到二氧化硅上。聚硅氧烷抑泡剂是本领域所熟知的,例如在1981年5月5日授权给Gandolfo等的US4265779和1990年2月7日公开的Starch,M.S.的欧洲专利申请号89307851.9中公开。
其他的聚硅氧烷抑泡剂公开在US3455839中,该专利涉及通过在组合物中掺入少量聚二甲基硅氧烷流体以消除水溶液泡沫的组合物和方法。
聚硅氧烷和硅烷化二氧化硅的混合物在如德国专利申请DOS2124526中描述。在颗粒洗涤剂组合物中的聚硅氧烷消泡剂和泡沫抑制剂在Barto lotta等的US3933672和1987年3月24日授权的Baginski等的US4652392中有描述。
用于本发明的以聚硅氧烷为携污体的抑泡剂的实例是泡沫抑制量的基本上由如下组成的泡沫控制剂:
(i)在25℃粘度为约20cs-约1500cs的聚二甲基硅氧烷流体;
(ii)按重量计每100份(i)约5-约50份(重量)的硅氧烷树脂,该树脂由(CH3)3SiO1/2单元和SiO2单元按(CH3)3SiO1/2单元与SiO2单元的比率为约0.6∶1-约1.2∶1的比率组成;和
(iii)按重量计每100份(i)约1-约20份固体硅胶;
本发明中使用的优选聚硅氧烷抑泡剂中,用于连续相的溶剂由某些聚乙二醇或聚乙二醇-聚丙二醇共聚物或其混合物(优选),或聚丙二醇组成。主要的聚硅氧烷抑泡剂是支链/交联,优选是非直链的。
为了进一步说明这一点,具有控制发泡作用的一般液体洗衣用洗涤剂组合物任选地含有按重量计约0.001%-约1%,优选约0.01%-约0.7%,最优选约0.05%-约0.5%的所述聚硅氧烷抑泡剂,该抑泡剂含有(1)主要抑泡剂的非水乳液,该抑泡剂是(a)聚硅氧烷,(b)树脂状硅氧烷或是可以产生聚硅氧烷树脂的聚硅氧烷化合物,(c)细分散的填料和(d)促使混合物组分(a),(b)和(c)反应以生成硅烷醇盐的催化剂;(2)至少一种非离子聚硅氧烷表面活性剂;和(3)室温下在水中的溶解度超过约2%(重量)的聚乙二醇或聚乙二醇-聚丙二醇的共聚物;其中没有聚丙二醇。类似的量可以用于颗粒组合物,凝胶等中。另外参见1990年12月18日授权的Starch的US4978471,和1991年1月8日授权的Starch的US4983316,1994年2月22日授权的Huber等人的US5288431和Aizawa等的US4639489和4749740,第一栏第46行至第4栏第35行。
本发明中的聚硅氧烷抑泡剂优选包括:聚乙二醇和聚乙二醇/聚丙二醇的共聚物,它们的平均分子量低于约1000,优选为约100-800。本发明的聚乙二醇和聚乙二醇/聚丙二醇共聚物室温下在水中的溶解度超过约2%(重量),优选超过约5%(重量)。
本发明优选的溶剂是平均分子量低于约1000,更优选为约100-800,最优选为200-400的聚乙二醇,和聚乙二醇/聚丙二醇的共聚物,优选PPG200/PEG300。聚乙二醇与聚乙二醇-聚丙二醇共聚物的重量比优选为约1∶1-1∶10,最优选为1∶3-1∶6。
本发明使用的优选聚硅氧烷抑泡剂不含聚丙二醇,尤其是不含分子量为4000的聚丙二醇。其还优选不含氧化乙烯和氧化丙烯的嵌段共聚物,如PLURONIC L101。
本发明使用的其他抑泡剂包括仲醇(如2-烷基链烷醇)以及这些醇与聚硅氧烷油的混合物,如公开在美国专利4798679,4075118和欧洲专利150872中的聚硅氧烷。仲醇包括具有C1-16链的C6-16烷基醇。优选的醇是2-丁基辛醇,该醇可以按商标ISOFOL 12从Condea得到。仲醇混合物可以以商标ISALCHEM 123从Enichem得到。混合抑泡剂一般含有重量比为1∶5-5∶1的醇和聚硅氧烷的混合物。
对于用于自动洗衣机的任何洗涤剂组合物而言,形成的泡沫不应溢出洗衣机。当使用抑泡剂时,优选其以"泡沫抑制量"存在。"泡沫抑制量"的含义是组合物的配方师可以选择泡沫控制剂的量,该量可以充分控制泡沫以得到可以用于自动洗衣机的低泡沫洗衣用洗涤剂。
本发明的组合物通常含有0%-约5%的抑泡剂。当使用单羧酸基脂肪酸和其盐作为抑泡剂时,其用量通常最高约为洗涤剂组合物重量的约5%。优选使用约0.5%-约3%的脂肪单羧酸盐抑泡剂。尽管可以采用更高的用量,但聚硅氧烷抑泡剂的用量一般最高为洗涤剂组合物重量的约2.0%。由于首先要考虑使成本保持最低和有效控制泡沫的较低用量的有效性,该上限是实际的。优选使用约0.01%-约1%的聚硅氧烷抑泡剂,更优选的是约0.25%-约0.5%。本发明中,这些重量百分数值中包括可以与聚硅氧烷一起使用的任何二氧化硅以及可能使用的任何添加剂材料。单硬脂烷基磷酸盐抑泡剂的用量一般为组合物重量的约0.1%-约2%。尽管可以使用更高用量的烃抑泡剂,但其用量一般为约0.01%至约5.0%。醇抑泡剂的用量一般为最终组合物重量的0.2%-3%。织物柔软剂-本发明组合物中可以任选地使用各种经历洗涤全过程的织物柔软剂,特别是1977年12月13日授权的Storm和Nirschl的US4062647中公开的细粒绿土粘土,以及在现有技术中已知的其它柔软剂粘土,其用量一般为按重量计约0.5%-约10%,从而使得在清洁织物的同时取得织物柔软剂的益处。可以将粘土柔软剂与胺和阳离子柔软剂一起使用,例如如1983年3月1日的Crisp等的US4375416和1981年9月22日授权的Harris等的US4291071中所公开的那样。染料转移抑制剂-本发明的组合物还可以包含一种或多种在洗涤过程中有效抑制染料从一种织物转移至另一种织物的物质。通常这种染料转移抑制剂包括聚乙烯基吡咯烷酮聚合物、聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物,酞菁锰、过氧化物酶和它们的混合物。如果使用,这些抑制剂一般占组合物重量的约0.01%至约10%,优选约0.01%至约5%,更优选约0.05%至约2%。
更具体地说,优选用于本发明的聚胺N-氧化物聚合物含有具有如下结构式的单元:R-Ax-P;其中P是可连接N-O基团的可聚合单元或N-O基团形成可聚合单元部分或N-O基团可连接于两种单元上;A是如下结构之一:-NC(O)-、-C(O)O-、-S-、-O-、-N=;x是0或1;和R是脂族、乙氧基化脂族、芳族、杂环或脂环基团或它们的任何组合,N-O基团的氮可连接于其上或N-O基团是这些基团的部分。优选的聚胺N-氧化物是其中R是杂环基团如吡啶、吡咯、咪唑、吡咯啉、哌啶和它们的衍生物的物质。
N-O基团可由如下一般结构表示:其中R1、R2、R3是脂族、芳族、杂环或脂环基团或它们的组合;x、y和z是0或1;和N-O基团的氮可连接于其上或形成上述任何基团的部分。聚胺N-氧化物的氧化胺单元的pKa<10,优选pKa<7,更优选pKa<6。
只要形成的氧化胺聚合物是水溶性的和具有染料转移抑制性质,可使用任何聚合物骨架。合适的聚合物骨架是聚乙烯、聚亚烷基、聚酯、聚醚、聚酰胺、聚酰亚胺、聚丙烯酸盐和它们的混合物。这些聚合物包括无规或嵌段共聚物,其中一种单体类型是胺N-氧化物,而另一种单体类型是N-氧化物。胺N-氧化物聚合物的胺与胺N-氧化物的比率通常为10∶1至1∶1000000。然而,在聚胺氧化物聚合物中存在的氧化胺基团的数目可通过合适的共聚或合适的N-氧化度改变。聚胺氧化物几乎可以任何聚合度得到。平均分子量通常为500-1000000;更优选为1000-500000;最优选为5000-100000。优选类的物质可称为“PVNO”。
用于本发明洗涤剂组合物的更优选的聚胺N-氧化物是聚(4-乙烯基吡啶-N-氧化物),它的平均分子量为约50000,胺与胺N-氧化物比率为约1∶4。
N-乙烯基吡咯烷酮和N-乙烯基咪唑聚合物的共聚物(指称为“PVPVI”的一类)也优选用于本发明中。PVPVI的平均分子量优选为5000-1000000,更优选5000-200000,最优选10000-20000。(平均分子量范围通过光散射法测定,如Barth等,在《化学分析》,卷113,“聚合物表征的现代方法”中所述,其内容引入本文作为参考)。PVPVI共聚物的N-乙烯基咪唑与N-乙烯基吡咯烷酮的摩尔比通常为1∶1至0.2∶1,更优选0.8∶1至0.3∶1,最优选0.6∶1至0.4∶1。这些共聚物可以是直链或支链的。
本发明的组合物还可使用平均分子量为约5000-约400000,优选约5000-约200000,更优选约5000-约50000的聚乙烯基吡咯烷酮(“PVP”)。PVP是洗涤剂领域的技术人员已知的,参见例如EP-A-262897和EP-A-256696,引入本文作为参考。含有PVP的组合物还可含有平均分子量为约500-约100000,优选约1000-约10000的聚乙二醇(“PEG”)。在洗涤溶液中提供的PEG与PVP的比率以ppm计优选为约2∶1至约50∶1,更优选约3∶1至约10∶1。
本发明的洗涤剂组合物还可任选地含有按重量计约0.005%至5%的某些类型的亲水荧光增白剂,它也提供了染料转移抑制作用。如果使用,本发明的组合物优选含有按重量计约0.01%-1%的该荧光增白剂。
在本发明中有用的亲水荧光增白剂具有如下结构式:其中R1选自苯胺基、N-2-双羟基乙基和NH-2-羟基乙基;R2选自N-2-双-羟基乙基、N-2-羟基乙基-N-甲基氨基、吗啉代、氯和氨基;M是成盐阳离子,例如钠或钾。
当在上式中,R1是苯胺基,R2是N-2-双-羟基乙基和M是阳离子如钠时,增白剂是4,4’-双[(4-苯胺基-6-(N-2-双-羟基乙基)-s-三嗪-2-基)氨基]-2,2’-芪二磺酸和二钠盐。具体的增白剂物质在商业上由Ciba-Geigy公司以商品名Tinopal-UNPA-GX销售。Tinopal-UNPA-GX是用于本发明洗涤剂组合物中的优选亲水荧光增白剂。
当在上式中,R1是苯胺基,R2是N-2-羟基乙基-N-2-甲基氨基和M是阳离子如钠时,增白剂是4,4’-双[(4-苯胺基-6-(N-2-羟基乙基-N-甲基氨基)-s-三嗪-2-基)氨基]-2,2’-芪二磺酸二钠盐。具体的增白剂物质在商业上由Ciba-Geigy公司以商品名Tinopal 5BM-GX销售。
当在上式中,R1是苯胺基,R2是吗啉代和M是阳离子如钠时,增白剂是4,4’-双[(4-苯胺基-6-吗啉代-s-三嗪-2-基)氨基]2,2’-芪二磺酸二钠盐。具体增白剂物质在商业上由Ciba-Geigy公司以商品名TinopalAMS-GX销售。
选择用于本发明的具体荧光增白剂物质在与选择的本文上述的聚合染料转移抑制剂结合使用时提供尤其有效的染料转移抑制效果。这种选择的聚合物(例如PVNO和/或PVPVI)与这种选择的荧光增白剂(例如Tinopal-UNPA-GX、Tinopal 5BM-GX和/或Tinopal AMS-GX)的组合与这两种洗涤剂组合物组分单独使用时相比在洗涤水溶液中提供了明显较好的染料转移抑制。不受理论限制,但我们相信,这些增白剂以这种方式作用是因为它们在洗涤溶液中有高的织物亲合力,因此相对快地沉积在织物上。在洗涤溶液中增白剂沉积至织物上的程度可由称为“耗尽系数”的参数定义。耗尽系数通常为a)沉积在织物上的增白剂物质与b)在洗涤液中的最初增白剂浓度的比率。在本发明中,有相对高的耗尽系数的增白剂最适合用于抑制染料转移。
当然,已知其他常规荧光增白剂类型的化合物可任选地用于本发明的组合物中以提供常规织物“增白”效果,而不是真正的染料转移抑制效果。这类使用是常规的,是洗涤剂配方师众所周知的。其他组分-在本发明组合物中可以包含各种洗涤剂组合物中有用的其他组分,其中包括其他活性组分,载体,水溶助长剂、加工助剂,染料或颜料、用于液体配方的溶剂、用于皂条组合物的固化填料等。如果需要高泡沫,则可以在该组合物中加入如C10-C16链烷醇酰胺的增泡剂,含量一般为1%-10%。C10-C14单乙醇和二乙醇酰胺是该类增泡剂的典型类别。将这类增泡剂与高泡辅助表面活性剂,如上述氧化胺,甜菜碱和磺基甜菜碱一起使用也是有利的。如果需要,也可以通常0.1%-2%的含量加入如MgCl2,MgSO4等的可溶性镁盐以提供附加泡沫和改善脱脂性能。
本发明组合物中使用的各种洗涤剂组分可以任选地通过将这些组分吸附在多孔疏水性携污体上,然后再用疏水性涂层将该携污体涂覆以进一步使其稳定化。优选在吸附进多孔携污体中之前将该洗涤剂组分与表面活性剂混合。在使用过程中,该洗涤剂组分从携污体释放到洗涤水溶液中,完成其预期的洗涤功效。
为了更详细地说明该技术,将多孔疏水性二氧化硅(商标SIPERNATD10,DeGussa)与含有3%-5%C13-15乙氧基化醇(EO7)的非离子表面活性剂的蛋白水解酶溶液混合。该酶/表面活性剂溶液的量一般是二氧化硅重量的2.5倍。将所得粉末在搅拌下分散在聚硅氧烷油中(可以使用粘度为500-12500的各种聚硅氧烷油)。将所得的聚硅氧烷油分散体乳化或者将其加至最终的洗涤剂携污体中。通过这种方法,可以将如上述的酶,漂白剂,漂白活化剂,漂白催化剂、光活化剂,染料,荧光增白剂,织物调理剂和可水解的表面活性剂"保护"而用于包括液体洗衣洗涤剂组合物的洗涤剂中。
液体洗涤剂组合物可含有用作载体的水和其它溶剂。低分子量伯或仲醇,例如甲醇、乙醇、丙醇和异丙醇是合适的。使表面活性剂增溶的一元醇是优选的,但也可以使用多元醇,例如含有2至约6个碳原子和2至约6个羟基的多元醇(例如,1,3-丙二醇、乙二醇、甘油和1,2-丙二醇)。组合物可含有5%至90%,通常为10%至50%的这种载体。
本发明的组合物优选配制成在用于含水洗涤操作过程中,洗涤水的pH为约6.5至约11,优选为约7.5至10.5。液体餐具洗涤产品配方优选具有约6.8至约9.0的pH。洗衣产物通常为pH9-11。用于控制pH在推荐的用量范围内的技术包括使用缓冲剂、碱、酸等,是本领域技术人员众所周知的。
本发明的漂白组合物理想地是适用于洗衣应用中。因此本发明包括洗涤织物的方法。该方法包括使需洗涤的织物与洗涤溶液接触。织物可包括大多数能够在通常消费者使用条件下被洗涤的任何织物。洗涤溶液包括上文详细描述的漂白增效剂和上文详细描述的过氧源。洗涤溶液还可含有任何上述的漂白组合物的添加剂,例如洗涤剂表面活性剂、螯合剂和洗涤剂酶。溶液优选具有约8至约10的pH。组合物优选以在溶液中约1000至约10000ppm的浓度使用。水温优选为约25℃至约50℃。水与织物的比率优选为约1∶1至约15∶1。
本发明的漂白增效剂还可用于洗涤添加剂产物中。含有本发明的漂白增效剂的洗涤添加剂产物理想地是适用于需要附加漂白效果的洗涤过程中。这种情况包括,但不限于,低温溶液洗涤应用。添加剂产物可含有上文详细描述的最简单形式的漂白增效剂。优选将添加剂包装成剂量形式用于加入使用过氧源并需要增加漂白效果的洗涤过程。该单剂量形式可包括丸剂、片剂、胶囊或其它单剂量形式,例如预定剂量的粉末或液体。根据需要可包括填料或载体物质以增加组合物的体积。合适的填料或载体物质可选自,但并不限于,各种硫酸盐、碳酸盐和硅酸盐,以及滑石、粘土等。液体组合物的填料或载体物质可以是水或低分子量伯或仲醇,包括多元醇和二醇。实例包括甲醇、乙醇、丙醇和异丙醇。也可以使用一元醇。组合物可含有约5%至约90%的这类物质。酸性填料可用于降低pH值。此外,洗涤添加剂可包括如上定义的过氧源或其它上文详细描述的附加组分。洗涤添加剂还可包括含有如上定义的过氧化氢源或过氧源的粉末或液体组合物。
在本发明的另外的实施方案中,漂白溶液包括选自氧杂亚铵两性离子、带有约-1至约-3净负电荷的氧杂亚铵多离子和它们的混合物的漂白物质的溶液。氧杂亚铵漂白物质以足以进行与溶液接触的携污体的漂白的量存在于溶液中。氧杂亚铵化合物优选由芳基亚铵化合物得到。氧杂亚铵漂白物质是通过过氧源和本文详细描述的亚胺漂白增效剂反应形成的漂白物质,优选由下式表示:漂白溶液还可包括任何上文详细描述的附加组分,例如洗涤剂表面活性剂、洗涤剂酶等。
包含氧杂亚铵漂白物质的漂白溶液与包含漂白增效剂的漂白组合物一样,可用于许多不同的用途和环境。含有氧杂亚铵化合物的漂白溶液优选用于漂白织物携污体的方法。该方法包括使需漂白或洗涤的织物携污体与含有氧杂亚铵化合物的漂白溶液接触。在通常消费者使用条件下接触进行足够的时间以实现织物携污体的漂白或洗涤。
本发明的漂白组合物可以以低密度(低于550g/l)和颗粒密度为至少550g/l的高密度颗粒组合物使用。低密度组合物可通过标准喷雾干燥方法制备。各种装置和设备适用于制备高密度组合物。本领域中的现行工业实践采用喷雾干燥塔制备密度低于约500g/l的组合物。因此,如果使用喷雾干燥作为整个方法的部分,得到的喷雾干燥的颗粒必须使用下文描述的装置和设备进一步致密。此外,配方师可通过使用工业上可得到的混合、致密和造粒装备而省去喷雾干燥。如下是适合于本发明的设备的非限定性描述。
在本发明的方法中可使用高速混合器/致密器。例如以商标“LodigeCB30”Recycler出售的装置包括静止圆筒形混合鼓,其装有中心旋转轴和安装在轴上的混合/切削叶片。其它装置包括以商标“ShugiGranulator”和以商标“Drais K-TTP 80”出售的装置。以商标“LodigeKM600 Mixer”出售的设备可用于进一步的致密过程。
在一种操作方式中,通过两个串联操作的混合器和致密机器制备和致密组合物。因此,可将所需组合物的组分混合,并通过所用停留时间为0.1至1.0分钟的Lodige混合器,然后通过所用停留时间为1分钟至5分钟的第二个Lodige混合器。
在另一种方式中,含有配方所需组分的含水浆状物被喷雾至颗粒的流化床中。得到的颗粒可通过如上所述的Lodige装置进一步致密。将得到的颗粒与Lodige装置中的组合物混合。
颗粒的最终密度可通过各种简单的技术测量,它通常包括将一定量的颗粒组合物分配在已知体积的容器内,测量组合物的重量并记录密度g/l。一旦低或高密度“基础”组合物制备后,通过任何合适的干混操作加入附聚的输料体系。
现通过参考如下实施例描述本发明。当然,本领域的普通技术人员将认识到,本发明并不限于本文描述的具体实施例或其中所包含的组分和步骤,而本发明可根据公开内容的较宽范围实施。
实施例I
3,4-二氢异喹啉(2)的制备
在装有机械搅拌器的5000ml三颈圆底烧瓶中加入1,2,3,4-四氢异喹啉(1)(25.005g)和二氯甲烷(750ml)。加入过硫酸钾(71.376g)和氢氧化钠(18.0456g)在去离子水(1650ml)中的溶液。在剧烈搅拌两相混合物下,向混合物中滴加硫酸镍六水合物(0.6499g)在去离子水(75ml)中的溶液。使反应混合物在室温下搅拌过夜。通过C盐真空过滤两相混合物,进行相分离,用二氯甲烷提取水层(3×300ml)。合并有机层,用硫酸镁干燥,通过旋转蒸发降低至粘稠的暗棕色油状物。通过Kugelrohr蒸馏(0.1mmHg,75℃)由油状物中分离所需产物。制备方法由如下反应表示:
实施例II
3-(3,4-二氢异喹啉鎓)丙磺酸盐(4)的制备
向装有机械搅拌棒、氩气入口管、添加漏斗和回流冷凝器的250ml圆底烧瓶中加入3,4-二氢异喹啉(2,5.005g)和甲醇(23ml)。用冰浴冷却混合物,向其中滴加1,3-丙烷磺内酯(3,4.670g)在甲醇(23ml)中的溶液。加完后,移去冰浴,加热反应混合物至回流过夜。使混合物冷却至室温,减压除去挥发物质。使固体产物成浆,用丙酮漂洗三次,进行空气干燥。制备方法由如下反应表示:
实施例III
4-(3,4-二氢异喹啉鎓)丁磺酸盐(6)的制备
向装有机械搅拌棒、氩气入口管、添加漏斗和回流冷凝器的100ml圆底烧瓶中加入3,4-二氢异喹啉(2,3.014g)和乙腈(10ml)。用冰浴冷却混合物,向其中滴加1,4-丁烷磺内酯(5,3.124g)在乙腈(5ml)中的溶液。加完后,移去冰浴,加热(45℃)反应混合物过夜。使混合物冷却至室温,经真空过滤收集产物,白色固体。使固体产物成浆,用丙酮漂洗三次,进行空气干燥。
实施例IV
由如下配方举例说明具有颗粒洗衣洗涤
剂形式的漂白洗涤剂组合物。
A B C D E漂白增效剂* 0.14 0.40 0.14 0.20 0.07过碳酸钠 5.30 0.00 0.00 4.00 0.00过硼酸钠单水合物 0.00 5.30 3.60 0.00 4.30直链烷基苯磺酸盐 12.00 0.00 12.00 0.00 21.00C45AE0.6S 0.00 15.00 0.00 15.00 0.00C2二甲胺N-氧化物 0.00 2.00 0.00 2.00 0.00C12椰子烷基酰氨基 1.50 0.00 1.50 0.00 0.00丙基甜菜碱棕榈N-甲基葡糖酰胺 1.70 2.00 1.70 2.00 0.00氯化C12二甲基羟基 1.50 0.00 1.50 0.00 0.00乙基铵AE23-6.5T 2.50 3.50 2.50 0.00 0.00C25E3S 4.00 0.00 4.00 0.00 0.00常规活化剂(NOBS) 0.00 0.00 0.60 0.00 0.00常规活化剂(TAED) 2.00 2.80 2.00 1.80 2.30三聚磷酸钠 25.00 25.00 15.00 15.00 25.00沸石A 0.00 0.00 0.00 0.00 0.00丙烯酸/马来酸共聚物 0.00 0.00 0.00 0.00 1.00聚丙烯酸,部分中和 3.00 3.00 3.00 3.00 0.00去污剂 0.00 0.00 0.50 0.40 0.00羧甲基纤维素 0.40 0.40 0.40 0.40 0.40碳酸钠 2.00 2.00 2.00 0.00 8.00硅酸钠 3.00 3.00 3.00 3.00 6.00碳酸氢钠 5.00 5.00 5.00 5.00 5.00Savinase(4T) 1.00 1.00 1.00 1.00 0.60Termamyl(60T) 0.40 0.40 0.40 0.40 0.40Lipolase(100T) 0.12 0.12 0.12 0.12 0.12Carezyme(5T) 0.15 0.15 0.15 0.15 0.15二亚乙基三胺五 1.60 1.60 1.60 1.60 0.40(亚甲基膦酸)增白剂 0.20 0.20 0.20 0.05 0.20磺化酞菁锌光漂白剂 0.50 0.00 0.25 0.00 0.00硫酸镁 2.20 2.20 2.20 2.20 0.64硫酸钠 余量 余量 余量 余量 余量
*根据实施例II制备的3-(3,4-二氢异喹啉鎓)丙磺酸盐
任何上述组合物以在水中3500ppm的浓度,在25℃和15∶1的水∶衣服比率用于洗涤织物。典型的pH为约9.5,但可通过改变烷基苯磺酸盐的酸与钠盐形式的比率调节。
实施例V
由如下配方说明具有颗粒洗衣洗涤剂形式的漂白洗涤剂组合物。
A B C D E漂白增效剂* 0.06 0.34 0.14 0.14 0.20过碳酸钠 5.30 0.00 0.00 0.00 0.00过硼酸钠单水合物 0.00 9.00 17.60 9.00 9.00直链烷基苯磺酸盐 21.00 12.00 0.00 12.00 12.00C45AE0.6S 0.00 0.00 15.00 0.00 0.00C2二甲胺N-氧化物 0.00 0.00 2.00 0.00 0.00C12椰子烷基酰氨基 0.00 1.50 0.00 1.50 1.50丙基甜菜碱棕榈N-甲基葡糖酰胺 0.00 1.70 2.00 1.70 1.70氯化C12二甲基羟基 1.00 1.50 0.00 1.50 1.50乙基铵AE23-6.5T 0.00 2.50 3.50 2.50 2.50C25E3S 0.00 4.00 0.00 4.00 4.00常规活化剂(NOBS) 0.00 0.00 0.00 1.00 0.00常规活化剂(TAED) 1.80 1.00 2.50 3.00 1.00三聚磷酸钠 25.00 15.00 25.00 15.00 15.00沸石A 0.00 0.00 0.00 0.00 0.00丙烯酸/马来酸共聚物 0.00 0.00 0.00 0.00 0.00聚丙烯酸,部分中和 0.00 3.00 3.00 3.00 3.00去污剂 0.30 0.50 0.00 0.50 0.50羧甲基纤维素 0.00 0.40 0.40 0.40 0.40碳酸钠 0.00 2.00 2.00 2.00 2.00硅酸钠 6.00 3.00 3.00 3.00 3.00碳酸氢钠 2.00 5.00 5.00 5.00 5.00Savinase(4T) 0.60 1.00 1.00 1.00 1.00Termamyl(60T) 0.40 0.40 0.40 0.40 0.40Lipolase(100T) 0.12 0.12 0.12 0.12 0.12Carezyme(5T) 0.15 0.15 0.15 0.15 0.15二亚乙基三胺五 0.40 0.00 1.60 0.00 0.00(亚甲基膦酸)增白剂 0.20 0.30 0.20 0.30 0.30磺化酞菁锌光漂白剂 0.25 0.00 0.00 0.00 0.00硫酸镁 0.64 0.00 2.20 0.00 0.00硫酸钠 余量 余量 余量 余量 余量
*根据实施例II制备的3-(3,4-二氢异喹啉鎓)丙磺酸盐
任何上述组合物以在水中3500ppm的浓度,在25℃和15∶1的水∶衣服比率用于洗涤织物。典型的pH为约9.5,但可通过改变烷基苯磺酸盐的酸与钠盐形式的比率调节。
实施例VI
含有如下组分的漂白洗涤剂粉末:
组分 重量%
漂白增效剂* 0.07
TAED 2.0
过硼酸钠四水合物 10
C12直链烷基苯磺酸盐 8
磷酸盐(作为三聚磷酸钠) 9
碳酸钠 20
滑石 15
增白剂、香料 0.3
氯化钠 25
水和少量组分* 余量至100%
*根据实施例II制备的3-(3,4-二氢异喹啉鎓)丙磺酸盐
实施例VII
适合于手洗沾污织物的洗衣条通过标准挤出方法制备,含有如下组分:
组分 重量%
漂白增效剂* 0.2
TAED 1.7
NOBS 0.2
过硼酸钠四水合物 12
C12直链烷基苯磺酸盐 30
磷酸盐(作为三聚磷酸钠) 10
碳酸钠 5
焦磷酸钠 7
椰子烷基单乙醇酰胺 2
沸石A(0.1-10微米) 5
羧甲基纤维素 0.2
聚丙烯酸盐(分子量1400) 0.2
增白剂、香料 0.2
蛋白酶 0.3
硫酸钙 1
硫酸镁 1
水 4
填料* 余量至100%
*根据实施例II制备的3-(3,4-二氢异喹啉鎓)丙磺酸盐
*可选自常规物质,例如碳酸钙、滑石、粘土、硅酸盐等,酸性填料可用于降低pH。
实施例VIII
适合于机器使用的洗衣洗涤剂组合物通过标准方法制备,含有如下组分:
组分 重量%
漂白增效剂* 0.82
TAED 7.20
过硼酸钠四水合物 9.2
碳酸钠 23.74
阴离子表面活性剂 14.80
硅铝酸盐 21.30
硅酸盐 1.85
二亚乙基三胺五乙酸 0.43
聚丙烯酸 2.72
增白剂 0.23
聚乙二醇固体 1.05
硫酸盐 8.21
香料 0.25
水 7.72
加工助剂 0.10
微量组分 0.43
*根据实施例II制备的3-(3,4-二氢异喹啉鎓)丙磺酸盐
组合物以在溶液中约1000ppm的浓度,在20~40℃的温度和约20∶1的水∶织物比率下用于洗涤织物。
实施例IX
组分 重量%
漂白增效剂* 1.0
TAED 10.0
过硼酸钠四水合物 8.0
碳酸钠 21.0
阴离子表面活性剂 12.0
硅铝酸盐 18.0
二亚乙基三胺五乙酸 0.3
非离子表面活性剂 0.5
聚丙烯酸 2.0
增白剂 0.3
硫酸盐 17.0
香料 0.25
水 6.7
微量组分 2.95
*根据实施例II制备的3-(3,4-二氢异喹啉鎓)丙磺酸盐
组合物以在溶液中约850ppm溶液中的浓度,在20~40℃的温度和约20∶1的水∶织物比率下作为洗涤辅助剂用于洗涤织物。
Claims (17)
1.一种漂白组合物,其含有选自两性离子亚胺、带有-1至-3的净负电荷的阴离子亚胺多离子和它们的混合物的漂白增效剂和按重量计0%至60%的过氧源。
2.权利要求1所述的漂白组合物,其中所述漂白增效剂占所述组合物重量的0.01%至10%,所述过氧源占所述组合物重量的0.01%至60%。
3.权利要求1-2中任何一项所述的漂白组合物,其中所述过氧源含有预先形成过酸的化合物,其选自过羧酸及其盐、过碳酸及其盐、过亚氨酸及其盐、过氧单硫酸及其盐和它们的混合物,或过氧化氢源和漂白活化剂。
4.权利要求3所述的漂白组合物,其中所述过氧化氢源选自过硼酸盐化合物、过碳酸盐化合物、过磷酸盐化合物和它们的混合物,所述漂白活化剂选自四乙酰基乙二胺、癸酰氧基苯磺酸钠、壬酰氧基苯磺酸钠、辛酰氧基苯磺酸钠、(6-辛酰氨基己酰基)氧苯磺酸盐、(6-壬酰氨基己酰基)氧苯磺酸盐、(6-癸酰氨基己酰基)氧苯磺酸盐和它们的混合物。
5.权利要求1-4中任何一项所述的漂白组合物,其中所述漂白增效剂选自芳基亚铵两性离子、带有-1至-3净负电荷的芳基亚铵多离子和它们的混合物。
9.根据权利要求1-8中任何一项的漂白组合物,其还含有用于配制洗涤和清洁组合物的组分,其选自至少一种洗涤剂表面活性剂、至少一种螯合剂、至少一种洗涤剂酶和它们的混合物。
10.一种两性离子洗涤漂白增效剂化合物,其具有下式:
11.一种洗涤织物的方法,所述方法包括使需洗涤的织物与含有根据权利要求1-9中任何一项的漂白组合物的洗涤溶液接触的步骤。
12.一种洗涤添加剂产物,其含有洗涤添加剂,所述添加剂含有根据权利要求1-9中任何一项的漂白组合物。
13.权利要求12所述的洗涤产物,其中所述添加剂是剂量形式,所述剂量形式包括丸剂、片剂、caplet、胶囊或其它单剂量形式。
14.一种漂白组合物,其包含含有效量的漂白物质的漂白溶液,所述漂白物质选自氧杂亚铵(oxaziridinium)两性离子、带有-1至-3净负电荷的氧杂亚铵多离子和它们的混合物。
15.权利要求14所述的漂白组合物,其中所述氧杂亚铵两性离子或多离子是氧杂芳基亚铵化合物。
16.权利要求15所述的漂白组合物,其中所述氧杂亚铵化合物由下式表示:
17.一种洗涤携污体的方法,所述方法包括使织物携污体与有效量的权利要求14-16中任何一项所述的漂白组合物接触的步骤。
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US08/526,623 US5576282A (en) | 1995-09-11 | 1995-09-11 | Color-safe bleach boosters, compositions and laundry methods employing same |
US08/526,623 | 1995-09-11 |
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EP (1) | EP0850296B1 (zh) |
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AR (1) | AR003548A1 (zh) |
AT (1) | ATE507280T1 (zh) |
BR (1) | BR9610602A (zh) |
CA (1) | CA2231540C (zh) |
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- 1996-08-30 CN CN96197991A patent/CN1105174C/zh not_active Expired - Lifetime
- 1996-08-30 WO PCT/US1996/013983 patent/WO1997010323A1/en active Application Filing
- 1996-08-30 EP EP96932158A patent/EP0850296B1/en not_active Expired - Lifetime
- 1996-08-30 CA CA002231540A patent/CA2231540C/en not_active Expired - Fee Related
- 1996-08-30 JP JP51199097A patent/JP4079995B2/ja not_active Expired - Lifetime
- 1996-09-11 AR ARP960104300A patent/AR003548A1/es unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103666874A (zh) * | 2013-11-22 | 2014-03-26 | 南通信一服饰有限公司 | 一种织物用油漆清洗剂 |
Also Published As
Publication number | Publication date |
---|---|
US5710116A (en) | 1998-01-20 |
ES2365841T3 (es) | 2011-10-11 |
JPH11513413A (ja) | 1999-11-16 |
DE69638360D1 (de) | 2011-06-09 |
ATE507280T1 (de) | 2011-05-15 |
JP4079995B2 (ja) | 2008-04-23 |
CN1105174C (zh) | 2003-04-09 |
CA2231540A1 (en) | 1997-03-20 |
EP0850296A1 (en) | 1998-07-01 |
CA2231540C (en) | 2003-01-14 |
MX9801939A (es) | 1998-08-30 |
US5576282A (en) | 1996-11-19 |
BR9610602A (pt) | 1999-07-13 |
WO1997010323A1 (en) | 1997-03-20 |
AR003548A1 (es) | 1998-08-05 |
EP0850296B1 (en) | 2011-04-27 |
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