CN1471570A - 含有阳离子聚硅氧烷的织物护理组合物及其使用方法 - Google Patents
含有阳离子聚硅氧烷的织物护理组合物及其使用方法 Download PDFInfo
- Publication number
- CN1471570A CN1471570A CNA018178111A CN01817811A CN1471570A CN 1471570 A CN1471570 A CN 1471570A CN A018178111 A CNA018178111 A CN A018178111A CN 01817811 A CN01817811 A CN 01817811A CN 1471570 A CN1471570 A CN 1471570A
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- alkyl
- independently selected
- alkenyl
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- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- 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
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3742—Nitrogen containing silicones
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/40—Monoamines or polyamines; Salts thereof
-
- 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
- C11D3/2051—Dihydric alcohols cyclic; polycyclic
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供了用于家庭洗衣的含有选择的阳离子聚硅氧烷的体系、组合物和方法。
Description
相关申请的交叉参者
按照37U.S.C.§119(e),本申请要求2000年8月28日申请的US临时申请系列号№60/228170(代理人案卷号8225P)、2000年10月27日申请的№60/243825(代理人案卷号8225P2)、2000年11月15日申请的№60/249059(代理人案卷号8225P3)和2001年2月12日申请的№60/268174(代理人案卷号8225P4)的优先权。
技术领域
本发明涉及用于家庭洗衣的含有配制用来改善织物护理的选择的阳离子聚硅氧烷的体系、组合物和方法。
发明背景
当消费者洗涤织物时,他们想要在清洁方面是优异的,而且寻求优异的织物护理或衣服护理。该护理可由以下的一种或多种来举例:优异的衣服外观;优异的触觉特征,例如织物手感;织物柔软;降低、去除或防止衣服收缩或皱褶;特别易于熨烫;衣服外形保持和/或形状恢复;和织物弹性。
在家庭洗衣中,存在获得织物护理的独特和明显的挑战,尤其是在与工业纺织品整理相比时。
尽管本领域有进展,但仍需要改善尤其在家庭洗衣中的织物护理。尤其是,在选择阳离子聚硅氧烷和其它添加剂从而组合提供不妥协程度的织物护理方面仍有重要的未解决的问题。当组合物是洗衣洗涤剂时,仍尤其难以组合洗涤剂添加剂和选择的阳离子聚硅氧烷,从而在获得优异织物护理的同时获得优异的清洁和配制稳定性或灵活性。
因此,本发明的目的包括解决上述技术问题,提供含有特定选择的阳离子聚硅氧烷和其它添加剂的获得优异织物护理的体系,组合物和方法。
发明概述
本发明解决了上述技术问题,具体地说,达到本发明的目的,提供组合物,体系和方法,它们在家庭洗衣中提供优异的织物护理。
本发明的基本组分是选择在如下详细说明的特定阳离子聚硅氧烷,它们能够提供家庭洗衣中的优异织物护理。
在本发明中重要的是在用于家庭织物护理的组合物,体系和方法中成功加入选择的聚硅氧烷。
本发明具有许多优点,包括,根据具体实施方案,优异的织物护理或衣服护理的一个或多个方面,由如下一种或多种举例:优异的衣服外观;优异的触觉特征,优异的织物手感;织物柔软;降低,去除或防止衣服收缩或皱褶;尤其易于熨烫;衣服形状保持和/或形状恢复;和织物弹性。此外,根据明确的实施方案,本发明具有其它优点,包括所提供的家庭洗衣组合物的优异配制灵活性和/或配制稳定性。
本发明包括其它分支,例如获得组合物的过程和方法,各种形式和类型的产品,例如单位液体洗衣洗涤剂及其固定在使用点的多隔室配方。
本发明包括出乎意料的发现,例如,我们惊奇地发现,同时适当注意阳离子聚硅氧烷和配制添加剂的选择,可得到出乎意料的家庭洗衣产品的良好织物护理和/或消费者赞同,这可能与多种织物护理效果的互相作用或织物护理和其它美学效果,例如其它已知香料物质的改善沉降的组合有关。此外,在本发明中发现的家庭洗衣中优异的织物护理或衣服护理效果可意外地包括在本发明的产品以不同模式使用时的效果,例如在自动洗衣机洗涤前的处理(预处理效果),洗涤过程中的效果和处理后效果,包括本发明的产品在漂洗或在织物或衣服离心干燥或在器具中或外干燥时获得的效果。此外发现了制度(regimen)效果,即由使用含有常规洗涤剂的产品体系转变为使用本发明的组合物和用其特定配制的组合物的产品体系的效果。
本发明包括组合物,其含有:(I)阳离子聚硅氧烷聚合物,其含有一个或多个聚硅氧烷,优选聚二甲基聚硅氧烷单元,优选两个或多个该单元和一个或多个,优选两个或多个季氮部分,后者两个或多个季氮部分优选共键连接以形成无有机聚硅氧烷的部分,或其中每个无有机聚硅氧烷部分含有两个或多个季氮原子。本发明包含其中阳离子聚硅氧烷聚合物是新颖的实施方案,具体参见下文结构2。
此外,当所选择的阳离子聚硅氧烷聚合物是本领域中已知的,并且在本发明的优选实施方案中,组合物还含有(II)一种或多种洗衣添加剂,其选自:(a)稳定剂,优选增稠稳定剂,更优选结晶含羟基稳定剂,更优选三羟基硬脂精、氢化油或它们的变体;(b)无氮非离子表面活性剂;(c)含氮洗涤表面活性剂,优选选自阳离子含氮洗涤表面活性剂,氧化胺表面活性剂、胺和酰胺官能化的洗涤表面活性剂(后者包括脂肪酰氨烷基胺)和它们的混合物;(d)偶合剂,优选选自脂肪胺、1,4-环己烷二甲醇和它们的混合物;(e)洗涤剂助洗剂,优选选自水溶性有机助洗剂;(f)织物直接香料;(g)清除剂,选自捕获褪色染料和/或阴离子表面活性剂和/或污垢,所述清除剂选自阴离子染料固定剂、阴离子表面活性剂的配合剂、粘土污垢控制剂和它们的混合物;(h)织物柔软剂;(i)洗涤酶;(j)螯合剂;(k)溶剂体系;(1)泡腾体系;(m)涂覆或包胶囊剂和(n)它们的混合物。
本发明的优选实施方案包括组合物,其含有按组合物重量计约0.001%到约10%,优选约0.001%-约5%的阳离子聚硅氧烷和此外,按组合物重量计总共至少约1%,优选至少约10%的洗衣添加剂,在一项实施方案中,包括至少一种稳定剂;在另一项实施方案中,一种稳定剂和助洗剂;在另一实施方案中,至少一种助洗剂和织物柔软剂;在另一实施方案中,至少一种助洗剂和清除剂;和在另一实施方案中,至少所述组合中的一种与此外至少一种溶剂体系,其含有水和至少一种,优选两种有机溶剂或有机溶剂和偶合剂。
本发明更优选的实施方案包括组合物,其含有按重量计至少约0.01%,优选约0.01%-约20%阳离子聚硅氧烷和此外的如下各自组分:结晶含羟基稳定剂;无氮非离子洗涤表面活性剂;阴离子染料固定剂;含有水和有机溶剂的溶剂体系;和洗涤剂助洗剂。令人惊奇的是,该混合物可进一步与阴离子表面活性剂和/或皂混合。
其它优选的实施方案包括组合物,其含有阳离子聚硅氧烷和此外的一种,优选至少两种如下组分:用于阳离子聚硅氧烷的稳定剂;织物直接香料;选择用于捕获褪色染料和/或阴离子表面活性剂的清除剂;和泡腾体系。
本发明的优选方法包括适用于家庭的处理织物,尤其是衣服包形式的方法,其包括纤维和织物类型与本发明组合物的不均匀混合。
在如下详细描述,实施例和所附的权利要求中,进一步证实本发明的目的,特征和优点。
所有百分数,比率和比例基于未稀释组合物的重量基准,除非另有说明。本文引用的所有文献均列为本文参考文献。
发明的详细描述定义-互换使用的术语“阳离子聚硅氧烷聚合物”和“阳离子聚硅氧烷”是指所选择的聚硅氧烷,它是本发明的基本组分。优选的阳离子聚硅氧烷可更具体地命名,包括例如“水不溶混阳离子聚硅氧烷无规嵌段共聚物”。本发明选择的阳离子聚硅氧烷聚合物在以下充分定义。
用于本文的“体系”是指许多进行常规计划或用作常规用途的部分形成的单元。该部分可以是物质、组合物、装置、应用、过程、方法或条件。不同的部分和/或不同类型的部分可表征不同的体系。
用于本文的术语“添加剂”是指在本发明组合物中选择与阳离子聚硅氧烷聚合物同时使用的任何液体、固体或气体物质。添加剂优选,但不是必需,与阳离子聚硅氧烷聚合物和本发明组合物中存在的其它组分内在地相容。当添加剂不是内在相容时,它们可通过各种技术包括,例如在制备过程中改变加入的顺序、通过包胶囊、通过使用在使用点混合的多部分组合物等。
用于本文的“处理的载污体”是指载污体,尤其是织物或衣服,具有一种或多种通过含有本发明的选择的阳离子聚硅氧烷的组合物所给予的本文所描述的织物护理效果。
在短语,例如“二价部分”或“二价烃基”中使用的术语“二价”是指具有两个用于将其连接到结构的共价化合价。例如,-(CH2)6-是这样一种部分。
“有效量”,按织物护理组合物重量计优选由约0.01%,更优选由约0.1%,更优选由约1%到约20%,更优选到约15%,更优选到约10%,更优选到约7%,最优选到约5%的一种或多种本发明的阳离子聚硅氧烷聚合物包括在用于洗衣和/或加香各种需要处理的织物的组合物中。用于本文中,物质或组合物的“有效量”是完成所需用途,例如向织物制品/载污体给予所需程度的织物护理效果而所需的数量。组合物的形式-组合物,尤其是本发明的织物护理组合物可以是任何形式,例如液体(含水或无水)、颗粒、膏、粉末、喷雾剂、泡沫、片、凝胶等。包括包胶囊和/或成单位剂量组合物,因为它们是形成两个或多个单独的但组合可分散的部分的组合物。颗粒组合物可以是“致密”或“低密度”形式,液体组合物也可以是“浓缩”或稀释形式。本发明优选的织物护理组合物包括液体,更优选重垢液体织物护理组合物和用于洗涤精细织物,例如丝、羊毛等的液体洗涤剂。包括通过混合所提供的组合物与各种比例的水形成的组合物。
本发明的织物护理组合物和/或香料组合物可以是喷雾组合物形式,优选包含在合适的喷雾分散器中。与形式相关的本发明的组合物的用途-用于本文,“织物护理组合物”包括用于手洗、机洗和其它用途的织物护理组合物,包括织物护理添加剂组合物和用于浸泡和/或预处理脏织物的组合物。
即使本文具体讨论了织物护理组合物,但本发明包括用于处理、清洁、调理和/或重新整理天然和合成纤维的含有本发明阳离子聚硅氧烷的组合物。香料组合物-本发明包括本发明的香料组合物,其含有本文随后充分定义的织物直接香料和用于本发明洗衣或织物护理组合物的阳离子聚硅氧烷聚合物。
本发明的香料组合物优选加入本发明的织物护理组合物中。例如本发明的香料组合物可以在加入本发明的织物护理组合物之前预先混合。
在织物护理组合物中香料组合物的含量按织物护理组合物重量计通常是约0.0001%到约2%或更高,例如约10%,优选约0.0002%-约0.8%,更优选约0.003%到约0.6%,最优选约0.005%-约0.5%。
在本发明的香料组合物中,织物直接香料组分的含量按香料组合物的组合物重量计通常是约0.0001%(更优选0.01%)-约99%,优选约0.01%-约50%,更优选约0.2%-约30%,还要优选约1%-约20%,最优选约2%-约10%。阳离子聚硅氧烷-选择用于本发明组合物的阳离子聚硅氧烷聚合物含有一个或多个聚硅氧烷单元,优选聚合度n为50-200的式-{(CH3)2SiO}n-的聚二甲基硅氧烷单元,和含有至少一个二季单元的无有机硅氧烷的单元。在本发明的优选实施方案中,选择的阳离子聚硅氧烷聚合物含有0.50-1.0重量部分的选自N,N,N’,N’-四甲基-1,6-己二铵单元的所述无有机硅氧烷单元。
选择的阳离子聚硅氧烷聚合物还可含有总共0.0-0.20重量部分,在某些实施方案中非零数量的-NHCH(CH3)CH2O(AO)aCH2CH(CH3)NH-单元的无有机硅氧烷单元,其中AO表示乙烯氧基、丙烯氧基、丁烯氧基和它们的混合物和a是5-70。
选择的阳离子聚硅氧烷聚合物还可含有总共由0.0,在某些实施方案中非零数量-0.20重量部分的-NR3+无有机硅氧烷单元,其中R是烷基,羟基烷基或苯基,这些单元可认为是封端基团。
此外,选择的阳离子聚硅氧烷聚合物通常含有阴离子,其选自无机和有机阴离子,更优选选自饱和和不饱和C1-C20羧酸盐和它们的混合物以平衡季部分的电荷,因此,阳离子聚硅氧烷聚合物还含有季电荷平衡比例的阴离子。
概念地说,本文所选择的阳离子聚硅氧烷聚合物作为非交联或“线性”嵌段共聚物是有利的,所述共聚物包括由聚硅氧烷单元和织物直接“钩”组成的非织物直接但表面能量改善的“环”。选择的阳离子聚硅氧烷的一种优选种类(下文结构1说明)可认为是包括单一的环和两个钩;其它,非常优选的含有两个或多个,优选三个或多个“环”和两个或多个,优选三个或多个“钩”(下文用结构2a和2b说明);另一种(下文用结构3说明)含有从单一的“钩”下垂的两个“环”。
在选择本发明阳离子聚硅氧烷聚合物中,特别令人感兴趣的是“钩”不含硅,且每个“钩”包含至少两个季氮原子。
在本发明选择的阳离子聚硅氧烷聚合物中,尤其感兴趣的是季氮优先位于“线性”聚合物的“骨架”中,与其中季氮加入构成“骨架”之外的“侧基”或“悬挂”结构部分的另外的和不太优选的结构相区别。
结构由末端基团完成,末端基团可以是不带电荷的,或在带电荷时,可仅含有一个季氮原子,如在基团-NR3+,其中R是烷基。此外,可存在一定比例的非季无硅氧烷部分,例如如上所述的基团-NHCH(CH3)CH2O(AO)aCH2CH(CH3)NH-。
当然,现有的概念模型不用来限制其它部分,例如接合部分,它可存在于选择的阳离子聚硅氧烷聚合物中,只要它们不明显破坏作为织物效果剂的所需的功能。
具体而言,本文的阳离子聚硅氧烷聚合物含有一个或多个聚硅氧烷单元和一个或多个季氮部分,包括其中阳离子聚硅氧烷聚合物具有下式的聚合物:(结构1)
(结构1)其中:-R1独立地选自C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基和它们的混合物;-R2独立地选自可含有一个或多个氧原子的二价有机部分(该部分优选主要由C和H或C、H和O组成);-X独立地选自开环环氧化物;-R3独立地选自下式的聚醚基团:
-M1(CaH2aO)b-M2其中M1是二价烃残基;M2是H、C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基;环烷基、C1-22羟基烷基、聚环氧烷或(聚)烷氧基烷基;-Z独立地选自含有至少一个季氮原子的单价有机部分;-a是2-4;-b是0-100;-c是1-1000,优选大于20,更优选大于30,甚至优选大于50,优选小于500,更优选小于300,甚至优选小于200,最优选约70-约100;-d是0-100;-n是与阳离子聚硅氧烷聚合物有关的正电荷数目,它是大于或等于2;和-A是单价阴离子。
在结构1阳离子聚硅氧烷聚合物的优选实施方案中,Z独立地选自如下基团:
(v)单价芳族或脂族杂环基团,取代或非取代的,含有至少一个季氮原子;其中:-R12、R13、R14是相同或不同的,选自:C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基;聚环氧烷;(聚)烷氧基烷基和它们的混合物;-R15是-O-或NR19;-R16是二价烃基残基;-R17、R18、R19是相同或不同的,选自:H、C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基;聚环氧烷;(聚)烷氧基烷基和它们的混合物;和-e是1-6。
在更优选实施方案中,本文的阳离子聚硅氧烷聚合物含有一个或多个聚硅氧烷单元和一个或多个季氮部分,包括其中阳离子聚硅氧烷聚合物具有下式的聚合物:(结构2a)结构2a:由如下交替单元组成的阳离子聚硅氧烷聚合物:
(i)下式的聚硅氧烷:和
(ii)含有至少两个季氮原子的二价有机部分。
注意结构2a含有所示式的聚硅氧烷和二价有机部分的不同组合,二价有机部分是相应于上述一般描述中优选的“钩”的无有机硅氧烷。
在该优选阳离子聚硅氧烷聚合物中,-R1独立地选自C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基和它们的混合物;-R2独立地选自可含有一个或多个氧原子的二价有机部分;-X独立地选自开环环氧化物;-R3独立地选自下式的聚醚基团:
-M1(CaH2aO)b-M2
其中M1是二价烃残基;M2是H、C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基;环烷基、C1-22羟基烷基、聚环氧烷或(聚)烷氧基烷基;-a是2-4;-b是0-100;-c是1-1000,优选大于20,更优选大于30,甚至优选大于50,优选小于500,更优选小于300,甚至优选小于200,最优选约70-约100;和-d是0-100。
在结构2a阳离子聚硅氧烷聚合物的更优选实施方案中,阳离子聚硅氧烷聚合物具有式结构2b,其中在结构2a中的上述式的聚硅氧烷与选自下式的阳离子二价有机部分一起存在:
(d)二价芳族或脂族杂环基团,取代或非取代的,含有至少一个季氮原子;和
(iii)任选地下式的聚环氧烷:
[Y-O-(CaH2aO)b-Y];和
(v)单价芳族或脂族杂环基团,取代或非取代的,含有至少一个季氮原子;其中:-R4、R5、R6、R7、R8、R9、R10、R11是相同或不同的,选自:C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基、聚环氧烷、(聚)烷氧基烷基和它们的混合物;或其中R4和R6,或R5和R7,或R8和R10,或R9和R11可以是桥接亚烷基的部分;-R12、R13、R14是相同或不同的,选自:C1-22烷基、C2-22链烯基、C6-22烷基芳基、C1-22羟基烷基、聚环氧烷、(聚)烷氧基烷基和它们的混合物;和-R15是-O-或NR19;-R16和M1是相同或不同的二价烃基残基;-R17、R18、R19是相同或不同的,选自:H、C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基;聚环氧烷、(聚)烷氧基烷基和它们的混合物;和-Z1和Z2是相同或不同的带有至少2个碳原子的二价烃基,并任选地含有羟基,它可以被一个或几个醚、酯或酰胺基团分隔;-Y是仲或叔胺;-e是1-6;-m是与阳离子二价有机部分有关的正电荷数目,它是大于或等于2;和-A是阴离子。
注意结构2b含有所示式的聚硅氧烷和二价有机部分的不同组合,二价有机部分是相应于上述一般描述中优选的“钩”的无有机硅氧烷。结构2b包括实施方案,其中选择性的聚环氧烷和/或端基部分是存在或不存在的。
(结构3)其中:-R1独立地选自C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基和它们的混合物;-R2独立地选自可含有一个或多个氧原子的二价有机部分;-X独立地选自开环环氧化物;-R3独立地选自下式的聚醚基团:
-M1(CaH2aO)b-M2
其中M1是二价烃残基;M2是H、C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基、聚环氧烷或(聚)烷氧基烷基;-X独立地选自开环环氧化物;-W独立地选自含有至少一个季氮原子的二价有机部分;-a是2-4;-b是0-100;-c是1-1000,优选大于20,更优选大于30,甚至优选大于50,优选小于500,更优选小于300,甚至优选小于200,最优选约70-约100;-d是0-100;-n是与阳离子聚硅氧烷聚合物有关的正电荷数目,它是大于或等于1;和-A是单价阴离子。
(d)二价芳族或脂族杂环基团,取代或非取代的,含有至少一个季氮原子;和-R4、R5、R6、R7、R8、R9、R10、R11是相同或不同的,选自:C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基、聚环氧烷、(聚)烷氧基烷基和它们的混合物;或其中R4和R6,或R5和R7,或R8和R10,或R9和R11可以是桥接亚烷基的部分;和-Z1和Z2是相同或不同的带有至少2个碳原子的二价烃基,并任选地含有羟基,它可以被一个或几个醚、酯或酰胺基团分隔。合成实施例
当在商业上不是已知或可得到时,本发明的阳离子聚硅氧烷聚合物可通过常规技术制备。如下是制备本发明的阳离子聚合物的非限定性实例。
实施例1
在氮气和室温下搅拌炔丙醇(497g,8.87mol),同时在1小时内滴加α-氯乙酰氯(955g,8.45mol)。在添加过程中温度上升到60℃,同时强烈形成HCl气体。混合物变黑,在130℃下加热1小时。分馏得到891g炔丙基α-氯乙酸酯BP179-181℃。
炔丙基α-氯乙酸酯(26.5g,0.2mol)和根据US3220972的含有3.43%Pt的Lamoreaux负载催化剂(44mg)在氮气和室温下混合,在30分钟内加入1,1,1,3,5,5,5-七甲基三硅氧烷,温度上升到60℃,最终加热到100℃4小时。
在2hPa下煮沸到120℃除去蒸馏物得到纯度为85%的下式的黄色液体(64.5g):
在氮气气氛下,上述得到的哌嗪硅氧烷(21.8g,0.05mol)和氯酯硅氧烷(17.7g,0.05mol)悬浮在甲基丙基酮(50ml)中,回流6小时。随后在4hPa下煮沸至100℃除去杂质,得到35.7g下式的棕色残余物:
实施例2
将具有下式的环氧硅氧烷(211.1g,0.15mol:和N-甲基哌嗪(15.2g,0.15mol)在异丙醇(225ml)中混合,加热到90℃4小时形成α,ω-氨基硅氧烷。通过蒸馏除去溶剂以得到217g透明产物。
在氮气气氛下,在30分钟内将3-氯丙酰氯(152.4g,1.2mol)加入平均分子量为300g/mol(每分子平均6.4乙烯化氧单元)的聚乙二醇。温度上升到70℃,产生大量HCl气体。在120℃下持续反应30分钟,随后在20hPa下煮沸到120℃除去杂质得到下式的化合物:
在氮气气氛下,α,ω-氨基硅氧烷(19.61g,6.5mmol)和α,ω-氯丙酸乙二醇酯(3.12g,6.5mmol)悬浮在异丙醇(50ml)中,回流12小时。随后在20hPa下煮沸至70℃除去杂质,得到21.6g下式的棕色残余物:实施例3
将具有下式的环氧硅氧烷(181.3g,0.5mol):和N-甲基哌嗪(101.2g,1mol)在异丙醇(100ml)中反应,在20hPa下到100℃蒸馏杂质得到276gα,ω-氨基硅氧烷的浅棕色透明残余物。在氮气气氛下,将α,ω-氨基硅氧烷(6.2g,11mmol)和实施例B的α,ω-氨基硅氧烷(33.21g,11mmol)与实施例B的α,ω-氯丙酸乙二醇酯(10.59g,22mmol)混合,悬浮在异丙醇(50ml)中,回流10小时。随后在20hPa下煮沸至40℃除去溶剂和原料得到48.7g如下平均式的棕色蜡状化合物:优选织物护理添加剂(a)稳定剂-本发明的组合物可优选包括稳定剂。该组分的合适含量按组合物重量计在约0.01%-约20%,更优选约0.1%-约10%的范围内。稳定剂用于稳定本发明组合物中的阳离子聚硅氧烷,防止其凝固和/或乳化。在本发明的组合物具有液体形式,例如香料组合物、用于重垢或精细织物洗涤使用的液体或凝胶形式洗衣洗涤剂和除洗衣洗涤剂之外的液体或凝胶形式织物处理时是尤其重要的。
适用于本文的稳定剂可选自增稠稳定剂。它们包括树胶和其它类似多糖,例如胶凝胶、角叉菜胶和除高度聚阴离子类型之外的其它已知类型的增稠剂和流变添加剂,因此,不包括常规粘土。
更优选的稳定剂是结晶含羟基稳定剂,更优选三羟基硬脂精(stearin)、氢化油或其变体。
不打算限制于理论,但结晶含羟基稳定剂是“线型结构体系”的非限制性实例。用于本文的“线型结构体系”是指含有体系,它含有一种或多种能够提供化学网络,从而降低物质结合以融合和/或分相趋势的试剂。一种或多种试剂的实例包括结晶含羟基稳定剂和/或氢化西蒙得木油。表面活性剂不包括在线型结构体系的定义中。尽管不打算限于理论,但我们相信线型结构体系在基体冷却时就地形成纤维或纠缠的线型网络。线型结构体系具有约1.5∶1,优选至少约10∶1-约200∶1的平均纵横比。
线型结构体系可形成在中等剪切范围(5s-150s-1)下具有约2000cps或以下的粘度,使得洗涤剂从标准瓶中倒出,而在0.1s-1下产品的低剪切粘度可以是至少约2000cps,但更优选大于约20000cps。
本发明的线型结构体系提供了具有改善的储存和应力稳定性的本发明的液体组合物,并且液体组合物能够使其效果提供试剂在使用时提供其效果。所使用的特定体系被发现与阳离子聚硅氧烷相容,而在例如基本上含有粘土,例如钠蒙脱石时则不能。
制备本发明的线型结构体系的方法合适地包括加热水和结晶含羟基稳定剂的混合物至结晶含羟基稳定剂的熔点之上,随后冷却混合物,同时连续混合至室温,从而形成线型结构体系。
在一项实施方案中,方法包括活化结晶含羟基稳定剂,其包括如下步骤:1)混合结晶含羟基稳定剂,优选按混合物重量计约0.1%-约5%与水,优选按混合物重量计至少约20%,和表面活性剂和任选地,一种盐以形成混合物;2)加热步骤1)中形成的混合物至结晶含羟基稳定剂的熔点之上;和3)冷却步骤2)中形成的混合物,同时搅拌混合物至室温,从而形成线型结构体系。
在步骤1)中形成的混合物还可含有表面活性剂。
在步骤1)中形成的混合物还可含有氧化胺。
有关制备该线型结构体系方法的详细描述可在属于The Procterand Gamble Company的US6080708中找到。
结晶含羟基稳定剂通常以按液体组合物重量计约0.1%-约10%,更常见约0.1%-约3%,最常见约0.3%-约2%的含量存在于本发明的液体组合物中。
结晶含羟基稳定剂可以是脂肪酸、脂肪酯或脂肪皂水不溶蜡状物质。
本发明的结晶含羟基稳定剂优选是蓖麻油衍生物,尤其是氢化蓖麻油衍生物,例如蓖麻油蜡。
此外,结晶含羟基稳定剂可以具有下式:CH3(CH2)aCHOH(CH2)xC(O)OCH2CH(O(O)C(CH2)yCHOH(CH2)bCH3)CH2O(O)C(CH2)zCHOH(CH2)cCH3其中:(x+a)是11-17;(y+b)是11-17;和(z+c)是11-17。优选其中x=y=z=10和/或其中a=b=c=5。
商业可获得的结晶含羟基稳定剂包括来自Rheox,Inc.的THIXCIN。
用于本文的其它不太优选的稳定剂包括树胶型聚合物(例如黄原胶)、聚乙烯基醇和它们的衍生物、纤维素和它们的衍生物和罗望籽果胶(优选由木葡聚糖聚合物),和其它工业胶和聚合物,它们包括,但不限于,塔兰、胡芦巴、芦荟、墨西哥油、亚麻子、车前子、槲栌籽、黄原胶、胶凝、welan、rhamsan、葡聚糖、curdlan、水溶性多糖、硬葡聚糖、schizophyllan、壳多糖、羟基烷基纤维素、阿拉伯胶(优选来自甜菜)、去支链阿拉伯胶(优选来自甜菜)、arabinoxylan(优选来自黑麦和小麦粉)、半乳聚糖(优选来自羽扇豆和土豆)、果胶半乳聚糖(优选来自土豆)、半乳甘露聚糖(优选来自角豆树,包括低和高粘度)、葡甘露聚糖、地衣聚糖(优选来自冰岛苔藓)、甘露聚糖(优选来自象牙坚果)、茯苓聚糖、鼠李半乳聚糖、阿拉伯树胶、琼脂、藻酸盐、角叉菜胶、壳聚糖、calvan、透明质酸、肝素、菊粉、纤维糊精、羧基甲基纤维素(CMC)、葡聚糖、糊精、乙基羟基乙基纤维素(EHBC)、瓜耳胶、羟基乙基纤维素(HEC)、羟基丙基纤维素(HPC)、羟基丁基纤维素(HBC)、卡拉牙胶、落叶松、甲基纤维素(MC)、罗晃子、硬葡聚糖、黄原胶、羧甲基羟基乙基纤维素(CMHEC)、甲氧基丙基甲基纤维素(MPMC)、己基羧基甲基纤维素、C12-C20烷基羧甲基纤维素、甲基羟基乙基纤维素(MHBC)、甲基羟基丙基纤维素(MHPC)、羟基乙基甲基纤维素(HEMC)、羟基丙基甲基纤维素(HPMC)、羟基丁基甲基纤维素(HBMC)和它们的混合物。
稳定剂优选以0.01%-10%,最优选0.1%-3%的含量存在。(b)无氮非离子表面活性剂-本发明可以并优选包括加入这类洗涤表面活性剂的优选实施方案。该组分的合适含量在按组合物重量计约0.01%-约80%,更常见约0.1%-约50%,优选约1%-约30%的范围内。这类合适的表面活性剂可由含有线性支链烃基部分的任何合适的洗涤剂醇的烷氧基化物,包括环氧乙烷、环氧丙烷、环氧丁烷和混合环氧化物缩合物得到。实例包括:含有约1-22摩尔环氧化物的C8-C18烷基和/或烷基芳基烷氧基化物,尤其是乙氧基化物。这包括所谓的窄峰烷基乙氧基化物和C6-C12烷基苯酚乙氧基化物,尤其是壬基苯基乙氧基化物。醇可以是伯、仲、Guerbet、中链支链或任何其它支链类型,尤其是更加可生物降解的。商业可得到的物质可由Shell Chemical,Condea或Procter&Gamble获得。当使用这些表面活性剂时,按重量计,本发明的组合物将含有至多约80%,优选1%-约50%,更优选2%-约20%。
用于本文的其它非离子表面活性剂包括,但不限于,在1986年1月22日授权给Llenado的US4565647中公开的烷基多糖,其含有约6-约30个碳原子,优选约10-约16个碳原子的疏水基团和多糖,例如含有约1.3-约10多糖单元的亲水基团的多糖苷。可以使用任何含有5或6个碳原子的还原糖类,疏水基任选地连接在2-、3-、4-等位置,从而得到相对于葡糖苷或半乳糖苷的葡萄糖或半乳糖。内糖键可在例如加入的糖单元的一个位置和先前糖单元的2-、3-、4-和/或6-位置之间。优选的烷基多糖苷具有下式:RO(CnH2nO)t(糖基)x,其中R选自烷基、烷基苯基、羟基烷基、羟基烷基苯基和它们的混合物,其中烷基含有约10-约18,优选约12-约14个碳原子;n是2或3,优选2;t是0-约10,优选0,x是约1.3-约10,优选约1.3-约3,最优选约1.3-约2.7,糖基优选由葡萄糖得到。(c)含氮洗涤表面活性剂-如果存在,该组分的合适含量是在按组合物重量计约0.01%-约20%,更优选约0.1%-约15%,典型地为约1%-约10%的范围内。本文的含氮洗涤表面活性剂优选选自阳离子含氮洗涤表面活性剂、氧化胺表面活性剂、胺和酰胺官能团洗涤表面活性剂(包括脂肪酰氨基烷基胺)和它们的混合物。含氮洗涤表面活性剂通常是水溶性的,不包括聚硅氧烷表面活性剂。这类不同的表面活性剂可以不同比例混合。
i)阳离子含氮洗涤表面活性剂-适合用于本发明的组合物中的阳离子含氮洗涤表面活性剂通常是水溶性的,含有至少一个季氮和一个长链烃基。该阳离子表面活性剂的实例包括水溶性烷基三甲基铵盐或其羟基烷基取代的类似物,优选具有下式的化合物:R1R2R3R4N+X-,其中R1是C8-C16烷基,每个R2,R3和R4独立地是C1-C4烷基,C1-C4羟基烷基、苄基,和-(C2H4O)xH,其中x是2-5的数值,和X是阴离子。不超过一个的R2、R3或R4应是苄基。R1的优选烷基链长度是C12-C15,优选的R2、R3和R4基团是甲基和羟基乙基,阴离子X可以选自卤化物、甲基硫酸盐、乙酸盐和磷酸盐。
ii)氧化胺表面活性剂-这些表面活性剂具有式:R(EO)x(PO)y(BO)zN(O)(CH2R’)2.qH2O(I)。R是相对长链的烃基部分,它可以是饱和或不饱和的,直链或支链的,能含有约8~约20,优选约10~约16个碳原子,更优选C12-C16伯烷基。R’是短链部分,优选选自H、甲基和-CH2OH。当x+y+z不是0时,EO是乙烯氧基,PO是丙烯氧基和BO是丁烯氧基。氧化胺表面活性剂由C12-14烷基二甲基氧化胺说明。
iii)胺和酰胺官能团洗涤表面活性剂-这些表面活性剂优选是胺表面活性剂,优选具有下式的胺表面活性剂:RX(CH2)xNR2R3,其中R是C6-C12烷基;X是桥接基团,其选自NH、CONH、COO,或O或X可以不存在;x是2-4;R2和R3各自独立地选自H、C1-C4烷基或(CH2-CH2-O(R4)),其中R4是H或甲基。尤其优选的这类表面活性剂包括选自癸基胺、月桂基胺、C8-C12双(羟基乙基)胺、C8-C12双(羟基丙基)胺、C8-C12酰氨基丙基二甲基胺和它们的混合物。
该组表面活性剂还包括具有式RC(O)NR’2的脂肪酸酰胺表面活性剂,其中R是含有约10-约20个碳原子的烷基,每个R’是短链部分,优选选自氢和C1-C4烷基和羟基烷基。也可以使用C10-C18N-烷基多羟基脂肪酸酰胺。典型实例包括C12-C18N-甲基葡糖酰胺。参见WO92/06154。其它糖衍生的含氮非离子表面活性剂包括N-烷氧基多羟基脂肪酸酰胺,例如C10-C18N-(3-甲氧基丙基)葡糖酰胺。(d)偶合剂-适用于本文的偶合剂包括除具有明显表面活性剂特征或是常规溶剂(例如低级链烷醇胺)之外的脂肪胺。这些偶合剂的实例包括己基胺、辛基胺、壬基胺和它们的C1-C3仲和叔类似物。如果存在,该组分的含量合适地在按组合物重量计约0.1%-约20%,更常见约0.5%-约5%的范围内。
尤其有用的偶合剂选自由被至少5,优选6个脂族碳原子彼此隔开的两个极性基团组成的分子;在该组中优选化合物没有氮,包括1,4环己烷二甲醇(CHDM)、1,6己二醇、1,7庚二醇和它们的混合物。1,4环己烷二甲醇可以顺式构型,反式构型或两种构型的混合物存在。(e)洗涤剂助洗剂-通常任何已知的洗涤剂助洗剂用于本文,包括无机类型,例如沸石、层状硅酸盐和磷酸盐,例如碱金属多磷酸盐,和有机类型,尤其包括柠檬酸、2,2-氧联琥珀酸、羧甲基氧联琥珀酸、次氮基三乙酸等的碱金属盐。具有相对低分子量,例如低于约1000的无磷水溶性有机助洗剂用于本文是十分优选的。其它合适的助洗剂包括碳酸钠和硅酸钠,它们具有不同比率的SiO2∶Na2O含量,例如1∶1-3∶1,通常是2∶1比率。(f)织物直接香料-本发明的织物护理组合物和香料组合物可含有香料以愉快气味的形式提供“香味信号”,它向洗涤的织物提供新鲜印象。织物直接香料组分含量合适地在按组合物重量计约0.0001%-约10%的范围内,以它们的沸点(B.P.)为特征。织物直接香料组分具有在760mmHg的正常,标准压力下,约240℃或更高,优选约250℃或更高的B.P.。优选织物直接香料组分具有大于3,更优选约3-约6的ClogP。
用于本发明的优选香料组合物含有至少2,优选至少3,更优选至少4,还更优选至少5,更加优选至少6,甚至更加优选至少7种不同织物直接香料组分。由天然来源得到的最常见的香料组分由许多组合组成。当每种该物质用于本发明的优选香料组合物的配制时,为用于定义本发明,它被算作单一组分。
用于本发明的组合物中的合适织物直接香料组分的非限制实例包括:(Z)-3-甲基-2-(2-戊烯基)-2-环戊烯-1-酮,3-甲基-丁酸4-甲基苯基酯,3,4-二甲基-5-亚戊基-2(5H)-呋喃酮,3-甲基-丁酸苯基甲基酯,(E)-2-甲基-2-丁酸苯基甲基酯,苯丁酸乙酯,苯乙酸丁酯,(1S)-6,6-二甲基-二环[3.1.1]庚-2-烯-2-甲醇乙酸酯,β,4-二甲基-3-环己烯-1-丙醛,2-(1-环己烯-1-基)-环己酮,丙酸2-甲基1-甲基-1-戊基乙酯,2,4-癸二醛,(E,E)-2,4-癸二醛,丁酸2-苯基乙酯,反-2-戊基-环丙烷羧酸,(E)-3-甲基-2-(2-戊烯基)-环戊烯-1-酮,6-己基四氢-2H-吡喃-2-酮,壬酸2-乙酰基-乙酯,AR-(1-甲基乙基)-苯乙醛,5-甲基-5-苯基-3-己酮,氧杂环十二烷-2-酮,2-甲基-丁酸2-苯基乙酯,6-亚乙基八氢-5,8-桥亚甲基-2H-1-苯并吡喃,1-[4-(1,1-二甲基乙基)苯基]-乙酮,丙酸苯丙醇酯,2-(2,6-二甲基-1,5-庚二烯基)-1,3-二氧戊环,[1,1’-双环己基]2-酮,5-丙基-1,3-苯并间二氧杂环戊烯,2-甲基-丙酸3-苯基丙基酯,1-(4,7,7-三甲基二环[4.1.0]庚-4-烯-3-基)-乙酮,(Z)-6-(3-己烯基)四氢-2H-吡喃-2-酮,甲基苯基甲基二硫化物,1-[4-(1-甲基乙基)苯基]乙酮,β,β,3-三甲基-苯丙醇,(+-)-3,7-二甲基-6-辛烯酸,3,7-二甲基-6-辛烯酸,4-乙基-α,α-二甲基-苯丙醛,5-庚基二氢-2(3H)-呋喃酮,壬酸,2-甲基-5-(1-甲基乙基)-苯酚乙酸酯,4-(1-甲基乙基)-乙酸苯甲醇酯,4-(1-甲基乙基)-苯乙醛,2-甲基-丙酸3-苯基-2-丙烯基酯,5-甲基-2-(1-甲基乙基)-苯酚乙酸酯,丁酸2-苯基丙酯1-[2-甲基-5-(1-甲基乙基)苯基]-乙酮,[(3,7-二甲基-6-辛烯基)氧基]-乙醛,2-呋喃丙酸2-甲基丙基酯,(2-丁氧基乙基)-苯,丁酸1-甲基-2-苯基乙基酯,四氢-4-甲基-2-苯基-2H-吡喃,(2-异硫氰酸酯基乙基)-苯,癸二酸二甲基酯,3-甲基-丁酸2-苯基乙基酯,5-(1-丙烯基)-1,3-苯并间二氧杂环戊烯,己二酸2-呋喃甲基酯,6,6-二甲基-二环[3.1.1]庚-2-烯-2-丙醛,(1,1-二甲基乙基)-4-甲氧基-苯酚,3,6-二氢-4-甲基-2-苯基-2H-吡喃,2-(1,1-二甲基乙基)-4-甲氧基-苯酚,3,7-二甲基-2,6-辛二烯酸,2-甲基-2-丙酸2-苯基乙酯,四氢-2,4-二甲基-4-苯基-呋喃,丁酸2-苯氧基乙基酯,八氢-4,7-桥亚甲基-1H-茚-5-醇乙酸酯,羟基-十一酸内酯,2-甲基-3-(4-甲基苯基)-环氧乙烷羧酸乙酯,1,2-二(2-丙烯基氧基)-苯,2-呋喃丙酸3-甲基丁酯,2-羟基-苯甲酯丙酯,2-甲氧基萘,γ-亚甲基-苯丙醇乙酸酯,2-甲基-1,3-辛烯二醇二乙酸酯,2-壬烯酸,2,5,5-三甲基-2-苯基-1,3-二噁烷,3A,4,5,6,7,7A-六氢-4,7-桥亚甲基-1H-茚-6-醇丙酸酯,3-苯基-2-丙酸1-甲基乙基酯,2-甲基-(E)-2-丁酸2-苯基乙基酯,2,3-二甲基-2-丁酸苯基甲基酯,辛二酸二乙基酯,α-甲基-4-(1-甲基乙基)-苯丙醛,3A,4,5,6,7,7A-六氢-4,7-桥亚甲基-1H-茚-5-醇丙酸酯,[2-(1-丙氧基乙氧基)乙基]苯,3-苯基-2-丙酸丙基酯,(α-(2-甲基亚丙基)-苯乙醛,丁二酸二丁酯,3-苯基-丁酸2-丙烯基酯,3,4,4A,5,8,8A-六氢-3’,7-二甲基-螺[1,4-桥亚甲基萘-2(1H),2’-环氧乙烷],1-乙氧基-2-甲氧基-4-(1-丙烯基)-苯,5-(2-丙烯基)-1,3-苯并间二氧杂环戊烯,3,4,4A,5,8,8A-六氢-3’,6-二甲基-螺[1,4-桥亚甲基萘-2(1H),2’-环氧乙烷],4,6,6-三甲基-2-苯基-1,3-二噁烷,3-(1,1-二甲基乙基)-4-甲氧基-苯酚,2-乙氧基-5-(1-丙烯基)-苯酚,β,δ-二甲基-苯丁醇,3-苯基-2-丙酸2-丙烯基酯,2-羟基-5-甲基-苯甲酸乙酯,1,3-壬二酸二乙酯,[1,1’-二环己基]4-酮,β-甲基-苯戊醇,2,4,6-三甲基-4-苯基-1,3-二噁烷,四氢-2-甲基-4-亚甲基-6-苯基-2H-吡喃,6-(1-甲基乙基)-喹啉,3,6-二氢-4,6-二甲基-2-苯基-2H-吡喃,3,6-二氢-2,4-二甲基-6-苯基-2H-吡喃,(E)-丁酸3-苯基-2-丙烯基酯,4-(1-甲基乙基)-苯丙醛,β-甲基-苯戊醛,2,6,10,10-四甲基-1-氧杂螺[4.5]癸-6-醇,4-(1-乙氧基乙烯基)-3,3,5,5-四甲基-环己酮,9-癸烯酸,γ-甲基-苯戊醇,壬二酸二乙基酯,4-(1,1-二甲基乙基)-苯丙醛,8,8-二乙氧基-2,6-二甲基-2-辛醇,(Z)-3-甲基-5-苯基-2-戊烯腈,3-氧代-(E)-丁酸3,7-二甲基-2,6-辛二烯基酯,β-甲基-3-(1-甲基乙基)-苯戊醛,4-羟基-苯甲酸丙基酯,十一碳二酸二甲基酯,2,3-二氢-2-(1-甲基乙基)-1H-茚-1-酮,4,6,6-三甲基-2-(苯基甲基)-1,3-二噁烷,1-(5,6,7,8-四氢-2-萘基)-乙酮,苯己醇,壬二醇二乙酸酯,3-(4-甲氧基苯基)-2-丙酸丙基酯,2-甲氧基-1,1’-联苯,苯甲酸苯基酯,1,1’-[氧基二(亚甲基)]联苯,4-羟基-苯甲酸丁基酯,八氢-4,7-桥亚甲基-1H-茚-2-甲醇乙酸酯,八氢-4,7-桥亚甲基-1H-茚甲醇乙酸酯,[1,1’-联苯基]-2-醇,2-羟基-4-甲氧基-6-甲基苯甲酸乙酯,4,7-二甲氧基-5-(2-丙烯基)-1,3-苯并间二氧杂环戊烯,二苯基-甲酮(methanone),3-亚丁基-1(3H)-异苯并呋喃酮,2-呋喃羧酸2-苯基乙基酯,苯甲酸苯基甲基酯,2-己基-3-氧代-环戊羧酸甲基酯,2,2’-[二硫代二(亚甲基)]联呋喃,N-(苯基甲基)-苯甲胺,2-(2-苯基乙基)-吡啶,1,3-二苯基-2-丙酮,四氢-2-[2-甲氧基-4-(2-丙烯基)苯氧基]-2H-吡喃,苯乙酸2-甲氧基苯基酯,2-甲基-4-氧代-6-苯基-2-环己烯-1-羧酸乙酯,1,3-二苯基-2-丙烯-1-酮,(2-羟基-4-甲氧基苯基)苯基-甲酮,十二烷二酸,十三烷二酸,(E,E)-1-[5-(1,3-苯并间二氧杂环戊烯-5-基)-1-氧代-2,4-戊二烯基]-哌啶。
任选地,织物直接香料组分可选自:烯丙基环己烷丙酸酯、黄葵内酯、戊基苯甲酸酯、戊基肉桂酸酯、戊基肉桂醛、戊基肉桂醛二甲基缩醛、异戊基水杨酸酯、aurantiol(羟基香茅醛-甲基氨茴酸酯的商品名)、二苯酮、苄基水杨酸酯、异丁基喹啉、β-石竹烯、杜松烯、雪松醇、雪松基乙酸酯、雪松基甲酸酯、肉桂基肉桂酸酯、环己基水杨酸酯、仙客来醛、二氢异茉莉酸酯、二苯基甲烷、二苯基氧化物、十二内酯、iso E super(1-(1,2,3,4,5,6,7,8-八氢-2,3,8,8-四甲基-2-萘基)-乙酮的商品名)、亚乙基巴西酸酯、乙基甲基苯基缩水甘油酸酯、乙基十一碳烯酸酯、异-丁子香酚、十五内酯(15-羟基十五酸,内酯的商品名)、galaxolide(1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊-γ-2-苯并吡喃的商品名)、香叶基氨茴酸酯、十六内酯、己烯基水杨酸酯、己基肉桂醛、己基水杨酸酯、lilial(对叔丁基-α-甲基氢化肉桂醛的商品名)、里哪基苯甲酸酯、2-甲氧基萘、甲基肉桂酸酯、甲基二氢茉莉酸酯、β-甲基萘基酮、麝香二氢茚酮、麝香酮、麝香tibetine、肉豆蔻油醚、δ-壬内酯、氧基十六内酯-10(oxahexadecanolide)、氧基十六内酯-11、绿叶醇、phantolide(5-乙酰基-1,1,2,3,3,6-六甲基二氢化茚的商品名)、苯基乙基苯甲酸酯、苯基乙基苯基乙酸酯、苯基庚醇、苯基己醇、α-檀香醇、thibetolide(15-羟基十五烷酸,内酯的商品名)、tonalid、δ-十一烷酸内酯、γ-十一烷酸内酯、岩兰基乙酸酯、β-萘基甲基醚、烯丙基苯氧基乙酸酯、肉桂醇、肉桂醛、肉桂基甲酸酯、香豆素、二甲基苄基卡宾基乙酸酯、乙基肉桂酸酯、乙基香兰素(3-甲氧基-4-乙氧基苯甲醛)、丁子香酚、丁子香基乙酸酯、天芥菜精、吲哚、异丁子香酚、香芹酮、甲基-β-萘基酮、甲基肉桂酸酯、甲基二氢茉莉酸酯、β甲基萘基酮、甲基-N-甲基氨茴酸酯、δ-壬内酯、γ-壬内酯、对甲氧基苯乙酮(acetanisole)、苯氧基乙基异丁酸酯、苯氧基乙基丙酸酯、胡椒醛、三乙基柠檬酸酯、香兰素和它们的混合物。
用于本发明的其它织物直接香料组分包括甲基-N-甲基氨茴酸酯、苄基丁酸酯、苄基异戊酸酯、香茅基异丁酸酯、香茅基丙酸酯、δ-壬内酯、二甲基苄基卡宾基乙酸酯、十二烷醛、香叶草基乙酸酯、香叶草基异丁酸酯、γ-紫罗兰酮、对异丙基苯基乙醛、顺茉莉酮、甲基丁子香酚、羟基香茅醛、苯氧基乙醇、苄基异戊酸酯、茴香醛、枯醇、甲基丁子香酚和它们的混合物。
用于本发明的织物直接香料组分包括任何具有上述物理性质的前香味或前香料组分,或更挥发的香料物质与聚合物或其它织物直接分子的任何加合物或配合物。具体包括a-紫罗兰酮、b-紫罗兰酮、二氢-b-紫罗兰酮、g-甲基紫罗兰酮、a-异-甲基紫罗兰酮、4-(3,4-亚甲二氧基苯基)丁-2-酮、4-(4-羟基苯基)丁-2-酮、甲基b-萘基酮、甲基雪松基酮、6-乙酰基-1,1,2,4,4,7-六甲基四氢萘(tonalid)、1-香芹酮、5-环十六烯-1-酮、α-二氢大马酮、β-二氢大马酮、δ-二氢大马酮、β-大马酮、麝香酮、6,7-二氢-1,1,2,3,3-五甲基-4(5H)-二氢茚酮(cashmeran)、苯乙酮、癸酮、2-[2-(4-甲基-3-环己烯基-1-基)丙基]环戊烷-2-酮、2-仲-丁基环己酮、b-二氢紫罗兰酮、烯丙基紫罗兰酮、a-鸢尾酮、a-鲸蜡酮、a-irisone、acetanisole、香叶草基丙酮、1-(2-甲基-5-异丙基-2-环己烯基)-1-丙酮、乙酰基二异戊烯、甲基cyclocitrone、4-t-戊基环己酮、p-t-丁基环己酮、o-t-丁基环己酮、乙基戊基酮、乙基戊基酮、薄荷酮、甲基-7,3-二氢-2H-1,5-苯并dioxepine-3-酮、葑酮。(g)清除剂-本发明的组合物可含有按重量计至少约0.001%,优选约0.5%-约10%,最优选到约5%的一种或多种清除剂。适用于本文的清除剂选自选择用于捕获褪色染料和/或表面活性剂和/或污垢的清除剂。
优选的清除剂选自用于阴离子染料的固定剂、阴离子表面活性剂的络合剂、粘土污垢控制剂和它们的混合物。这些物质可以任何合适的比率混合使用。合适的化合物包括在Gosselink等的普通专利中,商业上由BASF、Ciba等获得。
i)用于阴离子染料的固定剂-染料固定剂,“固定物”或“固定剂”是已知的,商业上可获得的物质,它们通过将洗涤过程中由织物损失的染料降低到最低来改善染色织物的外观。未包括在定义中的是在某些实施方案中用于织物柔软剂活性物质的组分。
用于阴离子染料的许多固定剂是阳离子的,基于季氮化合物或基于在使用条件下就地形成的带有强阳离子电荷的含氮化合物。
固定剂可由若干供应商以不同商品名称获得。代表实例包括:由Crosfield获得的CROSCOLOR PMF(1981年6月,代号7894)和CROSCOLOR PMF(1988年1月,代号8544);由Sandoz获得的INDOSOLE-50(1984年2月27日,索引号6008.35.84;聚乙烯亚胺基);由Sandoz获得的SANDOFIX TPS是用于本文的优选染料固定剂。其它非限制实例包括由Sandoz获得的SANDOFIX SWE(阳离子树脂化合物),由CHT-Belilich GMBH获得的REWIN SRF,REWIN SRF-O和REWINDWR;由Giba-Geigy获得,在WO99/14301中描述的TinofixECO,TinofixFRD和Solfin。用于本发明组合物的其它优选固定剂是由Clariant获得的CARTAFIX CB,在WO99/14300中描述的环胺基聚合物、齐聚物或共聚物。
用于本文的其它固定剂在“Aftertreatments for Improving thefastness of Dyes on Textlie Fibres”,Christopher C.Cook,Rev.Prog.Coloration,Vol.XII,(1982)中描述。适用于本发明中的染料固定剂是铵化合物,例如脂肪酸二胺缩合物,尤其是二胺酯的盐酸盐,乙酸盐,甲硫酸盐和苄基盐酸盐。非限制实例包括油基二乙基氨基乙酰胺、油基甲基二亚乙二胺甲基硫酸盐和单硬脂基乙二胺三甲基铵甲基硫酸盐。此外,除表面活性剂活性N-氧化物之外的N-氧化物,尤其是聚合N-氧化物,例如聚乙烯基吡啶N-氧化物用作本文的固定剂。其它有用的固定剂包括聚烷基二胺的衍生物,聚胺-氰尿酰氯缩合物和胺化甘油二氯醇。
用于阴离子染料的固定剂可以完全与本发明的组合物成整体的形式,或通过以能够与含阳离子聚硅氧烷组合物一起加入洗涤的单独制品,例如基质制品或薄片的形式包括在本发明的洗衣处理方法而用于本发明的方法中。在该方法中,固定剂可补充阳离子聚硅氧烷组合物的使用。该染料固定制品和含阳离子聚硅氧烷的组合可以成套的形式出售。
ii)用于阴离子表面活性剂和/或污垢的清除剂-用于阴离子表面活性剂和/或污垢的合适清除剂包括烷氧基化聚乙烯亚胺和/或基季化衍生物。(h)织物柔软剂-当存在于本发明的优选组合物中时,织物柔软剂合适地为按组合物重量计至多约30%的含量,在某些实施方案中,更常见为约1%-约20%,优选约2%-约10%。用于本发明的合适织物柔软剂包括所有目前商业化的季长链柔软剂,尤其是具有改变的碘值的至少部分不饱和酯季(esterquat)。合适的织物柔软剂通常包括织物柔软化合物,它们是阳离子,水溶性的季铵化合物,含有极性头基和两个长烃基部分,优选选自烷基,烯基和它们的混合物,其中每个该烃基部分具有等于或大于C12,优选大于C14,更优选大于C16的平均链长。更优选的是,至少50%的每个长链烷基或链烯基主要是线性的。优选的总链长是约C18,尽管具有非零比例的低级,例如C14,C16和某些高级,例如C20链的链长混合物也是相当希望的。阳离子柔软剂合适地是二硬脂基二甲基氯化铵或它们的不饱和类似物,但对于环境更优选的是,选择可生物降解的季铵织物柔软剂。该性质在例如通常商业酯季织物柔软剂,例如二(牛油基氧基乙基)二甲基氯化铵中是存在的。
在一优选实施方案中,织物柔软化合物是带有两个经至少一个酯部分,优选两个该酯部分连接于季铵部分的C12-22烷基或链烯基的季铵酯季化合物。用于本发明组合物的优选酯季铵织物柔软剂具有下式:
{(R1)2N((CH2)nER2)2}+X-,其中每个R1基团独立地选自C1-4烷基、羟基烷基或C2-4链烯基;和其中每个R2独立地选自C8-28烷基或链烯基;E是酯部分,即-OC(O)-或-C(O)O-,n是0-5的整数,和X-是合适的阴离子,例如氯化物,甲基硫酸盐和它们的混合物。
第二优选类型的季铵物质可用下式表示:{(R1)3N(CH2)nCH(O(O)CR2)CH2O(O)CR2}+X-,其中每个R1基团独立地选自C1-4烷基、羟基烷基或C2-4链烯基;和其中每个R2独立地选自C8-28烷基或链烯基;n是0-5的整数,和X-是合适的阴离子,例如氯化物,甲基硫酸盐和它们的混合物。后一种类例如1,2二[硬牛油酰氧基]-3-三甲基铵丙烷氯化物。
通常可获得的酯季织物柔软剂包括除二酯外含有改变比例的单酯的物质。
本文合适的织物柔软剂包括在20℃软化水中测定的具有低于1×10-3wt%,更优选低于1×10-4wt%,更优选低于1×10-6wt%-1×10-8wt%的溶解度的柔软化合物。(i)洗涤酶-用于本文的合适洗涤酶包括蛋白酶、淀粉酶、纤维素酶、甘露聚糖酶、内葡聚糖、脂酶和它们的混合物。酶可以现有技术中教导的含量使用,例如以供应商,例如Novo和Genencor建议的含量。组合物中的典型含量为约0%-约5%,当存在酶时,它们可以非常低的含量使用,例如在本发明的某些实施方案中,约0.001%或更低;或它们可以较高含量,例如约0.1%或更高的含量用于本发明的重垢洗衣洗涤剂配方中。根据某些消费者对“非降解”洗涤剂的偏爱,本发明同时包括含酶和无酶实施方案。(j)螯合剂-用于本文的合适螯合剂包括含氮,无P氨基羧酸盐,例如EDDS、EDTA和DTPA;氨基膦酸盐,例如二亚乙三胺五亚甲基膦酸,例如HEDP;和含氮和氧,无P,无羧酸根螯合剂,例如普通种类的某些大环N-配合物的化合物,例如已知用于漂白催化剂体系的物质。螯合剂的含量通常为低于约5%,更常见的是,如果存在,螯合剂为约0.01%-约3%的含量。(k)溶剂体系-在本发明的组合物中的溶剂体系可以是无水或含水的;可包括单独的水或有机溶剂和水的混合物。优选有机溶剂包括1,2-丙二醇,乙醇,甘油和它们的混合物。也可使用其它低级醇,C1-C4链烷醇胺,例如单乙醇胺和三乙醇胺。溶剂体系可不存在,例如本发明的无水固体实施方案,但更常见的是,以约0.1%-约98%,优选至少约10%-约95%,更常用为约25%-约75%的含量存在。(1)泡腾体系-适用于本文的泡腾体系包括通过混合酸和碳酸氢盐或碳酸盐,或通过混合过氢化氢和催化酶或任何其它释放小气泡的物质的组合得到。泡腾体系的组分可以是组合可分散的以便在混合时形成泡腾,或可一起配制,其前提是使用常规的涂层或保护体系。泡腾体系的含量可广泛变化,例如泡腾组分总共为组合物的约0.1%-约30%。过氧化氢和催化酶是非常质量有效的,可以非常低的含量使用产生优异的效果。(m)涂覆或包胶囊剂-任何合适的涂覆或包胶囊剂可用于本发明组合物的全部或部分。合适实例包括聚乙烯基醇薄膜或其它合适的改变;羧基甲基纤维素,纤维素衍生物,淀粉,改性淀粉,糖,PEG,蜡或它们的组合。涂层可以有一个或多个涂层。用于任何物质涂覆的涂覆物质的数量按需涂覆或包胶囊的物质重量计在约5%-约50%的范围内。(n)添加剂的混合物-上述组分的混合物可以任何比例制备。(o)其它添加剂-其它合适洗涤添加剂物质的实例包括,但不限于,脂肪酸、烷氧基化苯甲酸或其盐,例如三甲氧基苯甲酸或其盐(TMBA),常规(非织物直接)香料和前香料、阴离子表面活性剂,包括,但不限于,线性烷基苯磺酸盐、烷基硫酸盐、烷基乙氧基硫酸盐和它们的混合物,还包括该表面活性剂的线性和支链(包括中链支链形式)、两性离子和/或两性表面活性剂、漂白剂、漂白活性剂、漂白催化剂、酶稳定体系、荧光增白剂或荧光剂、去污聚合物、分散剂或聚合有机助洗剂,包括水溶性聚丙烯酸酯,丙烯酸酯/马来酸酯共聚物等、抑泡剂、染料、着色剂、填料盐,包括硫酸钠、水溶助剂,例如甲苯磺酸盐、枯烯磺酸盐和萘磺酸盐、光活性剂、可水解表面活性剂、防腐剂、抗氧化剂、抗收缩剂、抗皱褶剂、杀菌剂、杀真菌剂、色斑、有色珠、球或挤压物、防晒剂、氟化合物、粘土、珠光剂、发光剂或化学发光剂、防腐蚀或应用保护剂、碱性源或其它pH调节剂、增溶剂、载体、加工助剂、颜料、游离基清除剂和pH控制剂。合适物质包括在US5705464、5710115、5698504、5695679、5686014和5646101。阳离子聚硅氧烷加入本发明组合物的过程
阳离子聚硅氧烷加入本发明的组合物的过程可以任何合适的方法进行,通常可包括任何顺序的混合或添加。然而,我们发现存在某些优选方法以完成该加入过程。
第一种方法包括将由制造商获得的阳离子聚硅氧烷聚合物直接加入最终组合物的两种或多种其它组分的预形成混合物中。这可在制备最终组合物的方法中的任何点进行,包括在配制过程的最末尾时。
第二种方法包括预混合阳离子聚硅氧烷聚合物与一种或多种最终组合物的添加剂,并将该预混合物加入其余添加剂的混合物中。
更具体的优选方法具有将阳离子聚硅氧烷聚合物与选自阳离子表面活性剂、阳离子织物柔软剂、胺表面活性剂、氧化胺表面活性剂、烷氧基化醇、织物直接香料组分和它们的混合物的添加剂混合的步骤,更优选在所使用的部分总有机溶剂存在下,随后是将得到的阳离子聚硅氧烷聚合物预混合物与一种或多种组合物的其他添加剂、水和余量的有机溶剂混合的步骤,从而得到最终组合物。
阳离子聚硅氧烷聚合物加入最终组合物的这些方法优选通过使用常规高剪切混合装置来协助,这确保阳离子聚硅氧烷聚合物在最终组合物中的合适分散。
本发明的液体组合物,尤其是液体洗涤剂组合物优选包含稳定剂,尤其优选三羟基硬脂精或氢化蓖麻油,例如作为Thixcin商业获得的类型。当稳定剂加入本发明组合物中时,优选作为与组合物的一种或多种添加剂或非聚硅氧烷组分的单独稳定剂预混合物加入。当该稳定剂预混合物使用时,优选在已加入阳离子聚硅氧烷聚合物,并分散在组合物中后加入组合物。
实施例
如下非限定性实施例举例说明本发明,百分数为按重量计,除非另有说明。
实施例1
本发明的液体织物护理组合物A-D制备如下:
A B C D
(Wt%) (Wt%) (Wt%) (Wt%)
C13-15EO7乙氧基化表面活性剂 20 20 0 0
C12-14氧化胺表面活性剂 5 5 0 0
HLAS 0 0 20 20
柠檬酸 6 6 0 0
C12-18脂肪酸 0 0 15 15
二亚乙三胺五亚甲基膦酸 0.4 0.4 0 0
羟基乙基二亚甲基膦酸 0.45 0.45 0 0
乙氧基化聚乙烯亚胺,m.w.1600 2.65 2.65 0 0
硼酸 2 2 0 0
CaCl2 0.02 0.02 0.02 0.02
丙二醇 18 18 20 20
乙醇 1 1 0 0
单乙醇胺 至pH8.5 至pH8.5 0 0
NaOH 0 0 至pH8.5 至pH8.5
蛋白酶 0.77 0.77 0 0
淀粉酶 0.06 0.06 0.06 0.06
纤维素酶 0.16 0.16 0.16 0.16
阳离子聚硅氧烷聚合物* 1.0 1.0 2.5 2.5
阳离子织物柔软剂** 0 2 0 0
阴离子染料固定剂*** 0 0 0 1
水 至100 至100 至100 至100
份 份 份 份*结构2,R1=甲基,R2=(CH2)3,X=CH2CHOHCH2,阳离子二价部分ii(a)与R4,R5,R6,R7均为甲基和Z1是(CH2)6,A=50%乙酸酯,50%月桂酸酯,重量基准;结构2的聚氧化烯部分(iii)是NHCH(CH3)CH2O(C2H4O)38(C3H6O)6CH2CH(CH3)NH;结构2的阳离子单价部分iv(a)具有均为甲基的R12,R13和R14;a=0;b=1;c=150;d=0;m=2。**由Goldschmidt获得的REWOQUAT V3620(二酯铵季)***由Clariant获得的CARTAFIX CB。
任一的这些组合物在家庭中用于洗涤衣服捆,具有优异的清洁和织物护理效果。
实施例2本发明的颗粒织物护理组合物制备如下:
A B
助洗剂
沸石 21.53 21.53
Na2CO3(总共) 33.12 33.12层状硅酸盐SKS6(Clariant) 4.50 4.50
硅酸盐(2比率) 0.12 0.12
聚合物丙烯酸/马来酸共聚物 2.43 2.43羧甲基纤维素钠 0.15 0.15
表面活性剂
LAS 9.95 9.95阳离子表面活性剂(C12-C14 1.99 1.99二甲基羟基乙基氯化铵)漂白剂/螯合剂体系
过硼酸钠四水合物 9.0 9.0
乙酰基乙二胺 1.63 1.63羟基次乙基二膦酸(60%) 0.21 0.21
MgSO4 0.41 0.41S,S′-乙二胺二琥珀酸 0.18 0.18
酶
Savinase(13KNPU) 0.45 0.45Termamyl(130KNU/g) 0.14 0.14Carezyme(1000sCEVU/g) 0.19 0.19
抑泡剂
聚硅氧烷抑泡剂 1.17 1.17
美观/微量组分
甲苯磺酸钠 1.0 1.0
皂 0.75 0.75
硫酸钠 22.24 22.24
---阳离子聚硅氧烷聚合物* 6.75 2.75
织物直接香料 0.2 0.5*结构1,R1=甲基,R2=(CH2)3,X=CH2CHOHCH2,Z1=N+(CH3)2C12-14;A=乙酸酯,a=0;b=1;c=82;d=0;n=2。
任一的这些组合物在家庭中用于洗涤衣服捆,具有优异清洁和织物护理效果。
实施例3本发明的液体织物护理组合物制备如下:
A
(Wt%)
Neodol23-5 15
C12-14氧化胺表面活性剂 5
Neodol35-7 2
柠檬酸 6
二亚乙三胺五亚甲基膦酸 0.4
羟基乙基二亚甲基膦酸 0.45
乙氧基化聚乙烯亚胺 1
季化乙氧基化六亚甲基二胺 2
硼酸 2
CaCl2 0.02
丙二醇 23
乙醇 0.58
单乙醇胺 至pH8
蛋白酶 0.74
淀粉酶 0.223
纤维素酶 0.014
甘露聚糖酶 0.28
Thixcin 1
抑泡剂 0.095
分散剂 0.019
Aerosil R812/非离子 0.086
织物直接香料 0.6
阳离子聚硅氧烷聚合物* 1.5
水 至100份
*如实施例1
该组合物在家庭中用于洗涤衣服捆,具有优异的清洁和织物护理效果。
实施例4
本发明的双部分组合物制备并加入双隔室容器中。在使用中,隔室A组合物和隔室B组合物在每种情况下同时由容器加入测量杯中,在混合时产生泡腾。在这些实施例中,隔室A组合物和隔室B组合物因此被分离,但可分散地混合。在另外一种分离但可分散混合实施中,隔室A组合物和隔室B组合物贮存在设计以隔室A组合物与隔室B组合物的重量比为4∶1输送的双隔室容器中,A和B由位于朝向双隔室包装底部的分散器龙头分散,它是重力输送的,不需要由顶部倾倒。在每种情况下(实施例4a和4b),由混合A和B产生的组合物用于洗涤衣服捆,具有优异清洁和织物护理效果。
实施例4a 实施例4b
%wt. %wt.隔室A组合物实施例1的阳离子聚硅氧烷 1 35乙氧基化C12-C15烷基醇 20 20C12烷基二甲基胺氧化胺 5 5NaHCO3 3 3二丙醇 5 5枯烯磺酸 5 5单乙醇胺 2.9(至pH8.5) 2.9(至pH8.5)增效剂,酶,香料 5 5隔室B组合物邻苯二甲酰亚胺基过氧己酸 0 17柠檬酸 30 30NaOH 7.3(至pH3.0) 7.3(至pH3.0)
实施例5
适用于洗涤精细织物的本发明的洗涤剂泡沫通过混合两种含水液体组合物,如上所述,包含在双隔室瓶中的隔室A组合物和隔室B组合物组合物制备。两种液体在剂量装置或直接在织物上混合时形成泡沫。
隔室A 隔室B
组合物 组合物
重量% 重量%C12-15烷基7-乙氧基化物 12 15C12烷基二甲基胺N-氧化物 3.5 0甲基-N-(2-羟基乙基)-N,N-二 7 0(牛油酰氧基乙基)甲基硫酸铵实施例1的阳离子聚硅氧烷聚合物 0.75 1.5柠檬酸钠 0 1.7过氧化氢 4.0 0Catalase 0 0.2乙醇 8 4丙二醇 4 4增效剂,少量组分,香料 1.0 2.5水 余量 余量PH 3.0 8.0
实施例6
本发明的重垢液体洗涤剂制备如下:组分 (Wt%) (Wt%)Neodol45-7 15-17 12-14Neodol25-3 0-1 0-1C12-14氧化胺表面活性剂 4-5 3-4C8-10酰氨基丙基二甲基胺 0-1 0-1柠檬酸 5 4二亚乙三胺五亚甲基磷酸 0.3-0.6 0.2-0.5羟基乙烷二亚甲基膦酸 0.2-0.5 0.2-0.4乙氧基化聚乙烯亚胺 1 0.8-1季化乙氧基化六亚甲二胺 2 1.6硼酸 2.0-3.0 1.5-2.5CaCl2 0.02 0.02丙二醇 8.0-9.5 6.0-8.0乙醇 0-1 0-11,4环己烷二甲醇 0-2 0-2单乙醇胺 至pH8 至pH8蛋白酶 0.74 0.59淀粉酶 0.223 0.178纤维素酶 0.014 0.011甘露聚糖酶 0.05-0.28 0.04-0.22Thixcin(氢化蓖麻油) 0.5-1.0 0.5-1.0聚硅氧烷抑泡剂 0-0.1 0-0.1用作抑泡剂的聚硅氧烷分散剂 0-0.02 0-0.02分散的氧化硅/非离子 0-0.09 0-0.09织物直接香料 0.5-0.8 0.4-0.7实施例1的阳离子聚硅氧烷聚合物 1.0-1.5 1.0-1.5染料 0.001 0.001水 至100份 至100份吸水性和/或穿着合适优点
出乎意料的是,在优异穿着舒适和/或吸水性方面,尤其与基于二牛脂基二甲基氯化铵的常规织物柔软剂相比,本组合物被发现提供附加的织物护理效果,吸收性相等于最近开发的透明液体织物柔软剂。产品使用指导
本发明的组合物优选包括在产品中,产品优选包括本发明的织物护理组合物,并包括使用产品的指导,通过使需要处理的织物与有效量的组合物接触洗涤织物,使得组合物影响织物的一种或多种所需的织物护理效果。
因此,本发明还包括与含有本文组合物的包装一起的有关本发明织物护理组合物的使用说明或其它形成的有关组合物销售或使用的广告。说明可以任何消费者产品生产或供应公司使用的常见方法包括。实例包括在保存组合物的容器上所附的标签上提供指导;在容器所附的或在出售时附的纸上或在与使用的销售或使用相关联的广告,宣传和/或其它书面或口头指导。
具体地说,指导将包括组合物的使用说明,例如在洗衣机中使用组合物以清洁织物所要求的数量;施用于织物所要求的数量;是否需要浸泡或搓洗。服务商业应用
任何上述体系、组合物和方法可用于洗衣服务企业,例如在干洗企业,公共机构洗衣(例如学校、旅馆或军队野外洗衣)或类似情况,不违背本发明的精神和范围。
虽然描述了本发明的具体实施方案,但对本领域技术人员而言,可进行本发明的各种改变和改性而不违背本发明的精神和范围,在所附的权利要求书中,我们打算覆盖在本发明范围内的所有这种改性。
Claims (8)
1、用于家庭洗衣的织物护理组合物,其含有:
(I)阳离子聚硅氧烷聚合物,其含有一个或多个聚硅氧烷单元和一个或多个季氮部分和
(II)一种或多种洗衣添加剂,其选自:
(a)稳定剂,优选增稠稳定剂,更优选结晶含羟基稳定剂,仍更优选三羟基硬脂精、氢化油或它们的变体;
(b)无氮非离子表面活性剂;
(c)含氮洗涤表面活性剂,优选选自阳离子含氮洗涤表面活性剂,氧化胺表面活性剂、胺和酰胺官能化的洗涤表面活性剂(包括脂肪酰氨烷基胺)和它们的混合物;
(d)偶合剂,优选选自脂肪胺、1,4-环己烷二甲醇和它们的混合物;
(e)洗涤剂助洗剂,优选选自水溶性有机助洗剂;
(f)织物直接香料;
(g)清除剂,选自捕获褪色染料和/或阴离子表面活性剂和/或污垢,所述清除剂选自阴离子染料固定剂、阴离子表面活性剂的配合剂、粘土污垢控制剂和它们的混合物;
(h)织物柔软剂;
(i)洗涤酶;
(j)螯合剂;
(k)溶剂体系;
(l)泡腾体系;
(m)涂覆或包胶囊剂和
(n)它们的混合物。
2、权利要求1的组合物,其中阳离子聚硅氧烷聚合物具有下式:其中:-R1独立地选自C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基和它们的混合物;-R2独立地选自可含有一个或多个氧原子的二价有机部分;-X独立地选自开环环氧化物;-R3独立地选自下式的聚醚基团:
-M1(CaH2aO)b-M2
其中M1是二价烃残基;M2是H、C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基;环烷基、C1-22羟基烷基、聚环氧烷或(聚)烷氧基烷基;-Z独立地选自含有至少一个季氮原子的单价有机部分;-a是2-4;-b是0-100;-c是1-1000,优选大于20,更优选大于30,甚至优选大于50,优选小于500,更优选小于300,甚至优选小于200,最优选70-100;-d是0-100;-n是与阳离子聚硅氧烷聚合物有关的正电荷数目,它是大于或等于2;和-A是单价阴离子;优选Z独立地选自如下基团:
(v)单价芳族或脂族杂环基团,取代或非取代的,含有至少一个季氮原子;其中:-R12、R13、R14是相同或不同的,选自:C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基;聚环氧烷;(聚)烷氧基烷基和它们的混合物;-R15是-O-或NR19;-R16是二价烃基残基;-R17、R18、R19是相同或不同的,选自:H、C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基;聚环氧烷;(聚)烷氧基烷基和它们的混合物;和-e是1-6。
3、权利要求1的组合物,其中阳离子聚硅氧烷聚合物由如下交替单元组成:
(i)下式的聚硅氧烷:和
(ii)含有至少两个季氮原子的二价有机部分;其中:-R1独立地选自C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基和它们的混合物;-R2独立地选自可含有一个或多个氧原子的二价有机部分;-X独立地选自开环环氧化物;-R3独立地选自下式的聚醚基团:
-M1(CaH2aO)b-M2
其中M1是二价烃残基;M2是H、C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基;环烷基、C1-22羟基烷基、聚环氧烷或(聚)烷氧基烷基;-a是2-4;-b是0-100;-c是1-1000,优选大于20,更优选大于30,甚至优选大于50,优选小于500,更优选小于300,甚至优选小于200,最优选70-100;和-d是0-100。
4、权利要求1的组合物,其中阳离子聚硅氧烷聚合物由如下交替单元组成:
(i)下式的聚硅氧烷:和
(ii)选自如下的阳离子二价有机部分:
(d)二价芳族或脂族杂环基团,取代或非取代的,含有至少一个季氮原子;和
(iii)任选地下式的聚环氧烷:
[Y-O-(CaH2aO)b-Y];和
(iv)任选地用作端基的阳离子单价有机部分,其选自:(v)单价芳族或脂族杂环基团,取代或非取代的,含有至少一个季氮原子;其中:-R4、R5、R6、R7、R8、R9、R10、R11是相同或不同的,选自:C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基、聚环氧烷、(聚)烷氧基烷基和它们的混合物;或其中R4和R6,或R5和R7,或R8和R10,或R9和R11可以是桥接亚烷基的部分;-R12、R13、R14是相同或不同的,选自:C1-22烷基、C2-22链烯基、C6-22烷基芳基、C1-22羟基烷基、聚环氧烷、(聚)烷氧基烷基和它们的混合物;和-R15是-O-或NR19;-R16和M1是相同或不同的二价烃基残基;-R17、R18、R19是相同或不同的,选自:H、C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基;聚环氧烷、(聚)烷氧基烷基和它们的混合物;和-Z1和Z2是相同或不同的带有至少2个碳原子的二价烃基,并任选地含有羟基,它可以被一个或几个醚、酯或酰胺基团分隔;-Y是仲或叔胺;-e是1-6;-m是与阳离子二价有机部分有关的正电荷数目,它是大于或等于2;和-A是阴离子。
5、权利要求1的组合物,其中阳离子聚硅氧烷聚合物具有下式:其中:-R1独立地选自C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基和它们的混合物;-R2独立地选自可含有一个或多个氧原子的二价有机部分;-X独立地选自开环环氧化物;-R3独立地选自下式的聚醚基团:
-M1(CaH2aO)b-M2
其中M1是二价烃残基;M2是H、C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基、聚环氧烷或(聚)烷氧基烷基;-X独立地选自开环环氧化物;-W独立地选自含有至少一个季氮原子的二价有机部分;-a是2-4;-b是0-100;-c是1-1000,优选大于20,更优选大于30,甚至优选大于50,优选小于500,更优选小于300,甚至优选小于200,最优选70-100;-d是0-100;-n是与阳离子聚硅氧烷聚合物有关的正电荷数目,它是大于或等于1;和-A是单价阴离子,换句话说,合适的抗衡离子;优选其中W选自如下基团:
(d)二价芳族或脂族杂环基团,取代或非取代的,含有至少一个季氮原子;和-R4、R5、R6、R7、R8、R9、R10、R11是相同或不同的,选自:C1-22烷基、C2-22链烯基、C6-22烷基芳基、芳基、环烷基、C1-22羟基烷基、聚环氧烷、(聚)烷氧基烷基和它们的混合物;或其中R4和R6,或R5和R7,或R8和R10,或R9和R11可以是桥接亚烷基的部分;和-Z1和Z2是相同或不同的带有至少2个碳原子的二价烃基,并任选地含有羟基,它可以被一个或几个醚、酯或酰胺基团分隔。
6、上述任一权利要求的组合物降低和/或避免织物载污体收缩和/或给予织物载污体织物手感效果和/或形状保持效果和/或形状恢复和/或弹性和/或易于熨烫效果和/或香味效果的用途。
7、处理需要处理的载污体的方法,其包括使载污体与权利要求1的织物护理组合物接触从而处理载污体的步骤。
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GB9804725D0 (en) | 1998-03-05 | 1998-04-29 | Unilever Plc | Shampoo compositions |
GB9804720D0 (en) | 1998-03-05 | 1998-04-29 | Unilever Plc | Shampoo compositions |
EP0971025A1 (en) | 1998-07-10 | 2000-01-12 | The Procter & Gamble Company | Amine reaction compounds comprising one or more active ingredient |
US6426328B2 (en) | 1998-10-27 | 2002-07-30 | Unilever Home & Personal Care, Usa Division Of Conopco Inc. | Wrinkle reduction laundry product compositions |
DE19853720A1 (de) | 1998-11-20 | 2000-05-25 | Henkel Kgaa | Allzweckreiniger mit diquaternärem-Polysiloxan |
US6134810A (en) | 1999-03-18 | 2000-10-24 | Stockley; Philip E. | Washing machine insert |
DE60038797D1 (de) | 1999-05-21 | 2008-06-19 | Unilever Nv | Textilweichmacherzusammensetzungen und verfahren zur stabilisierung von textilweichmacherzusammensetzungen |
CA2279738A1 (en) † | 1999-08-04 | 2001-02-04 | Opal Limited | Ventilated footwear |
DE19944416A1 (de) | 1999-09-16 | 2001-03-22 | Henkel Kgaa | Klarspülmittel |
EP1116813A1 (en) * | 2000-01-10 | 2001-07-18 | Dow Corning Corporation | Hydrophilic softener for textiles comprising epoxy glycol siloxane polymers and amine funtional materials |
US7041767B2 (en) | 2000-07-27 | 2006-05-09 | Ge Bayer Silicones Gmbh & Co. Kg | Polysiloxane polymers, method for their production and the use thereof |
US6903061B2 (en) | 2000-08-28 | 2005-06-07 | The Procter & Gamble Company | Fabric care and perfume compositions and systems comprising cationic silicones and methods employing same |
DE10051258A1 (de) | 2000-10-16 | 2002-04-25 | Goldschmidt Rewo Gmbh & Co Kg | Verwendung von quaternären Polysiloxanen in Waschmittelformulierungen |
AU2002223648A1 (en) | 2000-10-31 | 2002-05-15 | Unilever Plc | Personal cleansing composition |
CN100335030C (zh) | 2002-06-04 | 2007-09-05 | 宝洁公司 | 包含氨基硅氧烷的调理洗发剂 |
-
2001
- 2001-08-23 US US09/935,927 patent/US6903061B2/en not_active Expired - Lifetime
- 2001-08-24 AU AU8670901A patent/AU8670901A/xx active Pending
- 2001-08-24 AU AU2001286709A patent/AU2001286709B2/en not_active Ceased
- 2001-08-24 MX MXPA03001789A patent/MXPA03001789A/es active IP Right Grant
- 2001-08-24 ES ES01966172T patent/ES2273881T5/es not_active Expired - Lifetime
- 2001-08-24 BR BR0113586-4A patent/BR0113586A/pt not_active IP Right Cessation
- 2001-08-24 DE DE60123811T patent/DE60123811T3/de not_active Expired - Lifetime
- 2001-08-24 WO PCT/US2001/026444 patent/WO2002018528A1/en active IP Right Grant
- 2001-08-24 JP JP2002524031A patent/JP4926366B2/ja not_active Expired - Fee Related
- 2001-08-24 KR KR1020037003134A patent/KR100558603B1/ko not_active IP Right Cessation
- 2001-08-24 CA CA002417654A patent/CA2417654C/en not_active Expired - Lifetime
- 2001-08-24 AT AT01966172T patent/ATE342331T1/de not_active IP Right Cessation
- 2001-08-24 CZ CZ2003561A patent/CZ2003561A3/cs unknown
- 2001-08-24 CN CNB018178111A patent/CN100422300C/zh not_active Expired - Fee Related
- 2001-08-24 EP EP01966172A patent/EP1313828B2/en not_active Expired - Lifetime
- 2001-08-27 AR ARP010104077A patent/AR033563A1/es active IP Right Grant
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2005
- 2005-01-21 US US11/040,038 patent/US7384903B2/en not_active Expired - Lifetime
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1296127C (zh) * | 2004-12-28 | 2007-01-24 | 中国日用化学工业研究院 | 一种含葡糖酰胺基的二聚三硅氧烷表面活性剂及制法 |
CN101117386B (zh) * | 2006-07-31 | 2011-09-28 | 赢创高施米特有限公司 | 含有季铵基团的新型聚硅氧烷、其制备方法以及作为纺织品柔软剂的用途 |
CN101765687B (zh) * | 2006-12-15 | 2013-07-24 | 陶氏康宁公司 | 用于纺织品处理的粒状材料 |
CN102614807A (zh) * | 2012-03-07 | 2012-08-01 | 中国日用化学工业研究院 | 一种二聚含四硅氧烷糖基表面活性剂及合成方法 |
CN104508013A (zh) * | 2012-07-27 | 2015-04-08 | 宝洁公司 | 包含有机聚硅氧烷调理聚合物的吸收制品 |
CN104508012A (zh) * | 2012-07-27 | 2015-04-08 | 宝洁公司 | 有机聚硅氧烷聚合物 |
CN104508014B (zh) * | 2012-07-27 | 2017-04-05 | 宝洁公司 | 有机聚硅氧烷聚合物 |
CN104508012B (zh) * | 2012-07-27 | 2017-05-24 | 宝洁公司 | 有机聚硅氧烷聚合物 |
CN105377955A (zh) * | 2013-07-29 | 2016-03-02 | 宝洁公司 | 支链的嵌段阳离子有机聚硅氧烷 |
CN105408398A (zh) * | 2013-07-29 | 2016-03-16 | 宝洁公司 | 嵌段阳离子有机聚硅氧烷 |
CN110106710A (zh) * | 2019-05-29 | 2019-08-09 | 苏州大学 | 一种多功能织物整理剂及其制备方法与应用 |
CN110106710B (zh) * | 2019-05-29 | 2021-06-18 | 苏州大学 | 一种多功能织物整理剂及其制备方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
US6903061B2 (en) | 2005-06-07 |
ES2273881T3 (es) | 2007-05-16 |
AU8670901A (en) | 2002-03-13 |
US7384903B2 (en) | 2008-06-10 |
AR033563A1 (es) | 2003-12-26 |
CA2417654C (en) | 2009-10-06 |
KR100558603B1 (ko) | 2006-03-13 |
US20050164900A1 (en) | 2005-07-28 |
CN100422300C (zh) | 2008-10-01 |
ES2273881T5 (es) | 2010-03-17 |
KR20030067663A (ko) | 2003-08-14 |
WO2002018528A1 (en) | 2002-03-07 |
EP1313828A1 (en) | 2003-05-28 |
EP1313828B1 (en) | 2006-10-11 |
JP2005513278A (ja) | 2005-05-12 |
CA2417654A1 (en) | 2002-03-07 |
ATE342331T1 (de) | 2006-11-15 |
JP4926366B2 (ja) | 2012-05-09 |
US20020103094A1 (en) | 2002-08-01 |
DE60123811D1 (de) | 2006-11-23 |
BR0113586A (pt) | 2003-07-22 |
DE60123811T3 (de) | 2010-05-20 |
CZ2003561A3 (cs) | 2003-06-18 |
AU2001286709B2 (en) | 2005-10-06 |
EP1313828B2 (en) | 2009-10-14 |
DE60123811T2 (de) | 2007-08-23 |
MXPA03001789A (es) | 2003-06-04 |
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