CN1046955C - Detergent composition for inhibiting dye transfer - Google Patents

Detergent composition for inhibiting dye transfer Download PDF

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Publication number
CN1046955C
CN1046955C CN 94193285 CN94193285A CN1046955C CN 1046955 C CN1046955 C CN 1046955C CN 94193285 CN94193285 CN 94193285 CN 94193285 A CN94193285 A CN 94193285A CN 1046955 C CN1046955 C CN 1046955C
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alkyl
detergent composition
preferably
acid
surfactants
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CN 94193285
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Chinese (zh)
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CN1130400A (en )
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A·布殊
A·C·康文斯
P·J·范卢文
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普罗格特-甘布尔公司
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/168Organometallic compounds or orgometallic complexes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite, attapulgite
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles, amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam

Abstract

本发明涉及一种洗涤剂组合物,它含有一种选自N-乙烯基咪唑和N-乙烯基吡咯烷酮的共聚物的聚合物,其特征为所说的聚合物的平均分子量在5,000至50,000范围内。 The present invention relates to a detergent composition, which comprises a vinylimidazole and N- vinylpyrrolidone copolymer is selected from N- polymer, wherein said polymer of an average molecular weight in the range of 5,000 to 50,000 Inside.

Description

抑制染料转移的洗涤剂组合物 The detergent compositions inhibiting dye transfer

发明领域本发明涉及一种在洗涤过程中抑制染料在织物之间转移的组合物及其实施方法。 Field of the Invention The present invention relates to a composition and method embodiments dye transfer between fabrics during washing suppressed. 更具体地说,本发明涉及一种洗涤剂组合物,它含有低平均分子量的N-乙烯基咪唑N-乙烯基吡咯烷酮的共聚物。 More particularly, the present invention relates to a detergent composition containing N- vinylimidazole N- vinylpyrrolidone copolymers of low average molecular weight.

发明背景在近代织物洗涤操作过程中遇见的最顽固和麻烦的问题之一,是一些染色的织物倾向于把染料释出到洗涤溶液中,然后转移到与它一起洗涤的其它织物上。 One of the most persistent and troublesome problems encountered during BACKGROUND OF THE INVENTION Modern fabric laundering operation, the fabric is dyed several tend to release the dye into the wash solution, and then transferred onto other fabrics being washed along with it.

克服这一问题的一种方法是在洗涤时在这些染料有机会连接到其它物品之前,把这些从染色织物上洗下来的易褪色的染料络合或吸附掉。 One approach to overcome this problem at the time of washing before these dyes have the opportunity to connect to other articles, these washing of dyed fabrics from fugitive dye complex or adsorb off.

已经在洗涤剂组合物中使用一些聚合物来抑制染料的转移。 Some polymers have been used in detergent compositions to inhibit dye transfer.

这些聚合物中的一种类型是N-乙烯基咪唑的均聚或共聚物,所说的这类聚合物的实例已在涉及洗涤剂组合物的先有技术诸如DE2814287-A中被描述过,组合物中含有0.1至10%(重量)的水溶性或可在水中分散的N-乙烯基咪唑的均聚物或共聚物,以及一些阴离子和/或非离子型的表面活性剂和其它洗涤剂组分。 One type of such polymers are N- vinylimidazole homo or copolymers, said polymers are examples of such detergent compositions involving the prior art, such as DE2814287-A are described, composition contains 0.1 to 10% (by weight) soluble or dispersible in water N- vinylimidazole homo- or copolymer, and a number of anionic and / or nonionic surfactants and other detergent components. EP372291涉及一种洗涤容易脱色的纺织物的方法,这种洗涤液中含有阴离子/非离子表面活性剂以及水溶性的聚合物,例如(共)聚合的N-乙烯基咪唑、N-乙烯基噁唑烷酮或N-乙烯基吡咯烷酮。 EP372291 relates to a bleaching of the textile easily washed way, this washing solution containing an anionic / nonionic surfactants and watersoluble polymers e.g. (co) polymerization of N- vinylimidazole, N- vinyl evil oxazolidone or N- vinyl pyrrolidone. EP327927描述了一种颗粒状的洗涤剂添加剂,其中含有的水溶性聚合物是基于N-乙烯基吡咯烷酮和/或N-乙烯基咪唑和/或N-乙烯基噁唑烷酮以及一些阳离子型化合物。 EP327927 describes a granular detergent additive comprising water-soluble polymer which is based on N- vinylpyrrolidone / vinylimidazole N- and / or N- and some vinyloxazolidone and cationic compounds or . 转让给Henkel的DE4027832-A公开了一种不含电解质的液体洗涤剂组合物,其中含有沸石A、非离子型表面活性剂以及抑制染料转移的聚合物。 , Assigned to Henkel, DE4027832-A discloses a liquid detergent composition which does not contain an electrolyte, which contains zeolite A, nonionic surfactants and dye transfer inhibiting polymers. 这种抑制染料转移的聚合物是选自N-乙烯基吡咯烷酮和/或N-乙烯基咪唑和/或N-乙烯基噁唑烷酮的均聚和共聚物。 Such dye transfer inhibiting polymers are vinyl pyrrolidone and / or N- vinylimidazole / homo- and copolymers and vinyl-oxazolidone or N- selected from N-.

这些先有技术文件中描述的用作抑制染料转移的聚合物,具有的平均分子量在10.000至1.000,000范围内。 These prior art documents described as dye transfer inhibiting polymers having an average molecular weight in the range of 10.000 to 1.000,000. 所描述的经优选的N-乙烯基咪唑共聚物的分子量为20,000至200,000。 N- vinylimidazole the molecular weight by the described preferred from 20,000 to 200,000.

不幸,用所说的N-乙烯基咪唑共聚物配制的洗涤剂组合物的整体洗涤性能,由于所说的这类聚合物的存在而受到影响。 Unfortunately, cleaning performance of said N- vinylimidazole detergent compositions formulated with the whole, due to the presence of said polymers is affected. 结果,配方设计师为提供具有优良的整体洗涤性能的洗涤剂组合物而面临着困难的工作。 As a result, the detergent formulator to provide a composition having excellent overall detergency performance of work and faced with difficulties.

现已发现,选自N-乙烯基咪唑的共聚物在消除溶解或悬浮的染料的转移、同时使得用它配制成的洗涤剂组合物的整体洗涤性能没有负面影响方面是很有效的。 It has been found, selected from N- vinylimidazole to eliminate transfer dye dissolved or suspended while it makes cleaning performance of detergent compositions formulated with no negative impact on the overall aspect is very effective in.

这一发现允许人们配制出呈现优良的洗涤性能和抑制染料转移性能的洗涤剂组合物。 This discovery allows one to formulate exhibit excellent cleaning performance and transfer performance of detergent compositions inhibiting dye.

按照本发明的另外的实施方案,本发明也提供一种涉及染色织物的洗涤操作的方法。 According to a further embodiment of the present invention, the present invention also provides a method for laundering dyed fabrics according to the operation.

发明概述本发明涉及一种洗涤剂组合物,它含有一种选自N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物的聚合物,其特征为所说的聚合物具有的平均分子量在5,000至50,000范围内。 SUMMARY The present invention relates to a detergent composition, which comprises a vinylimidazole N- vinylpyrrolidone copolymer is a polymer selected from N-, wherein said polymer has an average molecular weight of 5,000 to 50,000 range.

发明详述N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物本发明涉及的洗涤剂组合物含有一种选自N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物的聚合物,其特征为所说的聚合物具有5,000至50,000的平均分子量,更优选的是8,000至30,000的平均分子量,最优选的是10,000至20,000的平均分子量。 DETAILED DESCRIPTION N- vinylimidazole N- vinylpyrrolidone copolymer of the present invention relates to detergent compositions containing one N- vinylimidazole N- vinylpyrrolidone copolymers selected polymer, wherein said polymer has an average molecular weight of from 5,000 to 50,000, more preferably an average molecular weight of 8,000 to 30,000, most preferably from 10,000 to 20,000.

已经令人惊奇地发现,通过选择特定的5,000至50,000,更优选的是3,000至30,000,最优选的是10,000至20,000范围内的平均分子量,能够得到含有所说的共聚物的具有优良整体洗涤性能的洗涤剂组合物。 It has surprisingly been found that by selecting a particular from 5,000 to 50,000, more preferably 3,000 to 30,000, most preferably an average molecular weight range of 10,000 to 20,000, said copolymer containing can be obtained having excellent overall detergency performance detergent compositions. 这一平均分子量范围是用Barth HG和Mays JW在Chemical Analysis Vol.113“Modern Methods of PolymerCharacterization”中所叙述的光散射方法来测定的。 The average molecular weight range is in Barth HG and Mays JW light scattering Chemical Analysis Vol.113 "Modern Methods of PolymerCharacterization" determined as described in the.

其特征为具有所说的平均分子量范围的N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物可提供具有优良的抑制染料转移的性质,同时不会给用它配制的洗涤剂组合物的洗涤性能带来负面的影响。 Characterized N- vinylimidazole N- vinylpyrrolidone copolymers have an average molecular weight range of said properties can provide excellent dye transfer inhibition, but will not give as its cleaning performance of detergent compositions formulated tape to negative effects.

此外,已经发现,一些洗涤剂组分的洗涤性能由于存在所说的本发明的N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物而得到强化。 Further, it has been found that some detergent ingredients due to the wash performance N- vinylimidazole N- vinylpyrrolidone copolymers according to the present invention, the presence of said reinforced obtained.

在本发明的N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物中,N-乙烯基咪唑对N-乙烯基吡咯烷酮的摩尔比率为1至0.2。 At the N- vinylimidazole N- vinylpyrrolidone copolymer of the present invention, N- vinylimidazole to N- vinylpyrrolidone from 1 to 0.2 molar ratio. 更优选的是0.8至0.3,最优选的是0.6至0.4。 And more preferably from 0.8 to 0.3, most preferably 0.6 to 0.4.

这种N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物可以是线型的或带支链的。 Such N- vinylimidazole N- vinylpyrrolidone copolymers can be linear or branched. 存在于洗涤剂组合物中的N-乙烯基咪唑N-乙烯基吡咯烷酮的含量,基于洗涤剂组合物的重量计算为0.01至10%,更优选的是0.05至5%,最优选的是0.1%至1%。 The content of N- vinylimidazole N- vinylpyrrolidone present in the detergent composition, based on the calculated weight of the detergent composition is from 0.01 to 10%, more preferably 0.05 to 5%, most preferably 0.1% to 1%. 洗涤剂组分除N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物以外,本发明的组合物还含有一种表面活性剂体系,其中的表面活性剂可以选自非离子型和/或阴离子型和/或阳离子型和/或两性的和/或两性离子型和/或半极性型的表面活性剂。 The detergent components other than N- vinylimidazole N- vinylpyrrolidone copolymer composition of the present invention further contains a surfactant system wherein the surfactant can be selected from nonionic and / or anionic and / or cationic and / or amphoteric and / or zwitterionic and / or semipolar surfactant.

本发明使用的表面活性剂本系中作为表面活性剂,优选含有一种或多种这里所叙述的非离子型表面活性剂。 Based surfactants of the present invention for use as a surfactant, preferably comprising one or more non-ionic surfactants described herein. 这些非离子型表面活性剂已发现是非常有用的,因为在所说的表面活性剂存在时可增加N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物抑制染料转移的性能。 These nonionic surfactants have found to be very useful, because in the presence of said surfactant can increase the N- vinylimidazole N- vinylpyrrolidone copolymers dye transfer inhibiting properties. 非离子型表面活性剂聚环氧乙烷、聚环氧丙烷和聚环氧丁烷与烷基酚类的缩合物都可用作本发明的表面活性剂体系中的非离子型表面活性剂,其中优选的是聚环氧乙烷的缩合物。 Nonionic surfactants, polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkyl phenols are useful as nonionic surfactants of the surfactant system of the present invention, preferred among these are polyethylene oxide condensates. 这些化合物包括所带有的烷基中含有大约6至大约14个碳原子、优选的是含有大约8至14个碳原子,既可以是直链也可以是支链构型的烷基酚类与亚烷基氧化物的缩合产物。 These compounds include alkyl groups carried by containing from about 6 to about 14 carbon atoms, preferably contains from about 8 to 14 carbon atoms, may be straight chain or a branched chain configuration with alkylphenols condensation products of an alkylene oxide. 在一个优选的实施方案中,与每摩尔烷基酚对应存在的环氧乙烷的量,等于大约2至大约25摩尔,更优选的是大约3至大约15摩尔。 In a preferred embodiment, the amount of ethylene oxide per mole of alkyl phenol in the presence of the corresponding, equal to about 2 to about 25 moles, more preferably from about 3 to about 15 moles. 市场上能买到的这种类型的非离子表面活性剂,包括IgepalTMCO-630,是GAF Corporation出售的;还有TritonTMX-45、X-114、X-100和X-102,都是Rohm & Haas公司出售的。 Commercially available this type of nonionic surfactant, including IgepalTMCO-630, is the GAF Corporation; and TritonTMX-45, X-114, X-100 and X-102, all Rohm & amp; Haas company. 这些表面活性剂通常被称为烷基酚烷氧化物(例如烷基酚乙氧化物)。 These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).

伯和仲脂肪醇类与大约1至大约25摩尔环氧乙烷的缩合产物,也适宜于用作本发明的非离子表面活性剂体系中的非离子表面活性剂。 Primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide condensation products, also suitable non-ionic surfactants of the present invention as nonionic surfactant system. 脂肪醇的烷基链既可以是直链的也可以是带支链的,可以是伯醇或仲醇,并一般含有大约8至大约22个碳原子。 The fatty alkyl chain may be a straight chain or may be branched, primary or secondary alcohol, and generally contains from about 8 to about 22 carbon atoms. 优选的醇的缩合产物是其中的烷基含有大约8至大约20个碳原子,更优选的是烷基含有大约10至大约18个碳原子,并且每摩尔醇与大约2至大约10摩尔环氧乙烷缩合的产物。 Preferably condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably an alkyl group containing from about 10 to about 18 carbon atoms, per mole of alcohol and from about 2 to about 10 moles of ethylene ethane the condensation product. 市场上可买到的这种类型的非离子表面活性剂的实例包括TergitolTM15-S-9(C11-C15线型醇与9摩尔环氧乙烷缩合的产物),TergitolTM24-L-6 NMW(C12-C14伯醇与6摩尔环氧乙烷缩合的产物,并具有很狭窄的分子量分布),两种商品均由Union Carbide Corporation出售;还有Shell ChemicalCompany出售的NeodolTM45-9(C14-C15线型醇与9摩尔环氧乙烷缩合的产物),NeodolTM23-6.5(C12-C13线型醇与6.5摩尔环氧乙烷缩合的产物),NeodolTM45-7(C14-C15线型醇与7摩尔环氧乙烷缩合的产物),NeodolTM45-4(C14-C15线型醇与4摩尔环氧乙烷缩合的产物),以及Procter & Gamble Company出售的KyroTMEOB(C13-C15醇与9摩尔环氧乙烷缩合的产物)。 Examples of this type on the market of non-ionic surfactants include commercially available TergitolTM15-S-9 (product of C11-C15 linear alcohol condensed with 9 moles of ethylene oxide), TergitolTM24-L-6 NMW (C12 -C14 primary alcohol with 6 moles ethylene oxide condensation product, and having a very narrow molecular weight distribution), both commodities sold by Union Carbide Corporation; sold by Shell ChemicalCompany there NeodolTM45-9 (C14-C15 linear alcohol with the product of 9 moles of ethylene oxide), NeodolTM23-6.5 (C12-C13 linear alcohol with 6.5 moles of ethylene oxide condensation product), NeodolTM45-7 (C14-C15 linear alcohol with 7 moles of ethylene oxide alkoxy condensation product), NeodolTM45-4 (C14-C15 linear alcohol with 4 moles of ethylene oxide condensation product), and Procter & amp; KyroTMEOB Gamble Company sold by (C13-C15 alcohol with 9 moles of ethylene oxide product).

也适宜于用作本发明的表面活性剂体系中的非离子表面活性剂的,有于1986年1月21日颁发给Llenado的美国专利4,565,647中公开的烷基多糖类化合物,其中含有由大约6至大约30个碳原子,优选的是由大约10至大约16个碳原子组成的憎水基团,以及一种多糖,例如多糖苷亲水基团,其中含有大约1.3至大约10,更优选的是大约1.3至大约3,最优选的是大约1.3至大约2.7个糖单位。 Also suitable non-ionic surfactants as the surfactant system of the present invention, there is on January 21, 1986 to Llenado, issued alkyl in U.S. Patent No. 4,565,647 discloses polysaccharide compounds containing of from about 6 to about 30 carbon atoms, preferably from the hydrophobic group is from about 10 to about 16 carbon atoms, and a polysaccharide, eg a polyglycoside, hydrophilic group containing from about 1.3 to about 10, more preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. 可以使用任意一种含有5或6个碳原子的还原糖,例如葡萄糖、半乳糖和半乳糖基部分来取代糖基部分(憎水基团任选可连接在2-、3-、4-等位置上,从而给出一种与葡萄糖苷或半乳糖苷性质相反的葡萄糖或半乳糖衍生物)。 May be used Any reducing saccharide containing 5 or 6 carbon atoms, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group may be attached at the 2-, 3-, 4-, etc. position, thereby to give a glucoside or galactoside opposite properties glucose or galactose derivative). 连接糖分子的化学键可以,例如,在前一个糖单元的2-、3-、4-和/或6位与另一个糖单元的一个位置之间。 Linked carbohydrate bonds can be, e.g., between / or 6 with another saccharide units one position a saccharide units and the 2-, 3-, 4- and front. 优选的烷基聚糖苷具有下列式子:R2O(CnH2nO)t(糖基)x其中R2可选自烷基、烷基苯基、羟基烷基、羟基烷基苯基以及它们的混合物,其中的烷基含有大约10至大约18个,更优选的是大约12至大约14个碳原子;n值为2或3,优选的值为2;t值为0至大约10,优选的值是0;x值为大约1.3至大约10,更优选的值为大约1.3至大约3,最优选的值为大约1.3至大约2.7。 Preferred alkylpolyglycosides have the following formula: R2O (CnH2nO) t (glycosyl) x wherein R2 is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxy alkylphenyl, and mixtures thereof, wherein an alkyl group containing from about 10 to about 18, more preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably is 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, more preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. 糖基最好是由葡萄糖衍生的。 The glycosyl is preferably derived from glucose. 为制备这些化合物,可先形成醇或烷基聚乙氧基醇,然后与葡萄糖或一种葡萄糖原进行反应以形成葡萄糖苷(在1位连接)。 To prepare these compounds, the alcohol can first be formed or alkylpolyethoxy alcohol, then reacted with glucose, or one source of glucose reacted to form the glucoside (attachment at the 1). 然后可把前一个糖基单位的2-、3-、4-和/或6-位经优选优先选在2-位,与另一个糖基单元的1位之间进行连接。 Then the preceding glycosyl units 2-, 3-, 4- and / or 6-position is preferably selected preferably via the 2-position, the connection between one and another glycosyl units.

其它适用的非离子表面活性剂有环氧乙烷与由环氧丙烷与丙二醇缩合形成的憎水基的缩合产物,它们也适合于用作本发明的非离子表面活性剂体系中的其它非离子表面活性剂。 Other suitable nonionic surfactants are condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, which are also suitable for the present invention, other non-ionic as non-ionic surfactant systems of Surfactant. 这些化合物中的憎水部分最好是具有大约1,500至大约1,800的分子量并且不溶于水。 The hydrophobic portion of these compounds preferably has a molecular weight of about 1,500 to about 1,800 and is insoluble in water. 往这一憎水部分加上聚环氧乙烷部分,总体上是倾向于增加分子的水溶解度,并且产物作为液体的特征也只能维持到聚环氧乙烷的含量达到缩合产物总重量的50%,这相应于与至多大约40摩尔环氧乙烷缩合。 The hydrophobic portion coupled to the polyethylene oxide portion, generally tends to increase the water solubility of the molecule, and the product liquid character can only be maintained until the content of the polyethylene oxide to achieve the total weight of the condensation product 50%, which corresponds to up to about 40 moles of ethylene oxide. 这种类型化合物的实例包括一些市场上买到的PluronicTM表面活性剂,它是由BASF出售的。 Examples of compounds of this type include certain of the commercially available PluronicTM surfactants on the market, which is sold by BASF.

也适合于用作本发明非离子表面活性剂体系中的非离子表面活性剂的,有环氧乙烷与由环氧丙烷和乙二胺反应得到的产物进行缩合所得到的产物。 Also suitable for use as the nonionic surfactant of nonionic surfactant systems of the present invention, there are condensation products of ethylene oxide with the product obtained obtained by the reaction of propylene oxide and ethylenediamine. 这些产物的憎水部分包括乙二胺与过量环氧丙烷的反应产物,并一般具有约2,500至约3,000的分子量。 The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2,500 to about 3,000. 这一憎水部分与环氧乙烷进行缩合反应到这样的程度,即缩合产物中应含有大约40%至大约80%(重量)的聚环氧乙烷,并且具有大约5,000至大约11,000的分子量。 The hydrophobic portion of the condensation reaction with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% (by weight) polyethylene oxide, and having a molecular weight of about 5,000 to about 11,000 . 这种类型的非离子表面活性剂的实例包括一些市场上能买到的TetronicTM化合物,它们是由BASF出售的。 Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, which is sold by BASF.

经优选的用作本发明表面活性剂体系中的非离子表面活性剂的,是烷基酚的聚环氧乙烷缩合物、伯和仲脂肪醇与大约1至大约25摩尔环氧乙烷的缩合产物、烷基多糖类以及它们的混合物。 By the present invention it is preferably used as the nonionic surfactant of the surfactant system, the alkylphenol polyethylene oxide condensates of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide condensation products, alkyl polysaccharides, and mixtures thereof. 最优选的是含有3至15个乙氧基的C8-C14烷基酚乙氧化物以及具有2至10个乙氧基的C8-C18醇乙氧化物,和它们的混合物。 Most preferred are mixtures thereof and containing 3-15 ethoxy C8-C14 alkyl phenol ethoxylates having from 2 to 10 ethoxy groups and C8-C18 alcohol ethoxylates.

高度优选的非离子表面活性剂是具有下式的多羟基脂肪酸酰胺表面活性剂: Highly preferred nonionic surfactants having the formula polyhydroxy fatty acid amide surfactants:

其中R1是H,或者R1是C1-4烃基、2-羟基乙基、2-羟基丙基或它们的混合物,R2是C5-31烃基,Z是含有至少有3个直接连接在链上的羟基的线型烃基的多羟基烃基,或它的经烷氧化的衍生物。 Wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R2 of a C5-31 hydrocarbon group, Z is a direct containing at least three hydroxy groups connected to the chain polyhydroxyhydrocarbyl having a linear hydrocarbon group, or an alkoxylated derivative oxidized. 优选的是,R1是甲基,R2是直链的C11-15烷基或烯基链诸如椰油烷基或它们的混合物,Z是由一种还原糖诸如葡萄糖、果糖、麦芽糖、乳糖等在还原氨化反应中所衍生的。 Is preferably, Rl is methyl, R2 is straight C11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, Z is a reducing sugar such as glucose, fructose, maltose, lactose, in reductive amination reaction derived.

当被包含在这类供洗衣用的洗涤剂组合物中时,本发明的非离子表面活性剂体系可以在很宽广的洗涤条件范围内起到改进这类洗衣用洗涤剂组合物的除油脂/油污斑渍的作用。 When included in laundry detergent compositions for such use, the nonionic surfactant systems of the present invention may function in a very broad range of laundry conditions improved grease removal such laundry detergent compositions / the role of oil stains. 阴离子表面活性剂高度优选的阴离子表面活性剂包括烷基烷氧化硫酸盐表面活性剂,这里是指具有式子为RO(A)mSO3M的水溶性盐或酸,其中R是一个含有一个C10-C24烷基部分的、未被取代的C10-C24烷基或羟基烷基,优选的是C12-C20烷基或羟基烷基,更优选的是C12-C18烷基或羟基烷基,A是一个乙氧基或丙氧基单元;m值大于零,典型的值在大约0.5至大约6之间,更优选的值为大约0.5至大约3之间;M是H或一个阳离子,它可以是,例如,一种金属阳离子(例如钠、钾、锂、钙、镁等)、铵或取代的铵阳离子。 Anionic surfactants Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants having the formula herein refers to RO (A) mSO3M water soluble salts or acids, containing a wherein R is a C10-C24 the alkyl moiety, unsubstituted C10-C24 alkyl or hydroxyalkyl, preferably C12-C20 alkyl or hydroxyalkyl, more preferably the C12-C18 alkyl or hydroxyalkyl, a is a b or propoxy units; m is greater than zero, a typical value between about 0.5 to about 6, more preferably between about 3 to about 0.5 and; m is H or a cation which can be, e.g. a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium etc.), ammonium or substituted ammonium cation. 烷基乙氧化硫酸盐和烷基丙氧化硫酸盐在此是所期望的。 Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are desired. 取代的铵阳离子的具体实例包括甲基、二甲基、三甲基铵阳离子以及季铵盐阳离子诸如四甲基铵和二甲基哌啶阳离子,以及那些由烷基胺诸如乙胺、二乙胺、三乙胺和它们的混合物所衍生的阳离子等。 Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine , triethylamine, and mixtures thereof derived cation. 作为实例的表面活性剂有C12-C18烷基聚乙氧化物(1.0)硫酸盐(C12-C18E(1.0)M)、C12-C18烷基聚乙氧化物(2.25)硫酸盐(C12-C18E(2.25)M)、C12-C18烷基聚乙氧化物(3.0)硫酸盐(C12-C18E(3.0)M)、以及C12-C18烷基聚乙氧化物(4.0)硫酸盐(C12-C18E(4.0)M),其中的M可方便地选自钠和钾,所使用的合适的阴离子表面活性剂有烷基酯磺酸盐表面活性剂,包括按照“The Journal of the American Oil ChemistsSociety”,52(1975),第323-329页的方法,把C8-C20羧酸的线型酯用气态SO3进行磺化所得的产物。 As examples of surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (C12-C18E (1.0) M), C12-C18 alkyl polyethoxylate (2.25) sulfate (C12-C18E ( 2.25) M), C12-C18 alkyl polyethoxylate (3.0) sulfate (C12-C18E (3.0) M), and C12-C18 alkyl polyethoxylate (4.0) sulfate (C12-C18E (4.0 ) M), wherein M is conveniently selected from sodium and potassium, suitable anionic surfactants used are alkyl ester sulfonate surfactants, include according to "the Journal of the American Oil ChemistsSociety", 52 ( 1975), pp. 323-329, and the linear C8-C20 carboxylic ester product obtained sulfonation with gaseous SO3. 合适的原料包括天然的油脂物质如从牛脂、棕榈油等所衍生的物质。 Suitable starting materials would include natural fatty material from substances such as tallow, palm oil, etc. derived.

经优选的烷基酯磺酸盐表面活性剂,特别是供洗衣用的洗涤剂使用的,包括具有下列结构式的烷基醇磺酸盐表面活性剂: The preferred alkyl ester sulfonate by surfactants, especially for laundry detergent use, including alkyl alcohol sulfonate surfactant having the following structural formula:

其中的R3是一个C8-C20烃基,优选的是一种烷基,或它们的结合;R4是一个C1-C6烃基,优选的是一种烷基,或它们的结合;M是一个阳离子,它与烷基酯磺酸根形成一种水溶性的盐。 Wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof; R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof; M is a cation which with the alkyl ester sulfonate salt of a water soluble form. 合适的形成盐的阳离子包括金属诸如钠、钾和锂,以及取代或未取代的铵阳离子,诸如一乙醇胺、二乙醇胺、三乙醇胺。 Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine, triethanolamine. 优选的是,R3是一个C10-C16烷基,R4是甲基、乙基或异丙基。 Is preferably, R3 is a C10-C16 alkyl, R4 is methyl, ethyl or isopropyl. 特别优选的是甲基酯磺酸盐。 Especially preferred are the methyl ester sulfonates. 其中的R3是C10-C16烷基。 Wherein R3 is C10-C16 alkyl.

其它合适的阴离子表面活性剂包括烷基硫酸盐表面活性剂,这里是指具有式子为ROSO3M的水溶性盐或酸,其中的R最好是一个C10-C24烃基,优选的是一个含有C10-C20烷基组分的烷基或羟基烷基,更优选的一个C12-C18烷基或羟基烷基;M是H或一个阳离子,例如,一种碱金属阳离子(例如钠、钾、锂),或铵或取代的铵离子(例如甲基-、二甲基-、和三甲基铵阳离子和季铵盐阳离子诸如四甲基铵和二甲基哌啶阳离子以及由烷基胺诸如乙胺、二乙胺,三乙胺以及它们的混合物所衍生的季铵盐阳离子等)。 Other suitable anionic surfactants include the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula having ROSO3M wherein R preferably is a C10-C24 hydrocarbon group, preferably a C10- containing alkyl or hydroxyalkyl C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl group; M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium ions (e.g. methyl -, dimethyl -, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and quaternary ammonium cations derived etc.). 典型地,对于较低的洗涤温度(例如低于大约50℃),优选的烷基链为C12-C16,而对于较高的洗涤温度(例如高于大约50℃)则优选的烷基链为C16-C18。 Typically, for lower wash temperatures (e.g. below about 50 ℃), preferred alkyl chains are C12-C16, and for higher wash temperatures (e.g. above about 50 ℃) are preferably alkyl chains C16-C18.

其它可用于洗涤目的的阴离子表面活性剂也可被包括在本发明的洗衣用的洗涤剂组合物中。 Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. 这些包括肥皂的盐(包括,例如,钠、钾、铵和取代的铵盐诸如一、二和三乙醇胺的盐)、C9-C20线型烷基苯磺酸盐、C8-C22伯或仲烷磺酸盐、C8-C22烯磺酸盐。 These can include salts (including, e.g., sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), C9-C20 linear alkylbenzenesulfonates, C8-C22 primary or secondary alkyl sulfonates, C8-C22 alkenyl sulfonates. 通过磺化碱土金属柠檬酸盐的热解产物而制得的磺化聚羧酸,例如。 Sulfonation of the pyrolyzed product of alkaline earth metal citrates prepared sulfonated polycarboxylic acids, for example. 在英国专利说明书No.1,082,179中所描述的方法,C8-C24烷基聚乙二醇醚硫酸盐(含有最多10摩尔环氧乙烷);烷基甘油磺酸盐、脂肪酸酰基甘油磺酸盐、脂肪酸油酰甘油硫酸盐、烷基酚环氧乙烷醚硫酸盐、石蜡烃磺酸盐,烷基膦酸盐、羟乙磺酸盐诸如酰基羟乙磺酸盐、N-酰基氨基乙磺酸盐、烷基琥珀酰胺酸盐和磺酸基琥珀酸盐、磺酸基琥珀酸盐单酯(特别是饱和及不饱和的C12-C18单酯)以及磺酸基琥珀酸二酯(特别是饱和及不饱和的C6-C12二酯)、酰基肌氨酸盐、烷基多糖的硫酸盐诸如烷基聚葡糖苷的硫酸盐(非离子非硫酸化的化合物在下面叙述)、支链的伯烷基硫酸盐,以及烷基聚乙氧羧酸盐诸如那些具有式子为RO(CH2CH2O)k-CH2COO-M+的盐,其中R为C8-C22烷基,k值为0至10的整数,M是可溶性的形成盐的阳离子。 British patent specification No.1,082,179 the method described in, C8-C24 alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphonate, isethionates such as the acyl isethionates, N- acyl taurine salts, alkyl succinamates and succinate sulfonic acid group, a sulfonic acid monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as sulfates (non-sulfated compound nonionic alkyl polyglucoside be described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO (CH2CH2O) k-CH2COO-M + salt thereof, wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, M It is a soluble salt-forming cation. 树脂酸和氢化树脂酸也是适用的,诸如松香、氢化松香,以及存在于松浆油或由其中衍生的树脂酸和氢化树脂酸。 Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and wherein the derivatized resin acids and hydrogenated resin acids present in or tall oil. 进一步的实例被描述于“Surface Active Agents andDetergents”(第Ⅰ和第Ⅱ卷,由Schwartz、Perry及Berch编著)一书中,许多这类表面活性剂一般也已在1975年12月30日转让给Laughlin等人的美国专利3,929,678中的第23栏第58行至第29栏第23行中被公开(在此引入作为参考)。 Further examples are described in "Surface Active Agents andDetergents" (Vol. Ⅱ Ⅰ first and by Schwartz, Perry and Berch eds.), A book, many such surfactants are also generally transferred to the December 30, 1975 column 23, line 58 through column 29, line 23 of U.S. Patent No. 3,929,678 Laughlin et al., is disclosed in (herein incorporated by reference).

当含有它们时,本发明的洗衣用洗涤剂组合物中典型地含有大约1%至大约40%,优选地是大约3%至大约20%(重量)的这类阴离子表面活性剂。 When included therein, the laundry detergent compositions of the present invention was typically contain from about 1% to about 40%, preferably from about 3% to about 20% (by weight) of such anionic surfactants.

烷基烷氧化硫酸盐表面活性剂比烷基硫酸盐和烷基苯磺酸盐更为优选,因为这些烷基烷氧化硫酸盐表面活性剂能增效地改进N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物的抑制染料转移性能。 Alkyl alkoxylated sulfate surfactants are preferred over others sulfonates alkyl sulfates and alkyl benzene, because these alkyl alkoxylated sulfate surfactants synergistically improve the energy-vinylimidazole N- vinyl-N- dye transfer inhibiting performance pyrrolidone copolymers.

本发明的洗衣用洗涤剂组合物也可含有阳离子型、两性的、两性离子的和半极性的表面活性剂,以及除已经在这里描述过的以外的其它非离子表面活性剂。 The laundry detergent compositions may also contain cationic, ampholytic, zwitterionic and semi-polar surfactants, as well as other nonionic surfactants other than those already described herein. FIG. 优选的阳离子表面活性剂体系包括非离子和两性离子表面活性剂。 Preferred cationic surfactant systems include nonionic and zwitterionic surfactants.

适宜于在本发明的洗衣用洗涤剂组合物中使用的阳离子洗涤剂用表面活性剂是那些含有一个长链烃基的表面活性剂。 Suitable for use with the laundry detergent compositions of the present invention is a cationic detergent surfactants are those surfactants having one long-chain hydrocarbyl group. 这类阳离子表面活性剂的实例包括铵盐表面活性剂,诸如烷基二甲基卤化铵以及那些具有下式的表面活性剂:[R2(OR3)y][R4(OR3)y]2R5N+X-其中R2是一个在其烷基链中含有大约8至大约18个碳原子的烷基或烷基苄基;每个R3是选自-CH2CH2-、-CH2CH(CH3)-、-CH2CH(CH2OH)-、-CH2-CH2-CH2-这些基团或它们的混合物;当y值不是零时,每个R4是选自C1-C4烷基、C1-C4羟基烷基、通过连接两个R4基团形成的苄基环状结构、-CH2-CHOH-CHOH-COR6CHOHCH2OH、其中的R6是任何一种分子量小于大约1,000的己糖或己糖聚合物等基团以及氢;R5是和R4相同的基团,或者是一个烷基链,其中碳原子的总数和R2的加在一起不应超过18个;每个y值可从0至大约10,并且y值的总和为0至大约15;X是任何一种适当的阴离子。 Examples of such cationic surfactants include the ammonium surfactants such as alkyl dimethyl ammonium halides and those having the formula a surfactant: [R2 (OR3) y] [R4 (OR3) y] 2R5N + X - wherein R2 is an alkyl chain containing an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms; each R3 is selected from -CH2CH2 -, - CH2CH (CH3) -, - CH2CH (CH2OH ) -, - CH2-CH2-CH2- these groups, or mixtures thereof; when the y value is not zero, R4 is each selected from C1-C4 alkyl, C1-C4 hydroxyalkyl, by joining the two R4 groups benzyl group formed of a cyclic structure, -CH2-CHOH-CHOH-COR6CHOHCH2OH, wherein R6 is any molecular weight less than about 1,000 hexose or hexose polymer groups and hydrogen; R4 and R5 are the same groups group, or is an alkyl chain wherein the total number of carbon atoms, and R2 together are not more than 18; each y has a value from 0 to about 10 and the sum of the y values ​​is from 0 to about 15; X is any suitable anion.

用于本发明组合物中的经高度优选的阳离子表面活性剂是具有下式的水溶性季铵盐化合物:R1R2R3R4N+X-(ⅰ)其中R1是C8-C16烷基,每个R2、R3和R4可独自是C1-C4烷基、C1-C4羟基烷基、苄基以及-(C2H4O)xH基,其中的x值可从2至5,X是一个阴离子。 Cationic surfactants used in compositions of the invention by a height preferably is water-soluble quaternary ammonium compounds having the formula: R1R2R3R4N + X- (ⅰ) wherein R1 is a C8-C16 alkyl, each of R2, R3 and R4 can independently be C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and - (C2H4O) xH group, wherein x has a value of from 2 to 5, x is an anion. R2、R3、R4中不能有多于一个是苄基。 R2, R3, R4 can not have more than one is benzyl.

经优选的R1烷基的链长是C12-C15,特别是其中烷基是由椰油或棕榈仁油衍生的烷基链长的混合物,或者是通过烯烃或OXO醇合成而衍生的烷基。 Preferred alkyl groups R1 through chain length C12-C15, particularly where the alkyl group is derived from coconut or palm kernel oil is a mixture of alkyl chain length, or by an olefin build up or OXO alcohols synthesis derived alkyl group. 经优选的R2、R3和R4基团是甲基和羟基乙基,并且阴离子X可选自卤化物、甲基硫酸根、醋酸根和磷酸根离子。 By the preferred R2, R3 and R4 groups are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.

本发明使用的式(ⅰ)的合适的季铵盐化合物的实例有:椰油烷基三甲基铵氯化物或溴化物;椰油烷基甲基二羟乙基铵氯化物或溴化物;癸基三乙基氯化铵;癸基二甲基羟乙基铵氯化物或溴化物;C12-15二甲基羟乙基铵氯化物或溴化物;椰油烷基二甲基羟乙基铵氯化物或溴化物;肉豆蔻基三甲基铵甲基硫酸盐;月桂基二甲基苄基铵氯化物或溴化物;月桂基二甲基(氧乙烯)4铵氯化物或溴化物;胆碱酯(即具有上述式(ⅰ)的化合物,其中的R1是 Examples of suitable quaternary ammonium compounds of formula (i) of the present invention are: coconut trimethyl ammonium chloride or bromide; coconut alkyl dimethyl hydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C12-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut alkyl dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulfate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (oxyethylene) 4 ammonium chloride or bromide; choline esters (i.e., a compound of the above formula (i) have, in which R1 is

烷基,并且R2、R3、R4是甲基);二烷基咪唑啉[具有式(ⅰ)的化合物]。 Alkyl, and R2, R3, R4 are methyl); dialkyl imidazolines [compounds of formula (i) a].

在这里有用的其它阳离子表面活性剂也已在1980年10月14日发布的Cambre的美国专利4,228,044中被描述过。 Here Other useful cationic surfactants have also been described in the October 14, 1980 issued US Patent 4,228,044, Cambre.

当包含它们时,本发明的洗衣洗涤剂组合物中典型含0%至大约25%、优选地是大约3%至大约15%(重量)的这类阳离子表面活性剂。 When included therein, the laundry detergent compositions of the present invention typically contain 0% to about 25%, preferably from about 3% to about 15% (by weight) of such cationic surfactants.

两性表面活性剂也适宜于用在本发明的洗衣洗涤剂组合物中。 Amphoteric surfactants are also suitable for use in laundry detergent compositions of the present invention. 这些表面活性剂可广义地被描述为仲或叔胺的脂肪族衍生物,或者杂环仲和叔胺的脂肪族衍生物,其中的脂肪基可以是直链或带支链的。 These surfactants can be broadly described as aliphatic secondary or tertiary amines derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched. 脂肪取代基之一含有至少8个碳原子,典型地是大约8至大约18个碳原子,并且至少有一个含有一个阴离子水溶性基团,例如羧基、磺酸根、硫酸根。 Aliphatic substituents contains at least 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. 可参看1975年12月30日发布的已转让给Laughlin等人的美国专利No.3,929,678中第19栏,第18-35行有关两性表面活性剂的实例。 Can be found in column 19, December 30, 1975 issued and assigned to Laughlin et al in US Patent No.3,929,678, for examples of amphoteric surfactants, lines 18-35.

当包含它们时,本发明的洗衣洗涤剂组合物中典型地含有大约0%至15%,优选地是大约1%至大约10%(重量)的这类两性表面活性剂。 When included therein, the laundry detergent compositions of the present invention typically comprise from about 0% to 15%, preferably from about 1% to about 10% (by weight) of such ampholytic surfactants.

两性离子表面活性剂也适宜于用在本发明的洗衣洗涤剂组合物中。 Zwitterionic surfactants are also suitable for use in the laundry detergent compositions of the present invention. 这些表面活性剂可广义地被描述为仲和叔胺的衍生物,杂环仲和叔胺的衍生物,或季铵盐、季鏻盐或叔锍盐化合物的衍生物。 These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. 可参看1975年12月30日颁发给Laughlin等人的美国专利No.3,929,678中第19栏第38行至第22栏第48行有关两性离子表面活性剂的实例。 It may be issued to Laughlin et al Referring December 30, 1975 U.S. Patent No.3,929,678 at column 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants.

当包含它们时,本发明的洗衣洗涤剂组合物中典型地含有0%至大约15%,优选地是大约1%至大约10%(重量)的这类两性离子表面活性剂。 When included therein, the laundry detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% (by weight) of such zwitterionic surfactants.

半极性非离子表面活性剂是特别的一类非离子表面活性剂,它包括水溶性的胺氧化物,其中包含一个由大约10至大约18个碳原子组成的烷基部分和2个选自含有大约1至大约3个碳原子的烷基和羟基烷基部分;水溶性的氧化膦,其中包含一个由大约10至大约18个碳原子组成的烷基部分和2个选自含有大约1至大约3个碳原子的烷基和羟基烷基部分:以及水溶性的亚砜类,其中包含一个由大约10至大约18个碳原子组成的烷基部分和一个选自含有1至大约3个碳原子的烷基和羟基烷基部分。 Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing a from about 10 to about 18 carbon atoms in the alkyl moiety and 2 moieties selected from consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group containing from about 1 to alkyl and hydroxyalkyl moieties of from about 3 carbon atoms: and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a is selected from 1 to about 3 carbon alkyl and hydroxy alkyl moiety atom.

半极性非离子洗涤剂表面活性剂包括具有下式的胺氧化物表面活性剂: Semi-polar nonionic detergent surfactants include the amine oxide having the formula surfactants:

其中R3是一个含有大约8至大约22个碳原子的烷基、羟基烷基、或烷基苯基或它们的混合物;R4是一个含有大约2至大约3个碳原子的亚烷基或羟基亚烷基或它们的混合物;X值为0至大约3;并且每个R5是一个含有大约1至大约3个碳原子的烷基或羟基烷基,或是一个含有大约1至大约3个环氧乙烷单位的聚环氧乙烷基。 Wherein R3 is an alkyl group containing from about 8 to about 22 carbon atoms, hydroxyalkyl, or alkyl phenyl group or mixtures thereof; R4 is one containing from about 2 to about 3 carbon atoms or an alkylene hydroxy alkylene alkyl or mixtures thereof; X is from 0 to about 3; and each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms, or one containing from about 1 to about 3 ethylene polyethylene oxide units ethylene oxide groups. R5基团可以彼此连接,例如通过氧或氮原子,而形成一个环状结构。 R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a cyclic structure.

这些胺氧化物表面活性剂特别包括C10-C18烷基二甲基胺氧化物和C8-C12烷氧乙基二羟基乙基胺氧化物。 These amine oxide surfactants in particular include C10-C18 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.

当包含它们时,本发明的洗衣洗涤剂组合物中典型地含有0%至大约15%,优选地是大约1%至大约10%(重量)的这类半极性非离子表面活性剂。 When included therein, the laundry detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% (by weight) of such semi-polar nonionic surfactants.

本发明还进一步提供一种洗衣洗涤剂组合物,它含有至少1%(重量),优选地是大约3%至大约65%,更优选地是大约10%至大约25%(重量)的总表面活性剂。 The present invention further provides laundry detergent compositions comprising at least 1% (wt.), Preferably from about 3% to about 65%, more preferably from about 10% to about 25% (by weight) of the total surface active agent.

可被包括的经优选的洗涤剂组分有供洗涤剂用的酶,它被包括在洗涤剂配方中可达到广泛的目的,包括,例如,除去基于蛋白质、基于碳水化合物或基于甘油三酯所形成的污渍以及防止流失染料的转移。 May be included by the preferred detergent ingredients for the detergent enzyme, which is included in the detergent formulations can achieve a wide range of purposes, including, for example, removal of protein-based, carbohydrate-based or triglycerides the formation of stains and to prevent the loss of dye transfer. 被并入的酶包括蛋白酶、淀粉酶、脂肪酶、纤维素酶和过氧化物酶以及它们的混合物,也可包括其它类型的酶。 Enzymes are incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof, may also include other types of enzymes. 它们可以来自任何适当的来源,诸如植物、动物、细菌、霉菌和酵母源。 They can come from any suitable source, such as plant, animal, bacterial, fungal and yeast origin.

通常加入的酶的数量应使每克组合物中以重量计达到5毫克,更典型地是大约0.05毫克至大约3毫克的活性酶。 Enzymes are normally incorporated number shall per gram of the composition up to 5 mg by weight, more typically about 0.05 mg to about 3 mg, of active enzyme. 按照本发明的洗涤剂组合物中被并入的经高度优选的酶是纤维素酶或过氧化物酶以及它们的混合物。 Was highly preferred in accordance with the enzymatic detergent compositions of the present invention are incorporated are cellulases or peroxidases and mixtures thereof.

可用于本发明中的纤维素酶既包括细菌的也包括霉菌的纤维素酶。 Cellulases useful in the present invention include both bacterial or fungal cellulases. 优选地,它们应具有的最佳pH值范围在5至9.5之间。 Preferably, they will have a pH optimum of between 5 and 9.5. 合适的纤维素酶已在Barbegoard等人的美国专利4,435,307中被公开,其中公开的霉菌纤维素酶是由Humicola insolens产生的。 Suitable cellulases are disclosed in Barbegoard et al., U.S. Patent 4,435,307, which discloses fungal cellulase produced from Humicola insolens is. 合适的纤维素酶也在GB-A-2,075,028、GB-A-2,095,275和DE-OS-2,247,832中被公开。 Suitable cellulases are also GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832 are disclosed.

这类纤维素酶的实例有被Humicola insolens(Humicola griseavar.thermoidea)菌株,特别是Humicola菌株DSM 1800所产生的纤维素酶、被Bacilus N的霉菌所产生的纤维素酶、属于Aeromonas属的霉菌产生的纤维素酶212。 Examples of such cellulases are cellulases produced by Humicola insolens (Humicola griseavar.thermoidea) strain, particularly the Humicola strain DSM 1800 produced cellulase is produced by Bacilus N fungal cellulase, molds belonging to the genus Aeromonas produce 212 cellulase. 以及由一种海洋生软体动物(Dolabella Auricula Solander)的肝胰腺中提取的纤维素酶。 And extract from a marine mollusc (Dolabella Auricula Solander) hepatopancreas cellulase.

其它合适的纤维素酶有来源于Humicola Insulens、分子量为大约50KDa、等电点为5.5并含有415个氨基酸的纤维素酶。 Other suitable cellulases have from Humicola Insulens, molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids of a cellulase. 这种纤维素酶已在1993年3月19日申请的共同未决的欧洲专利申请书No.93200811.3中被描述过。 Co-pending European patent application No.93200811.3 such cellulases have applied in 1993, March 19 was described. 特别合适的纤维素酶是具有照顾颜色方面的益处的纤维素酶。 Especially suitable cellulases having color care benefits aspect cellulase. 这种纤维素酶的实例有1991年11月6日Carezyme(Novo)申请的欧洲专利申请书No.91202879.2中所描述的纤维素酶。 Examples of such cellulases are cellulases are European Patent Application No. 91202879.2, dated 1991 years. 6. 11 Day Carezyme (Novo) as described in the application. 已经发现,N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物在纤维素酶存在时能够增效地改进颜色外观方面的性能。 It has been found, N- vinylimidazole N- vinylpyrrolidone copolymers synergistically improve the performance in terms of color appearance when cellulases.

在洗涤剂中使用的合适的脂肪酶包括那些由Pseudomonas群的微生物所产生的酶,诸如在英国专利1,372,034中公开的Pseudomonas stutzeri ATCC 19.154。 Suitable lipases for detergent usage include those produced by microorganisms of the Pseudomonas group, an enzyme produced, such as disclosed in British Patent 1,372,034 Pseudomonas stutzeri ATCC 19.154. 合适的脂肪酶包括那些与脂肪酶的抗体显示出阳性免疫交叉反应的、由微生物Pseudomonasfluorescent LAM 1057产生的脂肪酶,这种脂肪酶可从AmanoPharmaceutical Co.Ltd.,Nagoya,Japan买到,其商品名称为脂肪酶P“Amano”,此后就称之为“Amano-P”。 Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism lipase Pseudomonasfluorescent LAM 1057, this lipase., Nagoya, Japan available from Amano Pharmaceutical Co. Ltd., trade name lipase P "Amano", hereinafter referred to "Amano-P".

特别合适的脂肪酶有诸如M1脂肪酶(Ibis)和Lipolase(Novo)等。 Especially suitable lipases such as M1 Lipase (Ibis) and Lipolase (Novo) and the like.

过氧化物酶要和氧源,例如过碳酸盐、过硼酸盐、过硫酸盐、过氧化氢等结合在一起使用。 To a peroxidase and an oxygen source, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. in combination. 它们被用于“溶液漂白”,即防止由底物除去的颜料的染料在洗涤操作过程中在洗涤溶液中转移到其它底物上去。 They are used for "solution bleaching," i.e. to prevent pigments removed from substrates during wash dye transfer operation in the wash solution up to other substrates. 过氧化物酶在本专业中是已知的,并包括,例如,辣根过氧化物酶、木素酶以及卤素过氧化物酶诸如氯-和溴-过氧化物酶。 Peroxidase enzymes are known in the professional, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro - and bromo - peroxidase. 含过氧化物酶的洗涤剂组合物已在,例如,PCT InternationApplication WO 89/099813以及1991年11月6日发布的欧洲专利申请EP No.91202882.6中被公开。 Peroxidase-containing detergent compositions have, for example, PCT InternationApplication WO 89/099813 and in European Patent November 6, 1991 published application is disclosed in EP No.91202882.6.

已经发现,N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物能够增效地改进过氧化物酶抑制染料转移的性能。 It has been found, N- vinylimidazole N- vinylpyrrolidone copolymers synergistically improve the dye transfer inhibiting performance peroxidase is.

蛋白酶的合适的实例有从B.subtilis和B.licheniformis的特别菌株中得到的枯草溶菌素。 Suitable examples of proteases are obtained from particular strains of B.subtilis and B.licheniformis subtilisin. 在市场上可以买到的适合于除去基于蛋白质的污渍的蛋白水解酶包括那些Novo Industies A/S(丹麦)生产的、以商品名称Alcalase、Savinase和Esperase出售的蛋白酶,International Bio-Synthetics,Inc.(荷兰)生产的Maxatase、Genencor生产的FN-base以及MKC生产的Optimase和Opticlean。 In the commercially available proteolytic enzymes suitable for removing protein-based stains include those Novo Industies A / S (Denmark) manufactured under the trade names Alcalase, Savinase and Esperase sold proteases, International Bio-Synthetics, Inc. Maxatase (Netherlands) production, Genencor production of FN-base and MKC production Optimase and Opticlean.

在这类蛋白水解酶中,特别对液体洗涤剂组合物有关的是这里称为蛋白酶A和蛋白酶B的酶。 In such proteolytic enzymes, especially for liquid detergent compositions is related enzymes referred to herein as Protease A and Protease B, respectively. 蛋白酶A已在欧洲专利申请130,756中被描述,蛋白酶B已在欧洲专利申请序列号No.87303761.8中被描述。 Protease A 130,756 has application are described in European Patent, Application Protease B has been described in Serial No. European Patent No.87303761.8.

淀粉酶包括,例如,由特别的菌株B.licheniforms中得到的淀粉酶,它被更为详尽地描述于英国专利说明书No.1,296,839(Novo)中。 Amylases include, for example, obtained from a special strain of B.licheniforms amylase, which is described in more detail in British Patent Specification No.1,296,839 (Novo). 分解淀粉的蛋白质包括,例如,Rapidase、Maxamyl(International Bio-Synthetics,Inc.生产)和Termamyl(NovoIndustries生产)。 Amylolytic proteins include, for example, Rapidase, Maxamyl (International Bio-Synthetics, Inc., Ltd.) and Termamyl (NovoIndustries production).

在液体配方中,最好应用一种酶稳定化系统。 In liquid formulations, an enzyme stabilization is preferred to use the system. 用于洗涤剂组合物水溶液的酶稳定化技术在本专业是众所周知的。 Aqueous detergent compositions for enzyme stabilization techniques are well known in the profession. 例如,一种在水溶液中使酶稳定化的技术涉及使用来源于诸如醋酸钙、甲酸钙和丙酸钙等的游离钙离子。 For example, an enzyme stabilized in an aqueous solution involves the use of free calcium ions such as calcium acetate, calcium formate and calcium propionate. 钙离子可以结合短链羧酸盐、优选的是甲酸盐一起使用。 Calcium ions can bind short chain carboxylic acid salts, preferably formates are used together. 可参看,例如,美国专利4,318,818。 See, for example, U.S. Patent No. 4,318,818. 也已经提出可使用多元醇诸如甘油和山梨醇、烷氧-醇、二烷基糖醚、多价醇与多官能脂肪胺(例如,诸如二乙醇胺、三乙醇胺、二异丙醇胺等)的混合物、以及硼酸或碱金属的硼酸盐。 Also it has been proposed to use polyols such as glycerol and sorbitol, alkoxy - alcohols, dialkyl sugar ether of polyvalent alcohols with polyfunctional aliphatic amines (e.g., such as diethanolamine, triethanolamine, diisopropanolamine, etc.) mixtures thereof, and boric acid or alkali borate metal. 此外,酶稳定化技术也已在美国专利4,261,868、美国专利3,600,319以及欧洲专利申请公开No.0199405、申请号No.86200586.5中被公开并示例说明。 Enzyme stabilization techniques No.0199405 has disclosed in U.S. Patent Application 4,261,868, U.S. Patent No. 3,600,319 and European Patent Application No. No.86200586.5 are disclosed and illustration. 其中优选的是非硼酸和硼酸盐。 Among the preferred non-boric acid and borate. 酶稳定化体系也被描述于,例如,美国专利4,261,868、3,600,319和3,519,570中。 Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319 and 3,519,570. 可以加入的其它合适的洗涤剂组分有酶氧化清除剂,它已在1992年1月21日发布的共同未决的欧洲专利申请N92870018.6中被描述过。 Other suitable detergent ingredients that can be added are enzyme oxidation scavengers, it has been described in co-pending European patent application N92870018.6 1992 Nian 1 released on May 21st in. 这类酶氧化清除剂的实例有乙氧化的四亚乙基多胺。 Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

特别优选的洗涤剂组分是与工艺相结合,它也提供一种类型的照顾到颜色方面的益处。 Especially preferred detergent ingredients are combinations with the process, it also provides a color care benefits to one type of aspect. 这些工艺的实例有EP0508034中描述的聚乙烯基吡咯烷酮聚合物以及诸如在共同未决的欧洲专利申请N92202168.8和N93201198.4中所描述的含聚胺-N-氧化物的聚合物。 Examples of these processes are polyvinylpyrrolidone polymers and polymers described in EP0508034-containing polyamine -N- oxide such as European Patent and copending application N92202168.8 N93201198.4 described. 其它实例有纤维素酶和/或过氧化物酶和/或用于颜色保持和复原的金属催化剂。 Other examples are cellulase and / or peroxidases metal catalyst and / or for color maintenance and restoration. 这类金属催化剂已在共同未决的欧洲专利申请No.92870181.2中被描述过。 Such metal catalysts have been described in co-pending European patent application No.92870181.2 in.

此外,已经发现本发明的N-咪唑N-乙烯基吡咯烷酮共聚物能消除或减少金属催化剂沉积在织物表面,从而获得改进的白度方面的益处。 Further, it has been found that N- imidazol-N- vinylpyrrolidone copolymer of the present invention can eliminate or reduce the metal catalyst is deposited on the fabric surface, thereby obtaining the benefit of improved whiteness.

能被包括在本发明的洗涤剂组合物中的经优选的组分还包括漂白剂。 Can include components in the detergent composition by the present invention preferably further comprises a bleaching agent.

这些漂白剂组分可包括一种或多种氧漂白剂以及,依赖于所选择的漂白剂,一种或多种漂白活化剂。 These bleaching agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one or more bleach activators. 当存在漂白化合物时,它在洗涤剂组合物中的含量典型地是大约1%至大约10%。 When present bleaching compounds, in which the content of the detergent composition is typically from about 1% to about 10%. 一般,在非液体配方,例如颗粒状的洗涤剂中,漂白化合物是供选择的组分。 Generally, in non-liquid formulations, eg granular detergents, bleaching compounds are optional ingredients. 如果存在,漂白活化剂的含量典型地是漂白组合物的大约0.1%至大约60%,更优选的是大约0.5%至大约40%。 If present, the amount of bleach activators will typically be from about 0.1% to about 60% of the bleaching composition, more preferably from about 0.5% to about 40%.

本发明所用的漂白剂组分可以是任何一种用于洗涤剂组合物中的漂白剂,包括氧漂白剂和本专业中已知的其它漂白剂。 The bleaching agent component used in the present invention may be any detergent compositions for bleaching agents, other bleaching agents including oxygen bleaches as those skilled in the art.

在方法方面,本发明进一步提供一种洗涤织物、纤维、纺织品的方法,它是在低于大约50℃,特别是低于大约40℃的温度下,用含有N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物的洗涤剂结合漂白剂来进行的。 In a method aspect, the present invention further provides a method for washing fabrics, fibers, textiles, methods, it is below about 50 ℃, especially below a temperature of about 40 ℃, containing vinyl-N- vinylimidazole N- the detergent bleach pyrrolidone copolymers to the binding.

适用于本发明的漂白剂可以是一种活化的或非活化的漂白剂。 Bleaches suitable for the present invention can be an activated or non-activated bleaching agent.

一类可使用的氧漂白剂包括过羧酸漂白剂和它的盐。 One category of oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. 这类漂白剂的合适的实例包括一过氧邻苯二甲酸镁六水合物、间-氯过苯甲酸的镁盐、4-壬基氨基-4-氧代过氧丁酸和二过氧十二烷二酸。 Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, m - chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxycarboxylic ten acid dioxane. 这类漂白剂已在美国专利4,483,781、美国专利申请740,446、欧洲专利申请0,133,354和美国专利4,412,934中被公开。 Such bleaching agents are described in US Patent 4,483,781, US Patent Application 740,446, European Patent Application 0,133,354 and US Patent 4,412,934 disclosed. 高度优选的漂白剂也包括6-壬基氨基-6-氧代-过氧己酸,它被描述于美国专利4,634,551中。 Highly preferred bleaching agents also include 6-nonyl amino-6-oxo - peroxy hexanoic acid, which is described in U.S. Patent No. 4,634,551.

另外一类可以使用的漂白剂包括卤素漂白剂。 Another category of bleaching agent that can be used encompasses the halogen bleaching agents. 次卤酸盐漂白剂的实例包括,例如,三氯异氰脲酸、二氯异氰脲酸的钠盐和钾盐以及N-氯和N-溴烷磺酰胺。 Examples of hypohalite bleaching agents include, for example, trichloroisocyanuric acid, dichloro isocyanuric acid and the sodium and potassium chloride and N- N- bromo alkane sulphonamides. 这类材料通常加入的量是最终产物的0.5-10%(重量),优选的是1-5%(重量)。 Such materials are normally added in an amount of 0.5 to 10% (by weight) of the final product, is preferably (by weight) 1-5%.

优选地,适合于本发明的漂白剂包括过氧漂白剂。 Preferably, the bleaches suitable for the present invention include peroxygen bleaches. 合适的水溶性固体过氧漂白剂的实例包括过氧化氢释放剂,诸如过氧化氢、过硼酸盐、例如过硼酸盐一水合物、过硼酸盐四水合物、过硫酸盐、过碳酸盐、过二硫酸盐、过磷酸盐和过氧水合物。 Examples of suitable water-soluble solid peroxygen bleaches include hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, eg perborate monohydrate, perborate tetrahydrate, persulfates, carbonates, persulfates, perphosphates and peroxyhydrates. 经优选的漂白剂是过碳酸盐和过硼酸盐。 Preferred bleaches are by percarbonates and perborates.

过氧化氢释放剂可以和漂白活化剂诸如四乙酰基乙二胺(TAED)、壬酰氧基苯磺酸盐(NOBS,被描述于US4,412,934)、3,5,-三甲基己醇氧苯磺酸盐(ISONOBS,被描述于EP120,591)或五乙酰基葡萄糖(PAG)等结合起来使用,后者被预先水解而形成过酸作为活性的漂白物种,从而导致改进的漂白效果。 The hydrogen peroxide releasing agents can be used with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene sulfonate (NOBS, described in US4,412,934), 3,5, - trimethyl hexanol oxybenzenesulfonate (ISONOBS, described in EP120,591) or pentaacetylglucose (PAG) used in combination and the like, which is previously hydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect. 酰化的柠檬酸酯诸如在共同未决的欧洲专利申请No.91870207.7中所公开的那些,也是合适的活化剂。 Those acylated citrate esters, are also suitable activators such as described in copending European Patent Application No.91870207.7 as disclosed.

过氧化氢也可通过一种酶体系来提供(即酶和一种相应的底物),后者在洗涤和/或漂洗的开始或过程中能够产生过氧化氢。 Hydrogen peroxide may also be provided (i.e. an enzyme and a substrate) by an enzyme system, in which the washing and / or rinsing process starts or is capable of generating hydrogen peroxide. 这类酶体系已在1991年10月9日发布的EP专利申请91202655.6中被公开。 Such enzymatic systems are disclosed in the application EP 91202655.6 patent October 9, 1991 release.

其它适用于本发明的过氧漂白剂包括有机过氧酸诸如过羧酸。 Other suitable peroxygen bleaches the present invention include organic peroxyacids such as percarboxylic acids.

除氧漂白剂以外的漂白剂在本专业中也是已知的,并且可在此处应用。 Bleaching agents other than oxygen bleaching agents are also known in the profession, and can be applied here. 一种类型特别令人感兴趣的非氧漂白剂包括光活化的漂白剂诸如磺化的酞菁锌和/或酞菁铝。 One type of non-oxygen of particular interest includes photoactivated bleaching agents and bleach / or aluminum phthalocyanines such as the sulfonated zinc phthalocyanine. 这些物质在洗涤过程中能沉积在底物上。 These materials can be deposited during the washing process on the substrate. 在氧存在的条件下,当被光照射、诸如把衣服悬挂在室外干燥时被太阳光照射,磺酸的酞菁锌即被活化,结果底物即被漂白。 In the presence of oxygen when irradiated with light, such as by hanging clothes out to dry in the outdoor sunlight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. 经优选的酞菁锌以及光活化的漂白方法被描述于美国专利4,033,718。 Preferred zinc phthalocyanine by and a photoactivated bleaching process are described in U.S. Patent No. 4,033,718. 典型地,洗涤剂组合物中可含有大约0.025%至大约1.25%(重量)的磺化的酞菁锌。 Typically, detergent compositions may contain sulfonated zinc phthalocyanine about 0.025% to about 1.25% (by weight) of.

优选地,本发明的组合物还含有一种白土。 Preferably, the compositions of the present invention further contains a clay. 已经发现本发明的N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物与白土是可以很好兼容的,即聚合物抑制染料转移的性质不会由于配方中存在白土而受到不良影响。 It has been found according to the present invention is N- vinylimidazole N- vinylpyrrolidone copolymers and clay are well compatible, i.e., dye transfer inhibiting properties of the polymer without the presence of clay in the formulation adversely affected. 此外,已经发现与N-乙烯基咪唑N-乙烯基吡咯烷酮一起配方仍能保持白土的软化性能。 Further, it has been found with the formulation can maintain the performance of the softening clay and N- vinylimidazole N- vinylpyrrolidone. 特别适用的白土是在EP0522206中被描述的诸如纤维软化用的白土。 Particularly suitable clays are clays such fibers are described in EP0522206 with softened.

本发明的组合物还可进一步包含一种增效体系。 The composition of the present invention may further comprise a synergistic system. 任何通常使用的增效体系在这里使用都是合适的,包括铝硅酸盐材料、硅酸盐、多羧酸盐和脂肪酸、以及诸如乙二胺四醋酸盐、金属离子螫合剂如氨基聚磷酸盐、特别是乙二胺四亚甲基膦酸和二亚乙基三胺五亚甲基膦酸这样的材料。 Any commonly used builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetic acid salts, metal ions, chelating agents such as aminopolycarboxylic phosphate, such materials particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine penta methylene phosphonic acid. 虽然由于明显的环保方面的理由而具有较小优选性,在此磷酸盐增效剂也是可以使用的。 Although for obvious environmental reasons, but less preferred, this phosphate builders may also be used.

合适的增效剂可以是一种无机离子交换材料,通常是一种无机的水合铝硅酸盐材料,更具体地说是一种水合的合成沸石诸如水合的沸石A、X、B或HS。 Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.

其它合适的无机增效材料是层状的硅酸盐,例如SKS-6(Hoechst生产)。 Other suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst Ltd.). SKS-6是一种结晶状的、由硅酸钠(Na2Si2O5)所组成的层状硅酸盐。 SKS-6 is a crystalline layered silicate consisting of sodium silicate (of Na2Si2O5) thereof.

合适的含有一个羧基的聚羧酸盐包括乳酸、羟基乙酸及它们的醚衍生物,如已在比利时专利Nos.831,368、821,369和821,370中已经公开的那些。 Suitable carboxy group containing one polycarboxylates include lactic acid, glycolic acid and ether derivatives thereof as disclosed already and in Belgian Patent 821,370 Nos.831,368,821,369 those. 含有两个羧基的聚羧酸盐包括丁二酸、丙二酸、(亚乙基二氧)二醋酸、马来酸、二乙醇酸、酒石酸、羟基丙二酸和富马酸的水溶性盐以及醚羧酸盐,如在德国专利2,446,686和2,446,687以及美国专利No.3,935,257中所描述的那些,以及比利时专利No.840,623中描述的亚硫酰基羧酸盐。 Polycarboxylates containing two carboxy groups include salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, water-soluble salts as well as the ether carboxylates, as described in German Patent 2,446,686 and 2,446,687 and the sulfinyl carboxylates those Belgian Patent No.840,623 and U.S. Patent No.3,935,257 as described herein. 含有三个羧基的聚羧酸盐具体包括英国专利No.1,379,241中描述过的水溶性的柠檬酸盐、乌头酸盐、柠康酸盐以及丁二酸盐衍生物诸如羧甲氧基丁二酸盐等;荷兰专利申请7205873中描述过的乳酰氧丁二酸盐,以及氧聚羧酸盐材料诸如英国专利No.1,387,447中描述过的2-氧杂-1,1,3-丙烷三羧酸盐。 Water-soluble salts of citric acid, aconitic acid, citraconic as well as succinate derivatives are described in British Patent No.1,379,241 Polycarboxylates containing three carboxy groups include, in particular two such carboxylic methoxybutanol acid salt; described in Netherlands Patent application 7205873 milk acyloxy succinate, and the oxypolycarboxylate materials such as described in British Patent No.1,387,447 had three 2-oxa-1,1,3-propane carboxylate.

含有四个羧基的聚羧酸盐包括英国专利No.1,261,829中公开的氧二丁二酸盐、1,1,2,2-乙烷四羧酸盐、1,1,3,3-丙烷四羧酸盐和1,1,2,3-丙烷四羧酸盐。 Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No.1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates carboxylates and 1,1,2,3-propane tetracarboxylates. 含有磺酸取代基的多羧酸盐包括英国专利Nos.1,398,421和1,398,422及美国专利No.3,936,448中公开的磺酸基丁二酸盐衍生物;英国专利No.1,082,179描述过的磺化的热解柠檬酸盐;而含有膦酸取代基的多羧酸盐则已在英国专利No.1,439,000中被公开。 Polycarboxylates containing a sulfonic acid group include substituted and 1,398,422 and British Patent Nos.1,398,421 acid sulfosuccinate derivatives disclosed in U.S. Patent No.3,936,448; described in British Patent No.1,082,179 pyrolyzed sulfonated citrate; and polycarboxylate containing phosphonic acid substituents are disclosed in British Patent already in No.1,439,000.

脂环和杂环的多羧酸盐包括环戊烷-顺、顺、顺四羧酸盐、环戊二烯五羧酸盐、2,3,4,5-四氢呋喃-顺、顺、顺四羧酸盐、2,5-四氢呋喃-顺二羧酸盐、2,2,5,5-四氢呋喃四羧酸盐、1,2,3,4,5,6-己烷六羧酸盐、以及多元醇诸如山梨醇、甘露糖醇和木糖醇的羧甲基衍生物。 Alicyclic polycarboxylates include cyclopentane and heterocyclic - cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-four carboxylate, 2,5-tetrahydrofuran - cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane hexacarboxylates and polyhydric alcohols such as sorbitol, mannitol and carboxymethyl derivatives of xylitol. 芳香族多羧酸盐包括英国专利No.1,425,343中公开的蜜石酸、1,2,4,5-苯四酸以及邻苯二甲酸的衍生物。 Aromatic polycarboxylates include mellitic acid rock in British Patent No.1,425,343 disclosed, pyromellitic acid and the phthalic acid derivatives.

在上面这些化合物中,经优选的多羧酸盐是每个分子中含有至多三个羧基的羟基多羧酸盐,更具体地说是柠檬酸盐。 Of the above, the preferred polycarboxylates are hydroxyl groups per molecule containing up to three carboxy groups polycarboxylates, more particularly citrates.

用于本发明的经优选的增效体系包括一种不溶于水的铝硅酸盐增效剂诸如沸石A或一种层状的硅酸盐(SKS/6),和一种可溶于水的羧酸盐螫合剂诸如柠檬酸所组成的混合物。 Preferred builder systems used by the present invention comprises a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS / 6), and a watersoluble carboxylate chelating agent such as a mixture consisting of citric acid.

在按照本发明的洗涤剂组合物中,一种为包合用的赘合剂是乙二胺-N,N′-二丁二酸(EDDS)或它的碱金属、碱土金属、铵或取代的铵盐,或它们的混合物。 In detergent compositions according to the present invention in a combination package of the chelator is ethylenediamine -N, N'- disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof. 经优选的EDDS化合物是游离酸的形式以及它的钠盐或镁盐。 Preferred EDDS compounds are the free acid form and the sodium or magnesium salt. 这类经优选的EDDS钠盐的实例包括Na2EDDS和Na4EDDS。 Such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. 这类经优选的EDDS镁盐的实例包括MgEDDS和Mg2EDDS。 Examples of such preferred magnesium salts of EDDS by include MgEDDS and Mg2EDDS. 在按照本发明的组合物中为包合用的最优选的是上述镁盐。 In the composition according to the present invention is most preferably used in combination package The magnesium salts.

特别对于本发明的液体制品,这里所用的合适的脂肪酸增效剂是饱和或不饱和的C10-C18脂肪酸以及相应的肥皂。 Especially for the liquid product of the present invention, suitable fatty acid builders for use herein are saturated or unsaturated C10-C18 fatty acids, and the corresponding soaps. 经优选的饱和物种在其烷基链中含有12至16个碳原子。 It preferred saturated species by containing 12 to 16 carbon atoms in the alkyl chain. 经优选的不饱和脂肪酸是油酸。 Preferred unsaturated fatty acids are oleic through. 用于颗粒型组合物中的经优选的增效剂体系包括由一种不溶于水的铝硅酸盐增效剂诸如沸石A以及一种水溶性的羧酸盐螫合剂诸如柠檬酸所组成的混合物。 Builder systems for use in granular compositions include preferably made by a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid mixture.

可形成颗粒型组合物中增效剂体系的一部分的其它增效剂材料包括无机材料,诸如碱金属的碳酸盐、碳酸氢盐、硅酸盐以及有机材料,诸如有机膦酸盐、氨基聚亚烷基膦酸盐以及氨基聚羧酸盐。 Other builder materials may form part of compositions in particulate builder system include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino poly alkylene phosphonates and amino polycarboxylates.

别的合适的水溶性有机盐有均聚或共聚的羧酸及它们的盐,其中的聚羧酸部分至少含有两个彼此被不多于两个碳原子分开的羧基。 Other suitable water soluble organic salts are the homo- or copolymeric acids or their salts in which the polycarboxylic acid comprises at least two portions is not more than two carbon atoms separate the carboxyl groups from each other.

这种类型的聚合物已在GB-A-1,596,756中被公开。 Polymers of this type are disclosed in GB-A-1,596,756 in. 这类盐的实例有分子量为2000-5000的聚丙烯酸盐以及它们与马来酸酐的共聚物,诸如具有分子最为20,000至70,000,特别是大约40,000的这类共聚物。 Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such as a molecule most 20,000 to 70,000, especially about 40,000 such copolymers.

包含在洗涤剂中的增效剂盐类的含量一般是组合物重量的10%至80%,优选地是20%至70%,最常用的是30%至60%(重量)。 Content included in the detergent builder salts is generally from 10 to 80% by weight of the composition, preferably 20-70%, is the most commonly used (by weight) 30 to 60%.

另一种供选择的组分是抑泡剂,具体实例有聚硅氧烷和硅石-聚硅氧烷混合物。 Another optional ingredient is a suds suppressor, exemplified by silicones, and silica - silicone mixtures. 聚硅氧烷一般可用烷基化的聚硅醚材料来代表,而硅石一般是以粉细的形式使用,具体实例有硅石-空气凝胶和干凝胶以及各种类型的疏水性硅石。 Silicone materials generally polysiloxanes represented by alkylated, while silica is normally used in the form of fine powder is, specific examples with silica - airgel and xerogels and hydrophobic silicas of various types. 这些材料可以微粒的形式被掺入,在微粒中抑泡剂可有益地释出,从而掺入到水溶性的或可在水中被分散的、基本上是非表面活性的洗涤剂的不透性载体中。 These materials can be incorporated as particulates, particulate suds suppressor may be advantageously releasably incorporated in a water-soluble or may be dispersed in water, substantially non-surface active detergent impermeable carrier in. 另一种方法是把抑泡剂溶解或分散到一种液体载体中,并通过喷雾施用到一种或多种其它组分上。 Another method is the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.

一种经优选的聚硅氧烷泡沫控制剂已在Bartollota等人的美国专利3,933,672中被公开。 Silicone suds controlling agent which has been disclosed by preferred in Bartollota et al., U.S. Patent No. 3,933,672. 另一种特别有用的抑泡剂是自乳化聚硅氧烷抑泡剂,已在1977年4月28日发行的德国专利申请DTOS2,646,126中被描述过。 Another particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent issued April 28, 1977 application was described in DTOS2,646,126. 这类化合物的一个实例是DC-544,可从Dow Corning公司买到,它是一种硅氧烷-乙二醇共聚物。 An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane - glycol copolymers. 特别优选的泡沫控制剂是含有硅氧烷油和2-烷基-烷醇的混合物的抑泡剂体系。 Especially preferred suds controlling agent containing silicone oils and 2-alkyl - suds suppressor system comprising a mixture of alkanol. 合适的2-烷基-烷醇有2-丁基-辛醇,它的商品名称为Isofol 12R,可从市场上买到。 Suitable 2-alkyl - 2-butyl alkanol - octanol, which is the trade name Isofol 12R, available from the market.

这类抑泡剂体系已在1992年11月10日提交的共同未决的欧洲专利申请N92870174.7中被描述过。 Such suds suppressor system in N92870174.7 has been described in co-pending European Patent November 10, 1992 filed.

特别优选的硅氧烷泡沫控制剂已在共同未决的欧洲专利申请N92201649.8中被描述过。 Especially preferred silicone suds controlling agents are described in application N92201649.8 in copending European Patent. 所说的组合物中可含有一种聚硅氧烷/硅石混合物,并与雾状无孔隙硅石诸如AerosilR结合在一起使用。 Said compositions may comprise a silicone / silica mixture, and with fumed nonporous silica such as AerosilR combined together.

上述抑泡剂通常使用的浓度为组合物重量的0.001%至2%,优选地是0.01%至1%(重量)。 The concentration of the suds suppressors used is generally from 0.001 to 2% by weight of the composition, preferably (by weight) from 0.01 to 1%.

生洗涤剂组合中还可使用别的组分,诸如污垢悬浮剂、污垢释放剂、荧光增白剂、研磨剂、杀菌剂、晦暗抑制剂、着色剂和/或包封或为包封的香料。 Students may also use other detergent composition components such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and / or encapsulated perfume is encapsulated or .

在这里适用的抗再沉积剂和污垢悬浮剂包括纤维素衍生物诸如甲基纤维素、羧甲基纤维素和羟乙基纤维素以及均聚或共聚的聚羧酸或它们的盐。 Here Suitable anti-redeposition and soil suspending agents include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarboxylic acids or their salts. 这种类型的聚合物包括前面作为增效剂叙述过的聚丙烯酸酯和马来酸酐-丙烯酸共聚物,以及马来酸酐和乙烯、甲基乙烯基醚或甲基丙烯酸的共聚物,其中马来酸酐应在共聚物中占有至少20%(摩尔)。 Polymers of this type include those previously described as builders polyacrylates and maleic anhydride - acrylic acid copolymers, and copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20% (by mole) in the copolymer. 这些材料在组合物中的用量通常为0.5%至10%(重量),更优选的是075%至8%,最优选的是1%至6%(重量)。 These materials are used in the composition is usually from 0.5 to 10% (by weight), and more preferably from 075 to 8%, most preferably (by weight) 1-6%.

优选的荧光增白剂在性质上是阴离子型的,它的实例有4,4′-双-(2-二乙醇氨基-4-苯胺基-s-三嗪-6-基氨基)芪-2:2′-二磺酸二钠盐、4,4′-双-(2-吗啉基-4-苯胺基-s-三嗪-6-基氨基)芪-2:2′-二磺酸二钠盐、4,4'-双-(2,4-二苯胺基-s-三嗪-6-基氨基)芪-2:2'-二磺酸二钠盐、4',4″-双(2,4-二苯胺基-s-三嗪-6-基氨基)芪-2-磺酸单钠盐、4,4'-双-(2-苯胺基-4-(N-甲基-N-2-羟乙基氨基)-s-三嗪-6-基氨基)芪-2,2'-二磺酸二钠盐、4,4′-双-(4-苯基-2,1,3-三唑-2-基)芪-2,2'-二磺酸二钠盐、4,4′-双-(2-苯胺基-4-(1-甲基-2-羟乙基氨基)-s-三嗪-6-基氨基)芪-2,2'-二磺酸二钠盐以及2-(芪基-4″-萘并-1',2':4、5)-1,2,3-三唑-2″-磺酸钠。 Preferred optical brighteners are anionic in nature, its examples are 4,4'-bis - (2-amino-4-anilino -s- alcohol triazin-6-ylamino) stilbene -2 : 2'-disulphonate, disodium 4,4'-bis - (2-morpholino-4-anilino -s- triazin-6-ylamino) stilbene-2: 2'-disulfonate disodium 4,4'-bis - (2,4-dianilino -s- triazin-6-ylamino) stilbene-2: 2'-disulphonic acid disodium salt, 4 ', 4 "- bis (2,4-dianilino -s- triazin-6-ylamino) stilbene-2-sulfonic acid monosodium salt, 4,4-bis - (2-anilino--4- (N- methyl -N-2- hydroxyethylamino) -s- triazin-6-ylamino) stilbene-2,2'-disulfonic acid disodium salt, 4,4'-bis - (4-phenyl-2, 1,3-triazol-2-yl) stilbene-2,2'-disulfonic acid disodium salt, 4,4'-bis - (2-anilino-4- (1-methyl-2-hydroxyethyl acetate yl amino) -s- triazin-6-ylamino) stilbene-2,2'-disulfonic acid disodium salt and 2- (stilbene-4 "- naphtho-1 ', 2': 4,5) 1,2,3-triazole-2 "- sodium.

其它有用的聚合材料有聚乙二醇,优选的是那些分子量为1,000~10,000,更优选的是2,000~8,000,最优选的是大约4,000的聚乙二醇。 Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight from 1,000 to 10,000, more preferably 2,000 to 8,000, and most preferably about 4000.. 这些材料使用的浓度为0.2%至5%,更好是0.25%至2.5%(重量)。 These are used at 0.2% to 5%, more preferably (by weight) from 0.25 to 2.5 percent. 这些聚合物和前面叙述的均聚或共聚的聚羧酸盐,在过渡金属杂质存在的条件下对于改进白度的维持、织物上灰尘沉积、对粘土、蛋白质的和可氧化的污垢的洗涤性能等方面都是有价值的。 These recited polymers and the previously mentioned homo- or copolymeric polycarboxylates, in the presence of transition metal impurities for improving whiteness maintenance, fabric ash deposition, wash performance on clay, proteinaceous and oxidizable soils etc. is valuable.

用于本发明组合物中的污垢释出剂通常是以不同的排列方式制成的对苯二甲酸与乙二醇和/或丙二醇单位的共聚物或三元共聚物。 Used in the compositions of the present invention is typically a soil release agent of terephthalic acid with ethylene glycol and / or propylene glycol units in a copolymer or terpolymer made different arrangements. 这类聚合物的实例已在共同转让的美国专利Nos.4116885和4711730以及欧洲公开专利申请No.0272033中被公开。 Examples of such polymers are disclosed in commonly assigned U.S. Patent Nos.4116885 and 4711730 and European Published Patent Application No.0272033 in.

按照EP-A-0272033,一种具体的经优选的聚合物具有下式:(CH3(PEG)43)0.75(POH)0.25[T-PO)2.8(T-PEG)0.4]T(PO-H)0.25((PEG)43CH3)0.75其中PEG是-(OC2H4)O-,PO是(OC3H6O),T是(PCOC6H4CO)。 According to EP-A-0272033, A particular preferred polymer in having the formula: (CH3 (PEG) 43) 0.75 (POH) 0.25 [T-PO) 2.8 (T-PEG) 0.4] T (POH ) 0.25 ((PEG) 43CH3) 0.75 where PEG is - (OC2H4) O-, PO is (OC3H6O), T is (pCOC6H4CO).

经修饰的聚酯,例如对苯二甲酸二甲酯、磺酸基间苯二甲酸二甲酯、乙二醇和1,2丙二醇的无规共聚物,其端基主要由磺基苯甲酸酯和其次由乙二醇和/或丙二醇的单酯所组成,也是非常有用的。 Modified polyesters such as dimethyl terephthalate, dimethyl sulfoisophthalic acid, ethylene glycol and 1,2-propylene glycol random copolymer, which end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and / or propane-diol, it is also useful. 目标是获得一种两端都带有磺基苯甲酸酯基的聚合物。 The goal is to obtain a polymer capped at both end by sulphobenzoate groups groups. 这里的上下文中“主要”是指大部分所说的共聚物都带有磺基苯甲酸酯基作为端基。 Context herein, "primarily" refers to most of said copolymers with sulfonic acid ester groups as end groups. 不过,有些共聚物没有完全带上这一种端基,因此它们的端基是由乙二醇和/或1,2-丙二醇的单酯所组成,即这类物种中“次要”的部分。 However, some copolymers will be less than fully capped end groups, and therefore their end groups are ethylene glycol and / or 1,2-propanediol monoester composed of such species "secondarily".

这里选择的聚酯含有大约46%(重量)的对苯二甲酸二甲酯,大约16%(重量)的1,2-丙二醇,大约10%(重量)的乙二醇,大约13%(重量)的磺基苯甲酸二甲酯以及大约15%(重量)的磺基间苯二甲酸,其分子量为大约3,000。 The selected polyesters herein contain about 46% (by weight) of dimethyl terephthalate, about 16% (by weight) of 1,2-propanediol, about 10% (by weight) ethylene glycol, about 13% (wt. ) between the dimethyl sulfobenzoic acid and about 15% (by weight) of sulfoisophthalic acid having a molecular weight of about 3,000. 这种聚酯以及它们的制备方法已在EPA311342中被详尽地描述过。 The polyesters and their method of preparation have been described in detail in EPA311342.

本发明的洗涤剂组合物可以是液体、糊状、凝胶或颗粒的形式。 The detergent compositions of the invention may be in the form of liquid, paste, gels or granular forms.

特别优选的洗涤剂组合物是那些pH值在7-11之间,更好是pH值在9-10.5之间的洗涤剂组合物。 Especially preferred detergent compositions are those pH between 7-11, more preferably a pH between 9-10.5 The detergent composition of.

本发明的颗粒状组合物也可以是“密实型”的,即它们具有比通常的颗粒状洗涤剂更高的密度,约为550至950克/升;在这种情况下,本发明的颗粒状洗涤剂组合物将包含比通常的颗粒状洗涤剂更少量的“无机填充盐”;典型的填充盐有碱土金属的硫酸盐和氯化物,典型地是硫酸钠;“密实型”的洗涤剂典型地含有不多于10%的填充盐。 Granular compositions according to the present invention may be a "dense", i.e. they have a higher density than conventional granular detergents, from about 550 to 950 g / l; in this case, particles of the invention shaped detergent compositions will contain a lower amount of "inorganic filler salt" than conventional granular detergents; typical filler salts are alkaline earth metal sulfates and chlorides, typically sodium sulphate; "dense" detergents typically contains more than 10% filler salt. 本发明的液体组合物也可以是“浓缩型”的,在这种情况下,本发明的液体洗涤剂组合物将含有比通常的液体洗涤剂更少的水。 Liquid compositions of the invention can also be in "concentrated form", in such case, the liquid detergent compositions of the present invention will contain less than the normal liquid detergent water. 典型地,浓缩型液体洗涤剂的水含量少于洗涤剂组合物重量的30%,更优选的是少于20%,最优选的少于10%。 Typically, the water content of the concentrated liquid detergent is less than 30% by weight of the detergent composition, more preferably less than 20%, most preferably less than 10%. 液体组合物的其它实例有基本上不含水的无水组合物。 Other examples of liquid compositions are anhydrous compositions containing substantially no water.

无论是水溶液的还是非水溶液的液体组合物都可以是有明确结构的或没有明确结构的。 Either aqueous or non-aqueous liquid composition may be a clear structure, or there is no clear structure.

本发明也涉及一种抑制溶解的或悬浮的染料从一种织物转移到另一种织物上去的方法,这种转移在涉及染色织物的洗涤操作过程中常会遇到。 The present invention also relates to a method of inhibiting dissolution or suspension of dye transfer from one fabric to another fabric up, this transfer during wash operations Central Standing Committee encountered relates to dyed fabrics.

这种方法包括将织物与前面所叙述的洗涤溶液进行接触。 Such methods include fabrics with a washing solution previously described contact.

本发明的方法可以在洗涤操作的进程中方便地实施。 The method of the present invention may be conveniently implemented in the process of the washing operation. 洗涤操作是在5℃至75℃实施,尤其是20至60℃,但聚合物在高至95℃或更高的温度下仍是有效的,处理溶液的pH值最好是由7至11,特别是由7.5至10.5。 Washing operation is at 75 deg.] C to 5 ℃ embodiment, in particular 20 to 60 ℃, but at a higher polymer to 95 deg.] C or higher is still valid, the process pH of the solution is preferably from 7 to 11, in particular from 7.5 and 10.5.

本发明的方法和组合物也能以洗涤剂添加剂产物的形式来使用。 The methods and compositions of the present invention can also be in the form of a detergent additive products to use.

这类添加剂产物是想用来补充或增进通常的洗涤剂组合物的性能。 Such additive products are intended to supplement or enhance wanted normal performance of the detergent composition.

本发明的洗涤剂组合物包括那些被用来洗涤底物,诸如织物、纤维、硬表面、皮肤等的组合物,例如硬表面洗涤组合物(带有或不带研磨剂)、洗衣洗涤剂组合物、自动和非自动的洗碟用组合物。 The detergent composition of the present invention include those compositions are used to wash a substrate, such as fabrics, fibers, hard surfaces, skin etc., for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions It was automatic and non automatic dishwashing compositions.

下面的实例意在举例说明本发明的组合物,但不是用来限制或定义本发明的范围,所说的范围应按照随后的权利要求来决定。 The following examples are meant to exemplify compositions of the present invention, but not intended to limit or define the scope of the invention, said scope being determined according to claims which follow. 实例Ⅰ(A/B/C/D)一种液体的本发明的洗涤剂组合物被制备,它具有下列组分: Examples Ⅰ (A / B / C / D) The detergent compositions of the present invention is a liquid preparation, having the following components:

在总的洗涤剂组合物中所占的重量%A B C D线型烷基苯磺酸盐 10 - - -聚羟基脂肪酸酰胺 - 5 - 3烷基烷氧基化的硫酸盐 - - 9 4烷基硫酸盐 4 8 4 15脂肪醇(C12-C15)乙氧化物 12 12 12 5脂肪酸 10 10 10 10油酸 4 4 4 -柠檬酸 1 1 1 1二亚乙基三胺五亚甲基膦酸 1.5 1.5 1.5 1.5NaOH 3.4 3.4 3.4 3.4丙二醇 1.5 1.5 1.5 1.5乙醇 10 10 10 10乙氧化的四亚乙基五胺 0.7 0.7 0.7 0.7Thermamyl R 300 KNU/g 0.1 0.1 0.1 0.1Carezyme R 5000 CEVU/g 0.02 0.02 0.02 0.02蛋白酶40mg/g In the total detergent composition weight% ABCD linear alkyl benzene sulfonate 10 - - - Poly hydroxy fatty acid amide --5--3 alkyl alkoxylated sulfate - - C4 alkyl sulfate. 9 salt 4 8 4 15 (C12-C15) fatty alcohol ethoxylate 1212125 fatty acid 10 10 10 10 oleic acid 4 4 4 - citric acid 1 1 1 1 diethylene triamine penta methylene phosphonic acid 1.5 1.5 1.5 1.5NaOH 3.4 3.4 3.4 3.4 1.5 1.5 1.5 propanediol 1.5 ethanol 10 10 10 10 ethoxylated tetraethylene pentamine 0.7 0.7 0.7 0.7Thermamyl R 300 KNU / g 0.1 0.1 0.1 0.1Carezyme R 5000 CEVU / g 0.02 0.02 0.02 0.02 protease 40mg / g 1.8 1.8 1.8 1.8Lipolase R 100 KLU/g 0.1 0.1 0.1 0.1Endoglucanase A 5000 CEVU/g 0.5 0.5 0.5 0.5抑泡剂(ISOFOLr) 2.5 2.5 2.5 2.5H2O27.5 7.5 - -N-乙烯基咪唑N-乙烯基 0.1-1 0.1-1 0.1-1 0.1-1吡咯烷酮共聚物次要的配合剂 加到100实例Ⅱ(A/B/C/D)一种液体的本发明的洗涤剂组合物被制备,它具有以下的组分:在总的洗涤剂组合物中所占的重量%A B C D线型烷基苯磺酸盐 10 - - -聚羟基脂肪酸酰胺 - 5 - 3烷基烷氧基化的硫酸盐 - - 9 4烷基硫酸盐 4 8 4 15脂肪醇(C12-C15)乙氧化物 12 12 12 5脂肪酸 10 10 10 10油酸 1.8 1.8 1.8 1.8Lipolase R 100 KLU / g 0.1 0.1 0.1 0.1Endoglucanase A 5000 CEVU / g 0.5 0.5 0.5 0.5 suds suppressors (ISOFOLr) 2.5 2.5 2.5 2.5H2O27.5 7.5 - -N- vinylimidazole N- vinyl-0.1 pyrrolidone copolymer 0.1-1 0.1-1 0.1-1 -1 minor ingredients to 100 examples ⅱ (a / B / C / D) the detergent compositions of the present invention is a liquid preparation, which has the following component: in the total detergent composition weight% ABCD linear alkyl benzene sulfonate 10 - - - poly hydroxy fatty acid amide --5--3 alkyl alkoxylated sulfate - - 9 4 48415 alkyl sulfates of fatty alcohols (C12-C15) ethoxylate 1,212,125 oleic fatty acid 10 10 10 10 4 4 4 -柠檬酸 1 1 1 1二亚乙基三胺五亚甲基膦酸 1.5 1.5 1.5 1.5NaOH 3.4 3.4 3.4 3.4丙二醇 1.5 1.5 1.5 1.5乙醇 10 10 10 10乙氧化的四亚乙基五胺 0.7 0.7 0.7 0.7Thermamyl R 300 KNU/g 0.1 0.1 0.1 0.1Carezyme R 5000 CEVU/g 0.02 0.02 0.02 0.02蛋白酶40mg/g 1.8 1.8 1.8 1.8Lipolase R 100 KLU/g 0.1 0.1 0.1 0.1Endoglucanase A 5000 CEVU/g 0.5 0.5 0.5 0.5抑泡剂(ISOFOLr) 2.5 2.5 2.5 2.5H2O27.5 7.5 - -N-乙烯基咪唑N-乙烯基 0.1-1 0.1-1 0.1-1 0.1-1吡咯烷酮共聚物金属催化剂 0.1-1 0.1-1 4 4 4 - Citric acid 1 1 1 1 Diethylene triamine penta methylene phosphonic acid 1.5 1.5 1.5 1.5NaOH 3.4 3.4 3.4 3.4 1.5 1.5 1.5 Propanediol 1.5 Ethanol 10 10 10 10 Ethoxylated tetraethylene pentamine 0.7 0.7 0.7 0.7Thermamyl R 300 KNU / g 0.1 0.1 0.1 0.1Carezyme R 5000 CEVU / g 0.02 0.02 0.02 0.02 protease 40mg / g 1.8 1.8 1.8 1.8Lipolase R 100 KLU / g 0.1 0.1 0.1 0.1Endoglucanase A 5000 CEVU / g 0.5 0.5 0.5 0.5 suds suppressors (ISOFOLr) 2.5 2.5 2.5 2.5H2O27.5 7.5 - -N- vinylimidazole N- vinyl pyrrolidone copolymer 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1 metal catalyst 0.1-1 0.1-1聚(4-乙烯基吡啶)-N-氧化物 0.1-1 0.1-1 0.1-1 0.1-1白土 - - 4 4过氧化物酶 0.1 0.1 - -次要的配合剂 加到100实例Ⅲ(A/B/C/D/E)本发明的一种紧密型颗粒状洗涤剂组合物被制备,它具有以下配方:在总的洗涤剂组合物中所占的重量%A B C D E线型烷基苯磺酸盐 11.40 - - - -聚羟基脂肪酸酰胺 - 10 - - -烷基烷氧基化的硫酸盐 - - 9 9 9牛脂烷基硫酸盐 1.80 1.80 1.80 1.80 1.80C45烷基硫酸盐 3.00 3.00 3.00 3.00 3.007倍乙氧基化的C45醇 4.00 4.00 4.00 4.00 4.0011倍乙氧基化的牛脂醇 1.80 1.80 1.80 1.80 1.80分散剂 0.07 0.07 0.07 0.07 0.07聚硅氧烷流体 0.80 0.8 0.1-1 0.1-1 Poly (4-vinylpyridine) -N--oxide 0.1-1 0.1-1 0.1-1 0.1-1 clay - - 4 4 peroxidase 0.1 0.1 - - minor ingredients plus examples 100 to ⅲ (a / B / C / D / E) of the present invention, one kind of compact granular detergent composition is prepared having the following formulation: in the total detergent composition weight% ABCDE linear alkyl benzene sulfonate 11.40 - - - - poly hydroxy fatty acid amide - 10 - - - alkyl alkoxylated sulfate - -. 9. 9. 9 tallow alkyl sulphate 1.80 1.80 1.80 1.80 1.80C45 alkyl sulphate 0.07 0.07 0.07 0.07 0.07 silicone fluid 1.80 1.80 1.80 1.80 1.80 dispersant 3.00 3.00 3.00 3.00 salt 3.007 times ethoxylated C45 alcohol 4.00 4.00 4.00 4.00 4.0011 times ethoxylated 0.80 tallow alcohol 0.8 0 0.80 0.80 0.80柠檬酸三钠 14.00 14.00 14.00 14.00 14.00柠檬酸 3.00 3.00 3.00 3.00 3.00沸石 32.50 32.50 32.50 32.50 32.50二亚乙基三胺五亚甲基磷酸 0.6 0.6 0.6 0.6 0.6马来酸丙烯酸共聚物 5.00 5.00 5.00 5.00 5.00纤维素酶(活性蛋白质) 0.03 0.03 0.03 0.03 0.03Alkalase/BAN 0.60 0.60 0.60 0.60 0.60Lipolase 0.36 0.36 0.36 0.36 0.36硅酸钠 2.00 2.00 2.00 2.00 2.00硫酸钠 3.50 3.50 3.50 3.50 3.50过碳酸盐 - - - 20 -过硼酸盐 15 15 15 - -TAED 5 - 5 5 -N-乙烯基咪唑N-乙 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1烯基吡咯烷酮共聚物次要的配合剂 0 0.80 0.80 0.80 citric acid acrylic acid copolymer 0.6 0.6 0.6 0.6 0.6 maleic trisodium citrate 14.00 14.00 14.00 14.00 14.00 3.00 3.00 3.00 3.00 3.00 32.50 32.50 32.50 32.50 32.50 Zeolite diethylene triamine penta methylene phosphonic acid 5.00 5.00 5.00 5.00 5.00 cellulase (active protein) 0.03 0.03 0.03 0.03 0.03Alkalase / BAN 0.60 0.60 0.60 0.60 0.60Lipolase 0.36 0.36 0.36 0.36 0.36 2.00 2.00 2.00 2.00 sodium silicate 2.00 sodium sulphate 3.50 3.50 3.50 3.50 3.50 percarbonate - - - 20 - 15 15 15 too borate - -TAED 5 - 5 5 -N--vinylimidazole N- 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1 acetate-vinylpyrrolidone copolymer with minor preparation 加到100实例Ⅳ(A/B/C/D/E)本发明的一种紧密型颗粒状洗涤剂组合物被制备,它具有以下的配方:在总的洗涤剂组合物中所占的重量%A B C D E线型烷基苯磺酸盐 11.40 - - - -聚羟基脂肪酸酰胺 - 10 - - -烷基烷氧基化的硫酸盐 - - 9 9 9牛脂烷基硫酸盐 1.80 1.80 1.80 1.80 1.80C45烷基硫酸盐 3.00 3.00 3.00 3.00 3.007倍乙氧基化的C45醇 4.00 4.00 4.00 4.00 4.0011倍乙氧基化的牛脂醇 1.80 1.80 1.80 1.80 1.80分散剂 0.07 0.07 0.07 0.07 0.07聚硅氧烷流体 0.80 0.80 0.80 0.80 0.80柠檬酸三钠 14.00 14.00 14.00 14.00 14.00柠檬酸 3.00 3.00 3.00 3.00 3.00沸石 32.50 32.50 32.50 32.50 32.50二亚乙基三胺五亚甲 Example 100 was added to one kind Ⅳ (A / B / C / D / E) of the present invention is compact granular detergent composition is prepared having the following formulation: in the total weight of the detergent composition % ABCDE linear alkyl benzene sulphonate 11.40 - - - - poly hydroxy fatty acid amide - 10 - - - alkyl alkoxylated sulfate - -. 9. 9. 9 tallow alkyl sulphate 1.80 1.80 1.80 1.80 1.80C45 alkyl 1.80 1.80 1.80 1.80 1.80 0.07 0.07 0.07 0.07 dispersant 0.07 silicone fluid 3.00 3.00 3.00 3.00 sulfates 3.007 times ethoxylated C45 alcohol 4.00 4.00 4.00 4.00 4.0011 times ethoxylated tallow alcohol 0.80 0.80 0.80 0.80 0.80 trisodium citrate 14.00 14.00 14.00 14.00 14.00 citric acid 3.00 3.00 3.00 3.00 3.00 32.50 32.50 32.50 32.50 32.50 zeolite diethylene triamine pentamethylene 膦酸 0.6 0.6 0.6 0.6 0.6马来酸丙烯酸共聚物 5.00 5.00 5.00 5.00 5.00纤维素酶(活性蛋白质) 0.03 0.03 0.03 0.03 0.03Savinase 0.60 0.60 0.60 0.60 0.60Lipolase 0.36 0.36 0.36 0.36 0.36硅酸钠 2.00 2.00 2.00 2.00 2.00硫酸钠 3.50 3.50 3.50 3.50 3.50过碳酸盐 - - - 20 -过硼酸盐 15 15 15 - -TAED 5 - 5 5 -N-乙烯基咪唑N-乙 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1烯基吡咯烷酮共聚物金属催化剂 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1聚(4-乙烯基吡啶) 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1-N-氧化物白土 - - - 4 4过氧化物酶 - 0.1 0.1 - -次要的配合剂 Phosphonic acid 0.6 0.6 0.6 0.6 0.6 Maleic acid acrylic acid copolymer 5.00 5.00 5.00 5.00 5.00 Cellulase (active protein) 0.03 0.03 0.03 0.03 0.03Savinase 0.60 0.60 0.60 0.60 0.60Lipolase 0.36 0.36 0.36 0.36 0.36 2.00 2.00 2.00 2.00 2.00 Sodium silicate sodium sulphate 3.50 3.50 3.50 3.50 3.50 percarbonate - - - 20 is - over perborate 15 15 15 - -TAED 5 - 5 5 -N- ethyl-vinylimidazole N- 0.1-1 0.1-1 0.1-1 0.1 1-vinylpyrrolidone copolymer 0.1-1 0.1-1 0.1-1 0.1-1 metal catalyst 0.1-1 0.1-1 poly (4-vinylpyridine) 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1- N- oxide clay - - -. 4. 4 peroxidase - 0.1 0.1 - - minor ingredients 到100 To 100

上述组合物(实例Ⅰ、Ⅱ(A/B/C/D)和实例Ⅲ、Ⅳ(A/B/C/D/E))是很好的洗涤剂组合物,它显示出优良的去污和洗涤性能,并且在洗涤染色织物以及染色织物和白色织物的混合物时具有显著的照顾颜色的性能。 The above-described composition (Example Ⅰ, Ⅱ (A / B / C / D), and examples Ⅲ, Ⅳ (A / B / C / D / E)) is a good detergent composition which exhibits excellent detergency and wash performance, with significant performance and color care when laundering dyed fabrics, and a mixture of dyed fabrics and white fabrics.

Claims (10)

  1. 1. 1. 一种含有一种表面活性剂体系和一种共聚物的洗涤剂组合物,其特征在于所说的组合物含有3%-65%的表面活性剂体系,0.01%-10%的共聚物,和平衡至100%量的其它洗涤剂组分,其中所说的共聚物为平均分子量范围为10,000至20,000的N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物。 Systems containing an active agent and a copolymer surface detergent composition, wherein said composition contains from 3% -65% of the surfactant system, from 0.01% to 10% of the copolymer, and balance to 100% of the amount of the other detergent ingredients, wherein said copolymer having an average molecular weight ranging from 10,000 to 20,000 N- vinylimidazole N- vinylpyrrolidone copolymers.
  2. 2. 2. 一种权利要求1的洗涤剂组合物,其中还进一步含有一种表面活性剂体系,其中的表面活性剂可以选自非离子型的和/或阴离子型的和/或阳离子型的和/或两性的和/或两性离子型的和/或半极性的表面活性剂。 A detergent composition as claimed in claim 1, wherein further comprising a surfactant system wherein the surfactant can be selected from nonionic and / or anionic and / or cationic and / or amphoteric and / or zwitterionic and / or semi-polar surfactants.
  3. 3. 3. 一种权利要求2的洗涤剂组合物,其中所说的表面活性剂体系含有一种选自烷氧基化的硫酸盐的阴离子型表面活性剂。 A detergent composition as claimed in claim 2, wherein said surfactant system comprising an anionic surfactant one compound selected from alkoxylated sulfates.
  4. 4. 4. 一种权利要求3的洗涤剂组合物,它含有一种选自阴离子型表面活性剂或阳离子型的和/或两性的表面活性剂的表面活性剂。 A detergent composition as claimed in claim 3, which contains a surfactant selected from anionic or cationic surfactants and / or amphoteric surfactants.
  5. 5. 5. 一种权利要求1的洗涤剂组合物,其中还进一步含有一种选自纤维素酶、过氧化物酶、淀粉酶、蛋白酶或它们的混合物的酶。 A detergent composition as claimed in claim 1, wherein further comprises one selected from a cellulase, a peroxidase enzyme, amylases, protease or mixtures thereof.
  6. 6. 6. 一种权利要求5的洗涤剂组合物,其中所说的酶是选自纤维素酶或过氧化物酶和它们的混合物。 A detergent composition as claimed in claim 5, wherein said enzyme is selected from cellulases or peroxidases and mixtures thereof.
  7. 7. 7. 一种权利要求1的洗涤剂组合物,它还进一步还含有一种白土。 A detergent composition as claimed in claim 1, which further contains a further clay.
  8. 8. 8. 一种权利要求1的洗涤剂组合物,它是颗粒型的、液体型的、凝胶型的或糊状的。 A detergent composition as claimed in claim 1, which is a granular type, liquid type, a gel type or a paste.
  9. 9. 9. 一种权利要求1的洗涤剂组合物,其中洗涤剂组合物的pH值是在7~11之间。 A detergent composition as claimed in claim 1, wherein the pH of the detergent composition is between 7-11.
  10. 10. 10. 一种权利要求1的洗涤剂组合物,它是一种非粉尘的颗粒型或液体型的洗涤剂添加剂。 The detergent composition which is a non-dusting granulates type or liquid type detergent additive of Claim.
CN 94193285 1993-07-23 1994-06-20 Detergent composition for inhibiting dye transfer CN1046955C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19930870154 EP0635565B1 (en) 1993-07-23 1993-07-23 Detergent compositions inhibiting dye transfer

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CN1130400A true CN1130400A (en) 1996-09-04
CN1046955C true CN1046955C (en) 1999-12-01

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EP (1) EP0635565B1 (en)
JP (1) JP3795067B2 (en)
CN (1) CN1046955C (en)
CA (1) CA2167371C (en)
DE (2) DE69315207T2 (en)
DK (1) DK0635565T3 (en)
ES (1) ES2109471T3 (en)
WO (1) WO1995003388A1 (en)

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GB9526181D0 (en) * 1995-12-21 1996-02-21 Unilever Plc A detergent composition
ES2163091T3 (en) 1996-01-25 2002-01-16 Unilever Nv Detergent composition.
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US5880081A (en) * 1997-04-07 1999-03-09 Gopalkrishnan; Sridhar Concentrated built liquid detergents containing a dye-transfer inhibiting additive
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DE10353310A1 (en) * 2003-11-10 2005-06-09 Maier, Ursula, Dipl.-Ing. Use of a solution with at least one nonionic surfactant
DE102005039580A1 (en) 2005-08-19 2007-02-22 Henkel Kgaa Color Protective detergent
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CN101531956B (en) 2009-04-27 2012-09-26 四川益欣精细化工有限责任公司 Environmental-friendly type foamless anti-staining detergent, preparing method and application thereof
DE102012219403A1 (en) 2012-10-24 2014-04-24 Henkel Ag & Co. Kgaa Use of metal ion chelates obtained by polymerization of monoethylenically unsaturated mono-or di-carboxylic polymers to e.g. prevent the transfer of textile dyes from dyed textiles to undyed textiles, or other color in the common laundry
DE102013203484A1 (en) 2013-03-01 2014-09-04 Henkel Ag & Co. Kgaa Color Protective detergent
DE102014220662A1 (en) 2014-10-13 2016-04-14 Henkel Ag & Co. Kgaa Color Protective detergent
DE102014220663A1 (en) 2014-10-13 2016-04-14 Henkel Ag & Co. Kgaa Color Protective detergent

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JPH09502744A (en) 1997-03-18 application
DE69315207T2 (en) 1998-04-16 grant
EP0635565A1 (en) 1995-01-25 application
DE69315207D1 (en) 1997-12-18 grant
DK635565T3 (en) grant
DK0635565T3 (en) 1997-12-22 grant
CA2167371A1 (en) 1995-02-02 application
ES2109471T3 (en) 1998-01-16 grant
EP0635565B1 (en) 1997-11-12 grant
CA2167371C (en) 1999-11-02 grant
CN1130400A (en) 1996-09-04 application
JP3795067B2 (en) 2006-07-12 grant
WO1995003388A1 (en) 1995-02-02 application

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