CN102257109B - Laundry detergent composition - Google Patents

Laundry detergent composition Download PDF

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CN102257109B
CN102257109B CN2009801510329A CN200980151032A CN102257109B CN 102257109 B CN102257109 B CN 102257109B CN 2009801510329 A CN2009801510329 A CN 2009801510329A CN 200980151032 A CN200980151032 A CN 200980151032A CN 102257109 B CN102257109 B CN 102257109B
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surfactant
composition according
composition
hydroxamate
ratio
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CN2009801510329A
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CN102257109A (en
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I.霍韦尔
A.麦克基
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荷兰联合利华有限公司
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Priority to EP08171904.9 priority
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Priority to PCT/EP2009/067193 priority patent/WO2010069957A1/en
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86Ternary Mixtures of anionic, cationic, and non-ionic compounds

Abstract

本发明涉及包含0.5到20wt%异羟肟酸盐和5到80wt%表面活性剂体系的洗衣组合物,该表面活性剂体系包含比例为1∶1.1到19∶1的阴离子表面活性剂和非离子表面活性剂。 The present invention relates to compositions comprising 0.5 to 20wt% hydroxamate 5 to 80wt% and a laundry composition of a surfactant system, the surfactant system contains a proportion of anionic surface active agents 1:1.1 to 19:1 and nonionic Surfactant. 该组合物显示出增强的污渍去除,特别是对于颗粒污渍。 The compositions exhibit enhanced stain removal, especially for particulate soiling.

Description

洗衣洗涤剂组合物 Laundry detergent composition

[0001] 本发明涉及在具有低浓度的沸石和磷酸盐助洗剂的洗衣洗涤剂组合物(laundrydetergent compositions)中使用异轻I亏酸及其相应的盐,导致改善的去污力和污溃去除。 [0001] The present invention relates to the use of different acids and corresponding loss of light I salts in phosphate builder and zeolite having a low concentration of laundry detergent compositions (laundrydetergent compositions), resulting in an improved detergency and sewage collapse removed.

[0002] 污溃去除的改善是洗涤剂工业的永久目标之一,因为这可以导致节省洗涤剂组合物中化学品的使用,或可以导致在更低的温度和/或用更短的时间洗涤,从而节约能量。 [0002] removing dirt collapse improvements are part of the permanent goals detergent industry, as this may result in savings in the detergent composition of chemicals, or may result in lower temperatures and / or washing with a shorter time , thus saving energy. 因此,仍然存在对改善去污效果,特别是洗衣洗涤剂组合物对纺织品污溃的首次去污效果(primary detergency effect)的兴趣,所述纺织品污溃例如是颗粒污溃(例如含有污物或粘土的污溃)、或基于植物的污溃(例如草)。 Thus, there remains to improve stain removal, especially laundry detergent compositions of the first textile stain removal of dirt ulcer (primary detergency effect) of interest, for example, the textile crush dirt collapse dirt particles (e.g. comprising soil or clay sewage collapse), or on crushed sewage plants (e.g. grasses). 特别地,在洗衣过程中,颗粒污溃是难以除去的。 In particular, during the laundering process, the particles are difficult to remove dirt collapse.

[0003] 异羟肟酸类是其中将羟胺插入到羧酸中的一类化学化合物。 [0003] hydroxamic acids in which the hydroxylamine compound is inserted into a chemical class of carboxylic acids. 异羟肟酸的一般结构如下: The general structure of the hydroxamic acid as follows:

[0004] [0004]

Figure CN102257109BD00041

[0005] 其中R1是有机残基,例如烷基或烯基(alkylene)基团。 [0005] wherein R1 is an organic residue, such as alkyl or alkenyl group (alkylene) group. 所述异羟肟酸可以以其相应的碱金属盐或异羟肟酸盐形式存在。 The hydroxamic acid may be an alkali metal salt or its corresponding hydroxamate presence of heterologous form.

[0006] 所述异轻]污酸盐可以方便地由相应的异轻]污酸(hydroxamic acid)通过用阳离子取代酸氢原子形成: [0006] The light-isobutyl] sewage salt may conveniently be formed from the corresponding light isobutyl] waste acid (hydroxamic acid) by replacing a hydrogen atom with an acid cation:

[0007] [0007]

Figure CN102257109BD00042

[0008] L+是一价阳离子例如碱金属(例如钾、钠)或铵或取代的铵。 [0008] L + is a monovalent cation such as an alkali metal (e.g. potassium, sodium) or ammonium or substituted ammonium.

[0009] 已知异羟肟酸类和异羟肟酸盐可用作金属螯合剂。 [0009] The known hydroxamic acids and hydroxamic acid salt useful as a metal chelator. 它们还被用于洗涤剂组合物中以改善漂白性能,以及用作助洗剂物质。 They are also used in detergent compositions to improve the bleaching performance, as well as builder materials.

[0010] EP 388 389 Α2公开了含有异羟肟酸类和它们的衍生物的不含漂白剂的助洗不足的(under built)液体洗涤剂组合物,所述异羟肟酸类和它们的衍生物在洗衣过程中有助于从织物除去可漂白的酒污溃。 [0010] EP 388 389 Α2 discloses a lack builder bleach- containing hydroxamic acids and derivatives thereof of (under built) detergent composition of the liquid, the hydroxamic acids and their alcohol derivatives assist in removing dirt from the collapse bleachable fabrics during laundering. 公开了式I中的异羟肟酸,其中R1代表任选被取代的直链或支链C5-C21烷基或C5-C21链烯基基团,或任选地被取代的苯基基团,和R2代表氢,或任选地被取代的(^-(:6烷基基团,或任选地被取代的苯基基团。在硬水(20°德国硬度,其是约143毫克钙/升)中当将异羟肟酸盐用于洗涤剂组合物时,实施例之一呈现改善的漂白性能。所述实施例在含有阴离子表面活性剂和非离子表面活性剂混合物的洗涤剂制剂中使用C12直链、C12支链、C13支链和C18异羟肟酸盐。在实施例1、II和IV中,存在至少1.25:1的过量非离子表面活性剂,和在实施例1II中是100%的阴离子表面活性剂。所述液体还含有至少6wt%的乙醇,其有助于溶解长链异羟肟酸盐。 Discloses compounds of formula I is a hydroxamic acid, wherein R1 represents an optionally substituted straight-chain or branched C5-C21 alkyl or C5-C21 alkenyl group, or an optionally substituted phenyl group , and R2 represent hydrogen, or optionally substituted (^ - (: 6 alkyl group, or an optionally substituted phenyl group in hard water (20 ° German hardness, which is about 143 mg of calcium. / liter) when the hydroxamates used in detergent compositions, one embodiment embodiment exhibit improved bleaching performance in detergent formulations and containing a nonionic surfactant mixture of anionic surfactants according to the embodiment . using C12 linear, branched, C12, C13 and C18 branched hydroxamate in Example 1, II and IV, the presence of at least 1.25: an excess of nonionic surfactant is 1, and in Example 1II 100% of an anionic surfactant. the liquid further contains at least 6wt% of the ethanol, which helps dissolving a long chain hydroxamates.

[0011] EP 384 912 A2公开了异羟肟酸类和它们的衍生物在经助洗的、主要是颗粒状的洗涤剂组合物中作为过氧漂白化合物的稳定剂的用途。 [0011] EP 384 912 A2 discloses hydroxamic acids and derivatives thereof by the builder, mainly granular detergent compositions as a stabilizer of peroxy bleaching compounds use. 含有2(^丨%沸石的全配方洗涤剂粉末实施例使用C12、C13和C12支链异羟厢酸盐。还使用了C18。 Containing 2 (Example C12 using fully-formulated detergent powder ^ Shu% zeolite, C13 and C12 branched hydroxamate salt compartment. C18 also used.

[0012] US 4,874,539公开了可用作洗涤剂添加剂尤其是作为金属离子螯合剂的聚合羧基异羟肟酸,并且与不含金属离子螯合剂的洗涤剂粉末相比,还导致了改善的从测试布除去茶污溃。 [0012] US 4,874,539 discloses a detergent additive particularly useful as polymeric sequestering agent carboxy hydroxamic acid, as compared with the detergent powder containing no metal ion chelating agent, also results in improve the removal of dirt tea collapse from the test cloth.

[0013] US 4, 863, 636公开了含有一种或多种清洁表面活性剂和一种或多种N-轻基酰亚胺或羧基异羟肟酸洗涤剂添加剂的液体洗涤剂组合物。 [0013] US 4, 863, 636 discloses compositions containing one or more cleaning surfactants and one or more light imide or N- carboxy hydroxamic acid detergent additive liquid detergent compositions. 这些化合物起到了活性金属离子螯合剂的作用,导致了改善的污溃去除。 These compounds acts as an active metal ion chelators, resulting in an improved removal of dirt collapse.

[0014] W097/48786公开了与洗涤剂物质一起使用的多组分体系,其含有氧化催化剂、适合的氧化剂、至少一种介体(其尤其选自异羟肟酸类和异羟肟酸衍生物)、辅助介体(co-mediator)和任选地少量的每一种插入的介体至少一种游离胺。 [0014] W097 / 48786 discloses a multi-component system for use with detergent substances, containing an oxidation catalyst, a suitable oxidizing agent, at least one mediator (which is in particular selected from hydroxamic acids and hydroxamic acid derivatives thereof), the auxiliary mediator (co-mediator), and optionally a small amount of insertion of each of at least one free amine mediator. 该体系导致改善的洗涤剂漂白功能和较少的介质消耗。 This system results in improved detergent bleach functionality and less dielectric loss.

[0015] GB 1317445公开了含有异羟肟酸的碱金属盐的洗涤剂组合物。 [0015] GB 1317445 discloses detergent compositions comprising the hydroxamic acid alkali metal salt. 这种盐的作用是防止洗衣机的构造中使用的铜和铜合金的腐蚀。 Such salts are acting to prevent corrosion of copper and copper alloys used in the washing machine configuration.

[0016] 我们现在已经出人意料地发现,可以通过在特定洗衣洗涤剂组合物中加入特定的异羟肟酸类和/或异羟肟酸盐改善首次去污效果,尤其是对于红粘土(red clay)颗粒污物。 [0016] We have now surprisingly found that by adding a specific hydroxamic acids and / or hydroxamate first decontamination effect improvement in specific laundry detergent composition, especially for red clay (red clay ) particulate soil.

[0017] 洗衣洗涤剂需要能够除去通常在洗涤载荷(wash load)中发现的日常污垢和污溃。 [0017] need to be able to remove the laundry detergent typically found in wash load (wash load) of the daily stains and collapse. 成问题的两种特定污溃,尤其是洗涤儿童衣物或运动衣物时,是粘土污物污溃和草污溃。 Two specific sewage collapse problematic, in particular children's clothing or washing during movement of the laundry, the clay soil pollution is crushed grass and dirt collapse. 特别耐通过表面活性剂单独除去的一种类型的粘土是红粘土,例如红陶土(redpottery clay)或红色Georgia 粘土(Red Georgia clay)。 Particularly resistant to removal by a surfactant alone type clay is clay, for example, red clay (redpottery clay) or red Georgia clay (Red Georgia clay). 其是颗粒污物污溃。 Which is crushed particulate soil pollution.

[0018] 因此,本发明提供了包含以下的洗衣洗涤剂组合物: [0018] Accordingly, the present invention provides a laundry detergent composition comprising the following composition:

[0019] a) 0.5到20 wt%,优选0.5到6wt%以下结构的异羟肟酸或其相应的异羟肟酸盐: [0019] a) 0.5 to 20 wt%, preferably 0.5 hydroxamic acid to 6wt% of the structure or its corresponding hydroxamate:

Figure CN102257109BD00051

[0021] 其中R1是 [0021] wherein R1 is a

[0022] 直链或支链的C4-C2tl烷基,或 [0022] a straight-chain or branched C4-C2tl alkyl, or

[0023] 直链或支链的取代的C4-C2tl烷基,或 [0023] a straight-chain or branched-chain alkyl substituted C4-C2tl, or

[0024] 直链或支链的C4-C2tl链烯基,或 [0024] a straight-chain or branched C4-C2tl alkenyl group, or

[0025] 直链或支链的取代的C4-C2tl链烯基,或 [0025] C4-C2tl substituted alkenyl, straight-chain or branched, or

[0026] 烷基醚基团CH3 (CH2)n(EO)m,其中η为2到20和m为I到12,或 [0026] alkyl ether group CH3 (CH2) n (EO) m, where η is 2 to 20 and m is from I to 12, or

[0027] 取代的烷基醚基团CH3 (CH2)n(EO)m,其中η为2到20和m为I到12,和 [0027] The substituted alkyl ether group CH3 (CH2) n (EO) m, where η is 2 to 20 and m is from I to 12, and

[0028] 取代的类型包括下面的一个或多个:-NH2、-0H、-S-、-O-、-COOH和 [0028] The substituents include one or more types of the following: -NH2, -0H, -S -, - O -, - COOH, and

Figure CN102257109BD00061

[0030] 和R2选自选自氢和与支链R1基团形成环状结构的一部分的部分, [0030] and R2 is selected from selected from hydrogen and a branched-chain moiety R1 is a cyclic structure portion is formed,

[0031] b)浓度为3到80wt%的清洁表面活性剂体系;所述清洁表面活性剂体系含有 [0031] b) at a concentration of 3 to 80wt% of surfactant cleaning system; cleaning said surfactant system comprising

[0032] (i)阴离子表面活性剂;和 [0032] (i) an anionic surfactant; and

[0033] (ii)非离子表面活性剂 [0033] (ii) a non-ionic surfactant

[0034] 其中⑴对(ii)的比值位于1:1.1到19:1的范围,和a)对b)的重量比位于1:5到1:15的范围 [0034] ⑴ wherein the ratio of (ii) is located at 1: 1.1 to 19: 1 range, and a) to b) is located at a weight ratio range of 1: 5 to 1:15

[0035] c)任选地,补足至100wt%的其它成分,条件是沸石和磷酸盐助洗剂以少于5wt%存在和乙醇以少于5wt%的浓度存在。 [0035] c) optionally, other ingredients to make up 100wt%, provided that the zeolite and phosphate builder is present at less than 5wt% and ethanol present in a concentration of less than 5wt% of.

[0036] 应该理解,提及碳原子数包括混合链长材料,条件是一些异羟肟酸盐材料位于指出的范围之内,并且比值和量通过排除落在指出范围之外的任何材料来确定。 [0036] It should be understood that reference number of carbon atoms including mixed chain length of material, that some of the material is located hydroxamate indicated range, and the ratio and amount determined by excluding any material falling outside the scope of the indicated .

[0037] 皂不包括在阴离子表面活性剂量和比值的计算之内。 [0037] The soaps are not included in the calculation of the ratio of the amount of surfactant and anions.

[0038] 完全不希望存在乙醇,因为在制造期间和之后其是爆炸危险。 [0038] absolutely does not want the presence of ethanol, because during and after manufacture, and it is a danger of explosion. 由于在制剂中存在相对较高浓度的异羟肟酸盐,所以如果存在高浓度的表面活性剂,则必需寻找替代水溶助长剂体系。 Due to the presence of relatively high concentration of hydroxamate in the formulation, so if there is a high concentration of surfactant, it is necessary to find alternative hydrotrope system. 我们优选浓度为至少6wt%,更优选至少10wt%的含有丙二醇和甘油的水溶助长剂体系。 We prefer a concentration of at least 6wt%, more preferably at least 10wt% of a hydrotrope system containing propylene glycol and glycerol. 通过在所述组合物中使用高浓度的异羟肟酸盐和表面活性剂,可以在每次洗涤中使用更少的组合物,这对于获得的浓缩制剂的贮存和运输具有随之而来的益处。 By using a high concentration of hydroxamate and a surfactant in the composition may be used in each wash less composition, which has the attendant for storage and transport of concentrated formulation obtained benefit. 此类浓缩制剂含有至少20wt%,优选至少30wt%和更优选超过40wt%的清洁表面活性剂体系。 Such concentrated formulations contain at least 20wt%, preferably at least 30wt% and more preferably more than 40wt% of the surfactant system cleaning.

[0039] 优选的异羟肟酸盐是其中R2是氢和R1是C8到C14烷基,优选正烷基(normalalkyl),最优选饱和的那些。 [0039] Preferred hydroxamate is wherein R2 is hydrogen and R1 is a C8 to C14 alkyl, preferably n-alkyl (normalalkyl), the most preferably saturated.

[0040] 所述洗涤剂组合物优选用于含水洗涤液,但可以含有一种或多种适合用于家庭洗衣目的的溶剂。 [0040] the detergent composition is preferably used an aqueous wash liquor, but may contain one or more suitable solvents for domestic laundry purposes. 优选地,在洗衣过程的主洗涤期间产生改善的污溃去除,即优选其中使用所述异羟肟酸盐的洗衣洗涤剂组合物是主洗涤产品。 Preferably, resulting in improved crush dirt removed during the main wash laundry process, i.e., preferably wherein the hydroxamate composition is a laundry main wash detergent product. 所述洗涤液优选不含甲酸盐。 The washing liquid is preferably free of formate. 此外,其优选不含漂白剂,特别是过氧漂白剂。 Further, it is preferably free of bleach, particularly peroxygen bleach.

[0041] 所述组合物可以含有I到15wt%的皂。 The [0041] composition may contain I to 15wt% soap. 优选的皂由饱和脂肪酸制造。 Preferred soap made from saturated fatty acids.

[0042] 特别优选的组合物含有至少0.5wt%的防污聚合物(soil release polymer)。 [0042] A particularly preferred composition comprises at least 0.5wt% of an antifouling polymer (soil release polymer). 这改善了用于除去粘土的洗涤剂体系的多次洗涤性能。 This improves the wash performance for a number of detergent system to remove the clay. 由于非常高的首次去污污物去除效率意味着洗涤液中增加的污物浓度,从而必须防止其再次沉积在相同或不同的织物部分,因此含有至少0.5wt%的抗再沉积聚合物也是有益的。 Due to the very high first decontamination soil removal efficiency means increasing the wash liquor concentration of contaminants, must be prevented so that it is again deposited in the same or different fabric portions, thus contains at least 0.5wt% of the anti-redeposition polymers are also useful of.

[0043] 对于最优的颗粒红粘土污物去除,异羟肟酸盐与清洁表面活性剂体系的优选比值位于1:7到1:13的范围。 [0043] For optimal particle red clay soil removal, preferably hydroxamate ratio surfactant system and cleaning the surface of the range of 1: 7 to 1:13. 甚至更优选的比值范围按重量份计算为1:9到1:11。 Even more preferred range of the ratio by parts by weight of 1: 9 to 1:11.

[0044] 对于颗粒红粘土污物去除,阴离子表面活性剂对非离子表面活性剂的优选比值至少为1:1,更优选为至少3:2。 [0044] For red clay soil removal particles, preferably anionic surfactant to nonionic surfactant ratio is at least 1: 1, more preferably at least 3: 2. 优选地,其最多为9:1。 Preferably, it is up to 9: 1. 因此最优选的范围是1:1到9:1,或3:2 到9:1。 Thus the most preferred range is 1: 1 to 9: 1, or 3: 2 to 9: 1.

[0045] 所述组合物特别适合用于颗粒污溃,例如污物和粘土,尤其是红粘土以及还出人意料地用于草。 The [0045] compositions are particularly suitable for sewage crushed particles, such as dirt and clay, red clay, and in particular for further surprisingly grass.

[0046] 本发明还延伸到0.5到20wt%的以下结构的异羟肟酸或其相应的异羟肟酸盐在洗衣洗涤剂组合物中的用途: [0046] The present invention also extends to the corresponding hydroxamic acid or hydroxamic acid salt 0.5 to 20wt% of the following structural use in laundry detergent compositions:

Figure CN102257109BD00071

[0048] 其中,R1是C8正烷基基团,和R2是氢原子,用于改善从纺织品基底除去颗粒污物污溃,其中所述组合物进一步含有浓度为3到80wt%的包含阴离子表面活性剂和非离子表面活性剂的清洁表面活性剂体系;和任选地补足至100wt%的其它成分。 [0048] wherein, Rl is a C8 n-alkyl group, and R2 is a hydrogen atom, for improving the removal of particulate soil from textile substrates collapse dirt, wherein the composition further comprises a concentration of 3 to 80wt% of an anionic surface comprising cleaning surfactant system active agents and nonionic surface active agent; and optionally other ingredients to make up 100wt% of.

[0049] 可以以在本领域普通技术人员知识范围内的任何适合的方式将异羟肟酸盐加入所述洗衣洗涤剂组合物中。 [0049] may be in any suitable manner within the purview of those of ordinary skill in the art will hydroxamate added to the laundry detergent composition.

具体实施方式 Detailed ways

[0050] 在本说明书中,当使用术语“异羟肟酸”或“异羟肟酸盐”时,除非另外说明,否则其包括异羟肟酸和相应的异羟肟酸盐(异羟肟酸的盐)。 [0050] In the present specification, when the term "hydroxamic acid" or "hydroxamate" is, unless otherwise specified, including hydroxamic acid and the corresponding hydroxamate (hydroxamic acids).

[0051] 除非另外说明,否则文中提及的所有百分数都基于整个组合物按重量计算。 [0051] Unless otherwise specified, all percentages mentioned herein are based on the total composition by weight. 缩写“wt%”应该理解为整个组合物的重量%。 The acronym "wt%" should be understood as% by weight of the total composition.

[0052] 用根据本发明的含有异羟肟酸盐的洗衣洗涤剂组合物处理被污染的织物,并且首次去污力是所述洗衣组合物对污溃的经测量的污溃去除。 [0052] The treatment of contaminated laundry detergent composition according to fabric containing hydroxamate of the invention, the first and the detergency of the laundry composition is collapsed on the measured pollution removal collapse of pollution. 这与所谓的使用聚合物的防污是不同的过程,其是使用聚合物对织物进行的处理(通过洗涤或其它此类处理),所述织物随后被污染,所述防污聚合物具有较易除去所述污溃的效果。 This so-called anti-fouling polymer is used is different from the process, which process is carried out using a polymer fabric (by washing or other such treatment), then the fabric is contaminated, the anti-fouling polymer having a relatively easily removing the dirt collapse effect.

[0053] 以下定义适合于化学结构、分子链段和取代基: [0053] The following definitions are adapted to the chemical structures, molecular segments and substituents:

[0054] 除非另外说明,否则单体和聚合物的分子量以重均分子量表示。 [0054] Unless otherwise noted, molecular weights of monomers and polymers of weight average molecular FIG.

[0055] 所使用的纺织品/织物基底可以是任何典型的纺织品/织物基底,例如棉(机织的、针织的和denim)、聚酯(机织的、针织的和微纤)、尼龙、丝(silk)、涤棉(聚酯/棉共混物)、聚酯elastane、棉弹性纤维、胶粘人造丝(viscose rayon)、丙烯酸类或羊毛。 [0055] As used textile / fabric substrate can be any typical textile / fabric substrate such as cotton (woven, knitted and Denim), polyester (woven, knitted and microfibers), nylon, silk (silk), polyester (polyester / cotton blend), polyester elastane, elastic fibers of cotton, rayon adhesive (viscose rayon), wool or acrylic. 特别适合的纺织品/织物基底是棉、涤棉和聚酯基底。 Particularly suitable textile / fabric substrate is cotton, polyester and polyester substrate.

[0056] 颗粒污溃是包括例如灰尘、污物、粘土、泥或煤灰的污溃。 [0056] particles include crushed dirt such as dust, dirt, clay, mud or dirt collapse ash. 它们本质上主要是固体并在织物的日常使用中与织物发生接触。 They are essentially solid, and primarily in contact with the fabric occurs in everyday use of the fabric.

[0057] 异羟肟酸和衍生物 [0057] The hydroxamic acid derivative and

[0058] 本发明的上下文中的异羟肟酸的一般结构在式3中示出,并且R1是如上所定义。 [0058] The general structure of the present invention in the context of the hydroxamic acid is shown in Formula 3, and R1 is as defined above. 当R1是烷基醚基团CH3 (CH2)n(EO)m,其中η为2到20和m为I到12时,那么所述烷基部分封端该侧基。 When R1 is an alkyl ether group CH3 (CH2) n (EO) m, where η is m is from 2 to 20 and 12 to I, then the alkyl portion of the closure base end side. 优选地,R1选自由C4、C5、C6、C7、C8、C9、C1(l、Cn、C12或C14正烷基基团组成的组,最优选R1是至少C8_14正烷基基团。当使用C8材料时,其称为辛基异羟肟酸。钾盐是特别有用的。 Group preferably, R1 is selected from C4, C5, C6, C7, C8, C9, C1 (l, Cn, C12 or C14 n-alkyl group consisting of C8_14 most preferably at least R1 is a n-alkyl group. When using when C8 material referred octyl hydroxamic acid. potassium salt are particularly useful.

[0059] [0059]

Figure CN102257109BD00072

[0060] 辛异羟肟酸K盐[0061] 但是,尽管不太优选,其它异羟肟酸也适合用于本发明。 [0060] oct-hydroxamic acid K salt [0061] However, although less preferred, other hydroxamic acids are also suitable for use in the present invention. 此类适合的化合物包括但不限于以下化合物: Suitable such compounds include, but are not limited to the following compounds:

[0062] [0062]

Figure CN102257109BD00081

[0063] 赖氨酸异羟肟酸盐*HC1 [0063] lysine hydroxamate * HC1

Figure CN102257109BD00082

[0065] 蛋氨酸异羟肟酸盐 正缬氨酸异羟肟酸盐 [0065] methionine hydroxamate norvaline hydroxamate

[0066] 此类异羟肟酸可商购获得。 [0066] Such hydroxamic acids are commercially available.

[0067] 不希望被理论所限,我们相信所述异羟肟酸盐通过与织物上的污物中存在的金属离子结合起作用。 [0067] Without wishing to be bound by theory, we believe that the hydroxamate metal ions present in the soil on the fabric binding function. 该结合作用(其实际上是所述异羟肟酸盐的已知的螯合性能)本身对从织物除去污物没有任何作用。 The binding effect (which is actually the known chelating properties of different hydroxamate) removing soil from the fabric itself does not have any effect. 关键是所述异羟肟酸盐的“尾部”即所述基团R1减少了通过基团R2折叠回到amate氮上的任何支化。 The key is the hydroxamate "tail" i.e., the group R1 is reduced by the group R2 is folded back on amate any branching nitrogen. 选择所述尾部以具有对表面活性剂体系的亲和力。 Selecting the tail to have an affinity for the surfactant system. 这意味着早已经过优化的表面活性剂体系的污物去除能力通过使用所述异羟肟酸盐进一步得到提高,因为其实际上把除去颗粒物质(粘土)的困难说成是通过作用在所述异羟肟酸盐分子上的所述表面活性剂体系除去“污物”,其中所述异羟肟酸盐分子现在通过它们与粘土型颗粒中嵌入的金属离子的结合而被固定到所述颗粒上。 This means that already after soil removal ability of the surfactant system is optimized by using the hydroxamate further improved, since it is actually difficult to remove the particulate matter (clay) is said to be acting through the the surfactant system on hydroxamate molecule remove "soils", wherein said molecule is now hydroxamate by combining them with a clay-type particle embedding metal ions fixed to the particle on. 所述清洁表面活性剂将粘附到所述异羟肟酸盐,整体上导致更多的表面活性剂与所述织物相互作用,导致更好的去污。 The cleansing surfactant adhering to the better soil release hydroxamate, lead to more surfactant interacts with the fabric as a whole, resulting in. 从而所述异羟肟酸起到连接分子的作用,促进颗粒污物从织物除去和悬浮到洗涤液中并从而提闻首次去污力。 Whereby the hydroxamic acid linker molecule acts to promote particulate soil removed from the fabric and the detergency of the first suspension and the wash solution thereby providing smell.

[0068] 当使用浓缩的液体洗涤剂组合物时,与使用颗粒洗涤剂组合物的传统洗衣过程(pH 9-10.5)相比,由于洗衣过程中pH相对较低(pH 7.5_8),所以表面活性剂体系的首次去污力的这种提高特别有价值。 [0068] When a concentrated liquid detergent composition, as compared with a conventional particulate laundry detergent composition process (pH 9-10.5), due to the relatively low pH during washing (pH 7.5_8), so the surface this increase for the first time detergency surfactant system is particularly valuable. 与传统的经良好助洗和缓冲的洗衣过程(采用常规的经沸石或磷酸盐助洗的粉末产品实现)中较高的PH相比,由于污物的表面电荷电负性更小,因此使用液体洗涤剂组合物的洗衣过程中较低的PH可能导致降低的防污。 Compared with the traditional washing process was good builder and buffering (product by using conventional powder zeolite or phosphate builders implementation) high in PH, since the surface electric charge of smaller dirt negative, so the use of laundry process liquid detergent composition may result in reduced low PH antifouling. 所述污物的这种表面电荷可能导致污物对表面活性剂增大的排斥性,可能导致降低的污物释放。 The surface charge of such contaminants may result in dirt repellency of the surfactant increases, may result in reduced soil release. 因此,在一个优选的实施方案中,所述异羟肟酸盐被用于液体洗涤剂组合物,并且更优选地在所述液体洗涤剂组合物中所述清洁表面活性剂浓度为20到80wt%。 Thus, in a preferred embodiment, the hydroxamate is used in liquid detergent compositions, and more preferably in the liquid detergent cleaning compositions in the surfactant concentration of 20 to 80wt %.

[0069] 所述异羟肟酸盐对过渡金属如铁比对碱土金属如钙和镁具有更高的亲和力,因此所述异羟肟酸主要起到改善织物上的污物,特别是颗粒污物的去除的作用,不是另外作为隹丐和镁的助洗剂。 [0069] The hydroxamate of transition metals such as calcium and magnesium, has a higher affinity for iron than the alkaline earth metal, and therefore the hydroxamic acid functions primarily to improve the dirt on the fabrics, especially dirt particles effect removal thereof, and not the other as a short-tailed hack magnesium builder. 如果所述洗衣组合物助洗不足(underbuilt);尤其当其含有少于5wt%的沸石或磷酸盐助洗剂时,这选择性地是特别有益的。 If the laundry composition is less than builder (underbuilt); especially when it contains less than 5wt% zeolite or phosphate builders, which optionally is particularly advantageous.

[0070] 表面活性剂 [0070] Surfactant

[0071] 其中使用所述异羟肟酸盐的洗衣洗涤剂组合物含有浓度为3到80wt%的清洁表面活性剂体系。 [0071] wherein the hydroxamate-containing laundry detergent compositions at a concentration of 3 to 80wt% of surfactant cleaning system. 对于清洁表面活性剂体系,我们指的是其中对作为洗衣过程的一部分处理的纺织品织物提供清洁即净化效果的表面活性剂。 For cleaning surfactant system, we refer to the part in which the textile fabrics as a laundry treatment process, i.e., providing a surfactant cleaning effect of the cleaning. 其它表面活性剂(其不是清洁表面活性齐IJ)可以用作所述组合物的一部分。 Other surfactants (cleansing surfactant which is not flush IJ) can be used as part of the composition.

[0072] 优选地,所述清洁表面活性剂以5到60wt%,更优选以10到50wt%的浓度存在。 [0072] Preferably, the cleansing surfactant is from 5 to 60wt%, more preferably present in a concentration of 10 to 50wt%. 甚至更优选地,所述清洁表面活性剂体系占所述组合物的至少20、或30或甚至40wt%。 Even more preferably, the cleansing surfactant system of the composition comprises at least 20 or even 30 or 40wt%.

[0073] 通常,任何表面活性剂都可以用作清洁表面活性剂,包括阴离子、非离子、阳离子和两性或两性离子表面活性剂,或这些的组合,条件存在上述规定的比例范围的阴离子和非离子表面活性剂。 [0073] Generally, any surfactant may be used as cleaning surfactants, including anionic, nonionic, cationic and amphoteric or zwitterionic surfactants, or combinations of these, the presence of the predetermined condition of anionic and non-ratio range ionic surfactants.

[0074] 阳离子表面活性剂可以任选地作为所述清洁表面活性剂的一部分存在。 [0074] Cationic surfactants may optionally be used as the cleaning part of the surfactant present.

[0075] 阴离子表面活性剂以0.1到50wt%,优选地以I到40wt%,更优选地以1.5到25wt%的浓度存在。 [0075] The anionic surfactant is 0.1 to 50wt%, preferably I to to 40wt%, more preferably at a concentration of 1.5 to 25wt% is present. 非离子表面活性剂以0.1到50wt%,优选I到40wt%,更优选1.5到25wt%的浓度加入。 Nonionic surfactant 0.1 to 50wt%, preferably I to 40wt%, more preferably from 1.5 to a concentration of 25wt% was added. 阴离子表面活性剂对非离子表面活性剂的比值为19:1到1:1.1,更优选为9:1到1:1。 Ratio of anionic surfactant to nonionic surfactant is 19: 1 to 1: 1.1, more preferably from 9: 1 to 1: 1.

[0076] 通常,所述表面活性剂体系的非离子和阴离子表面活性剂可以从以下文献中描述的表面活性剂中选择:Schwartz& Perry, “Surface Active Agents” Vol.1, Interscience 1949 ;Schwartz> Perry & Berch, Interscience 1958, Vol.2 ;Manufacturing Confectioners Company 出版的现版“McCutc!^!^ s Emulsifiers andDetergents,,,或“Tenside-Taschenbuch,,,H.Stache, 2nd Edn., Carl Hauser Verlag,1981。 [0076] Generally, the surfactant system of nonionic and anionic surfactants may be selected from the surfactants described in the following documents: Schwartz & Perry, "Surface Active Agents" Vol.1, Interscience 1949; Schwartz> Perry & Berch, Interscience 1958, Vol.2; Manufacturing Confectioners Company published in the current edition of "McCutc ^ ^ s Emulsifiers andDetergents ,,, or!!" Tenside-Taschenbuch ,,, H.Stache, 2nd Edn, Carl Hauser Verlag, 1981. .

[0077] 非离子表面活性剂 [0077] Nonionic surfactant

[0078] 对于本公开的目的,除非另外说明,“非离子表面活性剂”应该定义为具有少于约10,000的分子量的两亲分子,其基本上不含任何在6-11的正常洗涤pH呈现净电荷的官能团。 [0078] For the purposes of this disclosure, unless otherwise specified, "nonionic surfactant" shall be defined as having a molecular weight of less than about 10,000 amphiphile, in any normal washing thereof is substantially free of 6-11 pH functional group presented a net charge.

[0079] 尽管在下文中进一步讨论了优选的材料,但是可以使用任何类型的非离子表面活性剂。 [0079] While the preferred materials are further discussed below, may be used any type of non-ionic surfactants. 高度优选的是脂肪酸烷氧基化物,特别是乙氧基化物,具有含有C8-C35,优选C8-C30,更优选Cltl-C24,特别优选Cltl-C18碳原子的烷基链,例如来自Shell (The Hauge, TheNetherlands)的Neodol系列;环氧乙烧/环氧丙烧嵌段聚合物,其可以具有1,000到30, 000的分子量,例如来自BASF (Ludwigshafen, Germany)的Pluronic (商标);和烧基酌.乙氧基化物,例如可从Dow Chemical (Midland, Mich., USA)获得的Triton X-1OO0 Highly preferred are fatty acid alkoxylates, especially ethoxylates, containing having a C8-C35, preferably C8-C30, more preferably Cltl-C24, particularly preferably Cltl-C18 carbon atoms in the alkyl chain, e.g., from Shell ( the Hauge, TheNetherlands) of Neodol series; burning ethylene / propylene block polymer propan burning, which may have 30 to 1,000, 000 molecular weight, e.g. from BASF (Ludwigshafen, Germany) is as Pluronic (trademark); and burning the base discretion. ethoxylates, such as those available from Dow Chemical (Midland, Mich., USA) Triton X-1OO0

[0080] 应该认为其它非离子表面活性剂也在本发明的范围内。 [0080] It should be considered within the scope of other nonionic surfactants are also the present invention. 这些包括链烷醇胺与脂肪酸的缩合物,例如cocamide DEA、脂肪酸多元醇酯例如可从Uniqema(Gouda, TheNetherlands)获得的Span系列、乙氧基化的脂肪酸多元醇酯例如可从Uniqema (Gouda, TheNetherlands)获得的Tween系列、烧基多聚葡糖苷例如可从Cognis (Diisseldorf, Germany)获得的APG系列和正烷基吡咯烷酮例如由ISP (wayne,NJ,USA)销售的Surfadone系列产品。 These include alkanolamine condensates with fatty acids, for example cocamide DEA, polyol fatty acid esters such as those available from Uniqema (Gouda, TheNetherlands) Span series, ethoxylated fatty acid esters of polyhydric alcohols, for example, available from Uniqema (Gouda, the Netherlands) obtained Tween series, Quito burning polyglucoside e.g. Surfadone series of products available from Cognis (Diisseldorf, Germany) APG series, and n-alkylpyrrolidones, for example, sold by ISP (wayne, NJ, USA) in. 此外,也可以使用上文未特别提到但符合定义的非离子表面活性剂。 Further, it may also be used but are not particularly mentioned above meet the definition of a non-ionic surfactant.

[0081] 更优选的非离子表面活性剂是平均乙氧基化度为7的脂肪酸乙氧基化物、具有一个环氧丙烷和多个环氧乙烷单元的烷氧基化物、基于种子油的表面活性剂例如可从DowChemical获得的Ecosurf SA7或SA9、APGs和支链醇Guerbet非离子表面活性剂。 [0081] More preferred non-ionic surfactants are the average degree of ethoxylation of 7 fatty acid ethoxylates, alkoxylates having a plurality of propylene oxide and ethylene oxide units, based on the seed oil surfactants such as available from DowChemical Ecosurf SA7 or SA9, APGs and branched Guerbet alcohol nonionic surfactant.

[0082] 阴离子表面活性剂 [0082] Anionic surfactants

[0083] “阴离子表面活性剂”在这里定义为含有一个或多个在6到11的正常洗涤pH在水溶液中时呈现净阴离子电荷的官能团的两亲分子。 [0083] "Anionic surfactants" are defined herein as having one or more amphipathic molecules exhibit a net anionic charge when in aqueous solution, normal wash pH 6 through 11 functional groups.

[0084] 优选的阴离子表面活性剂是有机硫反应产物的碱金属盐,所述有机硫反应产物在其分子结构中具有含有约6到24个碳原子的烷基基团和选自由磺酸酯和硫酸酯基团组成的组的基团。 [0084] Preferred anionic surfactants are the alkali metal salts of organic sulfuric reaction products, the organic sulfuric reaction products having an alkyl group containing from about 6 to 24 carbon atoms and selected from the group consisting of sulfonates in the molecular structure group and the group consisting of sulfate groups.

[0085] 尽管可以使用下文描述的任何阴离子表面活性剂,例如烷基醚硫酸盐、皂、脂肪酸酯磺酸盐、烷基苯磺酸盐、磺基丁二酸酯、伯烷基硫酸盐、烯烃磺酸盐、烷烃磺酸盐和有机磷酸盐;但是优选的阴离子表面活性剂是以下的碱金属和碱土金属盐:脂肪酸羧酸盐,脂肪醇硫酸盐,优选伯烷基硫酸盐,更优选它们被乙氧基化,例如烷基醚硫酸盐;烷基苯磺酸盐,烷基酯脂肪酸磺酸盐,特别是甲基酯脂肪酸磺酸盐和它们的混合物。 [0085] Although described below may be used any of anionic surfactants, such as alkyl ether sulfates, soaps, fatty acid esters, alkylbenzenesulfonates, sulfosuccinates, alkyl sulphates , olefin sulfonates, paraffin sulfonates and organic phosphates; however, preferred anionic surfactants are the alkali metal and alkaline earth metal salts: salts of fatty acids, fatty alcohol sulfates, preferably primary alkyl sulfates, and more they are preferably ethoxylated, e.g. alkyl ether sulfate; alkylbenzene sulfonate, a fatty acid alkyl ester sulfonates, especially methyl ester sulfonates of fatty acids, and mixtures thereof.

[0086] 阳离子、两性表面活性剂和/或两性离子表面活性剂 [0086] cationic, amphoteric surfactants and / or zwitterionic surfactants

[0087] 在其中将所述异羟肟酸盐用作根据本发明的助表面活性剂(cosurfactant)的洗衣洗涤剂组合物中也可以存在阳离子、两性表面活性剂和/或两性离子表面活性剂。 [0087] in which the hydroxamate as a laundry detergent composition according to co-surfactant (Cosurfactant) of the present invention can also be present in the cationic, amphoteric surfactants and / or zwitterionic surfactants .

[0088] 优选的阳离子表面活性剂是通式R1R2R3R4N+X-的季铵盐,例如其中R1是C12-C14烷基基团,R2和R3是甲基基团,R4是2-轻乙基基团,和氯离子。 [0088] Preferred cationic surfactants are quaternary ammonium salts of the general formula R1R2R3R4N + X-, wherein R1 is, for example, C12-C14 alkyl group, R2 and R3 is a methyl group, R4 is 2-ethyl group of light group, and chloride ions. 该物质可以以Praepagen (商标)HY从Clariant GmbH以40wt%水溶液的形式商购获得。 The substance may Praepagen (trademark) in the form of HY 40wt% aqueous solution of commercially commercially available from Clariant GmbH.

[0089] 在一个优选的实施方案中,根据本发明其中使用所述异羟肟酸盐的洗衣洗涤剂组合物进一步包含两性或两性离子表面活性剂。 [0089] In a preferred embodiment, according to the present invention, wherein the hydroxamate laundry detergent compositions further comprise amphoteric or zwitterionic surfactants. 两性表面活性剂是含有酸性和碱性基团并且在6-11的正常洗涤pH将作为两性离子存在的分子。 Amphoteric surfactants containing both acidic and basic groups in the normal wash pH 6-11 and will exist as a zwitterion molecules. 优选地,两性或两性离子表面活性剂以0.1到20wt%,更优选地以0.25到15wt%,甚至更优选地以0.5到10wt%的浓度存在。 Preferably, amphoteric or zwitterionic surfactant is from 0.1 to 20wt%, more preferably from 0.25 to 15wt%, even more preferably at a concentration of 0.5 to 10wt% is present.

[0090] 适合的两性离子表面活性剂例示为可以广义上描述为脂肪族季铵、锍和鱗化合物的衍生物的那些,具有一个含有约8到约18个碳原子的长链基团和至少一个选自由硫酸根、磺酸根、羧酸根、磷酸根或膦酸根组成的组的水溶性基团。 [0090] Suitable zwitterionic surfactants embodiments shown can be described broadly as derivatives of aliphatic quaternary ammonium, those derivatives of sulfonium and scales compounds having a long chain group a contains from about 8 to about 18 carbon atoms and at least selected from the group consisting of a sulfate, sulfonate, carboxylate groups water-soluble group, phosphate or phosphonate thereof. 这些化合物的通式为: Formula for these compounds is:

[0091] R1 (R2) J+R3Z^ [0091] R1 (R2) J + R3Z ^

[0092] 其中R1包含具有8到18个碳原子的烷基、链烯基或羟烷基基团,O到10个亚乙基-氧基团或O到2个甘油基单元;Y是氮、硫或磷原子;R2是具有I到3个碳原子的烷基或羟烷基基团;当Y是硫原子时X为1,而当Y是氮或磷原子时X为2 ;R3是具有I到5个碳原子的烷基或羟烷基基团和Z是选自由硫酸根、磺酸根、羧酸根、磷酸根或膦酸根组成的组的基团。 [0092] wherein R1 comprises an alkyl group having from 8 to 18 carbon atoms, alkenyl or hydroxyalkyl group, O to 10 ethylene - group or a O to 2 glyceryl units; Y is nitrogen , sulfur or phosphorus atom; R2 is an alkyl group having I to alkyl or hydroxyalkyl group having 3 carbon atoms; when Y is a sulfur atom when X is 1 when Y is a nitrogen or phosphorus atom when X is 2; R3 is group I to the group having an alkyl or hydroxyalkyl group, and Z 5 carbon atoms selected from the group consisting of sulfate, sulfonate, carboxylate, phosphate or phosphonate thereof.

[0093] 优选的两性表面活性剂是胺氧化物,例如椰油基二甲基胺氧化物(coco dimethylamine oxide)。 [0093] Preferred amphoteric surfactants are amine oxides, such as coco dimethylamine oxide (coco dimethylamine oxide).

[0094] 优选的两性离子表面活性剂是甜菜碱类,特别是酰胺基甜菜碱类。 [0094] Preferred zwitterionic surfactants are betaines, amido betaines particular. 优选的甜菜碱是C8到C18烧基酰胺基烧基甜菜碱,例如椰油酰胺基甜菜碱(coco ami do betaine)。 Preferred betaines are C8 to C18 burn burn amido betaines, such as coco amido betaine (coco ami do betaine). 可以包含这些作为助表面活性剂,优选基于整个组合物的重量以O到10wt%,更优选以I到5wt%的量存在。 These may comprise a co-surfactant, preferably based on the weight of the entire composition to O to 10wt%, more preferably in an amount of I to 5wt% is present. 可以使用的其它甜菜碱是硫甜菜碱(sulfatobetaines),例如3_(十二烷基二甲基铵)-1_丙烷硫酸盐;和2-(椰油基二甲基铵)-1-乙烷硫酸盐。 Other sulfur can be used are betaine betaine (sulfatobetaines), e.g. 3_ (dodecyl dimethyl ammonium) sulfate -1_ propane; and 2- (coco dimethyl ammonium) -1- ethane sulfates. 磺基甜菜碱,例如:3-(十二烷基二甲基-铵)-2-羟基-1-丙烷磺酸盐;3_ (十四基-二甲基铵)-1-丙烷磺酸盐;3_ (C12-C14烧基-酰胺基丙基二甲基铵)-2_轻基-1-丙烧磺酸盐;和3-(椰油基二甲基铵)-1_丙烷磺酸盐。 Sulfobetaine, for example: 3- (dodecyl dimethyl - ammonium) -2-hydroxy-1-propane sulfonate; 3_ (tetradecyl - dimethyl-ammonium) -1-propane sulfonate ; 3_ (C12-C14 group burn - amidopropyl dimethyl) ammonium-1-propanesulfonic -2_ light burned sulfonate; and 3- (cocodimethyl ammonium) propane sulfonate -1_ salt. 羧基甜菜碱,例如(十二烷基二甲基铵)醋酸盐(也称为月桂基甜菜碱);(十四烷基二甲基铵)醋酸盐(也称为十四烷基甜菜碱);(椰油基二甲基铵)醋酸盐(也称为椰油甜菜碱(coconut betaine));(油基二甲基铵)醋酸盐(也称为油基甜菜碱);(十二烷氧基甲基二甲基铵)醋酸盐;和(椰油酰胺基-丙基二甲基铵)醋酸盐(也称为椰油酰胺基-丙基甜菜碱或CAPB)。 Carboxy betaines, such as (dodecyl dimethylammonium) acetate (also known as lauryl betaine); (tetradecyl dimethyl ammonium) acetate (also known as myristyl beet base); (coco dimethyl ammonium) acetate (also known as coco betaine (coconut betaine)); (oleyl dimethyl ammonium) acetate (also known as oleyl betaine); (dodecyloxy dimethyl ammonium methyl) acetate; and (cocamidopropyl - dimethyl ammonium propyl) acetate (also known as cocoamidopropyl - propyl betaine or CAPB) .

[0095] 锍甜菜碱(sulfoniumbetaines),例如:(十二烧基二甲基锍)醋酸盐;和3_(椰油基二甲基-锍)-1-丙烷磺酸盐。 [0095] sulfonium betaine (sulfoniumbetaines), e.g. :( twelve burning dimethyl sulfonium) acetate; and 3_ (coco dimethyl - sulfonium) -1-propane sulfonate.

[0096] 鱗甜菜碱(phosphoniumbetaines),例如4_ (三甲基鱗)-1-十六烧磺酸盐;3-(十二烷基二甲基鱗)-1-丙烷磺酸盐;和 [0096] Scale betaine (phosphoniumbetaines), e.g. 4_ (trimethyl scales) -l-hexadecyl sulfonate burning; 3- (dodecyl dimethyl scale) -1-propane sulfonate; and

[0097] 2-(十二烷基二甲基鱗)-1_乙烷硫酸盐。 [0097] 2- (dodecyl dimethyl scale) -1_ ethane sulfate.

[0098] 所述洗衣洗涤剂组合物优选含有羧基甜菜碱或磺基甜菜碱,或它们的混合物作为两性或两性离子表面活性剂。 [0098] The laundry detergent compositions preferably contain betaine or sulfobetaine, or mixtures thereof as amphoteric or zwitterionic surfactants. 特别优选的是月桂基甜菜碱。 Particularly preferred is lauryl betaine. 在根据本发明的组合物中当一起使用时,所述甜菜碱和异羟肟酸盐可以提供甚至进一步提高的颗粒污物去除。 When used with the compositions of the present invention as the betaines and hydroxamates may provide even further improved particulate soil removal.

[0099] 洗涤助洗齐[J [0099] Qi washed builder [J

[0100] 其中使用了所述异羟肟酸盐的洗衣洗涤剂组合物优选含有低浓度的洗涤助洗剂,基于整个组合物的总重量。 [0100] wherein the hydroxamate a laundry detergent compositions detergency builder is preferably a low concentration, based on the total weight of the entire composition. 无机助洗剂沸石和磷酸盐的量少于5wt%。 Inorganic builders and phosphate zeolite is less than 5wt%. 这些助洗剂被认为当大量使用时对环境有害。 These builders are considered when heavy use of environmentally hazardous. 此外,它们需要以高浓度使用以具有明显的助洗效果,而这与新式的浓缩高重量效率洗衣洗涤剂制剂相矛盾。 In addition, they need to use a high concentration of builder having a significant effect, which concentrates the new high efficiency laundry detergent formulations by weight contradict.

[0101] 优选所述助洗剂选自碱金属和碱土金属碳酸盐(例如碳酸钠)、硅酸盐(例如层状硅酸盐)和有机助洗剂例如柠檬酸盐(例如柠檬酸钠)、丁二酸盐、氨基磺酸盐和丙二酸盐以及这些的任何组合。 [0101] Preferably the builder is selected from alkali metal and alkaline earth metal carbonates (e.g. sodium carbonate), silicates (e.g., layered silicates) and organic builders such as citrate (e.g. sodium citrate ), succinate, malonate, and sulfamate, and any combination of these. 优选所述有机助洗剂。 The preferred organic builders. 它们可以以lwt%或更高,最高例如50被%的浓度使用。 They may be LWT% or more, e.g. up to 50% of the concentration used.

[0102] 可以存在的有机助洗剂包括多元羧酸盐聚合物例如聚丙烯酸盐和丙烯酸/马来酸共聚物;聚天冬氨酸盐;单体多羧酸盐例如柠檬酸盐、葡萄糖酸盐、氧基二丁二酸盐、甘油单_、二-和三丁二酸盐、羧甲基氧基丁二酸盐、羧基-甲基氧基丙二酸盐、二皮考啉酸盐(dipicolinates)、羟乙基亚氨基二乙酸盐、烷基-和链烯基丙二酸盐和丁二酸盐;和磺化的脂肪酸盐。 [0102] Organic builders that may be present include polycarboxylate polymers such as polyacrylates and acrylic / maleic copolymers; polyaspartates; monomeric polycarboxylates such as citrate, gluconate salts, oxy disuccinate, _ mono-, di - and tri succinate, carboxymethyl succinate group, a carboxyl group - methyloxy malonates, dipicoline acid (dipicolinates), hydroxyethyl iminodiacetate, alkyl - and alkenyl malonates and succinates; and sulphonated fatty acid salts.

[0103] 可以少量使用有机助洗剂。 [0103] Organic builders may be used in small amounts. 特别优选的有机助洗剂是柠檬酸盐,合适地以I到30wt%,优选以1.5到10wt%的量使用;和丙烯酸类聚合物,更特别的是丙烯酸/马来酸共聚物,合适地以0.5到15wt%,优选以I到10wt%的量使用。 Particularly preferred organic builders are citrates, suitably by I to 30wt%, preferably in an amount of 1.5 to 10wt% of use; and acrylic polymers, more especially acrylic / maleic copolymers, suitably 0.5 to 15wt%, preferably I to 10wt% of the amount used.

[0104] 助洗剂,无论是无机的还是有机的,都优选以碱金属盐,特别是钠盐的形式存在。 [0104] Builders, both inorganic or organic, it is preferably present in alkali metal salt especially a sodium salt.

[0105] 其它任选的成分 [0105] Other optional ingredients

[0106] 除了权利要求中详细描述的必要组分外,制剂可以包括一种或多种任选的成分以增强性能和特性。 [0106] In addition to the essential components described in detail in the claims to the ingredients, the formulations may comprise one or more optional ingredients to enhance performance and properties. 虽然为了实施本发明这些成分不必存在,但是此类材料的使用通常非常有助于使所述制剂为消费者使用所接受。 While the embodiment of the present invention to these components need not be present, but the use of such materials is usually very helpful in the preparation of consumer acceptance.

[0107] 任选组分的例子包括,但不限于:水溶助长剂、荧光增白剂、光漂白剂、纤维润滑齐U、还原剂、酶、酶稳定剂(例如硼酸盐/酯和多元醇)、粉末整理剂(powder finishingagent)、消泡剂、漂白剂、漂白催化剂、防污剂特别是用于棉或聚酯或两者的防污聚合物、抗再沉积剂特别是抗再沉积聚合物、染料转移抑制剂、缓冲剂、着色剂、香料、香料前体、流变改性剂、抗灰聚合物(ant1-ashing polymer)、防腐剂、驱虫剂、驱污剂、防水剂、悬浮剂、美观剂(aesthetic agent)、结构剂、消毒剂、溶剂(包括水性和非水性溶剂)、织物整理剂、固色剂、除皱剂(wrinkle-reducing agent)、织物调理剂和除臭剂。 [0107] Examples of optional components include, but are not limited to: hydrotropes, optical brighteners, photobleaching agents, lubricating homogeneous fiber U, reducing agents, enzymes, enzyme stabilizers (e.g. a borate / polyol ester and alcohol), powder finishing agents (powder finishingagent), defoaming agents, bleaching agents, bleach catalysts, especially fouling polymeric antifouling agent for cotton or polyester or both, anti-redeposition agents particularly anti-redeposition polymers, dye transfer inhibitors, buffers, colorants, perfumes, pro-perfumes, rheology modifiers, anti-ashing polymers (ant1-ashing polymer), preservatives, insect repellents, stain repellency agent, waterproofing agent , suspending agents, aesthetic agents (aesthetic agent), structuring agents, disinfectants, solvents (including aqueous and non-aqueous solvents), textile finishing agents, fixing agents, wrinkle agent (wrinkle-reducing agent), in addition to fabric conditioner and deodorant.

[0108] 这些任选的成分可以包括但不限于以下的任何一种或多种:皂、过酸和过酸盐漂白剂、漂白活化剂、螯合剂、纤维素醚和酯、其它抗再沉积剂、硫酸钠、硅酸钠、氯化钠、氯化钙、碳酸氢钠、其它无机盐、荧光剂、光漂白剂、聚乙烯基吡咯烷酮、其它染料转移抑制聚合物、泡沫控制剂、泡沫促进剂、丙烯酸类聚合物和丙烯酸/马来酸聚合物、蛋白酶、月旨肪酶、纤维素酶、淀粉酶、其他洗涤剂酶、柠檬酸、防污聚合物、织物调理化合物、colouredspeckles和芳香剂。 [0108] These optional ingredients may include, but is not limited to any one or more of the following: soap, peracids and persalt bleaches, bleach activators, sequestrants, cellulose ethers and esters, other antiredeposition agents, sodium sulphate, sodium silicate, sodium chloride, calcium chloride, sodium bicarbonate, other inorganic salts, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam control agents, foam boosters agents, acrylic polymer and acrylic / maleic polymers, proteases, lipases purpose month, cellulases, amylases, other detergent enzymes, citric acid, fouling polymers, fabric conditioning compounds, colouredspeckles and perfuming .

[0109] 所述洗衣洗涤剂组合物可以适当地含有基于过氧漂白化合物的漂白体系,所述过氧漂白化合物例如无机过酸盐或有机过酸,在水溶液中能够产生过氧化氢。 [0109] The laundry detergent compositions may suitably contain a bleach system based on peroxygen bleaching compound, a peroxygen bleaching compound, for example, inorganic persalt or an organic peracid, in an aqueous solution capable of generating hydrogen peroxide. 合适的过氧漂白化合物包括有机过氧化物例如过氧化脲,和无机过酸盐例如碱金属过硼酸盐、过碳酸盐、过磷酸盐、过硅酸盐和过硫酸盐。 Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. 优选的无机过酸盐是过硼酸钠一水合物和四水合物,以及过碳酸钠。 Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. 特别优选的是具有对抗由水分引起的不稳定的保护性涂层的过碳酸钠。 Particularly preferred is having a protective coating against moisture caused by the instability of sodium percarbonate. 具有含有偏硼酸钠和硅酸钠的保护性涂层的过碳酸钠在GB 2 123 044B(Kao)中公开。 Having a protective coating comprising sodium metaborate and sodium silicate is disclosed percarbonate in GB 2 123 044B (Kao) are.

[0110] 所述过氧漂白化合物适当地以5到35wt%,优选以10到25wt%的量存在。 [0110] The peroxygen suitably from 5 to 35wt%, preferably in an amount of 10 to 25wt% of the bleaching compounds is present.

[0111] 所述过氧漂白化合物可以与漂白活化剂(漂白剂前体)结合使用以改善在低洗涤温度的漂白作用。 [0111] The peroxy bleach compound may be used at lower wash temperatures in order to improve bleaching action in conjunction with a bleach activator (bleach precursor). 所述漂白剂前体适当地以I到8wt%,优选地以2到5wt%的量存在。 The bleach precursor is suitably in I to 8wt%, preferably present in an amount of 2 to 5wt%.

[0112] 优选的漂白剂前体是过羧酸前体,更特别地是过乙酸前体和过苯甲酸前体;和过碳酸前体。 [0112] Preferred bleach precursors front is too acid precursors, more especially peracetic acid precursors and perbenzoic acid precursors; percarbonate and the front thereof. 适合在本发明中使用的特别优选的漂白剂前体是N,N,N',N'_四乙酰基乙二胺(TAED)。 Particularly preferred for use in the present invention, the bleach precursor is N, N, N ', N'_ tetraacetylethylenediamine (TAED). 同样让人感兴趣的是过苯甲酸前体,特别是N,N, N-三甲基铵甲苯酰氧基苯磺酸盐。 Also interesting are perbenzoic acid precursors, in particular N, N, N- trimethyl ammonium toluyloxy benzene sulphonate.

[0113] 还可以存在漂白剂稳定剂(重金属螯合剂)。 [0113] There may also be a bleach stabilizer (heavy metal sequestrant). 适合的漂白剂稳定剂包括乙二胺四乙酸盐(EDTA)和多膦酸盐例如Dequest (商标),EDTMP。 Suitable bleach stabilizers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates e.g. as Dequest (trademark), EDTMP.

[0114] 但是,尽管上面这样描述,对于所述组合物优选不含漂白剂,并且依靠由所述新型异羟肟酸盐和表面活性剂组合获得的改善的粘土污溃去除。 [0114] However, despite such described above, for the composition is preferably free of bleach, and rely obtained by the combination of novel hydroxamate and a surfactant to improve the removal of clay sewage collapse. 对于液体组合物尤其如此。 Especially for the liquid composition.

[0115] 所述洗涤剂组合物还可以含有一种或多种酶。 [0115] The detergent composition may further contain one or more enzymes. 适合的酶包括可用于加入洗涤剂组合物中的蛋白酶、淀粉酶、纤维素酶、氧化酶、过氧化物酶和脂肪酶。 Suitable enzymes include the detergent composition may be used in the proteases, amylases, cellulases, oxidases, peroxidases and lipases.

[0116] 在颗粒洗涤剂组合物中,一般以约0.1到约3.0wt%的量以颗粒形式使用去污酶。 [0116] In particulate detergent compositions, typically in an amount of from about 0.1 to about 3.0wt% of detersive enzymes used in particulate form. 但是,也可以以任何有效的量使用任何适合的物理形式的酶。 However, it may also be used in any suitable physical form of enzyme in any effective amount.

[0117] 还可以存在抗再沉积剂,例如纤维素酯和醚,例如羧甲基纤维素钠。 [0117] There may also be antiredeposition agents, such as cellulose esters and ethers, such as sodium carboxymethyl cellulose.

[0118] 所述组合物还可以含有防污聚合物,例如磺化的和未磺化的ΡΕΤ/Ρ0ΕΤ聚合物(封端的和未封端的),和聚乙二醇/聚乙烯醇接枝共聚物例如Sokolan (商标)HP22。 [0118] The composition may further contain the antifouling polymers, such as sulfonated and unsulfonated ΡΕΤ / Ρ0ΕΤ polymer (capped and uncapped), and polyethylene glycol / polyvinyl alcohol graft copolymer For example was as Sokolan (trade mark) HP22. 特别优选的防污聚合物是WO 95 32997A (Rhodia Chimie)中描述和要求保护的磺化的未封端聚酯。 Particularly preferred anti-fouling polymer is not end-capped polyesters described and claimed in WO 95 32997A (Rhodia Chimie) sulfonated.

[0119] 产品形式和制备 [0119] Product Form and Preparation

[0120] 根据本发明的产品可以采取任何适合的形式,例如固体、液体或膏状(paste)组合物,例如作为粒子(粉末、颗粒)、片或条。 [0120] The product according to the present invention may take any suitable form, for example a solid, liquid or paste (Paste) compositions, such as particles (powders, granules), sheets or strips. 优选地,所述产品是具有至少30被%的表面活性剂浓度的浓缩液体。 Preferably, said product having at least 30 concentrated liquid surfactant concentration in percent. 此类组合物需要水溶助长剂的存在以溶解所述成分。 Such compositions require the presence of a hydrotrope to solubilize the ingredients. 优选避免乙醇。 Ethanol is preferably avoided. 优选的水溶助长剂是丙二醇和甘油。 The preferred hydrotrope is propylene glycol and glycerol. 基于该教导,技术人员不需创造性就能够选择其它水溶助长剂而避免使用高挥发性溶剂如乙醇。 Based on this teaching, the skilled artisan can select other inventive without hydrotropes avoid the use of highly volatile solvents such as ethanol.

[0121] 根据本发明的第二实施方案,所述洗涤剂组合物为粒子形式。 [0121] According to a second embodiment of the present invention, the detergent composition is in particulate form. 在所述清洁表面活性剂体系中,那么阴离子表面活性剂与非离子表面活性剂的比值优选至少为3:2,优选至少7:2。 In the cleaning system surfactant, the anionic surfactant to nonionic surfactant ratio is preferably at least 3: 2, preferably at least 7: 2.

[0122] 通过喷雾干燥浆(slurry),并任选地后掺入(干混)进一步的成分可以制备低到中等堆积密度的粉末。 [0122] By spray-drying the slurry (slurry), and optionally after the incorporation of (dry-blended) further ingredients may be prepared in low to medium bulk density powder. 可用于粉末制造的途径包括喷雾干燥、转鼓式干燥、流化床干燥和刮膜式干燥设备例如刮膜式蒸发器。 Route can be used for producing powders include spray drying, drum drying, fluidized bed drying, and scraped film drying apparatus such as a wiped film evaporator. 刮膜式设备的一种优选形式是刮膜式蒸发器。 A preferred form of apparatus of the wiped film evaporator is a wiped film. 一种这种合适的刮膜式蒸发器是基于可从Ballestra SpA获得的刮膜式蒸发器的“Dryexsystem”。 One such suitable wiped film evaporator is based, available from Ballestra SpA wiped film evaporator "Dryexsystem". 可供选择的设备将是Chemithon “Turbo Tube”干燥器系统,其中高活性表面活性剂糊被加热并计量加入到多管蒸汽套干燥容器中。 Alternatively the device will be Chemithon "Turbo Tube" dryer system, wherein the high active surfactant paste is metered into the heated and multi-tube steam jacket drying vessel.

[0123] 通过混合和造粒方法,例如使用高速混合器/造粒机或其它无塔方法(non-towerprocess),可以制备“浓缩的”或“压缩的”粉末。 [0123] By mixing and granulation methods, for example using high-speed mixer / granulator, or other non-tower methods (non-towerprocess), can be prepared in a "concentrated" or "compressed" powder.

[0124] 通过压制粉末,特别是“浓缩的”粉末可以制备片剂。 [0124] By pressing powders, especially "concentrated" powders may be prepared tablets.

[0125] 现在将参考以下非限定性实施例进一步描述本发明。 [0125] Reference will now be made to the following non-limiting examples further embodiment of the present invention will be described.

实施例 Example

[0126] 防污指数(SRI)的测量 [0126] The antifouling measurement index (SRI) of

[0127] SRI是洗涤过程期间纺织品上多少污溃被除去的量度。 [0127] SRI is a measure of how much dirt is removed from the crushed textile during the washing process. 任何污溃的强度都可以借助于反射计就污溃和清洁布料之间的差异对每一污溃给出ΛΕ*而测量。 Any collapse strength of sewage by means of a reflectometer can collapse on the difference between the sewage and the sewage cleaning cloth for each given ΛΕ * measured collapse. 其定义为ΛΕ*和计算如下: Defined as ΛΕ * and is calculated as follows:

[0128] [0128]

Figure CN102257109BD00131

[0129] L*、a*和b*是CIE 1976 {L*、a*、b*)色空间的坐标,使用标准反射计测定。 [0129] L *, a * and b * are 1976 {L *, a *, b *) color space coordinates, measured using a standard reflectometer CIE. 可以在洗漆污溃之前和之后测量ΔΕ*,以提供AE*bw(洗漆前)和ΔΕ*„(洗漆后)。那么SRI Wash the paint can before and after the collapse pollution measuring ΔΕ *, to provide AE ​​* bw (pre-wash paint) and ΔΕ * "(after washing the paint). Then SRI

定义为: defined as:

[0130] [0130]

Figure CN102257109BD00132

[0131] SRI为100意味着污溃被完全除去。 [0131] SRI is 100 means complete removal of dirt collapse.

[0132] 洗涤后的ΛΕ是清洁(未洗涤)织物和洗涤后污溃之间的L ab色空间差异。 [0132] The washed clean ΛΕ (unwashed) L ab color space difference between the fabric and the washing dirty collapse. 因此洗涤后的ΛΕ为O意味着污溃被完全除去。 Thus ΛΕ after washing is O means sewage collapse completely removed. 因此,SRIawS 100是完全除去的污溃。 Thus, SRIawS 100 collapse dirt is completely removed. 所述清洁(或未使用的)织物是未经洗涤的“绝对标准”。 The cleaning (or unused) unwashed fabrics are "absolute standard." 对于各实验,其是指与施加污溃的织物片等同的织物片。 For each experiment, which refers to the piece of fabric is applied to the fabric sheet collapse dirt equivalent. 因此,其在L ab色空间中的点保持不变。 Thus, the point in which L ab color space remains the same.

[0133] 实施例1:辛基异羟肟酸盐(钾盐)的制备 Octyl prepared hydroxamate (potassium salt) of: 1 case [0133] Embodiment

[0134] 通过Raghavan 和Fuerstenau(Journal of Colloid and Interface Science,1975,Vol.50,p.319-330)公开的方法制备辛基异羟肟酸盐的钾盐。 [0134] By Raghavan and Fuerstenau (Journal of Colloid and Interface Science, 1975, Vol.50, p.319-330) disclosed the method of preparation of potassium iso-octyl hydroxamate.

[0135] 实施例2:除去在针织聚酯(2:1)上的红粘土污溃 [0135] Example 2: removing the knitted polyester: red clay dirt ulcer (2 1)

[0136] 配制洗涤液,如表I中所示以所示浓度,含有作为表面活性剂的伯烷基硫酸盐(PAS,阴离子表面活性剂,来自Kao Emal PH10)和醇乙氧基化物(非离子表面活性剂C12-7E0, Neodol 25-7来自Shell)。 [0136] wash liquors, as shown in Table I at the indicated concentrations, comprising a primary alkyl sulphate (the PAS, an anionic surfactant, from Kao Emal PH10) as a surfactant and alcohol ethoxylate (non- nonionic surfactants C12-7E0, Neodol 25-7 from Shell). 此外,所述洗涤液含有浓度为5mM的NaCl。 Further, the scrubbing solution having a concentration of 5mM NaCl. 水硬度为6 °FH(软水,约24毫克钙/升),和水温为30°C。 A water hardness of 6 ° FH (soft water, about 24 mg of calcium / liter), and water temperature of 30 ° C. 由于使用软水不需要助洗剂或螯合剂,因此不向组合物加入这些成分。 It does not require the use of soft water builders or chelating agents, and therefore these components are not added to the composition.

[0137] 表I洗涤液中表面活性剂和异羟肟酸盐的浓度 Table I, the concentration of surfactant in the wash liquor and hydroxamic acid salt [0137]

[0138] [0138]

Figure CN102257109BD00141

[0139] 以下结果是使用Tergotometer洗衣机对于从针织聚酯布料除去红粘土污溃在以下标准规程(称为软水Tergotometer洗涤规程)中测定获得的。 [0139] The following results were obtained using red clay Tergotometer washing machine for measuring pollution in the following standard protocols collapse (referred to as soft Tergotometer wash protocol) is removed from the knitted fabric obtained from the polyester. 使用的红粘土是陶土形式。 Red clay is used in the form of clay.

[0140]软水 Tergotometer 洗漆规程: [0140] soft water wash paint Tergotometer Protocol:

[0141] 1.测量纺织品布料上污溃的颜色 [0141] 1. Measurement of the textile fabric colors sewage collapse

[0142] 2.设定Tergotometer 到25°C。 [0142] 2. Tergotometer set to 25 ° C.

[0143] 3.向每个罐中加入水和制剂储液(stock solutions),搅拌I分钟。 [0143] 3. Add the water reservoir and the formulation (stock solutions) to each pot, stirred for I min.

[0144] 4.加入污染的布料和压仓物(ballast),启动Tergotometer。 [0144] 4. Add the contaminated cloth and ballast material (ballast), start Tergotometer.

[0145] 5.使之洗涤12分钟 [0145] The so washed 12 minutes

[0146] 6.在6° French硬水中漂洗布料I分钟,重复漂洗。 [0146] 6. Rinse the fabric I min at 6 ° French hard water rinse is repeated.

[0147] 7.干燥布料过夜。 [0147] 7. The fabric was dried overnight.

[0148] 8.测量所述纺织品布料上污溃的颜色 [0148] The measuring of the contaminated textile fabrics on the color collapse

[0149] 表2 针织聚酯上红粘土污溃的污溃去除指数(SRI) [0149] TABLE 2 Red Clay polyester knitted collapse sewage pollution removal ulcer index (SRI)

Figure CN102257109BD00142

[0151] 该实验显示,含有辛基异羟肟酸盐的制剂导致在软水中从针织聚酯显著更好的红粘土污溃去除。 [0151] This experiment showed that the formulation of the octyl hydroxamate results in soft water containing polyester knitted from red clay significantly better dirt removal collapse. 由于这是在软水中的实验,所以所述异羟肟酸发生作用的机理不是作为助洗剂,因此排除了助洗剂效应作为改善去污效果的作用机理。 As this experiment is in soft water, so that the mechanism of action of hydroxamic acid is not occurring as a builder, thus excluding effects as builders to improve detergency effect mechanism.

[0152] 实施例3:从针织聚酯除去Georgia粘土污溃和从机织棉除去草污溃 [0152] Example 3: Georgia clay from knitted polyester dirt removed from the crushed and removed woven cotton grass sewage collapse

[0153] 配制两种液体洗涤剂。 [0153] formulated in two liquid detergents. 如表3中所示按指定的浓度,使用的表面活性剂为烷基苯磺酸钠(Na LAS,阴离子表面活性剂)、醇乙氧基化物(非离子表面活性剂C12_7E0,Neodol25-7来自Shell)和经中和的饱和皂(椰油脂肪酸(Prifac 5908来自Uniqema))。 As shown in Table 3 in the specified concentration, the surfactant used is sodium alkylbenzene sulfonate (Na LAS, anionic surfactant), alcohol ethoxylate (nonionic surfactant C12_7E0, Neodol25-7 from shell) and neutralized with saturated soap (coconut oil fatty acid (Prifac 5908 from Uniqema)). 还使用的是洗衣液体洗涤剂的标准化合物(助洗剂(柠檬酸钠)、水溶助长剂(5%甘油和9%丙二醇)、缓冲剂和螯合剂(Dequest 2066膦酸盐)、酶(Savinase Ultra 16L蛋白酶)。如表3中所列出,分别使用制剂3和4制备两种洗涤液,以提供表4中所示的表面活性剂和异羟肟酸盐浓度。在所述洗涤液中水硬度为26 TH(中等水,约104毫克钙/升),水温为40°C。将PH缓冲到7到8。 Also used was a standard laundry liquid detergent compound (builder (sodium citrate), hydrotropes (9% 5% glycerol and propylene glycol), a buffer and a chelating agent (Dequest 2066 phosphonate), an enzyme (Savinase Ultra 16L protease) as listed in table 3, 3, and 4 were used to prepare two liquid washing formulations, to provide a surface active agent and hydroxamate concentrations shown in table 4. in the wash liquor water hardness was 26 TH (aqueous medium, from about 104 mg of calcium / liter), a water temperature of 40 ° C. the buffered to PH 7-8.

[0154] 表3使用的制剂 [0154] formulations used in Table 3

[0155] [0155]

Figure CN102257109BD00151

[0156] 表4 基于表3中的制剂的洗涤液中表面活性剂和异羟肟酸盐的浓度 [0156] Table 4 based on the concentration of surfactant, and hydroxamate washing liquid formulations in Table 3

[0157] [0157]

Figure CN102257109BD00152

[0158] 以下结果是使用Linitest™洗衣机从针织聚酯布料除去Georgia污溃和从机织棉除去草污溃,按标准规程(称为Linitest™洗涤规程)测定而获得的。 [0158] The following results were measured knitted polyester fabric was removed and crushed Georgia dirt removed from woven cotton grass sewage collapse, according to the standard protocol (referred Linitest ™ wash protocol) obtained from the washing machine using Linitest ™.

[0159] Linitest™ 洗涤规程 [0159] Linitest ™ wash protocol

[0160] 1.洗涤污溃之前阅读。 [0160] 1. Read before washing dirty collapse.

[0161] 2.打开Linitester™并使之加热到40°C。 [0161] 2. Open Linitester ™ and allowed to heat to 40 ° C.

[0162] 3.将产品投入罐中,向罐中加入水。 [0162] 3. Place the product into the tank, water is added to the tank.

[0163] 4.在罐中放入污溃、压仓物和50个滚珠。 [0163] 4. Place collapse sewage in the tank and ballast material 50 balls.

[0164] 5.启动Linitester™并使之洗漆30分钟。 [0164] 5. Start Linitester ™ 30 minutes and allowed to wash the paint.

[0165] 6.漂洗压仓物和衣料5分钟。 [0165] 6. Rinse and ballast cloth was 5 minutes.

[0166] 7.重复漂洗。 [0166] 7. Repeat rinsing.

[0167] 8.干燥污溃过夜。 [0167] 8. The dried sewage collapse overnight. [0168] 9.洗涤污溃后读数。 [0168] 9. After washing dirty collapse reading.

[0169] 表5 针织聚酯和机织棉上Georgia粘土污溃和针织聚酯上草的污溃去除指数(SRI) [0169] Table 5 on woven cotton and knitted polyester Georgia clay, grass and dirt collapse dirt knitted polyester ulcer removal index (SRI)

[0170] [0170]

Figure CN102257109BD00161

[0171] 该实验示出所述异羟肟酸的使用导致针织聚酯上Georgia粘土以及草的更好去除和改善的Georgia粘土从机织棉的去除。 [0171] This experiment illustrates the use of different hydroxamic acid and results in a better removal of grass and improving Georgia clay of Georgia clay from knitted polyester woven cotton removed.

[0172] 尽管在所述洗涤剂组合物中存在Savinase (其改善了草污溃去除),但是通过所述异羟肟酸盐的添加进一步改善了草污溃去除。 [0172] Although there Savinase in the detergent composition (which improved grass collapse dirt removal), but is further improved by adding oxalyl sewage removal collapse hydroxamate said heterologous.

[0173] 实施例4.洗涤剂组合物的典型实例 [0173] Example 4. Typical examples of embodiment of the detergent composition

[0174] 在表6中给出了根据本发明的一些典型的洗涤剂组合物。 [0174] Table 6 is given in accordance with some typical detergent compositions of the present invention.

[0175] 表6根据本发明的典型洗涤剂组合物 [0175] Table 6 according to an exemplary of the present invention the detergent composition

[0176] [0176]

Figure CN102257109BD00162

[0177] 实施例5__具有不同烷基链长度的异羟肟酸盐[0178] 以下结果是使用Tergotometer洗衣机从针织棉布除去Georgia粘土污溃按以下标准规程(称为Tergotometer硬水洗涤规程)测定获得的。 [0177] Example 5__ hydroxamate having different alkyl chain lengths [0178] The following results were obtained using Tergotometer washing machine knitted cotton was removed from sewage Georgia clay crushed according to the following standard protocol (referred to as hard water Tergotometer wash protocol) assay obtained of. 根据表7使用不同的异羟肟酸盐。 Using different hydroxamate according to Table 7.

[0179] Tergotometer 硬水洗洛规程: [0179] Tergotometer hard water Los procedure:

[0180] 测量纺织品布料上污溃的颜色 [0180] Textile fabrics pollution measuring color collapse

[0181]将 Tergotometer 设定到3CTC。 [0181] will be set to the Tergotometer 3CTC.

[0182] 向各个iiS中加入水和制剂储液,揽祥I分钟。 [0182] Water was added and the formulation in the reservoir to each iiS, Cheung I embrace minutes.

[0183] 加入污染的布料和压仓物,启动Tergotometer。 [0183] added and the contaminated ballast cloth was started Tergotometer.

[0184] 使之洗涤12分钟 [0184] 12 minutes so as to wash

[0185] 在26° French硬水中漂洗布料I分钟,重复漂洗。 [0185] I rinsed cloth min 26 ° French hard water rinse is repeated.

[0186] 干燥布料过夜。 [0186] dry cloth overnight.

[0187] 测量在所述纺织品布料上的污溃的颜色。 [0187] Measurement of color collapse dirt on the textile fabric.

[0188]表 7 [0188] TABLE 7

[0189] [0189]

Figure CN102257109BD00171

[0190]表 8 [0190] TABLE 8

[0191] [0191]

Figure CN102257109BD00181

[0194] 表8和9总结了在不同布料上的结果。 [0194] Tables 8 and 9 summarize the results on different fabrics.

_5] 实施例6:阴离子表面活性剂非离子表面活性剂比值的影响 [5] Example 6: Effect of the ratio of anionic surfactant nonionic surfactant

[0196] 表10制剂A到F(对比一不含辛基异羟肟酸盐) [0196] Table 10 Formulation A to F (excluding a comparative octyl hydroxamate)

[0197] [0197]

Figure CN102257109BD00182

[0198] 表11含有辛基异羟肟酸盐的制剂 [0198] Table 11 formulation containing octyl hydroxamate of

[0199] [0199]

Figure CN102257109BD00191

[0200] 该实施例显示了以上述Tergotometer硬水洗漆规程测量,改变阴离子表面活性剂对非离子表面活性剂的比值对从针织聚酯去除Georgia粘土污溃的影响。 [0200] This example shows the above-described measuring procedure Tergotometer hard water paint, to remove the effect of changing Georgia clay from knitted polyester sewage collapse ratio of anionic surfactant to nonionic surfactant. 制剂在表11中给出和不含所述异羟肟酸盐的对比制剂在表10中给出。 Given formulation and comparative formulation does not contain the heterologous hydroxamate given in Table 10. In Table 11.

[0201] 结果总结在表12中。 [0201] The results are summarized in Table 12. 制剂A_0H、E_0H和F_0H是对比。 Formulation A_0H, E_0H and F_0H are comparative.

[0202]表 12 [0202] Table 12

[0203] [0203]

Figure CN102257109BD00192

[0204] 实施例7—较高的阴离子表面活性剂对非离子表面活性剂的比值(从机织棉除去Georgia 粘土) [0204] Example 7- higher ratio of anionic surfactant to nonionic surfactant of the embodiment (woven cotton removed from Georgia clay)

[0205] 制备了多种阴离子/非离子制剂,其中阴离子表面活性剂对非离子表面活性剂的比值至少为4:1。 1: [0205] a more anionic / nonionic formulations wherein the ratio of anionic surfactant to nonionic surfactant is at least 4 prepared. 首先按照表13制备了一组不含异羟肟酸盐的对比制剂。 First, in Table 13 contain a set of comparative formulations prepared hydroxamate. 然后根据表14制备了含5wt%的辛基异羟肟酸盐的一组相应制剂。 The table 14 is then a set of corresponding formulation containing 5wt% of octyl hydroxamate prepared.

[0206] 表13 (对比制剂) [0206] Table 13 (Comparative formulation)

[0207] [0207]

Figure CN102257109BD00201

[0208] 使用的皂是Prifac 5908。 [0208] soap used is Prifac 5908. 所述水溶助长剂是甘油和丙二醇。 The hydrotrope is propylene glycol and glycerol.

[0209] 表14 [0209] TABLE 14

[0210] [0210]

Figure CN102257109BD00202

[0211] 以下结果是使用上述标准硬水Tergotometer洗漆规程测量和对于表13和14中每种制剂以2.6g/L的洗漆中制剂浓度,从机织棉除去Georgia粘土污溃获得。 [0211] The following results were obtained using the above standard Tergotometer wash hard water paint and measurement procedures for each formulation in Tables 13 and 14 at 2.6g / L wash the paint formulation concentration, removal from woven cotton collapse sewage Georgia clay obtained. 结果在表15中给出。 The results are shown in Table 15. 实施例J_0H是对比性的。 Example J_0H are contrasting.

[0212]表 15 [0212] TABLE 15

[0213] [0213]

Figure CN102257109BD00211

[0214] 实施例8:可选择的阴离子表面活性剂:伯烷基硫酸盐.[0215] 表16 (对比制剂) [0214] Example 8: optional anionic surfactant: primary alkyl sulfate [0215] Table 16 (comparative formulation).

[0216] [0216]

Figure CN102257109BD00212

[0217] 表17(含异羟肟酸盐的制剂) [0217] Table 17 (formulation containing the hydroxamic acid salt)

[0218] [0218]

Figure CN102257109BD00213

[0219] 表18中的以下结果是在洗漆中使用2.6g/L制剂使用硬水Tergotometer洗漆规程测量从针织聚酯除去Georgia粘土污溃获得的。 [0219] The following results in Table 18, using 2.6g / L in formulations using hard water wash paint removers Tergotometer measurement procedure to remove dirt from Georgia clay collapse knitted polyester obtained. 在表16中给出了不含异羟肟酸盐的对比制剂和在表17中给出了含异羟肟酸盐的制剂。 A comparison of the formulation is free of hydroxamate in Table 16 and are given the hydroxamate-containing formulations are shown in Table 17. 通常,所述水溶助长剂体系含有5被%甘油和9wt%丙二醇。 Typically, the hydrotrope system and containing 5% glycerol was 9wt% propylene glycol. 由于阴离子表面活性剂对非离子表面活性剂的比值在所要求保护的范围之外,所以组合物Ν_0Η和Ρ_0Η是对比性的。 Since the ratio of anionic surfactant to nonionic surfactant in addition to the claimed range, and so the compositions Ν_0Η Ρ_0Η are contrasting.

[0220]表 18 [0220] Table 18

Figure CN102257109BD00221

Claims (24)

1.洗衣洗涤剂组合物,其含有a)0.5到20 wt%的以下结构的异羟肟酸或其相应的异羟肟酸盐: 1. A laundry detergent composition, comprising a) a hydroxamic acid of 0.5 to 20 wt% of the structure or its corresponding hydroxamate:
Figure CN102257109BC00021
其中R1是选自由c4、C5、C6、C7、C8、C9、C10, Cn、C12或C14正烷基组成的组; 和R2为氢, b)3到80wt%的清洁表面活性剂体系,其含有(i)阴离子表面活性剂;和(ϋ)非离子表面活性剂其中⑴对(ii)的比值位于1:1.1到19:1的范围,和a)对b)的重量比位于1:5到1:15的范围c)任选地,补足至100wt%的其它成分,条件是沸石和磷酸盐助洗剂分别以少于5wt%存在和乙醇以少于5wt%的浓度存在。 Wherein R1 is selected from the group consisting of c4, Group C5, C6, C7, C8, C9, C10, Cn, C12 or C14 n-alkyl thereof; and R2 is hydrogen, b) 3 to 80wt% of surfactant cleaning system, which comprising (i) an anionic surfactant; and (ϋ) a nonionic surfactant wherein ⑴ ratio of (ii) is located at 1: 1.1 to 19: 1 range, and a) by weight of b) is located at 1: 5 the range of 1:15 to c) optionally, other ingredients to make up 100wt%, provided that the zeolite and phosphate builder are present at less than 5wt% to less than 5wt%, and ethanol concentration.
2.根据权利要求1的组合物,其中异羟肟酸或其相应的异羟肟酸盐为6wt%。 2. The composition according to claim 1, wherein the corresponding hydroxamic acid or hydroxamic acid salt is 6wt%.
3.根据权利要求1的组合物,其中R1是C8、C9、C10, Cn、C12或C14正烷基。 3. A composition according to claim 1, wherein R1 is C8, C9, C10, Cn, C12 or C14 n-alkyl.
4.根据权利要求1的组合物,其中所述组合物含有浓度为I到50wt%的洗涤助洗剂。 4. A composition according to claim 1, wherein the composition contains a concentration of I to 50wt% detergency builder.
5.根据权利要求1的组合物,其含有至少20wt%的所述清洁表面活性剂体系。 5. The composition as claimed in claim 1, which contains at least 20wt% of said surfactant system cleaning.
6.根据权利要求1的组合物,其含有至少30wt%的所述清洁表面活性剂体系。 6. A composition according to claim 1, which contains at least 30wt% of said surfactant system cleaning.
7.根据权利要求1的组合物,其含有超过40wt%的所述清洁表面活性剂体系。 7. The composition according to claim 1, which contains more than 40wt% of the surfactant system cleaning.
8.根据权利要求1的组合物,其含有I到15wt%的皂。 8. The composition according to claim 1, containing I to 15wt% soap.
9.根据权利要求8的组合物,其中所述皂由饱和脂肪酸制备。 9 wherein the soap prepared from saturated fatty acid composition according to claim 8,.
10.根据权利要求1的组合物,其含有至少0.5wt%的防污聚合物。 10. The composition according to claim 1, which comprises at least 0.5wt% of the fouling polymer.
11.根据权利要求1的组合物,其含有至少0.5wt%的抗再沉积聚合物。 11. A composition according to claim 1, which comprises at least 0.5wt% of anti-redeposition polymer.
12.根据权利要求1的组合物,其中异羟肟酸盐对清洁表面活性剂体系的比值位于1:7到1:13重量份的范围。 12. The composition according to claim 1, wherein the ratio of hydroxamate cleaning surfactant system has a 1: 7 to 1:13 parts by weight.
13.根据权利要求1的组合物,其中异羟肟酸盐对清洁表面活性剂体系的比值位于1:9到1:11重量份的范围。 13. The composition according to claim 1, wherein the ratio of hydroxamate cleaning surfactant system has a 1: 9 to 1:11 parts by weight.
14.根据权利要求1的组合物,其中阴离子表面活性剂对非离子表面活性剂的比值至少为1:1。 14. The composition according to claim 1, wherein the ratio of anionic surfactant to nonionic surfactant is at least 1: 1.
15.根据权利要求1的组合物,其中阴离子表面活性剂对非离子表面活性剂的比值至少为3:2。 15. The composition according to claim 1, wherein the ratio of anionic surfactant to nonionic surfactant is at least 3: 2.
16.根据权利要求14的组合物,其中阴离子表面活性剂对非离子表面活性剂的比值为1:1 到9:1。 16. The composition according to claim 14, wherein the ratio of anionic surfactant to nonionic surfactant is from 1: 1 to 9: 1.
17.根据权利要求14的组合物,其中阴离子表面活性剂对非离子表面活性剂的比值为3:2 到9:1。 17. The composition according to claim 14, wherein the ratio of anionic surfactant to nonionic surfactant is from 3: 2 to 9: 1.
18.根据权利要求1的组合物,其中所述组合物是液体组合物。 18. The composition according to claim 1, wherein said composition is a liquid composition.
19.根据权利要求18的组合物,其以至少6wt%的浓度包含含有丙二醇和甘油的水溶助长剂体系。 19. The composition according to claim 18 in which the concentration of at least 6wt% hydrotrope comprises a system containing propylene glycol and glycerol.
20.根据权利要求18的组合物,其是液体组合物,含有浓度为总组合物的20到80wt%的清洁表面活性剂。 20. The composition as claimed in claim 18, which is a liquid composition in a concentration of 20 to 80wt% of the total composition of the cleansing surfactant.
21.根据上述权利要求1-20任意一项的组合物用于从聚酯和棉织物除去颗粒污物的用途。 1-20 21. A composition according to any one of the preceding claims for use particles of dirt removed from the polyester and cotton fabrics.
22.根据权利要求21的用途,其中所述颗粒污物是红粘土。 22. The use according to claim 21, wherein said particle is a red clay soil.
23.根据权利要求21的用途,其中所述颗粒污物是Georgia粘土。 23. Use according to claim 21, wherein said particulate soil is a Georgia clay.
24.0.5到20wt%以下结构的异羟肟酸或其相应的异羟肟酸盐在洗衣洗涤剂组合物中的用途: 24.0.5 to 20wt% a hydroxamic acid or its corresponding hydroxamate use in the structure of the laundry detergent composition:
Figure CN102257109BC00031
其中R1为C8正烷基基团,和R2为氢原子,用于改善从纺织品基底除去颗粒污物污溃,其中所述组合物进一步含有浓度为3到80wt%的清洁表面活性剂体系和任选地补足至100wt%的其它成分,该清洁表面活性剂体系含有阴离子表面活性剂和非离子表面活性剂。 Wherein R1 is n-C8 alkyl group, and R2 is a hydrogen atom, for improving the removal of particulate soil from textile substrates collapse dirt, wherein the composition further comprises a concentration of the system and any of claims 3 to 80wt% of a surfactant cleaner optionally other ingredients to make up 100wt% of the cleaning surfactant system comprising an anionic surfactant and a nonionic surfactant.
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