CN100457880C - Poly alkene oxide surfactant - Google Patents

Poly alkene oxide surfactant Download PDF

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CN100457880C
CN100457880C CN 02147508 CN02147508A CN100457880C CN 100457880 C CN100457880 C CN 100457880C CN 02147508 CN02147508 CN 02147508 CN 02147508 A CN02147508 A CN 02147508A CN 100457880 C CN100457880 C CN 100457880C
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dimethyl
preferably
ethoxylate
alkyl
methyl
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CN1441042A (en
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D·S·康诺尔
J·C·T·R·布尔克特-圣劳伦特
K·W·维尔曼
P·K·温森
T·A·克里佩
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宝洁公司
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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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/722Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Abstract

在洗衣和清洗组合物中,尤其是粒状和液体洗涤剂组合物中有用的中链支化的伯烷基聚氧化烯表面活性剂。 In the laundry and cleaning compositions, especially granular and liquid detergent compositions useful in the mid-chain branched primary alkyl polyoxyalkylene surfactants. 为了提供改进的表面活性剂体系的目的,尤其是为了用于在包括低水温洗涤条件的洗衣方法中使用的洗涤剂组合物,这些表面活性剂也适合于与其它表面活性剂配制。 For the purpose of providing improved surfactant systems, especially for use in detergent compositions for use in laundry washing methods include low temperature conditions, these surfactants are also suitable for formulation with other surfactants. 本发明还涉及新的适用于表面活性剂混合物中的中链支化的伯烷基聚氧化烯表面活性剂。 The present invention also relates to new primary alkyl polyoxyalkylene surfactants suitable for use in the chain in the surfactant mixture of branched.

Description

聚氧化烯表面活性剂 Polyoxyalkylene surfactant

本申请是1997年11月19日提交的、发明名称为"聚氧化烯表面活性剂"的97181417. 1号专利申请的分案申请。 1997. This application is filed November 19, as a divisional application entitled "polyoxyalkylene surfactant" Patent Application No. 97181417.1.

本发明涉及在洗衣和清洗组合物中,尤其是粒状和液体洗涤剂组合物中有用的中链支化的伯烷基聚氧化烯表面活性剂.这些表面活性剂也适合于与其它表面活性剂配制,得到改进的表面活性剂体系,尤其是用于在包括低水温洗涤条件的洗衣方法中使用的洗涤剂组合物中。 The present invention relates to laundry and cleaning compositions, especially granular and liquid detergent compositions useful in the mid-chain branched primary alkyl polyoxyalkylene surfactant. These surfactants are also suitable for use with other surfactants formulation, improved surfactant system, the detergent composition, especially for use in a laundry washing method include a low temperature condition in the. 本发明还涉及新的适用于表面活性剂混合物中的中链支化的伯烷基聚氧化烯表面活性刑. The present invention also relates to novel mid-chain branched primary alkyl polyoxyalkylene surfactants suitable penalty of surfactant mixture.

常规的洗涤表面活性剂包括具有水增溶取代基(亲水基团)和亲油取代基(疏水基团)的分子。 Conventional detersive surfactants comprise a water-solubilizing substituent (hydrophilic group) and an oleophilic substituent molecule group (hydrophobic group). 这样的表面活性剂一般包括亲水基团例如羧酸根、硫酸根、磺酸根、氧化胺、聚氧乙烯等,其连接到通常舍有约10-20个碳原子的烷基、链烯基或坑芳基疏水物上.因此,这样的表面活性剂的制造商必须获得通过化学方法将所需要的亲水物连接到其上的疏水基源.最早的疏水基源包括天然脂肪和油,其用碱通过皂化可以转变成皂(即羧酸盐亲水物)。 Such surfactants typically comprise hydrophilic groups such as carboxylate, sulfate, sulfonate, amine oxide, polyoxyethylene and the like, which is connected to a generally rounded about 10 to 20 carbon atoms, an alkyl group, an alkenyl group, or Hang aryl hydrophobes. Thus, the manufacturer of such surfactants must have access to the desired hydrophile connected to a source of hydrophobic groups thereon by chemical methods. the first hydrophobe sources include natural fats and oils, which saponification may be converted into soaps (i.e., carboxylate hydrophile) with a base. 椰子油和棕榈油仍然用于制造皂以及用于制造烷基碗酸盐("AS")类表面活性剂。 Coconut oil and palm oil are still used to manufacture soap surfactants and alkyl bowl for producing salts ( "AS"). 其它的疏水物可以从石油化学品得到,包括用于制造烷基苯磺酸盐表面活性剂("LAS")的烷基苯. Other hydrophobes are available from petrochemicals, including for producing alkyl benzene sulfonate surfactants ( "LAS") of the.

文献认为某些支链疏水物可以有利地用于制造烷基碟酸盐洗涤表面活性剂;见,例如,1969年11月25日deWitt等的US3480556。 Some literature suggests that branched hydrophobic may advantageously be used to wash the salt surface active agent manufactured Singles alkyl; see, e.g., 25 November 1969 deWitt like US3480556. 然而,已经确定的是:在US3480556专利中所述的p-支链表面活性剂就某些溶解度参数而论是差的,如由其克拉夫特温度所证明的。 However, it has been determined that: in the patent US3480556 p- branched chain surfactants respect to certain solubility parameters is poor, as evidenced by their Krafft temperatures. 还已经确定的是:具有向疏水物的碳链中心支链化的表面活性剂具有低得多的克拉夫特温度。 It has also been established that: a much lower Krafft temperature of the branched-chain carbon chains center surfactant hydrophobe. 见:"《表面活性剂的水相行为》(TheAqueous Phase Behavior of Surfactants) " , RG Laughlin, Academic Press, NY (1994) p. 347。 See:. "" Aqueous surfactant phase behavior "(TheAqueous Phase Behavior of Surfactants)", RG Laughlin, Academic Press, NY (1994) p 347.

通常,烷基硫酸盐是洗涤表面活性剂领域的技术人员已知的.烷基疏酸盐是作为对传统皂表面活性剂的功能改进而研制的并且已经发现其具有改进的溶解性和表面活性剂特性。 Generally, alkyl sulfates are in the field of detergent surfactant known to skilled artisans. Sparse alkyl formate is developed as a functional improvement to the traditional soap surfactants and have been found to have improved solubility and surfactant agent properties. 直链烷基硫酸盐是最常用 Linear alkyl sulfates are the most commonly used

发明领域 Field of the Invention

发明背景 BACKGROUND OF THE INVENTION

的烷基疏酸盐表面活性剂并且是最容易得到的.例如,长链直链烷基硫酸盐如牛脂烷基疏酸盐已经被用于洗衣洗涤剂中了.然而,这些表面活性剂有很大的清洗性能限制,尤其是在较低洗涤温度的趋势下. Alkyl and hydrophobic surfactant salts are the most readily available. For example, long-chain linear alkyl sulfates, such as tallow alkyl sparsely salts have been used in a laundry detergent. However, these surfactants are significant cleaning performance limitations, especially at lower wash temperature trend.

如上所迷,2-烷基或"P"支链烷基疏酸盐也是已知的.除了上面所述的US3480556外,最近1991年7月31日公开的EP439316和1995年11月29日公开的EP684300也描述了这些P -支链烷基疏酸盐.支链烷基破酸盐领域中的最近的其它科学论文包括R. Varadaraj 等的J.Phys. Che迈.,Vol. 95, (1991), pp 1671-1676,该文献描述了各种"直链Guerbet"和"支链Guerbet"类表面活性剂包括烷基疏酸盐的表面张力."直链Guerbet"类基本上是"Y-型"的,具有如下长直链的2-位支链: As fans, 2-alkyl or "P" sparsely branched alkyl salts are also known in addition to the above US3480556, recently July 31, 1991 and disclosed in EP439316 November 29, 1995 discloses these is also described EP684300 P - sparsely branched alkyl salts branched alkyl other recent scientific papers in the field break salts include R. Varadaraj like J.Phys Che step, Vol 95, (.... 1991), pp 1671-1676, which describes a variety of "linear the Guerbet" and "branched the Guerbet" type surfactants include alkyl repellent surface tension salts. "linear the Guerbet" type is substantially "Y - type ", and has a long straight-chain 2-bit branch:

其中Z是,例如,0S03Na,"支链Guerbet"类也是2-位支链的,但还具有另外的支链取代基,其如下: Wherein Z is, for example, 0S03Na, "branched Guerbet" type is the 2-position branched, but also have additional branching substituents, which are as follows:

其中Z是,例如,0SO3Na.参见Varadaraj等的J. Colloid and Interface Sci., Vol. 140, (1990), pp 31-34,该文献涉及包括分别含有3和4甲基支链的C12和C13烷基疏酸盐(具体见第32页)的 Wherein Z is, for example, 0SO3Na. Varadaraj etc. See J. Colloid and Interface Sci., Vol. 140, (1990), pp 31-34, this document relates to a C12 3 and 4 respectively containing methyl branch and C13 alkyl sparse salts (particularly see page 32)

表面活性剂的起泡数据. Data foaming surfactant.

已知的烷基硫酸盐还包括: Known alkyl sulfates also include:

1、 从通过对丙烯或正丁烯低聚物的羰基合成反应制备的醇得到的伯烷基琉酸盐,例如在转让给Mobil Corp的US5245072中所迷的; 1, the primary alkyl alcohol sulfur salts prepared by reaction of the carbonyl group of n-propylene or butene oligomers obtained by synthesis, for example, in US5245072, assigned to Mobil Corp of the fans;

2、 从含油酸的类脂斜如所谓的"异硬脂基"型得到的伯烷基破酸盐;见1990年12月12日公开的转让给Henkel的EP401462A,该文献描述了某些异硬脂基醇和乙氧基化的异硬脂基醇以及其制备相应烷基疏酸盐如异硬脂基硫酸钠的疏酸化; 2, breaking from the primary alkyl salts of oleic acid-containing lipid, such as the swash-called "isostearyl" type obtained; see transfer December 12, 1990 disclosed to Henkel, EP401462A, which describes certain iso stearyl alcohol and ethoxylated isostearyl alcohols and their salts to prepare the corresponding alkyl sparse sparse acidified as isostearyl sulfate;

3、 伯烷基疏酸盐,例如从用酸催化剂低聚丙烯接着羰基合成反应得到的所谓的"十三烷基"型; 3, primary alkyl hydrophobic salts, e.g. polyacrylic acid from the catalyst followed by low carbonyl-called "tridecyl" of the synthetic reaction;

4、 从"Neodol"或"Dobanol"方法(所得)醇得到的伯烷基疏酸盐:该醇是直链内烯烃的羰基合成产物或者是直链a-烯烃的羰基合成产物.该烯烃是通过乙烯低聚从而形成a -烯烃得到的,其直接使用或被异构化成内烯烃和置换易位从而得到不同链长度的内烯烃; 4, an alcohol derived from "Neodol" or "Dobanol" process (resulting) primary alkyl hydrophobic salt: the alcohol is oxoproduct linear internal olefins or linear a- olefins oxo product of the olefin Yes. by oligomerization of ethylene to form a - olefins obtained, which was directly used or isomerized to internal olefins and substituted olefin metathesis to give the different chain lengths;

5、 从对内烯烃使用"Neodol"或"Dobanol"型催化剂得到的伯垸基硫酸盐,该烯烃是从不同于通常用于制备"Neodol"或"Dobanol" 醇的原料得到的,该内烯烃是从石油的石蜡加氢得到的; 5, from internal olefins using the "Neodol" or primary alkyl with sulfate "Dobanol" type catalysts obtained from the olefin is different from commonly used, the internal olefin feedstock preparation "Neodol" or "Dobanol" alcohols obtained It was hydrogenated oil from paraffin;

6、 从内烯烃的常规(例如高压,钴催化)羰基合成反应得到的伯烷基硫酸盐,该内烯烃是从石油的石蜡加氢得到的; 6, synthesis from conventional (e.g., high-pressure, cobalt-catalyzed) carbonylation of internal olefins obtained by reacting a primary alkyl sulfates, the internal olefin from paraffin was hydrogenated oil;

7、 从a烯烃的常规(例如高压,钴催化)羰基合成反应得到的伯烷基硫酸盐; 7, from conventional (e.g., high-pressure, cobalt-catalyzed) carbonylation reaction of a-olefin synthetic primary alkyl sulphates;

8、 从天然直链脂肪醇如可从Procter & Gamble Co.购得的那些醇得到的伯烷基疏酸盐; 8, those obtained from natural linear fatty alcohols such as alcohols, available from Procter & Gamble Co. primary alkyl hydrophobic acid salts;

9、 从齐格勒醇如可从Alb咖arle购得的那些醇得到的伯烷基疏酸 9, an alcohol derived from Ziegler alcohols such as those commercially available from Alb coffee arle primary alkyl hydrophobic acid

盐; salt;

10、 从正醇与Guerbet催化剂(该众所周知的催化剂的功能是将2摩尔的正醇脱氢形成相应的搭,在窿醇缩合中将其缩合,并将a、 P不饱和醛的产物脱水,然后加氢形成2-烷基支链伯醇,所有反应都在一个反应釜中进行)反应得到的伯烷基疏酸盐; 10, the n-alcohol and Guerbet catalyst (the function of the catalyst is well known in the dehydrogenation of 2 moles of n-alcohols to form the corresponding ride, which is condensed in the condensation hole alcohol, and the a, P-unsaturated aldehyde product is dehydrated, is then hydrogenated to form 2-alkyl branched primary alcohol, all reactions are carried out in one pot reaction) obtained by reacting a primary alkyl hydrophobic acid salts;

11、 从异丁烯的二聚从而形成2,4,4,-三甲基-1-戊烯得到的伯烷基硫酸盐,该2,4,4,-三甲基-l-戊烯在羰基合成反应时形成醛,醛醇二聚,脱水和还原得到醇; 11, from the dimerization of isobutylene to form a 2,4,4, - trimethyl-1-pentene obtained primary alkyl sulfates, the 2,4,4, - trimethyl-pentene-carbonyl -l- synthesis reaction to form the aldehyde, aldol dimerization, dehydration and reduction to give the alcohol;

12、 从疏酸加成到a或内烯烃上得到的仲烷基破酸盐; 12, resulting from the addition of an acid to a hydrophobic internal olefin or a salt of secondary alkyl broken;

13、 从通过步樣(a)氧化石蜡形成脂肪羧酸;和(b)将该羧酸还原成相应伯醇的石蜡氧化得到的伯烷基疏酸盐; 13, the step-like by (a) oxidizing the paraffin to form an aliphatic acid; and (b) reducing the carboxylic acid to the corresponding primary alcohols obtained by oxidation of paraffin primary alkyl hydrophobic acid salts;

14、 从石蜡直接氧化成仲醇得到的仲烷基疏酸盐; 14, the direct oxidation of paraffins from the alkyl group to a secondary alcohol, secondary-repellent salt obtained;

15、 从各种增塑剂醇得到的伯或仲烷基疏酸盐,该醇一般是通过烯烃的羰基合成,醛醇缩合,脱水和加氢得到的(合适的羧基合成催化剂的例子是常规的Co,或最近是Rh催化剂);和 15, obtained from a variety of primary or secondary alkyl alcohol plasticizer sparse salt, the alcohol is typically Examples (synthesis catalyst suitable carboxyl groups obtained by the oxo-olefin, aldol condensation, dehydration and hydrogenation are conventional of Co, or more recently Rh catalysts); and

16、 从非直链伯型的醇例如从天然产物源分离的植醇、法呢醇得 16, from the non-linear primary type, for example, alcohols isolated from natural product sources phytol, farnesol to give

到的伯或仲烷基疏酸盐, Primary or secondary alkyl group to sparse salts,

然而,在上述已知的烷基疏酸盐之外的是一大系列其它可能的烷 However, in addition to the above known hydrophobic group is a series of salts of other possible alkyl

基疏酸盐化合物和混合物,其物理性质可以使得它们作为洗衣洗涤剂表面活性剂是有用或无用的.(I) - (XI)仅仅描述了一些可能的变化(盐仅用普通的钠盐表示).<formula>formula see original document page 7</formula> Acid compounds and mixtures hydrophobic group, its physical properties such that they can be used as laundry detergent surfactants are useful or useless (I) -. (XI) describes only some of the possible variations (the sodium salt represented only a modest ). <formula> formula see original document page 7 </ formula>

CH, CH (CH2>3 CH (CH:), CH (CH凼CH (CH:): OSpjNa CH, f CH! CH CH: CH: ipi CH2 C CH: CH, CH (CH2> 3 CH (CH :), CH (CH Taipa CH (CH :): OSpjNa CH, f CH CH CH:! CH: ipi CH2 C CH:

?H, ? ? H,? H3<pi3 ?H3 H3 <pi3? H3

CH(CH2)qCH2 0SOjNa R-CCH2OSOiNa RiicH"CH-R。 R已CR" CH (CH2) qCH2 0SOjNa R-CCH2OSOiNa RiicH "CH-R. R is CR"

X XI XII XIII X XI XII XIII

这些结构也用于说明这一领域中的术语:这样,(I)是"直链" 烷基疏酸盐。 These structures are also used to illustrate terminology in this field: Thus, (I) is a "linear" alkyl sparse salts. 与是"仲"烷基破酸盐的(VII)不同,(I)也是"伯" 烷基硫酸盐.(II)也是"伯"烷基硫酸盐,但它是"支链"的,该支链仅仅在"2-位",如在所谓的"直链Guerbet"烷基疏酸盐中: 根据惯例碳计数从碳原子共价连接到疏酸根部分的CI开始.(III) 可以用来表示支链烷基疏酸盐系列的任一个,当e是1或更大的整数时,它仅具有"非-2-位支链"。 Are different and "secondary" alkyl broken salt (VII), (I) is also a "primary" alkyl sulfate. (II) is also a "primary" alkyl sulfate but it is "branched", which branched-chain only in the "2-position" as in the so-called "linear the Guerbet" alkyl hydrophobic acid salt: start connection according to customary counting carbon from a carbon atom covalently bound to hydrophobic portion of the acid group CI (III) may be used. It represents a branched alkyl group when any one of a series of hydrophobic salts, when e is an integer of 1 or more, it is only "non-branched -2- bit." 根据常识,至少对于直链表面活性剂化合物,烃部分需要具有至少12个碳原子,优选更多,以便得到好的去污力。 According to common knowledge, at least for linear surfactant compounds, the hydrocarbon portion needs to have at least 12 carbon atoms, more preferably, in order to obtain good detergency. 原则上可以调节指数a、 b、 c、 d、 e、 f、 g、 h、 i、 j、 k、 1、迈、n、 o、 p、 q以便适应这一需要。 Modulation index can in principle a, b, c, d, e, f, g, h, i, j, k, 1, Mai, n, o, p, q in order to accommodate this need. 化合物(VIII)是从天然存在的支链醇植醇得到的烷基疏酸盐.化合物(IX)高度支链化的烷基疏酸盐,例如,它可以通过将醇破酸化制备,该醇是从异丁烯二聚并对产物进行羰基合成接着Guerbet或醛醇缩合得到的.化合物(X)当q =14时是异硬脂基烷基疏酸盐;另一个所谓的"异硬脂基烷基硫酸盐" 具有通式(III)结构-这样的化合物可以通过将得自具有18个碳原子即在(III)中d+ e= 14的油酸二聚的单体副产物制备.化合物(XI) 是"新"烷基疏酸盐,(XII)和(XIII)是亚结构,分别描述了"连位"(XII)和"孪位"或"偕"(XIII) 二甲基支链.原則上这样的亚结构可以出现在烷基疏酸盐和其它的表面活性剂中.此外,常规的烷基疏酸盐可以是饱和或不饱和的。 Compound (VIII) is an alkyl hydrophobic salts derived from a naturally occurring branched alcohol, phytol. Compound (IX) is a highly branched alkyl hydrophobic salts, e.g., it can be prepared by acidifying an alcohol break, the alcohol is oxo and the product from isobutylene dimerization followed by Guerbet condensation or aldol obtained compound (X) when q = 14 is sparse salts isostearyl alkyl; another so-called "isostearyl alkyl sulfates "having the formula (III) structure - i.e., such a compound can be in d (III) is obtained by having from 18 carbon atoms, oleic acid = 14 + e preparing dimeric byproduct monomeric compound (XI ) is the "new" sparse alkyl formate, (XII) and (XIII) are substructures are described in "vicinal" (XII) and "geminal" or "kai" (XIII) dimethyl branching. such substructures can in principle be present in the alkyl hydrophobic acid salts and other surfactants. in addition, conventional alkylation repellent salt may be saturated or unsaturated. 例如,油基硫酸钠是不饱和的烷基疏酸盐。 For example, oleyl sulfate are hydrophobic unsaturated alkyl salts. 不饱和的烷基疏酸盐如油基硫酸盐是相对贵和/或与洗涤剂配方尤其是含漂白剂的那些配方是相对不容的。 Unsaturated alkyl groups such as oleyl sulfate salts repellent is relatively expensive and / or detergent formulations, especially those containing bleach formulation is not opposed to.

除了上述结构上的变化外,在疏水物中具有季碳原子的复杂的高度支链化的伯烷基疏酸盐混合物也是可以制造的,例如通过疏睃化用 In addition to changes in the structure described above, was primary alkyl hydrophobic repellent salt complex mixture of highly branched having a quaternary carbon atom also can be produced, for example by use of thinning Suo

酸催化的聚合汽油反应制备的羧基合成醇;此外,在很多支链烷基疏酸盐中可能的立体异构化进一步增多了各种物质的数量;并且工业的烷基疏酸盐可以含有杂质包括相应的醇、无机盐如疏酸钠、烃和其合成的环状副产物. Synthetic alcohols prepared carboxyl acid-catalyzed polymerization of the reaction gas; Furthermore, in many branched alkyl hydrophobic salts of stereoisomers may further increase the number of various materials; and the alkyl-repellent salt may contain impurities industrial including the corresponding alcohol, an inorganic salt such as sodium sparse, hydrocarbons, and cyclic byproducts of their synthesis.

一个已知的材料是异硬脂基疏酸钠,它是沿另外的直链烷基骨架分布的甲基和/或乙基支链混合物,其中在整个分子中的碳原子总数是约18.该异硬脂基"混合物"是从天然原料(即妥尔油、酱油等)以低的收率通过导致以不可控制的方式出现的、并且可能随原料来源而变化的支链化方法制备的.1990年12月12日公开的转让给Henkel 的EP401462描述了某些异硬脂醇和乙氧基化的异硬脂醇和其制备相应烷基疏酸盐如"异硬脂基疏酸钠"(CAS 34481-82-8,有时称之为"异十八烷基疏酸钠")的疏酸化. One known material is sodium isostearyl-repellent, which is further along straight chain alkyl methyl backbone distribution and / or a mixture of ethyl branches, wherein the total number of carbon atoms in the entire molecule are about 18. this isostearyl "mixture" is from a natural feedstock (i.e. tall oil, soy, etc.) to result in low yields by the emergence of an uncontrolled manner, and branching approach may vary with the source of raw materials prepared the transfer of December 12, 1990 the disclosure to EP401462 Henkel describes certain isostearyl alcohols and ethoxylated isostearyl hydrophobic alkyl group to prepare the corresponding salts such as "sodium isostearyl sparse" alcohol and ( CAS 34481-82-8, sometimes referred acidified sparse "sodium isostearyl sparse") in.

再有,尽管RG Laughlin在"《表面活性剂的水相行为》(The Aqueous Phase Behavior of Surf actatants) " ( Academic Press, NY (1994))的第347页描述了这样的观察结果即由于支链从2-烷基位置移向该烷基疏水物的中心, 所以降低了克拉夫特温度(对15 %的溶液),但是上述溶解度观察结果并没有认识到这些化合物的表面活性或其加入到洗涤剂组合物中的用途.事实上,工业实用和公开文献对在中链区域中支链化的需要性都是不肯定的.这包括上迷描述P-支链烷基琉酸盐作为所需支链的专利公开以及Finger等的"《洗涤剂醇一醇结构和分子量对表面活性剂性质的影响》(Detergent alcohols—the effect of alcohol structure and molecular weight on surfactant properties) " , J, Amer. Oil Che迈ists, Society, Vol. 44, p. 525 (1967)或Technical Bulletin, Shell Chemical Co., SC: 364-80-关于在醇疏酸盐中可能i^的结构变化,这些参考文 Further, although RG Laughlin in "" aqueous phase behavior of surfactant "(The Aqueous Phase Behavior of Surf actatants)" (Academic Press, NY (1994)), page 347 describes the observation that that since branched from the 2-alkyl position towards the center of the alkyl hydrophobe, the Krafft temperature is reduced (15 percent solution), the above observations and the solubility did not recognize the surface activity of these compounds added to the wash, or the use of the composition. in fact, the industrial utility and desirability of the publications in the area of ​​branched chain are uncertain of which includes the above-described branched alkyl P- sulfur salts as required Patent Publication branched and Finger et al. "" Effect of a detergent alcohol of alcohol structure and molecular weight of the surfactant properties "(detergent alcohols-the effect of alcohol structure and molecular weight on surfactant properties)", J, Amer. Oil Che step ists, Society, Vol 44, p 525 (1967) or Technical Bulletin,, SC Shell Chemical Co.:.. 364-80- i about possible structural changes in the salt in an alcohol repellent ^ these reference text 认为:"移动CH3具有很小的作用"。 He said: "Mobile CH3 has a small effect." 在表中给出的数据表明:在C13 链长度时相对于未支链化的伯醇硫酸盐,棉去污力降低了29%和起泡性降低了77%.此外,JP721232描速了用未指定支链化的支链伯烷基疏酸盐替代Cll直链伯烷基疏酸盐的负去污力效果. Data given in Table indicated: When C13 chain length with respect to the non-branched primary alcohol sulphates, cotton detergency of 29% and reduced foaming 77% lower addition, JP721232 described with the speed. branched unspecified branched primary alkyl hydrophobic detergency salts alternate negative effect Cll linear primary alkyl hydrophobic salt.

另夕卜,KR Wormuth和S. Zushma在Lang迈uir, Vol. 7, (1991), Another Bu Xi, KR Wormuth and S. Zushma Lang in step uir, Vol. 7, (1991),

pp 2048-2053中描述了对支链烷基疏酸盐,尤其是从通过Exxon制备的高度支链化的"Exial"醇得到的"支链Guerbet"型疏酸盐的技术研究。 pp 2048-2053 describes branched chain alkyl hydrophobic salts, especially Research "branching the Guerbet" type of alcohol repellent salt obtained from highly branched prepared by Exxon "Exial". 相研究确立的亲油顺序即疏水物顺序如下:高度支链化s双尾〉 甲基支链化>直链.认为支链表面活性剂比直链表面活性剂混合油和水的效力低。 Phase studies establish a lipophile i.e. hydrophobic sequence were the following order: a highly branched s two-tail> methyl branched> linear low that branched surfactants mix oil and water than linear surfactants efficacy. 该效力顺序是直链>双尾》甲基直链化2高度直链化。 The order of potency is linear> double tail "of a linear methyl 2 highly linearized. 从这些结果看,在支链烷基疏酸盐中考虑进一步改进的研究方向并不是显而易见. From these results, consider further improvements in branched alkyl research hydrophobic acid salt is not obvious.

因此,超出如何达到一个纯表面活性剂化合物比另一个清洗性优异的简单技术理论范围,洗衣洗涤剂表面活性剂的研制者和配方师必须考虑各种有限(有时是不一致的)信息的可能性,然后争取提供一批指标的一种或多种的总改进,这些指标包括:存在表面活性剂复杂混合物中的性能,低洗涤温度的趋势,配方的变化,包括助洗剂、酶和漂白剂,消费者习惯和实践的各种变化,和可生物降解性的需要. 在以上述这些为条件的情况下,研制用于洗衣洗涤剂和清洗产品的改进的表面活性剂显然是一个复杂的任务.本发明涉及改进的烷基聚氧化烯表面活性剂。 Thus, beyond how to achieve superior cleaning properties than the other technology a simple theoretical range of pure surfactant compound, laundry detergent surfactants and developer of the formulator must consider the possibility of information limited (sometimes inconsistent) and for one or more of the total number of indicators to provide an improved, these indicators include: a performance, low tendency washing temperature, changes to the formulation of complex mixtures of surfactants, including builders, enzymes and bleaches task, various changes in consumer habits and practices, and the need for biological degradability. in the case of these conditions, the development of detergents for improved cleaning and laundry products is clearly a surfactant complex the present invention relates to improved alkyl polyoxyalkylene surfactants.

如从下文公开内容中所看到的,现在已经令人意想不到地确定了:某些含有中链支化的烷基聚氧化烯组合物优选用于清洗产品,尤其是在凉或冷水洗涤条件下(例如20-5t:)使用的洗衣组合物.优选的是这些中链支化的伯烷基聚氧化烯表面活性剂的两种或多种組合,该表面活性剂提供了较高表面活性并具有较好低温水溶解度的表面活性剂混合物.制备的这些混合物包括适用于本发明表面活性剂中的中链支链,或本文中公开的该表面活性剂混合物可以通过混合所需 As from the disclosure below we see now surprisingly identified: some containing medium chain branched alkyl polyoxyalkylene composition is preferably used cleaning products, especially under cool or cold water washing conditions (e.g. 20-5t :) laundry composition used. preferred combinations of two or more of these mid-chain branched primary alkyl polyoxyalkylene surfactant, the surfactant provides a high surface activity and having a surfactant mixture preferably low temperature water solubility. these mixtures include those suitable for preparation of surfactants of the present invention, the branched chain, or the surfactant mixtures disclosed herein can be prepared by mixing the desired

量的各个中链支化的表面活性剂来配制。 The respective amounts of medium-chain branched surfactant is formulated. 这样的优异的混合物并不限于与其它中链支化的表面活性剂的组合,而是(优选地)它们可以与 Such superior mixtures are not limited to combinations with other mid-chain branched surfactants but (preferably) they can be

一种或多种其它传统的洗涤剂表面活性剂(例如伯烷基硫酸盐;直链 One or more other traditional detergent surfactants (e.g., primary alkyl sulfates; linear

烷基笨磺酸盐;直链烷基乙氧基化的疏酸盐;非离子表面活性剂等) 适当的组合以便提供改进的表面活性剂体系. Stupid alkyl sulfonates; linear alkyl ethoxylated hydrophobic acid salt; nonionic surface active agent) suitable combination to provide improved surfactant systems.

这些中链支化的表面活性剂可以以相对高的纯度得到使得其工业成本对配方师有效。 These mid-chain branched surfactants can be relatively high purity such that it is cost-effective for industrial formulators. 可以从使用化石燃料源的工艺得到合适的产品混合物。 Suitable product mixture obtained from a process fossil fuel source. (本文中使用术语"得自化石燃料"或"化石燃料得到的"把煤、天然气、石油和其它石油化学品衍生的"合成"表面活性剂与得 (As used herein, the term "derived from fossil fuels" or "fossil-fuel derived" coal, natural gas, oil and other petrochemical derived, "synthetic" surfactants obtained with

自有生命的天然资源如家畜或植物如椰子棕榈的那些表面活性剂区别开来。 Own natural resources such as livestock or plant life such as surfactants distinguish the coconut palm open. )

设计一个这样的方法以便提供基本上(85%,或更多)是a-烯烃 One such method designed to provide a substantially (85% or more) is a- olefin

的支链反应产物,然后以羰基合成反应顺序将其转变成疏水物.这样的支链a-烯烃含有约11-18个总碳原子(平均值)并且包括平均长度在10-18范围的直链.该支链主要是单甲基,但也可以出现一些二 Branched reaction product, then the oxo reaction sequence which was converted into hydrophobes. Such branched chain a- olefin containing from about 11 to 18 total carbon atoms (average value) and comprising an average length in the 10-18 range linear chain. the branched primary mono-methyl, but some may be two

甲基和一些乙基支链.有利的是,这样的方法导致很少(1%或更低) 孪位支链即很少(如果有的话)的"季"碳取代物.此外,存在很少 Some methyl and ethyl branches. Advantageously, such process results in little (1%, or less) geminal branching chain i.e. little (if any) of the "quaternary" carbon substitution. Furthermore, there is seldom

(低于约20% )的连位支链.当然,在后续的羰基合成工艺中所用总原料的一些(约20% )可以仍然保持未支链化。 (Less than about 20%) vicinal branching. Of course, in the subsequent Oxo process as few (about 20%) of the total feed may remain with the non-branched. 一般和优选地从清洗性能和可生物降解性的观点看,该方法提供具有0.4-2.5范围支链 Generally and preferably from viewpoint of cleaning performance and biodegradability can be seen, the method providing a range of 0.4-2.5 branched

(最长链基)平均数的a -烯烃;在该支链材料中,基本上没有连接到碳l、碳2或支链材料的最长链的端(co )碳上的支链部分。 (Longest chain-yl) averages a - olefins; the branched material, substantially no carbon is connected to L, the longest carbon chain of 2 or ends (CO.'s) branched moieties branched on the carbon material.

形成和纯化支链a -烯炫后,原料经受羰基合成羰基化工艺,在该羰基合成步骤中,使用不使双键从其起始位置移动的催化剂(例如常规的羰基钴).这避免形成亚乙烯基中间体(其最终得到不好的表面活性剂)并可以在1号和2号碳原子上进行羰基化。 Formation and purification of the branched a - alkenyl Hyun, the raw material is subjected to the oxo hydroformylation process in the hydroformylation synthesis step, without double bond a catalyst (e.g., conventional cobalt carbonyl) start position from which it avoids formation. vinylidene intermediates (which ultimately obtained is not good surfactants), and may be in the carbonylation 1 and 2 carbon atoms.

因此,本发明的目的是提供具有大于14.5个碳原子的在清洗组合物中有用的中链支化的伯烷基聚氧化烯非离子表面活性剂.本发明还有一个目的是提供了中链支化的伯烷基聚氧化烯表面活性剂的混合物,该中链支化的伯烷基聚氧化烯表面活性剂可与其它表面活性剂配制以便给清洗组合物提供一种或多种优点,包括在低使用温度下的更大的表面活性,提高的耐水硬度性,在表面活性剂体系中的更大的效力,改进的从织物上去除油脂或人体污垢性,改进的与洗涤剂酶的相容性等. Accordingly, an object of the present invention is to provide a primary alkyl polyoxyalkylene nonionic surfactants having useful in cleaning compositions mid-chain branched greater than 14.5 carbon atoms. A further object of the present invention to provide a medium-chain a mixture of branched primary alkyl polyoxyalkylene surfactants, the mid-chain branched primary alkyl polyoxyalkylene surfactant may be formulated with other surfactants to provide one or more advantages to the cleaning composition, including greater surface activity at low use temperatures, increased water hardness resistance, greater efficacy in surfactant systems, and improved removal of grease or body soils from fabrics, improved detergent enzymes compatibility and so on.

背景技术 Background technique

1969年11月25日deWitt等的US3480556、 1991年7月31曰公开的Lever的EP439316和1995年11月29日公开的Lever的EP684300 描述了P -支链烷基疏酸盐.EP439316描述了某些含特定的工业C14/C15支链伯烷基疏酸盐即LIAL 145疏酸盐的洗衣洗涤剂.据信其具有61%的2-位支链,该支链的30%包括具有4个或更多个碳原子烃链的支链.US3480556描述了10-90份直链伯烷基硫酸盐和90- 10份下式的P支链(2 -位支链)伯醇疏酸盐:WCRSHC&OSOsX,其中碳原子总数在12-20的范闺,W是含9-17个碳原子的直链烷基,R2 是含l-9个碳原子的直链烷基(举例说明的是67%2-甲基和33% 2 -乙基支链)。 US3480556 1969 dated on 25 Day deWitt. 11 or the like, EP439316 and November 29, 1995, the disclosure of EP684300 1991 Lever July 31, said disclosure describes Lever P - sparsely branched alkyl describes an acid salt .EP439316 some specific industrial containing C14 / C15 branched primary alkyl hydrophobic acid salts i.e. LIAL 145 repellent laundry detergent. it is believed to have the 2-position of 61% branched and 30% of the branched chain having 4 comprising more carbon atoms or a branched hydrocarbon chain .US3480556 described parts 10-90 linear primary alkyl sulphate and 90-10 parts of a branched formula P (2 - position branched) primary alcohol repellent salt: WCRSHC & OSOsX, wherein the total number of carbon atoms in the range 12-20 Gui, W is a linear alkyl group having 9-17 carbon atoms, R2 of a linear alkyl group containing l-9 carbon atoms (exemplified is 67% and 33% 2-methyl-2 - ethyl branches).

如上所述,RG Laughlin在"《表面活性剂的水相行为》(The Aqueous Phase Behavior of Surfactatants) " (Academic Press, NY (1994))的第347页描述了这样的观察结果即由于支链从2-烷基位置移向该烷基疏水物的中心, 所以降低了克拉夫特温度.还参见Finger等的"《洗涤剂醇-醇结构和分子量对表面活性剂性质的影响》 (Detergent alcohols-the effect of alcohol structure and molecular weight on surfactant properties) " , J, Amer. Oil Ch柳ists, Society, Vol. 44, p. 525 (1967)和Technical Bulletin, Shell Chemical Co" SC: 364-80。 As described above, RG Laughlin in "" aqueous surfactant phase behavior "(The Aqueous Phase Behavior of Surfactatants)" (Academic Press, NY (1994)), page 347 describes the observation that since i.e. branched from 2-alkyl position towards the center of the alkyl hydrophobe, the Krafft temperature is reduced see also Finger like. "" detergent alcohols - ol of structure and molecular weight of the surfactant properties "(detergent alcohols- the effect of alcohol structure and molecular weight on surfactant properties) SC ", J, Amer Oil Ch Liu ists, Society, Vol 44, p 525 (1967) and Technical Bulletin, Shell Chemical Co...": 364-80.

1989年11月23日公开的Unilever的EP342917A描述了含表面活性剂体系的洗衣洗涤剂,其中主要的阴离子表面活性剂是具有认为是"宽范闺"的烷基链长度(试验好象包括混合椰子和牛脂链长度的表面活性剂)的烷基疏酸盐。 EP342917A 1989 to Unilever. 11 years Publication Date dated 23 is described in laundry detergent containing a surfactant system in which the major anionic surfactant is considered as having a "wide range Gui," the alkyl chain length (if the test mixture comprising coconut and tallow chain length surfactants) alkyl sparse salts.

US4102823和GB1399966描述了含常规烷基硫酸盐的其它洗衣组合物. US4102823 and GB1399966 describe other laundry compositions containing conventional alkyl sulfates.

1975年7月2日公开的Matheson等的GB1299966公开了一种洗涤剂組合物,其中表面活性剂体系由牛脂烷基疏酸钠和非离子表面活性剂的混合物组成. Matheson like GB1299966 1975 dated 2 years. 7 Publication Date discloses a detergent composition, wherein the surfactant system consists of sodium tallow alkyl hydrophobic and nonionic surfactant mixtures.

甲基取代的硫酸盐包括已知的"异硬脂基"疏酸盐;它们是具有 Methyl substituted sulfates include the known "isostearyl" sparse acid; they have

总共18个碳原子的异构琉酸盐的一般混合物.例如1990年12月12 曰公开的转让给Henkel的EP401462A描述了某些异硬脂基醇和乙氧基化的异硬脂基醇以及其制备相应烷基疏酸盐如异硬脂基疏酸钠的硫酸化。 Usually a mixture of isomers A total of 18 carbon atoms of sulfur salt. 12 December 1990, for example, assigned to Henkel said disclosed in EP401462A describes certain isostearyl alcohols and ethoxylated isostearyl alcohols and their hydrophobic alkyl group to prepare the corresponding salts such as sodium isostearyl sulfate repellent. 还参见KR Wormuth和S. Zushma在Langnmir, Vol. 7, (1991), pp 2048-2053 (对支链烷基硫酸盐,尤其是"支链Guerbet"型的数量的技术研究);R. Varadaraj等的J. Phys. Chem., Vol. 95, (1991), pp 1671-1676 (该文献描速了各种"直链Guerbet"和"支链Guerbet" 类表面活性剂包括烷基硫酸盐的表面张力);Varadaraj等的J. Colloid and Interface Sci., Vol. 140, (1990), pp 31—34 (该 See also KR Wormuth and S. Zushma in Langnmir, Vol 7, (1991), pp 2048-2053 (branched chain alkyl sulfates, especially the amount of Research "branching the Guerbet" type);.. R Varadaraj etc. J. Phys. Chem., Vol. 95, (1991), pp 1671-1676 (document described the various speed "linear the Guerbet" and "branched the Guerbet" surfactant include alkyl sulfate surface tension); Varadaraj like J. Colloid and Interface Sci, Vol 140, (1990), pp 31-34 (the.

文献涉及包括分别含有3和4甲基支链的C12和C13烷基碇酸盐的表面活性剂的起泡数据);和Varadaraj等,Langmuir, Vol. 6 (1990), 卯1376-1378 (该文献描迷了包括支链烷基疏酸盐的表面活性剂的含水胶束溶液的徵极性). Document relates to a foaming data respectively containing 3 and 4 C12 methyl branched and surfactant salts anchorage C13 alkyl);. Varadaraj and the like, Langmuir, Vol 6 (1990), 1376-1378 d (the Document intrinsic described lost polar surfactant comprises a hydrophobic branched alkyl salt in an aqueous micellar solution).

可从Henkel得到"直链Guerbet"醇,例如,EUTANOL G-16. Available "linear the Guerbet" alcohols from Henkel, e.g., EUTANOL G-16.

从通过丙烯或正丁烯的羰基合成反应制备的醇得到的伯烷基疏酸盐描述于Mobil Oil Corp.的US5245072中.还参见:转让给Mobil Oil Corp.的US5284989(在高温下用受限制的中孔含硅酸性沸石低聚低级烯烃制备基本上直链烃的方法),和Mobil Oil Corp.的US5026933 和US4870038(在高温下用含硅酸性ZSM-23沸石低聚低级烯烃制备基本上直链烃的方法)。 Obtained from the alcohol produced by the oxo reaction of propylene or n-butene primary alkyl hydrophobic salts described in US5245072 Mobil Oil Corp. See also: the transfer US5284989 Mobil Oil Corp. (the limited use at high temperatures the pore size siliceous acidic zeolite oligomerization of lower olefins prepared substantially linear hydrocarbons method), and the Mobil Oil Corp. in US5026933 and US4870038 (prepared at elevated temperature with a silicon-containing acidic ZSM-23 zeolite oligomerization of lower olefins substantially straight method chain hydrocarbon).

还参见:Surfactant Science Series, Marcel Dekker, NY (各巻包括标题为"阴离子表面活性剂"和"表面活性剂生物降解" 的那些巻,后者由RD S賣isher编,作为第18巻于1987年出版(第2版);具体见第20- 24页"疏水基及其来源";第28- 29页"醇"; 第34- 35页"伯烷基疏酸盐"和第35- 36页"仲烷基疏酸盐"); 和关于一般由其制备烷基疏酸盐的"高级"或"洗涤剂"醇的文献, 包括:RFModler等的《CEH市场研究报告"洗涤剂醇"》(CEH Marketing Research Report "Detergent Alcohols" ) , Chemical Economics Handbook, 1993, 609. 5000-609. 5002; Kirk 0thmer的《化学工艺百科全书》(Encyclopedia of Chemical Technology), 第四版,Wiley, NY, 1991,第1巻第865 - 913页的"Alcohols, Higher Aliphatic"和其中的参考文献- See also: Surfactant Science Series, Marcel Dekker, NY (each Volume including entitled "Anionic Surfactants" and "Surfactant Biodegradation" those Volume latter sold isher edited by RD S, as the first 18 Volume 1987 Publishing (2nd Edition); in particular, see "hydrophobic groups and their sources" on pages 20-24; "alcohol" p. 28-29; "primary alkyl hydrophobic salts" on page 34-35 and pages 35-36 "sparse secondary alkyl salt"); and the literature on the general sparse salt prepared therefrom alkyl "advanced" or "detergent" alcohols, comprising: RFModler like "CEH market Research report" detergent alcohols "" (CEH Marketing Research Report "Detergent Alcohols"), chemical Economics Handbook, 1993, 609. 5000-609 5002;. "Encyclopedia of chemical technology" Kirk 0thmer of (Encyclopedia of chemical technology), Fourth Edition, Wiley, NY, 1991 , Volume 1 of 865 - "Alcohols, Higher Aliphatic" 913 pages and references therein -

发明概述 SUMMARY OF THE INVENTION

本发明涉及表面活性剂组合物,其含有约0.001- 100%的一种或多种(优选两种或多种的混合物)具有下式的中链支化的伯烷基聚氧 The present invention relates to a surfactant composition comprising from about 0.001 to 100% of one or more (preferably a mixture of two or more) having the formula mid-chain branched primary alkyl polyoxyalkylene

化烯: Ethylenically:

<formula>formula see original document page 13</formula>其中在该式的支链伯烷基部分中的总碳原子数(包括R、 W和W支链, <Formula> 13 </ formula> wherein the total number of carbon atoms in formula see original document page in the branched primary alkyl moiety of this formula (including the R, W and W branched,

但不包括EO/PO烷氧基部分中的碳原子)是14-20,并且进一步地, 其中对于该表面活性剂混合物,在具有上式的支链伯烷基部分中的平均总碳原子数在大于14.5-约17.5的范围内(优选约15- 17) ; R、 W和W各自独立地选自氢和d-Ca烷基(优选甲基),条件是R、 R1 和W不都是氢,和当z是l时,至少R或W不是氢;w是0-13的整数;x是0-13的整数;y是0-13的整数;z是至少为l的整数;w + x+y+z|8-14;和EO/PO是烷氧基部分,包括例如乙氧基(约O -30),丙氧基(约0-30), 丁氧基(约0-30)等,优选选自乙氧基、丙氧基和混合的乙氧基/丙氧基基团,最优选乙氧基,其中m是至少约l,优选在约3-30的范围内,更优选约5-20,和最优选约5-15.应该认识到:(EO/PO),部分可以是具有相应于m的平均烷氧基化度的分布,或者可以是具有相应于迈的精确单元数烷氧基化(例如乙氧基化和/或丙氧基化)的单个 But does not include carbon atoms EO / PO alkoxy portion) is 14-20, and further, wherein for this surfactant mixture, having the formula in the branched primary alkyl moiety of an average total carbon atoms in the range of greater than 14.5 to about 17.5 (preferably from about 15- 17); R, W and W are each independently selected from hydrogen and d-Ca-alkyl (preferably methyl), provided R, R1 and W are not both hydrogen, and when z is l when at least R or W is not hydrogen; W is an integer from 0 to 13; x is an integer from 0 to 13; Y is an integer from 0 to 13; z is an integer of at least l,; w + x + y + z | 8-14; and EO / PO are alkoxy moieties including for example ethoxy (about O -30), propoxy (about 0-30), butoxy (about 0-30 ) and the like, preferably selected from ethoxy, propoxy, and mixed ethoxy / propoxy groups, most preferably ethoxy, wherein m is at least about l, preferably in the range of about 3-30, and more preferably about 5-20, and most preferably from about 5-15 will be appreciated that: (EO / PO), the distribution may be a part corresponding to m, the average degree of alkoxylation, or may be a step corresponding to the precise the number of alkoxylated units (e.g. ethoxylated and / or propoxylated) single 体的链. Chain body.

本发明优选还包括洗涤剂组合物,例如一种对洗涤织物,洗涤餐具和清洗硬表面有用的组合物,其含有: The present invention preferably further comprise a detergent composition, such as one for washing fabrics, washing dishes and cleaning hard surfaces useful compositions, comprising:

(a) 约0. 001 - 99%的一种或多种具有本文中化学式的中链支化的伯烷基聚氧化烯表面活性剂;和 (A) from about 0.001 - 99% of one or more primary alkyl polyoxyalkylene surfactants having various formulas herein are branched chain; and

(b) 约1- 99.999重量%的一种或多种洗涤剂添加剂成分. 所迷的洗涤剂组合物优选含有中链支化的伯烷基聚氧化烯表面活 Primary alkyl polyoxyalkylene surfactant (b) from about 1 to 99.999% by weight of one or more detergent additive components. The fans detergent composition preferably comprises medium chain branched

性剂的混合物,所述的混合物含有至少约2重量%的两种或多种具有下式的中链支化的伯烷基聚氧化烯或其混合物: Agent mixture, said mixture contains at least about 2% by weight of two or more having the formula mid-chain branched primary alkyl polyoxyalkylene, or mixtures thereof:

(〖) CH"CH2)aCH(C叫CH2(EO/PO)mOH (〖) CH "CH2) aCH (C called CH2 (EO / PO) mOH

CH3 (CH^CH (CH2), CHCH2 (EO/PO)raOH CH3 (CH ^ CH (CH2), CHCH2 (EO / PO) raOH

其中a、 b、 d和e是整数,a+b是10-16, d+e是8-14,并且进一步地,其中 Wherein a, b, d, and e are integers, a + b is 10-16, d + e is 8-14, and further wherein

当a+b-10时,a是2-9的整数并且b是l一8的整数; 当a+b-ll时,a是2-10的整数并且b是1-9的整数; When a + b-10, a is an integer of 2-9 and b is an integer of l-8; when a + b-ll, a is an integer from 2 to 10 and b is an integer of 1-9;

当a+b-12时,a是2 - 11的整数并且b是1 - 10的整数; 当a+b-13时,a是2-12的整数并且b是1-ll的整数; 当a+b-14时,a是2-13的整数并且b是l-12的整数; 当a+b-15时,a是2-14的整数并且b是1-13的整数; 当a+b-16时,a是2-15的整数并且b是1-14的整数; 当d+e-8时,d是2-7的整数并且e是1 —6的整数; 当d+e-9时,d是2-8的整数并且e是l-7的整数; 当d+e-10时,d是2-9的整数并且e是l-8的整数; 当d+e-ll时,d是2-10的整数并且e是1-9的整数; 当d+e-12时,d是2-11的整数并且e是1-IO的整数; 当d+e-13时,d是2"" 12的整数并且e是1-11的整数; 当d+e-14时,d是2-13的整数并且e是1-12的整数; While when a + b-12, a is 2 - 11 and b is an integer of 1 - is an integer of 10; when a + b-13 time, a is an integer of 2-12 and b is an integer of 1-ll; and when a when + b-14, a is an integer of 2-13 and b is an integer of l-12; when a + b 15-time, a is an integer of 2-14 and b is an integer of 1 to 13; when a + b -16, a is an integer of 2-15 and b is an integer of 1 to 14; when d + e-8 time, d is an integer from 2 to 7 and e is an integer of 1-6; when d + e-9 when, d is an integer from 2 to 8 and e is an integer of l-7; when d + 10 e-time, d is an integer of 2-9 and e is an integer of l-8; when d + e-ll, the d is an integer from 2 to 10 and e is an integer of 1-9; when d + when e-12, d is an integer from 2 to 11 and e is an integer of 1-IO; while when d + e-13, d is 2 "" is an integer of 12 and e is an integer of 1-11; when when d + e-14, d is an integer from 2-13 and e is an integer from 1 to 12;

其中对于该表面活性剂混合物,在具有上式的支链伯烷基部分中的平 Wherein for this surfactant mixture, having the formula a branched primary alkyl moiety of the flat

均总碳原子数在大于14.5-约17.5的范围内;和 Average total number of carbon atoms in the range of greater than 14.5 to about 17.5; and

其中E0/P0是烷氧基部分,优选选自乙氧基、丙氧基和混合的乙 Wherein E0 / P0 is an alkoxy moiety, preferably selected from ethoxy, propoxy, and mixed acetate

氧基/丙氧基基团,其中迈是至少约l,优选在约3-30的范围内,更 Group / propoxy groups, wherein step is at least about l, preferably in the range of about 3-30, and more

优选约5-20,和最优选约5-15. Preferably about 5-20, and most preferably from about 5-15.

本发明还有一个目的是提供了用于本文中所述表面活性剂混合物 Another object of the present invention to provide a surfactant mixture described herein for

中的新的中链支化的伯烷氧基化的表面活性剂.因此,本发明优选还 The new mid-chain branched primary alkoxylated surfactants. Accordingly, the present invention also preferably

涉及下式的新的聚氧化烯化合物: It relates to novel polyoxyalkylene compounds of formula:

OH, OH,

CH, (CHa)aiH (CHa^CH2 (EO/PO)mOH CH, (CHa) aiH (CHa ^ CH2 (EO / PO) mOH

其中,a是2-ll的整数,b是l-IO的整数,并且a+b是12或13; 和E0/P0是烷氧基部分,优选选自乙氧基、丙氧基和混合的乙氧基/ 丙氧基基团,其中m是至少约l,优选在约3-30的范围内,更优选约5 - 20,和最优选约5- 15, Wherein, a is an integer of 2-ll, b is an integer of l-IO, and a + b is 12 or 13; and E0 / P0 is an alkoxy moiety, preferably selected from ethoxy, propoxy, and mixed ethoxy / propoxy groups, wherein m is at least about l, preferably in the range of about 3-30, more preferably from about 5--20, and most preferably from about 5-15,

本文中还优选的是下式的聚氧化烯化合物: Also preferred herein are alkenyl polyoxyalkylene compound of the formula:

CHj CHj CHj (CH4 (EO/PO)mOH CHj CHj CHj (CH4 (EO / PO) mOH

其中, among them,

d和e是整数并且d+e是10或11,并且进一步地,其中当d+e-10时,d是2—9的整数并且e是l-8的整数; 当d+e-ll时,d是2-10的整数并且e是1-9的整数; 和E0/P0是烷氧基部分,优选选自乙氧基、丙氧基和混合的乙氧 d and e are integers and d + e is 10 or 11, and further, wherein when d + 10 e-time, d is an integer of 2-9 and e is an integer of l-8; when d + e-ll when , d is an integer from 2 to 10 and e is an integer of 1-9; and E0 / P0 is an alkoxy moiety, preferably selected from ethoxy, propoxy, and mixed ethoxy

基/丙氧基基团,其中m是至少约l,优选在约3-30的范围内,更优 Yl / propoxy groups, wherein m is at least about l, preferably in the range of about 3-30, more preferably

选约5-20,和最优选约5- 15. Preferably about 5-20, and most preferably from about 5-15.

除非另有说明,本文中的所有百分数、比率和比例均按重量计. Unless otherwise indicated, all percentages, ratios and proportions herein are by weight.

除非另有说明,所有的温度均用摄氏度(x:)表示。 Unless otherwise indicated, all temperatures are in degrees Celsius (x :) representation. 所有引用文献在 All citations

相关部分均在本文中引作参考。 In relevant part, incorporated herein by reference.

发明详述 DETAILED DESCRIPTION

本发明涉及中链支化的伯烷基聚氧化烯表面活性剂.该支链表面活性剂組合物含有一种或多种具有下式的中链支化的伯烷基聚氧化烯表面活,艮刑: Primary alkyl polyoxyalkylene surfactants of the present invention relates to mid-chain branched. The branched surfactant compositions comprise one or more compounds having the formula mid-chain branched primary alkyl polyoxyalkylene surfactants, Burgundy sentence:

CH3CH2(CH2)wCH(CH2)x^H(CH2)yCH{CH2)2{EO/PO)inOH CH3CH2 (CH2) wCH (CH2) x ^ H (CH2) yCH {CH2) 2 {EO / PO) inOH

本发明的表面活性剂混合物包括具有直链伯聚氧化烯链骨架(即包括烷氧基化碳原子的最长直链碳链)的分子.这些烷基链骨架含有12- 19个碳原子;并且该分子包括具有至少总数为14但不多于20个碳原子的支链伯烷基部分.另外,该表面活性剂混合物的支链伯烷基部分的平均碳原子总数在大于14.5到约17.5的范围.因此,本发明的混合物包括至少一种具有不少于12个碳原子或多于19个碳原子的最长直链碳链的聚氧化烯化合物和包括支链的总碳原子数必须至少是14,并且支链伯烷基链的平均碳原子总数在大于14.5到约17.5范围内. Surfactant mixture of the present invention include those having a linear primary polyoxyalkylene chain backbone chain alkenyl (i.e., the longest linear carbon chain comprising alkoxy carbon atoms) in the molecular skeleton of the alkyl chains containing 12-19 carbon atoms.; and the molecule having at least a total of 14, but not more than 20 carbon atoms in the branched primary alkyl moiety. in addition, the average total number of carbon atoms in the branched primary alkyl moiety of the surfactant mixture is greater than about 14.5 to 17.5 range. Accordingly, the present invention comprises a mixture of at least one of less than 12 carbon atoms or more than 19 carbon atoms in the longest linear carbon chain having a polyoxyalkylene compound comprises a total number of carbon atoms and branched chain must It is at least 14, and the average total number of carbon atoms in the branched primary alkyl chains is within the range of greater than 14.5 to about 17.5.

例如,在骨架中具有15个碳原子的C16总碳(在烷基链中)伯聚氧化烯表面活性剂必须具有甲基支链单元(R、 R'或f是甲基),由此分子中的碳原子总数是16. For example, a C16 total carbon 15 carbon atoms in a backbone (in the alkyl chain) primary polyoxyalkylene surfactant must have a methyl branching unit (R, R 'is methyl or f), whereby the molecule total number of carbon atoms is 16.

R、 R1和R2各自独立地选自氢和d - C3烷基(优选氢或d - C2烷基, 更优选氳或甲基,和最优选甲基),条件是R、 Ri和f不都是氢.此外,当z是l时,至少R或W不是氢。 R, R1 and R2 are each independently selected from hydrogen and d - C3 alkyl (preferably hydrogen or d - C2 alkyl, more preferably methyl or heavy atmosphere, and most preferably methyl), provided R, Ri, and f are not both It is hydrogen. Further, when z is l when at least R or W is not hydrogen.

尽管对于本发明表面活性剂组合物的目的来说,上式不包括其中R、 R'和RS单元都是氢的分子(即直链非支链的伯聚氧化烯),但是应该认识到:本发明的组合物还可以包括一定量的直链非支链的伯聚氧化烯.另外,该直链非支链伯聚氧化烯表面活性剂可以作为用于制备具有本发明必不可少的中链支化的伯聚氧化烯的表面活性剂混合物的方法的结果而存在,或者为了配制洗涤剂组合物的目的,可以将一定量的直链非支链伯聚氧化烯混入到最终的产品配方中。 Although for purposes of the surfactant composition of the present invention, the above formula does not include molecules wherein R, R 'and RS are hydrogen unit (i.e., a linear primary polyoxyalkylene unbranched), it will be appreciated that: the compositions of the invention may further comprise an amount of linear non-branched primary polyoxyalkylene. further, this linear non-branched primary polyoxyalkylene surfactant may be used as necessary for the preparation of the present invention having the results of the method of the surfactant mixtures chain branched primary polyoxyalkylene is present, or for purposes of formulating detergent compositions some amount of linear non-branched primary polyoxyalkylene may be incorporated into the final product formulation in.

此外类似地,应该认识到:非烷氧基化的中链支链醇可以含有一定量的本发明的含聚氧化烯的组合物,这样的材料可以作为用于制备聚氧化烯表面活性剂的醇的不完全烷氧基化的结果而存在,或者可以将这些醇与本发明的中链支化的聚氧化烯表面活性剂一起分別加入到本发明的洗涤剂组合物中。 Further Similarly, it should be appreciated that: the non-alkoxylated mid-chain branched-chain alcohols of the present invention may contain an amount containing polyoxyalkylene compositions, such materials can be prepared as polyoxyalkylene surfactants for incomplete alkoxylated alkanols result of the presence of, or medium-chain alcohols of the present invention which may be branched polyoxyalkylene surfactant were added together to the detergent compositions of the present invention.

进一步考虑上式,v是0-13的整数;x是0-13的整数;y是O -13的整数;z是至少为1的整数;并且v+ x + y + z是8 - 14的整数. Further considering the above formula, v is an integer from 0 to 13; x is an integer from 0 to 13; Y is an integer from O -13; and Z is an integer of at least 1; and v + x + y + z is an 8 - 14 integer .

EO/PO是烷氧基部分,优选选自乙氧基、丙氧基和混合的乙氧基/ 丙氧基基团,其中迈是至少约l,优选在约3-30的范围内,更优选约5-20,和最优选约5-15. (EO/PO),部分可以是具有相应于边的平均烷氧基化(例如乙氧基化和/或丙氧基化)度的分布,或者可以是具 EO / PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy / propoxy groups, wherein step is at least about l, preferably in the range of about 3-30, and more preferably about 5-20, and most preferably about 5-15. (EO / PO), may have a portion corresponding to the average edge alkoxylated (e.g. ethoxylated and / or propoxylated) degree distribution or may be having

有相应于m的精确单元数烷氧基化(例如乙氧基化和/或丙氧基化)的单个具体的链。 Precise number of units of alkoxylation (e.g., ethoxylation and / or propoxylation) corresponding to m of a single specific chain.

某些支化点(即在上式中沿R、 W和/或f部分的链的位置)比沿表面活性剂骨架的其它支化点是优选的.对于本发明的单甲基取代的直链烷基聚氧化烯,下式说明了中链支化范围(即在该处出现支链点),优选的中链支化范闺,和更优选的中链支化范围: Certain points of branching (i.e., along the above formulas R, W and / or the position of the chain part f) other than the branch point along the backbone of the surfactant is preferred for the present invention, monomethyl substituted linear polyoxyalkylene alkyl chain, of the formula described in chain branching range (i.e., where the branch points occur), preferred mid-chain branched Fan Gui, and more preferred mid-chain branched range:

CH3CH2CH2CH2CH2CH2(CH2)r7CH2ai2CH2CH2CH2CH2(EO/PO)xnOH CH3CH2CH2CH2CH2CH2 (CH2) r7CH2ai2CH2CH2CH2CH2 (EO / PO) xnOH

更优选的范围优选的范围中链支化范围 A more preferred range preferred range mid-chain branched range

应该指出的是:对于单甲基取代的表面活性剂,这些范围排除了 It should be noted that: for the mono-methyl substituted surfactants these ranges exclude

该链的2个端部的碳原子和2个直接连接到E0/P0部分的碳原子,对于包括两个或多个不是氢的R、 W或W的表面活性剂混合物,在2-碳原子处的烷基支链是在本发明表面活性剂范围内的.然而,在2-碳原子上具有比乙基更长的链(例如C3烷基取代基)的表面活性剂是不优选的。 2 carbon atoms of the chain end portion and two carbon atoms directly connected to the E0 / P0 portion, comprising two or more for other than hydrogen R, W, or W, surfactant mixture, the 2-carbon atom in alkyl branches are at the surfactant in the scope of the present invention, however, having chains longer than ethyl group at the 2-carbon atom (e.g. alkyl substituted C3) surfactant is not preferable.

对于本发明的二甲基取代的直链烷基聚氧化雄,下式说明了中链支化范围,优选的中链支化范闺,和更优选的中链支化范闺: For the present invention, the dimethyl substituted straight chain alkyl polyoxyalkylene male, the formula described in chain branching range, preferred mid-chain branched Fan Gui, and more preferred mid-chain branched Fan Gui:

CH3CH2CH2CH2CH2CH2(CH2)wCH2CH2CH2CH2CH2CH2(EO/PO)mOH CH3CH2CH2CH2CH2CH2 (CH2) wCH2CH2CH2CH2CH2CH2 (EO / PO) mOH

T更优选的范围个i—优选的范围—i 中链支化范围 A more preferred range T i- preferred range mid-chain branched range -i

当二烷基取代的伯烷基聚氧化烯与单取代的中链支化的伯烷基聚 When dialkyl substituted primary alkyl polyoxyalkylene with monosubstituted mid-chain branched primary alkyl poly

氧化烯组合时,在2-碳原子位置上具有1个甲基取代基和在如上指出的优选范围中有另一个甲基取代基的二烷基取代的伯聚氧化蜂在本发明组合物表面活性剂内. When a combination of alkylene oxide, having a methyl group at the 2-position carbon atom with a substituent group, and in the preferred range as indicated above in the other two methyl substituents substituted primary alkyl polyoxyalkylene compositions of the present invention bees surface the active agent.

本发明优选的表面活性剂混合物具有至少0.001重量%,更优选至少5重量%,最优选至少20重量%的一种或多种具有下式的中链支化的伯烷基聚氧化烯: The preferred surfactant mixtures of the present invention have at least 0.001% by weight, more preferably at least 5 wt%, most preferably at least 20 wt% of one or more having the formula mid-chain branched primary alkyl polyoxyalkylene:

Rl R2 CH3仁H2(CH2)xCH(CH2)yCH(CH2)z(EO/PO)mOH Rl R2 CH3 kernel H2 (CH2) xCH (CH2) yCH (CH2) z (EO / PO) mOH

其中包括支链的碳原子总数(在该分子的亲油部分中)是15-18,并且进一步地,其中对于该表面活性剂混合物,在具有上式的支链伯烷基部分中的平均碳原子总数在大于14.5-约17.5的范闺;W和ie各自独立地是氢或C广C4(优选C广C3)烷基;x是0-11; y是0-11; z是至少2; #ix+y+ z是9- 13;条件是R"和1?2不都是氢;和E0/P0 是选自乙氧基、丙氧基和混合的乙氧基/丙氧基基团的烷氧基部分,其中迈是至少约l,优选在约3-30的范围,更优选约5-20,最优选约 The total number of carbon atoms, including branched (in the lipophilic portion of the molecule) is 15-18, and further wherein the active agent is a mixture of the surface, on the average carbon formula branched primary alkyl moieties having the total number of atoms in the Inner range of greater than 14.5 to about 17.5; W is and ie are each independently hydrogen or C wide C4 (preferably C wide C3) alkyl group; x is 0-11; y is 0-11; z is at least 2; # ix + y + z is 9-13; with the proviso that R "and 1 2 are not both hydrogen;? and E0 / P0 is selected from ethoxy, propoxy, and mixed ethoxy / propoxy groups alkoxy moiety, wherein at least about step l, preferably in the range of about 3-30, more preferably about 5 to 20, most preferably from about

优选地,该表面活性剂混合物含有至少5% ,优选至少约20%的W和1?2各自独立地是氢或甲基的中链支化的伯烷基聚氧化烯,条件是W和R2不都是氢;x+y等于8、 9或10, z是至少2。 Preferably, the surfactant mixture containing at least 5%, preferably at least about 20% of W 1 and? 2 are each independently hydrogen or methyl medium chain branched primary alkyl polyoxyalkylene, with the proviso that R2 and W are not both hydrogen; x + y is equal to 8, 9 or 10, z is at least 2.

本发明优选的洗涤剂组合物,例如用于洗涤织物的组合物,含有约0.001- 99%的中链支化的伯烷基聚氧化蜂表面活性剂混合物,所迷的混合物含有至少约2重量%的两种或多种具有下式的中链支化的伯烷基聚氧化烯或其混合物: Preferred detergent compositions of the present invention, for example, compositions for washing fabrics, bee oxide primary alkyl surfactant mixture contains from about 0.001 to 99% of polyethylene of medium chain branched, the fans mixture contains at least about 2 wt. % of two or primary alkyl polyoxyalkylene having the formula or a mixture of various branched chain:

p3 p3

CHj(CH2^CH(CH^CH2(EO/PO)inOH CHj (CH2 ^ CH (CH ^ CH2 (EO / PO) inOH

?H, ? H,

(II) (II)

CHj (CHj^CH (CH;j》.CHCH2 (EO/PO)mOH CHj (CHj ^ CH (CH; j ".CHCH2 (EO / PO) mOH

其中a、 b、 d和e是整数,a+b是10-16, d+e是8-14,并且进一步地,其中 Wherein a, b, d, and e are integers, a + b is 10-16, d + e is 8-14, and further wherein

当a+b-10时,a是2—9的整数并且b是l-8的整数; 当a+b-ll时,a是2—10的整数并且b是l-9的整数; 当a+b-12时,a是2—11的整数并且b是l-10的整数; 当a+b-13时,a是2-12的整数并且b是l-ll的整数; 当a+b-14时,a是2-13的整数并且b是l-12的整数; 当a+b-15时,a是2-14的整数并且b是1-13的整数; 当a+b-16时,a是2-15的整数并且b是1-14的整数; 当d+e-8时,d是2—7的整数并且e是1 —6的整数; 当d+e-9时,d是2 —8的整数并且e是1 —7的整数; 当d+e-10时,d是2 — 9的整数并且e是1 —8的整数; 当d+e-ll时,d是2-10的整数并且e是1-9的整数; 当d+e-12时,d是2-ll的整数并且e是l-10的整数; 当d+e-13时,d是2-12的整数并且e是1-ll的整数; 当d+e-14时,d是2-13的整数并且e是l-12的整数; 其中对于该表面活性剂混合物,在具有上式的支链伯烷基部分中 When the time 10 b-a +, a is an integer of 2-9 and b is an integer of l-8; when a + b-ll, a is an integer from 2 to 10 and b is an integer of l-9; and when a + b 12-time, a is an integer of 2-11 and b is an integer of l-10; when a + b-13 time, a is an integer of 2-12 and b is an integer of l-ll; when a + b when -14, a is an integer of 2-13 and b is an integer of l-12; when a + b 15-time, a is an integer of 2-14 and b is an integer of 1 to 13; when a + b-16 when, a is an integer of 2-15 and b is an integer of 1 to 14; when d + e-8 time, d is an integer from 2 to 7 and e is an integer of 1-6; when d + e-9, d is an integer of 2-8 and e is an integer of 1-7; when d + 10 e-time, d is 2 - 9 and e is an integer of an integer of 1-8; when d + e-ll, d is an integer from 2-10 and e is an integer of 1-9; when d + e-12 time, d is an integer of 2-ll and e is an integer of l-10; when d + e-13, d is 2- integer 12 and e is an integer of 1-ll; when d + e-14, d is an integer from 2-13 and e is an integer from l-12; and wherein for this surfactant mixture, having the formula support primary alkyl portion

的平均总碳原子数在大于14.5-约17.5的范闺内;和其中E0/P0是选自乙氧基、丙氧基和混合的乙氧基/丙氧基基团的烷氧基部分,其中m是至少约l,优选在约3-30的范闺内,更优选约5-20,和最优选约5 - 15. The average total number of carbon atoms in the range of greater than 14.5 to about 17.5 of the Inner; and wherein E0 / P0 is selected from ethoxy, propoxy alkoxy moiety and mixed ethoxy / propoxy groups, wherein m is at least about l, preferably in the range of about 3-30 Gui, more preferably about 5 to 20, and most preferably from about 5--15.

此外,本发明的表面活性剂组合物可以含有下式的支链伯烷基聚氧化烯的混合物: Further, the surfactant composition of the present invention may contain a mixture of the formula branched primary alkyl polyoxyalkylenes:

R Rl R2 R Rl R2

其中每分子包括支链的碳原子总数是14-20,并且进一步地,其中对于该表面活性剂混合物,在具有上式的支链伯烷基部分中的平均总碳原子数在大于14.5-约17. 5的范围;R、 W和W各自独立地选自氢和d-C3烷基,条件是R、 Ri和W不都是氢;w是0-13的整数;x是0 -13的整数;y是0-13的整数;z是至少为l的整数;v+x+y+z 是8-14; E0/P0是烷氧基部分,优选选自乙氧基、丙氧基和混合的乙氧基/丙氧基基团,其中迈是至少约l,优选在约3-30的范围内,更优选约5-20,和最优选约5-15;条件是当W是d-&烷基时,z等于2或更大的表面活性剂与z等于1的表面活性剂之比至少是约1:1, 优选至少约1.5: 1,更优选至少约3: 1,和最优选至少约4: 1.含有低于约50%,优选低于约40%,更优选低于约25%,最优选低于约20%的具有上式的其中当f是d - Cs烷基时z等1的支链伯烷基聚氧化烯的表面活性剂组合物也是优选的。 Wherein the sum of each molecule comprises a branched carbon atoms is 14-20, and further, wherein for this surfactant mixture, at greater than about 14.5 having the formula in the branched primary alkyl moieties average total carbon atoms range of 17.5; R & lt, W and W are each independently selected from hydrogen and d-C3 alkyl, provided R, Ri and W are not both hydrogen; W is an integer from 0 to 13; x is 0-13 in integer; Y is an integer from 0 to 13; Z is an integer of at least l,; v + x + y + z is 8-14; E0 / P0 is an alkoxy moiety, preferably selected from ethoxy, propoxy, and mixed ethoxy / propoxy groups, wherein at least about step l, preferably in the range of about 3-30, more preferably about 5 to 20, and most preferably about 5 to 15; with the proviso that when W is d - & alkyl group, z is equal to 2 or more surfactants or equal to the z-surfactant ratio of 1 is at least about 1: 1, preferably at least about 1.5: 1, more preferably at least about 3: 1, and most preferably at least about 4: 1 containing less than about 50%, preferably less than about 40%, more preferably less than about 25%, most preferably less than about 20% when having the above formula wherein f is d - Cs alkyl 1 when z and other branched primary alkyl polyoxyalkylene surfactant composition is also preferred.

本发明还涉及具有下式的新的中链支化的伯烷基聚氧化烯表面活性剂: The present invention further relates to a primary alkyl polyoxyalkylene surfactants having the formula in the new chain branched:

Rl R2 Rl R2

CH3CH2(CH2)x^H(CH2)yCH(CH2)z(EO/PO)mOH CH3CH2 (CH2) x ^ H (CH2) yCH (CH2) z (EO / PO) mOH

其中W和R2各自独立地是氢或C广Cs烷基;x是0-14; y是0-14; z至少是2; x+y+z是7-17;和E0/P0是选自乙氧基、丙氧基和混合的乙氧基/丙氧基基团的烷氧基部分,其中m是至少约l,优选在约 Wherein W and R2 are each independently hydrogen or C wide Cs alkyl; x is 0-14; y is 0-14; z is at least 2; x + y + z is 7-17; and E0 / P0 is selected alkoxy moieties ethoxy, propoxy, and mixed ethoxy / propoxy groups, wherein m is at least about l, preferably from about

3-30的范围,更优选约5-20,最优选约5-15;条件是W和I^不都是氩. Range 3-30, more preferably about 5 to 20, most preferably from about 5 to 15; with the proviso that not both I ^ W and argon.

W和! And W! ^单元各自独立地选自氲或d- C3烷基(优选氢或d- C2烷 ^ Is independently selected from Yun unit or d- C3 alkyl (preferably hydrogen or alkoxy d- C2

基;更优选氢或甲基),条件是W和ie不都是氢. Group; more preferably hydrogen or methyl), with the proviso that W and ie are not both hydrogen.

对于本发明具有多于一个烷基支链的中链支化的伯聚氧化烯,该烷基链骨架含有12- 18个碳原子.构成本发明中链支化的伯烷基聚氧化烯的碳的最大数(包括所有支链)是20个碳原子。 For the present invention having more than one branch in the alkyl chain branched primary polyoxyalkylenes of the alkyl chain skeleton containing 12-18 carbon atoms. Primary alkyl group constituting the polyoxyalkylene chain of the present invention, branched alkylene the maximum number of carbon atoms (including all branched) of 20 carbon atoms.

优选的新的聚氧化烯化合物具有下式: Preferred novel polyoxyalkylene compounds have the formula:

其中:a和b是整数并且a+b是12或13, a是2-ll的整数,b是l -IO的整数,和EO/PO是烷氧基部分,优选选自乙氧基、丙氧基和混合的乙氧基/丙氧基基团,其中m是至少约1,优选在约3-30的范闺, 更优选约5-20,最优选约5-15. Wherein: a and b are integers and a + b is 12 or 13, a is an integer of 2-ll, b is an integer of l -IO, and EO / PO are alkoxy moieties, preferably selected from ethoxy, propoxy, group and mixed ethoxy / propoxy groups, wherein m is at least about 1, preferably in the range of about 3-30 Gui, more preferably about 5 to 20, most preferably from about 5-15.

还优选的新中链支化的伯烷基聚氧化烯化合物具有下式: Branched primary alkyl polyoxyalkylene compound is preferably in the new chain also has the formula:

CH3 (CHa)rfCH (CHj)'CHCH! CH3 (CHa) rfCH (CHj) 'CHCH! (EO/PO)mOH (EO / PO) mOH

其中: among them:

d和e是整数并且d+e是10或11,并且进一步地,其中当d+e-10时,d是2-9的整数并且e是1-8的整数; 当d+e-ll时,d是2-10的整数并且e是1-9的整数; 和EO/PO是烷氧基部分,优选选自乙氧基、丙氧基和混合的乙氧 d and e are integers and d + e is 10 or 11, and further, wherein when d + 10 e-time, d is an integer of 2-9 and e is an integer from 1 to 8; when d + e-ll when , d is an integer from 2 to 10 and e is an integer from 1 to 9; and EO / PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy

基/丙氧基基团,其中迈是至少约l,优选在约3-30的范围内,更优 Yl / propoxy groups, wherein at least about step l, preferably in the range of about 3-30, more preferably

选约5-20,和最优选约5- 15。 Preferably about 5-20, and most preferably from about 5-15.

优选的单甲基支化的伯烷基乙氧基化物选自:3-甲基十五烷醇乙 Preferred mono-methyl branched primary alkyl ethoxylates are selected from: 3-methyl pentadecanol B

氧基化物、4-甲基十五烷醇乙氧基化物、5-甲基十五烷醇乙氧基化 Alkoxylates, 4-methyl pentadecanol ethoxylate, 5-methyl pentadecanol ethoxylated

物、6-甲基十五烷醇乙氧基化物、7-甲基十五烷醇乙氧基化物、8 Product, 6-methyl pentadecanol ethoxylate, 7-methyl pentadecanol ethoxylate, 8

-甲基十五烷醇乙氧基化物、9-甲基十五烷醇乙氣基化物、10-甲基十五烷醇乙氧基化物、11-甲基十五烷醇乙氧基化物、12-甲基十五烷醇乙氧基化物、13-甲基十五烷醇乙氧基化物、3-曱基十六烷醇乙氧基化物、4-甲基十六烷醇乙氧基化物、5-甲基十六烷醇乙氧基化物、6-甲基十六垸醇乙氧基化物、7-甲基十六烷醇乙氧基化物、8 -甲基十六烷醇乙氣基化物、9-甲基十六烷醇乙氧基化物、10-甲基十六烷醇乙氧基化物、11-甲基十六烷醇乙氧基化物、12-甲基十六烷醇乙氧基化物、13-甲基十六烷醇乙氧基化物、14-甲基十六烷醇乙氧基化物,和其混合物,其中该化合物是乙氧基化的,平均乙氧基化度为约5-15. - methyl pentadecanol ethoxylate, 9-methyl pentadecanol gas B group compound, 10-methyl pentadecanol ethoxylate, 11-methyl pentadecanol ethoxylate , 12-methyl pentadecanol ethoxylate, 13-methyl pentadecanol ethoxylate, 3-yl Yue hexadecanol ethoxylate, 4-methyl hexadecanol ethoxylated based compound, 5-methyl hexadecanol ethoxylate, 6-methyl sixteen embankment alcohol ethoxylate, 7-methyl hexadecanol ethoxylate, 8 - methyl hexadecanol b group compound gas, 9-methyl hexadecanol ethoxylate, 10-methyl hexadecanol ethoxylate, 11-methyl hexadecanol ethoxylate, 12-methyl sixteen alcohol ethoxylate, 13-methyl hexadecanol ethoxylate, 14-methyl hexadecanol ethoxylate, and mixtures thereof, wherein the compound is an ethoxylated, ethoxy mean yl degree of about 5-15.

M的二甲基支化的伯)^乙4R^化物选自:2, 3 -二甲基十四烷醇乙IBl^化物、2,4-二甲基十四烷醇乙承基化物、2,5-二甲基十四烷醇乙氧基化物、2,6-二甲基十四烷醇乙氧基化物、2,7-二甲基十四烷醇乙緣化物、2,8-二甲基十四烷醇乙li^化物、2,9-二甲基十四烷醇乙fUi化物、2,10-二甲基十四烷醇乙舉基化物、2,11-二甲基十四烷醇乙氣基化物、2,12-二甲基十四烷醇乙氣基化物、2,3-二甲基十五烷醇乙氧基化物、2,4-二甲基十五烷醇乙築基化物、2,5-二甲基十五烷醇乙乘基化物、 2, 6 -二曱基十五烷醇乙^^化物、2, 7 -二甲基十五烷醇乙^^化物、2, 8 -二甲基十五烷醇乙^^化物、2,9-二甲基十五烷醇乙JR4化物、2, 10 -二甲基十五烷醇乙fU^化物、2,11-二甲基十五烷醇乙jjyi化物、2,12 -二甲基十五烷醇乙氣基化物、2,13-二甲基十五烷醇乙舉J^化物,和其 M di-methyl branched primary) ^ B ^ 4R compound selected from: 2, 3 - dimethyl tetradecanol IBL ^ B compound, 2,4-dimethyl tetradecanol ethyl group bearing compound, 2,5-methyl tetradecanol ethoxylate, 2,6-methyl tetradecanol ethoxylate, 2,7-methyl tetradecanol acetate edge thereof, 2,8 - dimethyl tetradecanol li ^ b compound, 2,9-dimethyl tetradecanol fUi compound b, 2,10-methyl tetradecanol give ethyl arylate, 2,1 l-dimethyl tetradecanol gas yl group b compound, 2,12-dimethyl tetradecanol gas b group compound, 2,3-dimethyl pentadecanol ethoxylate, 2,4-dimethyl ten five building alkanol group b compound, 2,5-dimethyl pentadecanol by group b compound, 2, 6 - two Yue-yl ^^ pentadecanol b compound, 2,7 - dimethyl - pentadecane alcohol ethoxylates thereof ^^, 2, 8 - dimethyl pentadecanol ^^ b compound, 2,9-dimethyl pentadecanol JR4 compound b, 2, 10 - dimethyl pentadecanol b fU ^ compounds, ll-dimethyl pentadecanol jjyi compound b, 2,12 - dimethyl pentadecanol gas b group compound, 2,13- dimethyl pentadecanol b ^ J give compound , and its

'*物,其中该一掩是乙氧基化的,平均乙氣基化度为约5-15。 '*, Wherein the mask is a ethoxylated, acetate average degree of gas-yl about 5-15.

中链支化的聚氯化錄的制备下面的反应路线图概迷了使用本领域技术人员熟悉的标准有机化学反应烦序制备中链支化的伯醇的一般方法,该酵用于烷氧基化以制备本发明的中链支化的伯烷基聚氧化烯表面活性剂:<formula>formula see original document page 23</formula>将烷基卣转变成格利雅试剂并使该格利雅试剂与卣代酮反应,常规的酸水解后,乙酰化并热消去乙酸,制备中间体烯烃(在该闺中没有示出),使用任何常规的加氢催化剂例如Pd/C立即将其加氳。 Mid-chain branched poly recorded chloride prepared following reaction scheme using standard Almost lost familiar to those skilled in organic chemical reactions chain branched primary alcohols prepared annoying sequence the general method for the ferment alkoxy group of medium-chain branched primary alkyl preparation of the present invention polyoxyalkylene surfactants: <formula> formula see original document page 23 </ formula> wine container will be converted into an alkyl Grignard reagent and the Grignard reagent the reaction with the wine container-ketone, after conventional acid hydrolysis, acetylation and thermal elimination of acetic acid, the preparation of the intermediate alkene (not shown in the Gui), using any conventional hydrogenation catalyst such as Pd / C was added immediately to its heavy atmosphere.

该路线优于其它路线,西为在反应顺序中先引入支链,在本说明 The route over other routes, for the first Branched west in the reaction sequence, in the present description

中是5-甲基支链. It is 5-methyl branch.

从第一加氢步骤得到的烷基卣的甲酰化得到醇产物,如在该图中所示的。 Formylation alkyl wine container obtained from the first hydrogenation step to give the alcohol product, as shown in the figure. 可以使用标准技术将其烷氧基化从而得到最终的支链伯烷基聚氧化烯表面活性剂.除了通过单一的甲酰化实现外,将支链延长增加一个另外的碳原子可以有灵活性。 Using standard techniques alkoxylated to produce the final branched primary alkyl polyoxyalkylene surfactant addition by a single formylation outer achieved, the addition of a branched chain extension additional carbon atoms may be flexibility . 例如,这样的延长可以通过与环氧乙烷反应完成.见"《非金属物质的格利雅反应》(Grignard Reactions of No咖etallic Substrances) " , MS Kharasch和0, Rei咖uth, Prentice-Hall, NY, 1954; J. Org. Cheni., j". Cason 和WR Hnans, Vol. 15(1950),卯139-147; J. Org. Ch柳.,J. Cason等,Vol. 13(1948), pp 239-248; J. Org. Ch棚.,J. Cason 等,Vol. 14(1949), pp 147-154;和J. Org. Che血.,J. Cason等, Vol. 15(1950), pp 135-138;所有这些文献在本文中均引作参考。 For example, such an extension can be accomplished by reaction with ethylene oxide. See "" Grignard reactions of nonmetallic substances "(Grignard Reactions of No coffee etallic Substrances)", MS Kharasch and 0, Rei coffee uth, Prentice-Hall, NY, 1954;.. J. Org Cheni, j "Cason and WR Hnans, Vol 15 (1950), d 139-147;..... J. Org Ch Liu, J Cason, etc., Vol 13 (1948). , pp 239-248;.... J. Org Ch shed, J Cason, etc., Vol 14 (1949), pp 147-154;... and J. Org Che blood, J Cason, etc., Vol 15 (1950. ), pp 135-138; all of which are incorporated herein by reference.

在上述方法的变化中可以使用另外的卣代酮或格利雅试剂。 Additional wine container may be used on behalf of one or Grignard reagent in a variation of the above method. 可以使用得自甲酰化或乙氧基化的醇的PBr3离化来实现迭代链的延长。 You may be used from formylation or ethoxylated alcohols PBr3 ionization iterative chain extension is achieved.

本发明的优选的中链支化的伯烷基聚氧化烯可以容易地如下制 Preferably the present invention mid-chain branched primary alkyl polyoxyalkylene can be readily prepared as follows

备: <formula>formula see original document page 24</formula> Preparation: <formula> formula see original document page 24 </ formula>

适宜地在二甲基亚砜/四氢呋喃中将常规的溴代醇与三笨基鳞反应,接着与氢化钠反应,从而形成维悌希加合物。 Suitably in dimethylsulfoxide / tetrahydrofuran in the bromohydrin is reacted with a conventional three scales stupid group, followed by reaction with sodium hydride, to form a Wittig Xijia thereof. 该维悌希试剂加合物与cc甲基酮反应形成内不饱和的甲基支化的醇化物.加氲接着烷氧 The Wittig reagent adduct formed in the reaction of unsaturated methyl-branched alcoholate and cc methyl ketone. Next add Yun alkoxy

基化得到所需要的中链支化的伯烷基聚氧化烯.尽管该维悌希试剂方法不能象格利雅试剂方法那样允许专业人员延长烃链,但是维悌希试剂方法一般提供较高的收率.见包括在本文中引作参考的 Hydroformylation to give the desired mid-chain branched primary alkyl polyoxyalkylene. Although this method does not Wittig reagent that allows professionals to extend the hydrocarbon chain, such as a Grignard reagent method, but the method of Wittig reagent generally provide higher yield see comprising herein incorporated by reference

Agricultural and Biological Chemistry, M. Horiike等,Vol. 42(1978), pp 1963-1965. Agricultural and Biological Chemistry, M. Horiike the like, Vol. 42 (1978), pp 1963-1965.

根据本发明,可以使用任何其它的合成方法来制备支链的伯烷基聚氧化烯。 According to the present invention can be prepared using any other branched primary alkyl synthetic methods polyoxyalkylene. 另外,可以在常规同系物,例如在作为加氢甲酰化的结果生产2-烷基支链的工业方法中形成的那些常规同系物中任何一种的存在下合成或配制中链支化的伯烷基聚氧化烯.通常可以将本发明的中链支化的表面活性剂混合物加入到含于最终洗衣产品配方中的其它已知的工业烷基聚氧化烯中. Additionally, the presence of any synthetic or those formulated in the conventional homologs may, for example be formed in an industrial process for producing a 2-alkyl branched as a result of hydroformylation in a conventional homolog of one of the mid-chain branched primary alkyl polyoxyalkylenes may generally be in the chain of the invention branched surfactant mixture is added to other known industrial contained in the final laundry product formulation of the polyoxyalkylene alkyl.

在本发明表面活性剂混合物的某些优选的实施方案中,尤其是得自化石燃料源包括工业方法的那些表面活性剂混合物包括至少1种, 优选至少2种,更优选至少5种,最优选至少8种中链支化的伯烷基聚氧化烯. In certain preferred embodiments of the present invention, mixtures of surfactants, in particular from fossil fuel sources that include a surfactant mixture comprising at least one industrial process, preferably at least two, more preferably at least 5, most preferably at least a mid-chain branched primary alkyl polyoxyalkylene eight kinds.

特别适合于制备本发明的某些表面活性剂混合物的是"羰基合成"反应,其中支链烯烃在烷氧基化之前经受催化异构化和加氢甲酰化.得到这样混合物的优选的方法使用化石燃料作为原料。 Particularly suitable for preparation of certain surfactant mixtures of the present invention are "oxo" reactions wherein a branched chain olefin is subjected to catalytic isomerization and hydroformylation prior to alkoxylation. The mixture obtained is preferably such a method use of fossil fuels as a raw material. 优选的方法对具有有限量支链的直链烯烃(a或内烯烃)使用羰基合成反应. 以任何顺序地,通过直链a或内烯烃的二聚,通过低分子量直链烯烃 The preferred method of linear olefins (internal olefins, or a) with a limited amount of branched oxo reaction. Any order, by a linear or dimerized internal olefins, by the low molecular weight linear olefins

的控制低聚,通过洗涤剂范闺的燁烃的骨架重排,通过洗涤剂范围的石蜡的脱氢/骨架重排,或者通过费-托反应,可以制备合适的烯烃. Oligomerization control by the detergent range hydrocarbons Ye Gui skeletal rearrangement, rearrangement of detergent range paraffins via dehydrogenation / skeletal, or by the Fischer - Tropsch reaction, can be prepared by suitable olefin.

通常控制这些反应以便:l)得到大部分的在所需洗涤剂范围的烯烃(尽管在后续的羰基合成反应中可以加成上碳原子),2)制备有限数量的支链,优选中链,3)制备d-C3支链,更优选乙基,最优选甲基,4) 限制或除去偕二烷基支链,即避免形成季碳原子。 These reactions are typically controlled to: l) to give olefins of detergent range most desired (although in the subsequent Oxo reaction may be addition of a carbon atom), 2) the preparation of a limited number of branches, preferably medium chain, 3) preparation of d-C3 branched chain, more preferably ethyl, most preferably methyl, 4) limit or eliminate gem-branched alkyl group, i.e. to avoid formation of quaternary carbon atoms. 直接或间接地通过相应的醛该合适的蜂烃可以进行羰基合成反应以便得到伯醇。 Directly or indirectly, the bee suitable hydrocarbon synthesis reaction may be performed by a carbonyl group to obtain the corresponding aldehyde primary alcohol. 当使用内烯烃时,通常使用羰基合成催化剂,它能够将内烯烃基本上先预异构化成为a烯烃.尽管分开来将内烯烃催化(即非羰基合成)成a异构化也是可以进行的,但这是任选的。 When the olefin used, it is generally used Oxo catalysts, internal olefins which can be substantially a first pre-isomerized olefins. Although separate internal olefins catalyzed (i.e. non-Oxo) into a isomerisation can be performed also , but this is optional. 另一方面,如果形成烯烃的步骤本身就直接得到oc烯烃(例如用洗涤剂范闺的高压费-托烯烃), 那么不但可以而且优选使用非异构化的羰基合成催化剂。 On the other hand, if the step of forming the olefin itself directly oc-olefin (e.g. with high pressure Fischer detergent range Gui - Tropsch olefins), and then only can be preferably used a non-isomerizing Oxo catalyst.

本文中的上述方法以比较不优选的2,4-二甲基十五烷基聚氧化烯更高的收率得到更优选的5-甲基-十六烷基聚氧化烯.这一混合物在本发明的范围内是合乎要求的,因为每个产物包括总共17个碳原子,直链烷基链具有至少13个碳原子, The method described herein above to less preferred polyoxyalkylene higher yields peroxide, 2,4-dimethyl pentadecyl be more preferably 5-methyl - hexadecyl polyoxyalkylene in the mixture within the scope of the present invention it is desirable, because each product comprises a total of 17 carbon atoms, a straight-chain alkyl chain having at least 13 carbon atoms,

下面实施例提供了本发明组合物中有用的各种化合物的合成方法。 The following embodiment provides a method for synthesizing various compounds useful in the compositions of the present invention.

实施例I Example I

7_甲基十六烷基乙氣基化物(E2)的制备溴化(6-羟基己基)三笨基辚的合成在氮气下向5L装有氮气入口管,冷凝器,温度计,机械搅拌器和氮气出口管的3颈园底烧瓶中加入6-溴-1-己醇(500g, 2. 76mol), 三笨基膦(768g, 2.9mol)和乙腈(1800ml)。 7_ Preparation of methyl bromide gas hexadecyl group B compound (E2) of (6-hydroxyhexyl) Synthesis of Tri-yl rumbling stupid to 5L equipped with a nitrogen inlet tube under nitrogen, a condenser, a thermometer, a mechanical stirrer 3 neck round bottom flask and a nitrogen outlet tube was charged with 6-bromo-1-hexanol (500g, 2. 76mol), three stupid phosphine (768g, 2.9mol) and acetonitrile (1800ml). 将该反应混合物加热回流72小时.将反应混合物冷却到室温并转移到5L烧杯中。 The reaction mixture was heated at reflux for 72 hours. The reaction mixture was cooled to room temperature and transferred into a 5L beaker. 在10C 将产物从无水乙醚(1.5L)中重结晶出来.真空过滤接着用乙醚洗涤并在50C在真空烘箱中干燥2小时得到1140g白色结晶的所需产物。 The product from 10C in anhydrous diethyl ether (1.5 L of) the recrystallized. Of the desired product by vacuum filtration washed with ether and then dried for 2 hours at 50C to give white crystals 1140g in a vacuum oven.

7-甲基十六碳烯-1-醇的合成向干燥的5L装有机械搅拌器,氮气入口管,滴液漏斗,温度计和氮气出口管的3颈园底烧瓶中加入70. 2g的60%在矿物油中的氢化钠(1. 76mol).通过用己烷洗涤除去矿物油.将无水二甲基亚砜(500ml) 加入到该烧瓶中并将该混合物加热至70C直到停止放出氢.将该反应混合物冷却到室温,接着加入1L无水四氩呋喃。 Synthetic carbon sixteen 7-methyl-1-ol] To a dry 5L equipped with a mechanical stirrer, a nitrogen inlet tube, a dropping funnel, a thermometer and a nitrogen outlet pipe 3-neck round bottom flask was added 60 70. 2g % sodium hydride in mineral oil (1. 76mol). by removing the mineral oil was washed with hexane. anhydrous dimethyl sulfoxide (500ml) was added to the flask and the mixture was heated to 70C until hydrogen evolution ceased the reaction mixture was cooled to room temperature, followed by addition of 1L of anhydrous argon four furan. 溴化(6-鞋基己基) 三苯基辚(443.4g, l迈ol)与温的无水二甲基亚砜(50X:, 500迈1)搅拌混合并通过滴液漏斗緩慢地加入到该反应混合物中同时将其保持在25- 30TC。 Bromide (6 shoe ethylhexyl) triphenylphosphonium jingle (443.4g, l step OL) with warm anhydrous dimethyl sulfoxide (50X :, 500 step 1) were mixed and stirred slowly added via a dropping funnel the reaction mixture, while kept at 25- 30TC. 在室温搅拌该混合物30务钟,此时通过滴波漏斗緩侵地加入2-十一烷酮(187g, ll边ol)。 The mixture was stirred at room temperature for 30 clock service, this time by the slow dropwise addition funnel wave Invasion 2- undecanone (187g, ll edge ol). 反应略徵放热并需要冷却以维持在25- 30C搅拌该混合物18小时,然后倾倒进含1L纯水的5L烧瓶中同时搅拌.让油相(上部)在分液漏斗中分离出来并除去水相. 用己烷(500ml)洗涤该水相和分离有机相并与得自水洗涤的油相合并.然后用水3次(每次500迈1)萃取该有机混合物,接着在140"和lmmHg下真空蒸馏以收集透明的油状产物(132g)。 The reaction is slightly exothermic and requires cooling intrinsic to maintain the mixture was stirred at 25- 30C 18 hours and then poured into a 5L flask containing 1L purified water while stirring. Let the oil phase (top) is separated in a separatory funnel and the water removed phase. the organic phase was separated and the aqueous phase were combined and washed with washing water from the oil with hexane (500ml). the organic mixture is then extracted with water 3 times (each 500 step 1), followed by 140 "and in lmmHg vacuum distillation to collect the clear, oily product (132g).

7-甲基十六碳烯-1-醇的加氢 Hydrogenation of 7-methyl-hexadecene-1-ol

向3L摇摆式高压釜衬里中加入7-甲基十六碳烯-1-醇(130g, 0.508迈o1),甲醇(300ml)和负栽在碳上的铂(10重量%, 35g). 在180C、 1200psig的氬下将该混合物加氬13小时,冷却并通过Celite 545真空过滤,同时适当地用二氯甲烷洗涤该Celite 545. 如果需要,可以重复该过滤以便消除痕量的Pt催化剂,使用疏酸镁干燥该产物。 It was added to a 3L rocking autoclave liner 7-methyl-hexadecene-1-ol (130g, 0.508 step o1), methanol (300ml) and negative planted platinum on carbon (10 wt%, 35g). In 180C, the mixture was added 1200psig argon argon for 13 h, cooled and vacuum filtered through Celite 545, washed with dichloromethane while appropriately the Celite 545. If desired, the filtration can be repeated to eliminate traces of Pt catalyst, using the product was dried over magnesium repellent. 在旋转蒸发器上浓缩产物溶液得到透明的油(124g). On a rotary evaporator, the product solution was concentrated to give a clear oil (124g).

7-甲基十六烷酵的烷氣基化 7-methyl-hexadecane yeast alkyl group of gas

向干燥的1L装有氮气入口管,机械搅拌器,和装有温度计的Y-形管和气体出口管的3颈园底烧瓶中加入从上迷步骤中得到的醇。 To a dry 1L equipped with a nitrogen inlet pipe, 3 neck round bottom flask equipped with mechanical stirrer, and equipped with a thermometer and a gas outlet tube Y- tube was added the alcohol from the above-obtained step. 为了除去痕量水的目的,在80-IOOC用氮气鼓泡该醇约30分钟。 For the purpose of removing traces of water, the alcohol is sparged with nitrogen in a 80-IOOC for about 30 minutes. 继续用氮气吹扫,加入金属钠作为催化剂并让其在120- 140t:下搅拌熔融.在剧烈搅拌下,在140分钟内加入环氧乙烷气体同时将反应温度保持在120- 140X:。 Continue purged with nitrogen, sodium metal is added as the catalyst and allowed to 120- 140t:. Melted with stirring under vigorous stirring, ethylene oxide gas is added in 140 minutes while the reaction temperature was maintained at 120- 140X :. 加入合适重量(等于2当量的环氧乙烷)之后, 用氮气吹扫该装置20- 30分钟让样品冷却.然后收集所需要的7-甲基十六烷基乙氧基化物(每分子平均2乙氧基化物)产物. After adding a suitable weight (equal to two equivalents of ethylene oxide), the apparatus was purged with nitrogen for 20-30 minutes to allow the sample is cooled then collected the desired 7-methyl hexadecyl ethoxylate (average per molecule 2 ethoxylates) of product.

实施例II Example II

7-甲基十五烷基乙氧基化物(E8)的合成溴化(6-羟基己基)三笨基镌的合成在氮气下向5L装有氮气入口管,冷凝器,温度计,机械搅拌器和氮气出口管的3颈园底烧瓶中加入6-溴-1-己醇(500g, 2,76迈o1), 三苯基膦(768g, 2. 9迈o1)和乙腈(1800迈1)。 7-methyl pentadecyl ethoxylate (E8) Synthesis of bromide (6-hydroxyhexyl) Synthesis of three stupid group Juan 5L under nitrogen equipped with a nitrogen inlet tube, a condenser, a thermometer, a mechanical stirrer 3 neck round bottom flask and a nitrogen gas outlet tube was charged with 6-bromo-1-hexanol (500g, 2,76 step o1), triphenylphosphine (768g, 2. 9 step O1) and acetonitrile (step 1 1800) . 将该反应混合物加热 The reaction mixture was heated

回流72小时.将反应混合物冷却到室温并转移到5L烧杯中。 Reflux for 72 hours. The reaction mixture was cooled to room temperature and transferred into a 5L beaker. 在10C 将产物从无水乙醚(1.5L)中重结晶出来.真空过滤该混合物接着用乙醚洗涤该白色结晶并在50t:真空烘箱中干燥2小时得到1140g的所 The product from 10C in anhydrous diethyl ether (1.5 L of) the recrystallized mixture was vacuum filtered out of the white crystals with ethyl ether and then washed with 50t:. In a vacuum oven for 2 hours to obtain 1140g

需产物。 The desired product.

7 -甲基十五碳烯-1-酵的合成向干燥的5L装有机械搅拌器,氮气入口管,滴液漏斗,温度计和氮气出口管的3颈园底烧瓶中加入80g的60%在矿物油中的氢化钠 7-- methyl-pentadecene -1- Synthesis of To a dry yeast 5L equipped with a mechanical stirrer, a nitrogen inlet tube, a dropping funnel, a thermometer and a nitrogen outlet pipe 3-neck round bottom flask was added 60% 80g in sodium hydride in mineral oil

(2.0边o1).通过用己烷洗涤除去矿物油.将无水二甲基亚砜(500ml) 加入到该烧瓶中并将该混合物加热至70C直到停止放出氢.将该反应混合物冷却到室温,接着加入IL无水四氢呋喃.溴化(6-羟基己基) 三苯基辚U43.4g, lmol)与温的无水二甲基亚砜(501C, 500ml)搅拌混合并通过滴液漏斗援慢地加入到该反应混合物中同时将其保持在25- 30t:。 (2.0 O1 side).. Anhydrous dimethyl sulfoxide (500ml) removed by addition of a mineral oil was washed with hexane to the flask and the mixture was heated to 70C until hydrogen evolution ceased. The reaction mixture was cooled to room temperature followed by addition of IL of anhydrous tetrahydrofuran. tribromide (6-hydroxyhexyl) triphenylphosphonium clattering U43.4g, lmol) with warm anhydrous dimethyl sulfoxide (501C, 500ml) was stirred and mixed slowly through a dropping funnel aid was added to the reaction mixture while it was kept at 25- 30t :. 在室温搅拌该反应混合物30分钟,此时通过滴液漏斗緩慢地加入2-癸酮(171.9g, ll迈ol)。 The reaction mixture was stirred at room temperature for 30 minutes, and at this time the dropping funnel was slowly added 2-decanone (171.9g, ll step ol). 反应略微放热并需要冷却以维持在25 - 30X:,搅拌该混合物18小时,然后倾倒进含600ml纯水和300ml己烷的分液漏斗中.摇动后,让油相(上部)分离出来并除去水相。 The reaction slightly exothermic and cooling is required to maintain a 25 - 30X :, a separatory funnel and the mixture was stirred for 18 hours, then poured into water and 600ml containing 300ml of hexane after shaking, so that the oil phase (top) is separated and aqueous phase was removed. 使用水萃取该油相直到2相都是透明的.收集有机相,真空蒸馏并用液相色谱(90: IO己烷:乙酸乙醏,硅胶固定相)得到透明的油状产物(119. lg)' . The oil phase was extracted with water until two phases is transparent organic phase was collected and vacuum distilled by liquid chromatography to give the product as a clear oil (119. lg) (90: Du ethyl acetate, silica gel stationary phase: IO hexane) '

7-甲基十五碳烯-1-醇的加氢向3L摇摆式高压釜玻璃衬里中加入7-甲基十五碳烯-1-醇 Hydrogenation of 7- methyl-pentadecene-1-ol was added to the 3L rocking autoclave glass liner pentadecene 7-methyl-1-ol

(122g, 0.508迈o1),甲醇(300ml)和负栽在破上的铂(10重量%, 40g)。 (122g, 0.508 step o1), methanol (300ml) and planted in breaking negative platinum (10 wt%, 40g). 在180X:在1200psig的氢下将该混合物加氬13小时,冷却并通过Celite 545真空过滤,同时用二氯甲烷洗涤该Celite 545.由于铂催化剂该有机混合物仍然是深色的,所以重复该过滤过程同时在旋转蒸发器上浓缩;用二氯甲烷(500ml)进行稀释并加入疏酸镁干燥产物。 In 180X: This mixture was added at 1200psig hydrogen argon for 13 h, cooled and vacuum filtered through Celite 545, and the methylene chloride was washed with a platinum catalyst Celite 545. Since the organic mixture is still dark, so that the filter is repeated process simultaneously concentrated on a rotary evaporator; diluted with dichloromethane (500ml) and magnesium sulfate was added repellent product. 通过Celite 545真空过滤器并在旋转蒸发器上浓缩过滤物得到透明的油(119g). Vacuum filter through Celite 545 and concentrated on a rotary evaporator was filtered to give a clear oil (119g).

7-甲基十五烷酵的烷氧基化向干燥的1L装有氮气入口管,机械搅拌器,和装有温度计的Y-形管和气体出口管的3颈园底烧瓶中加入从上述步骤中得到的醇。 7-3-methyl-necked round bottom flask fermentation pentadecane alkoxylated To a dry 1L equipped with a nitrogen inlet tube, mechanical stirrer, and equipped with a thermometer and a gas outlet tube Y- tube from the above step was added obtained alcohol. 为了除去痕量水的目的,在80- 100t:用氮气鼓泡该醇约30分钟,继续 For the purpose of removing traces of water in 80- 100t: the alcohol is sparged with nitrogen for about 30 minutes, and

用氮气吹扫,加入金属钠作为催化剂并让其在120- 140t:下搅拌熔融.在剧烈搅拌下,在140分钟内加入环氧乙烷气体同时将反应温度保持在120- 140TC.加入合适重量(等于8当量的环氧乙烷)之后, 用氮气吹扫该装置20- 30分钟让样品冷却.然后收集所需要的7-甲基十五烷基乙氧基化物(每分子平均8乙氧基化物)产物。 Was purged with nitrogen, sodium metal is added as the catalyst and allowed to 120- 140t:.. A melt with stirring under vigorous stirring, ethylene oxide gas is added in 140 minutes while the reaction temperature was maintained at 120- 140TC addition of suitable weight after (equivalent to 8 equivalents of ethylene oxide), the apparatus was purged with nitrogen for 20-30 minutes to allow the sample is cooled then collected the desired 7-methyl pentadecyl ethoxylate (average of 8 ethoxy per molecule arylate) of product.

实施例III 7-甲基十七烷基乙氣基化物(E5)的合成溴化(6-羟基己基)三苯基镌的合成在氮气下向5L装有氮气入口管,冷凝器,温度计,机械搅拌器和氮气出口管的3颈园底烧瓶中加入6-溴-1-己醇(500g, 2.76迈o1), 三笨基膦(768g, 2.9mol)和乙腈(1800ml).将该反应混合物加热回流72小时。 Example III 7-methyl gas heptadecyl group B compound (E5) Synthesis of bromide (6-hydroxyhexyl) triphenylphosphonium Synthesis engraved under nitrogen inlet tube equipped with a nitrogen to 5L, a condenser, a thermometer, 3 neck round bottom flask equipped with mechanical stirrer, and a nitrogen outlet tube was charged with 6-bromo-1-hexanol (500g, 2.76 step o1), three stupid phosphine (768g, 2.9mol) and acetonitrile (1800ml). the reaction The mixture was heated at reflux for 72 hours. 将反应混合物冷却到室温并转移到5L烧杯中.在10C 将产物从无水乙醚(1.5L)中重结晶出来.真空过滤该混合物接着用乙酸洗涤该白色结晶并在50*C真空烘箱中干燥2小时得到1140g的所需产物。 The reaction mixture was cooled to room temperature and transferred to a 5L beaker. The product from 10C in anhydrous diethyl ether (1.5 L of) the recrystallized. The mixture was vacuum filtered followed by washing the white crystals with acetic acid and dried in a vacuum oven at 50 * C 2 hours to obtain 1140g of the desired product.

7-甲基十七碳烯-1-酵的合成向干的5L装有机械搅拌器,氮气入口管,滴液漏斗,温度计和氮气出口管的3颈园底烧瓶中加入80g的60%在矿物油中的氢化钠 7-methyl-heptadecene -1- Synthesis of yeast dry 5L equipped with a mechanical stirrer, a nitrogen inlet tube, a dropping funnel, a thermometer and a nitrogen outlet pipe 3-neck round bottom flask was added 60% 80g in sodium hydride in mineral oil

(2.0迈o1)。 (2.0 step o1). 通过用己烷洗涤除去矿物油.将无水二甲基亚砜(500ml) 加入到该烧瓶中并加热至70K直到停止放出氢.将该反应混合物冷却到室温,接着加入1L无水四氢呋喃。 Anhydrous dimethyl sulfoxide (500ml) removed by addition of a mineral oil was washed with hexane to the flask and heated to 70K until hydrogen evolution ceased. The reaction mixture was cooled to room temperature, followed by addition of 1L of anhydrous tetrahydrofuran. 溴化(6-羟基己基)三苯基镌 Bromide (6-hydroxyhexyl) triphenylphosphonium engrave

(443. 4g, l迈ol)与温的无水二甲基亚砜(50t:, 500ml)搅拌混合并通过滴液漏斗緩慢地加入到该反应混合物中同时将其保持在25 -30C。 (443. 4g, l step OL) with warm anhydrous dimethyl sulfoxide (50t :, 500ml) were mixed and stirred slowly added to the reaction mixture through the dropping funnel while keeping it at 25 -30C. 在室温搅拌该反应混合物30分钟,此时通过滴液漏斗緩慢地加入2-十二烷酮(184.3g, Llmol)。 The reaction mixture was stirred at room temperature for 30 minutes, and at this time the dropping funnel was slowly added 2-dodecanone (184.3g, Llmol). 反应略徵放热并需要冷却以维持在25 - 30C搅拌该混合物18小时,然后倾倒进含600ml纯水和300迈1己烷的分液漏斗中.摇动后,让油相(上部)分离出来并除去混浊的水相。 The reaction is slightly exothermic and cooling is required to sign maintained at 25 - 30C and the mixture was stirred for 18 hours, then poured into a separatory funnel containing 600ml of purified water and 300 step 1 hexane After shaking, so that the oil phase (top) is separated. and removing the aqueous phase turbid. 使用水萃取该油相直到水相和油相都是透明的,收集有机相,用液相色谱(流动相-己烷,固定相-硅胶)纯化得到透明的油状产物(116gK最终产物(在氧化氘中)的HNMR表明:在3. 8ppm 共振处的Cg2 - OSCV三重峰,在1. 5ppm共振处的Cg2 - Cg2 - OS(V多重峰,在0.9-1.3 pp迈共振处的烷基链Cg2和在0.8ppm共振处的重 The oil was extracted with water until the aqueous phase and oil phase are transparent, organic phase was collected, by liquid chromatography (mobile phase - hexanes, stationary phase - silica gel) to give the product as a clear oil (116gK final product (oxidation deuterium) is HNMR showed: 3. in Cg2 resonance at 8ppm - OSCV triplet, Cg2 1. resonance in at 5ppm - Cg2 - OS (V multiplet, 0.9-1.3 pp step in the alkyl chain resonance at Cg2 and a weight at the resonance at 0.8ppm

叠R - CHz - Cgs端基甲基的CH - Cg3支链点. Stack R - CHz - Cgs terminal methyl group of CH - Cg3 branch point.

7-曱基十七碳烯-l-醇的加氢 Hydrogenation of 7- yl Yue heptadecene -l- alcohol

向3L摇摆式高压釜玻璃村里(Autoclave Engineers)中加入7 -甲基十七碳烯-1-醇(116g, 0.433mol),甲醇(300ml)和负栽在碳上的铂(10重量%, 40g),在180C在1200psig的氢下将该混合物加氲13小时,冷却并通过Celite 545真空过滤,用二氯甲烷洗涤Celite 545.通过Celite 545真空过滤器并在旋转蒸发器上浓缩过滤物得到透明的油(108g). To a 3L rocking autoclave glass village (Autoclave Engineers) is added 7 - methyl-heptadecene 1-ol (116g, 0.433mol), methanol (300ml) and negative planted platinum on carbon (10 wt%, 4Og), the mixture was Yun at 180C for 13 h, cooled and vacuum filtered through Celite 545 at 1200psig hydrogen, washed with dichloromethane 545. Celite and concentrated on a rotary evaporator was filtered through Celite 545 to give vacuum filter clear oil (108g).

7-甲基十七烷醇的烷氧基化 Methyl 7- alkoxylated alkanols seventeen

向干燥的1L装有氮气入口管,机械搅拌器,和装有温度计的Y-形管和气体出口管的3颈园底烧瓶中加入从上迷步骤中得到的醇.为了除去痕量水的目的,在80-ioox:用氮气鼓泡该醇约30分钟.继续用氮气吹扫,加入金属钠作为催化剂并让其在120-H0X:下搅拌熔融.在剧烈搅拌下,在140分钟内加入环氧乙烷气体同时将反应温度保持120- 140'C.加入合适重量(等于5当量的环氧乙烷)之后,用氮气吹扫该装置20- 30分钟让样品冷却.然后收集所需要的7-甲基十七烷基乙氧基化物(每分子平均5乙氧基化物)产物。 To a dry 1L equipped with a nitrogen inlet tube, a mechanical stirrer, 3 neck round bottom flask and Y- shaped tubes and a gas outlet tube equipped with a thermometer was charged with the alcohol obtained from the above-steps. In order to remove traces of water objects in 80-ioox: the alcohol is sparged with nitrogen for about 30 minutes with continued nitrogen sweep, sodium metal is added as the catalyst and allowed to 120-H0X:.. was stirred under vigorous stirring melted, added over 140 minutes loop after the ethylene oxide gas while the reaction temperature was maintained 120- 140'C. adding a suitable weight (equal to five equivalents of ethylene oxide), the apparatus was purged with nitrogen for 20-30 minutes to allow the sample is cooled then collected required 7 - methylheptadecyl ethoxylate (average of 5 ethoxylates per molecule thereof) of product.

实施例IV 7-甲基十七烷基乙氣基化物(E9.0) Example IV 7- methylheptadecyl B group compound gas (E9.0) Embodiment

向干燥的1L装有氮气入口管,机械搅拌器,和装有温度计的Y-形管和气体出口管的3颈园底烧瓶中加入从上迷实施例中得到的醇. 为了除去痕量水的目的,在80-IOOC用氮气鼓泡该醇约30分钟.继续用氮气吹扫,加入金属钠作为催化剂并让其在120- 140C下搅拌熔融。 To a dry 1L equipped with a nitrogen inlet tube, 3 neck round bottom flask equipped with mechanical stirrer, and equipped with a thermometer and a gas outlet tube Y- tube was charged with the alcohol obtained in the embodiment from the fans. To remove traces of water purpose, the alcohol 80-IOOC bubbled with nitrogen for about 30 minutes. continue purged with nitrogen, sodium metal is added as the catalyst and allowed to melt with stirring at 120- 140C. 在剧烈搅拌下,在140分钟内加入环氧乙烷气体同时将反应温度保持120- 140t:。 Under vigorous stirring, ethylene oxide gas is added in 140 minutes while keeping the reaction temperature 120- 140t :. 加入合适重量(等于9.0当量的环氧乙烷)之后, 用氮气吹扫该装置20- 30分钟让样品冷却。 After adding a suitable weight (equal to 9.0 equivalents of ethylene oxide), the apparatus was purged with nitrogen for 20-30 minutes to allow the sample is cooled. 收集所需要的7-甲基十七烷基乙氧基化物(每分子平均9.0乙氧基化物)产物. Collecting the desired 7-methyl heptadecyl ethoxylate (average of 9.0 ethoxylates per molecule thereof) of product.

实施例V Example V

用下面方法将下面的Shell Research试验醇样品乙氧基化(平均 By the following method to test the following Shell Research alcohol samples ethoxylate (average

2.5乙氧基化度)。 2.5 degree of ethoxylation).

<table>table see original document page 30</column></row> <table> <Table> table see original document page 30 </ column> </ row> <table>

向干燥的250ml的装有氮气入口管,机械搅拌器,和装有温度计的Y -形管和气体出口管的3颈园底烧瓶中加入上述的C16斷48.4g, 0.2mol)。 To a dry 250ml fitted with a nitrogen inlet tube, a mechanical stirrer, a thermometer, and with Y - C16 was added the above 3-neck round bottom flask and a gas outlet tube down tube 48.4g, 0.2mol). 为了除去痕量水的目的,在80-IOOX:用氮气鼓泡该醇约30分钟.继续用氮气吹扫,加入金属钠(0.23g, O.Olmol)作为催化剂并让其在120-140C下搅拌熔融.在剧烈搅拌下,在140分钟内加入环氧乙烷气体(22g, 0. 5mo1)同时将反应温度保持在120- 140C. 加入合适重量环氧乙烷(每分子2. 5乙氧基化物)之后,用氮气吹扫该装置20- 30分钟让样品冷却.在氮气下将金黄色的液体产物(69g, 0. 196mol)装入瓶中. For the purpose of removing traces of water in 80-IOOX:. The alcohol is sparged with nitrogen for about 30 minutes with continued nitrogen purge, was added sodium metal (0.23g, O.Olmol) as a catalyst at 120-140C and allowed molten stirring. under vigorous stirring, ethylene oxide gas (22g, 0. 5mo1) over 140 minutes while the reaction temperature was maintained at 120- 140C. suitable wt added ethylene oxide (2.5 per molecule ethoxyethyl after the base compound), the apparatus was purged with nitrogen for 20-30 minutes to allow the sample was cooled under nitrogen golden liquid product (69g, 0. 196mol) into the bottle.

下面的2种表征本发明表面活性剂组合物中支化的分析方法是有用的: Characterized by the following two kinds of branching in a composition analysis of surfactants useful in the present invention is:

1) 在烷氧基化前分离和确定脂肪醇中的组分.用GC/MS技术确定在前体脂肪醇材料中的支链位置和长度[见:DJ Harvey, Bio鹏d, Environ. Mass Spectro迈(1989). 18(9), 719-23; DJ Harvey, JM Tiffany, J. Chromatogr. (1984), 301(1), 173— 87; KA Karlsson, BE Samuelsson, G. 0. Steen, Che迈. Phys. Lipids(1973), 11(1), 17—38]. 1) Isolation and identification of aliphatic alcohol components prior art alkoxylation MS determined by GC / branch positions and lengths [see the precursor fatty alcohol materials:.. DJ Harvey, Bio Peng d, Environ Mass Spectro step (1989) 18 (9), 719-23;. DJ Harvey, JM Tiffany, J. Chromatogr (1984), 301 (1), 173- 87;. KA Karlsson, BE Samuelsson, G. 0. Steen, Che step. Phys. Lipids (1973), 11 (1), 17-38].

2) 在烷氧基化前用MS/MS技术确定分离了的脂肪醇组分.对预先 2) prior to alkoxylation by MS / MS techniques to determine the fatty components isolated. For pre

分离了的脂肪醇组分也可用离子喷雾_ MS/MS或FAB - MS/MS技术确定支链的位置和长度. Isolated fatty alcohol components may also be used _ ion spray MS / MS or FAB - determining the position and length of the branched MS / MS techniques.

一旦确定了分离开的醇组分,该分离开的醇的烷氧基化可得到对标定和解释中链支化的伯烷基聚氧化烯表面活性剂的GC色谱有用的标准. Once separated from the alcohol component, alkoxylated alcohols obtained the separated calibration and interpretation of mid-chain branched primary alkyl polyoxyalkylene surfactants useful criteria GC chromatogram.

根据通常的方法,例如在"Bailey's Industrial Oil and Fat Products" , Vol. 2,第四版,Daniel Svern编,pp. 440-441中概述的方法,可以从前体脂肪醇混合物的羟基值计算本文中的支链伯烷基聚氧化烯的平均总碳原子。 The conventional method, for example. 2, Fourth Edition, Daniel Svern compiled in "Bailey's Industrial Oil and Fat Products", Vol, process pp. 440-441 outlined, from the front of the hydroxyl value thereof is calculated herein, a mixture of fatty alcohols the branched primary alkyl poly average total carbon atoms of the alkylene oxide.

工业适用性 Industrial Applicability

本文中类型的支链伯聚氧化烯表面活性剂可以用于所有形式的清洗组合物.因此本发明的洗涤剂组合物也可以含有附加的洗涤剂组分.这些附加组分的确切性质和其加入的含量取决于组合物的物理形式和使用组合物进行的洗涤操作的确切性质,较长链的衍生物比预期的溶解性更大而较短链的衍生物比预期的清洗性更好.本文中的清洗组合物包括,但不限于,粒状、条状和液体洗衣洗涤剂;液体手洗餐具组合物;液体、凝胶和条状个人清洗产品;洗发剂;牙粉;硬表面清洗剂等.上述组合物可以含有各种常规的洗涤組分. Of the type described herein branched primary polyoxyalkylene surfactant may be used for all types of cleaning compositions. Thus the detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components and their added depends on the precise nature of the washing operation the content of the physical form of the composition and use of the composition will be, the longer chain derivatives greater solubility better than shorter chain derivatives contemplated than expected cleaning properties. cleaning compositions herein include, but are not limited to, granular, bar and liquid laundry detergent; liquid hand dishwashing compositions; liquid, gel strips, and personal cleansing products; shampoos; dentifrices; hard surface cleaning agents the above composition may contain various conventional detergent ingredients.

下面列出的这些组分是为了便于配方设计师,而不是对可与本文中的支链的表面活性剂一起使用的各类组分的限制。 These components are listed below for convenience of the formulator, and not limitation of various types of components may be used with surfactants herein branched chain. 本发明的組合物优选含有一种或多种附加的洗涤剂組分,其选自:表面活性剂,助洗剂,碱性体系,有机聚合物,抑泡剂,污垢悬浮和抗再沉积剂,和腐蚀抑制剂。 The compositions of the invention preferably contain one or more additional detergent components selected from: surfactants, builders, alkaline systems, organic polymers, suds suppressors, soil suspension and anti-redeposition agents , and corrosion inhibitors.

漂白化合物-漂白剂和漂白活化剂-本文中的洗涤剂组合物优选还含有漂白剂或含有漂白剂和一种或多种漂白活化剂的漂白组合物. 漂白剂的量一般是洗涤剂组合物的约1-30%,更一般是约5-20%, 尤其是用于织物洗涤.如果存在的话,那么漂白活化剂的量一般是包括漂白剂加漂白活化剂的漂白组合物的约0.1- 60%,更一般是约0.5 - 40 % 。 Bleaching Compounds - Bleaching Agents and Bleach activators - The detergent compositions herein preferably further contain bleaching agents or bleaching compositions containing bleaching agent and one or more bleach activators typically an amount of bleach detergent composition about 1-30%, more typically about 5-20%, especially for fabric laundering. If present, the amount of bleach activators typically include bleach plus bleach activator bleaching composition is about 0.1 60%, more typically from about 0.5 - 40%.

用于本文中的漂白剂可以是任何对在织物洗涤、硬表面清洗,或者其它现在已知或将知的洗涤目的中的洗涤剂组合物有用的漂白剂。 Bleaching agents used herein can be any of the known object in the wash detergent composition useful for fabric washing, hard surface cleaning, or other now known or bleach. 这些包括氧漂白剂以及其它漂白剂.本文中可以使用过硼酸盐漂白 These include oxygen bleaches as well as other bleaching agents. Herein may be used perborate bleach

剂,例如,过硼酸钠(如一水合物或四水合物)。 Agents, e.g., sodium perborate (e.g., mono- or tetra-hydrate).

另一类可不受限制使用的漂白剂包括过羧酸漂白剂和其盐.这类 Another class of unrestricted use of bleaching agents include percarboxylic acid bleaching agents and salts thereof. Such

试剂的合适的例子包括:单过氧邻笨二甲酸镁六水合物、间氯过笨甲酸、4-壬氨基-4-氧代过氧丁酸和二过氧十二烷双酸的镁盐.这样的漂白剂公开于US4483781 ( Hartman, 1984年11月20曰颁布)、 美国专利申请740446C Burns等人,1985年6月3日申请)、EP0133354 Examples of suitable reagents include: monoperoxyphthalate hexahydrate, magnesium stupid acid, m-chloroperbenzoic acid stupid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxy dodecanedioic acid, magnesium salt such bleaching agents are disclosed in US4483781 (Hartman, 1984 November 20, said promulgated), U.S. Patent application No. 740446C Burns et al, June 3, 1985 application), EP 0,133,354

(Banks等人,1985年2月20日公开)和US4412934 ( Chung等人, 1983年11月1日颁布)中.非常优选的漂白剂也包括如在US4634551 (Banks et al., February 20, 1985 Publication) and US4412934 (Chung et al, 1 November 1983 issued) in. Highly preferred bleaching agents also include, for example in US4634551

(Burns等人,1987年1月6日颁布)中所迷的6-壬氨基-6-氧代过氧己酸。 (Burns et al., January 6, 1987 issued) as fans 6-nonylamino-6-oxoperoxycaproic acid.

也可以使用过氧漂白剂.合适的过氧漂白剂化合物包括:碳酸钠过氧水合物和等价的"过碳酸盐"漂白剂、焦裤酸钠过氧水合物、尿素过氧水合物、和过氧化钠.本文中也可以使用过疏酸盐漂白剂(例如,0X0NE, DuPont工业生产). Peroxygen bleaching agents can also be used Suitable peroxygen bleaching compounds include: sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate pants, urea peroxyhydrate , and sodium peroxide. herein may be used hydrophobic bleach salts (e.g., 0X0NE, DuPont industrial production).

优选的过碳酸盐漂白剂包括平均粒径是约500- 1000微米的干顆粒,不多于约10% (重量)的所述颗粒小于约200微米和不多于约10 % (重量)的所述顆粒大于约1250徵米.任选地,过碳酸盐可以用硅酸盐、硼酸盐或水溶性表面活性剂涂覆。 A preferred percarbonate bleach comprises an average particle size of about 500 to 1000 microns dry particles, the particles are more than about 10% (by weight) less than about 200 microns and no more than about 10% (by weight) of said particles being larger than about 1,250 meters intrinsic optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactant coating. 过碳酸盐可以从各种商业来源如FMC、 Solvay和Tokai Denka购得. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

也可以使用漂白剂的混合物. Mixture of bleach may be used.

过氧漂白剂、过硼酸盐、过碳酸盐等优选与漂白活化剂组合在一起,这导致在含水溶液(即在洗涤过程中)中就地产生相应于漂白活化剂的过氧酸.活化剂的各种非限制性例子公开于US4915854 ( Mao 等人,1990年4月10日颁布)和US4412934中.壬酰氧基笨磺酸盐(NOBS)和四乙酰基乙二胺(TAED)活化剂是典型的,也可以使用其混合物.对于本文中有用的其它的一般漂白剂和活化剂参见US4634551. Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators together, which results in an aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the in situ bleach activator in. various nonlimiting examples of activators are disclosed in US4915854 (Mao et al, April 10, 1990 issued), and in US4412934. nonanoyloxybenzenesulphonate stupid sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used for other general bleaches and activators useful herein, see also U.S. 4,634,551.

非常优选的酰氨基衍生的漂白活化剂是下式的那些: Highly preferred amido-derived bleach activators are those of the formulas:

RlN (R5) C (0) R2C (0) L或R力(0) N (R5) R2C (0) L 其中W是含有约6- 12个碳原子的烷基,W是含有1-约6个碳原子 RlN (R5) C (0) R2C (0) L or R Force (0) N (R5) R2C (0) L wherein W is an alkyl group containing from about 6 to 12 carbon atoms, W contains 1 to about 6 carbon atoms

的亚烷基,^是氲或含有约1-IO个碳原子的烷基、芳基、或烷芳基, L是任何合适的离去基团.离去基闭是任何由于过水解阴离子亲核进攻漂白活化剂而从漂白活化剂上被替换的基团.优选的离去基团是苯基磺酸盐. Alkylene group, or Yun ^ is an alkyl group containing from about 1-IO carbon atoms, aryl, or alkaryl group, L is any suitable leaving group. The leaving group is any closed by the perhydrolysis anion pro nucleophilic attack bleach activator is replaced from the bleach activator group. a preferred leaving group is phenyl sulfonate.

上式的漂白活化剂的优选例子包括:如在本文引作参考的US4634551中描述的(6-辛酰氨基己酰基)氧化苯磺酸盐、(6-壬酰氨基己酰基)氧化苯磺酸盐、(6-癸酰氨基己酰基)氧化笨磺酸盐和其混合物。 Preferred examples of bleach activators of the above formulas include: as described (6-oct-caproyl) in US4634551 incorporated herein by reference in oxybenzenesulfonate, (6-nonyl-caproyl) oxide benzenesulfonic salt, (6-decanamido-caproyl) stupid oxide sulfonates, and mixtures thereof.

另一类漂白活化剂包括由Hodge等人在US4966723 ( 1990年10 月30日颁布)中公开的笨并嚼嚷型活化剂,该文献引入本文作为参考.非常优选的笨并嫩秦型活化剂是: Another class of bleach activators comprises US4966723 (1990 issued 30 dated 10 years) by a disclosed by Hodge et al in stupid shouting activators and chewing, which is incorporated herein by reference. Highly preferred stupid tender and Qin activators Yes:

又一类优选的漂白活化剂包括跣基内酰胺活化剂,尤其是如下式的酰基己内酰胺和酰基戊内乾胺: A further class of preferred bleach activators includes the Municipal yl lactam activators, especially the dry amine of the formula acyl caprolactams and acyl valerolactams:

0 0

0 C—CH2—CH2 0 C-CH2-CH2

a II I \ a II I \

、CH2—CH2Z , CH2-CH2Z

0 0

0 C—CH广CH2 0 C-CH wide CH2

R6—C一N R6-C-N

CH之一CH之 One of CH CH

其中R6是H或含有1-约12个碳原子的烷基、芳基、烷氧芳基或烷芳基。 Wherein R6 is H or an alkyl group containing 1 to about 12 carbon atoms, aryl, alkoxyaryl or alkaryl group. 非常优选的内酰胺活化剂包括:笨甲跣基己内酰胺、辛酰基己内酰胺、3,5,5-三甲基己酰基己内酰胺、壬跣基己内酰胺、癸酰基己内觥胺、十一碳烯酰基己内酰胺、笨甲酰基戊内跣胺、辛酰基戊内酰胺、 癸酰基戊内酰胺、十一碳烯酰基戊内酰胺、壬跣基戊内酰胺、3,5,5 -三甲基己酰基戊内酰胺和其混合物。 Highly preferred lactam activators include: Municipal stupid methyl caprolactam, octanoyl caprolactam, 3,5,5-trimethyl hexanoyl caprolactam, nonanoyl caprolactam Municipal, Gong amine decanoyl caprolactam, undecenoyl caprolactam , the amine Municipal Ben-formylvalerate, acyl valerolactam octanamide, decanoyl pentyl lactam, acyl valerolactam undecylenamide, pentyl nonyl Municipal lactam, 3,5,5 - trimethyl hexanoyl valerolactam amides and mixtures thereof. 还参见美国专利4545784 (Sanderson, 1985年10月8曰颁布)(该文献引入本文作为参考), See also U.S. Patent No. 4545784 (Sanderson, 1985 promulgated said October 8) (which is incorporated herein by reference),

它公开了酰基己内酰胺,包括吸附在过硼酸钠上的苯甲酰基己内酰胺。 Which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed on the sodium perborate.

除了氧漂白剂以外的漂白剂也是本领域已知的并且可以在本文中使用。 Bleaching agents other than oxygen bleaching agents are also known in the art and may be used herein. 特別关心的一类非氧漂白剂包括光活化漂白剂,例如磺化的锌 One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc

和/或铝舦菁.参见1977年7月5日授权给Holco迈be等人的US 4033718.如果使用的话,洗涤剂组合物一般含有约0. 025- 1.25%(重量)的这样的漂白剂,尤其是橫化的锌鈦菁. And / or aluminum phthalocyanine Tai Referring authorized July 5, 1977 to be step Holco et al US 4033718. If used, detergent compositions will typically contain from about 0.5 025 1.25% (by weight) of such bleaches , in particular of cross-zinc phthalocyanine.

如果需要,漂白化合物可以用锰化合物催化.这样的化合物是本领域已知的并且包括:例如,公开于美国专利5246621; 5244594; 5194416; 5114606;和欧洲专利申请公开号549271A1、 549272Al、 544440A2、和544490A1中的锰基催化剂。 If desired, the bleaching compounds can Such compounds are manganese catalytic compounds known in the art and include: for example, disclosed in U.S. Patent No. 5,246,621; 5,244,594; 5,194,416; 5,114,606; and European Patent Application Publication No. 549271A1, 549272Al, 544440A2, and manganese-based catalyst 544490A1. 这些催化剂的优选例子包括:MnIV2(u- 0)3(1,4,7-三甲基-1,4,7-三氮杂环壬烷)广(PF6)2、 Mnm2 (u - 0) i(u - 0Ac)2 (1, 4, 7 -三甲基-1, 4, 7 -三氮杂环壬烷)2 -(C104)2、 MnIV4(u-0)6(1,4,7-三氮杂环壬烷)广(C104)4、 MnmMnIV4(u -Oh(u- 0Ac)2 (1,4, 7-三甲基-1,4, 7-三氮杂环壬烷)2-(C104)3 、 MnIV(l,4,7,-三甲基-1,4,7 -三氮杂环壬烷)-(0CH3)s(PF6)、和其混合物.其它的金属基漂白活化剂包括在美国专利4430243和5114611中公开的那些.使用具有各种增强漂白作用的络合物配位体的锰在下面美国专利中有报道:4728455; 5284944; 5246612; 5256779; 5280117; 5274147; 5153161;和5227084. Preferred examples of these catalysts include: MnIV2 (u- 0) 3 (1,4,7- trimethyl-1,4,7-triazacyclononane) wide (PF6) 2, Mnm2 (u - 0) i (u - 0Ac) 2 (1, 4, 7 - trimethyl-1, 4,7 - tris triazacyclononane) 2 - (C104) 2, MnIV4 (u-0) 6 (1,4, 7- triazacyclononane alkyl) wide (C104) 4, MnmMnIV4 (u -Oh (u- 0Ac) 2 (1,4, 7- trimethyl-1,4, 7-triazacyclononane) 2- (C104) 3, MnIV (l, 4,7, - trimethyl -1,4,7 - Tri-triazacyclononane) - (0CH3) s (PF6), and mixtures thereof other metal-based. bleach activators include those disclosed in U.S. Patent No. 4,430,243 and 5,114,611 have enhanced bleaching use manganese complexes of the various ligands are reported in the following U.S. patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147 ; 5,153,161; and 5,227,084.

作为实际情况,而非限制方式,可以调节本文的组合物和方法以便在洗涤水溶液中提供至少约1千万分之一份的活性漂白催化剂物质,在洗涤液中,优逸提供约0. lppm- 700卯m,更优选约1 - 50ppm 的催化剂物质. As a practical matter, and not by way of limitation, the compositions and methods may be adjusted herein to provide at least about 1 per ten million of the active bleach catalyst a substance in the aqueous washing liquor, the wash liquor, preferably provide from about 0. lppm Yat - 700 d m, more preferably from about 1-- 50ppm of catalyst species.

本文中有用的钴漂白催化剂是已知的并且描述于,例如,ML Tobe, "Base Hydrolysis of Transition-Metal Complexes" , Adv. Inorg. Bioinorg Mech. , ( 1983), 2,第1-94页中.本文中有用的最优选的钴催化剂是具有式[Co (NH3) 50Ac]TV的钴五胺乙酸盐,其中 Useful herein are cobalt bleach catalysts are known and described, for example, ML Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg Mech., (1983), 2, pages 1-94 . useful herein most preferred cobalt catalysts having the formula [Co (NH3) 50Ac] TV cobalt pentaamine acetate salts, wherein

"OAc"表示乙酸根部分,"Ty"是阴离子,尤其是钴五胺乙酸盐氯化物,[Co(NlU 60Ac]Cl2;以及[Co(NHa)sOAc] (0Ac)2:[Co(NH3)s0Ac] "OAc" represents an acetate portion, "Ty" is an anion, especially cobalt pentaamine acetate chloride, [Co (NlU 60Ac] Cl2; as well as [Co (NHa) sOAc] (0Ac) 2: [Co (NH3 ) s0Ac]

(PF6) 2; [Co ( NH3) 50Ac] ( S04) ; [Co ( NH3) 50Ac] ( BF4) 2;和[Co (PF6) 2; [Co (NH3) 50Ac] (S04); [Co (NH3) 50Ac] (BF4) 2; and [Co

(NH3) 50Ac] (N03) 2(本文中的"PAC"). (NH3) 50Ac] (N03) 2 (herein "PAC").

这些钴催化剂是容易用已知的方法制备的,例如在下面文献中所 These cobalt catalysts are readily prepared by known methods, for example in the following literature

教导的:Tobe的文章中和其中引用的参考文献中,US4810410( Diakun 等人,1989年3月7曰颁布),.T. Ch柳,Ed, (1989). 66 (12). 1043 -45:无机化合物的合成和表征(The Synthesis and Characterization of Inorganic Compounds ) , WL Jolly (Prentice-Hall; 1970), pp. 461-3: Inorg. Ch棚.,迅1497 -1502(1979): Inorg. Chem., 2881 - 2885(1982); Inorg. Che迈.. Taught: References Tobe article and cited therein, US4810410 (Diakun et al., 1989 March 7, said promulgated) ,. T Ch Liu, Ed, (1989) 66 (12) 1043 -45... : synthesis and Characterization of inorganic compound (the synthesis and Characterization of inorganic compounds), WL Jolly (Prentice-Hall; 1970), pp 461-3:. Inorg Ch shed, Xun 1497 -1502 (1979): Inorg Chem... ., 2881 - 2885 (1982); Inorg Che mai ...

2023 - 2025(1979): Inorg. Sythesis, 173 - 176(1960):和Journal of Physical Chemistry,旌22 - 25(1952)• 2023 - 2025 (1979): Inorg Sythesis, 173 - 176 (1960):. And Journal of Physical Chemistry, Jing 22 - 25 (1952) •

作为实际情况,而非限制方式,可以调节本文的组合物和洗涤方法以便在含水洗涤介质中提供至少约1千万分之一份的活性漂白催化剂物质,优选在洗涤液中提供约0.01-25卯迈,更优选约0.05-10卯m,最优选约0. l-5ppm的漂白催化剂物质.为了在自动洗涤方法的洗涤液中得到这样的含量,按清洗组合物重量计, 一般本文中的组合物含有约0.0005- 0.2%,更优选约0. 004- 0.08%的漂白催化剂, As a practical matter, and not by way of limitation, the compositions and methods described herein may be washed adjusted to provide at least about 1 per ten million of the active bleach catalyst a substance in the aqueous washing medium, preferably from about 0.01 to 25 provided in the wash liquor step d, more preferably from about 0.05 to 10 d m, most preferably from about 0. l-5ppm bleach catalyst species. to wash liquid obtained in an automatic washing process such content, by weight of the cleaning composition, generally herein composition contains about 0.0005 to 0.2%, more preferably from about 0. 004 0.08% bleach catalyst,

尤其是锰或钴催化剂. Especially manganese or cobalt catalysts.

座-为了各种目的,包括从被洗物去除蛋白质基、碳水化合物基或甘油三酯基污斑,为了防止短效染料在织物洗涤中转移和为了织物整新,本发明的洗涤剂组合物优选包括酶.合适的酶包括任何合适来源例如植物、动物、细菌、霉菌和酵母来源的蛋白酶、淀粉酶、脂肪酶、纤维素酶、过氧化物酶,和其混合物。 Block - for various purposes including laundry is removed from the protein-based, carbohydrate-based, or triglyceride-based stains, to prevent fugitive dye transfer, and for fabric washing fabrics refurbishment, the detergent compositions of the present invention preferably including enzymes. suitable enzymes include any suitable source such as vegetable, animal, bacterial, fungal and yeast-derived proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof. 优逸的逸择受这些因素的影响:例如最佳pH活性和/或稳定性,热稳定性和对活性洗涤剂、助洗剂等的稳定性。 Optional preferred Yi Yi affected by these factors: for example, the optimum pH stability of activity and / or stability optima, thermostability, and stability to active detergents, builders and so on. 在这方面,细菌和霉菌酶是优选的,例如细菌淀粉酶和蛋白酶,和霉菌纤维素酴. In this respect bacterial and fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases yeast.

如本文中所使用的,"洗涤酶"是指任何在洗衣、硬表面清洗或个人护理洗涤剂組合物中具有清洗、去除污斑或其它有益作用的酶. 优选的洗涤酶是水解酶,例如蛋白酶、淀粉酶和脂肪酶.用于洗衣目的优选酶包括,但不限于,蛋白酶、纤维素酶、脂肪酶和过氧化物酶。 As used herein, "Detersive enzyme" means any enzyme in a laundry, hard surface cleaning or personal care detergent composition having a cleaning, stain removing or otherwise beneficial effect. Preferred detersive enzymes are hydrolases, e.g. proteases, amylases and lipases. preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. 用于自动洗涤餐具非常优选的是淀粉酶和/或蛋白酶,包括目前市场上可得到类型和改进类型,该改进类型通过不断的改进尽管与漂白剂更相容,但仍然有一定程度的漂白剂减活敏感性. Highly preferred for automatic dishwashing are amylases and / or proteases, including currently available types and improved types on the market, although this improvement is more compatible with the type of bleach through continuous improvement, but still have some degree of bleach deactivation susceptibility.

一般以足以提供"清洗有效量"的量将酶加入到洗涤剂或洗涤剂 Usually an amount sufficient to provide a "cleaning effective amount" will be added to the detergent or detergent enzyme

添加剂组合物中。 Additive composition. 术语"清洗有效量"是指能够对被洗物例如织物、 餐具等产生清洗、污斑去除、污垢去除、增白、去味或新度改进作用的量.实际上对于目前市场上的制剂, 一般的量为每克洗涤剂组合物 The term "cleaning effective amount" refers to an amount of the laundry is generated, for example of fabrics, dishes and other cleaning, stain removal, soil removal, whitening, deodorizing, or improving effect of the new practice for the formulation currently on the market, compositions generally in an amount per gram of the detergent composition

最高达约5mg(重量),更一般0. 01 - 3mg活性酶。 Up to about 5mg (by weight), more typically 0. 01 - 3mg active enzyme. 换句话说,本文中的组合物一般含有0.001-5% (重量),优选0.01-1% (重量) 的商品酶制剂.在上述商品制剂中蛋白酶通常存在的量为足以提供每克组合物0.005- 0.1Anson单位(AU)的活性,对某些洗涤剂,例如自动洗餐具的洗涤剂,为了使提供的非催化活性材料的总量最小并因此改进成斑/成膜或其它最终结果,理想的是提高商品制剂的活性酶含量.在高浓缩洗涤剂配方中较高活性物含量也是理想的. In other words, the compositions herein generally contain from 0.001 to 5% (by weight), preferably 0.01 to 1% (by weight) of a commercial enzyme preparation. In the commercial preparations Protease enzymes are usually present in an amount sufficient to provide a composition of 0.005 g of - 0.1 Anson units (AU) of activity, certain detergents, dishwashing detergents such as automatic washing, in order that the total amount of non-catalytically active materials and thereby improve the minimum provided spotting / filming or other end-results, over It is to increase the active enzyme content of the commercial preparations in highly concentrated detergent formulations high active content is also desirable.

蛋白酶的合适例子是从特定的枯草芽孢杆菌和地衣形芽孢杆菌菌抹中得到的枯草溶菌素. 一个合适的蛋白酶是从芽孢杆菌菌抹中得到的,其在pH8- 12的范围内具有最大活性,由丹麦的Novo Industries A/S (下文中为"Novo")研制并以注册商标ESPERASE销售.在Novo 的英国专利说明书1,243,784中描述了该酶和类似酶的制备。 Suitable examples of proteases are from Bacillus subtilis and specific B. licheniformis bacteria obtained wipe subtilisin. A suitable protease is obtained from a strain of Bacillus in wiping, having maximum activity in the range of pH8- 12 , Denmark developed by Novo Industries a / S (hereinafter "Novo") and sold under the registered trade mark ESPERASE. describes the preparation of this enzyme and analogous enzymes is described in British Patent specification 1,243,784 Novo's. 其它合适的蛋白酶包括Novo的ALCALASER和SAVINASEr, International Bio - Synthetics , Inc.(荷兰)的MAXATASER以及1985年1月9日的欧洲专利申请130756A中公开的蛋白酶A和1987年4月28日的EP 303, 761A和1985年1月9日的EP 130756A中的蛋白酶B.还参见描述于Novo的W09318140A中的从芽孢杆菌属NCIMB 40338得到的高pH蛋白酶。 Other suitable proteases include Novo and the ALCALASER SAVINASEr, International Bio - Synthetics, MAXATASER Inc. (The Netherlands) and Protease A European Patent Application No. 130756A 1985 January 9 years. 1 disclosed in EP 1987 and February 28 years. 4 303 , 761A and EP 130756A 1985 January 9 years. 1 protease B. see also described in W09318140A to Novo genus Bacillus NCIMB 40338 obtained in a high pH protease. 包括蛋白酶、 一种或多种其它酶和可逆蛋白酶抑制剂的酶洗涤剤描迷于Novo的W09203529A中。 Comprising protease, one or more other enzymes, and a reversible protease inhibitor of the enzyme was washed with Ji described in W09203529A fans to Novo. 其它优选的蛋白酶包括Procter & Gamble的W09510591A中的那些。 Other preferred proteases include those to Procter & Gamble in W09510591A. 当需要时,可以得到降低吸附性和增加水解性的蛋白酶,如Procter & Gamble的W09507791所述的. 适合于本文洗涤剂中的重組体胰蛋白酶状的蛋白酶描迷于Novo的W09425583中. When desired, it can be reduced adsorption and increased hydrolysis of the protease, as described in W09507791 to Procter & Gamble. Protease suitable for recombinant trypsin-like protease in the detergent herein described in W09425583 fans to Novo.

更详细地, 一种特别优选的称为"蛋白酶D"的蛋白酶是具有在自然界中没有发现的氨基酸序列的羰基水解酶变体,它是通过下面方式从前体羰基水解酶衍生的:通过在所述羰基水解酶等价于+76位置,优选也在按照解淀粉芽孢杆菌枯草溶菌素的编号等价于选自+ 99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, Protease, one particularly preferred is referred to in more detail "Protease D" is an amino acid sequence not found in nature in the carbonyl hydrolase variant, which is obtained by the following manner from a precursor carbonyl hydrolase derived: by the said carbonyl hydrolase enzyme is equivalent to position +76, preferably also according to Bacillus amyloliquefaciens subtilisin equivalent to the number of selected + 99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206,

+ 210, +216, +217, +218, + 222, + 260> + 265,和/或+ 274 的一种或多种氨基酸残基位置,用不同的氨基酸代替多种氨基酸残基,如在Genencor International的TO 95/10615 ( 1995年4月20 曰公开)中所描述的。 +210, +216, +217, +218, + 222, + 260> +265, and / or one kind + 274 or more amino acid residue positions, replaced with a different amino acid residues more, as Genencor International, TO 95/10615 (1995 April 20, said the public) as described.

有用的蛋白酶也描述于下面的PCT公开中:1995年11月9日公开的Procter & Gamble Company的W095/30010、 1995年11月9曰公开的Procter & Gamble Co即any的f095/30011、 1995年11月9 曰公开的Procter & Gamble Company的W095/29979. Useful proteases are also described in the following PCT Publication: 1995 November 9 public Procter & Gamble Company of W095 / 30010, 1995 November 9, saying the disclosure of Procter & Gamble Co, ie any of f095 / 30011, 1995 November 9, saying public Procter & Gamble Company of W095 / 29979.

适合于本文中尤其是但不限于自动洗餐具目的的淀粉酶包括,例如,在GB 1296839 (Novo)中描述的a -淀粉酶,RAPIDASES (International Bio- Synthetics, Inc,)和TERMAMYI/ ( Novo)。 Herein particularly suitable for, but not limited to automatic dishwashing purposes amylases include, for example, A is described in GB 1296839 (Novo) - amylase, RAPIDASES (International Bio- Synthetics, Inc,) and TERMAMYI / (Novo) . Novo的FUNGAMYl/是特别有用的.改进稳定性,例如氧化稳定性的酶工程是已知的.见,例如,J. Biological Chem., Vol. 260, No. 11, 1985年6月,卯6518- 6521.本发明組合物的某些优逸实施方案可利用在洗涤剂如自动洗餐具类型洗涤剂中具有改进稳定性,尤其是改进氧化稳定性的淀粉酶,其是相对于1993年商业使用的TERMAMYl/参考点测定的.本文中这些优选的淀粉蘇具有"稳定性增强"的淀粉酶的特性,其特征至少为下面一种或多种稳定性的可测量的改进:例如对在pH为9- 10的緩冲溶液中的过氧化氢/四乙酰基乙二胺的氧化稳定性;例如在普通洗涤温定如约60t:下的热稳定性;或例如pH为约8 - ll的碱性稳定性;所有的测量均是与上面指出的参考淀粉酶比较测定的。 To Novo FUNGAMYl / is particularly useful. Improved stability, e.g. Engineering of enzymes oxidative stability is known. See, e.g., J. Biological Chem., Vol. 260, No. 11, 1985 June 6518 d - Yi 6521. certain preferred embodiments of the composition of the present invention may be utilized with improved stability in detergents such as automatic dishwashing types of detergents, especially improved oxidative stability amylases, which is with respect to commercial use in 1993 . the TERMAMYl / reference point measuring herein having the preferred starch Su "stability-enhanced" amylases characteristic, measurable improvement wherein at least one or more of the following stability: for example, at a pH of 9-10 in a buffer solution of hydrogen peroxide / tetraacetylethylenediamine in oxidative stability; for example, a general washing predetermined temperature such as from about 60t: thermal stability under; or for example a pH of about 8 - ll of basic stability; All measurements are indicated above with reference to amylase assay comparison. 可以使用任何现有技术公开的试验测定稳定性.见,例如公开于W09402597中的参考文献。 Stability can be measured using any test prior art disclosed. See, for example, disclosed in references W09402597. 稳定性增强的淀粉酶可以从Novo或Genencor International得到。 Stability-enhanced amylases can be obtained from Novo or Genencor International.

一类本文中非常优选的淀粉酶具有从一种或多种芽孢杆菌淀粉酶,尤其是芽孢杆菌a -淀粉酶使用定点诱变衍生的共性,而与一种、 A class of highly preferred herein amylases having from one or more of the Bacillus amylases, especially the Bacillus a - Common amylase derived using site-directed mutagenesis, and with one,

两种或多种淀粉酶菌抹是否是中间前体无关。 Two or multiple amylase strains are the immediate precursors wiping whether intermediate. 相对于上述参考淀粉酶氧化稳定性增强的淀粉酶优选用于尤其是漂白的,更优选氧漂白(与氯漂白不同)的本文洗涤剂组合物中。 With respect to the reference amylases oxidative stability enhanced amylase especially preferred for bleaching, more preferably oxygen bleaching (the chlorine bleach different) detergent compositions herein. 这样的优选的淀粉酶包括:(a) Such preferred amylases include: (a)

根据上文引入的1994年2月3日的Novo的W0 94/02597的淀粉酶, 如由突变体所进一步说明的,其中使用丙氨酸或苏氨酸,优选苏氨酸取代位于称之为TERMAMYL⑧的地衣形芽孢杆菌a -淀粉酶197位置的 The Amylase Novo, Feb. 3, 1994, in W0 94/02597 incorporated hereinabove, as further illustrated by a mutant in which, using alanine or threonine, preferably threonine referred located Bacillus licheniformis TERMAMYL⑧ a - amylase position 197

蛋氨酸残基,或类似的亲本淀粉酶,例如解淀粉芽孢杆菌、枯草芽孢 Methionine residue, or a similar parent amylase, such as B. amyloliquefaciens, B. subtilis

杆菌、或嗜热脂肪芽孢杆菌的同源位置变种构成的;(b)如Genencor International在由C. Mitchinson于1994年3月13 - 17日在207th American Chemical Society National Meeting上提交的题为"抗氧化的a-淀粉酶(Oxidatively Resistant a - Amylases)"的文章中所描述的稳定性增强的淀粉酶。 Coli, Bacillus stearothermophilus, or the homologous position variation of the configuration; (b) such as by C. Mitchinson Genencor International in March 1994 13-- 17, entitled, filed on 207th American Chemical Society National Meeting "anti stability-enhanced amylases "described in the article - oxidized a- amylase (amylases Oxidatively Resistant a). 其中提到在自动洗餐具洗涤剂中的漂白剂使ct -淀粉酶减活,但改进氧化稳定性的淀粉酶是由Genencor从地衣形芽孢杆菌NCIB8061制造的,蛋氨酸(Met)被认为是最可能被改性的残基。 Wherein said in automatic dishwashing detergents bleach so ct - amylase deactivation, but improve the oxidative stability amylases are made by Genencor from Bacillus licheniformis NCIB8061 of methionine (Met) is considered the most likely residues are modified. 在8, 15, 197, 256, 304, 366和438位一次一个地取代Met导致了特定的突变体,特别重要是M197L和M197T, M197T变体是最稳定表达的变体.在CASCADE"和SUNLIGHT8中测定稳定性;(c)本文中特别优选的淀粉酶包括在W09510603A所述的中间亲本中具有另外改性的淀粉酶变种并可从受让人Novo以DURAMYL逸得到.其它特别优选的氧化稳定性增强的淀粉酶包括在G節encor International的W09418314和Novo的WO9402597中所迷的那些.可以使用任何其它的氧化稳定性增强的淀粉酶,例如从可得到淀粉酶的已知嵌合,杂种或简单突变体亲本形式通过定点诱变衍生的。其它优选的淀粉酶改性是可以达到的。见Novo的W09509卯9A. 8, 15, 197, 256, 304, 366 and 438 once a substituted Met leads to specific mutants, particularly important being M197L and M197T, M197T variant is a variant of the most stable expressed in CASCADE "and SUNLIGHT8 Determination of stability; (c) particularly preferred herein are amylase enzymes include intermediate parent having additional modification in the W09510603A amylase variants can be obtained from the assignee, Novo Plaza to DURAMYL other particularly preferred oxidative stability. enhanced amylases include in the section G encor International W09418314 and WO9402597 to Novo as fans that may be used in any other oxidative stability-enhanced amylase, such as a chimeric amylases obtained from known, or hybrids simple mutant parent forms derived by site-directed mutagenesis. other preferred amylases modification are achievable. see W09509 d. 9A to Novo.

其它淀粉酶包括描述于W095/26397和Novo Nordisk的未结案申请PCT/DK96/00056中所述的那些酶.用于本发明洗涤剂组合物中的具体淀粉酶包括其特征为在25- 55X:的温度范围和在8- 10的pH范围下具有比Ter边amylR的比活性高至少25%的比活性的《 -淀粉酶, 它是用PhadebasR a -淀粉酶活性试验测定的.(上述Phadebas8 a -淀粉酶活性试验描述于W095/26397的9 - 10页。)还包括在本文中的是与示于参考文献的SEQ ID列表中的氨基酸序列至少80%同源的a-淀粉酶。 Other amylase enzymes include those described in W095 / 26397 and Novo Nordisk of those enzymes described in application PCT / DK96 / 00056 copending detergent compositions of the present invention comprises a specific amylases characterized in 25- 55X.: the temperature range and "having at least 25% higher than the specific activity of Ter side amylR specific activity at a pH in the range of 8-10 - amylase, which is PhadebasR a -. test amylase activity assay (described above Phadebas8 a - amylase activity described in test 9 W095 / 26397 - a 10) further included herein are the amino acid sequence shown in SEQ ID reference list of at least 80% homologous to a- amylase. 按总组合物重量计,优选将这些酶以0.00018- 0.060% 纯酶,更优选0.00024- 0.048%纯酶的量加入到洗衣洗涤剂组合物中。 By weight of the total composition, preferably these enzymes 0.00018- 0.060% pure enzyme, and more preferably an amount 0.00024- 0.048% pure enzyme was added to the laundry detergent composition.

可用于本发明中的纤维素酶包括细菌和霉菌型纤维素酶,优选最佳pH在5-9. 5之间.US4435307 ( Barbesgoard等人,1984年3月6 曰颁布)公开了从H咖icola insolens或腐质霉菌株DSM1800或属于气单胞菌属的生产纤维素酶212的霉菌生产的霉菌纤维素酶,和从 Cellulase may be used in the present invention include bacterial and fungal cellulases type, preferably between pH optimum of 5-9. 5 .US4435307 (Barbesgoard et al, 1984 promulgated said March 6) discloses a coffee from H icola insolens or Humicola strain DSM1800 or belonging to the genus Aeromonas cellulase 212-producing fungus fungal cellulase production, and from

海洋软体动物(Dolabella Auricula Solander)的肝胰腺提取的纤维素酶.合适的纤维素酶也公开于GB-A- 2075028; GB-A- 2095275 和DE - OS _ 2247832中,CAREZYME逸和CELLUZYME ® (Novo)是特别有用的'参见W09117243 (Novo)。 Marine mollusk (Dolabella Auricula Solander) extracted from the hepatopancreas of cellulase Suitable cellulases are also disclosed in GB-A- 2075028; GB-A- 2095275 and DE - OS _ 2247832 in, CAREZYME Yi and CELLUZYME ® ( Novo) is especially useful 'see W09117243 (Novo).

用于洗涤剂用途的合适的脂肪酶包括如在英国专利GB 1372034 中公开的,由假单胞菌的微生物,例如司徒茨氏假单胞菌ATCC19. 154 生产的那些.还参见在日本专利申请53, 20487 ( 1987年2月24曰特许公开)中的脂肪酶。 Suitable lipase enzymes for detergent usage include those as disclosed in British Patent GB 1372034 in the microorganism Pseudomonas, for example Pseudomonas stutzeri Stuart Heights ATCC19. 154 those produced. See also Japanese Patent Application 53, 20487 (1987 February 24, saying Laid-open) lipases. 该脂肪酶可以从Amano Pharmaceutical Co. Ltd., Nagoya, Japan以商品名Lipase P "Amano"或"Amano-P" 购得.其它合适的商售脂肪酶包括Amano-CES,来自Chr咖obacter viscosum的脂肪酶,如Chro迈obacter viscos咖var. lipolytic咖NRRLB 3673 (来自Toyo Jozo Co., Tagata , Japan );和来自US Biochemical Corp.(美国)和Disoynth Co.(荷兰)的其它Chromobacter viscos咖脂肪酶,和来自唐菖蒲假单胞菌的脂肪酶. 从H咖icola lanuginosa得到的并从Novo购得的LIP0LASE逸酶(还参见EP 341947)是用于本发明的优选脂肪酶。 The lipase may Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the trade name Lipase P "Amano" or "Amano-P" available from. Other suitable commercially available lipases include Amano-CES, from Chr of coffee obacter viscosum lipases, such as coffee Chro step obacter viscos var lipolytic coffee NRRLB 3673 (from Toyo Jozo Co., Tagata, Japan);., and from US Biochemical Corp. (USA) and other Chromobacter Disoynth Co. (Netherlands) viscos coffee lipase , and the lipase from Pseudomonas gladioli. H obtained from coffee icola lanuginosa and commercially available from Novo LIP0LASE Yi enzymes (see also EP 341947) are preferred lipases for the present invention. 对过氧化物酶稳定的脂肪酶和淀粉酶变种描述于W09414951A (Novo)中.还参见W09205249 和RD9435卯44。 Stabilized against peroxidase enzymes lipase and amylase variants described in W09414951A (Novo). See also W09205249 RD9435 and 44 d.

尽管公开了很多脂肪酶,但到现在为止仅仅发现从Humicola lanuginosa得到并在米曲酶中作为宿主生产的脂肪酶作为织物洗涤产品添加剂有广泛的应用.如上所述,它是从NovoNordisk以商品名LipolaseT"购得的.为了使脂肪酶的去污垢性能最佳,Novo Nordisk 已经制造了很多变种.如在W092/05249中所述的,与野生型的脂肪酶相比(在每升0. 075 - 2. 5迈g蛋白质的范闺比较这些酶),天然H咖icola lanuginosa脂肪酶的D96L变种去除猪油污斑的效力改进了4. 4倍. NovoNordisk在1994年3月10日公开的研究公开号35944中公开了可以以相当于每升洗涤液O. 001- 100mg( 5 - 500000LU/升)脂肪酶变种的量加入该脂肪酶变种(D96L)。在含有中链支化的伯烷基聚氧化烯表面活性剂的洗涤剂组合物中,本发明以本文中公开的方式使用低含量的D96L变种,尤其是以每升洗涤液约50- 8500LU的含量使用D96L时提供了改进织物白 Although a lot of lipase disclosed, but until now only been found from Humicola lanuginosa and Aspergillus as a host enzyme lipase produced as a fabric washing product additives are widely used. As described above, it is the tradename from NovoNordisk LipolaseT "available. in order to make the best soil removal performance of lipase, Novo Nordisk have been manufactured in many varieties. as in W092 / 05249 was used, compared to the wild-type lipase (per liter 0.075 - Fan Gui 2.5 g protein comparison step these enzymes), natural coffee icola D96L variant H lanuginosa lipase lard stain removal efficacy improves 4.4 times NovoNordisk disclosed in Research 10 March 1994 disclosed. No. 35944 discloses equivalent per liter of wash solution may be O. 001- 100mg. - the amount of lipase variant (5 500000LU / liter) was added to the lipase variant (the D96L) containing mid-chain branched primary alkyl poly the detergent composition of the alkylene oxide surfactant in the present invention in the manner disclosed herein using low levels of D96L variant, in particular, is to provide an improved fabric whiteness when the content was about 50- 8500LU per liter of wash used D96L 度维持性的益处. Maintenance of the degree of benefit.

适用于本文中的角质素酶描迷于Genencor的W08809367A中。 Suitable for use herein cutinase described in W08809367A Genencor's fans.

过氧化物餘可以与氧源例如过碳酸盐、过硼酸盐、过氧化氲等结合用于"溶液漂白"或防止在洗涤操作期间脱离的染料或颜料在洗涤溶液中从一个被洗物转移到另一个被洗物.已知的过氧化物酶包括辣根过氧化物酶、木质素蘇和商代过氧化物酶例如氯代或溴代过氧化物 I peroxides with oxygen sources, e.g., percarbonate, perborate, peroxide, in conjunction with other heavy atmosphere used for "solution bleaching" or prevented during the washing operation out of dyes or pigments in the laundry from a wash solution the laundry is transferred to another. known peroxidases include horseradish peroxidase, lignin peroxidase Su Shang e.g. chloro or bromo peroxidase

酶。 Enzyme. 含有过氧化物酶的洗涤剂組合物公开于W089099813A( 1989年10 Peroxidase-containing detergent compositions are disclosed in W089099813A (1989 October

月19日,Novo)和W08909813A ( Novo)中. May 19, Novo) and W08909813A (Novo) in.

各种酶材料以及将它们加入到合成洗涤剂组合物中的方法还公开于Ge廳cor International的簡307263A和W09307260A、 Novo的WO 8908694A和US3553139 ( 1971年1月5日颁发给McCarty等人) Wide range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in Ge cor International Office Jane 307263A and W09307260A, Novo and WO 8908694A in US3553139 (issued January 5, 1971 to McCarty et al.)

中。 in. 酶还公开于US4101457 ( Place等人,1978年7月18曰颁布)中和US4507219 ( Hughes等人,1985年3月26曰颁布)中,用于液体洗涤剂配方中的酶材料和将其加入到这样的配方中公开于US4261868 Enzymes are further disclosed in US4101457 (Place et al., 1978 July 18, said issued) and US4507219 (Hughes et al, 1985, March 26, said issued), the detergent formulations for liquid material and an enzyme is added to to such formulations are disclosed in US4261868

(Hora等人,1981年4月14曰)中.用于洗涤剂中的酶可以用各种技术稳定。 (, Hora et al., 1981, April 14, said) in. The enzyme for use in detergents can be stabilized by various techniques. 酶稳定技术公开和举例说明于US3600319 (Gedge等人, 1971年8月17日颁布)中和欧洲专利申请EP 199405和EP 200586 Enzyme stabilization techniques are disclosed and exemplified in US3600319 (Gedge et al, issued August 17, 1971) and European Patent Application EP 199405 and EP 200586

(Venegas, 1986年10月29日)中,酶稳定体系也描述于,例如US3519570中.得到蛋白酶、木聚糖酶和纤维素酶的有用的芽孢杆菌属AC13描述于W09401532A (Novo)中. (Venegas, 1986 years 10 29 May), the enzyme stabilization systems are also described, for example in US3519570. Obtained useful Bacillus proteases, xylanases and cellulases, is described in the case of AC13 W09401532A (Novo) in.

酶稳定体系-本文中的含酶组合物可以任逸地含有约0.001-10 % (重量),优选约0.005- 8% (重量),最优选约0.01-6% (重量)的酶稳定体系.该酶稳定体系可以是与洗涤酶相容的任何酶稳定体系。 Enzyme stabilization systems - enzyme-containing compositions herein may contain any of Yi about 0.001% (by weight), preferably about 0.005 to 8% (wt), most preferably from about 0.01 to 6% (by weight) of an enzyme stabilizing system. the enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme detersive enzyme. 这样的体系可以用其它配方活性物固有地来提供,或者例如由配方师或洗涤剂备用酶的制造商分别来加入.这样的稳定体系可以包括例如:钩离子、硼酸、丙二醇、短链羧酸、boronic酸,和其混合物,并根据洗涤剂组合物的类型和物理形式被设计以解决不同的稳定化问题。 Such a system may be inherently other formulation actives to provide, or be added separately, for example, the formulator or by a manufacturer of detergent enzymes such alternate stabilizing system may include for example: hooks ion, boric acid, propylene glycol, short chain carboxylic acid , boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.

一种稳定方法是在最终组合物中使用水溶性的钙和/或镁离子源(它将上述离子提供给酶)。 A stabilized approach is to use a water-soluble calcium and / or magnesium ions (which provide such ions to the above-described enzyme) in the final composition. 如果仅使用一种类型阳离子的话,那么钙离子通常比镁离子稍微更有效一些并且在本文中是优选的. 一般的洗涤剂组合物,尤其是液体组合物每升最终洗涤剂组合物包括约1-30,优选约2-20,更优选约8-12咖o1的钙离子,尽管可能有变化, 这取决于这些因素:包括加入酶的多样性、类型和含量。 If only one type of cation, then calcium ions are generally somewhat more effective than magnesium ions and are preferred in some of the herein general detergent compositions, especially liquid detergent composition per liter of the final composition comprises from about 1 -30, preferably about 2-20, more preferably about 8-12 coffee o1 calcium, although it may vary depending on such factors include: the addition of enzyme diversity type and content. 优选使用水溶性的钙或镁盐,包括,例如:氯化努、氢氧化钙、甲酸钩、苹果酸钙、马来酸钙、氲氧化钙和乙酸钙,更一般地,可以使用疏酸钙或相应于例举的钾盐的镁盐.进一步增加鈣和/或镁的含量当然也是有用的,例如促进某些类型表面活性剂的去除油脂作用. Preferably water-soluble calcium or magnesium salts, including, for example: efforts chloride, calcium hydroxide, formic acid hook, malate, calcium maleate, calcium oxide, and calcium acetate Yun, more generally, calcium may be used sparsely potassium or magnesium salts corresponding to the exemplified further increase the calcium content and / or magnesium are of course also useful, grease removal action of certain types of surfactant, for example, to promote.

另一个稳定方法是使用硼酸盐物质,见Severson的US4537706. 当使用时,硼酸盐稳定剂的含量最高达组合物的10%或更高,但更一般是最高达约3% (重量)的硼酸或其它硼酸盐化合物,例如硼砂或正硼酸盐适用于液体洗涤剂使用。 Another stabilizing approach is by use of borate species. See Severson, US4537706. When used, the content of borate stabilizers of up to 10% or more of the composition, but more usually up to (by weight) from about 3% boric acid or other borate compounds such as borax or orthoborate salts suitable for liquid detergent use. 可以用取代的硼酸例如笨基硼酸, 丁烷硼酸,对溴代苯基硼酸或类似物代替硼酸,并且尽管使用这样的取代的硼衍生物,但可以降低洗涤剂组合物中的总硼含量。 Substituted boric acids may be used e.g. stupid acid, butane boronic acid, p-bromo phenylboronic acid in place of boronic acid, or the like, and while the use of such substituted boron derivatives, but can reduce the total boron content of the detergent composition.

某些清洗組合物例如自动洗餐具组合物的稳定体系还可以含有0 -约10% (重量),优选约0.01-6% (重量)的氯漂白剂清除剂, 加入该清除剂以便防止存在于很多水源中的氯漂白剂物质破坏和使醃失活,特别是在碱性条件下.尽管在水中的氯含量是很小的, 一般在约0.5ppm- 1.75ppm的范围,但是在餐具或织物洗涤期间与酶接触的总水量中的有效氯会是较大量的,因此在使用中的酶稳定性有时有问题.由于过硼酸盐或过碳酸盐(其具有与氯漂白剂反应的能力)可以存在于某些本发明的組合物中,其量与蘇稳定体系是分开来计的,所以通常并不需要使用另外的氯稳定剂,但使用氯稳定剂可以得到改进的结果。 Some stabilizing system cleaning compositions such as automatic dishwashing composition may also contain 0 - about 10% (by weight), preferably from about 0.01 to 6% (by weight) of chlorine bleach scavengers, added to prevent the scavenger is present in the many physical destruction of chlorine bleach and water to make pickled inactivation, especially under alkaline conditions While chlorine content in the water is very small, typically in the range of about 0.5 ppm to 1.75 ppm, but in the fabric or dishware the total amount of water in contact with the enzyme during washing in a relatively large amount of chlorine would, therefore enzyme stability in-use is sometimes problematic. Since perborate or percarbonate (which have the ability to react with chlorine bleach ) may be present in certain compositions of the present invention in an amount and Su stabilizing system is separate meter, it is generally not necessary to use additional stabilizers chlorine, but chlorine stabilizers may get improved results. 合适的氯清除剂阴离子是广泛已知并可易于得到的,并且, 如果使用的话,它可以是铵阳离子与亚疏酸盐、亚疏酸氬盐、疏代亚硫酸盐、硫代硫酸盐、碘化物等的盐.也可以使用抗氧化剂例如氨基甲酸酯、抗坏血酸等,有机胺例如乙二胺四乙酸(EDTA)或其碱金属盐、单乙醇胺(MEA),和其混合物.同样,可以掺入特殊的酶抑制体系使得不同的酶具有最大的相容性。 Suitable chlorine scavenger anions are widely known and readily available, and, if used, it may be a salt of an ammonium cation and hydrophobic alkylene, alkylene-repellent argon acid salts, sparse generation of sulfite, thiosulfate, the iodide salt may also be used antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salt, monoethanolamine (MEA), and mixtures thereof. Likewise, special enzyme inhibition systems incorporated such that different enzymes have maximum compatibility. 如果需要,可以使用其它常规的清除剂例如疏酸氢盐、硝酸盐、氯化物、过氧化氢源例如过硼酸钠四水合物、过硼酸钠一水合物和过碳酸钠以及磷酸盐、缩聚磷酸盐、乙酸盐、笨甲酸盐、柠檬酸盐、甲酸盐、乳酸盐、苹果酸盐、酒石酸盐、 水杨酸盐等,和其混合物.通常由于可以由以更妤认识到其功能分别列出的组分(例如过氧化氢源)进行氯清除剂的功能,所以没有绝对需要加入单独的氯清除剂,除非在本发明的含酶实施方案中没有进行 If desired, other conventional scavenger such repellent bicarbonate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate and a phosphate, condensed phosphoric acid salts, acetates, benzene formate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof. generally since more of its recognized yu component (e.g., hydrogen peroxide sources) listed functions are a function of the chlorine scavenger, there is no absolute need to add a separate chlorine scavenger unless no enzyme-containing embodiment of the present invention

该功能至所需程度的化合物;甚至在这种情况下,也仅是为了最佳结 The desired degree of functionality to the compound; even in this case, merely in order to best junction

果加入该清除剂.此外,配方师可以运用化学家的常规技能以避免使用配制时与其它反应性组分基本不相容的酶清除剂或稳定剂。 If the scavenger is added. Moreover, the formulator chemist can use routine skill to avoid the use of other reactive components substantially incompatible formulated enzyme scavenger or stabilizer. 关于使用铵盐,可以简单地与洗涤剂组合物混合该盐但该盐易于吸水和/或在储存时释放出氨。 On the use of ammonium salts can be simply admixed with the detergent composition but the salt is a salt readily water-absorbing and / or release ammonia during storage. 因此,如果存在的话,那么这样的材料最好保护在 Therefore, if there is, then this material is the best protection

颗粒中,如在Baginski等的US4652392中所迷, Particle, as in US4652392 Baginski fans or the like,

助洗剂-选自硅铝酸盐和硅酸盐的洗涤剂助洗剂优选包括在本文中的组合物中,以便例如有助于控制洗涤水中的矿物尤其是Ca和/或Mg硬度或有助于从表面去除顆粒污垢. Builders - is selected from aluminosilicates and silicates preferably comprises a detergent builder in the compositions herein, for example to assist in controlling mineral, especially in the washing water is Ca and / or Mg, hardness or assist in the removal of particulate soils from surfaces.

合适的硅酸盐助洗剂包括水溶性和含水的固体类型的并且包括链状、层状或三维结构以及无定型的固体或非结构化的液体类型.优选的是碱金属硅酸盐,尤其是Si02:Na20比在1. 6:1 - 3.2:1范闺的那些液体和固体,包括,特别是对于自动洗餐具目的,由PQCorp.以商品名BRITESIl/例如BRITESIL H20销售的固体含水的2-比例的硅酸盐;和层状硅酸盐例如在US4664839 (HP Rieck , 1987年5月12 曰颁布)中所^^的层状硅酸钠.NaSKS-6,有时缩写为"SKS-6", 是由Hoechst销售的结晶层状、无铝、S-Na2Si0s形态的硅酸盐并且特別优选用于粒状洗衣组合物中.在DE-A- 3417649和DE-A-3742043中可以看到其制备方法。 Suitable silicate builders include water-soluble and hydrous solid types and including a chain, a layered or three dimensional structure and a liquid type amorphous solid or unstructured. Preferred are the alkali metal silicates, particularly a Si02: Na20 ratio of 1.6: 1 - 3.2: 1 range Gui those liquids and solids, including, particularly for automatic dishwashing purposes, tradename BRITESIl / BRITESIL H20 e.g. sold by the solids aqueous PQCorp 2. - ratio silicates; and layered silicates, for example, in US4664839 (HP Rieck, 1987 may 12 reads issued) as the layered sodium silicate ^^ .NaSKS-6, sometimes abbreviated "SKS-6 ", is a crystalline layered marketed by Hoechst, aluminum-free, S-Na2Si0s morphology silicate and particularly preferably used in granular laundry compositions. which can be seen in DE-A- 3417649 and in DE-a-3742043 Preparation. 其它层状硅酸盐,例如具有通式NaMSi,02:^yH20的那些,其中M是钠或氢,x是1.9-4,优选2,和y 是0-20,优选0,也可以或另外用于本文中.得自Hoechst的层状硅酸盐包括:作为a、卩和Y形式的NaSKS-5、NaSKS-7和NaSKS-11。 Other layered silicates, such as having the general formula NaMSi, 02: those ^ yH20 wherein M is sodium or hydrogen, x is from 1.9 to 4, preferably 2, and y is 0 to 20, preferably 0, can also or additionally used herein, layered silicates from Hoechst include: as a, Jie and Y form NaSKS-5, NaSKS-7 and NaSKS-11. 其它硅酸盐也是有用的,例如硅酸镁,它可以在顆粒配方中作为松脆(crispening)剂,作为漂白剂的稳定剂,和作为泡沫控制体系的组分。 Other silicates may also be useful, for example magnesium silicate, which can serve as a crispening (CRISPENING) agent in granular formulations, as bleaching agent stabilizers and as a component of suds control systems.

还适用于本文中的是如在US5427711 ( Sakaguchi等,1995年6 月27日)中所公开的具有链结构并具有由肝式通式xM20'ySi02-zM'0, 其中M是Na和/或K, M,是Ca和/或Mg; y/x是0. 5 - 2. 0和z/x是0.005 -1.0,表示的组成的合成结晶离子交换材料或其水合物. Also suitable for use herein are as described in US5427711 (Sakaguchi et al, June 27, 1995) disclosed having a chain structure and having the formula xM20'ySi02-zM'0 liver by the general formula wherein M is Na and / or K, M, is Ca and / or Mg; y / x is 0.5 - 2.0 and z / x is 0.005 -1.0, composition represented synthetic crystalline ion exchange materials or hydrates thereof.

在粒状洗涤剂中硅铝酸盐助洗剂是特别有用的,但也可以加入到液体、膏体或凝胶组合物中。 Aluminosilicate builders are especially useful in granular detergents, but can also be added to the liquid, paste or gel composition. 适合于本发明目的是具有经验式[^(A102),(SiO2)T] .xH2O的那些,其中z和v为至少6的整数,z与v 的摩尔比为1.0-0.5, x是15- 264的整数。 Suitable for the purposes of the present invention having the empirical formula [^ (A102), (SiO2) T] those .xH2O wherein z and v are integers of at least the molar ratio of z to v is 6 1.0-0.5, x is 15 integer 264. 硅铝酸盐可以是结晶的或无定形的、可以是天然存在的或者合成得到的,在US3985669 Aluminosilicates can be crystalline or amorphous, naturally-occurring or may be synthetically derived, in US3985669

(Krummel等人,1976年10月12曰颁布)中公开了一种生产硅铝酸盐的方法.优选的合成结晶硅铝酸盐离子交换材料可以沸石A,沸石P (, Krummel et al., 1976 October 12, said promulgated) discloses a method for producing aluminosilicate. Preferred synthetic crystalline aluminosilicate ion exchange materials Zeolite A, Zeolite P

(B)、沸石X和与沸石P不同的所谓的滞石MAP的名称得到.可以使用天然型的,包括斜发沸石。 (B), Zeolite X and zeolite P and different from a so-called lag MAP stone name obtained may be used natural type, including clinoptilolite. 也可以使用具有式Nai2[(A102)i2(Si02)u]xH20的沸石A,其中x是20- 30,特别是27. 脱水的沸石(xO-10)也可以使用.优选地,硅铝酸盐的颗粒直径是O. 1-10微米, It may also be used having the formula Nai2 [(A102) i2 (Si02) u] Zeolite A xH20 wherein x is 20-30, particularly 27. The dehydrated zeolite (xO-10) may also be used. Preferably, the aluminosilicate particle diameter salts are O. 1-10 microns,

代替或除了上文所述的硅酸盐和硅铝酸盐以外的洗涤剂助洗剂也可以任逸地包括在本文的组合物中以便例如有助于控制洗涤水中的矿物质,尤其是Ca和/或Mg硬度或有助于从表面去除顆粒污垢.助洗剂可以通过各种机理起作用,包括通过离子交换与硬度离子形成可溶的或不溶的络合物,和提供比被清洗物品表面更利于沉淀硬度离子的表面.助洗剂含量可以大范围地变化,这取决于组合物的最终用途和物理形式.复配的洗涤剂一般含有至少约1%的助洗剂。 Instead of or in addition to the silicates and aluminosilicates described above detergent builders may be included in any of Yi compositions herein, for example to assist in controlling mineral wash water, especially Ca and / or Mg, hardness or facilitate removal of particulate soils from surfaces. builders can act by various mechanisms, including a complex formed by ion exchange with a soluble or insoluble hardness ions, and provide specific item being cleaned surface more conducive to the precipitation of hardness ions surface. levels of builder can vary widely depending on the end use and physical form of the composition. complex detergents typically comprise at least about 1% builder. 液体配方一般含有约5-50% (重量),更一般5-30% (重量)的助洗剂。 Liquid formulations typically comprise about 5-50% (wt.), More typically 5-30% (wt) builder. 按洗涤剂组合物重量计,顆粒配方一般含有约10-80% (重量),更一般15 -50% (重量)的助洗剂.然而,并不排除较低或较高含量的助洗剂。 By weight of the detergent composition, Granular formulations typically comprise from about 10 to 80% (by weight), more typically 15-50% (wt) builder, however, does not exclude builders Lower or higher levels of . 例如某些洗涤剂添加剂或高表面活性剂配方可以是复配不足的。 For example, certain detergent additive or high-surfactant formulations can be insufficient compound.

本文中合适的助洗剂选自:磷酸盐和聚磷酸盐,尤其是钠盐;碳酸盐;碳酸氬盐;倍半碳酸盐和非碳酸钠或倍半碳酸钠的碳酸盐矿物质;酸、钠、钾或链烷醇铵盐形式的有机单、二、三和四羧酸盐,尤其是水溶性的非表面活性剂羧酸盐;以及低聚的或水溶性低分子量聚合物羧酸盐,包括脂族和芳香族型的;和肌醇六磷酸,其可以用硼酸盐,例如用于pH緩冲目的,或用硫酸盐,尤其是硫酸钠和对含有稳定的表面活性剂和/或助洗剂的洗涤剂组合物的工程是重要的其它填料或载体来补充. Suitable builders herein are selected from: phosphates and polyphosphates, especially the sodium salts; carbonates; Ar carbonate salts; non sesquicarbonate and sodium sesquicarbonate or carbonate minerals ; acid, sodium, potassium or alkanolammonium salt form of an organic mono-, di-, tri- and tetra-carboxylates, especially water-soluble nonsurfactant carboxylates; and oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic type; and phytic acid, which can be treated with a borate, for example, for pH-buffering purposes, or by sulfates, especially sodium sulfate and a surfactant containing a stable and / or engineering detergent composition builders are important to supplement other fillers or carriers.

可以使用助洗剂混合物,有时称之为"助洗剂体系",其一般包括两种或多种常规的助洗剂,任选地补充有螯合剂、pH緩冲剂或填料,后面这些材料通常是描述本发明材料量时分別说明的.根据本发明洗涤剂中的表面活性剂和助洗剂的相对量,优选的助洗剂体系一般 The mixture may be used builders, sometimes called "builder systems", which generally comprise two or more conventional builders, optionally supplemented with a chelating agent, pH buffers or fillers, usually these latter materials are respectively illustrated to describe the amount of material of the present invention. according to the present invention the relative amounts of detergent surfactant and builders, preferred builder systems are typically

以约60: 1 - 1: 80的表面活性剂与助洗剂的重量比配制。 About 60: 1 - 1: 1 weight of surfactant to builder ratio 80 formulation. 某些优选的洗衣洗涤剂的该比例在0.90 : 1.0-4.0 : lO的范围,更优选0.95 : The proportions of certain preferred laundry detergent at 0.90: 1.0-4.0: lO range, and more preferably 0.95:

1.0-3.0 : 1.0. 1.0 to 3.0: 1.0.

在法律允许的地方,经常优选的含轔洗涤剂助洗剂包括,但不限于:聚磷酸盐的碱金属、铵和链烷醇铵盐,例如三聚磷酸盐、焦磷酸盐、玻璃状的聚偏磷酸盐和膦酸盐。 Where permitted by law, is often preferred clattering containing detergent builders include, but are not limited to: alkali metal polyphosphates, ammonium and alkanolammonium salts, e.g. tripolyphosphates, pyrophosphates, glassy polyvinylidene phosphates and phosphonates.

合适的碳酸盐助洗剂包括在德国专利申请号2321001( 1973年11 月15日公开)中公开的碱土金属和碱金属碳酸盐,不过碳酸氢钠、碳酸钠、倍半碳酸钠和其它碳酸盐矿物质例如二碳酸氢三钠或任何常规的碳酸钠和碳酸钾的复盐例如当其无水时组成为2Na2C03 ■ CaC03,和甚至是碳酸钙,包括方解石、文石和vaterite,尤其是相对于致密的方解石具有高表面积的形式可以是有用的,例如作为晶种或用于合成洗涤剂皂条中. Suitable carbonate builders include (published November 15, 1973) in German Patent Application No. 2,321,001 alkaline earth and alkali metal carbonates as disclosed in, but sodium bicarbonate, sodium sesquicarbonate, and other carbonate complex salt, for example, two mineral sodium sesquicarbonate and sodium carbonate or potassium carbonate, any conventional composition, for example, when it is over anhydrous 2Na2C03 ■ CaC03, and even calcium carbonate, including calcite, aragonite and vaterite, especially with respect to the compact form of a high surface area calcite may be useful, for example as seeds or for the syndet soap bars.

合适的有机助洗剂包括多羧酸盐化合物,包括水溶性的非表面活性剂二羧酸盐和三羧酸盐.更一般地,助洗剂多羧酸盐具有多个羧酸根基团,优逸至少3个羧酸根.可以以酸、部分中和的、中性或过碱性的形式配制羧酸盐助洗剂.当为盐形式时,碱金属例如钠、钾和锂或链烷醇铵盐是优选的。 Suitable organic builders include polycarboxylate compounds, including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More generally, builder polycarboxylates have a plurality of carboxylate groups, Yi preferably at least 3 carboxylates. polycarboxylate builder can be formulated in acid, neutral or overbased form partially neutralized. when in salt form, alkali metals such as sodium, potassium, and lithium or paraffinic alcohol salts are preferred. 多羧酸盐助洗剂包括酸多羧酸盐例如氧联二琥珀酸盐,见US3128287 ( Berg, 1964年4月7日)和US3635830 (Lamberti等,1972年1月18日);US4663071 ( Bush等,1987年5月5日)的"TMS/TDS"助洗剂;和其它的酸羧酸盐助洗剂,包括环状和脂环化合物,例如在下面美国专利中描述的那些:US3923679、 US3835163、 US4158635、 US4120874和US4102903. Polycarboxylate builders include acid polycarboxylates e.g. oxydisuccinic acid, see US3128287 (Berg, 1964 years. 4 7 May) and US3635830 (Lamberti et al., January 18, 1972); US4663071 (Bush et al., May 5, 1987) the "TMS / TDS" builders; and those other acids polycarboxylate builders, including cyclic and alicyclic compounds, such as described in the following U.S. patents: US3923679, US3835163, US4158635, US4120874 and US4102903.

其它合适的助洗剂是酸羟基多羧酸盐,马来酸酐与乙烯或乙烯基甲基酸的共聚物,1,3,5-三羟基笨-2,4,6-三磺酸,和羧甲氧基琥珀酸,多乙酸的各种碱金属、铵和取代的铵盐例如乙二胺四乙酸和次氮基三乙酸,以及苯六甲酸、琥珀酸、聚马来酸、笨1,3,5-三羧酸、 羧甲氧基琥珀酸和其可溶性盐。 Other suitable builders are polycarboxylates hydroxy acid, copolymers of maleic anhydride with ethylene or vinyl methyl acid, 1,3,5-trihydroxy-2,4,6 stupid acid, and carboxymethyloxysuccinic acid, multi-acid, the various alkali metal, ammonium and substituted ammonium salts such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as mellitic acid, succinic acid, polymaleic acid, benzene 1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

柠檬酸盐助洗剂,例如柠檬酸和其可溶性盐,由于其从可再生来源的可得到性和其生物可降解性,所以例如对于重垢液体洗涤剂是特别重要的羧酸盐助洗剂。 Citrate builders, e.g., citric acid and soluble salts thereof, due to their degradability is obtained from renewable sources and their biological properties, for example, so that heavy duty liquid detergent are particularly important carboxylate builders . 柠檬酸盐也可以用于颗粒组合物中,特别是与沸石和/或层状硅酸盐组合使用.在这样的组合物和组合中氧联二琥珀酸盐也是特别有用的。 Citrates can also be used in granular compositions, especially in the use and / or layered silicates in combination with zeolites. Oxydisuccinic acid salt in such compositions and combinations are particularly useful.

当允许时,特别是用于手洗操作的皂条配方中,可以使用碱金属 Where permitted, especially soap bar formulations for hand-laundering operations, alkali metals

裤酸盐例如三聚轔酸钠、焦轔酸钠和正磷酸钠,也可以使用膦酸盐助洗剂例如乙烷-1-羟基-1,1- 二膦酸盐和其它已知的膦酸盐,例如 Salts such as sodium pants trimerization jingle, jingle sodium pyrophosphate and sodium orthophosphate may be used Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates acid salts, e.g.

US3159581; US3213030; US3422021; US3400148和US3422137中的那些,其具有理想的防垢性质. US3159581; US3213030; US3422021; US3422137 those in US3400148, which has the desired antifouling properties.

某些洗涤表面活性剂或其短链同系物也具有助洗剂作用。 Certain detersive surfactants or their short-chain homologs also have a builder action. 为了明确配方计算^目的,当它们具有表面活性剂能力时,把这些材料归结为洗涤表面活性剂.用于助洗剂功能的优选类型说明如下:公开于US4566984 ( Bush, 1986年1月28日)中的3,3 - 二羧基-4 -氧杂- 1,6-己二酸盐和相关的化合物,琥珀酸助洗剂包括C5-C加烷基和链烯基琥珀酸和其盐.琥珀酸盐助洗剂也包括:月桂基琥珀酸盐、肉豆蔻基琥珀酸盐、棕榈基琥珀酸盐、2-十二烯基琥珀酸盐(优选的)、 2-十五烯基琥珀酸盐等。 To clarify ^ recipe calculation purposes, when they have surfactant capability, these materials are attributed to the detergent surfactant is preferably Type Description builder functions as follows: as disclosed in US4566984 (Bush, 1986 dated 28 years. 1 Day 3,3) - a two carboxy-4 - oxa - 1,6 adipate and related compounds, succinic acid builders include the C5-C plus alkyl and alkenyl succinic acids and salts thereof. succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate salt. 月桂基琥珀酸盐描述于1986年11月5曰公开的欧洲专利申请86200690.5/0200263中.也可以将脂肪酸例如C12 -C18单羧酸作为表面活性剂/助洗剂材料单独掺入到组合物中或与上述助洗剂尤其是柠檬酸盐和/或琥珀酸盐助洗剂组合,以便提供附加的助洗剂活性.其它合适的多羧酸盐公开于US4144226 ( Crutchfield 等,1979年3月13日)和US3308067 ( Diehl等,1967年3月7曰) 中.还参见Diehl的US3723322. European Patent lauryl succinates described November 5, 1986, the disclosure of said Application 86200690.5 / 0 200 263, also may be a fatty acid such as a C12 -C18 monocarboxylic acid surfactant / builder materials incorporated into the compositions alone or the aforesaid builders, especially citrate and builder composition / or the succinate and, to provide additional builder activity. other suitable polycarboxylates are disclosed in US4144226 (Crutchfield et al, 1979, March 13 day) and US3308067 (Diehl et 1967 March 7 said) in. see also US3723322 Diehl's.

可以使用的其它类型的无机助洗剂材料具有式(MJiCe^(C03)z,其中x和i是1-15的整数,y是l-IO的整数,z是2-25的整数,Mt Other types of inorganic builder materials which can be used have the formula (MJiCe ^ (C03) z, wherein x and i are integers from 1 to 15, y is an integer of l-IO, z is an integer from 2 to 25, Mt

是阳离子,其至少一个是水溶性的,并且满足公式E严iM5 (i乘Mi Is a cation which is at least one water-soluble, and satisfies the formula E Yan iM5 (i Mi by

的价态)+2y-2z,致使配方具有中性或"平衡的"电荷,这些助洗剂本文中称之为"矿物助洗剂".可以加入水合作用的水或非碳酸根的阴离子,条件是总电荷是平衡或中性的.这些阴离子的电荷或价态作用应该加到上式的右边,优选存在选自氢、水溶性金属、氢、硼、 铵、硅和其混合物的水溶性阳离子,更优选钠、钾、氢、理、铵和其混合物,钠和钟是非常优选的-非碳酸根阴离子的非限制性例子包括选自下面的那些:氯化物、硫酸根、氟化物、氧、氢氧化物、二氧化硅、铬酸根、硝酸根、硼酸根和其混合物。 Valence state) + 2y-2z, resulting formulation has a neutral or "balanced" charge, these builders are referred to herein as "Mineral Builders." Water may be added or carbonate anion hydration with the proviso that the overall charge is balanced or neutral. charge or valence effects of these anions should be added to the right side of the above formula, there is preferably selected from hydrogen, a water-soluble water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof cation, more preferably sodium, potassium, hydrogen, Li, ammonium, and mixtures thereof, sodium and clock are highly preferred - Nonlimiting examples of carbonate anions include those selected from: chloride, sulfate, fluoride , oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof. 其最简单形式的这类优选的助洗剂选自:Na2Ca(C0a)2、 K2Ca(C03)2、 Na2Ca2 (C03) 3、 NaKCa(C03)2、 NaKCa2(C03)3、 1^&2(0)3)3和其混合物.本文中所述的特別优选的助洗剂材料是任何其结晶改性形式的Na2Ca(C03)2。 Such preferred builders its simplest form is selected from: Na2Ca (C0a) 2, K2Ca (C03) 2, Na2Ca2 (C03) 3, NaKCa (C03) 2, NaKCa2 (C03) 3, 1 ^ & 2 (0 ) 3) 3, and mixtures thereof. the particularly preferred herein the builder material is any crystal modification of Na2Ca (C03) 2. 上述类型的合适的助洗 The above-described type of suitable builder

剂还用下面的物质来说明,其包括天然或合成下面矿物质的任一个或 Agents also be described by the following substances, which include any natural or synthetic minerals or below

其组合形式:阿,霞石、水钠钩铀矿、Y型钾杆沸石、碳铋45石、碳硼镁钙石、黄菱锶镩矿、水碳酸钾钙石、钙霞石、石铈钠石、碳硅碱钙石、钾钙霞石、Y型碳钇锶石、碳钾钙石、Ferrisurite、弗钙霞石、 碳硼锰辨石、单斜钠钙石、Girvasite、 Gregoryite、硫碳钩锰石、 Kamphaugite Y、 Kettnerite、 Khanneshite、 LepersonniteGd、利钩霞石、Y型碳钡钇矿、微碱钙霞石、破碲钙石、尼碳钠钙石、尼碳钠钙石、RemonditeCe、萨钾钙霞石、板碳铀矿、碳酸钠钙石、碳硅铝铅石、碳钠45铝石、硫硅钙钾石、铜泡石、疏酸钙霞石和Ze迈korite. 优选的材料形式包括尼碳钠钙石、碳钾钙石和碳酸钠钙石。 Combination thereof: A, nepheline, sodium and water hook uranium, Y-type zeolite potassium rod, stone 45 carbon bismuth, boron, carbon, magnesium, calcium stone, yellow strontianite Cuan ore colemanite aqueous potassium carbonate, nepheline calcium, cerium stone sodalite, carbon canasite, potassium cancrinite, Y type carbon strontium yttrium stone, carbon, potassium, calcium stone, Ferrisurite, Vladimir cancrinite, carbon manganese boron identified stone monoclinic soda lime stone, Girvasite, Gregoryite, sulfur carbon manganese hook stone, Kamphaugite Y, Kettnerite, Khanneshite, LepersonniteGd, nepheline hook Lee, Y-xenotime barium carbonate, slightly alkaline cancrinite, calcium stone breaking tellurium, carbon soda lime stone Nigeria, Niger carbon soda lime stone, RemonditeCe , Sa cancrinite potassium, uranium plate carbon, calcium carbonate rock, stone carbon lead aluminosilicate, sodium dawsonite 45 carbon, sulfur, potassium, calcium silicate stone, sepiolite copper, calcium nepheline sparse and Ze step korite. preferred carbon material forms include sodium lime stone nylon, carbon, potassium carbonate and calcium stone colemanite. 洗涤表面活性剂: Detergent surfactant:

本发明的洗涤剂组合物优选还包括附加的表面活性剂,本文中也称之为辅助表面活性剂.应该懂得,用本发明方法制备的支链表面活性剂可以单独地或者与其它洗涤表面活性剂组合地用于清洗组合物中, 一般全配方清洗组合物含有各类表面活性剂的混合物以便对各种污垢和污斑并且在各种使用条件下得到宽范围的清洗性能。 The detergent compositions of the invention preferably further comprise additional surfactants, herein also referred to as co-surfactants. It should be understood, branched-chain surfactants prepared by the process of the present invention may be used alone or in combination with other detergent surfactants agent composition used in the cleaning compositions, typically the fully formulated cleaning compositions contain mixtures of various types of surfactants in order to obtain a variety of soils and stains and in a wide range of cleaning performance under various conditions. 本文中的支链表面活性剂的一个优点是其容易与其它已知表面活性剂类型一起配制的能力。 One advantage of the herein branched surfactant is its ability to be easily formulated with other known surfactant types. 一般可以以约1-55重量%使用的附加表面活性剂的非限制性例子包括:不饱和的疏酸盐如油基疏酸盐、C1()-Cw烷基烷氧基疏酸盐("AE:S",尤其是E0 1-7乙氧基疏酸盐)、C1()-Cw烷基烷氧基羧酸盐(尤其是E0 1 - 5乙氧基羧酸盐),d。 Non-limiting examples may generally additional surfactants from about 1-55% by weight include: unsaturated sparse sparse acid salts such as oleyl, C1 () - Cw alkyl alkoxy sparse acid ( " AE: S ", especially E0 1-7 ethoxy sparse acid), C1 () - Cw alkyl alkoxy carboxylates (especially E0 1 - 5 ethoxycarboxylates), d. - ds甘油鍵疏酸盐、 C10-Cw烷基多苷和其相应的硫酸化的多苷、以及C12-C18ot -磺化脂肪酸酯.也可以使用非离子表面活性剂如乙氧基化的d。 - ds-repellent salt bond glycerol, C10-Cw alkyl polyglycosides and their corresponding sulfated polyglycosides, and C12-C18ot -. Sulfonated fatty acid esters may be used nonionic surfactants such as ethoxylated d. -Cw醇和烷基酚(例如d。-C1B EO(l-lO)).如果需要,其它常规的表面活性剂如C12-ds甜菜碱和磺基甜菜碱("sultaines" )、 do-ds氧化胺等也可以包括在总的组合物中。 -Cw alcohols and alkyl phenols (e.g. d.-C1B EO (l-lO)). If desired, other conventional surfactants such as the C12-ds betaines and sulfobetaines ( "sultaines"), do-ds oxide amine and the like may also be included in the overall compositions. 还可以使用d。 You may also be used d. -dsN-烷基多羟基脂肪酸酰胺。 -dsN- alkyl polyhydroxy fatty acid amides. 一般例子包括C12-C18N-甲基葡糖酰胺,见W09206154,其它的糖衍生的表面活性剂包括N-烷氧基多羟基脂肪酸酰胺,例如C10-C18N- (3-甲氧基丙基)葡糖酰胺。 Typical examples include C12-C18N- methyl glucamide, see W09206154, Other sugar-derived surfactants include N--alkoxy polyhydroxy fatty acid amides, such as C10-C18N- (3- methoxypropyl) glucoside sugar amide. N-丙基至N-己基Cu-Cw葡糖酰胺可用于低发泡.也可以使用d。 N- propyl through N- hexyl Cu-Cw glucamides can be used for low foaming. D may also be used. -C加的常规皂类.如果需要高起泡性,可以使用支链的C1Q-Cw皂。 -C conventional soaps plus. If high sudsing, may be used branched C1Q-Cw soap. 常常用于洗衣洗涤剂组合物中的C10 -CH烷基笨磺酸盐(LAS)也可以与本文中的支链表面活性剂一起使用. Are often used in laundry detergent compositions stupid C10 -CH alkyl sulfonates (LAS) may also be used with the branched surfactants herein, the active agent.

在本发明的洗涤剂组合物中可以使用宽范围的辅助表面活性剂. In the detergent compositions of the invention may be used in a wide range of co-surfactants.

在1972年5月23日颁布的Norris的US3664961中给出了这些辅助表面活性剂的阴离子、非离子、两性和两性离子类的列表和种类。 Given these anionic, nonionic, ampholytic and zwitterionic classes, and species list cosurfactant in US3664961 1972 years. 5, Norris, issued dated 23 is in. 在EG Lomax编的"两性表面活性剂(第2版)"(Marcel Dekker, Inc. ,1996年出版)中也详细地描述了两性表面活性剂. In EG Lomax series "amphoteric surfactant (2nd Edition)" (Marcel Dekker, Inc., published in 1996) is also described in detail amphoteric surfactants.

本发明的洗衣洗涤剂组合物一般含有约0.1-35重量%,优选约0.5-15重量%的辅助表面活性剂。 The laundry detergent compositions of the present invention generally contain from about 0.1 to 35 wt%, preferably from about 0.5 to 15% by weight of co-surfactants. 选择的表面活性剂进一步说明如下: The surfactant is further selected as follows:

(1)阴离子辅助表面活性剂: (1) an anionic cosurfactant:

含量一般为约0.1- 50重量%的本文中有用的阴离子辅助表面活性剂的非限制性的例子包括:常规的Cu-Cu烷基苯磺酸盐("LAS") 和伯、支链和无规的d。 Non-limiting examples of content is generally about 0.1 to 50% by weight herein useful anionic co-surfactants include: Cu-Cu conventional alkylbenzene sulfonate ( "LAS") and primary, branched-chain and no gauge d. -C加烷基琉酸盐("AS"),式CH3(CH2):(CH0S03 -MT) CH3和CH3 (CH2) y (CH0S03- if) CH2CH3的C!。 -C alkyl sulfur plus salts ( "AS"), the formula CH3 (CH2) :( CH0S03 -MT) CH3 and CH3 (CH2) y (CH0S03- if) CH2CH3 of C !. - C18仲(2, 3)烷基疏酸盐,其中x和(y+l)是至少为约7,优选至少为约9的整数,和M是水溶性阳离子,尤其是钠,不饱和疏酸盐例如油基破酸盐,C1()-C18a-磺化脂肪酸醋,C1()-Cw烷基多苷,C1()-Cw烷基烷氧基疏酸盐("AEzS", 尤其是EO 1-7乙氧基疏酸盐),d。 - C18 secondary (2,3) alkyl-repellent salt, wherein x and (y + l) is at least about 7, preferably an integer of at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sparse oleyl acid salts such as breaking, C1 () - C18a- sulfonated fatty vinegar, C1 () - Cw alkyl polyglycoside, C1 () - Cw alkyl alkoxy sparse acid ( "AEzS", in particular EO 1-7 ethoxy sparse acid), d. -ds烷基烷氧基羧酸盐(尤其是E0 1-5乙氧基羧酸盐).C12-C"甜菜碱和磺基甜菜碱("sultaine"), -ds alkyl alkoxy carboxylates (especially E0 1-5 ethoxy carboxylates) .C12-C "betaines and sulfobetaine (" sultaine "),

d。 d. -ds氧化胺等也可以包括在整个组合物中.也可以使用d。 -ds amine oxides and the like may also be included. d may be used throughout the composition. -C2。 -C2. of

常规皂类。 Conventional soaps. 如果需要高起泡性,可以使用支链的d。 If high sudsing, branched chain may be used. D. -Cw皂.其它常规有用的阴离子辅助表面活性剂列于标准教科书中。 -Cw soap. Other conventional useful anionic co-surfactants are listed in standard texts.

本文中有用的烷基烷氧基碟酸盐表面活性剂优选是式R0(A),S03M 的水溶性盐或酸,其中R是未取代的C113-C24烷基或具有d。 Useful herein Singles alkyl alkoxy surfactant is preferably a salt of formula R0 (A), S03M water soluble salts or acids, wherein R is an unsubstituted alkyl or a C113-C24 d. -Cw烷基部分的羟基烷基,优选d2-Cw烷基或羟基烷基,更优选C"-ds烷基或羟基烷基,A是乙氧基或丙氧基单元,m大于0, 一般为约0.5-6, 更优选约0.5-3,和M是H或阳离子,该阳离子可以是:例如金属阳离子(如钠、钾、锂、钙、镁等)、铵或取代铵阳离子。本文中预计使用烷基乙氧基化硫酸盐以及烷基丙氧基化硫酸盐。取代铵阳离子的具体例子包括:乙醇、三乙醇、甲基、二甲基、三甲基铵阳离子和季铵阳离子四甲基铵和二甲基派咬铩阳离子和从烷基胺如乙胺、二乙胺、三乙胺、其混合物衍生的那些阳离子等。举例说明的表面活性剂 Hydroxyalkyl -Cw alkyl component, preferably d2-Cw alkyl or hydroxyalkyl, more preferably C "-ds alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically about 0.5 to 6, more preferably about 0.5 to 3, and M is H or a cation which can be: for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium etc.), ammonium or substituted ammonium cation herein estimated alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates specific examples of substituted ammonium cations include: ethanol, triethanolamine, methyl, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl dimethyl-ammonium cations and send bite spear surfactants from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and those cations. exemplified

是:d广d6烷基聚乙氧基化物(1.0)硫酸盐(C12-C1BE(1.0)M) 、 C12 - Cu烷基聚乙氧基化物(2.25)硫酸盐(C12 - C15E(2. 25)M) 、 C12 — C15 烷基聚乙氧基化物(3.0)硫酸盐(C12_C15E(3.0)M)和d广ds烷基聚乙氧基化物(4.0)疏酸盐(C12-C15E(4.0)M),其中M方便地选自钠和钾。 They are: d d6 wide alkyl polyethoxylate (1.0) sulfate (C12-C1BE (1.0) M), C12 - Cu alkyl polyethoxylate (2.25) sulfate (C12 - C15E (2 25. ) M), C12 - C15 alkyl polyethoxylate (3.0) sulfate (C12_C15E (3.0) M), and d ds wide alkyl polyethoxylate (4.0) repellent salt (C12-C15E (4.0) M), wherein M is conveniently selected from sodium and potassium.

本文中有用的烷基疏酸盐表面活性剂优选是式ROS03M的水溶性盐或酸,其中R优选是d。 Alkyl groups useful herein is preferably hydrophobic surfactant salts are water soluble salts or acids of the formula ROS03M wherein R preferably is d. -Cs4烃基,优选具有d。 -Cs4 hydrocarbon group, preferably having a d. -Cw烷基部分的烷基或羟基烷基,更优选d2-ds烷基或羟基烷基,和M是H或阳离子,例如碱金属阳离子(如钠、钾、锂),或铵或取代铵(如甲基、二甲基和三甲基铵阳离子和季铵阳离子例如四甲基铵和二甲基派啶铩阳离子 Alkyl or hydroxyalkyl -Cw alkyl component, more preferably d2-ds alkyl or hydroxyalkyl, and M is H or a cation, e.g. an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidine spear cation sent

和从烷基胺例如乙胺、二乙胺、三乙胺和其混合物衍生的季铵阳离子等)。 And from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and quaternary ammonium cations, etc.).

其它可以使用的合适的阴离子表面活性剂是烷基酯磺酸盐表面活性剂,包括按照"The Journal of the American Oil Ch棚ists Society" , 52 (1975), pp. 323 - 329用气态S03磺化的C8- C卯羧酸(即脂肪酸)的直链酯.合适的原料包括从牛脂、棕榈油等衍生的天然脂肪物质, Other suitable anionic surfactants may be used are alkyl ester sulfonate surfactants, include according to "The Journal of the American Oil Ch shed ists Society", 52 (1975), pp 323 -. 329 sulfo gaseous S03 C8- C d of the carboxylic acid (i.e., fatty acids) linear ester. suitable starting materials would include from tallow, palm oil, natural fatty substances as derived,

优逸的烷基酯磺酸盐表面活性剂(尤其是用于洗衣用途的)包括下面结构式的烷基酯磺酸盐表面活性剂: Yi preferred alkyl ester sulfonate surfactants (especially for laundry applications) comprises the following structural formula alkyl ester sulfonate surfactant:

R3-CH(S0sM) -C(0) - OR4 R3-CH (S0sM) -C (0) - OR4

其中R3是Cs-C加烃基,优选烷基,或其组合,W是d-C6烃基,优选烷基,或其组合,和M是与烷基酯磺酸根形成水溶性盐的阳离子.合适的形成盐的阳离子包括金属阳离子如钠、钾和锂和取代或未取代的铵阳离子如单乙醇胺、二乙醇胺和三乙醇胺,优选地,R3是d。 Wherein R3 is Cs-C plus hydrocarbyl, preferably an alkyl, or combination thereof, W is d-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a sulfonate alkyl ester of a water soluble salt. Suitable salt-forming cations include metal cations such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine, preferably, R3 is d. -C16 烷基,和W是甲基、乙基或异丙基。 -C16 alkyl, and W is a methyl, ethyl or isopropyl. 特别优选的是甲基酯磺酸盐,其 Especially preferred are the methyl ester sulfonates which

中R3是Chj - de烷基。 R3 is Chj - de alkyl.

其它对洗涤目的有用的阴离子辅助表面活性剂也可以包括在本发 Other useful anionic detersive purposes of cosurfactants may also be included in the present

明的洗衣洗涤剂组合物中.它们可以包括:皂的盐(包括,例如钠、 Ming laundry detergent compositions thereof may include: salts (including, for example, sodium,

钾、铵、和取代的铵如单、二和三乙醇胺盐)、C8- C22伯或仲烷烃磺酸盐、C8- C24烯烃磺酸盐、通过碱土金属拧檬酸盐热解产物的磺化制 Potassium, ammonium, and substituted ammonium such as mono-, di- and triethanolamine salts), C8- C22 primary or secondary alkanesulfonates, C8- C24 olefinsulfonates, pyrolyzed product of alkaline earth metal salts of sulfonated citric system

备的磺化的多羧酸(例如,如在英国专利说明书号1082179中所述 Sulfonated polycarboxylic acids prepared (e.g., as described in British patent specification No. 1,082,179

的)、C8- C24烷基聚乙二醇醚疏酸盐(含有最多达10摩尔的环氧乙 A), C8- C24 alkyl polyglycol ethers repellent salt (containing up to 10 moles of ethylene oxide

烷);烷基甘油磺酸盐、脂肪酰基甘油磺酸盐、脂肪油基甘油疏酸盐、 烷基酴环氧乙烷鍵疏酸盐、石蜡烃磺酸盐、烷基褲酸盐、羟乙磺酸盐如酰基羟乙磺酸盐、N-酰基牛磺酸盐、烷基琥珀酰胺酸盐和磺基琥珀酸盐、磺基琥珀酸的单酯(特别是饱和和不饱和C12- U单酯)和磺基琥珀酸的二酯(特别是饱和和不饱和Ce- Cu二酯)、烷基多糖的疏酸盐例如烷基多葡糖苦(下面所述的非离子非疏酸化的化合物)的疏酸盐和烷基聚乙氧基羧酸盐例如那些式R0(CH2CH20)k- CH2COCTlT的盐, 其中R是Cs-Cw烷基,k是0-IO的整数,和M是形成可溶性盐的阳离子。 Alkyl); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol hydrophobic salts, alkyl ethylene oxide yeast key repellent salt, paraffin sulfonates, alkyl pants salts, hydroxyalkyl ethanesulfonate as the acyl isethionates, N- acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12- U monoesters) diesters of sulfosuccinate (especially saturated and unsaturated diester Ce- Cu), alkyl polysaccharides sparse salts e.g. glucose bitter alkyl (hydrophobic nonionic acidified described below compound) hydrophobic salts, and alkyl polyethoxy carboxylates such as those of formula R0 (CH2CH20) k- CH2COCTlT salt thereof, wherein R is a Cs-Cw alkyl, k is an integer of 0-IO, and M is formed soluble cation salt. 树脂酸及氢化的树脂酸也是合适的,例如松香、氢化松香以及存在于或衍生于松浆油的树脂酸和氢化树脂酸.其它例子描迷于 Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and present in or derived from resin acids and hydrogenated resin acids in tall oil. Other examples of fans described in

"Surface Active Agents and Detergents"(巻I和II, Schwartz, Perry和Berch)中。 "Surface Active Agents and Detergents" (Volume I and II, Schwartz, Perry and Berch). 各种这样的表面活性剂也一般地公开于US3929678 A variety of such surfactants are also generally disclosed in US3929678

(Laughlin等人,1975年12月30日颁布)的23栏58行- 29栏23 行中(该文献引入本文作为参考)。 (Laughlin et al., December 30, 1975 promulgated) 23 bar 58 OK - Column 29, line 23 (which is incorporated herein by reference).

优逸的二疏酸盐表面活性剂具有下式: Yi dicarboxylic acid preferably hydrophobic surfactant having the formula:

A—X'M A-X'M

B—YM B-YM

其中R是链长度为C2B,优选"-C24,最优选Cs-C加的烷基、取代的烷基、链烯基、芳基、烷芳基、醚、酯、胺或酰胺基团,或者氢;A 和B各自独立地选自链长度为d-C28,优选d-C5,最优选d或C2的烷基、取代的烷基和链烯基,或共价键,并且A和B总共含有至少2 个原子;A、 B和R总共含有4-约31个碳原子;X和Y是选自硫酸根和磺酸根的阴离子基团,条件是X或Y中至少一个是硫酸根;M是阳离子部分,优选取代或未取代的铵离子,或者碱金属或碱土金属离子. Wherein R is a chain length of the C2B, preferably "-C24, most preferably Cs-C plus alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group, or hydrogen; a and B are each independently selected from a chain length of d-C28, preferably d-C5, most preferably d or C2 alkyl, substituted alkyl and alkenyl, or a covalent bond, and a and B in total containing at least 2 atoms; a, B, and R in total contain from 4 to about 31 carbon atoms; X and Y are selected from sulfate and sulfonate anionic group, with the proviso that at least one of X or Y is a sulfate; M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali metal or alkaline earth metal ions.

最优选的二硫酸盐表面活性剂具有上式,其中R是链长度为C10 -Cw的烷基,A和B各自独立地是d或C2, X和Y都是硫酸根,M是钾、铵或钠离子。 The most preferred disulfate surfactant has the formula wherein R is a chain length of C10 -Cw alkyl group, A and B are each independently a d or C2, X and Y are sulfate, M is potassium, ammonium, or sodium ions.

按洗涤剂組合物重量计,该二硫酸盐表面活性剂存在的量一般是 By weight of the detergent composition, the presence of the disulfate surfactant is typically an amount

约O. 1-50%,优选约O, 1-35%,最优选约0.5-15%. 本文中优选的二硫酸盐表面活性剂包括: From about O. 1-50%, preferably about O, 1-35%, most preferably from about 0.5 to 15% preferred herein disulfate surfactant comprising:

(a) 1,3二硫酸盐化合物,优选1,3 C7-C23(即分子中碳总数) (A) 1,3 disulfate compounds, preferably 1,3 C7-C23 (i.e., the total number of carbons in the molecule)

-二疏酸盐,更优选具有下式: - two sparse salt, more preferably having the formula:

其中R是链长度为约Cd Wherein R is a chain length of about Cd

(b) 1,4 二碇酸盐化合物,优选1,4 C8-C22直链或支链烷基或链烯基二疏酸盐,更优选具有下式: (B) 1,4 two anchor acid compounds, preferably 1,4 C8-C22 straight or branched chain alkyl or alkenyl group sparse two salts, more preferably the formula:

0S03' M OSO,.M + 0S03 'M OSO, .M +

其中R是链长度为约C4 - C18的直链或支链烷基或链蟑基;优选的R选自:辛基、壬基、癸基、十二烷基、十四烷基、十六烷基、十八烷基, 和其混合物;和 Wherein R is a chain length of from about C4 - C18 straight or branched chain alkyl or cockroach group; preferably R is selected from: octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, , octadecyl, and mixtures thereof; and

(c) 1,5二疏酸盐化合物,优选1,5 C9-C23直链或支链烷基或链蜂基二疏酸盐,更优选具有下式: (C) 1,5 sparse two acid compounds, preferably 1,5 C9-C23 straight or branched chain alkyl or two hydrophobic groups bee salts, more preferably the formula:

<formula>formula see original document page 50</formula> <Formula> formula see original document page 50 </ formula>

其中R是链长度为约C4-Cw的直链或支链烷基或链烯基. Wherein R is a chain length of from about C4-Cw straight or branched chain alkyl or alkenyl group.

某些二硫酸盐表面活性剂的已知合成通常使用烷基或链烯基琥珀酸酐作为主要原料.其开始经受还原步骤,由这一步艰得到二醇.接着,该二醇经受疏酸化步骤从而得到二疏酸化产物.作为例子,US-A -3634269描迷了2 -烷基或链烯基-1, 4- 丁二醇二硫酸盐,它是这 Some known synthetic disulfate surfactant is typically an alkyl or alkenyl succinic anhydride as the principal starting material. It begins to be subjected to the reduction step, this step is difficult to obtain the diol. Then, the diol is subjected to the acidification step such sparse to give the product as a two sparse acidified example, US-a -3634269 described lost 2 - alkyl or alkenyl-1,4-butanediol disulfate, it is this

样制备的:通过链烯基琥珀酸酐用氢化铝锂还原从而制备链烯基或烷基二醇,然后将该二醇硫酸化.另外,US-A- 3959334和US-A-4000081描述了2_烃基-1,4- 丁二醇二硫酸盐,它也是使用包括用氢化铝锂还原链烯基琥珀酸酐从而制备链烯基或烷基二醇,然后将其硫酸化的方法来制备的. Sample preparation: The alkenyl succinic anhydrides with lithium aluminum hydride reduction to prepare alkenyl or alkyl diols, glycols and the sulfated Further, US-A- 3959334 and US-A-4000081 describes 2. _ hydrocarbyl-1,4-butanediol disulfate, it is prepared using lithium aluminum hydride comprises alkenyl succinic anhydride to prepare alkenyl or alkyl diols which are then sulfated method.

还参见US-A- 3832408和US-A- 3860625,其描述了2 -烷基或链烯基-1, 4 - 丁二醇乙氧基化物二疏酸盐,它是用氢化铝锂还原链烯基琥珀酸酐制备链蜂基或烷基二醇,然后在疏酸化前乙氧基化制备的. See also US-A- 3832408 and US-A- 3860625, which describes a 2 - alkyl or alkenyl-1, 4 - butanediol ethoxylate two sparse salt, which is a lithium aluminum hydride chain chain alkenyl succinic anhydride prepared bees or alkyl diols, ethoxylated and then acidified before thinning prepared.

这些化合物也可以通过这样的方法制备,该方法包括从取代的环酐合成二疏酸盐表面活性剂,该环酐具有一个或多个总数至少为5个碳原子的碳链取代基,其包括下面步骤: These compounds may also be prepared by a method which comprises synthesizing from a substituted cyclic anhydride of two hydrophobic surfactants acid, the cyclic anhydride having a total of at least one or more of the carbon chain of 5 carbon atoms substituents comprising the following steps:

(1) 将所述的取代的环酐还原以形成二醇;和(ii)将所述的二醇硫酸化从而形成二硫酸盐 (1) said substituted cyclic anhydride to form a diol reduction; and (ii) sulfation of said diol to form a disulfate

其中所述的还原步骒包括在含过渡金属的加氢催化剂存在下的加压加氢步骤. Wherein said reducing step comprises pressing Ke hydrogenation step in the presence of a hydrogenation catalyst containing a transition metal.

当其包括时,本发明的洗衣洗涤剂组合物一般含有约0.1-50 %,优选约1-40重量%的阴离子表面活性剂. When it includes, the laundry detergent compositions of the invention typically contain about 0.1-50%, preferably about 1 to 40 wt% of an anionic surfactant.

(2) 非离子辅助表面活性剂: (2) Nonionic cosurfactant:

其量一般为约0.1- 50重量%的在本文中有用的非离子辅助表面活性剂的非限制性例子包括:烷氧基化的醇(AE)和烷基酚,多羟基脂肪酸跣胺(PFM),烷基多苷(APG) , C1()-Cm甘油酸等. In an amount typically from about 0.1 to 50 wt% of useful herein Nonlimiting examples of nonionic co-surfactants include: alkoxylated alcohols (AE) and alkyl phenols, polyhydroxy fatty acid amine Municipal (PFM ), alkyl polyglycosides (APG), C1 () - Cm glyceric acid and the like.

更具体地,伯和仲脂族醇与约1-25摩尔的环氧乙烷缩合物(AE) 适合用作本发明的非离子表面活性剂.该脂族醇的烷基链可以是直链或支链的、伯或仲的,并且通常含有约8-22个碳原子.优选的是具有含约8-20个碳原子,更优选约10- 18个碳原子烷基的醇与每摩尔醇约l-IO摩尔,优选2-7摩尔,最优选2-5摩尔环氧乙烷的缩合产物。 More specifically, primary and secondary aliphatic alcohols with about 1 to 25 moles of ethylene oxide condensate (AE) Suitable nonionic surfactants to be used herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to 22 carbon atoms. preferably having from about 8-20 carbon atoms containing, and more preferably from about 10 to 18 carbon atoms and an alkyl alcohol per mole alcohols having from about l-IO moles, preferably 2-7 moles, most preferably a condensation product of 2-5 moles of ethylene oxide. 特别优选的这类非离子表面活性剂是每摩尔醇含有3- 12摩尔环氧乙烷的C9-ds伯醇乙氧基化物,特别是每摩尔醇含有5- IO摩尔环氧乙烷的C12 - ds伯醇. Such particularly preferred nonionic surfactant per mole of alcohol contain 3-12 moles of ethylene oxide C9-ds primary alcohol ethoxylates, especially containing 5- IO per mole of alcohol moles of ethylene oxide C12 - ds primary alcohol.

可从市场上购得的这类非离子表面活性剂的例子包括:由Union Carbide Corporation铕售的Tergitol™ 15 - S - 9 ( C" - C15直链醇 Examples of this type of nonionic surfactant may be commercially available on the market include: europium sold by Union Carbide Corporation of Tergitol ™ 15 - S - 9 (C "- C15 linear alcohol

与9摩尔环氧乙烷的缩合产物)和Tergito^24-L-6NMW(窄分子量分布的C12-Cm伯醇与6摩尔环氧乙烷的缩合产物);和由Shell Chemical Company销售的Neodol™ 45 - 9 ( C"- C15直链醇与9摩尔环氧乙烷的缩合产物)、Neodol™ 23-3 (C12-ds直链醇与3.0摩尔环氧乙烷的缩合产物)、Neodol™ 45-7 (C14-ds直链醇与7摩尔环氧乙烷的缩合产物)、Neodol™ 45-5 (C"-ds直链醇与5摩尔环氧乙烷的缩合产物);由Procter & Gamble Company铕售的Kyro™ EOB (C13-ds醇与9摩尔环氧乙烷的縮合产物);和由Hoechst铕售的Genapol LA 030或050 (C12-C"醇与3或5摩尔环氧乙烷的縮合产物).这些AE非离子表面活性剂的HLB的优选范围是8-17,最优选8-14。也可以使用与环氧丙烷和环氧丁烷的缩合物. The condensation product of 9 moles of ethylene oxide) and Tergito ^ 24-L-6NMW (narrow molecular weight distribution of C12-Cm primary alcohol and the condensation product of 6 moles of ethylene oxide); and sold by Shell Chemical Company of Neodol ™ 45 - 9 (C "- C15 linear alcohol with 9 moles ethylene oxide), Neodol ™ 23-3 (C12-ds linear alcohol and the condensation product of 3.0 moles of ethylene oxide), Neodol ™ 45 7 (the condensation product of C14-ds linear alcohol with 7 moles of ethylene oxide), Neodol ™ 45-5 (C "-ds linear alcohol with 5 moles of ethylene oxide); manufactured by Procter & Gamble europium Company sold Kyro ™ EOB (C13-ds alcohol with 9 moles ethylene oxide); and europium sold by Hoechst Genapol LA 030 or 050 (C12-C "alcohol with 3 or 5 moles of ethylene oxide condensation products). preferred range of HLB in these AE nonionic surfactants is 8-17, most preferably 8-14 may be used with propylene oxide and butylene oxide condensates.

用于本文中的另一类优选的非离子辅助表面活性剂是下式的多幾基脂肪酸酰胺表面活性剂: Another preferred for use herein nonionic cosurfactant of the formula is a few more fatty acid amide surfactant:

其中Ri是H,或W是d-4烃基、2-羟基乙基、2-羟基丙基或其混合物,W是(VM烃基,和Z是具有直链烃基链、至少3个羟基直接连接到该链上的多鞋基烃基,或其烷氧基化的衍生物.优选地,W是甲基, Wherein Ri is H, or W is d-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, W is (VM hydrocarbyl, and Z is a straight chain hydrocarbon chain with at least 3 hydroxyls directly connected to the many shoes on the chain hydrocarbon group, or an alkoxylated derivative thereof. preferably, W is methyl,

W是直链Cu。 W is a linear Cu. 5烷基或d6-n烷基或链烯基链,例如椰子烷基或其混合 5-alkyl or alkyl or d6-n alkenyl chain such as coconut alkyl or mixtures thereof

物,和Z是在还原胺化反应中从还原糖如葡萄糖、果糖、麦芽糖、乳糖衍生的. 一般例子包括C^-dB和C12-C" N-甲基葡糖酰胺。见US5194639和US5298636,也可以使用N-烷氧基多羟基脂肪酸酰胺; 见US5489393. Thereof, and Z is in the reductive amination reaction is derived from a reducing sugar such as glucose, fructose, maltose, lactose general examples include C ^ -dB and C12-C "N- methyl glucamide., See US5194639 and US5298636, N- may also be used-alkoxy polyhydroxy fatty acid amides; see US5489393.

作为本发明的非离子辅助表面活性剂也有用的是烷基多糖,例如在US4565647( Llenado, 1986年1月21日颁布)中公开的烷基多糖, 该多糖具有含约6 - 30,优选约10- 16个碳原子的疏水基团和含约1. 3 -10,优选约1.3-3,最优选约1.3-2.7个糖单元的多糖如多苦亲水基团。 Also useful as the nonionic co-surfactants of the present invention are alkylpolysaccharides agents, for example, in US4565647 (Llenado, 1986, issued May 21 years. 1) alkylpolysaccharides disclosed in the polysaccharide having containing from about 6--30, preferably from about 10-16 hydrophobic group carbon atoms and containing from about 1.3 - 10, preferably about 1.3 to 3, most preferably from about 1.3-2.7 polysaccharide saccharide units, such as how hard hydrophilic group. 可以使用任何含有5或6个碳原子的还原糖,例如,可以用葡萄糖、半乳糖和半乳糖基部分代替葡糖基部分(任选地,在2-, 3 -,4-等位连接疏水基团从而得到对应于葡糖普或半乳糖苷的葡萄糖 Any reducing saccharide containing 5 or 6 carbon atoms, for example, glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally substituted at the 2-, 3 -, 4-, etc. positions joining the hydrophobic group P to give the corresponding glucose or galactose glucose

或半乳糖).该糖间键可以在,例如,附加糖单元的一个位置和上述 Or galactose). The inter-sugar linkages may be, for example, a position of the additional saccharide units and said

糖单元的2-, 3-, 4-,和/或6-位之间. 优选的烷基多苷具有下式: . 2-, 3-, 4- and / or 6-position of the sugar units is preferably alkylpolyglycosides have the formula:

R20 (CBH2nO) t (糖基): R20 (CBH2nO) t (glycosyl):

其中f选自:烷基、烷基苯基、雍基烷基、羟基烷基苯基、和其混合物,其中烷基含有约10-18,优选约12-14个碳原子;n是2或3, 优选2; t是0-约IO,优选O; x是约1.3-10,优选约1.3-3,最优选约1.3-2.7.该糖基优选是从葡萄糖衍生的.为了制备这些化合物,先形成醇或烷基聚乙氧基醇,然后与葡萄糖,或葡萄糖源反应, 形成葡糖苷(在1-位连接).然后在其1-位和上迷糖基单元的2-, 3-, 4-,和/或6-位,优选主要在2-位之间连接上另外的糖基单元。 Wherein f is selected from: alkyl, alkylphenyl, Yong alkyl group, hydroxy alkyl group, and mixtures thereof, wherein the alkyl groups contain about 10-18, preferably about 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about the IO, preferably O; x is from about 1.3 to 10, preferably from about 1.3 to 3, most preferably from about 1.3 to 2.7 the glycosyl is preferably derived from glucose to prepare these compounds. to form an alcohol or alkylpolyethoxy alcohol, and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). then their 1-position and the above-glycosyl units 2-, 3- , 4- and / or 6-position, preferably predominately the 2-position on the connected additional glycosyl units. 这类化合物及其用于洗涤剂中公开于EP-B- 0070077、 0075996 和0094118中。 Such compounds are disclosed for use in detergents and in EP-B- 0070077, 0075996 and 0094118..

烷基酚的聚环氧乙烷、聚环氧丙烷和聚环氧丁烷缩合物适用于作为本发明表面活性剂体系的非离子表面活性剂,聚环氧乙烷的缩合物是优选的.这些化合物包括:具有含约6-14个碳原子,优选约8-14个碳原子的直链或支链烷基的烷基酚与烯化氧的缩合产物.在优选的实施方案中,环氧乙烷的存在量等于每摩尔烷基酚约2-25摩尔, 更优选约3- 15摩尔的环氧乙烷.可从市场上购得的这类非离子表面活性剂包括:由GAF Corporation铕售的Igepal™ CO - 630;和均由Rohm & Haas Company铕售的Triton™ X — 45、 X— 114、 X — 100和X -102.这些表面活性剂通常被称之为烷基酚烷氧基化物(例如,烷基酚乙氧基化物)。 Alkylphenol polyethylene oxide, polypropylene oxide and polybutylene oxide condensates suitable as the nonionic surfactant of the surfactant systems of the present invention, the polyethylene oxide condensates are preferred. these compounds include: the condensation product contains from about having 6-14 carbon atoms, a straight-chain or branched-chain alkyl group is preferably from about 8 to 14 carbon atoms, alkylphenol alkylene oxide and in a preferred embodiment, ring. ethylene oxide is present in an amount equal to about 25 moles per mole of alkyl phenol, more preferably about 3-15 moles of ethylene oxide such nonionic surfactants may be commercially available on the market include: manufactured by GAF Corporation europium sold Igepal ™ CO - 630;. by Rohm & Haas Company and sold by europium Triton ™ X - 45, X- 114, X - 100 X -102 and these surfactants are commonly referred to as alkylphenol alkoxylates alkoxylates (e.g., alkyl phenol ethoxylates).

环氧乙烷与通过环氧丙烷与丙二醇缩合形成的疏水基的缩合产物也适合用作本发明的附加非离子表面活性剂。 Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable non-ionic surfactants additionally used according to the present invention. 这些化合物的疏水部分的分子量优选为约1500- 1800并显示出水不溶性。 The molecular weight of the hydrophobic portion of these compounds is preferably about 1500-1800 and exhibits water insolubility. 将聚氧乙烯部分加成到该疏水部分会增加整个分子的水溶性,并且保持该产品的液体性质最高到聚氧乙蜂含量是该縮合产物总重量的约50%,它相应于与最多约40摩尔的环氧乙烷縮合.这类化合物的例子包括某些可从市场上购得的由BASF销售的PluronicT"表面活性剂。 The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is maintained up to bee polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to the most about 40 moles of ethylene oxide. examples of compounds of this type include certain of the commercially available on the market, marketed by BASF PluronicT "surfactant.

也适合用作本发明非离子表面活性剂体系的非离子表面活性剂是环氧乙烷与从环氧丙烷和乙二胺反应得到的产物的缩合产物.这些产物的疏水部分由乙二胺和过量环氧丙烷的反应产物组成,并且分子量 Also suitable nonionic surfactant systems of the present invention as nonionic surfactants are condensation products of ethylene oxide with propylene oxide and ethylenediamine from the product obtained from the reaction of the hydrophobic moiety of these products consists of ethylenediamine and reaction products of excess propylene oxide composition and the molecular weight

一般是约2500- 3000.该疏水部分与环氧乙烷缩合,其程度为该缩合产物含有约40- 80% (重量)的聚氧乙烯并且分子量为约5000-11000.这类非离子表面活性剂的例子包括某些可从市场上购得的由BASF销售的Tetronic""化合物. Typically from about 2500 to 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40 to 80% (by weight) polyoxyethylene and a molecular weight of about 5000-11000. Such non-ionic surfactant examples of agents include certain commercially available from marketed by BASF Tetronic "" compound.

还优选的非离子表面活性剂是氧化胺表面活性剂.本发明的组合物可以包括下面通式I的氧化胺: Also preferred nonionic surfactants are the amine oxide surfactant composition of the present invention may comprise amine oxide of the general formula I:

R1 (E0): (P0) y (B0)豕N (0) (CH2R,) 2 • qiW (I) R1 (E0): (P0) y (B0) hog N (0) (CH2R,) 2 • qiW (I)

通常可以看到结构式(I)提供了1个长链部分R1 (E0), (P0) 7 (BO)豕和2个短链部分CH2R,. R,优选选自氢、甲基和-CHjjOH.通常R1是伯或支链的烃基部分,它可以是饱和或不饱和的,优选W是伯烷基部分. 当x+y+z-0时,W是具有约8-18链长度的烃基部分.当x+y+z 不等于0时,W可以稍微长一些,具有d广Cw的链长度.该通式也可以包括其中x+y+z= 0, R1-"-C18, R,-H和q-0-2,优选2的氧化胺.这些氧化胺说明如下:Cu-"烷基二甲基氧化胺,十六烷基二甲基氧化胺,十八烷基氧化胺和其水合物,尤其是二水合物,如在US5075501和US5071594中所公开的,这2篇文献在本文中引作参考. See generally provides a long-chain moiety R1 (E0) of formula (I), (P0) 7 (BO) and two short chain hog portion CH2R ,. R, is preferably selected from hydrogen, methyl and -CHjjOH. typically R1 is a primary or branched hydrocarbyl moiety, which may be saturated or unsaturated, preferably W is a primary alkyl moiety. when x + y + when z-0, W is a hydrocarbyl moiety having a chain length of about 8 to 18 when x + y + z is not equal to 0, W may be somewhat longer, having a chain length d of this broad formula Cw may also include those wherein x + y + z = 0, R1 -. "- C18, R, - . H and q-0-2, preferably 2. these amine oxide amine oxides as follows: Cu- "alkyl dimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and hydrated thereof, particularly the dihydrate, as disclosed in US5075501 and US5071594, which two documents incorporated by reference herein.

本发明也包括这样的氧化胺,其中x+y+z不等于0,尤其是x + 7+2是约1-10, W是含有8-约24个碳原子,优选约12-16个碳原子的伯烷基;在这些实施例中,y+z优选是0, x优选是约l-6, 更优选约2-4; E0表示乙烯氧基;P0表示丙烯氧基;B0表示丁烯氧基。 The present invention also encompasses amine oxides wherein x + y + z is not equal to 0, in particular x + 7 + 2 is about 1-10, W containing 8 to about 24 carbon atoms, preferably from about 12 to 16 carbon primary alkyl atoms; in these embodiments, y + z is preferably 0, x is preferably from about l-6, and more preferably from about 2-4; E0 represents an ethyleneoxy group; P0 represents a propyleneoxy group; B0 represents butene group. 通过常规的合成方法,例如通过烷基乙氧基疏酸盐与二甲基胺反应接着用过氧化氢将乙氧基化的胺氧化可以制备这样的氧化胺。 By conventional synthetic methods, e.g., by hydrophobic alkyl ethoxy dimethyl amine salt with the amine oxides, ethoxylated amine oxide can be prepared and then hydrogen peroxide.

本文中非常优选的氧化胺在室温下是溶液'适用于本文中的氧化胺是由很多制造商工业制造的,他们包括Akzo Chemie, Ethyl Corp. 和Procter & Gamble.对于其它的氧化胺制造商见McCutcheon的汇编和Kirk - Othmer的综述文章. Highly preferred herein is amine oxide solution at room temperature 'suitable amine oxides herein by many manufacturers of industrial manufacturing, they include Akzo Chemie, Ethyl Corp., and Procter & Gamble. For other amine oxide manufacturers see McCutcheon's compilation and Kirk - Othmer review article.

尽管在某些优选实施例中R,是H,但对于比H略徵长些的R,可以有一些宽容度.具体地,本发明还包括其中R,是CH20H的实施例,例如十六烷基双(2-羟乙基)氧化胺、牛油双(2-羟乙基)氧化胺、 硬脂基双(2-羟乙基)氧化胺和油基双(2-羟乙基)氧化胺、十二烷基二曱基氧化胺二水合物. Although in certain embodiments preferred embodiment R is H, but the intrinsic slightly longer than H, R, can have some tolerance. In particular, the present invention further include those wherein R is CH20H embodiments, e.g. hexadecane bis (2-hydroxyethyl) amine oxide, tallow bis (2-hydroxyethyl) amine oxide, stearyl bis- (2-hydroxyethyl) oleyl amine oxide, and bis (2-hydroxyethyl) oxide amine, dodecyl dimethyl amine oxide dihydrate Yue.

(3)阳离子辅助袅面活性剂: (3) cationic co-surfactants delicate:

其量一般为约0.1-50重量%的阳离子辅助表面活性剂的非限制性例子包括:胆碱酯型季铵和烷氧基化的季铵(AQA)表面活性剂化合物等。 Non-limiting examples of which amount is generally from about 0.1 to 50 wt% of cationic co-surfactants include: quaternary ammonium and choline ester alkoxylate quaternary ammonium (AQA) and other surface-active compounds.

作为表面活性剂体系组分有用的阳离子辅助表面活性剂是胆碱醋型季铵阳离于表面活性剂,其优选是具有表面活性剂性质并且包括至少一个酯(即-coo-)键和至少一个阳离子带电基团的水分散性的化 Useful as a component of the surfactant system is a cationic choline cosurfactant vinegar quaternary ammonium type cationic surface active agent in which preferably having surfactant properties and comprise at least one ester (i.e. -COO-) linkage and at least one cationic water-dispersible charged group of

合物.例如,合适的阳离子酯表面活性剂,包括胆械酯表面活性剂, Thereof. For example, a suitable cationic ester surfactants, including bile mechanical ester surfactant,

已经在US4228024、 US 4239660和US4260529中公开了。 Already in US4228024, US 4239660 and US4260529 disclose. 优选的阳离子酯表面活性剂是具有下式的那些化合物: Preferred cationic ester surfactants are those having the formula:

?5 节2 R,〖0[(CH)n。 ? Section 5 2 R, 〖0 [(CH) n. 〗b)厂(X)^(CH2)『(Y)^"(CH2)^N^R3 NT 〗 B) Factory (X) ^ (CH2) "(Y) ^" (CH2) ^ N ^ R3 NT

R4 R4

其中&是Cs-Cw直链或支链烷基、链烯基或烷芳基链或者是M—N+ (R«R7R8) (C迅)s; X和Y各自独立地选自COO、 OCO、 0、 CO、 0C00、 C0NH、 NHCO、 OCONH和NHCOO,其中X或Y中至少一个是C00、 0C0、 0C00、 0C0NH或NHC00基团;R2、 R3、 R" RB、 &和Rb各自独立地选自具有1 -4个碳原子的烷基、链烯基、羟基烷基、羟基链烯基和烷芳基;和Rs独立地是H或C广C3烷基;其中迈、n、 s和t的值各自独立地在0 -8的范围,b的值在0-20的范围,a、 u和v的值各自独立地是O 或1,条件是u或v中的至少一个必须是1;和其中M是抗衡阴离子. R2、 Ra和&优选各自独立地选自CHa和-CH2CH20H, M优选选自卣化物、甲基疏酸根、硫酸根和硝酸根,更优选甲基硫酸根、氯化物、溴化物或碘化物. Wherein & Cs-Cw is straight or branched alkyl, alkenyl or alkaryl chain or M-N + (R «R7R8) (C Motion) s; X and Y are each independently selected from COO, OCO, 0, CO, 0C00, C0NH, NHCO, OCONH and NHCOO, wherein at least one of X or Y is a C00, 0C0, 0C00, 0C0NH or NHC00 group; R2, R3, R "RB, & and Rb are each independently selected from having 1-4 carbon atoms, alkenyl, hydroxyalkyl, hydroxy alkenyl and alkaryl groups; and Rs are independently H or C wide C3 alkyl group; wherein Mai, n, s and t values ​​independently in the range of 0-8, b is a value in the range of 0 to 20, the value of a, u and v are each independently O or 1, with the proviso that u or v must be a least 1; and wherein M is a counter anion. R2, Ra, and preferably are each independently selected from & CHa and -CH2CH20H, M is preferably selected from compounds wine container, methyl sparse, sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or iodide.

优选的水分散性的阳离子酯表面活性剂是具有下式的胆碱酯: Cationic ester surfactant is preferably water-dispersible are the choline esters having the formula:

R,COCH2CH2N二CH3 M CH3 R, COCH2CH2N two CH3 M CH3

其中Ri是Cn _ C19直链或支链烷基链. Wherein Ri is Cn _ C19 straight or branched alkyl chain.

特别优选的这类胆碱酯包括:硬脂跣基胆碱酯季甲基铵齒化物(R1 二Cn烷基)、棕榈跣基胆碱酯季甲基铵卣化物(R^Cw烷基)、肉豆蔻跣基胆碱酯季甲基铵卣化物(R^Cu烷基)、月桂酰基胆碱酯季甲基铵卣化物(R^Cu烷基)、挪子酰基胆碱酯季甲基铵卣化物(R1-Cu - C13烷基)、牛油酰基胆碱酯季甲基铵卤化物(R1 = C15 - C17烷基), 和其任意混合物. Particularly preferred choline esters of this type include: stearyl Municipal yl choline ester quaternary ammonium compound of teeth (R1 Cn two alkyl), palmitoyl choline ester quaternary methylammonium Municipal yl wine container ammonium compounds (R ^ Cw alkyl), myristyl Municipal choline ester quaternary methylammonium wine container compounds (R ^ Cu alkyl), lauroyl choline ester quaternary methylammonium wine container compounds (R ^ Cu alkyl), move the sub-acyl choline ester quaternary methylammonium wine container compounds (R1-Cu - C13 alkoxy yl), tallowyl choline ester quaternary methylammonium halides (R1 = C15 - C17 alkyl), and any mixtures thereof.

通过所需链长度的脂肪酸与二甲基氨基乙醇在酸催化剂存在下直接酯化可以制备上面给出的特别优选的胆碱酯.然后该反应产物用甲基卣优选在溶剂如乙醇、丙二醇或优选脂肪醇乙氧基化物如乙氧基化度为每摩尔3-50个乙氧基的d。 By the desired chain length with dimethylaminoethanol fatty acid direct esterification in the presence of an acid catalyst can be prepared particularly preferred choline esters, given above. The reaction product is then preferably methyl wine container in a solvent such as ethanol, propylene glycol or preferably fatty alcohol ethoxylates, such as degree of ethoxylation of 3-50 ethoxy groups per mole. d. -Cw脂肪醇乙氧基化物存在下季铵化从而形成所需要的阳离子材料。 -Cw alcohol ethoxylates under the presence of a cationic material to form a quaternized required. 它们也可以通过将所需链长度的长链脂肪酸与2-卣代乙醇一起在酸催化剂材料存在下直接酯化来制备。 They may also be desired chain length long chain fatty acid with 2-generation ethanol wine container prepared with an acid catalyst material is present in the direct esterification. 然后将反应产物用三甲基胺季铵化从而形成所需要的阳离子材料. The reaction product was then trimethylamine quaternized to form cationic materials required.

其它合适的阳离子酯表面活性剂具有下面结构式,其中d可以是0 一20: Other suitable cationic ester surfactants have the structural formulas below, wherein d may be 0 to 20:

<formula>formula see original document page 56</formula> <Formula> formula see original document page 56 </ formula>

在优选的方面,这些阳离子酯表面活性剂是在洗衣洗涤方法条件下可水解的。 In a preferred aspect these cationic ester surfactants under process conditions hydrolyzable laundry wash.

本文中有用的阳离子辅助表面活性剂包括具有下式的烷氣基化的 Useful herein include cationic co-surfactants having the formula alkyl group of gas

季铵(AQA)表面活性剂化合物(下文中称之为"AQA化合物"): Quaternary ammonium (AQA) surfactant compounds (hereinafter referred to as "AQA compounds"):

<formula>formula see original document page 57</formula>其中W是含有约8-18个碳原子,优选10-约16个碳原子,最优选约10- 14个碳原子的直链或支链烷基或链雄基部分;1?2是含有l-3 个碳原子的烷基,优选甲基;W和R"可以各自独立地变化并且选自氬(优选的)、甲基和乙基;X—是足以提供电中性的阴离子,例如氯化物、溴化物、甲基疏酸根、疏酸根或类似物.A和A,可以各自独立地变化并且分别选自d-"烷氧基,尤其是乙氧基(即-CH2CH20-), 丙氧基,丁氧基和混合的乙氧基/丙氧基;p是0-约30,优选l-约4; q是0-约30,优选1-约4,最优选-约4;优选p和q都是1。 <Formula> formula see original document page 57 </ formula> where W containing about 8-18 carbon atoms, preferably 10 to about 16 carbon atoms, a straight-chain or branched alkyl and most preferably from about 10 to 14 carbon atoms, group or a chain male moiety;? 12 is an alkyl group containing l-3 carbon atoms, preferably methyl; W is and R "may each vary independently and are selected from argon (preferred), methyl and ethyl; X- - it is sufficient to provide electrical neutrality of the anions such as chloride, bromide, methyl acid radical thinning, thinning .A acid radical or the like and a, can vary independently and are selected from d- "alkoxy, especially ethoxy (i.e., -CH2CH20-), propoxy, butoxy and mixed ethoxy / propoxy; p is from 0 to about 30, preferably from about l- 4; q is from 0 to about 30, preferably 1 - about 4, most preferably - to about 4; p and q are preferably 1. 还参见:1979年5月30曰公开的Procter & Gamble Company的EP2084,它描迷了在本文中有用的这类阳离子辅助表面活性剂, See also: Procter & Gamble Company of EP2084 1979 on May 30, said disclosure, which describe fans useful herein such cationic co-surfactant,

其中烃基取代基Ri是C8-Cn,尤其是d。 Wherein the hydrocarbyl substituent Ri is C8-Cn, especially d. 的AQA化合物与较高链长度材料相比增强了洗衣顆粒的溶解速率,尤其是在冷水条件下.因此,某些配方师可以优选Cs-CuAQA表面活性剂.用于制备成品洗衣洗涤剂组合物的AQA表面活性剂的含量可以在约0.1-5重量%的范围, 一般约0.45-2.5重量%. The AQA compounds compared to higher chain length material enhances the dissolution rate of laundry granules, especially under cold water conditions. Thus, the formulator can in some Cs-CuAQA preferred surfactant for the preparation of the finished laundry detergent compositions content of AQA surfactants may be in the range of from about 0.1 to 5% by weight, generally from about 0.45-2.5 wt%.

根据上面所述,下面是本文中使用的AQA表面活性剂的非限制性的具体说明。 From the above, the following are non-limiting detailed description AQA surfactants used herein. 应该懂得:根据常规乙氧基化的非离子表面活性剂的通常惯例,本文中说明的AQA表面活性剂的烷氧基化度是平均值.这是因为乙氧基化反应一般产生具有不同乙氧基化度的各材料的混合物. 因此,非整数的总EO值例如"E0 2.5" 、 "E0 3.5"等是正常的.符号 £2 AdR3 A'aR4 It should be understood: according to the usual practice of conventional ethoxylated nonionic surfactants, herein described degree of alkoxylation AQA surfactants is an average because the ethoxylation reactions typically produce different B. mixture of alkoxylated material degree. Therefore, the total EO e.g. non-integer value "E0 2.5", "E0 3.5" and the like are normal symbol £ 2 AdR3 A'aR4

AQA.l C12-Cl4 CH3 EO EO AQA.l C12-Cl4 CH3 EO EO

(也称为椰于 (Also known as coconut in

甲基E02) Methyl E02)

AQA-2 Cl2《16 CH3 (EO)2 EO AQA-2 Cl2 "16 CH3 (EO) 2 EO

AQA-3 CH3 (EO)2 (EO)2 AQA-3 CH3 (EO) 2 (EO) 2

(椰于曱基E04) (Yeyuyueji E04)

AQA4 CH3 EO EO AQA4 CH3 EO EO

AQA-5 Ci2-Ci4 CH3 (EO)2 (EO)3 AQA-5 Ci2-Ci4 CH3 (EO) 2 (EO) 3

AQA-6 C12-C14 CH〗 (EO)2 (EO)3 AQA-6 C12-C14 CH〗 (EO) 2 (EO) 3

AQA-7 CH3 (EO)3 (EO)2 AQA-7 CH3 (EO) 3 (EO) 2

AQA-8 Cl2-仁i4 CH3 (EO)4 (EO)4 AQA-8 Cl2- kernel i4 CH3 (EO) 4 (EO) 4

AQA-9 (EO)3 (EO)3 AQA-9 (EO) 3 (EO) 3

AQA-10 C3H7 (EO)3 (EO)4 AQA-10 C3H7 (EO) 3 (EO) 4

AQA-11 CH3 (丙氧基) (EO)3 AQA-11 CH3 (propoxy) (EO) 3

AQA-I2 C2H5 (异丙氧基^ (EO)3 AQA-I2 C2H5 (isopropoxy ^ (EO) 3

AQA-13 CH3 (EO)3 AQA-13 CH3 (EO) 3

AQA-14 仁8化 CH3 (EO)15* (EO)15* AQA-14 kernel 8 of CH3 (EO) 15 * (EO) 15 *

AQA-15 C】D CH3 EO EO AQA-15 C] D CH3 EO EO

AQA-16 CH3 EO EO AQA-16 CH3 EO EO

AQA-17 CH3 -平均EO 3.5 AQA-17 ​​CH3 - average EO 3.5

AQA"8 Cl2 CH3 -平均E03.5 一 AQA "8 Cl2 CH3 - a average E03.5

CH3 阔o CH3 wide o

C2H5 (EO)3 C2H5 (EO) 3

C2H5 (EO)5 (EO)3 C2H5 (EO) 5 (EO) 3

C3H7 Bu (EO)2 C3H7 Bu (EO) 2

AQA.19 AQA-20 AQA-2】 AQA-22 AQA.19 AQA-20 AQA-2] AQA-22

*乙氧基,任选地用甲基或乙基封端. * Ethoxy, optionally capped with methyl or ethyl.

本文中的优选的双乙氧基化的阳离子表面活性剂可从Akzo Nobel Chemicals Company以商品名ETHOQUAD购得。 It preferred herein dual ethoxylated cationic surfactant available from Akzo Nobel Chemicals Company under the trade name ETHOQUAD.

用于本文中的非常优选的双-AQA化合物具有下式: Bis -AQA compound used herein is highly preferred has the formula:

1 ,CH2CH2OH 1, CH2CH2OH

N+、 X CH2CH2OH N +, X CH2CH2OH

其中R'是d。 Wherein R 'is d. -ds烃基和其混合物,优选do、 C12、 C"烷基和其混合物, X是任何提供电荷平衡的合适的阴离子,优选氯化物.参考上述一般AQA结构式,因为在优选的化合物中W是从椰子(C12-C"烷基)馏份脂肪酸衍生的,f是甲基和ApW和A,qW分别是单乙氧基,所以在本文中该优选类型的化合物在上表中称为"椰子甲基E02"或"AQA- 1"。 -ds hydrocarbyl and mixtures thereof, preferably do, C12, C "alkyl, and mixtures thereof, X is any suitable anion to provide charge balance, preferably chloride. AQA reference to the above general formula, because the preferred compounds from the W coconut (C12-C "alkyl) fraction fatty acid-derived, f is methyl and ApW and a, qW ethoxy are single, it is the preferred type of compound is referred to in the table herein" coconut a group E02 "or" AQA- 1 ". 本文中的其它优选的AQA化合物包括下式的化合物: Other preferred AQA compounds herein include compounds of the formula:

<formula>formula see original document page 59</formula> <Formula> formula see original document page 59 </ formula>

其中Ri是d。 Wherein Ri is d. -C"烃基,优选d。-C"烷基,独立地,p是l-约3, Q 是1-约3, W是d-C3烷基,优选甲基,X是阴离子,尤其是氯化物。 -C "hydrocarbyl, preferably d.-C" alkyl, independently, p is l- about 3, Q is 1 to about 3, W is d-C3 alkyl, preferably methyl, X is an anion, especially chlorine compounds. 其它上述类型的化合物包括其中乙氧基(CHaCHsO)单元(E0)被 Other compounds of the type described above include those wherein the ethoxy (CHaCHsO) units (E0) are

丁氧基(Bu)、异丙氧基[CH(CHa)CH20]和[CH,CH(CH3)0]单元(i-Pr) 或正丙氧基单元(Pr),或EO和/或Pr和/或i-Pr单元的混合物代替的那些化合物。 Butoxy (Bu), isopropoxy [CH (CHa) CH20] and [CH, CH (CH3) 0] units (i-Pr) or n-propoxy units (Pr), or the EO and / or Pr a mixture of those compounds and / or i-Pr units replaced.

下面说明可以用于本发明组合物中的其它添加剂组分,但并不打算限于这些组分。 Other additives described below may be components of the compositions used in the present invention, but are not intended to be limited to these components. 尽管中链支化的伯烷基聚氧化烯表面活性剂与这些添加剂组合物组分的组合可以使用常规技术以液体、凝胶、条或类似物的形式作为成品提供,但是本文中的粒状洗衣洗涤剂的制造需要一些特珠的加工技术以便达到最佳的性能.因此,为配方师的方便,下文中在顆粒制造部分(见下面)单独叙述洗衣颗粒的制造. Although the mid-chain branched primary alkyl polyoxyalkylene surfactant composition of these composition components and additives using conventional techniques in the form of liquids, gels, bars or the like provided as a finished product, but granular laundry article making a detergent requires some special beads processing techniques in order to achieve optimal performance. Accordingly, for the convenience of the formulator, the following particles making section (see below) is described in laundry particles alone.

附加的阳离子辅助表面活性剂描述于,例如,"Surfactant Science Series, Volume 4, Cationic Surfactants"或"Industrial Surfactants Handbook"中.描述于这些参考文献中的有用的阳离子表面活性剂类型包括酰胺季铵化合物(即Le叫uat AMG&Schercoquat CAS)、缩水甘油酸季铵化合物(即Cyostat 609)、羟基烷基季铵化合物(即Dehyquart E)、烷氧基丙基季铵化合物(即To迈ah Q-17-2)、 聚丙氧基季铵化合物(E边col CC-9)、环烷基铵化合物(即吡啶铕或咪唑铕季铵化合物)和/或节烷铵季铵化合物。 Additional cationic co-surfactants are described in, for example, "Surfactant Science Series, Volume 4, Cationic Surfactants" or "Industrial Surfactants Handbook". Described Useful surfactant types cations in these references include amide quats (i.e., called Le uat AMG & Schercoquat CAS), glycidyl acid quaternary ammonium compounds (i.e., Cyostat 609), hydroxyalkyl quats (i.e., Dehyquart E), alkoxypropyl quats (i.e., To step ah Q-17- 2), polypropoxylated quaternary ammonium compound (E side col CC-9), cyclic alkylammonium compounds (i.e., imidazol-europium or europium pyridine quaternary ammonium compound) and / or section benzalkonium quaternary ammonium compounds.

聚合的污垢解脱剂-在本发明的洗涤剂组合物中可以任选地使用已知的聚合的污垢解脱剂,下文中称之为"SRA"。 Polymeric soil release agent - in the detergent compositions of the present invention may optionally using known polymeric soil release agents, hereinafter referred to as "SRA". 如果使用的话,SRA 通常占组合物重量的0.01-10.0%, —般0.1-5%,优选0.2-3.0 %• If used, SRA generally comprise 0.01-10.0% by weight of the composition, - generally from 0.1 to 5%, preferably 0.2-3.0% •

优选的SRA —般具有使疏水纤维例如聚癍和尼龙表面亲水的亲水部分,和沉积在疏水纤维上并保持粘附其上直到完成洗涤和漂洗循环,由此对亲水部分起一个锚作用的疏水部分。 Preferred SRA - generally has a hydrophobic fibers such as hydrophilic nylon partial polymerization plaques and hydrophilic surface, and to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby starting an anchor for the hydrophilic portion the hydrophobic portion role. 这能够使得用污垢解脱剂处理后存在的污垢在后面的洗涤过程中更容易地清洗. This can enable stains present after treatment with the soil release agent is more easily cleaned in later washing procedures in.

SRA可以包括各种带电荷的例如阴离子或甚至阳离子的单体单元(见US4956447),以及不带电荷的单体单元,并且其结构可以是直链、支链或甚至是星形的.它们可以包括在控制分子量或者改变物理或表面活性性质方面特别有效的封端部分。 SRA, for example, may include various anionic or even cationic monomer units (see US4956447), and uncharged monomer units charged, and the structure may be linear, branched or even star-shaped. They may be including particularly effective in controlling molecular weight or altering the physical or surface-active properties end-capping moiety. 为了应用于不同的纤维或织物类型和为了各种洗涤剂或洗涤剂添加剂产品,可以调整结构和电荷分布. For application to different fiber or textile types and for a variety of detergent or detergent additive products, the structure and charge distribution can be adjusted.

优选的SRA包括低聚的对笨二酸酯,其一般是通过包括至少一个 Preferred SRA's include oligomeric terephthalate of stupid, generally by including at least one

常常使用金属催化剂例如烷醇钛(IV)的酯基转移/低聚反应的方法制备的.使用通过l、 2、 3、 4或更多位置能够加入到酯结构中(当然不形成稠密交联整体结构)的另外单体可以制备这样的酯. Are often prepared using a metal catalyst such as alkanol titanium (IV) transesterification / oligomerization reaction. By using l, 2, 3, 4 or more positions can be added to the ester in structure (of course, does not form a dense crosslinked overall configuration) additional monomers can be prepared esters.

合适的SRA包括:基本上直链酯低聚物的碌化产物,它由对苯二酰基的低聚癬骨架和氧化烯氧基重复单元和共价连接到骨架的烯丙基衍生的磺化端基部分组成,例如在US4968451 ( JJ Scheibel和EPGosselink, 1990年11月6日颁布)中所描述的.这样的酯低聚物可以通过下面步骤制备:(a)将烯丙醇乙氧基化;(b)在2步酯基转移/低聚方法中将(a)的产物与对苯二甲酸二甲酯("DMT")和1,2-丙二醇("PG")反应;和(c)将(b)的产物在水中与偏亚疏酸氢钠反应;US4711730 (Gosselink等人,1987年12月8日颁布)的非离子封端的1,2-丙蟑/聚氧乙烯对苯二酸酯聚醋,例如通过聚(乙二醇)甲基酸、DMT、 PG和聚(乙二醇)("PEG")的醋基转移/低聚制备的那些;US4721580 (Gosselink, 1988年1月26日颁布)的部分和全部阴离子封端低聚物酯,例如得自乙二醇("EG" ) 、 PG、 DMT 和3,6 - 二氧杂_ 8 -羟基辛烷磺酸钠 Suitable SRA's include: Lu product substantially linear ester oligomer, it is made up of repeating units of terephthaloyl backbone ringworm oligomeric oxyalkylene groups covalently to the backbone derived sulfonated allyl end group components, for example, in US4968451 (JJ Scheibel and EPGosselink, 1990 issued February 6 years. 11) as described in this ester oligomer can be prepared by the following steps:. (a) allyl alcohol ethoxylate ; (b) the product in step 2 transesterification / oligomerization in the method (a) and 1,2-propanediol with ( "PG") reaction of dimethyl terephthalate ( "DMT"); and (c ) (b) to the product of the reaction of the water repellent with sodium hydrogen metabisulfite; US4711730 (Gosselink et al., December 8, 1987 issued) nonionic-capped 1,2-propylene cockroach / polyoxyethylene terephthalate polyester esters, for example by a poly (ethylene glycol) methyl acid, DMT, PG and poly (ethylene glycol) ( "PEG") vinegar transferase / oligomeric those prepared; US4721580 (Gosselink, 1988 January promulgated 26) of the partial and total anionic capping oligomer esters, for example, from ethylene glycol ( "eG"), PG, DMT and 3,6 - dioxa _ 8 - hydroxy-octane sulfonate 低聚物;US4702857 (Gosselink, 1987年10月27日颁布)的非离子封端的嵌段聚酯低聚物,例如从DMT、甲基(Me)封端的PEG和EG和/或PG、或DMT、 EG 和/或PG、 Me封端的PEG和5-磺酸钠间苯二酸二甲酯制备的那些化合物;和US4877896 ( Maldonado, Gosselink等,1989年10月31 日颁布)的阴离子,特别是磺基芳酰基封端的对苯二酸酯,后者是一般用于洗衣和织物调理产品中的SRA,例子是从间磺基笨甲酸单钠盐、PG和DMT,任选但优选还包括加入的PEG例如PEG 3400,制备的酯组合物。 Oligomer; US4702857 (Gosselink, enacted October 27, 1987) nonionic-capped block polyester oligomers, such as from DMT, methyl (Me) capped PEG and EG and / or your PG, or DMT , EG and / or PG, PEG Me terminated and 5-sodium among those of the compound prepared dimethyl terephthalate; and US4877896 (Maldonado, Gosselink et al., October 31, 1989 issued) anions, in particular sulfoaroyl, end-capped terephthalate esters, which are generally used for laundry and fabric conditioning products SRA, examples from m-sulfobenzoic acid monosodium salt stupid, PG, and the DMT, optionally but preferably further comprising added the PEG example PEG 3400, prepared ester composition.

SRA还包括:对苯二酸乙二醇酯或对苯二酸丙二醇酯与对笨二酸聚环氧乙烷或聚环氧丙烷醋的简单共聚嵌段,见US3959230 ( Hays, 1976年5月25日頒布)和US3893929 ( Basadur, 1975年7月8曰颁布);纤维素衍生物例如从Dow以METHOCEL得到的羟基酸纤维聚合物; d - C4烷基纤维素和"羟基烷基纤维素,见US4000093( Nicol等,1976 年12月28日颁布).特征为聚(乙烯基酯)疏水部分的合适的SRA 包括接技在聚烯化氧骨架上的聚(乙烯基酯)例如C广Ce乙烯基酯, 优选聚(乙酸乙埽酯)的接枝共聚物。见Kud等1987年4月22曰公 SRA further comprising: a pair of ethylene terephthalate or propylene glycol esters of terephthalic acid and simple copolymeric blocks stupid acid polyethylene oxide or polypropylene oxide vinegar, see US3959230 (Hays, 1976 dated. 5 years promulgated 25) and US3893929 (Basadur, 1975 July 8, said issued); cellulose derivatives from Dow under the hydroxy acid polymer fibers obtained e.g. METHOCEL; d - C4 alkyl celluloses and "hydroxyalkyl cellulose, see US4000093 (Nicol et al., December 28, 1976 issued). suitable SRA's characterized by poly (vinyl ester) hydrophobe segments include graft on the backbone of the polyalkylene oxide, poly (vinyl esters) such as C wide Ce vinyl esters, preferably poly (ethyl acetate broom) a graft copolymer. see Kud et al. 1987, April 22, said well

开的欧洲专利申请0219048.商业购得的例子包括S0KALAN SRA例如从德国BASF得到的S0KALAN HP - 22.其它SRA是具有含10 _ 15 % (重量)对笨二酸乙二醇酯和80- 90% (重量)从平均分子量为300- 5000 的聚氧乙烯二醇衍生的聚氧乙烯对笨二酸酯重复单元的聚酯。 Examples of European Patent Application 0219048. apart commercially available include, for example, from BASF, Germany S0KALAN SRA obtained S0KALAN HP - 22. Other SRA is (by weight) having a 10 _ containing 15% of ethylene terephthalate and dumb 80-90 % (weight) average molecular weight of from 300-5000 polyoxyethylene diol-derived polyester of polyoxyethylene terephthalate repeating units stupid. 商业例子包括Dupont的ZELCON 5126和ICI的MILEASE T. Commercial examples include the ZELCON 5126 Dupont and ICI's MILEASE T.

另一个优选的SRA是具有经验式(CAP)2(EG/PG)s(T)5(SIPh的低聚物,其含有对笨二酰基(T),磺基间笨二酰基(SIP),氧化乙雄氧基和氧化-1,2-亚丙基(EG/PG)单元并且其优选是用封端基(CAP),优选改性的羟乙磺酸盐终止的,作为低聚物其包括l个磺基间苯二酰基单元,5个对笨二酰基单元,限定比例,优选约0.5: l-10: 1的氧化乙烯氧基和氧化-1,2-丙烯氧基单元,和2个从2-(2 -羟基乙氧基)-乙烷磺酸钠衍生的封端单元.按低聚物重量计,所述的SRA优逸还含有0.5-20%的降低结晶度的稳定剂,例如阴离子表面活性剂如直链十二烷基苯磺酸钠或选自二甲笨、枯烯和甲苯磺酸盐或其混合物的物质,将这些稳定剂或改性剂加入到合成容器中,如在US5415807 ( Gosselink, Pan, Kellet和Hall, 1995年5月16日頒布)所教导的.用于上式51^的合适的单体包括2- (2-羟基乙氧基) -乙烷磺酸钠、DMT、 5-磺酸钠间 Another preferred SRA having empirical formula (CAP) 2 (EG / PG) s (T) 5 (SIPh oligomers which contain diacyl stupid (T), diacyl sulfoisophthalic stupid (the SIP), ethoxylated male group and oxy-1,2-propylene (EG / PG) units and which is preferably terminated with a group (CAP), preferably modified isethionates terminated, as oligomer comprising l a sulfoisophthalic terephthaloyl units, 5 pairs stupid diacyl unit defined ratio, preferably about 0.5: l-10: 1 ethylene oxide group and oxy-1,2-propyleneoxy units, and 2 from 2- (2 - hydroxyethoxy) - ethane sulfonate derived end-capping units by weight of the oligomer, said Yi SRA preferably further contains a stabilizer of 0.5 to 20% reduction in the degree of crystallinity, for example, an anionic surfactant such as linear sodium dodecylbenzenesulfonate or xylene and selected, cumene and toluene sulfonate, or a mixture of substances, these stabilizers or modifiers added into the synthesis vessel, suitable monomers as in US5415807 (Gosselink, Pan, Kellet and Hall, 1995, issued on 16 May) teaches a formula 51 ^ include 2- (2-hydroxyethoxy) - ethane sulfonic among sodium, DMT, 5- sulfonate 二酸二甲酯、EG和PG. Dimethyl, EG and PG.

再一类优选的SRA是低聚醋,其包括:(l)一个骨架,该骨架包括:(a)至少一个选自下面的单元:二羟基磺酸盐、多羟基磺酸盐、至少是三官能团因此形成酯键导致支链低聚物骨架的单元,和其混合物;(b)至少一个对笨二甲酰基单元;和(c)至少一个未磺化的单元, 该单元是1,2-氧化亚烷氧基;和(2) —个或多个选自下面的封端单元:非离子封端单元,阴离子封端单元例如烷氧基化的,优选乙氧基化的羟乙磺酸盐、烷氧基化的丙烷磺酸盐、烷氧基化的丙烷二磺酸盐、 烷氧基化的苯酚磺酸盐,磺基芳酰基衍生物和其混合物.优选的是具有下面经验式的酯: Another class of preferred SRA's are oligomeric vinegar, which comprises: (L) a backbone, the backbone comprising: (a) at least one unit selected from the following: a dihydroxy sulfonates, polyhydroxy sulfonates, at least three functional group thus forming an ester bond resulting in a branched oligomer backbone units, and mixtures thereof; (b) at least one pair of stupid diformyl units; and (c) at least one unsulfonated unit which is a 1,2- oxyalkylene group; and (2) - one or more capping units selected from the following: a nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated isethionate salts, alkoxylated propane sulfonates, alkoxylated propane disulfonate, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. preferred having the empirical formula esters:

{(CAP) x (EG/PG) y, (DEG) y" (PEG) y," (T) z (SIP) z, (SEG) q (B)迈} {(CAP) x (EG / PG) y, (DEG) y "(PEG) y," (T) z (SIP) z, (SEG) q (B)} step

其中CAP, EG/PG, PEG, T和SIP与上面的定义相同,(DEG)表示二(氧化乙烯)氧基单元,(SEG)表示从甘油的磺基乙基醚和相关部分单元衍 Wherein CAP, EG / PG, PEG, T and SIP are as defined above and, (DEG) represents di (oxyethylene) oxy units, (SEG) represents a sulfo group from a glycerol ether derivative unit and related portions

生的单元,(B)表示至少是三官能团因此形成醱键导致支链低聚物骨架的支链化单元,x是约1-12, y,是约0.5-25, y"是0-约12, y," 是0-约IO, y, + y"+y,"总和是约0.5-25, z是约1.5-25, z,是0 -约12, z+ z,总和是约1.5-25, q是约0.05- 12; m是约0. 01 - 10; 并且x、 y,、 y"、 y,"、 z、 z,、 q和m表示每摩尔所述酯相应单元的平均摩尔数,并且所述薛的分子量在约500- 5000的范围. Health units, (B) is represented by at least trifunctional Po bond thus forming unit results in branched-chain branched oligomer backbone, x is about 1-12, y, is about 0.5-25, y "is from 0 to about 12, y, "is from 0 to about IO, y, + y" + y, "the sum is about 0.5-25, z is from about 1.5-25, z, is 0 - about 12, z + z, the sum is about 1.5 25, q is from about 0.05- 12; m is from about of 0. the 01--10; and x, y ,, y ", y,", z, z ,, q and m represent the average of the respective units of mole per mole of ester number, and a molecular weight in the range of Xue from about 500 to 5000.

上述酯的优选的SEG和CAP单体包括:2- (2 - , 3 - 二羟基丙氧基) 乙烷磺酸钠("SEG" ), 2-{2- (2-羟基乙氧基)乙氧基}乙烷磺酸钠("SE3")和其同系物和其混合物和乙氧基化和磺化烯丙醇的产物. 这类中的优选的SRA酯包括用适当的Ti(IV)催化剂将下面物质酯基转移和低聚的产物:2 - {2- (2-羟基乙氧基)乙氧基}乙烷磺酸钠和/或2- [2- {2- (2-羟基乙氧基)乙氧基)乙氧基]乙烷磺酸钠,DMT, 2_ (2,3 - 二羟基丙氧基)乙烷磺酸钠,EG和PG;其可以被称为(CAP)2(T〉5(EG/PG)1.4(SEG)2.5(B)0.13 , 其中CAP是(Na+ 一03S[CH2CH20]3.5)-和B是得自甘油的单元,并且EG/PG摩尔比是约1.7: 1,其是在完全水解后用常规的气相色谱测定的. Preferred SEG and CAP above-described ester monomers include: 2- (2 -, 3 - dihydroxy-propoxy) ethane sulfonate ( "SEG"), 2- {2- (2- hydroxyethoxy) ethoxy} ethane sulfonate ( "SE3") and its homologs and mixtures thereof and the products and sulfonated ethoxylated allyl alcohol. preferred SRA of this type include esters with an appropriate Ti (IV ) catalyst product material following transesterification and oligomerization of: 2 - {2- (2-hydroxyethoxy) ethoxy} ethane sulfonate and / or 2- [2- {2- (2- hydroxyethoxy) ethoxy) ethoxy] ethane sulfonate, DMT, 2_ (2,3 - dihydroxy-propoxy) ethane sulfonate, EG, and the PG; it may be referred to as (CAP ) 2 (T> 5 (EG / PG) 1.4 (SEG) 2.5 (B) 0.13, wherein CAP is (Na + a 03S [CH2CH20] 3.5) - and B is obtained glycerol units derived, and EG / PG molar ratio from about 1.7: 1, which is measured by conventional gas chromatography after complete hydrolysis.

另一类SRA包括:(I)用二异氰酸酯偶联剂连接聚合的醋结构的非离子对笨二酸酯,见US4201824 ( Violland等)和US4240918 (Lagasse等);和(II)通过将偏苯三酸酑加入到已知的SRA中从而将端羟基转变成偏苯三酸酯制备的具有羧酸酯端基的SRA.适当地选择催化剤,该偏笨三酸肝通过偏苯三酸肝的分离的羧酸的酯而不是通过打开酸酐键形成连接聚合物端基的键.可以使用非离子或阴离子SRA作为原料,只要它们具有可以酯化的羟基端基就行。 Another SRA comprising: (I) nonionic diisocyanate coupling link aggregation structure of vinegar stupid terephthalate, see US4201824 (Violland etc.) and US4240918 (Lagasse, etc.); and (II) by adding trimellitic Yu triacid added to known SRA so as to have a terminal hydroxyl group into a carboxylic acid ester end groups SRA's prepared trimellitic triglycerides. Ji suitably selected catalyst, the partial stupid tricarboxylic acid, trimellitic acid by the liver liver the isolated carboxylic acid ester linkage is formed instead of the polymer end groups by opening the anhydride linkages may be nonionic or anionic SRA used as starting materials as long as they have hydroxyl end groups can be esterified on the line. 见US4525524 (Tung等人);(III)尿烷键连变体的阴离子对笨二酸醋基的SRA, 见US4201824 ( Violland等);(IV)聚(乙烯基己内酰胺)和相关的与诸如乙烯基吡咯烷酮和/或甲基丙烯酸二甲基氨基乙基醋的单体的共聚物,包括非离子和阳离子聚合物,见4579681 (Ru卯ert等); (V)接技共聚物,除了得自BASF的SOKALAN类型之外,其是通过将丙烯酸单体接枝在磺化的聚癍上制备的。 See US4525524 (Tung et al.); (III) anionic urethane bond even stupid two variants of vinegar group SRA, see US4201824 (Violland et); (IV) poly (vinyl caprolactam) and related such as ethylene polyvinylpyrrolidone copolymer of a monomer and / or methacrylic acid dimethylaminoethyl vinegar, include nonionic and cationic polymers, see 4579681 (Ru et ert d); (V) graft copolymers, in addition to from addition SOKALAN types from BASF, which is prepared by grafting acrylic monomers on to sulfonated poly Ban. 这些SRA肯定具有类似于已知的纤雉素瞇的污垢解脱和抗再沉积活性:见EP279134A ( Rhone -Poulenc Chemie, 1988); (VI)乙烯基单体例如丙烯酸和乙酸乙烯酯在蛋白质例如酪蛋白上的接枝物,见BASF的EP457205 ( 1991); These soils have certainly similar to known SRA pheasant fiber element Mi release and anti-redeposition activity: see EP279134A (Rhone -Poulenc Chemie, 1988); (VI) vinyl monomers such as acrylic acid and vinyl acetate in a protein such as casein grafts on the protein, the see EP457205 BASF (1991);

(vn)通过缩合己二酸、己内酰胺和聚乙二醇制备的聚醋-聚酰胺 (VN) by condensing adipic acid, caprolactam, and polyethylene glycol prepared polyester - polyamide

SRA,尤其是用于处理聚酰胺织物,见Bevan等的DE2335044( Unilever NV, 1974)。 DE2335044 SRA, in particular for treating polyamide fabrics, see Bevan et al.'s (Unilever NV, 1974). 其它有用的SRA描迷于美国专利4240918、 4787989、 4525524和4877896中。 Other useful SRA fans described in U.S. Patent 4,240,918, 4,787,989, 4,525,524, and 4,877,896 are.

粘土污垢去除/抗再沉积剂-本发明的组合物也可以任选地含有具有釉土污垢去除和抗再沉积性质的水溶性乙氧基化的胺.含有这些化合物的顆粒洗涤剂组合物一般含有约0.01-10.0% (重量)的水溶性乙氧基化的胺;液体洗涤剂组合物一般含有约0.01-5% (重量). Clay soil removal / antiredeposition agent - The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil removal and enamel antiredeposition properties of granular detergent compositions which contain these compounds typically water-soluble ethoxylated amines containing from about 0.01 to 10.0% (by weight); a liquid detergent compositions typically contain about 0.01 to 5% (by weight).

最优选的污垢解脱和抗再沉积剂是乙氧基化的四亚乙基五胺。 The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene pentamine. 说明性的乙氧基化胺在US4597898 ( VanderMeer , 1986年7月1日颁布)中有进一步的描述.另一类优选的粘土污垢去除-抗再沉积剂是公开于欧洲专利申请111965 (Oh和Gosselink, 1984年6月27曰公开)中的阳离子化合物.可以使用的其它粘土污垢去除/抗再沉积剂包括公开于欧洲专利申请111984 (Gosselink, 1984年6月27曰公开)中的乙氧基化的胺聚合物;公开于欧洲专利申请112592 (Gosselink, 1984年7月4日公开)中的两性离子聚合物;和公开于US4548744 ( Connor, 1985年10月22日颁布)中的氧化胺。 Illustrative ethoxylated amines in US4597898 (VanderMeer, 1986 years. 7 dated issued. 1) are further described in Another group of preferred clay soil removal - antiredeposition agents are disclosed in European Patent Application 111965 (Oh and Gosselink, 1984 June 27, discloses said cationic compound) in. other clay soil can be used removal / anti-redeposition agents include those disclosed in European Patent application 111984 (Gosselink, 1984 June 27, said disclosure) ethoxymethyl amine polymers; disclosed in European Patent application 112592 (Gosselink, 1984 dated Tuesday for years. 7) the zwitterionic polymers; and disclosed in US4548744 (Connor, 1985 dated 22 is issued 10 years) amine oxide. 其它本领域已知的粘土污垢去除和/或抗再沉积剂也可以用于本文的组合物中.参见1990年1月2日授权的VanderMeer的US4891160和1995 年11月30日公开的W0 95/32272。 Other known in the art clay soil removal and / or anti-redeposition agents may be used in the compositions herein. See, January 2, 1990 and US4891160 authorized VanderMeer, 30 November 1995, disclosed in W0 95 / 32272. 另一类优选的抗再沉积剂包括羧甲基纤维素(CMC)材料.这些材料在本领域是熟知的. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

聚合的分散剂-聚合的分散剂可以以约0.1-7% (重量)的量有利地用于本文中的组合物中,尤其是存在沣石和/或层状硅酸盐助洗剂时.合适的聚合的分散剂包括聚合的多羧酸盐和聚乙二醇,尽管也可以使用本领域已知的其它分散剂。 Polymeric dispersing agent - when polymeric dispersants may advantageously be used in an amount of about 0.1-7% (by weight) of the compositions herein, especially in the presence Feng stone and / or layered silicate builders suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others may be used dispersing agents known in the art. 尽管不打算受理论限制,但是据信: 当与其它助洗剂(包括低分子量多羧酸盐)组合使用时,通过晶体生长抑制、颗粒污垢解脱胶溶和抗再沉积,聚合的分散剂增强了总的洗涤剂助洗剂性能. While not intending to be bound by theory, it is believed that: when other builders (including lower molecular weight polycarboxylates) are used in combination, by the crystal growth inhibition, particulate soil release peptization, and anti-redeposition, polymeric dispersants enhance the overall detergent builder performance.

通过将合适的不饱和单体优选以其酸形式聚合或共聚可以制备聚合的多羧酸盐材料.可以聚合形成合适的聚合多羧酸盐的不饱和单体酸包括:丙烯酸、马来酸(或马来酸酐)、富马酸、衣康酸、乌头酸、 中康酸、柠康酸和亚甲基丙二酸。 By suitable unsaturated monomers preferably in their acid form or copolymerized polymeric polycarboxylate polymeric material may be prepared polymerized to form suitable polymeric polycarboxylates acids include unsaturated monomers: acrylic acid, maleic acid ( or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene malonic acid. 在本文中的聚合的多羧酸盐中存在 Herein is present in the polymeric polycarboxylates

不含羧酸根基团的单体片段例如乙烯基甲基醚、苯乙烯、乙烯等是合 Monomeric segments containing no carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc. is bonded

适的,条件是这样的片段不构成大于约40% (重量). Suitable, provided that such segments do not constitute more than (by weight) to about 40%.

特别合适的聚合的多羧酸盐可以从丙烯酸得到,这样的在本文中有用的丙烯酸基的聚合物是聚合的丙烯酸的水溶性盐.酸形式的这样的聚合物的平均分子量优选在约2000- 10000的范闺,更优选约4000 -7000,最优选约4000- 5000.这样的丙烯酸聚合物的水溶性盐可以包括:例如碱金属、铵和取代铵的盐.这类可溶性聚合物是已知的材料。 Particularly suitable polymeric polycarboxylates can be derived from acrylic acid, such useful herein are polymers of acrylic acid based water-soluble salts of polymerized acrylic acid. Acid form of such polymers in the average molecular weight is preferably about 2000 Gui Fan 10000, more preferably about 4000-7000, most preferably about 4,000 to water-soluble salts of such acrylic acid polymers 5000. may include: for example, alkali metal, ammonium and substituted ammonium salts of such soluble polymers are known s material. 这类聚丙烯酸盐在洗涤剂组合物中的用途已经公开于例如US3308067 ( Mehl, 1967年3月7日颁布)中. Such polyacrylates use in detergent compositions has been disclosed, for example, US3308067 (Mehl, 1967 years. 3 dated issued. 7) in the.

丙烯酸/马来酸基的共聚物也可以用作分散剂/抗再沉积剂的优选组分.这样的材料包括丙烯酸和马来酸共聚物的水溶性盐.酸形式的这样的共聚物的平均分子量优选在约2000- 100000的范围,更优选约5000- 75000,最优选约7000- 65000.在这样共聚物中的丙烯酸盐与马来酸盐片段之比通常在约30: 1-1: l的范围,优选约10: 1 - 2: 1.这样的丙烯酸/马来酸共聚物的水溶性盐包括:例如,碱金属、铵和取代铵的盐.这类可溶性丙蜂酸盐/马来酸盐共聚物是已知的材料, 其*描逸于欧洲专利申请66915( 1982年12月15日公开)以及EP193360 (1986年9月3日公开),其还描述了含有羟基丙基丙烯酸盐的这种聚合物.也有用的其它分散剂包括马来酸/丙烯酸/乙烯醇三元共聚物.这样的材料也公开于EP193360中,包括例如丙烯酸/马来酸/乙烯醇的45/45/10三元共聚物- Such copolymers mean copolymers of acrylic acid / maleic acid groups may also be used as a dispersant / anti-redeposition agent is preferably the component. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The acid form molecular weight is preferably in the range of about 2,000 to 100,000, more preferably from about 5000-75000, ratio of acrylate to maleate segments most preferably from about 7000- 65000. in such a copolymer is generally from about 30: 1-1: l range, preferably from about 10: 1 - 2: 1. Water-soluble salts of such acrylic acid / maleic acid copolymers can include: for example, alkali metal, ammonium and substituted ammonium salts of such soluble propionic acid salt bee / maleic. acid copolymers are known materials which * Yi described in European Patent application No. 66915 (December 15, 1982 Publication) and EP 193,360 (Publication September 3, 1986) which also describes acrylate containing hydroxypropyl such polymers. other useful dispersants also include the maleic / acrylic / vinyl alcohol terpolymers. such materials are also disclosed in EP193360, including, for example, acrylic / maleic / vinyl alcohol 45/45 / 10 terpolymer -

另一个可以包括的聚合的材料是聚乙二醇(PEG) 。 Another polymeric material which can be included is polyethylene glycol (PEG). PEG可以显示出分散剂的性能以及起粘土污垢去除-抗再沉积剂的作用.用于这一目的的一般分子量范围在约500- 100000的范闺,优选约1000-50000,更优选约1500- 10000. PEG can exhibit a clay soil removal performance as well as from dispersant - antiredeposition agents acting molecular weight range for this purpose is generally in the range of about 500 to 100,000 Gui, preferably about 1000-50000, more preferably about 1500. 10000.

也可以使用聚天冬氨酸盐和聚谷氨酸盐分散剂,尤其是与沐石助洗剂一起使用.分散剂如聚天冬氨酸盐优选具有约10000的分子量(平 May also be used as polyaspartate and polyglutamate dispersing agents, especially for use with Mu stone builders dispersant such as polyaspartate preferably have a molecular weight of about 10,000 (the

均值)。 Mean).

增白剂-可以将任何本领域已知的荧光增白剂或其它增艳或增白 Brightener - Any known in the art may be optical brighteners or other brightening or whitening

剂加入到本文的洗涤剂组合物中,其量一般是约0.01-1.2°/。 It is added to the detergent compositions herein, typically an amount of about 0.01-1.2 ° /. (重量)。 (weight). 可以有用于本发明的市售荧光增白剂可以分成亚组,它包括, 但不必限于,芪、吡唑啉、香豆素、羧酸、次甲基花青、二笨并噻吩 Commercial optical brighteners which can be used in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, thiophene and two stupid

-5,5-二氧化物、吡咯、5-和6-元杂环的衍生物、和其它各种试剂.这样的增白剂的例子公开于"荧光增白剂的生产和应用(The Production and Application of Fluorescent Brightening Agents)", M. Zahradnik, Jone Wiley & Sons, New York出版(1982), 本发明组合物中有用的荧光增白剂的具体例子是在US4790856 (Wlxon, 1988年12月13日颁布)中指出的那些.这些增白剂包括Verona的PHOR冊ITE系列增白剂.其它公开于该参考文献中的增白剂包括:可从Ciba-Geigy获得的Tinopal證A, Tinopal CBS和Tinopal 5BM; Artie White CC和Artie White CWD; 2— (4—苯乙烯基-笨基)-2H-萘并[1,2-d]三唑;4,4,-双-(1,2,3-三唑-2 -基)-芪;4,4,-双(笨乙烯基)联笨;和氨基香豆素.这些增白剂的特定例子包括4-甲基-7-二乙基氨基香豆素;1,2-双(-苯并咪唑-2-基)乙烯;1,3-二笨基-吡唑啉;2,5-双(笨并嗨唑-2-基) 瘗吩;2-苯乙烯基一萘并—[1,2-d]離哇 5,5-dioxide, azoles, 5- and 6-membered heterocyclic derivatives of, and other various agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent brightener (The Production and Application of fluorescent Brightening Agents) ", M. Zahradnik, Jone Wiley & Sons, New York Publishing (1982), specific examples of compositions useful in the present invention, the fluorescent whitening agent in US4790856 (Wlxon, 1988 Dec 13 issued) indicated that these brighteners include PHOR book series of brighteners from Verona ITE other brighteners disclosed in this reference include:.. Tinopal card a, available from Ciba-Geigy, Tinopal CBS and Tinopal 5BM; Artie White CC and Artie White CWD; 2- (4- styryl - Ben-yl) -2H- naphtho [1,2-d] triazole; 4,4 - bis - (1,2, 3- triazol - 2 - yl) - stilbene; 4,4, - bis (Ben vinyl) biphenyl stupid;. aminocoumarin and specific examples of these brighteners include 4-methyl-7-ethyl amino coumarin; 1,2-bis (- benzimidazol-2-yl) ethylene; 1,3-yl stupid - pyrazoline; 2,5-bis (stupid and HI-2-yl) bury thiophene; 2-styryl group, and a naphthyl - [1,2-d] from wow ;和2- (芪—4—基)-2H -萘并[1,2 - d]三唑.还参见US3646015 ( 1972年2月29日颁发给Hamilton). ;. And 2- (stilbene-4-yl) -2H - naphtho [1,2 - d] triazol See also US3646015 (issued February 29, 1972 to Hamiltonian).

染料转移抑制剂-本发明的组合物也可以包括一种或多种在洗涤过程中对抑制染料从一个织物转移到另一个织物有效的材料.通常这 Dye Transfer Inhibiting Agents - The compositions of the invention may also include one or more of the dye transfer inhibiting effective from one fabric to another fabric material during washing is usually this.

样的染料转移抑制剂包括聚乙烯吡咯烷稱聚合物、聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、锰酞菁、过氧化物酶、和其混合物.如果使用的话,这些试剂的含量一般是组合物重量的约0. 01-10%,优选约O. 01-5%,和更优选约0.05-2%. Kind of dye transfer inhibiting agents include polyvinyl pyrrolidine said polymers, polyamine N- oxide polymers, N- vinylpyrrolidone and N- vinylimidazole, manganese phthalocyanine, peroxidases, and its mixture. If used, these agents typically from about 0. 01-10% by weight of the composition, preferably from about O. 01-5%, and more preferably about 0.05 to 2%.

更具体地,优选的用于本文中的聚胺N-氧化物聚合物含有下面结构式的单元:RA,-P;其中P是可聚合单元,N-0基团可以连接到可聚合单元上或者N- O基团可以形成可聚合单元的一部分或者NO基团可以连接到这两个单元上;A是下面结构之一:-NC(O)-、 -C(0)0-、 -S—、 -0-、 —N=; x是0或l; R是脂族、乙氧基化的脂族、芳香族、杂环或脂环基团或者是其混合物,N-0基团的氮原子可以连接到其上或者N-0基团是这些基团的一部分。 More specifically, the polyamine N- oxide polymers preferred for use herein contain units of the structural formula: RA, -P; wherein P is a polymerisable unit, N-0 group can be attached to the polymerisable unit or NO group can form part of the polymerizable unit or the NO group can be attached to both units; a is one of the following structures: -NC (O) -, -C (0) 0-, -S- , -0-, -N =; x is 0 or l; R are aliphatic, ethoxylated nitrogen aliphatic, aromatic, heterocyclic or alicyclic groups or a mixture thereof, N-0 group atoms may be attached thereto or N-0 group is part of these groups. 优选的聚胺N-氧化物是其中R是杂环基团例如吡啶、吡咯、咪唑、吡咯烷、旅啶和其衍生物的那些. Preferred polyamine N- oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof brigade.

N - 0基团可以由下面通式来表示: N - 0 group can be represented by the following general formula:

0 0 00

其中Rh R2、 Ra是脂族、芳香族、杂环或脂环族基团或者是其混合物, x, y和z是0或l; NO基团的氮原子可以被连接或形成任一上述基团的一部分.聚胺N-氧化物的氧化胺单元的pKa<10,优选pKa〈7, 更优选pKa<6, Wherein Rh R2, Ra is an aliphatic, aromatic, heterocyclic or alicyclic group or a mixture thereof, x, y and z are 0 or L; nitrogen of the NO group can be attached or form any of the base part groups. pKa amine oxide unit of the polyamine N- oxides <10, preferably pKa <7, more preferred pKa <6,

可以使用任何聚合物骨架,只要形成的氧化胺聚合物是水溶性的并具有染料转移抑制性质就行.合适的聚合骨架的例子是聚乙烯基、 聚亚烷基、聚酯、聚酸、聚酰胺、聚酰亚胺、聚丙蜂酸盐和其混合物. 这些聚合物包括其中一种单体类型是胺N-氧化物和其它单体类型是N-氧化物的无规或嵌段共聚物.胺N-氧化物聚合物的胺与胺N-氧化物的比一般是10: 1- 1: 1000000.然而,存在于聚胺氧化物聚合物中的氧化胺基团的数量可以通过适当的共聚或者通过适当的N-氧化度而改变。 Any polymer backbone can be used, as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties of the line. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polylactic acid, polyamide , polyimide, polypropylene bee salts and mixtures thereof. these polymers include those in which one monomer type is an amine N- oxide and the other monomer type is an N- oxide random or block copolymer of amine N- ratio of amine to the amine oxide polymers of N- oxides is generally 10: 1 to 1: 1000000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or It is changed by an appropriate degree of oxidation N-. 可以以几乎任何的聚合度得到聚氧化胺. 一般地,平均分子量在500- 1000000的范围;更优选1000- 500000;最优选5000 - 100000.优选的这类材料可以称之为"PYN0"。 It can be obtained in almost any degree of polymerisation polyamine oxides Generally, an average molecular weight in the range of 500-1000000; more preferably 1000-500000; most preferably 5000-- 100000. preferred such materials may be called "PYN0".

在本文洗涤剂组合物中有用的最优选的聚胺N-氧化物是聚(4-乙烯基吡啶-N-氧化物),其平均分子量是约50000和胺与胺N-氧化物的比是约1: 4. In the detergent compositions herein most useful Preferred polyamine N- oxides are poly (4-vinylpyridine -N- oxide), which is the ratio of the average molecular weight of about 50,000 and an amine to amine N- oxide is about 1: 4.

N-乙烯基吡咯烷酮和N-乙烯基咪唑聚合物的共聚物(称之为"PVPVI"类)也优选用于本文中。 Copolymers of N- vinylpyrrolidone and N- vinylimidazole polymers (referred to as "PVPVI" class) is also preferred for use herein. PVPVI的平均分子量范围优选是5000 -1000000,更优选5000- 200000,和最优选10000- 20000。 PVPVI has an average molecular weight range is preferably 5000-1000000, and more preferably 5000-200000, and most preferably 10000-20000. (平均分子量范闺是通过如Barth等人,在《化学分析》Chemical Analysis, Vol 113 "聚合物表征的现代方法(Modern Methods of Polymer Characterization)"中所述的光散射确定的,该文献公开的内容引入本文作为参考')PVPVI共聚物的N-乙烯基咪唑与N-乙烯基吡咯烷酮的摩尔比一般是1: 1-0.2: 1,更优选0.8: 1-0.3: 1,最优选O. 6: 1-0.4: 1.这些共聚物可以是直链的也可以是支链的。 (The average molecular weight range is achieved by Gui as described in Barth, et al., In "Chemical Analysis" Chemical Analysis, Vol 113 "Modern Methods of Polymer Characterization (Modern Methods of Polymer Characterization)" determined in the light scattering, which is disclosed in literature the molar ratio of incorporated herein by reference ') PVPVI N- vinylimidazole N- vinylpyrrolidone and copolymers is generally 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, most preferably O. 6 : 1 to 0.4: 1. these copolymers can be straight chain it may also be branched.

本发明组合物也可以使用平均分子量为约5000- 400000,优选约5000- 200000,更优选约5000- 50000的聚乙烯基吡咯烷嗣("PVP"). PVP对于洗涤剂领域的技术人员是已知的;见,例如,EP-A- 262897 和EP - A - 256696,它们引入本文作为参考。 Compositions of the invention may also be used an average molecular weight of from about 5,000 to 400,000, preferably about 5,000 to 200,000, polyvinylpyrrolidine Si 50,000 more preferably from about 5,000 ( "PVP"). PVP art for detergent field is already known; see, e.g., EP-A- 262897 and EP - a - 256696, which are incorporated herein by reference. 含有PVP的组合物也可以含有平均分子量为约500- 100000,优选约1000- 10000的聚乙二醇("PEG" ), PEG与PVP的比例以释放在洗涤液中的ppm计优选是约2: 1-50: 1,更优选约3: 1-10: 1. ppm, compositions containing PVP can also contain an average molecular weight from about 500 to 100,000, preferably from about 1,000 to 10,000, polyethylene glycol ( "PEG"), the ratio of PEG to PVP to release in the wash liquor is preferably from about 2 : 1-50: 1, more preferably from about 3: 1 to 10: 1.

本文中的洗涤剂组合物也可以任选地含有约0.005- 5% (重量) 的特定类型的也提供染料转移抑制作用的亲水荧光增白剂.如果使用的话,本文中的组合物优选包括约0.01-1% (重量)的这样的荧光增白剂. The detergent compositions herein may also optionally contain from about 0.005 to 5% (by weight) of a particular type of dye transfer inhibition provides hydrophilic optical brighteners. If used, the compositions herein preferably comprises about 0.01 to 1% (by weight) of such optical brighteners.

本发明中有用的亲水的荧光增白剂是具有下面结构式的那些化合 Useful in the present invention, the hydrophilic optical brighteners are those compounds having the following structural formula

物: Material:

其中Ri选自笨胺基、N-2-双-幾乙基和NH-2-羟乙基;R2选自N —2—双—鞋乙基、N-2-羟乙基-N-甲基氨基、吗啉代、氯基和氨基;和M是形成盐的阳离子例如钠或钾. Wherein Ri is selected from stupid amine, N-2- bis - several ethyl and NH-2- hydroxyethyl; R2 is selected from N -2- bis - shoes ethyl, N-2- hydroxyethyl methyl -N- amino, morpholino, chloro and amino; and M is a cation such as sodium or potassium salt formation.

当在上式中的Ri是笨胺基,R2是N-2 -双-羟乙基和M是阳离子例如钠时,该增白剂是4,4,,-双[(4 -苯胺基-6- (N- 2 -双-羟乙基)-s -三溱-2 -基)氨基]-2, 2,-芪二磺酸和二钠盐.这一特定的增白剂是以商品名Tinopal- UNPA- GX由Ciba- Geigy Corporation 销售的。 When Ri in the formula is a stupid group, R2 is N-2 - bis - hydroxyethyl and M is a cation such as sodium, the brightener is 4,4 ,, - bis [(4 - anilino - 6- (N- 2 - bis - hydroxyethyl) -s - three Qin 2 - yl) amino] -2, 2, -. stilbenedisulfonic acid and disodium salt this particular brightener species is commercially name Tinopal- UNPA- GX sold by the Ciba- Geigy Corporation. Tin叩al-UNPA-GX是在本文洗涤剂组合物中有用的优选亲水焚光增白剂. Tin knock-UNPA-GX is Al useful in the detergent compositions herein are preferably hydrophilic optical brighteners burning.

当在上式中的Ri是笨胺基,R2是N-2-羟乙基-N-2-甲基氨基和M是阳离子例如钠时,该增白剂是4,4,-双[(4-笨胺基-6- (N-2 -鞋乙基-N-甲基氨基)-s -三漆-2 -基)氨基]-2,2,-芪二磺酸二钠盐。 When Ri in the formula is a stupid group, R2 is N-2- hydroxyethyl -N-2- methylamino and M is a cation such as sodium, the brightener is 4,4, - bis [( 4- stupid amino -6- (N-2 - ethyl shoes -N- methylamino) -s - three paint 2 - yl) amino] -2,2, - stilbene disulfonic acid disodium salt. 这一特定的增白剂是以商品名Tinopal-5腿-GX由Ciba - Geigy Corporation销售的。 This particular brightener under the trade name Tinopal-5 legs -GX by the Ciba - Geigy Corporation of sales.

当在上式中的Ri是笨胺基,R2是吗啉代和M是阳离子例如钠时, 该增白剂是4,4,-双[(4-笨胺基-6-吗啉代-s -三嗪-2-基)氨基]2,2'-芪二磺酸,钠盐.这一特定的增白剂是以商品名TinopalAMS - GX由Ciba- Geigy Corporation销售的。 When Ri in the formula is a stupid group, R2 is morpholino and M is a cation such as sodium, the brightener is 4,4, - bis [(4-morpholino-6-stupid - s - triazin-2-yl) amino] 2,2'-stilbene disulfonic acid, sodium salt this particular brightener species is commercially name TinopalAMS -. GX sold by the Ciba- Geigy Corporation.

特定的经选择用于本发明的荧光增白剂当与经选择的前文所述的聚合染料转移抑制剂组合使用时,提供特别有效的染料转移抑制性能益处„与当单独使用时的这两种洗涤剂组合物组分相比,上述选择的聚合材料(例如,PVN0和/或PVPVI)与上述选择的荧光增白剂(例如, Tin叩al UNPA - GX、 Tin叩al 5BM- GX和/或Tinopal AMS - GX)的混合物在含水洗涤液中提供明显更好的染料转移抑制作用.不受理论限制,我们相信上述增白剂以这种方式起作用,即由于它们在洗涤液中对织物具有高的亲和性,所以它们相对快地沉积在这些织物上.在洗涤溶液中增白剂沉积在织物上的程度可以用称之为"消耗系数"的参数定义。消耗系数一般来说是a)沉积在织物上的增白剂材料与b)在洗涤液中起始的增白剂浓度的比例.具有相对高的消耗系数的增白剂最适于用在本发明中抑制染料转移. Selected for particular optical brighteners according to the present invention when used in combination with polymeric dye transfer inhibiting agents hereinbefore described and selected to provide especially effective dye transfer inhibition performance benefits "when used with two separate compared detergent composition components, the selection of polymeric materials (e.g., PVN0 and / or the PVPVI) with said selected optical brighteners (e.g., Tin knock al UNPA - GX, Tin knock al 5BM- GX and / or Tinopal AMS - mixture GX) provided in an aqueous wash liquor significantly better dye transfer inhibition bound by theory, we believe that the above brighteners work this way, i.e., since they have fabrics in the wash solution. high affinity, they are deposited on the fabrics relatively quickly in the wash solution extent brighteners deposit on fabrics can be called the "exhaustion coefficient" parameter definitions. exhaustion coefficient is in general a ) brightener material deposited on fabric to b) the ratio of initial brightener concentration in the wash liquor. whitener has a relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer by the present invention.

当然,应该理解:可以将其它的常规荧光增白剂型化合物任选地用于本发明的組合物中以便提供常规的织物"增白"益处,而不是真正的染料转移抑制作用.这样的使用对洗涤剂配方师来说是常规的并且是已知的. Of course, it should be understood that: optical brighteners other conventional compounds may be optionally used in the compositions of the present invention to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibition using such pairs. detergent formulators are routine and are known.

螯合剂-本文中的洗涤剂组合物也可以任选地含有一种或多种铁和/或锰螯合剂.这样的螯合剂可以选自:如下文所定义的氨基羧酸盐、氨基膦酸盐、多官能团取代的芳香螯合剂和其混合物.不打算受理论限制,据信这些材料的益处部分是由于其通过形成可溶螯合物从洗涤溶液中去除铁和锰离子的特殊能力。 Chelating Agents - The detergent compositions herein may also optionally contain one or more iron and / or manganese chelating agents such chelating agents may be selected from: amino carboxylic acid salts as defined below, an amino acid. salt, polyfunctionally-substituted aromatic chelating agents and mixtures thereof without intending to be bound by theory, it is believed that the benefit of these materials is due to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.

作为任选的螯合剂有用的氨基羧酸盐包括乙二胺四乙酸盐、N-羟基乙基乙二胺三乙酸盐、次氮基三乙酸盐、乙二胺四丙酸盐.三亚乙基四胺六乙酸盐、二亚乙基三胺五乙酸盐和羟乙基二甘氨酸,和其碱金属、铵和取代铵盐,和其混合物。 Useful as optional chelating agents include amino carboxylates ethylenediamine tetraacetate, N- hydroxyethyl-ethylenediamine triacetates, nitrilo-triacetates, ethylenediamine tetraproprionates. triethylenetetraamine hexaacetates, diethylenetriamine pentaacetic acid salt and two-hydroxyethyl glycine, and their alkali metal, ammonium and substituted ammonium salts, and mixtures thereof.

当至少在洗涤剂组合物中允许低的总磷量时,氨基膦酸盐也适用作本发明组合物中的螯合剂,并且它包括为DEQUEST的乙二胺四(亚甲基膦酸盐).优选地,这些氨基膦酸盐不含有多于约6个碳原子的 Allowed when at least low levels of total phosphorus in the detergent compositions Amino phosphonates are also suitable for use in the compositions of the present invention, a chelating agent, and it comprises as DEQUEST ethylene diamine tetra (methylene phosphonate) preferably, these amino phosphonates do not contain more than about 6 carbon atoms,

多官能取代的芳香螯合剂在本文中的组合物中也是有用的.见 Polyfunctional substituted aromatic chelating agents are also useful in the compositions herein in See

Connor等人1974年5月21日颁布的US3812044.酸形式的这类优逸的化合物是二羟基二磺基笨例如1, 2 - 二羟基-3, 5 - 二磺基笨. . US3812044 preferred compounds of this type in acid form Yi, to Connor et al., May 21, 1974, issued sulfo groups are dihydroxydisulfobenzenes stupid e.g. 1, 2 - dihydroxy-3, 5 - disulfo stupid.

用于本文中的优选的可生物降解的螯合剂是如在US4704233 (Hartman和Perkins, 1987年11月3曰颁布)中所迷的乙二胺二琥珀酸盐("EDDS"),尤其是[S,S]异构体. Biodegradable chelating agent for use herein is preferably as described in US4704233 (Hartman and Perkins, 1987, November 3 said promulgated) as fans ethylenediamine disuccinate ( "EDDS"), especially the [ S, S] isomer.

本文中的组合物也可以含有水溶性的甲基甘氨酸二乙酸(MGDA) 盐(或酸形式)作为螯合剂或与例如不溶的助洗剂例如沸石、层状硅酸盐等一起使用的共助洗剂. The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-promoter, for example, washing with an insoluble builders for use, for example, zeolites, layered silicates and the like agents.

如果使用的话,这些螯合剂通常占本文中洗涤剂组合物重量的约0.1-15%。 If utilized, these chelating agents will generally comprise from about 0.1 to 15% by weight of the detergent compositions herein is. 更优选地,如果使用的话,该螯合剂占上述組合物重量的约O. 1-3. 0%. More preferably, if utilized, the chelating agents will comprise from about O. by weight of the above composition 1-3. 0%.

抑泡剂-可以将降低或抑制泡沫形成的化合物加入到本发明的组合物中。 Antifoam agent - can reduce or inhibit the formation of foam is added to the composition of the present invention. 泡沫抑制如在美国专利4489455和4489574中描迷的所谓的"高浓度清洗方法"中和在前栽的欧洲型洗衣机中是特别重要的. Suds suppression as described in U.S. Patent No. 4,489,455 and 4,489,574 describe the fans called "high concentration cleaning method" in the European type washing machine and the preceding plant is particularly important.

可以使用各种材料作为抑泡剂,并且抑泡剂对于本领域技术人员是熟知的.例如,见Kirk 0thmer的《化学工艺百科全书》 (Encyclopedia of Chemical Technology)第3版,第7巻,第430-447页(Jone Wiley & Sons, Inc. 1979). —类特别重要的抑泡剂包括单羧酸脂肪酸和其可溶性盐。 Various materials may be used as suds suppressors, and suds suppressors of ordinary skill in the art are well known. See, e.g., Kirk 0thmer the "Encyclopedia of Chemical Technology" (Encyclopedia of Chemical Technology) 3rd Edition, Volume 7, first pages 430-447 (Jone Wiley & Sons, Inc. 1979) -. class of suds suppressor of particular importance include monocarboxylic fatty acids and soluble salts thereof. 见US2954347 ( Wayne St. John, 1960年9月27日颁布).用作抑泡剂的单羧酸脂肪酸和其盐一般具有10-约24个碳原子,优选12-18个碳原子的烃基链。 See US2954347 (Wayne St. John, 1960 dated 27 years issued. 9) used as a suds suppressor monocarboxylic fatty acids and salts generally have 10 to about 24 carbon atoms, preferably 12-18 carbon atoms in the hydrocarbon chain, . 合适的盐包括碱金属盐,例如钠、钾和锉盐,和铵和链烷醇铵盐。 Suitable salts include alkali metal salts such as sodium, potassium, and file salts, and ammonium and alkanolammonium salts.

本文中的洗涤剂组合物也可以含有非表面活性剂抑泡剂。 The detergent compositions herein may also contain non-surfactant suds suppressors. 它们包括:例如,高分子量烃如石蜡、脂肪酸酯(例如,甘油三脂肪酸酯)、 一价醇的脂肪酸酯、脂族d广C"酮(如硬脂酮)等等.其它抑泡剂包括:N-烷基化的氨基三漆例如三-到六-烷基蜜胺或者作为氰脲酰氯与2或3摩尔的含有1 - 24个碳原子的伯或仲胺的产物形成的二-到四-烷基二胺氯化三溱、环氧丙烷、和磷酸单硬脂基酯例如磷酸单硬脂醇酯和单硬脂基磷酸二碱金属盐(例如K、 Na和Li)和裤酸酯.可以以液体形式使用烃,例如石蜡和卣代石蜡。液体烃在室温和大气压 They include: for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic broad d C "ketones (eg stearone), etc. Other suppressors. foaming agents include: N- alkylated amino tri paint e.g. three - to six - or a melamine alkyl containing 1 2 or 3 moles of a cyanuric chloride - forming a primary product 24 carbon atoms or a secondary amine of two - or four - Qin trialkyl diamine chloride, propylene oxide, and monostearyl phosphate esters such as stearyl methacrylate monophosphate and monostearyl di-alkali metal salt of phosphoric acid (e.g., K, Na, and Li) pants and esters can be used as a liquid hydrocarbon such as paraffin and paraffin substituting wine container. liquid hydrocarbons at room temperature and atmospheric

下是液体,并且倾点是约-40t;到约50*c,最低沸点不低于约iiox: (大气压下).使用蜡状烃也是已知的,优选其熔点低于约iooc. 烃构成了一类优选的用于洗涤剂组合物的抑泡剂.烃抑泡剂在,例如, The liquid, and a pour point of about -40t; to about 50 * c, a minimum boiling point not less than about iiox: (at atmospheric pressure) is also known to utilize waxy hydrocarbons, preferably having a melting point below about iooc hydrocarbons configuration. a preferred class of suds suppressor for detergent compositions. hydrocarbon suds suppressors, e.g.,

US4265779 ( Gandolfo等人,1981年5月5日颁布)中有描述。 US4265779 (Gandolfo et al, May 5, 1981 promulgation) are described. 因此, 烃包括饱和的或不饱和的具有约12-70个碳原子的脂肪族、脂环族、 芳香族和杂环烃.如在该抑泡剂讨论中使用的,术语"石蜡"意在包括真正的石蜡和环烃的混合物. Thus, the hydrocarbon include saturated or unsaturated aliphatic having from about 12-70 carbon atoms, cycloaliphatic, aromatic and heterocyclic hydrocarbons. As used in this suds suppressor discussion, the term "paraffin" is meant They include mixtures of true paraffins and cyclic hydrocarbons.

另一类优选的非表面活性剂抑泡剂包括硅氧烷抑泡剂.该类包括使用聚有机硅氧烷油如聚二甲基硅氧烷,聚有机硅氧烷油或者树脂的分散液或乳液,和聚有机硅氧烷与二氧化硅颗粒的组合物,其中聚有机硅氧烷化学吸附或熔融在二氧化硅上。 Another preferred class of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions of polyorganosiloxane oils or resins or emulsions, and the compositions of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. 硅氧烷抑泡剂在本领域是熟知的并且公开于,例如US4265779 ( Gandolfo等人,1981年5月5曰颁布)和欧洲专利申请89307851. 9 (Starch, MS, 1990年2月7 曰公开)中. Silicone suds suppressors are well known in the art and are disclosed in, for example US4265779 (Gandolfo et al., 1981 May 5, said issued) and European Patent Application 89307851. 9 (Starch, MS, 1990 disclosed February 7, said )in.

其它的硅氧烷抑泡剂公开于US3455839中,它涉及通过往其中加入少量的聚二甲基硅氧烷流体用于水溶液消泡的组合物和方法. Other silicone suds suppressors are disclosed in US3455839, which relates to compositions and methods polydimethylsiloxane fluid was added to a small amount of a defoaming aqueous solutions.

硅氧烷和硅烷化二氧化硅的混合物公开于,例如德国专利申请DOS 2124526中。 Mixtures of silicone and silanated silica are described, for example in the German patent application DOS 2124526. 在颗粒洗涤剂组合物中的硅氧烷消泡剂和泡沫控制剂公开于US3933672 ( Bartolotta等人)和US4652392 ( Baginski等人, 1987年3月24日颁布)中. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in US3933672 (Bartolotta et al.) And US4652392 (Baginski et al, March 24, 1987 issued) in.

用于本文中的说明性的硅氧烷基的抑泡剂是泡沫抑制量的泡沫控制剂,它基本由下列物质组成: Suds suppressor for use herein are illustrative of the silicone-based suds suppressing amount of a suds controlling agent consisting essentially of consisting:

(i) 粘度为约20- 1500cs ( 25C )的聚二甲基硅氧烷流体; (I) a viscosity of about 20- 1500cs (25C) of the polydimethylsiloxane fluid;

(ii) 每100重量份的(i)约5-50重量份的硅氧烷树脂,该树脂由(CH3)aSi0v2单元和Si02单元组成,(CH3)sSiO!/2单元与Si02单元的比例为约0.6: 1- 1.2: 1;和 (Ii) per 100 parts by weight of (i) about 5-50 parts by weight of a silicone resin, the resin consists of (CH3) aSi0v2 units and Si02 units, (CH3) sSiO! Proportion of the units and Si02 units / 2 from about 0.6: 1 to 1.2: 1; and

(iii) 每100重量份的(i )约1 - 20重量份的固体硅胶。 (Iii) per 100 parts by weight of (i) about 1 - 20 parts by weight of a solid silica gel.

在用于本文中的优选的硅氧烷抑泡剂中,用于连续相的溶剂是由 In the silicone foam suppressing agents preferably used herein, the solvent for a continuous phase is made

特定的聚乙二醇或聚乙二醇-聚丙二醇共聚物或其混合物(优选的), 或者聚丙二醇构成的.主要的硅氧烷抑泡剂是支链/交联的并且优选是 Certain polyethylene glycols or polyethylene glycol - polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol mainly composed of silicone suds suppressor is branched / crosslinked and preferably Yes.

非直链的。 Non-linear.

为了进一步说明这一点, 一般的具有控制泡沫的液体洗衣洗涤剂 To illustrate this point further, typical liquid laundry detergent with controlled foam

组合物任选地包括约0.001-1% (重量),优选约0.01-0.7% (重量),更优选约0.05-0.5% (重量)的所述的珪氧烷抑泡剂,该珪氧烷抑泡剂包括:(1)主要抗泡沫剂的非水乳液,它是(a)聚有机硅氧烷,(b)树脂状硅氧烷或产生硅氧烷树脂的硅氧烷化合物,(c)细分散的填料物质,和(d)促进混合物組分(a), (b)和(c)反应形成硅烷醇盐的催化剂的混合物;(2)至少一种非离子硅氧烷表面活性剂;和(3) 聚乙二醇或在室温下在水中的溶解度大于约2% (重量)的并且无聚丙二醇的聚乙二醇-聚丙二醇共聚物.在颗粒组合物,凝胶等中可以 Composition optionally comprises from about 0.001% (by weight), preferably from about 0.01 to 0.7% (by weight), more preferably from about 0.05 to 0.5% of the (by weight) of the alumoxane Gui suds suppressor, which Gui siloxane suds suppressors comprises: (1) primary antifoam nonaqueous emulsion, it is (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone compound to produce the silicone resin, (C ) finely divided filler material, and (d) promoting mixture of components (a), (b) and (c) forming a reaction mixture of silane alkoxide catalyst; (2) at least one nonionic silicone surfactant ;., and (3) polyethylene glycol or a solubility in water at room temperature is greater than (by weight) to about 2% and without polypropylene glycol polyethylene glycol - polypropylene glycol copolymer can be particulate composition, gel or the like

使用类似的量。 A similar amount. 还参见US4978471( Starch, 1990年12月18日颁布), 和US4983316 ( Starch, 1991年1月8日颁布)、US5288431 ( Huber 等人,1994年2月22曰颁布)、和US4639489和US4749740 ( Aizawa 等人,1栏46行-4栏35行). See also US4978471 (Starch, 1990 On 12 Yue 18 issued), and US4983316 (Starch, 1991 in 1 issued January 8), US5288431 (Huber et al., 1994 February 22, saying enacted), and US4639489 and US4749740 (Aizawa et al., column 1, line 46 -4 bar, line 35).

本文中的硅氧烷抑泡剂优选包括聚乙二醇和聚乙二醇/聚丙二醇的共聚物,其平均分子量全都是低于约1000,优选在约100- 800之间.本文中的聚乙二醇和聚乙二醇/聚丙二醇的共聚物在室温下在水中的溶解度是大于约2%,优选大于约5% (重量)。 Herein silicone foam inhibitor preferably comprises polyethylene glycol and polyethylene glycol / polypropylene glycol copolymers having an average molecular weight of less than about 1000 all, paper is polyethylene preferably between about 100-800 glycols and polyethylene glycol / polypropylene glycol copolymer solubility in water at room temperature of greater than about 2%, preferably greater than (by weight) about 5%.

本文中的优逸溶剂是平均分子量小于约1000,更优选在约100-800之间,最优选在200- 400之间的聚乙二醇、和聚乙二醇/聚丙二醇的共聚物,优选PPG 200/PEG 300。 The preferred solvent herein is an average molecular weight Yi of less than about 1000, more preferably between about 100-800, most preferably between 200-400 polyethylene glycol, and polyethylene glycol / polypropylene glycol copolymer, preferably PPG 200 / PEG 300. 优选的是聚乙二醇:聚乙二醇_聚丙二醇的共聚物的重量比在约1: 1-1: IO之间,最优选在l: 3 -1: 6之间. Preferred are polyethylene glycol: _ by weight of polyethylene glycol polypropylene glycol copolymer ratio of about 1: 1-1: between IO, most preferably l: 3 -1: between 6.

用于本文中的优选的硅氧烷抑泡剂不含有聚丙二醇,尤其是分子量为4000的聚丙二醇.它们也优选不含有环氧乙烷和环氧丙烷的嵌段共聚物,如PL圃NIC L101' Preferred silicone suds suppressor used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight polyethylene glycol. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PL NIC po L101 '

其它本文中有用的抑泡剂包括仲醇(例如2-烷基链烷醇)和上述醇与硅油例如公开于US4798679、 4075118和EP150872中的硅氧烷的混合物.该仲醇包括具有d-Cw链的C6-de烷基醇。 Other useful herein include suds suppressors in US4798679, a mixture of secondary alcohols (e.g., 2-alkyl alkanols) and said alcohols with silicone oils, for example, disclosed in EP150872 4,075,118 and silicone. The secondary alcohols include d-Cw C6-de chain alkyl alcohol. 优选的醇是2 -丁基辛醇,它可从Condea以商品名ISOFOL 12得到.仲醇的混合物可从Eniche迈以商品名ISALCHEM 123得到。 A preferred alcohol is 2 - butyl octanol, which is available under the trade name ISOFOL 12 from Condea Mixtures of secondary alcohols are available from Eniche step tradename ISALCHEM 123.. 混合的抑泡剂一般包括重量比为1: 5-5: l的醇+硅氧烷的混合物。 Mixed suds suppressors typically comprise a weight ratio of 1: 5-5: l + silicone mixtures of alcohols.

对于用于自动洗衣机的洗涤剂组合物,不应形成使其溢流出洗衣机程度的泡沫.当其使用时,抑泡剂优选以"泡沫抑制量"存在。 For detergent compositions used for automatic washing machines, so that it should not form to the extent of foam overflow the washing machine. When used, foam inhibitor is preferably in a "suds suppressing amount." turn off

于"泡沫抑制量"是指组合物的配方设计师可以选择泡沫控制剂的量使得足以控制泡沫,结果形成用于自动洗衣机的低泡洗衣洗涤剂。 In "suds suppressing amount" is meant that the formulator of the composition can select an amount of suds controlling agent that will sufficiently control the suds to result in the formation of low-sudsing laundry detergent for use in automatic laundry washing machines.

本文中的组合物通常包括0-约10?i的抑泡剂.当单羧酸脂肪酸及其盐作为抑泡剂使用时,其存在的量一般最多至洗涤剂组合物的约5 % (重量).优选使用约0.5-3%的脂肪单羧酸盐抑泡剂.珪氧烷抑泡剂的使用量一般最多至洗涤剂组合物的约2.0% (重量),尽管也可以使用更高的量.该上限是实际的,主要是由于与保持最小成本和较低量有效地控制起泡性的效率有关.使用的硅氧烷抑泡剂的量优选约0.01_1%,更优选约0.25-0.5%.如在本文中所使用的,这些重量百分数值包括任何可以与聚有机硅氧烷组合使用的二氧化硅,以及可以使用的任何附加材料,通常使用的单硬脂基磷酸酯抑泡剂的量为组合物的约0.1-2% (重量).使用的烃抑泡剂的量一般是约0.01 -5.0%,尽管可以使用更高的量。 The compositions herein typically comprise from 0 to about 10? I of suds suppressor. When the monocarboxylic fatty acids and salts thereof used as suds suppressors, typically present in an amount up to about 5% of the detergent composition (wt. ). preferably, from about 0.5 to 3% of fatty monocarboxylate suds suppressor. Gui siloxane suds suppressors are typically used in an amount up to about 2.0% (by weight) of the detergent composition, although higher may also be used amount. this upper limit is practical, mainly due to the holding costs and lower minimum amount effective to control foaming efficiency related use amount of silicone suds controlling agent is preferably from about 0.01_1%, more preferably from about 0.25 to 0.5%. as used herein, these weight percentage values ​​include any silica that may be used in combination with polyorganosiloxane, as well as any additional material which may be used, monostearyl phosphate suds suppressors generally used dose is about 0.1 to 2% (by weight) of the composition. weight hydrocarbon suds suppressors are typically used from about 0.01 to 5.0%, although higher amounts may be used. 使用的醇抑泡剂的量一般是最终产品組合物的0.2-3% (重量). The amount of alcohol suds suppressors are typically used from 0.2 to 3% of the final product composition (by weight).

烷氣基化的多羧酸盐-烷氧基化的多羧酸盐例如从聚丙烯酸盐制备的那些在本文中是有用的以便提供附加的去除油脂性能.这样的材料描述于W091/08281和PCT卯/01815的第4页以及下页中,这2篇文献引入本文作为参考。 Alkyl group of gas polycarboxylates - Alkoxylated polycarboxylates, for example, those prepared from polyacrylates are useful to provide additional grease removal performance herein, such materials are described in W091 / 08281 and. d page 4 PCT / 01815 and the lower page, which two documents incorporated herein by reference. 这些材料化学上每7 - 8个丙蜂酸盐单元含有具有1个乙氧基倒链的聚丙烯酸盐。 Each of these materials chemically 7--8 bee propionic acid unit comprising an ethoxylate having an inverted polyacrylate chains. 该倒链具有式-(CH2CH20)B(CH2)nCH3,其中迈是2-3, n是6-12.该側链是薛连接到聚丙烯酸盐"骨架"上以便提供"梳"聚合物状结构.其分子量可以变化,但一般在约2000- 50000。 The inverted chain having the formula - (CH2CH20) B (CH2) nCH3, wherein the step is 2-3, n is 6-12 is that the side chains in order to provide a "comb" polymer shaped Xue connected to the polyacrylate "backbone" on. structure its molecular weight can vary, but generally about 2000 to 50000. 这样的烷氧基化的多羧酸盐可以占本文中組合物重量的约0. 05- 10%. Such alkoxylated polycarboxylates can comprise from about 0. 05-10% by weight of the compositions herein.

织物柔软剂-在本发明的组合物中,可以任选地使用各种通过洗涤的织物柔软剂,尤其是US4062647 ( Stor迈和Nirschl, 1977年12 月13日颁布)中的细粒绿土,以及其它本领域已知的柔软剂粘土,其用量一般是约0.5-10% (重量),以便洗涤织物同时提供织物柔软剂益处。 Fabric Softeners - in the compositions of the present invention may optionally be used by a variety of wash fabric softeners, especially US4062647 (Stor step and Nirschl, 1977 years 12 is dated 13 is issued) in fine smectite, as well as other softener clays known in the art, typically in an amount of from about 0.5 to 10% (by weight), while providing for fabric laundering fabric softener benefits. 粘土柔软剂可以与胺和阳离子柔软剂組合使用,如在,例如US4375416( Crisp等人,1983年3月1日颁布)和US4291071( Harris 等人,1981年9月22曰颁布)公开的. Clay softeners can be a combination of a cationic softener and amine and used, as, for example, US4375416 (Crisp et al, March 1, 1983 issued) and US4291071 (Harris et al., 1981 September 22 said promulgated) disclosed.

ift-在本发明组合物和方法中有用的香料和香料组分包括各种 ift- useful in the compositions and methods of the present invention, flavors and flavor ingredients include various

天然和合成的化学组分,包括,但不限于:醛、酮、酯等,还包括的 Natural and synthetic chemical ingredients, including, but not limited to: aldehydes, ketones, esters and the like, comprising the further

是各种天然提取物和香精油,其包括各组分的复杂混合物,例如橙油、 柠檬油、玫瑰提取物、黨衣草、麝香、绿叶剌蕊草、香脂香精油、檀香油、松油、雪松等.最终的香料可以包括这样组分的极复杂的混合 Various natural extracts and essential oils which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender party, musk, patchouli puncture core grass, balsam essential oil, sandalwood oil, pine oil, the final flavor cedar may include such highly complex mixture of components

物.最终的香料一般占本文中洗涤剂组合物重量的约0.01-2%,各个香料组分可以占最终香料组合物的约0. 0001 _ 90 % , Was final perfumes herein generally comprise from about 0.01 to 2% by weight of the detergent composition, the individual flavor component can comprise from about 0.0001 _ 90% of the final perfume composition,

几种香料配方描述于下文中的实施例XXI中,本文中有用的香料组分的非限制性例子包括:7-乙酰基-1,2,3,4,5,6,7,8-八氬-1,1,6,7-四甲基萘、曱基紫罗酮、y甲基紫罗嗣、甲基柏木酮、二氳茉莉酸甲酯、甲基1,6,10-三甲基-2,5,9-环十二碳三炔-l-基嗣、7-乙酰基-1,1,3,4,4,6-六甲基-1,2,3,4-四氢化萘、4-乙酰基-6-叔丁基-1,1-二甲基-1,2-二氢化茚、对羟基苯基丁酮、 二笨酮、甲基P萘基酮、6-乙酰基-1,1,2,3,3,5-六甲基-1,2-二氢化茚、5-乙酰基-3-异丙基-1,1,2,6-四甲基-1,2-二氲化茚、1-十二醛、4- (4-羟基-4-甲基戊基)-3-环己烯-1-甲醛、 7 -羟基-3, 7 - 二甲基辛搭、10 -十一碳烯-1 -搭、异己烯基环己基甲窿、甲酰基三环癸烷、羟基香茅醛和氨茴酸甲酯的缩合产物、羟基香茅搭和吲哚的缩合产物、笨基乙醛和丐l哚的缩合产物、2-甲基-3 - (对叔丁基笨基)-丙醛、乙基香草膳、天芥菜精、 Several perfume formulations described in Example XXI, hereinafter herein Non-limiting examples of useful perfume components include: 7-acetyl-1,2,3,4,5,6,7,8-eight argon -1,1,6,7- tetramethyl naphthalene, ionone Yue group, y Si methyl violet, methyl cedryl ketone, di Yun methyl jasmonate, methyl 1,6,10- trimethyl yl -2,5,9- cyclododecanone three -l- alkynyl group Si, -1,1,3,4,4,6- hexamethyl-7-acetyl-1,2,3,4-tetrahydronaphthalene naphthyl, 4-acetyl-6-tert-butyl-1,1-dimethyl indane p-hydroxybenzoate, butyl ketone, diethyl ketone stupid, P-methyl naphthyl ketone, 6-acetyl yl -1,1,2,3,3,5- hexamethyl indane, 5-acetyl-3-isopropyl--1,1,2,6- tetramethyl-1 , Yun of 2-indenyl, 1-dodecanal, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carbaldehyde 7 - hydroxy - 3 7 - dimethyl oct-ride, 10 - undecene -1-- ride, isohexyl condensation product of an alkenyl carboxylic hole cyclohexyl, formyl tricyclodecane, hydroxycitronellal and methyl anthranilate and hydroxycitronellal and indol-ride condensation products of acetaldehyde and hack stupid group indole condensation products of l, 2-methyl-3 - (tert-butyl-p-stupid) - propionaldehyde, ethyl vanillin meal, heliotropine, 己基肉桂醛、戊基肉桂醛、2-甲基-2-(对异丙基笨基)-丙醛、香豆素、Y癸内酯、 环十五烷醇酑、16-羟基-9-十六碳烯酸内酯、1,3,4,6,7,8-六氬-4,6, 6,7,8,8-六甲基环五-y - 2-苯并吡喃、P -萘酚甲基鲢、 ambroxane、十二氢-3a, 6, 6, 9a-四甲基萘并[2, lb]呋喃、雪松醇、 5 - (2,2,3-三甲基环戊-3-烯基)-3 -甲基戊-2-醇、2 -乙基-4_ (2,2,3-三甲基-3~环戊烯-1-基)-2-丁烯-1-醇、石竹烯醇、丙酸三环癸烯基酯、乙酸三环癸烯基酯、水杨酸千酯、乙酸柏木酯和乙酸对-(叔丁基)环己基酯。 Hexyl cinnamic aldehyde, amyl cinnamic aldehyde, 2-methyl-2- (p-isopropyl stupid-yl) - propionaldehyde, coumarin, Y decalactone, Yu ring pentadecanol, 16-hydroxy-9- hexadecenoic acid lactone, 1,3,4,6,7,8 six argon 4,6, 6,7,8,8- hexamethyl cyclopenta -y - 2- benzopyran, P - naphthol methyl silver carp, ambroxane, dodecahydro -3a, 6, 6, 9a--tetramethyl-naphtho [2, lb] furan, cedrol, 5 - (2,2,3-trimethyl-ring pent-3-enyl) -3 - methyl-2-ol, 2 - ethyl -4_ (2,2,3-trimethyl -3-cyclopenten-1-yl) -2-butene 1-ol, thousands Caryophyllenol, tricyclo decenyl propionate, acetate, tricyclo decenyl acetate, salicylate, cedryl acetate and acetic acid - acetate (t-butyl) cyclohexyl group.

特别优选的香料材料是在含有纤维素酶的最终产品组合物中提供了最大气味改进的那些香料。 Particularly preferred perfume materials to provide the largest odor improvements of those flavors in the final product composition containing cellulase. 这些香料包括,但不限于:己基肉桂醛、 2-甲基-3-(对叔丁基笨基)-丙醛、7-乙酰基-1,2,3,4,5,6,7,8 -八氢-1, 1,6, 7 -四甲基萘、水杨酸苄酯、7-乙酰基-1,1,3, 4, 4, 6 -六甲基-1,2,3,4-四氢化萘、乙酸对叔丁基环己基酯、二氢茉莉酸甲酯、P -萘酚甲基醚、甲基P -萘基酮、2-甲基-2-(对异丙基苯 These flavors include, but are not limited to: hexyl cinnamic aldehyde, 2-methyl-3- (p-tert-stupid-yl) - propionaldehyde, 7-acetyl -1,2,3,4,5,6,7, 8 - octahydro-1, 1,6, 7-- tetramethyl naphthalene, benzyl salicylate, 7-acetyl-1,1,3,3, 4, 4, 6 - hexamethyl -1,2,3,4 , 4-tetrahydronaphthalene acetate, p-tert-butylcyclohexyl acrylate, methyl dihydro jasmonate, P - naphthol methyl ether, methyl P - naphthyl ketone, methyl-2- (p-cymene

基)-丙醛、1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环五-Y - 2 -笨并吡喃、十二氢-3a,6,6,9a-四甲基萘并[2, lb]呋喃、茴香搭、 香豆素、雪松醇、香草醛、环十五烷醇酐、乙酸三环癸蜂基酯和丙酸三环癸烯基H. Yl) - propionaldehyde, -4,6,6,7,8,8- hexahydro-1,3,4,6,7,8-hexamethyl cyclopenta -Y - 2 - benzopyran Ben, dodecyl hydrogen -3a, 6,6,9a- tetramethyl-naphtho [2, lb] furan, fennel ride, coumarin, cedrol, vanillin, pentadecanol cyclic anhydride, acid ester and bee tricyclodecanyl tricyclo decenyl propionate H.

其它的香料材料包括:香精油、香树脂和来自各种来源的树脂, 这些来源包括,但不限于:秘鲁香脂、乳香香树脂、苏合香、岩蔷菱树脂、肉豆蔻、肉桂油、安息香树脂、芫荽和重衣草素.其它的香料化学品还包括:笨基乙醇、薛品醇、里哪醇、里哪基乙酸酯、香叶醇、 橙花醇、乙酸2- (1,1-二甲基乙基)-环己醇酯、乙酸节酯和丁子香纷。 Other perfume materials include: essential oils, resinoids, and resins from a variety of sources, these sources include, but are not limited to: Peru balsam, frankincense resinoids, storax, Yan Ling Qiang resin, nutmeg, cassia oil, benzoin resin, . coriander and other heavy lavender fragrance chemicals element further comprising: a stupid-ethanol, Xue terpineol, linalool, linalyl acetate, geraniol, nerol, 2- (1,1- dimethylethyl) - cyclohexanol acetate, eugenol acetate and sections divergent. 在最终的香料组合物中可以使用载体例如邻笨二甲酸二乙酯. Vectors may be used such as phthalic stupid dicarboxylate in the final perfume composition.

其它组分-在洗涤剂組合物中有用的各种其它组分可以包括在本文的组合物中,其包括其它活性组分、载体、水溶助长剂、加工助剂、 染料或颜料、用于液体配方的溶剂、用于条状组合物的固体填料等. 如果需要高起泡性,那么可以将增泡剂例如d。 Other components - useful in the detergent compositions may comprise various other components in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, for liquid the solvent formulations for solid filler bar compositions, etc. If high sudsing, foaming agent, it can be e.g. D will increase. -d6链烷醇酰胺加入到组合物中,其量一般是1-10% (重量).d。 -d6 alkanolamides added to the composition in an amount generally 1 to 10% (by weight) .d. -C"单乙醇和二乙醇酕胺说明一般类型的这样的增泡剂.与上迷高起泡性的辅助表面活性剂例如氧化胺、甜菜碱和磺基甜菜碱一起使用这样的增泡剂也是有利的。如果需要的话,可以加入水溶性镁和/或钙盐例如MgCl2、 MgS04、 CaCl2、 CaS04等,其量一般为0.1-2%,以便提供附加的泡沫和以便增强油脂去除性能. -C "monoethanol and diethanol amine Mao described general type of such suds boosters. With the fan on high sudsing surfactants such as auxiliary amine oxides, betaines and sulfobetaines with the use of such suds boosters it is also advantageous, if desired, may be added a water-soluble magnesium and / or calcium salts, for example MgCl2, MgS04, CaCl2, CaS04 and the like, generally in an amount of 0.1-2%, to provide additional suds and to enhance grease removal performance.

在本发明组合物中使用的各种洗涤组分任选地还可以通过将所述组分吸附在多孔疏水基质上,然后用疏水涂料涂覆所述基质来进一步稳定„优选地,在被吸附进多孔基质中之前,将洗涤組分与表面活性剂混合.在使用中,洗涤组分从基质释放出来进入含水洗涤液,在舍水洗涤液中它起其预定的洗涤功能. Various detersive ingredients optionally used in the compositions of the present invention, the components can also be adsorbed onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating to further stabilize "Preferably, the adsorbed prior to the matrix, the components are mixed in a porous washed with a surfactant. in use, the detersive ingredient is released from the substrate into the aqueous wash out in aqueous wash liquor round it from its intended washing function.

为了更详细地说明这一技术,将多孔疏水二氧化硅(商品名SIPERNATD10, DeGussa)与含有3 — 5% CI3-16乙氧基化醇(E0 7)非离子表面活性剂的蛋白酶溶液混合。 To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNATD10, DeGussa) containing 3 - 5% CI3-16 ethoxylated alcohol (E0 7) nonionic surfactant mixing the protease solution. 一般地,酶/表面活性剂溶液是二氧化硅重量的2.5倍。 Typically, the enzyme / surfactant solution is 2.5 times the weight of silica. 在搅拌下将得到的粉末分散在硅油(可以使用粘度在500- 12500范围的各种硅油)中.将所得的硅油分散体乳化或用其它方法将其加入到最终的洗涤剂基体中.用这种方法,可以保护用于洗涤剂包括液体洗衣洗涤剂组合物中的组分例如上述的酶、漂白 Stirring the resultant powder was dispersed in silicone oil (various silicone oil viscosity may be used in a range of 500-12500) in. The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. This use method, can be used to protect the liquid laundry detergent comprises the detergent composition components such as the aforementioned enzymes, bleaches

剂、漂白活化剂、漂白催化剂、光活化剂、染料、荧光剂、织物调理剂和可水解的表面活性剂. Agents, bleach activators, bleach catalysts, photo activators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants.

液体洗涤剂组合物可以含有水和其它溶剂作为栽体.低分子量的伯或仲醇例如甲醇、乙醇、丙醇和丁醇是合适的,对于增溶表面活性 Liquid detergent compositions can contain water and other solvents as plant material. Low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and butanol are suitable for solubilizing surfactant

剂一元醇是优选的,但也可以使用多元醇例如含有2-约6个碳原子和2-约6个羟基的那些醇(例如l,3-丙二醇、乙二醇、甘油和1,2 -丙二醇)。 Monool is preferred, it is also possible to use polyols such as those containing from 2 to about 6 carbon atoms to those alcohols and 2 to about 6 hydroxy groups (e.g. l, 3- propanediol, ethylene glycol, glycerol and 1,2 - propylene glycol). 组合物可以含有5-90%, —般10-50%这样的栽体. The composition may contain 5-90%, - 10-50% such as plant material.

本文中的洗涤剂组合物优选是这样配制的,使得用于含水清洗搡作时洗涤水的pH在约6.5-ll之间,优选约7.5-10.5.液体洗餐具产品配方的pH优选在约6.8-9. 0之间.洗衣产品的pH—般为9-11。 The detergent compositions herein are preferably formulated such that a pH of the wash water during aqueous cleaning shoving be between about 6.5-ll, preferably between about 7.5 and 10.5. Dishwashing product formulations preferably between about 6.8 pH of the liquid between -9. 0. pH- laundry products like 9-11. 将pH控制在所推荐使用含量的技术包括使用緩冲剂、碱、酸等并且本领域技术人员是熟知的. Controlling pH at recommended use levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the.

组合物的形式-本发明的组合物可以泉用各种物理形式,包括粒状、片状、条状和液体形式.特别地,该组合物是所谓浓缩的粒状洗涤剂组合物,其适合于通过分配装置加入到洗衣机中,该分配装置与脏织物一起放在洗衣机转筒中. Form of the composition - The composition may be in various physical forms springs, including granular, sheet, strip, and in particular in liquid form, the composition is a so-called concentrated granular detergent compositions, which are suitable in the present invention by dispensing device is added to the washing machine, on the washing machine drum, together with the dispensing device soiled fabric.

根据本发明的粒状组合物的组分的平均粒径应该优选是这样的, 它使得不多于5%的顆粒直径大于1. 7mm,不多于5%的顆粒直径小于0, 15咖. The average particle size of the particulate components of the composition of the present invention should preferably be such that it allows a particle diameter of not more than 5% larger than 1. 7mm, the particle diameter of not more than 5% less than 0, 15 coffee.

本文中所定义的术语平均粒径是通过将组合物样品在一系列Tyler筛子上歸分成很多粒度级( 一般是5个粒度级)计算的.由此得到的重量粒度级对筛子的孔径作图.平均粒径为样品通过50% (重量)的孔径。 The term average particle size as defined herein is a sample of the composition through a series of Tyler sieves in normalized granularity divided into a number (typically 5 fractions thus) is calculated. The weight thus obtained are plotted against the aperture size fraction sieves the average particle diameter of the sample (by weight) of the aperture by 50%.

本发明粒状洗涤剂组合物的堆密度一般是至少600g/l,更优选650- 1200g/L堆密度是通过由简单的漏斗和量杯装置测定的,其由刚性安装在底座上的國锥状漏斗组成并在其下端装有一个片状阀以便让漏斗中的物体排空到放在漏斗下面的轴向对准的圓锥状量杯中。 The bulk density of granular detergent compositions of the present invention is generally at least 600g / l, more preferably 650- 1200g / L by measuring the bulk density of a simple funnel and cup device, which is rigidly mounted on the base by the country tapered funnel composition and its lower end is provided with a flap valve to allow an object hopper emptied into a funnel below axially aligned conical beaker. 该漏斗130迈边高,上下端内径分別为130mm和40mm.它是这样安装的, 使得下端在底座上面140mm处.量杯的总高为90mm,内高为87迈m,内径为84mm.其标定体积是500ml. The funnel 130 step high side, the upper and lower ends of the inner diameter were 130mm and 40mm. It is mounted so that the lower end of 140mm at the base above the total height cup is 90mm, the height 87 step m, an inner diameter of 84mm. Its nominal volume was 500ml.

为了进行测定,用手倾倒将该漏斗填满粉末,打开片状阀并让粉末满出量杯.从底座中取出该填满的量杯并用一直边工具例如刀通过 For measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the base and with a knife by a straight edged implement e.g.

其上边缘除去过量的粉末.然后称重该填满的量杯,由粉末重量乘以2 得到的值提供了堆密度(g/1)。 Its upper edge to remove excess powder. The filled cup is then weighed, the weight of powder provided by multiplying the bulk density (g / 1) to obtain the value of 2. 如果需要,重复进行测定. 中链支化的伯垸基聚氣化烯附聚物顆粒 If necessary, repeat the measurement. The mid-chain branched primary alkyl with poly alkenyl vaporized particles agglomerate

本文中的中链支化的伯烷基聚氧化烯体系优选以中链支化的伯烷基聚氧化烯附聚物颗粒的形式存在于粒状组合物中,该附聚物顆粒可以是片、小球、丸、条、带状形式的,但优选是颗粒形式的。 Herein, the mid-chain branched primary alkyl polyoxyalkylene system preferably mid-chain branched primary alkyl polyoxyalkylene polymeric form of agglomerates of particles present in the granular compositions, the agglomerate particles may be a sheet, pellets, pellet, strip, strip form, but is preferably in particulate form. 最优选的加工该颗粒的方法是通过将粉末(例如硅铝酸盐、碳酸盐)与高活性的中链支化的伯烷基聚氧化烯青附聚并将得到的附聚物的粒径控制在特定的限度内.这样的方法包括将有效量的粉末与高活性的中链支化的伯烷基聚氧化烯奮体在一个或多个附聚机例如盘式附聚机、Z型叶片混合机中,或者更优选在串联的混合机例如由Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands和Gebruder Lodige Mascliinenbau GmbH, D - 4790 Paderbron 1, Elsenerstrasse 7-9, Postfach 2050, Germany生产的那些。 The most preferred method of processing the particles are agglomerates by powders (e.g. aluminosilicate, carbonate) with high active mid-chain branched primary alkyl polyoxyalkylene green agglomerated grain and the resulting diameter controlled within specified limits. such methods include administering an effective amount of powder with a high active mid-chain branched primary alkyl polyoxyalkylene Fen body pan agglomerator e.g. one or more machines in the agglomerator, Z type blade mixer or more preferably in a series of mixer such as a Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands and Gebruder Lodige Mascliinenbau GmbH, D - 4790 Paderbron 1, Elsenerstrasse 7-9, Postfach 2050, Germany production of those. 最优选使用高剪切混合机,例如Lodige CB(商品名). Most preferably a high shear mixer, e.g. Lodige CB (trade name).

一般使用含有50- 95% (重量),优选70_85% (重量)中链支化的伯烷基聚氧化烯的高活性中链支化的伯烷基聚氧化烯骨体.可以在高到足以维持可泵抽的黏度但低到足以避免所用表面活性剂降解的温度将该青体泵送到附聚机中.该骨体的操作温度一般是50 - . Primary alkyl polyoxyalkylene bone material typically containing 50-95% (wt), preferably 70_85% (by weight) of a high activity chain branched primary alkyl polyoxyalkylene chain branching in may be high enough to maintain a pumpable viscosity, but low enough to avoid the green body is pumped into the agglomerator surfactant degradation temperature of the operating temperature used, the bone material is generally 50 -.

洗衣洗涤方法-本文中的机洗洗衣方法一般包括在洗衣机中用在其中溶解或分散了有效量的本发明机洗洗衣洗涤剂组合物的含水洗涤液处理污垢衣服。 Laundry washing method - a laundry machine washing method herein typically comprises a dissolved or dispersed therein an effective amount of a machine of the present invention with an aqueous wash liquor in a washing machine laundry detergent compositions soils clothes washing process. 关于有效量的洗涤剂组合物,它指的是20- 300g 的产品溶解或分散在5-65升的洗涤溶液中,这是在常规的机洗洗衣方法中通常使用的一般产品剂量和洗涤溶液体积, On the detergent composition an effective amount, it refers to 20- 300g of product dissolved or dispersed in a wash solution of 5-65 liters, as are typical product dosages and wash solution a laundry washing machine in a conventional method commonly used in volume,

如上所述,本文中中链支化的伯烷基聚氧化烯表面活性剂用于洗涤剂組合物中,其优选与其它洗涤表面活性剂組合,其量对达到至少是清洗性能方面的直接改进是有效的.在织物洗衣组合物中,上述"使用量"可以变化,这不仅取决于污垢和污斑的类型和严重程度,而且还取决于洗涤水温度、洗涤水体积和洗衣机的类型。 As described above, herein, mid-chain branched primary alkyl polyoxyalkylene surfactants for use in detergent compositions, preferably in combination with other active detergent surfactants, is at least an amount of cleaning performance improvements directly is effective in fabric laundering compositions, the above "usage amount" can vary, depending on not only the type of soils and stains and severity, but also on the type of the wash water temperature, the volume of wash water and the washing machine.

例如,在洗涤浴中使用约45- 83升水,洗涤循环约10-14分钟和洗涤水温度约10-50C的上栽垂直轴的美国型自动洗衣机中,优选的是在洗涤液中包括约2- 625卯迈,优选约2- 550ppm,更优选约10 -235pp班的中链支化的伯烷基聚氧化烯表面活性剂.根据每洗涤负载约50- 150ml的使用比例,对于重垢液体洗衣洗涤剂来说,其转化成中链支化的伯烷基聚氧化烯表面活性剂的产品中浓度(重量)为约0.1 -40%,优选约0.1-35%,更优选约O. 5-15%,根据每洗涤负载约30- 950g的使用比例,对于稠密("致密")粒状洗衣洗涤剂(密度大于约650g/1)来说,其转化成中链支化的伯烷基聚氧化烯表面活性剂的产品中浓度(重量)为约Ol-50%,优选约0.1-35%,更优选约0.5-15%.根据每负栽约80- 100g的使用比例,对于喷雾干燥的顆粒(即"蓬松的";密度低于约650g/1)洗涤剂来说,其转化成中链支化的伯烷基聚氣化烯表 U.S.-type automatic washing machine for example, about 45-83 liters of water in the wash bath, a wash cycle of about 10-14 minutes and a wash water temperature of about 10-50C are planted in the vertical axis, it is preferably included in the wash liquor to about 2 --625 step d, preferably from about 2- 550ppm, more preferably from about mid-chain branched primary alkyl classes 10 -235pp polyoxyalkylene surfactants for use in accordance with a ratio of about 50- 150ml per wash load, for heavy duty liquid. laundry detergent, its conversion into mid-chain branched primary alkyl polyoxyalkylene surfactant product concentration (wt.) of about 0.1 -40%, preferably about 0.1-35%, more preferably from about O. 5 for 15%, according to the use ratio of about 30- 950g per wash load, for the dense ( "compact") granular laundry detergents (density greater than about 650g / 1), which is converted to the mid-chain branched primary alkyl poly alkylene oxide surfactant product concentration (wt.) of about Ol-50%, preferably about 0.1-35%, more preferably about 0.5 to 15%. use according to each of the negative ratio of about 80- 100g plant, for the spray-dried particles (i.e., "fluffy"; density below about 650g / 1) for the detergent, which was converted to mid-chain branched primary alkyl poly gasification alkenyl table 面活性剂的产品中浓度(重量)为约0.07 -35D/。 Product concentration of the surfactant (by weight) of about 0.07 -35D /. ,优选约0.07- 25%,更优选约0.35-11%, , Preferably from about 0.07 to 25%, more preferably about 0.35-11%,

例如,在洗涤浴中使用约8- 15升水,洗涤循环约10-60分钟和洗涤水温度约30- 95C的前栽水平轴的欧洲型自动洗衣机中,优选的是在洗涤液中包括约3- 14000ppm,优选约3- 10000ppia,更优选约15- 4200ppm的中链支化的伯烷基聚氧化烯表面活性剂.根据每洗涤负栽约45- 270ml的使用比例,对于重垢液体洗衣洗涤剂来说,其转化成中链支化的伯烷基聚氧化烯表面活性剂的产品中浓度(重量)为约O. 1-50%,优选约0.1-35%,更优选约0.5-15%.根据每洗涤负栽约40-210g的使用比例,对于稠密("致密")粒状洗衣洗涤剂(密度大于约650g/l)来说,其转化成中链支化的伯烷基聚氧化蜂表面活性剂的产品中浓度(重量)为约0.12-53%,优选约0.12-46 %,更优选约0.6-20%.根据每负栽约140- 400g的使用比例,对于喷雾干燥的颗粒(即"蓬松的";密度低于约650g/l)洗涤剂来说, 其转化成中链支化的伯烷基聚氧化烯 For example, about 8-15 liters of water in the wash bath, a wash cycle of about 10 to 60 minutes and European-type automatic washing machine washing water temperature before planting the horizontal axis about 30- 95C, preferably from about 3 to include in the washing liquid 14000ppm, preferably about 3- 10000ppia, more preferably about 15 to 4200ppm of the mid-chain branched primary alkyl polyoxyalkylene surfactant according to each washing negative plant used in a proportion of about 45 to 270ml, for a heavy-duty liquid laundry detergent , its conversion into a mid-chain branched primary alkyl polyoxyalkylene surfactant product concentration (wt.) of about O. 1-50%, preferably about 0.1-35%, more preferably from about 0.5 to 15% according negative each plant was washed using a ratio of about 40-210g, for dense ( "compact") granular laundry detergents (density greater than about 650g / l), its conversion into a mid-chain branched primary alkyl polyoxyalkylene bee product concentration of surfactant (by weight) of about 0.12-53%, preferably about 0.12-46%, more preferably about 0.6 to 20%. the use of a ratio of about 140- 400g per negative plant for spray dried particles ( i.e., "fluffy"; density below about 650g / l) detergent, its conversion into the mid-chain branched primary alkyl polyoxyalkylene 面活性剂的产品中浓度(重量)为约0.03- 34%,优选约0.03- 24%,更优选约0.15- 10% 。 Product concentration of the surfactant (by weight) about 0.03 to 34%, preferably from about 0.03 to 24%, more preferably from about 0.15 to 10%.

例如,在洗涤浴中使用约26- 52升水,洗涤循环约8-15分钟和洗涤水温度约5-25C的上载垂直轴的日本型自动洗衣机中,优选的是在洗涤液中包括约0.67- 270pp迈,优选约0.67- 236卯m,更优选约3.4- 100pp迈的中链支化的伯烷基聚氧化烯表面活性剂,根据每洗涤负栽约20- 30ml的使用比例,对于重垢液体洗衣洗涤剂来说,其转化成中链支化的伯烷基聚氧化烯表面活性剂的产品中浓度(重量)为约0.1-40%,优选约O. 1-35%,更优选约O. 5_15%。 E.g., about 26-52 liters of water in the wash bath, a wash cycle of about 8-15 minutes and a wash water temperature of the Japanese-type automatic washing machine about a vertical axis uploaded 5-25C, it is preferred to include from about 0.67 in wash liquor 270pp step, preferably from about 0.67 d 236 m, more preferably from about 3.4- 100pp step of mid-chain branched primary alkyl polyoxyalkylene surfactants, each negative washed using a ratio of about 20- 30ml plant, and for heavy duty according to liquid laundry detergent, its conversion to a mid-chain branched primary alkyl polyoxyalkylene surfactant product concentration (wt.) of about 0.1 to 40%, preferably from about O. 1-35%, more preferably from about O. 5_15%. 根据每洗涤 According to each washing

负栽约18-35g的使用比例,对于稠密("致密")粒状洗衣洗涤剂(密度大于约650g/1)来说,其转化成中链支化的伯烷基聚氧化烯表面活性剂的产品中浓度(重量)为约0.1-50%,优选约0.1- 35%, 更优选约0.5-15%.根据每负载约30-40g的使用比例,对于喷雾干燥的顆粒(即"蓬松的";密度低于约650g/l)洗涤剂来说,其转化成中链支化的伯烷基聚氧化烯表面活性剂的产品中浓度(重量)为约0.06- 44%,优选约0.06- 30%,更优选约0.3-13%. Negative plant used in a proportion of about 18-35g, for dense ( "compact") granular laundry detergents (density greater than about 650g / 1), its conversion into a mid-chain branched primary alkyl polyoxyalkylene surfactant product concentration (wt.) of about 0.1 to 50%, preferably from about 0.1 to 35%, more preferably from about 0.5 to 15%. the use of a ratio of about 30-40g per load for spray-dried granules (i.e., "fluffy" ; density of less than about 650g / l) detergent, its conversion into the mid-chain branched primary alkyl polyoxyalkylene surfactant product concentration (wt.) of about 0.06 to 44%, preferably from about 0.06 to 30 %, more preferably about 0.3-13%.

从上面可以看出:用于机洗洗衣方面的中链支化的伯烷基聚氧化烯表面活性剂的量可以变化,这取决于使用者的习惯和实践情况、洗衣机的类型等.然而,在这方面,中链支化的伯烷基聚氧化烯表面活性剂的一个迄今为止未知的优点是:其对各种污垢和污斑在性能上提供了至少直接改进的能力,甚至当在最终组合物中相对于其它表面活性剂(通常为阴离子或阴离子/非离子表面活性剂混合物)以相对低的含量使用时也是如此. As can be seen from the above: the amount of primary alkyl polyoxyalkylene surfactants machine laundry aspect of the branched chain may vary, depending on the habits and practices, the type of washing machine, however the user. in this regard, a heretofore unknown advantage of mid-chain branched primary alkyl polyoxyalkylene surfactants are: it provides at least a direct capacity improvement in performance on a variety of soils and stains even when in the final composition relative to other surfactants (typically anionic or anionic / nonionic surfactant mixture) is true when used at relatively low levels.

在优选的使用方面,在洗涤方法中使用分配装置.该分配装置充满了洗涤剂产品,并用其将产品在洗涤循环开始之前直接引入到洗衣机的转筒中.其体积容量应该是这样的以便能够含有足够的作为在该洗涤方法中通常使用的洗涤剂产品. In a preferred aspect the use, use of the dispensing device in a washing process. The dispensing device is filled with the detergent product, and used the product before the washing cycle starts directly into the drum of the washing machine. Volume capacity should be such as to be able to contain as sufficient detergent product in the washing method generally used.

一旦洗衣机负栽有衣服,含有洗涤剂产品的分配装置就被放进转筒中.在洗衣机的洗涤循环开始时,水被引入该转筒中并且转筒周期地旋转.该分配装置的设计应该是这样的,致使其可以含有干的洗涤剂产品,然后在洗涤循环期间随着其搅拌(由于转筒旋转)和也作为与洗涤水接触的结果而使该产品释放. Once the washing machine negative planted with clothes, the dispensing device detergent product containing it is put into the drum in the wash cycle is started the washing machine, water is introduced into the drum and rotating the drum periodically. The design of the dispensing device should be such that , resulting in a detergent which may contain a dry product, as it was then stirred during the washing cycle (due to the rotation of the drum), and also as a result of contact with the wash water so that release of the product.

为了便于在洗涤期间释放洗涤剂产品,该装置可以具有很多开孔,洗涤剂产品可以通过这些孔。 In order to facilitate the release of the detergent product during the wash the device may have many openings detergent product through the apertures. 另外,该装置可以由可渗透液体但不能渗透固体产品的材料制成,这可以释放溶解的产品。 Further, the apparatus may, but not permeable by the material of the solid product made of a liquid permeable, which can release soluble products. 优选地,该洗涤剂产品在洗涤循环开始时就迅速释放从而在该洗涤循环阶段在洗衣机的转筒中提供暂时的局部高浓度的产品. Preferably, the detergent product during the wash cycle begins rapidly released to provide temporary localized high concentrations of product in the drum of the washing machine at this stage of the wash cycle.

优选的分配装置是可再使用的,并且是以这样的方式设计的即在干状态中和洗涤循环期间均保持容器的完整性。 Preferred dispensing devices are reusable and are designed in such a way that the integrity of the dry state and during the wash cycle was maintained in the vessel. 在下面专利中已经叙述了用于本发明组合物中的特别优选的分配装置:GB-B-2157717、 GB-B-2157718、 EP - A - 0201376、 EP - A - 0288345和EP - A - In the following patents it has been described dispensing apparatus used in the compositions of the present invention particularly preferred: GB-B-2157717, GB-B-2157718, EP - A - 0201376, EP - A - 0288345 and EP - A -

0288346,由J. Bland在1989年11月的Manufacturing Chemist的 0288346 by J. Bland in Manufacturing Chemist 1989 in November of

第41-46页公开的文章也描迷了用于粒状洗衣产品的特别优选的分 Pp. 41-46 article also describes public lost for granular laundry products are particularly preferred points

配装置,它是通常称之为"granulette"类型的.另一个与本发明組合物一起使用的优选的分配装置公开于PCT专利申请W094/11562中. Dispensing device, which is commonly referred to as "granulette" type. Another preferred dispensing device for use with the compositions of the present invention is disclosed in PCT Patent Application W094 / 11562 in.

特别优选的分配装置公开于欧洲专利申请公开号0343069和0343070中.后一申请公开了包括从限定孔口的支撑环延伸的袋形式的挠性套的装置,使该孔口通向袋子,该袋有用于洗涤过程中一次洗涤循环的足够产品.部分洗涤介质通过该孔口流进该袋中,溶解该产品,然后溶液通过该孔口向外流出进入洗涤介质中.该支撑环装有屏蔽装置以防止湿的未溶解产品外流出,该装置一般包括从在辐条轮构型的中心轮毂延伸的辐射状延伸壁或类似的结构,其中该壁具有螺线形式。 Especially preferred dispensing devices are disclosed in European Patent Application Publication No. 0343069 and 0343070 in. The latter Application discloses a device comprising a flexible sheath in the form of the bag extending from a support ring defining an orifice, the orifice leading to the pouch so that the Bag for one washing cycle in a washing process sufficient product portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution flows outwardly through the orifice into the washing medium. the support ring is provided shield means to prevent the outside of wetted, undissolved product flows, generally comprises from the apparatus in the radial spoked wheel configuration extending central hub extending wall or similar structure, wherein the walls have a helical form.

另外,该分配装置可以是可挠性的容器,例如袋或盒.该袋可以是用水不可渗透的保护材料涂覆的纤维状结构以便保持其中的内容物,例如在欧洲专利申请0018678中所公开的.另外,它可以是由水不溶性合成聚合材料形成的,该材料有设计成在含水介质中破裂的边缘密封物或闭合物,如在欧洲公开专利申请号0011500、 0011501、 0011502和0011968中所公开的。 Further, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a protective material impermeable to water in order to maintain the contents therein, for example as disclosed in European Patent Application No. 0018678 in Further, it may be insoluble by the water-synthetic polymeric materials, which materials are designed to rupture in aqueous media edge seal or closure, as described in European Published Patent application No. 0,011,500, 0,011,501, 0,011,502 and 0,011,968 as the public. 方便形式的水易碎闭合物包括水溶性粘合剂,它沿水不可渗透的聚合膜例如聚乙烯或聚丙烯形成的袋的一个边放置并将其密封. A convenient form of water frangible closure comprises a water-soluble binder, such as one side of it is placed and sealed in bags formed of polyethylene or polypropylene along the water-impermeable polymeric membrane.

机洗餐具方法 Machine dishwashing method

任何合适的机洗或清洗脏餐具尤其是脏的银餐具的方法都可以考虑使用. Any suitable machine washing or cleaning soiled tableware, especially dirty silverware method can be considered to use.

优选的机洗餐具的方法包括:用在其中溶解或分散了有效量的本发明机洗餐具组合物的水溶液处理选自陶器、玻璃器皿、凹型器皿、 银器和刀具和其混合物的污垢物品'关于有效量的机洗餐具组合物, 它指的是8 - 60g的产品溶解或分散在3_ IO升的洗涤溶液中,这是在 A preferred method of machine dishwashing comprising: a machine used in the present invention, dissolved or dispersed therein an effective amount of an aqueous solution of washing dishes treated soil composition selected items crockery, glassware, vessels concave, silver and mixtures thereof, and the tool ' on effective amount of a machine dishwashing composition, it refers 8 - 60g of product dissolved or dispersed in a wash solution 3_ IO l, which is

常规的机洗餐具方法中通常使用的一般产品剂量和洗涤溶液体积。 Typical product dosages and wash solution volumes commonly used in dishwashing methods conventional machine. 组合物的包装 Packaging of the composition

该漂白组合物的市售实施方案可以被包装在任何合适的容器中, 包括从纸、纸板、塑料材料和任何合适层压物构成的那些容器。 Commercially available embodiments of the bleaching compositions can be packaged in any suitable container, the container including those constructed from paper, cardboard, plastic materials and any suitable laminates. 优选 Preferred

的包装实施方案描述于欧洲专利申请94921505. 7中。 Packaging embodiments described in the European Patent Application No. 94921505.7.

在下面实施例中,用于组合物中的各种组分的缩写符号具有下面 In the following examples, the abbreviations for the various components have the following composition

的意义: Meaning:

LAS :直链烷基苯磺酸钠 LAS: linear alkyl benzene sulfonate

MBxAEy :中链支化的伯烷基(平均碳原子数- x)乙氧基 MBxAEy: mid-chain branched primary alkyl (average number of carbon atoms - x) ethoxy

化物(平均EO-y) Compound (average EO-y)

Endolase :由NOVO Industries A/S销售的活性为 Endolase: sold by NOVO Industries A / S of activity

3000CEVU/g的Endogl咖se 3000CEVU / g of coffee Endogl se

MEA :单乙醇胺 MEA: monoethanolamine

PG : 丙二醇 PG: Propylene glycol

BPP : 丁氧基-丙氧基-丙醇 BPP: butoxy - propoxy - propanol

EtOH :乙醇 EtOH: Ethanol

NaTS :甲笨磺酸钠 NaTS: A sodium stupid

NaOH :氢氧化钠溶液 NaOH: sodium hydroxide solution

柠檬酸:无水柠檬酸 Citric acid: Anhydrous citric acid

CxyFA : Cu-d,脂肪酸 CxyFA: Cu-d, fatty acids

CxyEz :与平均z摩尔环氧乙烷缩合的Cn—ly支链伯醇 CxyEz: average of z moles of ethylene oxide Cn-ly branched primary alcohol

*CxyEz :与平均z摩尔环氧乙烷缩合的C,,支链伯醇 * CxyEz: average z moles of ethylene oxide condensed C ,, branched primary alcohols

碳酸盐:粒径为200- 900Mm的无水破酸钠 Carbonate: 200- 900Mm particle size of anhydrous sodium broken

柠檬酸盐:活性为86.4%的柠檬酸三钠二水合物,粒径分 Citrate: 86.4% of the activity of trisodium citrate dihydrate, sub-particle size

布在425- 850pm之间 Cloth between the 425- 850pm

TFAA : C16-18烷基N-甲基葡糖跣胺 TFAA: C16-18 alkyl amine N- methyl glucose Municipal

LMFAA : C12 - 14烷基N-甲基葡糖跣胺 LMFAA: C12 - 14 alkyl amine N- methyl glucose Municipal

APA : C8-CIO酰氨基丙基二甲基胺 APA: C8-CIO amidopropyl dimethylamine

脂肪酸(C12/14) : C12-C14脂肪酸脂肪酸(TPK):拔顶的棕榈仁脂肪酸脂肪酸(RPS):菜子脂肪酸 Fatty acid (C12 / 14): C12-C14 fatty acid Fatty Acid (TPK): Topped palm kernel fatty acid Fatty Acid (RPS): rapeseed fatty acid

硼砂、 :四硼酸钠十水合物 Borax: sodium tetraborate decahydrate

PAA : 聚丙烯酸(mw= 4500) PAA: polyacrylic acid (mw = 4500)

PEG : 聚乙二醇(mw= 4600) PEG: polyethylene glycol (mw = 4600)

MES :烷基甲基酯磺酸盐 MES: alkyl methyl ester sulfonates

SAS : 仲烷基硫酸盐 SAS: secondary alkyl sulfates

NaPS :石蜡烃磺酸钠 NaPS: Sodium paraffin

C45AS : Cu-ds直链烷基疏酸钠 C45AS: Cu-ds sodium linear alkyl hydrophobic

CxyAS : d: - d,烷基疏酸钠(或其它盐,如果具体说明 CxyAS: d: - d, sodium alkyl sparse (or other salts, if specifically described

的话) if)

CxyEzS :与z摩尔环氧乙烷缩合的Cu-"烷基疏酸钠 CxyEzS: with z moles of ethylene oxide condensed Cu- "sparse Sodium alkyl

(或其它盐,如果具体说明的话) 皂:C12-18烷基羧酸盐,钠盐 (Or other salts, specify if any) soap: C12-18 alkyl carboxylate, sodium salt

AQA : R2.lT(CH8)"(C2H40hH)豕,Rz-Cs-Cm, x+z=3, AQA: R2.lT (CH8) "(C2H40hH) hog, Rz-Cs-Cm, x + z = 3,

x=0- 3, z=0- 3, y = 1 - 15 STPP :无水三聚磷酸钠 x = 0- 3, z = 0- 3, y = 1 - 15 STPP: Anhydrous sodium tripolyphosphate

滞石A :式Na12(A102Si0)12.27H20的初级粒径为0.1- Lag stone A: formula Na12 (A102Si0) primary particle diameter of from 0.1 to 12.27H20

IO微米的水合硅铝酸钠NaSKS - 6 :式5 - Na2Si20s的结晶层状硅酸盐碳酸盐:粒径在200-900M迈之间的无水碳酸钠 Hydrated sodium aluminosilicate micrometers NaSKS IO - 6: Formula 5 - Na2Si20s crystalline layered silicate Carbonate: Anhydrous sodium carbonate particle size of the step between 200-900M

碳酸氢盐:粒径分布在400- 1200Mm之间的无水碳酸氳 Bicarbonate: particle size distribution between 400- 1200Mm Yun carbonate anhydrous

sodium

硅酸盐:无定型硅酸钠(Si02: Na20比-2.0) Silicate: Amorphous Sodium Silicate (Si02: Na20 ratio -2.0)

硫酸盐:无水硫酸钠 Sulfate: Anhydrous sodium sulfate

PAE :乙氧基化(15-18)的四亚乙基五胺 PAE: ethoxylated (15-18) tetraethylene pentamine

PIE :乙氧基化聚乙烯亚胺 PIE: ethoxylated polyethyleneimine

PAEC :甲基季铵化的乙氧基化二亚己基三胺 PAEC: Methyl quaternized ethoxylated hexamethylene triamine two

MA/AA : 1: 4的马来酸/丙蜂酸共聚物,平均分子量约 MA / AA: 1: 4 maleic acid / propionic acid copolymer bee, average molecular weight about

70000 70,000

CMC :羧甲基纤维素钠 CMC: Sodium carboxymethyl cellulose

蛋白酶:由NOVO Industries A/S以商品名Savinase Protease: by the NOVO Industries A / S under the tradename Savinase

销售的活性为4KNPU/g的蛋白酶纤维素酶:由NOVO Industries A/S以商品名Carezy迈e Sales activity 4KNPU / g protease Cellulase: / S tradename Carezy step of NOVO Industries A e

销售的活性为1000CEVU/g的纤维素酶淀粉酶:由NOVO Industries A/S以商品名Ter迈amyl Sales activity 1000CEVU / g cellulase amylases: a NOVO Industries A / S under the tradename step amyl Ter

60T销售的活性为60KNU/g的淀粉分解酶脂肪酶:由NOVO Industries A/S以商品名Lipolase 60T sales activity 60KNU / g amylolytic enzyme Lipase: by the NOVO Industries A / S under the tradename Lipolase

销售的活性为100kLU/g的脂解酶PB4 :标称式为NaB02 • 3H20 • H202的过硼酸钠四水合 Sales activity 100kLU / g lipolytic enzyme PB4: Sodium nominal formula NaB02 • 3H20 • H202 perborate tetrahydrate

Thing

PB1 :标称式为NaB02 •払02的无水过硼酸钠漂白剂 PB1: nominal formula NaB02 • partial payment of 02 in anhydrous sodium perborate bleach

过碳酸盐:标称式为2Na2C03.3H202的过碳酸钠 Percarbonate: nominal formula 2Na2C03.3H202 sodium percarbonate

NaDCC : 二氯异氰脲酸钠 NaDCC: Sodium dichloroisocyanurate urea

NOBS :钠盐形式的壬酰氧基笨碌酸盐 NOBS: nonanoyl sodium salt form salts bunk stupid

EDDS :乙二胺二琥珀酸盐 EDDS: Ethylenediamine disuccinate

TAED :四乙耽基乙二胺 TAED: tetraacetyl ethylenediamine Delays

磺基琥珀酸盐:琥珀酸月桂酯磺酸二钠 Sulfosuccinates: disodium lauryl ester sulfonate

DTPMP : 由Monsanto以商品名Dequest 2060销售的二 DTPMP: by Monsanto under the trade name Dequest 2060 sold two

亚乙基三胺五(亚甲基膦酸盐) 光活化的漂白剂:包胶在糊精可溶的聚合物中的磺化的锌舦菁 Triamine penta (methylene phosphonate) photoactivated bleaches: encapsulated in dextrin soluble polymer sulfonated zinc phthalocyanine Tai

增白剂l : 4,4,-双(2-磺基笨乙烯基)联苯二钠 Brightener l: 4,4, - bis (2-sulfo stupid) biphenyl

增白剂2 : 4,4,-双[(4-苯胺基-6-吗啉代-l,3,5- Brightener 2: 4,4, - bis [(4-anilino-6-morpholino -l, 3,5-

三溱- 2 - 基) 氨基]芪-2, 2, - 二磺酸二钠 Three Qin - 2 - yl) amino] stilbene -2, 2, - disodium

HEDP : 1,1-羟基乙烷二膦酸 HEDP: 1,1- hydroxyethane diphosphonic acid

SRP 1 :具有氧化乙烯氧基和对笨二酰基骨架的磺基笨 SRP 1: has an ethylene oxide group and a sulfo stupid skeleton of diacyl stupid

甲酰基封端的酯 A end-capped ester

SRP 2 :磺化的乙氧基化的对苯二酸酯聚合物 SRP 2: Sulfonated ethoxylated terephthalate polymer

SRP 3 :甲基封端的乙氧基化的对笨二酸酯聚合物 3 SRP: ethoxylated methyl-capped terephthalate polymers stupid

聚硅氧烷抗泡剂:含有硅氧烷-氧化烯共聚物作为分散剂的聚二 Silicone anti-foaming agent: silicone-containing - oxyalkylene copolymer as dispersing agent polydimethyl

甲基硅氧烷泡沫控制剂,所述泡沫控制剂与所述分散剂的比例为IO: 1-100: 1 Methyl silicone suds controlling agents, suds control agents and the proportion of the dispersant is IO: 1-100: 1

Isofol 16 : C16 (平均值)Guerbet醇的Condea商标 Condea trademark C16 (average) the Guerbet alcohols: Isofol 16

CaCl2 :氯化钙 CaCl2: calcium chloride

MgCl2 :氯化镁 MgCl2: magnesium chloride

DTPA : 二亚乙基三胺五乙酸 DTPA: Diethylene triamine pentaacetic acid

在下面实施例中,所有含量均是按组合物重量计的百分数.下面实施例说明本发明,而不是限制或另外限定其范闺.除非另有说明, 本文中使用的所有份数、百分数和比例均以重量百分数表示. In the following examples, all contents are by weight percent of the composition. The following examples illustrate embodiments of the present invention, and not to limit or otherwise define its scope Gui. Unless otherwise indicated, all parts used herein, percentages and proportions are expressed in weight percent.

实施例1 根据本发明制备下面洗衣洗涤剂组合物A- I:<table>table see original document page 84</column></row> <table><table>table see original document page 85</column></row> <table><table>table see original document page 86</column></row> <table>下面备质的任意組合: C25ExS*Na(x- 1.8-2.5) C2S AS(直链到高2-烷基) C14-17NaPS C12-16SAS C18 1,4-二疏酸盐C1I.3LAS C12-】6MES <table>table see original document page 86</column></row> <table>下面物质的任意组合: APA AQA<table>table see original document page 86</column></row> <table> Embodiment 1 of the present invention is prepared according to the following laundry detergent compositions of Example A- I: <table> table see original document page 84 </ column> </ row> <table> <table> table see original document page 85 </ column> </ row> <table> <table> table see original document page 86 </ column> </ row> <table> prepared by any combination of the following quality: C25ExS * Na (x- 1.8-2.5) C2S AS (linear to high 2-alkyl) C14-17NaPS C12-16SAS C18 1,4- two-repellent salt C1I.3LAS C12-] 6MES <table> table see original document page 86 </ column> </ row> <table> The following substances any combination of: APA AQA <table> table see original document page 86 </ column> </ row> <table>

<table>table see original document page 87</column></row> <table>实施例7 <Table> table see original document page 87 </ column> </ row> <table> Example 7

通过合适的支链醇与环氧乙烷反应制备支链的乙氧基化的表面活性剂。 By a surfactant suitable ethoxylated alcohols and branched chain branched preparing ethylene oxide. 从已经通过暴露在合适的催化剂中分子重排了的直链烯烃(a 和/或内烯烃)制备该支链醇。 The branched-chain alcohol has been exposed to a suitable catalyst in a molecular rearrangement of the linear olefin (a and / or internal olefins) prepared by the. 在该分子重排中没有加入另外的碳,但开始的烯烃被异构化使得它含有一个或多个沿其主烷基链上的烷基支链,由于在整个分子重排期间烯烃部分保持完整,于是通过加氢甲酰化可以加上CH20H基团。 In the molecular rearrangement additional carbon is not added, but the starting olefin is isomerized so that it contains one or more alkyl branches along the main alkyl chain, since the portion of the olefin molecule during the entire holding rearrangement complete, it can then be coupled with group CH20H by hydroformylation. 将下面的Shell Research试验醇样品乙氧基化(平均乙氧基化度为7). The following Shell Research alcohol samples Experimental ethoxylated (average ethoxylation degree of 7).

制备的支链醇的13C-NMR结果<table>table see original document page 88</column></row> <table> 制备如下表所示的洗衣原型配方(prototype formula)的溶液. Laundry solution formulation prototype (prototype formula) The 13C-NMR branched alcohol produced results <table> table see original document page 88 </ column> </ row> <table> prepared as shown in the table below.

在洗涤溶液中的组分(PPM) Component (PPM) in the wash solution

<table>table see original document page 88</column></row> <table> <Table> table see original document page 88 </ column> </ row> <table>

实施例8 Example 8

制备如下表所示的洗衣原型配方的溶液. Solution of laundry prototype formulation was prepared as shown in the following table.

在洗涤溶液中的组分(PPM) Component (PPM) in the wash solution

<table>table see original document page 89</column></row> <table>含有非水载体介质的重垢液体洗涤剂组合物尤其是设计用于织物洗涤的那些组合物的生产可以用下文中更详细公开的方法进行。 <Table> table see original document page 89 </ column> </ row> <table> heavy duty liquid detergent composition comprising a non-aqueous carrier medium of the composition, especially those designed for fabric washing may be produced in the following method disclosed in more detail. 在另一个方法中,可以按照下面的专利文献的公开内容制备这样的非水组 In another method, can be prepared according to published nonaqueous group content of the following Patent Document

合物:US4753570、 US4767558、 US4772413、 US4889652、 US4892673、 GB-A- 2158838、 GB-A- 2195125、 GB-A- 2195649、 US4988462、 US5266233、 EP - A - 225654(6/16/87)、 EP - A - 510762(10/28/92)、 EP-A- 540089(5/5/93)、 EP - A - 5400卯(5/5/93) 、 US4615820、 EP -A- 565017(10/13/93)、 EP - A - 030096 (6/10/81),这些文献在本文中引作参考.这样的组合物可以含有稳定地悬浮在其中的各种颗粒洗涤组分(包括漂白剂,如上文中所公开的).因此这样的非水组合 Compound: US4753570, US4767558, US4772413, US4889652, US4892673, GB-A- 2158838, GB-A- 2195125, GB-A- 2195649, US4988462, US5266233, EP - A - 225654 (6/16/87), EP - A - 510762 (10/28/92), EP-A- 540089 (5/5/93), EP - A - 5400 d (5/5/93), US4615820, EP -A- 565017 (10/13 / 93), EP - a - 030096 (6/10/81), which are incorporated herein by reference such compositions can contain stably suspended therein various components in the washed particles (including the bleaching agents, as described above. the disclosed). such non-aqueous compositions thus

的固体相.用上文中所述的方法和含量将中链支化的伯烷基聚氧化烯加入到组合物中以便制备其它的洗衣洗涤剂组合物. 液体相 The solid phase. Hereinabove with the methods and the content of the mid-chain branched primary alkyl polyoxyalkylene is added to the composition to prepare other laundry detergent compositions. Liquid phase

液体相通常占本文中洗涤剂组合物重量的约35- 99%.更优选该 Liquid phase generally comprise from about 35 to 99% by weight of the detergent compositions herein More preferably the

液体相占组合物重量的约50- 95%.最优选该液体相占本文中组合物重量的约45- 75%.本文中洗涤剂組合物的液体相基本上含有相对高浓度的特定类型的阴离子表面活性剂,并结合有特定类型的非水的液体稀释剂。 The liquid phase comprises about 50-95% of the composition by weight. Most preferably, the liquid phase comprises about 45 to 75% by weight of the compositions herein. Liquid detergent compositions herein essentially contains certain types with relatively high concentrations anionic surfactants, in combination with a liquid diluent with a particular type of non-aqueous.

(A) 基本的阴离子表面活性剂 (A) basic anionic surfactant

主要用作非水液体相的基本组分的阴离子表面活性剂选自:其中烷基含有约10-16个碳原子的直链或支链构型的烷基苯磺酸的碱金属盐。 Is mainly used as an essential component of the nonaqueous liquid phase of the anionic surfactant is selected from: wherein the alkyl group contains an alkali metal salt of benzene sulphonic acid, linear or branched chain configuration of from about 10 to 16 carbon atoms. (见US2220099和US2477383,这2篇文献在本文中引作参考.) 特別优选的是其中烷基中的平均碳原子数是约11-14的直链烷基笨磺酸钠和钾(LAS)。 (See US2220099 and US2477383, these two documents are incorporated herein by reference.) Particularly preferred are wherein the average number of carbon atoms in the alkyl group is from about 11 to 14 stupid linear alkyl sulphonates (LAS) . Cn-C"LAS钠是特别优选的。 Cn-C "LAS Sodium is particularly preferred.

将烷基笨磺酸盐阴离子表面活性剂溶解在构成该非水相第2个基本组分的非水液体稀释剂中.为了形成适合的相稳定性和可接受的流变学性质所需要的结构化的液体相,烷基苯磺酸盐阴离子表面活性剂通常存在的量是该液体相的约30- 65%.更优选该烷基笨磺酸盐阴离子表面活性剂占本文组合物非水液体相重量的约35- 50%.以这些浓度使用这一阴离子表面活性剂相当于在总组合物中的阴离子表面活性剂浓度为组合物重量的约15-60%,更优选约20- 40%. The stupid alkyl sulfonate anionic surfactant is dissolved in a non-aqueous phase constituting the second essential component of the nonaqueous liquid diluent in order to form a suitable phase stability and acceptable rheological properties required structured liquid phase, alkylbenzene sulfonate anionic surfactant is generally present in an amount from about 30 to 65% of the liquid phase. more preferably, the alkyl sulfonate anionic surfactants stupid accounting nonaqueous compositions herein about 35 to 50% by weight of the liquid phase. the use of these concentrations corresponds to an anionic surfactant concentration of the anionic surfactant in the total composition is about 15-60% by weight of the composition, more preferably from about 20-40 %.

(B) 非水液体稀释剂 (B) a non-aqueous liquid diluent

为了形成洗涤剂组合物的液体相,将上文中所述的烷基笨磺酸盐阴离子表面活性剂与含有2种基本组分的非水液体稀释剂混合.这2 种组分是液体醇烷氧基化物材料和非水低极性有机溶剂。 To form the liquid phase of the detergent compositions, the hereinbefore described liquid diluent alkyl sulfonates stupid anionic surfactant containing two kinds of non-essential components of water. These two components are a liquid alcohol alkoxylate group-containing material and a non-aqueous low-polarity organic solvent.

i)醇烷氧基化物 i) alcohol alkoxylates

一种用于形成本文中組合物的液体稀释剂的基本组分包括烷氧基化的脂肪醇材料.这样的材料本身也是非离子表面活性剂。 A method for forming a basic component of the liquid diluent in the compositions herein comprises an alkoxylated fatty alcohol material. Such materials are themselves non-ionic surfactant. 这样的材料相应于下面通式: Such materials correspond to the following general formula:

R、CJU))nOH R, CJU)) nOH

其中W是C8-d6烷基,迈是2-4, n在约2-12的范围.优选W是烷基,其可以是伯或仲的,含有约9-15个碳原子,更优选约10-14 个碳原子的烷基.还优选该烷氧基化的脂肪醇是每分子含有约2-12 个环氧乙烷部分,更优选每分子含有约3-10个环氧乙烷部分的乙氧 Wherein W is alkyl C8-d6, step is 2-4, n is in the range of about 2-12. W is preferably an alkyl group, which may be primary or secondary, it contains from about 9 to 15 carbon atoms, more preferably from about alkyl of 10-14 carbon atoms. preferably also the alkoxylated fatty alcohols containing per molecule from about 2 to 12 ethylene oxide moieties, and more preferably from about 3 to 10 per molecule of ethylene oxide moieties ethoxy

基化的材料, Glycosylated material,

液体稀释剂的烷氧基化的脂肪醇组分的亲水亲油平衡值(HLB)经 HLB value of the alkoxylated fatty alcohol component of the liquid diluent (an HLB) via

常在约3-17的范围.更优选该材料的HLB在约6-15的范闺,最优选约8- 15, Often in the range of about 3-17. HLB is more preferably in the range of the material of the Inner about 6-15, most preferably from about 8-15,

用作本文组合物中非水液体稀释剂基本组分之一的脂肪醇烷氧基化物的例子包括由12- 15个碳原子的醇制备的并且含有约7摩尔环氧乙烷的那些。 Examples of fatty alcohol alkoxylates used as one of the essential components of the compositions herein comprises nonaqueous liquid diluent prepared from alcohols of 12-15 carbon atoms and those containing from about 7 moles of ethylene oxide. 这样的材料由Shell Chemical Company以商标名Neodol 25-7和Neodo1 23-6.5铕售.其它有用的Neodol包括:Neodol 1 -5,其烷基链中平均有11个碳原子的具有约5摩尔环氧乙烷的乙氧基化的脂肪醇;Neodol 23-9,具有约9摩尔环氧乙烷的乙氧基化的C!2-da伯醇和Neodol 91-10,具有约10摩尔环氧乙烷的乙氧基化的C9 - Cu伯醇.这类醇乙氧基化物也由Shell Ch棚ical Company以商品名Dobanol铕售.Dobanol 91-5是具有平均5摩尔环氧乙烷的乙氧基化的C广Cu脂肪醇,Dobanol 25 - 7是每摩尔脂肪醇具有平均7摩尔环氧乙烷的乙氧基化的C12- Cw脂肪醇, Such materials are the trade names Neodol 25-7 and europium Neodo1 23-6.5 by Shell Chemical Company sold other useful include Neodol:. Neodol 1 -5, the alkyl chain having an average of about 5 moles of 11 carbon atoms, ethoxylated fatty alcohols of ethylene oxide;! Neodol 23-9, an ethoxylated C having about 9 moles of ethylene oxide 2-da primary alcohols Neodol 91-10, having about 10 moles of ethylene oxide the alkyl ethoxylated C9 -. Cu primary alcohol ethoxylates of such alcohols are also shed from the Shell Ch ical Company sold under the tradename Dobanol .Dobanol 91-5 europium having an average of 5 ethoxy moles of ethylene oxide Cu wide group of fatty alcohol C, Dobanol 25 - 7 per mole of fatty alcohol having a fatty alcohol ethoxylated C12- Cw average of 7 moles of ethylene oxide,

合适的乙氧基化醇的其它例子包括均由Union Carbide Corporation销售的直链仲醇乙氧基化物Tergitol 15 - S - 7和Tergitol 15-S-9.前者是Cu-ds直链仲链烷醇与7摩尔环氧乙烷的混合乙氧基化产物,后者是d广Cw直链仲链烷醇与9摩尔环氧乙烷反应的类似的混合乙氧基化产物。 Other examples of suitable ethoxylated alcohols include sold by Union Carbide Corporation linear secondary alcohol ethoxylate Tergitol 15 - S -. 7 and Tergitol 15-S-9 is the former Cu-ds linear secondary alkane mixed ethoxylated product alcohol with 7 moles of ethylene oxide, which is a mixed ethoxylated product of similar broad d Cw linear secondary alkanol moles of ethylene oxide reacted with 9.

在本发明组合物中有用的其它类型的醇乙氧基化物是高分子量的非离子表面活性剂例如Neodol 45-11,它是类似的高级脂肪醇的环氧乙烷缩合产物,高级脂肪醇具有14-15个碳原子,每摩尔的环氧乙烷基团数是约11.这样的产品由Shell Chemical Company商业销售, In the compositions of the present invention is useful in other types of alcohol ethoxylates of high molecular weight non-ionic surfactants such as Neodol 45-11, which are similar higher fatty alcohol ethylene oxide condensation products of higher fatty alcohols having 14-15 carbon atoms, the number of ethylene oxide groups per mole of from about 11. such products sold commercially by Shell Chemical Company,

主要用作本文非水組合物中部分液体稀释剂的该醇烷氧基化物组分存在的量通常是该液体相组合物的约1-60%。 The Main herein as part of the liquid diluent in the non-aqueous composition of the alcohol alkoxylate component is typically an amount of about 1-60% of the liquid phase of the composition. 更优选该醇烷氧基化物组分占液体相的约5-40%,最优选地,该主要使用的醇烷氧基化物组分占洗涤剂组合物液体相的约5-30%.在液体相中以这样的浓度使用醇烷氧基化物相当于按组合物重量计在总组合物中的醇烷氧基化物浓度为约1-60%,更优选约2-40%,最优选约5-25%。 More preferably, the alcohol alkoxylate component comprises from about 5-40% of the liquid phase, most preferably, the alcohol alkoxylate component of the main use comprise from about 5-30% of the detergent composition liquid phase. In such a liquid phase to a concentration of alcohol alkoxylates corresponding to the composition of the total weight of the composition of the alcohol alkoxylate concentration of about 1-60%, more preferably from about 2 to 40%, most preferably from about 5-25%.

ii)非水的低极性有机溶剂 ii) non-aqueous low-polarity organic solvent

形成本文洗涤刑组合物部分液体相的该液体稀释剂的第2个基本 Forming the second liquid diluent is the basic part of this wash composition liquid phase Penalty

组分包括非水的低极性有机溶剂,本文中使用的术语"溶剂"指的是组合物液体相的非表面活性栽体或稀释剂部分.尽管一些本文中组合物的基本和/或任选组分实际上可以溶解在含该"溶剂"的液体相中, 但其它组分将作为分散在含该"溶剂"的液体相中的顆粒而存在.闺此术语"溶剂"并不意味着需要该溶剂材料能够真正地溶解加入到其中的所有洗涤剂组合物组分. Component comprises a non-aqueous low-polarity organic solvent, the term "solvent" as used herein refers to a plant or non-surfactant diluent composition liquid phase portion of the basic and / or any While the compositions herein, some optional components may actually dissolve in the liquid containing the "solvent" phase, other components will be dispersed as particles in a liquid phase, containing the "solvent" of the present. Gui term "solvent" is not meant the solvent is required to dissolve the material it can actually be added to all detergent composition therein.

本文中用作溶剂的非水有机材料是低极性的液体.为了本发明的目的,"低极性"液体是具有很低的(如果有的话)溶解用于本文组合物中优选类型顆粒材料之一即过氧漂白剂、过硼酸钠或过碳酸钠的倾向。 The non-aqueous organic material is used as a solvent herein, the low polarity liquid. For purposes of this invention, "low-polarity" liquids having a low (if any) was dissolved in the compositions herein preferably used types of particles That is one of the materials peroxygen bleach, sodium perborate, or the tendency of sodium percarbonate. 因此不应当使用相对极性的溶剂例如乙醇.本文的非水液体洗 Therefore, you should not use a relatively polar solvent such as ethanol. Nonaqueous liquid washing herein

涤剂组合物中有用的低极性溶剂的合适的类型包括:非连位的C4-C8 亚烷基二无醇、亚烷基二元醇单低级烷基瞇、低分子量聚乙二醇、低分子量甲基酯和酰胺等。 Useful in detergent compositions suitable type of low-polarity solvents include: non-vicinal C4-C8 alcohol-alkylene, alkylene glycols mono-lower alkyl blind, low molecular weight polyethylene glycol, low molecular weight methyl esters and amides and the like.

用于本文組合物中的一类优选的非水低极性溶剂包括:非连位的C4-Cs支链或直链亚烷基二元醇.这类材料包括:已二醇(4-甲基-2,4-戊二醇)、1,6-己二醇、1,3-丁二醇和1,4-丁二醇.己二醇是最优选的. Non-aqueous low-polarity solvent used in the compositions herein is a preferred class comprises: a non-vicinal C4-Cs branched or straight chain alkylene glycols such materials include: hexylene glycol (4- yl-2,4-pentanediol), 1,6-hexanediol, 1,3-butanediol and 1,4-butanediol. hexanediol is most preferred.

用于本文中的另一类优选的非水低极性溶剂包括:单、二、三或四C2- C3亚烷基二元醇单C2-C6烷基醚.这样化合物的具体例子包括: 二甘醇单丁基醚、四甘醇单丁基醚、二丙二醇单乙基醚和二丙二醇单丁基醚.二甘醇单丁基醚和二丙二醇单丁基醚是特別优选的.这类化合物已经以商品名Do買anol、 Carbitol和Cellosolve销售。 Another preferred non-aqueous low-polarity solvent for use herein include: mono-, di-, tri- or tetra-C2- C3 alkylene glycols mono C2-C6 alkyl ethers Specific examples of such compounds include: II. glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are particularly preferred. such the compound has the trade name Do buy anol, Carbitol, and Cellosolve sales.

另一类本文中有用的优选非水低极性有机溶剂包括低分子量聚乙 Another class of useful herein is preferably a non-aqueous low-polar organic solvents include low molecular weight polyethylene

二醇(PEG)。 Glycol (PEG). 这样的材料是分子量为至少约150的那些。 Such materials are those having a molecular weight of at least about 150. 分子量在约200 - 600范闺的PEG是最优选的, A molecular weight of from about 200--600 Gui range of PEG is most preferred,

还一类优选的非极性非水溶剂包括低分子量甲基酯.这样的材料是通式为:R1-C(O)-0013的那些物质,其中1^在1-约18的范闺。 A further preferred class of non-polar non-aqueous solvent comprises lower molecular weight methyl esters of such materials are of the general formula:. R1-C (O) -0013 those materials, wherein the range of 1 to about Gui 1 ^ 18. 合适的低分子量甲基醋的例子包括乙酸甲酯、丙酸甲酯、辛酸甲醋和十二烷酸甲酯。 Examples of suitable lower molecular weight methyl acetate include methyl acetate, methyl propionate, methyl octanoate, and methyl laurate vinegar.

当然,使用的非水低极性有机溶剂应当是与用于本文液体洗涤剂组合物中的其它组合物组分例如漂白剂和/或活化剂相容和没有反应性的.按液体相重量计,通常以约1-70%的量使用这样的溶剂组分。 Of course, a non-aqueous low-polarity organic solvent used should be such as bleaching agents and / or activators compatible and no reactivity with other components of the composition used in the liquid detergent compositions herein in the. Liquid phase by weight , typically in an amount of about 1 to 70% of the use of such a solvent component.

更优选地,该非水低极性有机溶剂占组合物液体相重量的约10-60 %,最优选约20- 50%.在液体相中以这样的浓度使用该有机溶剂相当于按组合物重量计在总組合物中的溶剂浓度为约1-50%,更优选约5-40%,最优选约10-30%。 More preferably, the nonaqueous low-polarity organic solvent comprises from about 10-60% by weight of the composition of the liquid phase, most preferably from about 20-50% using the organic solvent corresponds to the composition in such concentration in the liquid phase, weight of solvent concentration in the total composition is from about 1 to 50%, more preferably from about 5 to 40%, most preferably from about 10 to 30%.

"i)醇烷氧基化物与溶剂的比例 Ratio "i) alcohol alkoxylates of the solvent

可以用在液体稀释剂中的醇烷氧基化物与有机溶剂的比例来改变最终形成的洗涤剂组合物的流变学性质.通常醇垸氧基化物与有机溶剂的重量比在约50: 1- 1: 50的范围。 A liquid diluent may be used in the alcohol alkoxylate to organic solvent ratio changing rheological properties of the detergent compositions eventually formed embankment weight alcohol alkoxylates typically the organic solvent is from about 50: 1. range of 50: 1 - 更优选地,这一比例在约3: l- 1: 3的范围。 More preferably, this ratio from about 3: in the range of 3: l- 1.

iv)液体稀释剂的浓度 Concentration iv) a liquid diluent

至于烷基苯磺酸盐阴离子表面活性剂的浓度,本文非水液体相中的液体稀释剂的总量是由其它组合物组分的类型和量并由所需要的组 As the concentration of alkyl benzene sulphonate anionic surfactant, the total amount of non-aqueous liquid diluent is a liquid phase herein by the type and amount of other composition components required to set

合物的性质确定的.该液体稀释剂通常占本文组合物非水液体相的约35- 70%.更优选该液体稀释剂占非水液体相的约50- 65%.这相当于按組合物重量计在总组合物中的非水液体稀释剂浓度为约15-70 %,更优选约20- 50%。 Properties of the compound determined. The liquid diluent is typically accounts for about 35 to 70% of the nonaqueous liquid compositions herein phase. More preferably, the liquid diluent comprises from about 50-65% of a non-aqueous liquid phase. This is equivalent to a combination of press It was the total weight of the composition of a nonaqueous liquid diluent concentration of about 15-70%, more preferably from about 20-50%. 固体相 Solid phase

本文中的非水洗涤剂组合物主要还包括约1-65重量%,更优选约5-50重量%的分散在和悬浮在液体相中的類粒材料的固体相,通常这样顆粒材料的粒径在约0.1- 1500微米的范围.更优选这样材料的粒径在约5- 200微米的范围. Herein primarily non-aqueous detergent compositions comprising from about 1-65% by weight of further, and the solids suspended in the liquid phase based particulate material phase, so that the particulate material is generally grain and more preferably from about 5-50% by weight of the dispersion diameter in the range from about 0.1 to 1500 microns. more preferably the particle size of such materials is in the range from about 5 to 200 microns.

用于本文中的顆粒材料可以包括一种或多种类型的洗涤剂组合物组分,它以颗粒形式基本上不溶于组合物非水液体相中.可以使用的这类顆粒材料详细叙述如下: The particulate material used herein may comprise one or more types of detergent composition components which in particulate form are substantially insoluble in the nonaqueous liquid phase of the composition of such particulate material which may be used is described in detail as follows:

组合物的制备和使用 Preparation and use of the composition

可以通过以任何方便的顺序混合组合物的基本和任选组分,和通过混合例如搅拌得到的组分混合物从而形成本文中的相稳定的组合物来制备本文中的非水液体洗涤剂組合物.在制备该组合物的一般方法中,以特定的顺序和在特定的条件下混合基本的和某些优选的任选組分. Can be prepared by a non-aqueous liquid detergent compositions herein and optional components in substantially any order convenient mixed composition, and component mixtures are obtained by mixing, for example, stirring to form a phase stable compositions herein in a general method for preparing the composition in a specific order and mixing the basic and certain preferred optional components under certain conditions.

在上述一般制备方法的第1步中,通过将这些材料的混合物加热 In the first step in a general production method, by heating the mixture of these materials

到约30- ioox:的温度形成烷基苯磺酸盐阴离子表面活性剂和非水稀 To about 30- ioox: forming temperature alkylbenzene sulfonate anionic surfactant and a non-aqueous dilute

释剂的2种基本组分的混合物. The basic components of a mixture of two kinds of release agent.

在第2工艺步壤中,将上迷形成的加热的混合物在约40-ioox: The mixture was heated in the second process step in the soil, the above-formed in the approximately 40-ioox:

的温度下维持剪切攬拌约2分钟-20小时.任选地,在这时可以将真空施加于该混合物.第2工艺步骤起将阴离子表面活性剂完全溶解于非水液体相中的作用. Shear is maintained at a temperature embrace stirred for about 2 minutes to 20 hours. Optionally, at this time may be a vacuum applied to the mixture. Since the second step of the process to completely dissolve the anionic surfactant in the nonaqueous liquid phase of the action .

在第3工艺步骤中,将材料的液体相混合物冷却到约0-35C的温度.该冷却步骤起形成结构化的含表面活性剂的液体基料的作用, 可以将本文洗涤剂组合物的顆粒材料加入到和分散在该液体基料中. In the third process step, the liquid phase of the material mixture is cooled to a temperature of about 0-35C. This cooling step is formed from a liquid base containing a surfactant action structured detergent compositions herein may be particles material is added to and dispersed in the liquid base.

在第4工艺步骤中,通过将顆粒材料与维持在剪切搅拌条件下的液体基料混合加入顆粒材料.当要加入多于一种颗粒材料时,优选的是遵守特定的加入次序.例如,当维持剪切搅拌时,可以加入粒径在约0.2- 1000微米范闺的顆粒形式的基本上所有固体顆粒形式的任选的表面活性剂。 In the fourth process step, the particulate material is maintained under conditions of shear agitation mixing liquid base particulate material is added when more than one particulate material to be added, is preferably added in order to comply with a specific example, when shear agitation is maintained, substantially all of the particle diameter can be added in the form of solid particles of about 0.2 to 1000, optionally in the form of micro-particles of the Inner Mifan surfactant. 加入任何任选的表面活性剂颗粒后,可以加入基本上 After addition of any optional surfactant particles, may be added substantially

颗粒,同时继续将该组合物组分的混合物维持在剪切搅拌条件下.然后在这时,可以将其它固体形式的任选组分加入到组合物中.继续搅拌该混合物,并且如果需要的话,可以在这时提高搅拌从而形成不溶性固体相颗粒在液体相中的均匀的分散液. Particles while the mixture was continued to maintain the composition components under shear agitation. Then at this time, may be added other solid form optional ingredients in the composition. The mixture was continued stirring, and if desired can be increased at this time was stirred to form a homogeneous particulate insoluble solid phase dispersion in a liquid phase.

将一些或所有上述固体材料加入到该搅拌的混合物中后,可以将漂白剂的颗粒加入到組合物中,同时再将混合物维持在剪切挽拌条件下.通过最后或者在所有或大部分其它组分之后,并且特别是在碱性源顆粒被加入之后加入漂白剂材料,可以得到理想的漂白剂稳定益处.如果加入酶小球的话,那么优选最后将它们加入到非水液体基体中- After some or all of the solid material is added to the stirred mixture, the particles of bleaching agent can be added to the composition, again while the mixture is maintained under shear mixing conditions harness by the last or most or all other after the component, and in particular after addition of an alkaline bleaching agent is added to the source material particles, can be obtained over the benefits of stabilizing bleaches If enzyme prills were added, then they are preferably finally added to the nonaqueous liquid matrix. -

作为最后的工艺步骤,在所有顆粒材料加入之后,继续搅拌该混合物一段时间,其足以形成具有所需粘度和相稳定特性的组合物.通常这包括搅拌约1- 30分钟的一段时间。 As a final process step, after all of the particulate material was added, and the mixture stirring is continued for some time, which is sufficient to form compositions having the requisite viscosity and phase stability characteristics. Typically this includes from about 1 to 30 minutes stirring time.

作为上述组合物制备方法的一个变化,可以将一种或多种固体組分加入到作为与少部分一种或多种液体组分预混合的颗粒浆液的搅拌着的混合物中。 As a variation of the above methods of preparing the compositions, one or more solid components may be added to a stirred slurry of particles with a minor portion of one or more liquid components of the premixed mixture. 因此,可以分別形成少部分醇烷氧基化物和/或非水低极性溶剂与有机助洗剂材料的颗粒和/或无机碱性源的颗粒和/或漂白活化剂的颗粒的预混合物并作为浆液将其加入到搅拌着的组合物组分 Thus, the particles may be formed in a small part of the alcohol alkoxylate and / or nonaqueous low-polarity solvent with particles of the organic builder material and / or inorganic sources of alkalinity or premix granules and / bleach activator, respectively, and as a slurry which was added to a stirred solution of composition components

的混合物中.上迷浆液预混合物的加入应当先于其本身可以是部分以类似方式形成的预混合浆液的漂白剂和/或酶顆粒的加入。 Mixture. The slurry from the fan premix added should first be added to its own premixed slurry formed in a similar manner portions of bleach and / or enzyme particles.

如上所迷制备的本发明组合物可以用来形成用于织物洗涤和漂白的含水洗涤溶液.通常优选在常规的织物洗涤自动洗衣机中将有效量的上述组合物加入到水中从而形成这样的含水洗涤/漂白溶液.然后将如此形成的含水洗涤/漂白溶液优选在攬拌下与要用其洗涤和漂白的织物相接触. As compositions of the invention may be used to form fans prepared washing solution for washing and bleaching fabrics aqueous usually preferably in an automatic washing machine in the conventional fabric washing effective amount of a composition is added to water to form such aqueous wash / bleaching solution is then washed with aqueous thus formed / bleaching solution is preferably contacted with the use of bleaching fabrics washed and stirred at embrace.

有效量的加入到水中形成含水洗涤/漂白溶液的本文液体洗涤剂 An effective amount of water to form a wash is added to the aqueous / liquid detergent bleaching solution described herein

组合物可以包括其量足以在水溶液中形成约500- 7000ppm组合物的量。 The composition may comprise an amount sufficient an amount from about 500 to 7000 ppm of the composition in aqueous solution. 更优选地,在含水洗涤/漂白溶液中提供约800- 3000pp迈的本发明洗涤剂组合物. More preferably, from about 800- 3000pp step provides detergent compositions of the invention in aqueous washing / bleaching solution.

实施例9 用作结构剂的LAS粉末的制备将012直链烷基苯璜酸钠(NaLAS)加工成含有2相的粉末.这2 相之一可溶于本文非水液体洗涤剂組合物中,而另一个相是不溶的. 该不溶部分用来增加结构和增加顆粒悬浮于本文组合物非水相中的能力. Example 9 Preparation of LAS Powder used as a structural example of the agent 012 Sodium linear alkylbenzene Huang (NaLAS) is processed into a powder containing two phases. One of these two phases herein are soluble in nonaqueous liquid detergent compositions and the other phase is insoluble. the insoluble portion is used to increase the structural capacity and the increase in particles are suspended in the nonaqueous phase of the compositions herein.

用NaLAS在水中的浆液(约40- 50%活性物),并结合溶解的破酸钠(3- 15% )和水溶助长剂璜基琥珀酸钠(1- 3% )制备NaLAS 粉末.水溶助长剂和疏酸盐用于改善干粉末的特性.使用转鼓式干燥机将浆液干燥成片状。 NaLAS with the slurry (approximately 40-50% active) in water and dissolved sodium broken binding (3-15%) and hydrotrope sulfonated sodium sulfosuccinate (1-3%) NaLAS powder prepared. Hydrotropes salts and hydrophobic agents for improving the properties of a dry powder using a drum dryer drying the slurry into a sheet. 当NaLAS与疏酸钠一起干燥时,在该片状粉末内形成了2个不同的相,不溶的相形成聚集体小颗粒(0.4-2Mm)的网络结构,其可以使最终的非水洗涤剂产物稳定地悬浮固体. When the sodium sulfate together with sparse NaLAS, in the flake form two distinct phases, phase forms insoluble aggregates of small particles (0.4-2 mm) network structure, which can make the final non-aqueous detergent the product is stably suspended solids.

根据这一实施例制备的NaLAS粉末具有下面表I中所示的组成: Having the composition shown below in Table I NaLAS powder prepared according to this Example of embodiment:

<table>table see original document page 95</column></row> <table> <Table> table see original document page 95 </ column> </ row> <table>

表I (续) Table I (continued)

<table>table see original document page 96</column></row> <table> <Table> table see original document page 96 </ column> </ row> <table>

表II Table II

含有本发明中链支化的表面活性剂的非水基重垢液体洗衣洗涤剜 Washed in non-aqueous heavy duty liquid laundry according to the present invention, branched chain surfactants of enucleation

组合物(AE)表示如下。 Composition (AE) as follows.

含有漂白剂的非水液体洗涤剂 组合物 <table>table see original document page 96</column></row> <table> Non-aqueous liquid detergent compositions containing bleach <table> table see original document page 96 </ column> </ row> <table>

所得的表n组合物是稳定的无水重垢液体洗衣用洗涤剂,当用于普通的织物洗涤操作时,其提供了极好污斑和污垢去除性能。 The resulting compositions are n Table stable anhydrous heavy duty liquid laundry detergents, during ordinary operation for fabric laundering, which provides excellent stain and soil removal performance. 关于手洗餐具液体,下面的实施例进一步说明了本发明. About hand dishwashing liquid, the following examples further illustrate the present invention.

实施例10 Example 10

组分 范围f%wU Composition range f% wU

MB16.5AE10 2.0 0.15-15 MB16.5AE10 2.0 0.15-15

CZJAS 7.0 2-35 CZJAS 7.0 2-35

C23E1S 20.5 5-35 C23E1S 20.5 5-35

椰子烷基氧化胺 2.6 2-5 Coconut alkyl amine oxide 2.6 2-5

甜果碱汀c加nic 704®" on 10 0-2 (混合物) Sweet fruit base statin plus c nic 704® "on 10 0-2 (mix)

5.0 2-10 5.0 2-10

二甲笨磺酸钠 4.0 1-6 1-6 4.0 Sodium xylene and

EtOH 4.0 (V7 EtOH 4.0 (V7

柠檬酸盐 0.06 (MO Citrate 0.06 (MO

MgC12 3.3 CH.O MgC12 3.3 CH.O

CaCl2 2.5 0-4.0 CaCl2 2.5 0-4.0

硫酸铵 0.08 (MO Ammonium sulfate 0.08 (MO

过氧化氢 200 ppm 10-300 ppm Hydrogen peroxide 200 ppm 10-300 ppm

香料 0.18 0>0.5 Perfume 0.18 0> 0.5

Maxatase® 蛋白酶 0.50 0-1.0 0.50 0-1.0 Maxatase® protease

水和次要組分 -余量 Water and minors - balance

••椰子烷基甜菜碱 •• coconut betaine

关于粒状含轔酸盐自动洗餐具洗涤剂,下面实施例进一步说明了本发明, About clattering salt containing particulate automatic dishwashing detergents, following examples further illustrate the present invention,

实施例11 Example 11

活性物的重量% % By weight of the active substance

組分STPP Component STPP

MB16.5AE7 MB16.5AE7

碳酸盐硅酸盐 Silicate Carbonate

表面活性剂(非离子) NaDCC Surfactant (non-ionic) of NaDCC

Bl Bl

vo 1 2 vo 1 2

2 3 twenty three

5 5

、11 12 , 1112

A3 3 2 A3 3 2

9 3 2 932

过硼酸盐TAED TAED perborate

Savinase (Au/g) Savinase (Au / g)

丁ennamyl (Amu/g) D ennamyl (Amu / g)

硫酸盐 Sulfate

21 到100% 21-100%

25 25

到,0 To, 0

香*#欠要组分 Hong * # owe to component

本发明的硬表面清洗组合物还可以含有一种或多种任选的已知用于硬表面清洗组合物中的组分,条件是该任选组分与本文中所述的基本组分是物理和化学相容的,或者换句话说不会不适当地损害产品穗定性、美学性或性能,当其存在时,这样的任选组分的浓度一般在硬表面清洗组合物重量的约0. 001- 30%的范围. Hard surface cleaning compositions of the present invention may further contain one or more optional components known for use in hard surface cleaning compositions, with the proviso that the essential components and optional components described herein is physically and chemically compatible, or in other words do not otherwise unduly impair product qualitative ear, aesthetics or performance, when present, the concentration of such optional components typically by weight of the cleaning composition the hard surface of approximately 0 the range of 001-30% by weight.

任选组分包括:染料、稀释剂、抗微生物剂、抗真菌剂、抗霉菌剂、防霉剂、驱虫剂、抑泡剂、酶、增稠剂、稀释剂、流变学试剂(即改变或稳定组合物流变学性质的试剂)、触变剂、泡沫促进剂、香料、 防腐剂、抗氧化剂和美学性质组分例如香料、着色剂等.列出的任选组分并不是全部的,还可以使用其它的任选组分。 Optional components include: dyes, diluents, antimicrobial agents, antifungal agents, antimycotic agents, preservatives, insect repellents, suds suppressors, enzymes, thickeners, diluents, rheological agents (i.e. or a combination of changing the rheological properties stabilizing agent), thixotropic agents, foam boosters, perfumes, preservatives, antioxidants and aesthetic properties of components such as perfumes, colorants, etc. the optional components listed are not all , also other optional components.

硬表面清洗剂组合物的包装形式 Packing hard surface cleaner composition

本文中的組合物可以包装在本领域技术人员已知的各种合适的洗涤剂包装物中.液体組合物优选包装在常规的洗涤剂塑料瓶中。 The compositions herein may be packaged in the art known to the art a variety of suitable detergent packaging The liquid compositions are preferably packaged in conventional detergent plastic bottles.

在一个实施方案中,可以将本文中的组合物包装在手动操作的喷雾分配容器中,它通常是由合成有机聚合塑料材料制成的.因此本发明也包括包装在喷雾分配器中,优选包装在扳机喷雾分配器或泵喷雾分配器中的本发明液体清洗组合物。 In one embodiment, the compositions herein may be packaged in manually operated spray dispensing containers, which are usually made of synthetic organic polymeric plastic material. Thus, the present invention also includes packaged in a spray dispenser, preferably packaged in the present invention the liquid dispenser trigger spray dispenser or pump spray cleaning composition.

实际上,所迷的喷雾型分配器可以均匀地将适用于本发明的液体清洗組合物施用到相对大面积的要清洗的表面上。 In practice, the fan spray-type dispenser may be uniformly applied to the cleaning liquid of the present invention to a surface cleaning composition is applied to a relatively large area. 这样的喷雾型分配器特别适合于清洗垂直的表面. Such spray-type dispensers are particularly suitable to clean vertical surfaces.

用于本发明中的合适的喷雾型分配器包括例如由Specialty Packaging Products, Inc.或Continental Sprayers, Inc,销售的手动操作的扳机型泡沫分配器.这些类型的分配器公开于例如Dunnining等的US4701311和Focarracci的US4646973及US4538745 中.特别优选用于本文中的是喷雾型分配器,例如从Continental Spray International购得的T 850(^或从北爱尔兰Canyon购得的T 8100R.在这样的喷雾型分配器中,液体组合物被分成细小的液滴结果形成指向要处理表面上的喷雾.实际上,在这样的喷雾型分配器中, 当所述的使用者驱动所述的泵送机构时,使用者把能量传递到泵送机构,含于所述分配器体中的组合物借助该能量通过喷雾型分配器的头.更具体地,在所迷的喷雾型分配器头中,该组合物被强压到一个障碍物例如格槺或國锥体或类似物上,由此形成冲击以有助于使液体组合物雾化,即有助于形成液滴. Used in the present invention Suitable spray-type dispenser comprises Specialty Packaging Products Inc. or Continental Sprayers, Inc, trigger type foam dispenser e.g., manually operated sales of these types of dispensers are disclosed, for example like Dunnining US4701311 and US4646973 and US4538745 in the Focarracci. particularly preferred for use herein are spray-type dispenser, for example, commercially available from Continental spray International T 850 (^ or available from Northern Ireland Canyon T 8100R. in such a spray-type dispenser the liquid composition is divided in fine liquid droplets resulting in a spray point on the surface to be treated. in fact, in such a spray-type dispenser, the user actuates the pumping mechanism when the time, energy transfer to the user the pumping mechanism contained in the body of the dispenser head the composition by means of energy through the spray-type dispenser. more specifically, in a spray-type dispenser head the fans, the composition It is forced against an obstacle, for example, on a national grid or a cone or the like Kang, to thereby form the impact helps to atomise the liquid composition, i.e. to help the formation of liquid droplets.

实施例12 Example 12

通过以下面所列出的比例混合所列的組分制备下面组合物„以纯净形式使用这些组合物以清洗大理石,并以稀释形式使用组合物以清洗刷了油漆的木地板.現察到极好的清洗性和表面安全性. Listed in the following proportions by mixing the components listed below was prepared composition "used in pure form of these compositions to clean marble and dilute composition used to clean the paint brush in the form of wood now to the pole observed good cleaning and surface safety.

A B C D E F G H A B C D E F G H

MB15AE7 3.0 3.0 5.0 3.2 3.2 3_2 S.0 8.0 MB15AE7 3.0 3.0 5.0 3.2 3.2 3_2 S.0 8.0

C23E3 1.0 1.0 1.5 1.3 1.3 1.5 3.0 3.5 C23E3 1.0 1.0 1.5 1.3 1.3 1.5 3.0 3.5

C24E21 2.0 2.0 2.5 1.9 1.9 2.0 5.0 6.0 C24E21 2.0 2.0 2.5 1.9 1.9 2.0 5.0 6.0

NaPS 2,0 1.5 12 1.0 U 3.0 2.5 NaPS 2,0 1.5 12 1.0 U 3.0 2.5

SCS 1.2 3.0 2.2 2.0 2.0 1.5 4.0 5.0 SCS 1.2 3.0 2.2 2.0 2.0 1.5 4.0 5.0

MgS04 (U0 0.9 0.30 0.50 U 2.0 1.0 3.0 MgS04 (U0 0.9 0.30 0.50 U 2.0 1.0 3.0

柠檬酸盐. 0.3 1.0 0.5 0.75 3.0 1.5 6.0 Citrate. 0.75 0.3 1.0 0.5 3.0 1.5 6.0

碳酸氬盐 0.06 0.1 0.1 - 0.2 - - Argon carbonate salt 0.06 0.1 0.1 - 0.2 - -

Na2HP04 - - 0.1 - - - • Na2HP04 - - 0.1 - - - •

02 0.5 02 0.5

Na2H2P207 - - pH 8.0 7.5 7.0 725 8.0 7.4 7.5 7.2 Na2H2P207 - - pH 8.0 7.5 7.0 725 8.0 7.4 7.5 7.2

水和次要 适量至 Secondary and water qs to

組分 100% Component 100%

实施例13 Example 13

通过以下面所列出的比例混合所列的组分制备下面组合物.所以比例均是按总组合物重量计的%. Component is prepared by the compositions listed in the following proportions listed below are mixed, so the ratio are by weight% of the total composition.

在純净或稀释例如50: 1- 200: 1 (水:组合物)的稀释量的条件下使用这些组合物均给清洗过的硬表面提供了极好的第一次和下次清洗性能和良妤的光泽. In neat or diluted, e.g. 50: 1 to 200: 1: hard surfaces using the following amount of dilution conditions (aqueous composition) the compositions were cleaned to provide excellent first time and next time cleaning performance and good yu luster.

組合物(重量% ): Composition (wt%):

非离子表面活性剂 Nonionic surfactant

MB15AE7 C24E5 C23E3 C24E21 MB15AE7 C24E5 C23E3 C24E21

阴离子表面活性剂 Anionic surfactant

NaPS NaPS

LAS LAS

SCS SCS

Isalchem逸AS Isalchem ​​Yat AS

salt

泡沫控制剂 Foam control agents

脂肪酸~ I幼fd 12逸 Immature fd 12 fatty acid ~ I Yi

聚合物 polymer

Je&mine逸£D~2001 Polygiycol AM⑧1100 PVPK60® PEG (2000) Je & mine Yi £ D ~ 2001 Polygiycol AM⑧1100 PVPK60® PEG (2000)

次要組分和水 Minors and water

, 2 2 2 , 222

- 3 1 1* --311 *

w w

V V

5 5

71 • • 71 • •

5 5 55

2 2 twenty two

"9 "9

o o

H4 6 - o H4 6 - o

o 1 o 1

9 2,- 92, -

2 2

r4 oJ r4 oJ

5 6 56

cS cS G? cS cS G?

o o

o o

6 5 3 653

c5 o- cJ c5 o- cJ

3 6 3 363

ooo ooo

vo j 3 vo j 3

5 3 53

4 3 43

4 3 43

3 3 33

6 3 63

3- 3-

7 7

QS o QS o

oo oo

o o

to

4; 4;

2 • 2 •

6 6

o o

5 5

4 4

1 1

*0 * 0

剂盐酸碱 Alkali agent hydrochloride

冲酸^逸 Acid red Yi ^

緩碳柠斧 Huantanningfu

100 100

PVPK6(f是可从ISP Corporation, New York, NY和Montreal, Canada PVPK6 (f, available from ISP Corporation, New York, NY and Montreal, Canada

购得的乙烯基吡咯烷稱均聚物(平均分子量160,000)。 Available vinylpyrrolidine said homopolymer (average molecular weight 160,000).

PEG DME- 200t)8是可从Hoescht购得的二甲基聚乙二醇(Mf 2000). PEG DME- 200t) 8 is commercially available from Hoescht dimethyl polyethylene glycol (Mf 2000).

JeffamineR ED-2001是可从Huntsman购得的封端的聚乙二醇。 JeffamineR ED-2001 is commercially available from Huntsman terminated polyethylene glycol.

PEG ( 2000)是聚乙二醇(MW2000). PEG (2000) is polyethylene glycol (MW2000).

Isofol 12*是2-丁基辛醇. Isofol 12 * is 2-butyl octanol.

IsalchemR AS是可从Eniche边购得的支链醇烷基疏酸盐。 IsalchemR AS are commercially available from a branched alcohol alkyl side Eniche repellent salt.

实施例H Example H

当对油脂污垢稀幹使用时,试验下面组合物的清洗性能。 When using dry lean greasy soil, composition cleaning performance test described below. 通过以所列出的比例混合所列组分制备下面组合物. Mixing the components listed in the following composition was prepared by the listed proportions.

<table>table see original document page 101</column></row> <table><table>table see original document page 102</column></row> <table>实施例16 <Table> table see original document page 101 </ column> </ row> <table> <table> table see original document page 102 </ column> </ row> <table> Example 16

组分 JJJ KKK Component JJJ KKK

3-(N-十二烷JN,N- 二甲基 羟基• 丙烷-1- 2.0 - 3- (N- dodecyl JN, N- dimethyl-1-hydroxy • 2.0 -

确酸盐 Indeed salt

MB16AE7 2.0 2.0 2.0 MB16AE7 2.0 2.0 2.0

•C9_i】E6 2.0 - - • C9_i] E6 2.0 - -

•Cg.10E6 2.0 • Cg.10E6 2.0

椰子酰氨基丙基甜菜械 - 2.0 - Cocamidopropyl mechanical beet - 2.0 -

N-( 椰子syt基亚乙基)-N-( 鞋乙基 )•甘氨酸4 - - 2,0 N- (coconut syt methylethylidene) -N- (shoes ethyl) glycine • 4 - - 2,0

BPP 8.0 8.0 8.0 BPP 8.0 8.0 8.0

柠檬酸 6.0 6.0 6.0 Citric Acid 6.0 6.0 6.0

scs !.6 1.6 】.6 scs! .6 1.6] .6

水,緩冲刑和次类^紐分 适量至100 pH 2.97 2.97 2.97 Water, buffered penalty points, and sub-category New ^ qs 100 pH 2.97 2.97 2.97

Claims (4)

1、一种具有下式的中链二甲基支化的烷基聚氧化烯化合物: 其中, d和e是整数并且d+e是10或11,并且进一步地,其中当d+e=10时,d是2-9的整数并且e是1-8的整数; 当d+e=11时,d是2-10的整数并且e是1-9的整数; EO/PO是烷氧基部分,选自乙氧基、丙氧基和混合的乙氧基/丙氧基基团,其中m在5-15的范围内。 Alkyl polyoxyalkylene compound 1, having the formula in dimethyl branched chain: wherein, d and e are integers and d + e is 10 or 11, and further, wherein when d + e = 10 when, d is an integer of 2-9 and e is an integer from 1 to 8; when d + e = 11 time, d is an integer from 2 to 10 and e is an integer from 1-9; EO / PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy / propoxy groups, wherein m is in the range of 5-15.
2 、权利要求1的中链二甲基支化的烷基聚氧化烯化合物,它选自: 2, 3 - 二甲基十四烷醇乙氧基化物、2, 4 - 二甲基十四烷醇乙氧基化物、 2, 5 - 二甲基十四烷醇乙氧基化物、2, 6 - 二甲基十四烷醇乙氧基化物、 2, 7 - 二甲基十四烷醇乙氧基化物、2, 8 - 二甲基十四烷醇乙氧基化物、 2, 9 - 二甲基十四烷醇乙氧基化物、2, 10 - 二甲基十四烷醇乙氧基化物、2,11-二甲基十四烷醇乙氧基化物、2,12-二甲基十四烷醇乙氧基化物、2,3-二甲基十五烷醇乙氧基化物、2,4-二甲基十五垸醇乙氧基化物、2,5-二甲基十五烷醇乙氧基化物、2,6-二甲基十五烷醇乙氧基化物、2,7-二甲基十五烷醇乙氧基化物、2,8-二甲基十五烷醇乙氧基化物、2,9-二曱基十五烷醇乙氧基化物、2,10-二甲基十五烷醇乙氧基化物、2,11-二甲基十五烷醇乙氧基化物、2,12-二甲基十五烷醇乙氧 2, branched alkyl polyoxyalkylene chain-dimethyl-1 compound of claim 1, which is selected from: 2, 3 - dimethyl tetradecanol ethoxylate, 2, 4 - dimethyl fourteen alkanol ethoxylates, 2, 5 - dimethyl tetradecanol ethoxylate, 2, 6 - dimethyl tetradecanol ethoxylate, 2,7 - dimethyl - tetradecanol ethoxylates, 2, 8 - dimethyl tetradecanol ethoxylate, 2, 9 - dimethyl tetradecanol ethoxylate, 2, 10 - dimethyl tetradecanol ethoxylated based compound, ll-dimethyl tetradecanol ethoxylate, 2,12-dimethyl tetradecanol ethoxylate, 2,3-methyl pentadecanol ethoxylate , 2,4-dimethyl fifteen embankment alcohol ethoxylate, 2,5-dimethyl pentadecanol ethoxylate, 2,6-dimethyl pentadecanol ethoxylate, 2 , 7-methyl pentadecanol ethoxylate, 2,8-methyl pentadecanol ethoxylate, 2,9-Yue-yl pentadecanol ethoxylate, 2,10 - dimethyl pentadecanol ethoxylate, ll-dimethyl pentadecanol ethoxylate, 2,12-dimethyl pentadecanol ethoxylated 化物、2,13-二甲基十五烷醇乙氧基化物,该化合物的平均乙氧基化度为5-15。 Compound, 2,13- dimethyl pentadecanol ethoxylate, average degree of ethoxylation of the compound is 5-15.
3、 一种具有下式的中链二甲基支化的烷基聚氧化烯化合物的混合物: <formula>formula see original document page 3</formula>其中,d和e是整数并且d + e是10或11,并且进一步地,其中当d + e=10时,d是2-9的整数并且e是l-8的整数j 当d + e=ll时,d是2-10的整数并且e是1 - 9的整数i E0/P0是烷氧基部分,选自乙氧基、丙氧基和混合的乙氧基/丙氧基基团,其中ffl在5-15的范围内。 A mixture of alkyl polyoxyalkylene compound 3, having the formula in dimethyl branched chain: <formula> formula see original document page 3 </ formula> where, d and e are integers and d + e is 10 or 11, and further, wherein when when d + e = 10, d is an integer of 2-9 and e is an integer of l-8 j when d + e = ll, d is an integer from 2 to 10 and e 1 - is an integer of i E0 9 / P0 are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy / propoxy groups, wherein ffl in the range of 5-15.
4、权利要求3的中链二甲基支化的烷基聚氧化烯化合物的混合物,所述中链二甲基支化的烷基聚氧化烯化合物选自:2,3-二甲基十四烷醇乙氧基化物、2,4-二甲基十四烷醇乙氧基化物、2,5-二甲基十四烷醇乙氧基化物、2,6-二甲基十四烷醇乙氧基化物、2,7-二甲基十四烷醇乙氧基化物、2,8-二甲基十四烷醇乙氧基化物、2,9-二甲基十四烷醇乙氧基化物、2,10-二甲基十四烷醇乙氧基化物、2,11 - 二甲基十四烷醇乙氧基化物、2, 12 - 二甲基十四烷醇乙氧基化物、 2, 3 - 二甲基十五烷醇乙氧基化物、2, 4 - 二曱基十五烷醇乙氧基化物、 2, 5 - 二甲基十五烷醇乙氧基化物、2, 6 - 二甲基十五烷醇乙氧基化物、 2, 7 - 二甲基十五烷醇乙氧基化物、2, 8 - 二甲基十五烷醇乙氧基化物、 2, 9 - 二甲基十五烷醇乙氧基化物、2, 10 - 二甲基十五烷醇乙氧基化物、2,11-二 Mixture of dimethyl-chain branched alkyl polyoxyalkylene compound 4, as claimed in claim 3, wherein the medium-chain branched alkyl dimethyl polyoxyalkylene compound selected from: 2,3-dimethyl ten tetracosanol ethoxylate, 2,4-methyl tetradecanol ethoxylate, 2,5-methyl tetradecanol ethoxylate, 2,6-dimethyl-tetradecane alcohol ethoxylate, 2,7-methyl tetradecanol ethoxylate, 2,8-methyl tetradecanol ethoxylate, 2,9-methyl tetradecanol b alkoxylates, 2,10-methyl tetradecanol ethoxylate, 2,11 - dimethyl tetradecanol ethoxylate, 2,12 - dimethyl tetradecanol ethoxylate compound, 2, 3 - dimethyl pentadecanol ethoxylate, 2, 4 - yl two Yue pentadecanol ethoxylate, 2, 5 - dimethyl pentadecanol ethoxylate, 2, 6 - dimethyl pentadecanol ethoxylate, 2,7 - dimethyl - pentadecanol ethoxylate, 2, 8 - dimethyl pentadecanol ethoxylate, 2, 9 - dimethyl pentadecanol ethoxylate, 2, 10 - dimethyl pentadecanol ethoxylate, ll- 基十五烷醇乙氧基化物、2,12-二甲基十五烷醇乙氧基化物、2, 13-二甲基十五烷醇乙氧基化物,该化合物的平均乙氧基化度为5-15。 Yl pentadecanol ethoxylate, 2,12-dimethyl pentadecanol ethoxylate, 2, 13-methyl pentadecanol ethoxylate, the compound average ethoxylation 5-15 degrees.
CN 02147508 1996-11-26 1997-11-19 Poly alkene oxide surfactant CN100457880C (en)

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CA2272139A1 (en) 1998-06-04
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CA2272139C (en) 2002-12-17

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