CN1352677A - fabric softening components - Google Patents

Abstract

Translated fromChinese

本发明涉及一种织物软化组分,其包括粘土、絮凝剂、表面活性剂和载体材料。优选所述载体材料为粉末或颗粒助洗剂或碱源。优选所述组分为喷雾干燥颗粒、挤出物或附聚物。优选其包括至少一种硫酸盐和/或磺酸盐表面活性剂、沸石和/或磷酸盐助洗剂和碳酸盐。高度优选所述组分还包括一种增白剂。The present invention relates to a fabric softening component comprising clay, flocculant, surfactant and carrier material. Preferably the carrier material is a powder or granular builder or a source of alkalinity. Preferably the components are spray dried granules, extrudates or agglomerates. Preferably it comprises at least one sulphate and/or sulphonate surfactant, zeolite and/or phosphate builder and carbonate. It is highly preferred that the components also include a whitening agent.

Description

Translated fromChinese

织物软化组分fabric softening components

技术领域technical field

本发明涉及用作织物软化剂的软化组分，其包括粘土和絮凝剂、表面活性剂体系和载体材料。所述组分也可以用于洗涤剂组合物中。The present invention relates to a softening component for use as a fabric softener comprising a clay and a flocculant, a surfactant system and a carrier material. Said components may also be used in detergent compositions.

本发明背景Background of the invention

几年来粘土已被用于各种洗涤剂中从而提供采用所述组合物洗涤的织物软化作用。它们被描述为可以干添加至其它洗涤剂颗粒或者可以与其它成分混合的材料。EP-A-313146描述了将60％-99％粘土和润湿剂的粘土颗粒加入到洗涤剂组合物中。Clays have been used in various detergents for several years to provide fabric softening benefits washed with said compositions. They are described as materials that can be dry added to other detergent granules or mixed with other ingredients. EP-A-313146 describes the incorporation of clay granules of 60% to 99% clay and wetting agents into detergent compositions.

几年来已经知道粘土絮凝剂可以改善粘土向织物上传递。EP-A-313146也描述了含有粘土颗粒的洗涤剂优选包括一种粘土絮凝剂。Clay flocculants have been known for several years to improve the transfer of clay to fabrics. EP-A-313146 also describes that clay particle-containing detergents preferably include a clay flocculant.

本发明人现已发现当粘土和絮凝剂相互之间以紧密混合物的形式存在时，可以提高粘土的沉积效率。它不仅提高了粘土的沉积效率，还可以较低水平的粘土达到传递相同的软化性能。The present inventors have now found that the clay deposition efficiency can be increased when the clay and flocculant are present in an intimate mixture with each other. Not only does it increase the clay deposition efficiency, it also delivers the same softening properties at lower levels of clay.

在通过使用紧密混合物改善粘土的沉积的同时，还发现在洗涤中有效分配絮凝剂也是重要的。本发明人已经发现通过粘土和絮凝剂的混合物与表面活性剂进行混合可以实现这一点。但是，还发现当粉末状或颗粒状载体与粘土、絮凝剂和表面活性剂混合时，所述传递得到进一步提高。此外，使用表面活性剂改善了粘土和絮凝剂的混合，同时使用所述载体材料可以形成非粘性和易手洗(handable)的混合物，其可以容易加工成其所需形式。还发现这种形式的混合物具有更好的贮存稳定性，这一点是有益的，因为所述混合物可以随后进行贮存直至最后的使用，并且它不必马上作进一步处理。While the deposition of clay is improved through the use of intimate mixtures, it has also been found important to effectively distribute the flocculant in the wash. The present inventors have found that this can be achieved by mixing a mixture of clay and flocculant with a surfactant. However, it has also been found that the transfer is further enhanced when the powdered or granular carrier is mixed with clay, flocculants and surfactants. Furthermore, the use of surfactants improves the mixing of the clay and flocculant, while the use of the carrier material allows for the formation of a non-sticky and handable mixture which can be easily processed into its desired form. It has also been found that the mixture in this form has better storage stability, which is advantageous since the mixture can then be stored until final use and it does not have to be further processed immediately.

高度优选所述载体材料包括碱源和/或助洗剂，因为这样可以获得多功能的软化组分。这种组分可以用于数种应用中，包括用作洗涤剂组合物的组分、织物软化剂组合物的组分或自身用作洗涤和软化组分，尤其用于手洗或小负荷洗涤或者非重垢负荷的洗涤。It is highly preferred that the carrier material includes a source of alkalinity and/or builders, as this results in a multifunctional softening component. This component can be used in several applications, including as a component of detergent compositions, as a component of fabric softener compositions or as a washing and softening component itself, especially for hand washing or light load washing or Washing for non-heavy duty loads.

本发明综述Summary of the invention

本发明涉及一种固体织物软化组分，其包括：The present invention relates to a solid fabric softening component comprising:

a)粘土；a) clay;

b)至少5％的表面活性剂体系；b) a surfactant system of at least 5%;

c)至少15％(重量)的固体载体材料；c) at least 15% by weight of solid carrier material;

d)絮凝剂。d) flocculants.

所述组分优选为喷雾干燥颗粒、附聚体或挤出物。但是所述组分也可以加工成片状形式或块状形式。可以采用这些形式的任一种来处理织物，或者它可以用作洗涤剂组合物或织物软化剂组合物的一个部分。所述组分可以用于自动洗涤和手洗(还包括预处理或浸泡)或者后处理如织物的调理。软化组分The components are preferably spray-dried granules, agglomerates or extrudates. However, the components can also be processed in tablet form or in block form. Either of these forms can be used to treat fabrics, or it can be used as part of a detergent composition or fabric softener composition. The components can be used in automatic and hand washes (also including pre-treatment or soaking) or in post-treatments such as conditioning of fabrics. softening component

本发明组分包括至少一种粘土、一种絮凝剂、一种表面活性剂和一种固体载体材料。The components of the invention include at least one clay, a flocculant, a surfactant and a solid carrier material.

在所述组分中的表面活性剂的总水平优选为所述组分重量的5-90％，更优选10-70％或甚至60％，更优选15％-60％或甚至50％。The total level of surfactant in the component is preferably 5-90%, more preferably 10-70% or even 60%, more preferably 15-60% or even 50% by weight of the component.

优选所述表面活性剂含有至少一种阴离子硫酸盐表面活性剂或阴离子磺酸盐表面活性剂。此后将对优选的磺酸盐和硫酸盐表面活性剂进行描述。Preferably the surfactant comprises at least one anionic sulfate surfactant or anionic sulfonate surfactant. Preferred sulfonate and sulfate surfactants are described hereafter.

优选所述磺酸盐或硫酸盐表面活性剂或其混合物的存在水平为所述组分重量的5-60％，更优选为所述组分重量的10-60％或者甚至15-50％。Preferably the sulphonate or sulfate surfactant or mixtures thereof are present at a level of 5-60% by weight of the components, more preferably 10-60% or even 15-50% by weight of the components.

可以优选所述组分含有非离子表面活性剂或其混合物，可作为所述组分中唯一一种表面活性剂或但也可与其它表面活性剂组合。优选非离子表面活性剂的存在水平为所述组分重量的2-60％，更优选为所述组分重量的5-50％或者甚至10％-45％。It may be preferred that the component contains a nonionic surfactant or a mixture thereof, either as the only surfactant in the component or but also in combination with other surfactants. Preferably the nonionic surfactant is present at a level of 2-60% by weight of the components, more preferably 5-50% or even 10%-45% by weight of the components.

优选所述载体材料为颗粒或粉末形式。优选所述载体材料为碱源和/或助洗剂。优选的碱源为无机碳酸盐。优选的助洗剂(通常也是碱)为硅铝酸盐、结晶硅酸盐、无定形硅酸盐、结晶层状硅酸盐、磷酸盐、羧酸或其盐。但是还可以使用其它无机盐如硫酸盐。优选的上述类型盐为钠盐。可以优选至少一种钾盐以与粘土紧密混合物的形式存在。Preferably the carrier material is in granular or powder form. Preferably the carrier material is a source of alkalinity and/or a builder. Preferred sources of alkalinity are inorganic carbonates. Preferred builders (usually also bases) are aluminosilicates, crystalline silicates, amorphous silicates, crystalline layered silicates, phosphates, carboxylic acids or salts thereof. However, other inorganic salts such as sulfates can also be used. A preferred salt of the above type is the sodium salt. It may be preferred that at least one potassium salt is present in intimate admixture with the clay.

优选所述载体材料的存在水平为20-95％(重量)，更优选25％至90％(重量)或者甚至到80％(重量)，甚至更优选30-70％(重量)。Preferably the carrier material is present at a level of 20-95% by weight, more preferably 25% to 90% by weight or even up to 80% by weight, even more preferably 30-70% by weight.

因此可以优选所述无机碳酸盐的存在水平为所述组分重量的至少10％或者甚至15％，优选最高水平为60％或者甚至50％或者甚至40％。It may thus be preferred that the inorganic carbonate is present at a level of at least 10% or even 15% by weight of the component, preferably at a maximum level of 60% or even 50% or even 40%.

此处高度优选存在至少一种磷酸盐或硅铝酸盐助洗剂。因此可以优选所述助洗剂(优选磷酸盐和/或硅铝酸盐助洗剂)的存在水平为所述组分重量的至少10％或者甚至15％，优选最高水平为60％或者甚至50％或者甚至40％。It is highly preferred herein that at least one phosphate or aluminosilicate builder is present. It may thus be preferred that the builder (preferably phosphate and/or aluminosilicate builder) is present at a level of at least 10% or even 15% by weight of the components, preferably at a maximum level of 60% or even 50%. % or even 40%.

由于硅酸盐适用并且甚至优选用于此处，除了至少一种其它助洗剂或碱源外也优选使用硅酸盐。Since silicates are suitable and even preferred for use herein, it is preferred to use silicates in addition to at least one other builder or source of alkalinity.

优选所述粘土的存在水平为所述组分重量的至少1％，更优选其水平为2-60％，更优选为5-40％或者甚至5-30％或者甚至7-25％。Preferably the clay is present at a level of at least 1% by weight of the component, more preferably at a level of 2-60%, more preferably 5-40% or even 5-30% or even 7-25%.

通过混合粘土、絮凝剂、载体材料和表面活性剂制备所述组分。因此这些材料相互之间紧密混合。这可以通过本领域已知的任何混合法或造粒法来进行。但是混合的次序可能显著影响所述组分的最后性能。优选混合方法如下：The components are prepared by mixing clay, flocculant, carrier material and surfactant. These materials are therefore intimately mixed with each other. This can be done by any mixing or granulation method known in the art. But the order of mixing can significantly affect the final properties of the components. The preferred mixing method is as follows:

-在一个实施方案中，粘土和絮凝剂是相互之间的紧密混合物(通过混合粘土和絮凝剂获得)，将其随后分散至表面活性剂体系、载体材料或表面活性剂和载体材料的紧密混合物或与上述物质一起进行分散。- In one embodiment, the clay and flocculant are an intimate mixture with each other (obtained by mixing clay and flocculant), which is subsequently dispersed into a surfactant system, carrier material or intimate mixture of surfactant and carrier material Or disperse together with the above substances.

-在另一个高度优选的实施方案中，首先紧密混合絮凝剂和表面活性剂体系或其部分，或者载体材料或其部分，但优选表面活性剂体系和载体材料或其部分，随后将该混合物与粘土混合或分散。任选随后将剩余的载体材料和/或表面活性剂与得到的混合物进行混合。- in another highly preferred embodiment, first the flocculant and the surfactant system or part thereof, or the carrier material or part thereof, but preferably the surfactant system and the carrier material or part thereof, are intimately mixed, and the mixture is subsequently mixed with Clay mixed or dispersed. The remainder of the carrier material and/or surfactant is optionally subsequently mixed with the resulting mixture.

-在另一个优选实施方案中，首先将粘土与载体材料或其部分进行均质混合，此后将该混合物与絮凝剂和表面活性剂和任选的剩余的载体材料进行分散或混合。任选表面活性剂的一部分可以在第一步骤中与粘土和载体材料或其部分进行混合。- In another preferred embodiment, the clay is first homogeneously mixed with the carrier material or parts thereof, after which the mixture is dispersed or mixed with the flocculant and the surfactant and optionally the remainder of the carrier material. Optionally a part of the surfactant may be mixed with the clay and carrier material or parts thereof in a first step.

优选粘土与絮凝剂聚合物的重量比为1000∶1-1∶1，更优选为500∶1-1∶1，最优选为300∶1-1∶1，或者甚至更优选为80∶1-10∶1，或者在某些应用中甚至为60∶1-20∶1。Preferably the weight ratio of clay to flocculant polymer is from 1000:1 to 1:1, more preferably from 500:1 to 1:1, most preferably from 300:1 to 1:1, or even more preferably from 80:1 to 10:1, or even 60:1-20:1 in some applications.

优选粘土与载体材料的重量比为1∶30-5∶1，更优选1∶20-3∶1，甚至更优选为1∶15-1∶1或者甚至为1∶10-1∶2。优选表面活性剂与粘土的重量比为1∶30-10∶1，更优选为1∶15-5∶1，甚至更优选为1∶10-3∶1或者甚至为1∶5-1∶1。Preferably the weight ratio of clay to support material is from 1:30 to 5:1, more preferably from 1:20 to 3:1, even more preferably from 1:15 to 1:1 or even from 1:10 to 1:2. Preferably the weight ratio of surfactant to clay is from 1:30 to 10:1, more preferably from 1:15 to 5:1, even more preferably from 1:10 to 3:1 or even from 1:5 to 1:1 .

高度优选存在增白剂，不仅提供织物亮度和白度，还提高所述组分的外观。优选所述增白剂的存在水平为所述组分重量的至少0.05％，更优选至少0.1％或者甚至0.15％或者甚至0.2％。The presence of brighteners is highly preferred not only to provide fabric brightness and whiteness but also to enhance the appearance of the components. Preferably the brightener is present at a level of at least 0.05%, more preferably at least 0.1% or even 0.15% or even 0.2% by weight of the component.

所述组分还可包括游离水分，优选不大于所述组分重量的30％，更优选为所述组分重量的0.5-20％或者甚至1％至15％或者甚至至少5％。但是可以优选存在对水敏感的成分如泡腾系统、酶、漂白剂、香料，在这种情况下可以优选游离水的水平小于上述水平，如低于所述组分重量的12％，更优选低于6％或者甚至5％，最优选低于4％或甚至3％。The components may also include free moisture, preferably no more than 30% by weight of the components, more preferably 0.5-20% or even 1% to 15% or even at least 5% by weight of the components. However, it may be preferred that water sensitive ingredients are present such as effervescent systems, enzymes, bleaches, fragrances, in which case it may be preferred that the level of free water is less than the above levels, such as less than 12% by weight of the components, more preferably Below 6% or even 5%, most preferably below 4% or even 3%.

在一个优选实施方案中，所述组分包括有机酸或无机酸(尤其当存在碳酸盐时)从而与碳酸盐一起提供泡腾作用。优选的酸包括柠檬酸、酒石酸、乳酸、马来酸、苹果酸、戊二酸、己二酸、乙酸和氨基酸。In a preferred embodiment, the components include organic or inorganic acids (especially when carbonates are present) to provide effervescence together with the carbonates. Preferred acids include citric, tartaric, lactic, maleic, malic, glutaric, adipic, acetic and amino acids.

所述组分也可以包括其它织物护理剂如去污聚合物、纤维素聚合物、染料迁移抑制剂、阳离子软化剂或其混合物。也可以存在香料组分(高度优选)以及酶或螯合剂。The component may also include other fabric care agents such as soil release polymers, cellulosic polymers, dye transfer inhibiting agents, cationic softeners or mixtures thereof. Perfume components (highly preferred) as well as enzymes or chelating agents may also be present.

优选所述组分为喷雾干燥颗粒或附聚颗粒，或者为挤出物或薄片或者它可以加工成片状形式或块状形式。这些颗粒可以通过已知的造粒、喷雾干燥、附聚、挤出或压片法来制备，所述方法涉及均质混合各种成分，任选加入水或其它溶剂和任选干燥。粘土Preferably the components are spray dried or agglomerated granules, or are extrudates or flakes or it can be processed into sheet form or block form. These granules can be prepared by known granulation, spray-drying, agglomeration, extrusion or tabletting processes involving homogeneous mixing of the ingredients, optionally adding water or other solvents and optionally drying. clay

此处粘土可以为能够提供织物软化作用的任何粘土。为了清楚起见，需要注意的是此处所用术语粘土不包括硅铝酸钠沸石助洗剂化合物，但是该沸石助洗剂可以包括在本发明的组分中作为载体材料或其部分。The clay here can be any clay that is capable of providing fabric softening. For the sake of clarity, it is to be noted that the term clay as used herein does not include sodium aluminosilicate zeolite builder compounds, however such zeolite builders may be included in the compositions of the present invention as carrier material or part thereof.

可以优选所述组分包括一种粘土的混合物。It may be preferred that the components comprise a mixture of clays.

一种优选的粘土可以为膨润土。高度优选绿土型粘土，其例子公开于美国专利号3862058、3948790、3954632和4062647以及欧洲专利号EP-A-299575和EP-A-313146(均来自Procter and GambleCompany)。A preferred clay may be bentonite. Highly preferred are smectite-type clays, examples of which are disclosed in U.S. Patent Nos. 3,862,058, 3,948,790, 3,954,632, and 4,062,647 and European Patent Nos. EP-A-299575 and EP-A-313146 (both from the Procter and Gamble Company).

此处术语绿土型粘土包括氧化铝存在于硅酸盐晶格中的粘土和氧化镁存在于硅酸盐晶格中的粘土。典型的绿土型粘土化合物包括通式为Al₂(Si₂O₅)₂(OH)₂.nH₂O的化合物以及通式为Mg₃(Si₂O₅)₂(OH)₂.nH₂O的化合物。绿土型粘土倾向于采用可膨胀的三层型结构。The term smectite-type clay here includes clays in which alumina is present in a silicate lattice and clays in which magnesium oxide is present in a silicate lattice. Typical smectite-type clay compounds include compounds with the general formula Al₂ (Si₂ O₅ )₂ (OH)₂ .nH₂ O and compounds with the general formula Mg₃ (Si₂ O₅ )₂ (OH)₂ .nH₂ O compounds. Smectite-type clays tend to adopt an expandable three-layer structure.

合适的绿土型粘土的具体例子包括选自蒙脱石、锂蒙脱石、铬蒙脱石、绿脱石、皂石和锌蒙脱石，特别是在晶体点阵结构中具有碱金属或碱土金属离子的那些粘土。尤其优选钠蒙脱石或钙蒙脱石。Specific examples of suitable smectite-type clays include clays selected from the group consisting of montmorillonite, hectorite, montmorillonite, nontronite, saponite, and sauconite, especially those having an alkali metal or alkaline earth Those clays with metal ions. Sodium montmorillonite or calcium montmorillonite is especially preferred.

合适的绿土型粘土，尤其蒙脱土由不同供应商提供，这些供应商包括English China Clays、Laviosa、Georgia Kaolin和Colin StewartMinerals。Suitable smectite-type clays, especially montmorillonite, are available from various suppliers including English China Clays, Laviosa, Georgia Kaolin and Colin Stewart Minerals.

优选此处所用粘土的最大粒径为0.01微米至800微米，更优选为1毫米至400毫米，最优选为5毫米至200毫米。Preferably the clay used herein has a maximum particle size of 0.01 micron to 800 micron, more preferably 1 mm to 400 mm, most preferably 5 mm to 200 mm.

粘土无机化合物的颗粒可以包括在含有其它洗涤剂化合物的附聚颗粒中作为其组分。当存在这些组分时，术语粘土无机化合物的“最大颗粒尺寸”是指粘土无机化合物而不是指作为一个整体的附聚颗粒的最大尺寸。Particles of clay inorganic compounds may be included as components in agglomerated granules containing other detergent compounds. When these components are present, the term "maximum particle size" of the clay inorganic compound refers to the largest dimension of the clay inorganic compound and not the agglomerated particles as a whole.

通常可以在绿土型粘土的晶体点阵结构中进行小阳离子如质子、钠离子、钾离子、镁离子和钙离子的取代以及包括带正电官能团的某些有机分子的取代。可以选择对一种阳离子具有优先吸收能力的粘土，这种能力通过测量相对离子交换容量来进行评定。此处适用的绿土型粘土通常具有至少50meq/100g的阳离子交换容量。美国专利号3954632描述了一种测量阳离子交换容量的方法。Substitution of small cations such as protons, sodium ions, potassium ions, magnesium ions and calcium ions as well as substitution of certain organic molecules including positively charged functional groups can generally be performed in the crystal lattice structure of smectite-type clays. Clays can be selected for their preferential absorption capacity for one cation as assessed by measuring relative ion exchange capacity. Smectite-type clays suitable for use herein generally have a cation exchange capacity of at least 50 meq/100 g. US Patent No. 3954632 describes a method for measuring cation exchange capacity.

粘土无机化合物的晶体点阵结构可以具有其中取代的阳离子织物软化剂(优选例子)。这种取代的粘土称为“疏水活性”粘土。通常阳离子织物软化剂的存在重量比(以阳离子织物软化剂对粘土)为1∶200至1∶10，优选1∶100至1∶20。合适的阳离子织物软化剂包括公开于GB-A-1154276和EP-B-0011340的水不溶性的叔胺或二长链酰胺材料。The crystal lattice structure of the clay inorganic compound may have cationic fabric softeners (preferred examples) substituted therein. Such substituted clays are known as "hydrophobically activated" clays. Typically the cationic fabric softener is present in a weight ratio (as cationic fabric softener to clay) of from 1:200 to 1:10, preferably from 1:100 to 1:20. Suitable cationic fabric softeners include the water insoluble tertiary amine or dilong chain amide materials disclosed in GB-A-1154276 and EP-B-0011340.

优选的“疏水活性粘土”商品为含有约40％(重量)的二甲基二牛油基季铵盐的膨润土，其由English China Clays International以Claytone EM的商品名出售。A preferred commercial "hydrophobic activated clay" is bentonite clay containing about 40% by weight of dimethyl ditallowyl quaternary ammonium salt, sold under the tradename Claytone EM by English China Clays International.

此处也可以使用亲有机物质的粘土。它们为疏水改性的粘土，其具有通过本领域已知的离子交换法置换无机金属离子的有机离子。这类粘土易与有机溶剂混合并且在层间吸收有机溶剂。适用于本发明的亲有机物质的粘土的合适的例子为来自Rheox of Highstown，N.j.的Bentone SD-1、SD-2和SD-3。Organophilic clays can also be used here. They are hydrophobically modified clays that have organic ions that have replaced inorganic metal ions by ion exchange methods known in the art. Such clays are readily miscible with organic solvents and absorb organic solvents between layers. Suitable examples of organophilic clays suitable for use in the present invention are Bentone SD-1, SD-2 and SD-3 from Rheox of Highstown, N.j.

可以任选所述粘土与蜡和结构剂以及还任选絮凝聚合物一起存在于一种混合物中。絮凝剂The clay may optionally be present in a mixture with waxes and structurants and optionally also flocculating polymers. flocculant

本发明的所述组分可以含有一种粘土絮凝剂，优选其存在水平为所述组分重量的0.005-10％，更优选0.05-5％，最优选0.1-2％。The components of the present invention may contain a clay flocculant, preferably present at a level of 0.005-10%, more preferably 0.05-5%, most preferably 0.1-2% by weight of the component.

粘土絮凝剂的功能是在洗涤溶液中将粘土化合物颗粒结合到一起并因此有助于它们沉积于洗涤的织物表面。因此这种功能要求不同于通常加入衣物洗涤组合物有助于从织物去除粘土污垢并可使它们分散在洗涤溶液中的粘土分散化合物。The function of clay flocculants is to bind clay compound particles together in the wash solution and thus facilitate their deposition on the surface of washed fabrics. This functional requirement therefore differs from clay dispersing compounds which are typically added to laundry detergent compositions to aid in the removal of clay soils from fabrics and allow them to disperse in the wash solution.

此处优选的粘土絮凝剂为有机聚合物材料，其分子量为100,000-10,000,000，优选150,000-5,000,000，更优选200,000-2,000,000。Preferred clay flocculants herein are organic polymeric materials having a molecular weight of 100,000-10,000,000, preferably 150,000-5,000,000, more preferably 200,000-2,000,000.

合适的有机聚合物材料包括一些均聚物或共聚物，其含有选自烯化氧(尤其环氧乙烷)、丙烯酰胺、丙烯酸、乙烯醇、乙烯吡咯烷酮以及乙烯亚胺的单体单元。尤其优选环氧乙烷、丙烯酰胺和丙烯酸的均聚物。Suitable organic polymeric materials include homopolymers or copolymers containing monomer units selected from the group consisting of alkylene oxides (especially ethylene oxide), acrylamide, acrylic acid, vinyl alcohol, vinylpyrrolidone, and ethyleneimine. Homopolymers of ethylene oxide, acrylamide and acrylic acid are especially preferred.

Procter and Gamble Company的欧洲专利号EP-A-299,575和EP-A-313,146描述了优选的用于此处的有机聚合粘土絮凝剂。European Patent Nos. EP-A-299,575 and EP-A-313,146 to the Procter and Gamble Company describe preferred organopolymeric clay flocculants for use herein.

无机粘土絮凝剂也适用于此，典型例子包括石灰和明矾。碳酸盐Inorganic clay flocculants are also suitable here, typical examples include lime and alum. carbonate

此处适合的碱金属和/或碱土金属无机碳酸盐包括钾、锂、钠等的碳酸盐和碳酸氢盐和过碳酸盐，其中优选碳酸钠和碳酸钾。适用于此的碳酸氢盐包括碳酸氢盐的任何碱金属盐如锂、钠和钾盐，其中优选碳酸氢钠和碳酸氢钾。但是，根据所述干燥泡腾颗粒溶于其中的水介质的所需pH值，可以选择干燥泡腾颗粒中的碳酸盐或碳酸氢盐或其混合物，其中。例如当需要较高pH的水介质时(如高于pH9.5)，可以优选单独使用碳酸盐或组合使用碳酸盐和碳酸氢盐(其中碳酸盐的水平高于碳酸氢盐的水平)。优选本发明组分的无机碱金属和/或碱土金属盐包括碳酸盐和/或碳酸氢盐的钾盐或更优选的钠盐。优选碳酸盐包括碳酸钠，任选还包括碳酸氢钠。Suitable alkali metal and/or alkaline earth metal inorganic carbonates herein include carbonates and bicarbonates and percarbonates of potassium, lithium, sodium, etc., of which sodium carbonate and potassium carbonate are preferred. Bicarbonates suitable for use herein include any alkali metal salts of bicarbonate such as lithium, sodium and potassium, with sodium and potassium bicarbonates being preferred. However, the carbonate or bicarbonate salts or mixtures thereof in the dry effervescent granule can be selected according to the desired pH value of the aqueous medium in which the dry effervescent granule is dissolved. For example, when a higher pH aqueous medium is required (such as above pH 9.5), it may be preferable to use carbonate alone or in combination with carbonate and bicarbonate (wherein the level of carbonate is higher than the level of bicarbonate) ). Preferred inorganic alkali metal and/or alkaline earth metal salts of the components of the invention include potassium or more preferably sodium salts of carbonates and/or bicarbonates. Preferred carbonates include sodium carbonate, optionally also sodium bicarbonate.

在本发明的一个实施方案中，存在一种泡腾源，优选其包括有机酸(如羧酸或氨基酸)和碳酸盐。然后可以优选此处碳酸盐的部分或全部与有机酸进行预混合，并由此以独立的颗粒组分存在。In one embodiment of the invention there is an effervescent source, preferably comprising an organic acid (such as a carboxylic acid or amino acid) and a carbonate. It may then be preferred here that part or all of the carbonate is premixed with the organic acid and thus present as a separate particle component.

所述碳酸盐可以具有任何颗粒尺寸。在一个实施方案中，尤其当碳酸盐存在于颗粒中时或者不是作为单独加入的化合物时，优选所述碳酸盐的体积中值粒径为5-375微米，由此优选至少60％，优选至少70％(体积)或者甚至至少80％或者甚至至少90％的粒径为1-425微米。更优选二氧化碳源的体积中值粒径为10-250，由此优选至少60％，或甚至至少70％或者甚至至少80％或者甚至至少90％(体积)的粒径为1-375微米；或者甚至优选体积中值粒径为10-200微米，由此优选至少60％，优选至少70％或者甚至至少80％或者甚至至少90％(体积)的粒径为1-250微米。助洗剂材料The carbonates can be of any particle size. In one embodiment, especially when the carbonate is present in the granules or not as a separately added compound, it is preferred that the carbonate has a volume median particle size of 5-375 microns, whereby at least 60% is preferred, Preferably at least 70% by volume or even at least 80% or even at least 90% have a particle size of 1-425 microns. More preferably the carbon dioxide source has a volume median particle size of 10-250, whereby preferably at least 60%, or even at least 70% or even at least 80% or even at least 90% by volume, has a particle size of 1-375 microns; or Even preferred is a volume median particle size of 10-200 microns, whereby preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume of particles have a particle size of 1-250 microns. builder material

优选的助洗剂材料为硅铝酸盐材料如沸石和/或磷酸盐。Preferred builder materials are aluminosilicate materials such as zeolites and/or phosphates.

水溶性磷酸盐助洗剂的合适例子为碱金属的三聚磷酸盐、焦磷酸的钠盐、钾盐和铵盐、正磷酸盐的钠盐和钾盐、聚偏磷酸/磷酸的钠盐(其中聚合度范围为约6-21)以及植酸的盐。最优选磷酸盐助洗剂材料包括焦磷酸四钠或者更优选无水三聚磷酸钠。Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymetaphosphoric acid/phosphoric acid ( wherein the degree of polymerization ranges from about 6-21) and salts of phytic acid. Most preferably the phosphate builder material comprises tetrasodium pyrophosphate or more preferably anhydrous sodium tripolyphosphate.

合适的硅铝酸盐沸石的单胞式为Na_z[(AlO₂)_z(SiO₂)_y].xH₂O，其中z和y为至少6；z与y的摩尔比为1.0-0.5，并且x为至少5，优选7.5-276，最优选10-264。硅铝酸盐材料为水合形式，优选为晶体，其含有10-28％，更优选18-22％的结合水。A suitable aluminosilicate zeolite has the unit cell formula Na_z [(AlO₂ )_z (SiO₂ )_y ].xH₂ O, where z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5, And x is at least 5, preferably 7.5-276, most preferably 10-264. The aluminosilicate material is in a hydrated form, preferably crystalline, containing 10-28%, more preferably 18-22%, bound water.

所述硅铝酸盐沸石可以为天然存在材料，但优选为合成材料。合成的结晶硅铝酸盐离子交换材料的商品为Zeolite A、Zeolite B、Zeolite P、Zeolite X、Zeolite HS及其混合物。Zeolite A具有下式：The aluminosilicate zeolites may be naturally occurring materials, but are preferably synthetic materials. Commercially available synthetic crystalline aluminosilicate ion exchange materials are Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the following formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂ONa₁₂ [(AlO₂ )₁₂ (SiO₂ )₁₂ ].xH₂ O

式中x为20-30，尤其为27。ZeoliteX具有式Na₈₆[(AlO₂)₈₆(SiO₂)₁₀₆].276H₂O。In the formula, x is 20-30, especially 27. ZeoliteX has the formula Na₈₆ [(AlO₂ )₈₆ (SiO₂ )₁₀₆ ].276H₂ O.

另一种优选的硅铝酸盐沸石为沸石MAP助洗剂。沸石MAP描述于EP384070-A。它被定义为硅铝比不大于1.33，优选在0.9-1.33范围更优选在0.9-1.2范围内的沸石P型的碱金属硅铝酸盐。Another preferred aluminosilicate zeolite is zeolite MAP builder. Zeolite MAP is described in EP384070-A. It is defined as an alkali metal aluminosilicate of the zeolite P type with a silicon to aluminum ratio not greater than 1.33, preferably in the range 0.9-1.33 and more preferably in the range 0.9-1.2.

尤其重要的为沸石MAP，其硅铝比不大于1.15，更优选不大于1.07。Of particular importance is zeolite MAP having a silicon to aluminum ratio not greater than 1.15, more preferably not greater than 1.07.

在一个优选方面，沸石MAP助洗剂的粒径(以d₅₀表示)为1.0-10.0微米，更优选2.0-7.0微米，最优选2.5-5.0微米。In a preferred aspect, the zeolite MAP builder has a particle size (expressed as_d50 ) of 1.0-10.0 microns, more preferably 2.0-7.0 microns, most preferably 2.5-5.0 microns.

d₅₀值表示50％(重量)的颗粒的粒径小于该值。所述粒径可以，尤其通过常规分析技术如采用扫描电子显微镜或通过激光粒径仪的显微测量进行测定。确定d₅₀值的其它方法公开于EP384070A。The d₅₀ value indicates that 50% by weight of the particles have a particle size smaller than this value. The particle size can be determined, inter alia, by conventional analytical techniques such as microscopic measurement with a scanning electron microscope or by a laser particle sizer. Other methods of determining_d50 values are disclosed in EP384070A.

还优选可以为结晶层型硅酸盐材料如SKS-6(由Clariant出售)以及还有无定形硅酸盐，优选1.6或2比的硅酸钠。它可以为低密度如低于40克/升的粉末材料或以通过辊压获得的致密材料(如密度大于400克/升)。它也可以相互之间的混合物，或者与其它助洗剂材料或无机盐的混合物的形式存在。Also preferred may be crystalline layer silicate materials such as SKS-6 (sold by Clariant) and also amorphous silicates, preferably 1.6 or 2 ratio sodium silicate. It may be a powder material of low density, eg below 40 g/l, or a dense material (eg density greater than 400 g/l) obtained by rolling. It may also be present in admixture with each other or with other builder materials or inorganic salts.

所述组分也优选包括水溶性单体型多元羧酸盐或它们的酸型、均聚或共聚的多元羧酸或它们的盐(其中多元羧酸盐包括相互之间被不多于2个碳原子隔开的至少两个羧基)、硼酸盐及前述物质的混合物。Said components also preferably comprise water-soluble monomeric polycarboxylates or their acid forms, homopolymeric or copolymeric polycarboxylic acids or their salts (wherein the polycarboxylates comprise no more than 2 At least two carboxyl groups separated by carbon atoms), borates and mixtures of the foregoing.

羧酸盐或多元羧酸盐助洗剂可以为单体或低聚型，但是由于价格和性能的原因，通常优选单体多元羧酸盐。Carboxylate or polycarboxylate builders can be monomeric or oligomeric, but monomeric polycarboxylates are generally preferred for reasons of price and performance.

含有一个羧基的适合的羧酸盐包括乳酸、羟基乙酸及其醚衍生物的水溶性盐。含有两个羧基的多元羧酸盐包括丁二酸、丙二酸、(乙烯二氧)二乙酸、马来酸、二甘醇酸、酒石酸、丙醇二酸和富马酸的水溶性盐以及醚羧酸盐和亚磺酰基羧酸盐。含有三个羧基的多元羧酸盐或它们的酸尤其包括水溶性柠檬酸盐、乌头酸盐和柠康酸盐以及丁二酸衍生物如英国专利号1,379,241中所述的羧甲基氧丁二酸盐、英国专利号1,389,732中所述的lactoxy丁二酸盐以及荷兰专利申请7205873中所述的氨基丁二酸和氧聚碳酸盐材料如描述于英国专利号1,387,447中所述的2-氧杂-1，1，3-丙烷三酸盐。最优选的含有三个羧基的多元羧酸为柠檬酸，优选其存在水平为所述组合物重量的0.1-15％，更优选0.5-8％。Suitable carboxylates containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylene dioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, and fumaric acid, and Ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxy groups or their acids include especially the water-soluble citrates, aconitates and citraconic acid derivatives and succinic acid derivatives such as carboxymethyloxybutane as described in British Patent No. 1,379,241 Dibasic acid salts, lactoxysuccinates described in British Patent No. 1,389,732 and aminosuccinic acid and oxygen polycarbonate materials described in Dutch Patent Application 7205873 as described in British Patent No. 1,387,447 2- Oxa-1,1,3-propane trisalt. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of 0.1-15%, more preferably 0.5-8% by weight of the composition.

含有四个羧基的多元羧酸盐包括公开于英国专利号1,261,829中的氧二丁酸盐，1，1，2，2-乙烷四酸盐、1，1，3，3-丙烷四酸盐和1，1，2，3-丙烷四酸盐。含有磺基取代基的多元羧酸盐包括公开于英国专利号1,398,421和1,398,422和美国专利号3,936,448中的磺化丁二酸衍生物以及描述于英国专利号1,439,000中的磺化热解柠檬酸盐。优选的多元羧酸盐为每个分子含有高达三个羧基的羟基羧酸盐，更优选柠檬酸盐。Polycarboxylates containing four carboxyl groups include oxydibutyrate, 1,1,2,2-ethane tetra-acid, 1,1,3,3-propane tetra-acid disclosed in British Patent No. 1,261,829 and 1,1,2,3-propane tetrasalt. Polycarboxylates containing sulfo substituents include the sulfonated succinic acid derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and US Patent No. 3,936,448 and the sulfonated pyrolyzed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more preferably citrates.

单体或低聚物的多元羧酸盐螯合剂或其与它们的盐(如柠檬酸或柠檬酸盐/柠檬酸混合物)的混合物也适用作助洗剂组分。Monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts such as citric acid or citrate/citric acid mixtures are also suitable as builder components.

硼酸盐助洗剂以及含有在洗涤条件下可以生成硼酸盐的形成硼酸盐材料的助洗剂也是此处有用的水溶性助洗剂。表面活性剂体系Borate builders and builders containing borate-forming materials which, under the wash conditions, will form borate are also water-soluble builders useful herein. Surfactant system

所述组分包括一种表面活性剂体系。所述表面活性剂体系可以含有常用于洗涤剂组合物中的任何表面活性剂如阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性表面活性剂、两性离子表面活性剂或其混合物。如上所述，优选存在至少一种阴离子硫酸盐和/或磺酸盐表面活性剂。也优选为非离子表面活性剂。The components include a surfactant system. The surfactant system may contain any surfactant commonly used in detergent compositions such as anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants or mixtures thereof . As mentioned above, it is preferred that at least one anionic sulfate and/or sulfonate surfactant is present. Also preferred are nonionic surfactants.

当存在阳离子表面活性剂、两性离子表面活性剂或两性表面活性剂时，还可以优选存在至少一种阴离子表面活性剂或非离子表面活性剂。阴离子表面活性剂When cationic, zwitterionic or amphoteric surfactants are present, it may also be preferred that at least one anionic or nonionic surfactant is present. anionic surfactant

任何用于去污目的的阴离子表面活性剂均是合适的。它们可以包括阴离子硫酸盐、磺酸盐、羧酸盐和肌氨酸盐表面活性剂的各种盐(包括如钠、钾、铵和取代铵盐如单-、二-和三乙醇胺盐)。Any anionic surfactant used for detersive purposes is suitable. These may include various salts of anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts).

优选阴离子磺酸盐表面活性剂作为所述阴离子表面活性剂或阴离子表面活性剂的一部分存在。Preferably an anionic sulphonate surfactant is present as or part of the anionic surfactant.

其它合适的阴离子表面活性剂包括羟乙磺酸盐如乙酰基羟乙磺酸盐、N-酰基牛磺酸盐、脂肪酸酰胺的甲基氨基乙磺酸盐、烷基琥珀酸盐和磺基琥珀酸盐、磺基琥珀酸的单酯(尤其饱和和不饱和C₁₂-C₁₈单酯)、磺基琥珀酸的二酯(尤其饱和和不饱和C₆-C₁₄二酯)、N-酰基肌氨酸盐。树脂酸和氢化树脂酸也是适合的，如松香、氢化松香，以及存在于或源于牛油的树脂酸和氢化树脂酸。Other suitable anionic surfactants include isethionates such as acetyl isethionates, N-acyl taurates, methyl taurates of fatty acid amides, alkyl succinates and sulfosuccinates salts, monoesters of sulfosuccinic acid (especially saturated and unsaturated C₁₂ -C₁₈ monoesters), diesters of sulfosuccinic acid (especially saturated and unsaturated C₆ -C₁₄ diesters), N-acyl Sarcosinate. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow.

当阴离子表面活性剂也用于本发明组分时产生的有益性能尤其适用于长碳链的阴离子表面活性剂如碳链长度为C₁₂或更大的那些阴离子表面活性剂，尤其C_14-15或甚至高达C_16-C18碳链长度。阴离子硫酸盐表面活性剂The beneficial properties that result when anionic surfactants are also used in the components of the invention are especially applicable to long carbon chain anionic surfactants such as those with a carbon chain length of C₁₂ or greater, especially C_14-15 Or even up to_C16-C18 carbon chain lengths. Anionic Sulfate Surfactant

适用于本发明组分的阴离子硫酸盐表面活性剂包括伯和仲烷基硫酸盐(具有9-22个碳原子的直链和支链烷基或链烯基部分或更优选C₁₂-C₁₈烷基)、烷基乙氧基硫酸盐、脂肪油酰甘油硫酸盐、烷基酚氧化乙烯醚硫酸盐、C₅-C₁₇酰基-N-(C₁-C₄烷基)和-N-(C₁-C₂羟烷基)葡糖胺硫酸盐以及烷基多糖的硫酸盐如烷基多葡糖苷的硫酸盐(此处所述的非离子非硫酸盐的化合物)。Anionic sulfate surfactants suitable for use in the components of the present invention include primary and secondary alkyl sulfates (straight and branched chain alkyl or alkenyl moieties having from 9 to 22 carbon atoms or more preferably_C12 -_C18 Alkyl), Alkyl Ethoxy Sulfate, Fatty Oleoyl Glycerol Sulfate, Alkylphenol Oxyethylene Ether Sulfate, C₅ -C₁₇ Acyl-N-(C₁ -C₄ Alkyl) and -N- (C₁ -C₂ hydroxyalkyl)glucosamine sulfates and sulfates of alkyl polysaccharides such as alkyl polyglucoside sulfates (non-ionic, non-sulfate compounds described herein).

优选烷基乙氧基硫酸盐表面活性剂选自C₉-C₂₂烷基硫酸盐(每个分子用0.5-20摩尔的环氧乙烷进行乙氧基化)。更优选所述烷基乙氧基硫酸盐表面活性剂为C₁₁-C₁₈，最优选C₁₁-C₁₅烷基硫酸盐(每个分子用0.5-7，优选1-5摩尔环氧乙烷进行乙氧基化)。Preferably the alkyl ethoxy sulphate surfactants are selected from_C9 -_C22 alkyl sulphates (ethoxylated with 0.5-20 moles of ethylene oxide per molecule). More preferably the alkyl ethoxy sulfate surfactant is C₁₁ -C₁₈ , most preferably C₁₁ -C₁₅ alkyl sulfate (0.5-7, preferably 1-5 moles of ethylene oxide per molecule ethoxylation).

本发明的一个特别优选方面采用优选的烷基硫酸盐和和烷基乙氧基硫酸盐表面活性剂的混合物。这些混合物已公开于PCT专利申请号WO93/18124中。阴离子磺酸盐表面活性剂A particularly preferred aspect of the present invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. These mixtures are disclosed in PCT Patent Application No. WO 93/18124. Anionic Sulfonate Surfactant

此处适用的阴离子磺酸盐表面活性剂包括C₅-C₂₀、更优选C₁₀-C₁₆、更优选C₁₁-C₁₃(直链)烷基苯磺酸盐、烷基酯磺酸盐、C₆-C₂₂伯或仲烷磺酸盐、C₆-C₂₄烯烃磺酸盐、磺化多元羧酸、烷基甘油磺酸盐、脂肪酰基甘油磺酸盐、脂肪油酰甘油磺酸盐、脂肪油基甘油磺酸盐及其混合物。Anionic sulfonate surfactants suitable for use herein include C₅ -C₂₀ , more preferably C₁₀ -C₁₆ , more preferably C₁₁ -C₁₃ (linear) alkylbenzene sulfonates, alkyl ester sulfonates , C₆ -C₂₂ primary or secondary alkane sulfonate, C₆ -C₂₄ olefin sulfonate, sulfonated polycarboxylic acid, alkyl glycerol sulfonate, fatty acyl glycerol sulfonate, fatty oleoyl glycerol sulfonate Salt, fatty oleyl glyceryl sulfonates and mixtures thereof.

优选所述烷基酯的磺化表面活性剂具有下式：Preferably the alkyl ester sulfonated surfactant has the formula:

R¹-CH(SO₃M)-(A)_x-C(O)-OR²R¹ -CH(SO₃ M)-(A)_x -C(O)-OR²

式中R¹为C₆-C₂₂烃基，R²为C₁-C₆烷基，A为C₆-C₂₂亚烷基、亚烯基，x为0或1，M为阳离子。优选相反离子M为钠、钾或铵。In the formula, R¹ is a C₆ -C₂₂ hydrocarbon group, R² is a C₁ -C₆ alkyl group, A is a C₆ -C₂₂ alkylene or alkenylene group, x is 0 or 1, and M is a cation. Preferably the counterion M is sodium, potassium or ammonium.

优选烷基酯的磺化表面活性剂为具有上式的α-磺基烷基酯，因此x为0。优选R¹为具有10-22，优选16个碳原子的烷基或链烯基，x优选为0。R²优选为乙基或更优选为甲基。Preferred alkyl ester sulfonated surfactants are alpha-sulfoalkyl esters having the above formula, whereby x is zero. Preferably R¹ is an alkyl or alkenyl group having 10-22, preferably 16, carbon atoms, x is preferably 0.^R2 is preferably ethyl or more preferably methyl.

可以优选酯中的R¹衍生自优选具有1、2或3个双键的不饱和脂肪酸。也可以优选酯中的R¹衍生自天然存在的脂肪酯(优选棕榈酸或硬脂酸或其混合物)。双阴离子表面活性剂It may be preferred that^R1 in the ester is derived from an unsaturated fatty acid preferably having 1, 2 or 3 double bonds. It may also be preferred that^R1 in the ester be derived from a naturally occurring fatty ester (preferably palmitic or stearic acid or mixtures thereof). double anionic surfactant

双阴离子表面活性剂也是适用于本发明组分的阴离子表面活性剂。优选下式的双阴离子表面活性剂：

式中R为任选取代的具有C₁-C₂₈，优选C₃-C₂₄，最优选C₈-C₂₀链长的烷基、链烯基、芳基、烷芳基、醚、酯、胺或酰胺基团或氢；A和B独立选自具有C₁-C₂₈，优选C₁-C₅，最优选C₁或C₂链长的亚烷基、亚烯基、(聚)烷氧亚基、羟基亚烷基、芳基亚烷基或酰氨亚烷基，或共价键，优选A和B总共含有至少2个原子；A、B和R总共含有4至约31个碳原子；X和Y为选自羧酸根，优选硫酸根和磺酸根的阴离子基团，z为0或优选1；M为阳离子部分，优选为取代或未取代的铵离子或碱金属或碱土金属离子。Dianionic surfactants are also suitable anionic surfactants for use in the components of the present invention. Preferred are dianionic surfactants of the formula:

In the formula, R_isan optionally substituted_alkylgroup ,_alkenyl group,_aryl group, alkaryl group, ether, ester, Amine or amide group or hydrogen; A and B are independently selected from alkylene, alkenylene, (poly)alkane having C₁ -C₂₈ , preferably C₁ -C₅ , most preferably C₁ or C₂ chain length Oxyalkylene, hydroxyalkylene, arylalkylene or amidoalkylene, or covalent bond, preferably A and B together contain at least 2 atoms; A, B and R together contain 4 to about 31 carbons atom; X and Y are anionic groups selected from carboxylate, preferably sulfate and sulfonate, z is 0 or preferably 1; M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion or an alkali metal or alkaline earth metal ion .

最优选双阴离子表面活性剂具有其中R为C₁₀-C₁₈链长的烷基，A和B独立为C₁或C₂，X和Y均为硫酸根，M为钾、铵或钠离子的上式。The most preferred dianionic surfactant has wherein R is an alkyl group of C₁₀ -C₁₈ chain length, A and B are independently C₁ or C₂ , X and Y are both sulfate groups, and M is potassium, ammonium or sodium ion above formula.

此处优选的双阴离子表面活性剂包括：Preferred dianionic surfactants herein include:

(a)3二硫酸盐化合物，优选1，3-C7-C23(即分子中的总碳数)直链或支链烷基或链烯基二硫酸盐，更优选具有下式：(a) 3 disulfate compounds, preferably 1,3-C7-C23 (i.e. the total number of carbons in the molecule) linear or branched chain alkyl or alkenyl disulfates, more preferably having the following formula:

式中R为链长约C₄-C₂₀的直链或支链烷基或链烯基；In the formula, R is a linear or branched alkyl or alkenyl group with a chain length of about C₄ -C₂₀ ;

(b)1，4二硫酸盐化合物，优选1，4 C₈-C₂₂直链或支链烷基或链烯基二硫酸盐，更优选具有下式：

(b) 1,4 disulfate compounds, preferably 1,4 C₈ -C₂₂ linear or branched chain alkyl or alkenyl disulfates, more preferably having the formula:

式中R为链长为约C₄-C₁₈的直链或支链烷基或链烯基；优选R选自辛基、壬基、癸基、十二烷基、十四烷基、十六烷基、十八烷基及其组合；和In the formula, R is a straight chain or branched chain alkyl or alkenyl group with a chain length of about C₄ -C₁₈ ; preferably R is selected from octyl, nonyl, decyl, dodecyl, tetradecyl, decanyl Hexaalkyl, octadecyl, and combinations thereof; and

(c)1，5二硫酸盐化合物，优选1，5 C₉-C₂₃直链或支链烷基或链烯基二硫酸盐，更优选具有下式：

(c) 1,5 disulfate compounds, preferably 1,5 C₉ -C₂₃ linear or branched chain alkyl or alkenyl disulfates, more preferably having the formula:

式中R为链长为约C₄-C₁₈的直链或支链烷基或链烯基。In the formula, R is a linear or branched alkyl or alkenyl group with a chain length of about C₄ -C₁₈ .

可以优选所述双阴离子表面活性剂为烷氧基化的双阴离子表面活性剂。It may be preferred that the dianionic surfactant is an alkoxylated dianionic surfactant.

优选的烷氧基化的双阴离子表面活性剂具有下式：

式中R为任选取代的具有C₁-C₂₈，优选C₃-C₂₄，最优选C₈-C₂₀链长的烷基、链烯基、芳基、烷芳基、醚、酯、胺或酰胺基团或氢；A和B独立选自(任选取代)具有C₁-C₂₈，优选C₁-C₅，最优选C₁或C₂链长的的烷基和链烯基或共价键，EO/PO为选自乙氧基、丙氧基、和组合的乙氧基/丙氧基的烷氧基部分，其中n和m独立地在约0至10之间，但至少m或n为至少1；优选A和B总共含有至少2个原子；A、B和R总共含有4至约31个碳原子；X和Y为选自硫酸根和磺酸根的阴离子基团，条件是X或Y的至少一个为硫酸根；M为阳离子部分，优选为取代或未取代的铵离子或碱金属或碱土金属离子。Preferred alkoxylated dianionic surfactants have the formula:

In the formula, R_isan optionally substituted_alkylgroup ,_alkenyl group,_aryl group, alkaryl group, ether, ester, Amine or amide groups or hydrogen; A and B are independently selected from (optionally substituted) alkyl and alkenyl groups having a chain length of C₁ -C₂₈ , preferably C₁ -C₅ , most preferably C₁ or C₂ or a covalent bond, EO/PO is an alkoxy moiety selected from ethoxy, propoxy, and combined ethoxy/propoxy, wherein n and m are independently between about 0 and 10, but at least m or n is at least 1; preferably A and B together contain at least 2 atoms; A, B and R together contain 4 to about 31 carbon atoms; X and Y are anionic groups selected from sulfate and sulfonate, Provided that at least one of X or Y is sulfate; M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion or an alkali metal or alkaline earth metal ion.

最优选的烷氧基化双阴离子表面活性剂具有其中R为C₁₀-C₁₈链长的烷基，A和B独立为C₁或C₂，n和m均为1，X和Y均为硫酸根，M为钾、铵或钠离子的上式。中链分支烷基硫酸盐或磺酸盐The most preferred alkoxylated dianionic surfactants have wherein R is an alkyl chain of C₁₀ -C₁₈ chain length, A and B are independently C₁ or C₂ , n and m are both 1, and X and Y are both Sulfate, M is the above formula of potassium, ammonium or sodium ion. Medium Chain Branched Alkyl Sulfate or Sulfonate

中链分支烷基硫酸盐或磺酸盐也是适用于本发明组分的合适的阴离子表面活性剂。优选中链分支的烷基硫酸盐。Mid-chain branched alkyl sulfates or sulfonates are also suitable anionic surfactants for use in the components of the present invention. Mid-chain branched alkyl sulfates are preferred.

优选中链分支的烷基硫酸盐表面活性剂具有下式：

Preferred mid-chain branched alkyl sulfate surfactants have the formula:

这些表面活性剂具有线性伯烷基硫酸盐主链(即包括硫酸盐化碳原子的最长线性碳链)，所述主链优选含有12-19个碳原子，并且优选它们的分支伯烷基部分总共含有至少14，优选不大于20个碳原子。在含有超过一个这些硫酸盐表面活性剂的本发明的组分中，优选分支的伯烷基部分的平均总碳数为大于14.5至约17.5的范围内。因此所述表面活性剂体系优选含有至少一个分支的伯烷基硫酸盐表面活性剂化合物，所述化合物的最长线性碳链不小于12个碳原子或不大于19个碳原子，并且包括支链的总碳原子数必须为至少14，进一步而言，分支伯烷基部分的平均总碳原子数的范围为大于14.5至约17.5。These surfactants have a linear primary alkyl sulfate backbone (i.e. the longest linear carbon chain including the sulfated carbon atoms), preferably containing 12-19 carbon atoms, and preferably their branched primary alkyl groups The moieties contain at least 14, preferably no more than 20 carbon atoms in total. In compositions of the present invention containing more than one of these sulfate surfactants, it is preferred that the average total carbon number of the branched primary alkyl moieties be in the range of greater than 14.5 to about 17.5. The surfactant system therefore preferably contains at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms and including branched must be at least 14 total carbon atoms, and furthermore, the average total carbon number of the branched primary alkyl moieties ranges from greater than 14.5 to about 17.5.

优选的单甲基分支的伯烷基硫酸盐选自：3-甲基十五醇硫酸盐、4-甲基十五醇硫酸盐、5-甲基十五醇硫酸盐、6-甲基十五醇硫酸盐、7-甲基十五醇硫酸盐、8-甲基十五醇硫酸盐、9-甲基十五醇硫酸盐、10-甲基十五醇硫酸盐、11-甲基十五醇硫酸盐、12-甲基十五醇硫酸盐、13-甲基十五醇硫酸盐、3-甲基十六醇硫酸盐、4-甲基十六醇硫酸盐、5-甲基十六醇硫酸盐、6-甲基十六醇硫酸盐、7-甲基十六醇硫酸盐、8-甲基十六醇硫酸盐、9-甲基十六醇硫酸盐、10-甲基十六醇硫酸盐、11-甲基十六醇硫酸盐、12-甲基十六醇硫酸盐、13-甲基十六醇硫酸盐、14-甲基十六醇硫酸盐及其混合物。Preferred monomethyl branched primary alkyl sulfates are selected from the group consisting of: 3-methylpentadecanol sulfate, 4-methylpentadecanol sulfate, 5-methylpentadecanol sulfate, 6-methylpentadecanol sulfate Pentaol Sulfate, 7-Methylpentadecanyl Sulfate, 8-Methylpentadecanyl Sulfate, 9-Methylpentadecanyl Sulfate, 10-Methylpentadecanyl Sulfate, 11-Methyldecadecayl Sulfate Pentaol Sulfate, 12-Methylpentadecanyl Sulfate, 13-Methylpentadecanyl Sulfate, 3-Methylhexadecanyl Sulfate, 4-Methylhexadecanyl Sulfate, 5-Methyldecadecanol Sulfate Hexadecyl sulfate, 6-methyl cetyl sulfate, 7-methyl cetyl sulfate, 8-methyl cetyl sulfate, 9-methyl cetyl sulfate, 10-methyl cetyl sulfate Hexyl alcohol sulfate, 11-methyl cetyl alcohol sulfate, 12-methyl cetyl alcohol sulfate, 13-methyl cetyl alcohol sulfate, 14-methyl cetyl alcohol sulfate and mixtures thereof.

优选的二甲基分支的伯烷基硫酸盐选自：2，3-甲基十四醇硫酸盐、2，4-甲基十四醇硫酸盐、2，5-甲基十四醇硫酸盐、2，6-甲基十四醇硫酸盐、2，7-甲基十四醇硫酸盐、2，8-甲基十四醇硫酸盐、2，9-甲基十四醇硫酸盐、2，10-甲基十四醇硫酸盐、2，11-甲基十四醇硫酸盐、2，12-甲基十四醇硫酸盐、2，3-甲基十五醇硫酸盐、2，4-甲基十五醇硫酸盐、2，5-甲基十五醇硫酸盐、2，6-甲基十五醇硫酸盐、2，7-甲基十五醇硫酸盐、2，8-甲基十五醇硫酸盐、2，9-甲基十五醇硫酸盐、2，10-甲基十五醇硫酸盐、2，11-甲基十五醇硫酸盐、2，12-甲基十五醇硫酸盐、2，13-甲基十五醇硫酸盐及其混合物。Preferred dimethyl branched primary alkyl sulfates are selected from the group consisting of: 2,3-methyltetradecyl sulfate, 2,4-methyltetradecyl sulfate, 2,5-methyltetradecyl sulfate , 2,6-methyltetradecyl sulfate, 2,7-methyltetradecyl sulfate, 2,8-methyltetradecyl sulfate, 2,9-methyltetradecyl sulfate, 2 , 10-methyl tetradecyl sulfate, 2,11-methyl tetradecyl sulfate, 2,12-methyl tetradecyl sulfate, 2,3-methyl pentadecyl sulfate, 2,4 -Methylpentadecanyl sulfate, 2,5-methylpentadecanyl sulfate, 2,6-methylpentadecanyl sulfate, 2,7-methylpentadecanyl sulfate, 2,8-methanol Pentadecyl alcohol sulfate, 2,9-methylpentadecanyl sulfate, 2,10-methylpentadecanyl sulfate, 2,11-methylpentadecanyl sulfate, 2,12-methylpentadecanol sulfate Pentaol sulfate, 2,13-methylpentadecyl sulfate and mixtures thereof.

含有16个碳原子并且具有一个分支单元的下面的分支的伯烷基硫酸盐为用于本发明组分中的优选分支表面活性剂的例子：The following branched primary alkyl sulfates containing 16 carbon atoms and having one branching unit are examples of preferred branched surfactants for use in the compositions of the present invention:

具有下式的5-甲基十五烷基硫酸盐：

5-Methylpentadecyl sulfate having the formula:

具有下式的6-甲基十五烷基硫酸盐：6-methylpentadecyl sulfate having the formula:

具有下式的7-甲基十五烷基硫酸盐：

7-Methylpentadecyl sulfate having the formula:

具有下式的8-甲基十五烷基硫酸盐：

8-Methylpentadecyl sulfate having the formula:

具有下式的9-甲基十五烷基硫酸盐：

9-Methylpentadecyl sulfate having the formula:

具有下式的10-甲基十五烷基硫酸盐：

10-methylpentadecyl sulfate having the formula:

式中M优选为钠。In the formula, M is preferably sodium.

含有17个碳原子并且具有两个分支单元的下面的分支的伯烷基硫酸盐为本发明的优选分支表面活性剂的例子：The following branched primary alkyl sulfates containing 17 carbon atoms and having two branching units are examples of preferred branched surfactants of the invention:

具有下式的2，5-二甲基十五烷基硫酸盐：

2,5-Dimethylpentadecyl sulfate having the formula:

具有下式的2，6-二甲基十五烷基硫酸盐：

2,6-Dimethylpentadecyl sulfate having the formula:

具有下式的2，7-二甲基十五烷基硫酸盐：

2,7-Dimethylpentadecyl sulfate having the formula:

具有下式的2，8-二甲基十五烷基硫酸盐：2,8-Dimethylpentadecyl sulfate having the formula:

具有下式的2，9-二甲基十五烷基硫酸盐：

2,9-Dimethylpentadecyl sulfate having the formula:

具有下式的2，10-二甲基十五烷基硫酸盐：

2,10-Dimethylpentadecyl sulfate having the formula:

其中优选M为钠。阴离子羧酸盐表面活性剂Wherein M is preferably sodium. Anionic Carboxylate Surfactants

适合的阴离子羧酸盐表面活性剂包括烷基乙氧基羧酸盐、烷基多乙氧基多羧酸盐表面活性剂和皂(‘烷基羧化物(carboxyls)’)，尤其此处所述的某些仲皂(secondary soap)。Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ('alkyl carboxyls'), especially as herein Certain secondary soaps mentioned above.

适合的烷基乙氧基羧酸盐包括式RO(CH₂CH₂O)_xCH₂COO^-M⁺的那些化合物，式中R为C₆-C₁₈烷基，x为0-10，乙氧基化物分布使得x为0的材料的量小于20％(以重量计)，M为阳离子。适合的烷基聚乙氧基多羧酸盐表面活性剂包括那些具有式RO-(CHR₁-CHR₂-O)-R₃的物质，式中R为C₆-C₁₈烷基，x为1-25，R₁和R₂选自氢、甲基酸基团、丁二酸基团、羟基丁二酸基团及它们的混合物，R₃选自氢、具有1-8个碳原子的取代或未取代烃及其混合物。Suitable alkyl ethoxy carboxylates include those compounds of formula RO(CH₂ CH₂ O)_x CH₂ COO^- M⁺ , wherein R is C₆ -C₁₈ alkyl, x is 0-10, E The oxide distribution is such that the amount of material where x is 0 is less than 20% by weight and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR₁ -CHR₂ -O)-R₃ wherein R is C₆ -C₁₈ alkyl and x is 1-25, R₁ and R₂ are selected from hydrogen, methyl acid groups, succinic acid groups, hydroxysuccinic acid groups and mixtures thereof, R₃ is selected from hydrogen, carbon atoms with 1-8 carbon atoms Substituted or unsubstituted hydrocarbons and mixtures thereof.

适合的皂类表面活性剂包括含有与仲碳相连的羧基单元的仲皂表面活性剂。用于此处的优选仲皂表面活性剂为水溶性物质，其选自2-甲基-1-十一酸、2-乙基-1-癸酸、2-丙基-1-壬酸、2-丁基-1-辛酸和2-戊基-1-庚酸的水溶性盐。Suitable soap surfactants include secondary soap surfactants comprising a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants for use herein are water soluble materials selected from 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, Water-soluble salts of 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.

某些皂也可以包括在抑泡剂中。碱金属肌氨酸盐表面活性剂Certain soaps can also be included in the suds suppressor. Alkali metal sarcosinate surfactant

其它适合的阴离子表面活性剂为式R-CON(R¹)CH₂COOM的碱金属肌氨酸盐，式中R为C₅-C₁₇直链或支链烷基或链烯基，R¹为C₁-C₄烷基，M为碱金属离子。优选的例子为肉豆蔻基和油酰基甲基肌氨酸的钠盐。非离子表面活性剂体系Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CON(R¹ )CH₂ COOM, wherein R is a C₅ -C₁₇ linear or branched chain alkyl or alkenyl group, and R¹ is a C₁ -C₄ alkyl group, and M is an alkali metal ion. Preferred examples are the sodium salts of myristyl and oleoyl methyl sarcosine. Nonionic Surfactant System

所述洗涤剂组分可以包括或也包括一种非离子表面活性剂体系(含有至少两种非离子烷氧基化的表面活性剂)。The detergent components may or may also comprise a nonionic surfactant system comprising at least two nonionic alkoxylated surfactants.

几乎任何烷氧基化的非离子表面活性剂均适用于此。优选乙氧基化和丙氧基化的非离子表面活性剂。Almost any alkoxylated nonionic surfactant is suitable for use herein. Ethoxylated and propoxylated nonionic surfactants are preferred.

优选的烷氧基化的表面活性剂可以选自烷基酚的非离子缩合物、非离子乙氧基化醇、非离子烷氧基化脂肪酰胺、非离子乙氧基化/丙氧基化脂肪醇、非离子乙氧基化物/丙氧基化物与丙二醇的缩合物、以及与环氧丙烷/乙二胺加合物的非离子乙氧基化物的缩合产物。Preferred alkoxylated surfactants may be selected from nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic alkoxylated fatty amides, nonionic ethoxylated/propoxylated Condensation products of fatty alcohols, nonionic ethoxylates/propoxylates with propylene glycol, and condensation products of nonionic ethoxylates with propylene oxide/ethylenediamine adducts.

优选至少一种非离子表面活性剂为后面所述的烷氧基化醇表面活性剂。Preferably at least one nonionic surfactant is an alkoxylated alcohol surfactant as described hereinafter.

也优选非离子烷氧基化脂肪酸酰胺，其可以提供对织物或者皮肤(在所述洗涤剂与皮肤接触时)更多的软化性能。Also preferred are nonionic alkoxylated fatty acid amides, which may provide more softening properties on fabrics or on skin where the detergent is in contact with the skin.

最优选非离子表面活性剂体系包括至少两种非离子烷氧基化醇表面活性剂，优选其一种表面活性剂的平均烷氧化程度为5或更小，一种表面活性剂的平均烷氧化程度大于5。高度优选的系统包括至少一种平均烷氧化程度为3或5的非离子烷氧基化醇和至少一种平均烷氧化程度为5.5至15，优选6或9的非离子烷氧基化醇。Most preferably the nonionic surfactant system comprises at least two nonionic alkoxylated alcohol surfactants, preferably one having an average alkoxylation degree of 5 or less and one surfactant having an average alkoxylation degree of 5 or less. The degree is greater than 5. A highly preferred system comprises at least one nonionic alkoxylated alcohol having an average degree of alkoxylation of 3 or 5 and at least one nonionic alkoxylated alcohol having an average degree of alkoxylation of 5.5 to 15, preferably 6 or 9.

非离子表面活性剂的烷氧化基团优选为丙氧化物基团，更优选乙氧基化物基团。The alkoxylated groups of the nonionic surfactant are preferably propoxylated groups, more preferably ethoxylated groups.

在此中的非离子表面活性剂体系中优选脂族醇与1-25摩尔烯化氧，尤其环氧乙烷和/或环氧丙烷的缩合产物。脂族醇的烷基链可以为直链或支链，伯或仲烷基链，并且通常含有6-22个碳原子。尤其优选具有8-20个碳原子的烷基的醇的缩合产物。Condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and/or propylene oxide, are preferred among the nonionic surfactant systems here. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Particular preference is given to condensation products of alcohols having alkyl groups of 8 to 20 carbon atoms.

本发明的非离子表面活性剂体系可以含有一种烷氧基化脂肪酸酰胺，其优选含有一种下式的化合物：The nonionic surfactant system of the present invention may contain an alkoxylated fatty acid amide, which preferably contains a compound of the formula:

式中R₁为C₁₂-C₁₈烷基或链烯基，R₂为C₂-C₄亚烷基，R₃为氢或C₁-C₄烷基，R₄为C₁-C₄烷基或氢，n为3-12的一个数。In the formula, R₁ is C₁₂ -C₁₈ alkyl or alkenyl, R₂ is C₂ -C₄ alkylene, R₃ is hydrogen or C₁ -C₄ alkyl, R₄ is C₁ -C₄ Alkyl or hydrogen, n is a number from 3-12.

优选烷氧基化脂肪酸酰胺具有C₁₂-C₁₄或C₁₆-C₁₈烷基的R₁、亚丙基或更优选亚乙基的R₂，n为5-10，R₄为甲基或氢，R₃为氢或甲基或乙基。Preferred alkoxylated fatty acid amides have R₁ of C₁₂ -C₁₄ or C₁₆ -C₁₈ alkyl, R₂ of propylene or more preferably ethylene, n is 5-10, R₄ is methyl or Hydrogen, R₃ is hydrogen or methyl or ethyl.

此处的洗涤剂组分也可以含有包括多羟基脂肪酸酰胺的其它非烷氧基化非离子表面活性剂，适用于此的多羟基脂肪酸酰胺具有结构式R²CONR¹Z，式中R¹为H、C₁-C₄烃基、2-羟乙基、2-羟丙基、乙氧基、丙氧基或其混合物，优选C₁-C₄烷基，更优选C₁或C₂烷基，最优选C₁烷基(即甲基)；R²为C₅-C₃₁烃基，优选直链C₅-C₁₉烷基或链烯基，更优选直链C₉-C₁₇烷基或链烯基，最优选直链C₁₁-C₁₇烷基或链烯基，或其混合物；Z为具有直接相连了至少3个羟基的直链烃基链的多羟基烃基，或其烷氧基化衍生物(优选乙氧基化或丙氧基化)。Z优选在还原胺化反应中由还原糖衍生而来；更优选Z为glycityl。^The detergent components herein may also contain other non-alkoxylated nonionic surfactants including polyhydroxy fatty acid amides, polyhydroxy fatty acid amides suitable for use herein having the formula^R2CONR1Z where^R1 is H , C₁ -C₄ alkyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or mixtures thereof, preferably C₁ -C₄ alkyl, more preferably C₁ or C₂ alkyl, Most preferably C₁ alkyl (i.e. methyl); R² is C₅ -C₃₁ hydrocarbon group, preferably straight chain C₅ -C₁₉ alkyl or alkenyl, more preferably straight chain C₉ -C₁₇ alkyl or chain Alkenyl, most preferably straight chain C₁₁ -C₁₇ alkyl or alkenyl, or mixtures thereof; Z is a polyhydroxyhydrocarbyl having a straight chain hydrocarbyl chain directly attached to at least 3 hydroxyl groups, or an alkoxylated derivative thereof substances (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl.

此处洗涤剂组分还可包括其它烷基多糖，如公开于1986年1月21日授权予Llenado的美国专利4,565,647的烷基多糖，所述烷基多糖具有6-30个碳原子的疏水基团和含有1.3-10个糖单元的亲水性基团的多糖如聚葡糖苷。Detergent components herein may also include other alkyl polysaccharides, such as those disclosed in U.S. Patent 4,565,647, issued January 21, 1986 to Llenado, which have hydrophobic groups of 6 to 30 carbon atoms Groups and polysaccharides with hydrophilic groups containing 1.3-10 sugar units such as polyglucosides.

优选的烷基多苷具有式R²O(C_nH_2nO)_t(糖基)_x，式中R²选自烷基、烷基苯基、羟烷基、羟烷基苯基及其混合物，其中烷基含有10-18个碳原子；n为2或3；t为0-10，x为1.3-8。糖基优选衍生自葡萄糖。两性表面活性剂Preferred alkyl polyglycosides have the formula R² O(C_n H_2n O)_t (glycosyl)_x , wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and The mixture, wherein the alkyl group contains 10-18 carbon atoms; n is 2 or 3; t is 0-10, and x is 1.3-8. The glycosyl is preferably derived from glucose. amphoteric surfactant

此处适用的两性表面活性剂包括氧化胺表面活性剂和烷基两性羧酸。Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkyl amphocarboxylic acids.

适合的氧化胺包括具有式R³(OR⁴)_xO(R⁵)₂的那些化合物，式中R³选自含有8-26个碳原子的烷基、羟烷基、酰氨基丙基和烷基苯基团或其混合物；R⁴为含有2-3个碳原子的亚烷基或羟基亚烷基，或其混合物；x为0-5，优选0-3；R⁵各自为含有1-3的烷基或羟烷基，或含有1-3个环氧乙烷基团的聚环氧乙烷基团。优选C₁₀-C₁₈烷基二甲基氧化胺和C₁₀-C₁₈酰氨基烷基二甲基氧化胺。Suitable amine oxides include those compounds having the formula R³ (OR⁴ )_x O(R⁵ )₂ wherein R³ is selected from the group consisting of alkyl, hydroxyalkyl, amidopropyl and Alkylphenyl group or a mixture thereof; R⁴ is an alkylene or hydroxyalkylene group containing 2-3 carbon atoms, or a mixture thereof; x is 0-5, preferably 0-3; R⁵ is each containing 1 -3 alkyl or hydroxyalkyl groups, or polyethylene oxide groups containing 1-3 oxirane groups. Preference is given to C₁₀ -C₁₈ alkyldimethylamine oxides and C₁₀ -C₁₈ amidoalkyldimethylamine oxides.

烷基两性羧酸的适合例子为由Miranol，Inc.，Dayton，NJ生产的Miranol^TM C2M Conc。两性离子表面活性剂A suitable example of an alkyl amphocarboxylic acid is Miranol^™ C2M Conc manufactured by Miranol, Inc., Dayton, NJ. zwitterionic surfactant

两性离子表面活性剂也可以加入本发明的洗涤剂组合物中。这些表面活性剂可以广义描述为仲胺和叔胺的衍生物、杂环仲胺和叔胺的衍生物或季铵、季鏻或叔锍化合物的衍生物。甜菜碱和磺基甜菜碱表面活性剂为用于此处的两性离子表面活性剂的例子。Zwitterionic surfactants can also be incorporated into the detergent compositions of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are examples of zwitterionic surfactants useful herein.

适合的甜菜碱为具有式R(R’)₂N⁺R²COO^-的化合物，式中R为C₆-C₁₈烃基，R¹各自通常为C₁-C₃烷基，R²为C₁-C₅烃基。优选的甜菜碱为C_12-18二甲基铵己酸盐和C_10-18酰氨基丙烷(或乙烷)二甲基(或二乙基)甜菜碱。络合甜菜碱表面活性剂也适用于此处。阳离平表面活性剂Suitable betaines are compounds having the formula R(R')₂ N⁺ R^2COO- , wherein R is C₆ -C₁₈ hydrocarbyl, R¹ is each typically C₁ -C₃ alkyl, R² is C₁ -C₅ Hydrocarbyl. Preferred betaines are C_12-18 dimethylammonium hexanoate and C_10-18 amidopropane (or ethane) dimethyl (or diethyl) betaine. Complex betaine surfactants are also suitable for use herein. cationic planar surfactant

此处适用的阳离子表面活性剂包括季铵表面活性剂。优选的季铵表面活性剂为单C₆-C₁₆，优选C₆-C₁₀N-烷基或链烯基铵表面活性剂，式中剩余的N位被甲基、羟乙基或羟丙基取代。也优选单烷氧基化和双烷氧基化胺表面活性剂。Cationic surfactants suitable for use herein include quaternary ammonium surfactants. Preferred quaternary ammonium surfactants are mono C₆ -C₁₆ , preferably C₆ -C₁₀ N-alkyl or alkenyl ammonium surfactants in which the remaining N positions are replaced by methyl, hydroxyethyl or hydroxypropyl base substitution. Also preferred are monoalkoxylated and bisalkoxylated amine surfactants.

可以用于此处的洗涤剂组合物或其组分的另一类适合的阳离子表面活性剂为阳离子酯表面活性剂。所述阳离子酯表面活性剂为(优选水分散的)具有表面活性剂性质的包括至少一个酯(即-COO-)键和至少一个阳离子带电基团的化合物。Another class of suitable cationic surfactants which may be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a (preferably water-dispersible) compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.

适合的阳离子酯表面活性剂(包括胆碱酯表面活性剂)已公开于如美国专利号4228042、4239660和4260529。Suitable cationic ester surfactants, including choline ester surfactants, are disclosed, for example, in US Pat. Nos. 4,228,042, 4,239,660 and 4,260,529.

在一个优选方面，酯键和阳离子带电基团在表面活性剂分子中相互被间隔基分开，所述间隔基由含有至少3个原子(即三个原子的链长)，优选3-8个原子，更优选3-5个原子，最优选3个原子的链组成。形成间隔基链的原子选自碳、氮和氧原子及其任意组合，条件是在所述链上的任意氮和氧原子只与链上的碳原子相连。因此不包括具有如-O-O-(即过氧化物)、-N-N-和-N-O-键的间隔基，而包括具有如-CH₂-O-CH₂-和-CH₂-NH-CH₂-键的间隔基。在一个优选方面，间隔基链只包括碳原子，最优选所述链为烃基链。阳离子单-烷氧基化胺表面活性剂In a preferred aspect, the ester bond and the cationically charged group are separated from each other in the surfactant molecule by a spacer consisting of at least 3 atoms (i.e. a chain length of three atoms), preferably 3-8 atoms. , more preferably 3-5 atoms, most preferably 3 atoms chain composition. The atoms forming the spacer chain are selected from carbon, nitrogen and oxygen atoms and any combination thereof, provided that any nitrogen and oxygen atoms in said chain are bonded only to carbon atoms in the chain. Spacers with bonds such as -OO- (ie peroxide), -NN- and -NO- are thus excluded, but spacers with bonds such as -CH₂ -O-CH₂ - and -CH₂ -NH-CH₂ - Bond spacer. In a preferred aspect, the spacer chain comprises only carbon atoms, most preferably said chain is a hydrocarbyl chain. Cationic mono-alkoxylated amine surfactants

此处高度优选的阳离子单-烷氧基化胺表面活性剂优选具有以下通式I，

式中R¹为含有约6至18个碳原子，优选6至约16个碳原子，最优选约6至14个碳原子的烷基或链烯基部分；R²和R³各自独立地为含有1至约3个碳原子的烷基，优选甲基，最优选R²和R³均为甲基；R⁴选自氢(优选)、甲基和乙基；X^-为阴离子如氯负离子、溴负离子、甲基硫酸根、硫酸根等从而提供电中性；A为烷氧基，尤其乙氧基、丙氧基或丁氧基；p为0至约30，优选2至约15，最优选2至约8。Highly preferred cationic mono-alkoxylated amine surfactants herein preferably have the following general formula I,

wherein^R is an alkyl or alkenyl moiety containing from about 6 to 18 carbon atoms, preferably from 6 to about 16 carbon atoms, most preferably from about 6 to 14 carbon atoms; R^andR are each independently An alkyl group containing 1 to about 3 carbon atoms, preferably methyl, most preferably^both R and^R are methyl;^R is selected from hydrogen (preferred), methyl and ethyl; X^- is an anion such as a chloride anion , bromide, methylsulfate, sulfate, etc. to provide electrical neutrality; A is alkoxy, especially ethoxy, propoxy or butoxy; p is 0 to about 30, preferably 2 to about 15, 2 to about 8 are most preferred.

优选式I中ApR⁴基团的p＝1并且为羟烷基，碳原子数不超过6，由此-OH基团被不超过3个的碳原子与季铵的氮原子分开。尤其优选ApR⁴基团为-CH₂CH₂OH、-CH₂CH₂CH₂OH、-CH₂CH(CH₃)OH和-CH(CH₃)CH₂OH，尤其优选-CH₂CH₂OH。优选R¹基团为直链烷基。优选具有8-14个碳原子的直链R¹基团。Preferably the ApR group in formula I has p=1 and is a hydroxyalkyl group with no more than 6 carbon atoms, whereby the -OH group is separated from^the nitrogen atom of the quaternary ammonium by no more than 3 carbon atoms. Especially preferred ApR⁴ groups are -CH₂ CH₂ OH, -CH₂ CH₂ CH₂ OH, -CH₂ CH(CH₃ )OH and -CH(CH₃ )CH₂ OH, especially preferred -CH₂ CH₂ Oh. Preferably the^R1 group is a straight chain alkyl group. Straight-chain R¹ groups having 8-14 carbon atoms are preferred.

用于此处的另一类高度优选的阳离子单-烷氧基化胺表面活性剂具有下式

式中R¹为C₁₀-C₁₈烃基及其组合，尤其C₁₀-C₁₄烷基，优选C₁₀-C₁₂烷基，X为任意方便的阴离子从而提供电荷平衡，优选氯负离子或溴负离子。Another highly preferred class of cationic mono-alkoxylated amine surfactants for use herein has the formula

In the formula,^R is a C₁₀ -C₁₈ hydrocarbon group and combinations thereof, especially a C₁₀ -C₁₄ alkyl group, preferably a C₁₀ -C₁₂ alkyl group, and X is any convenient anion to provide charge balance, preferably a chloride anion or a bromide anion .

需要注意的是，前面类型的化合物包括那些其中乙氧基(CH₂CH₂O)单元(EO)被丁氧基、异丙氧基[CH(CH₃)CH₂O]和[CH₂CH(CH₃)O]单元(i-Pr)或正丙氧基单元(Pr)，或EO和/或Pr和/或i-Pr单元的组合置换的化合物。It should be noted that compounds of the preceding type include those in which the ethoxy (CH₂ CH₂ O) units (EO) are replaced by butoxy, isopropoxy [CH(CH₃ )CH₂ O] and [CH₂ CH Compounds substituted by (CH₃ )O] units (i-Pr) or n-propoxy units (Pr), or combinations of EO and/or Pr and/or i-Pr units.

在本发明的洗涤剂组分中所用的阳离子单-烷氧基化胺表面活性剂的优选水平为所述组分的0.5％-30％，更优选1％-25％，最优选1％-10％(重量)。阳离子双-烷氧基化胺表面活性剂Preferred levels of cationic mono-alkoxylated amine surfactants used in the detergent ingredients of the present invention are from 0.5% to 30%, more preferably from 1% to 25%, most preferably from 1% to 10% by weight. Cationic bis-alkoxylated amine surfactants

优选阳离子双烷氧基化胺表面活性剂具有通式II，

式中R¹为含有约8至约18个碳原子，优选10至约16个碳原子，最优选约10至约14个碳原子的烷基或链烯基部分；R²为含有1-3个碳原子的烷基，优选甲基；R³和R⁴可以独立变化并且选自氢(优选)、甲基和乙基，X-为阴离子如氯负离子、溴负离子、甲基硫酸根、硫酸根等，足以提供电中性。A和A’可以独立变化并且各自选自C₁-C₄烷氧基，尤其乙氧基(即-CH₂CH₂O-)、丙氧基、丁氧基及其组合；p为1至约30，优选1至约4，q为1至约30，优选1至约4，最优选p和q均为1。Preferred cationic bis-alkoxylated amine surfactants have the general formula II,

In the formula R¹ is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably from 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R² is an alkyl or alkenyl moiety containing 1-3 Alkyl of carbon atoms, preferably methyl;^R3 and^R4 can vary independently and be selected from hydrogen (preferred), methyl and ethyl, X- is an anion such as chloride anion, bromide anion, methylsulfate, sulfuric acid roots, etc., sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C₁ -C₄ alkoxy, especially ethoxy (ie -CH₂ CH₂ O-), propoxy, butoxy and combinations thereof; p is 1 to About 30, preferably 1 to about 4, q is 1 to about 30, preferably 1 to about 4, most preferably both p and q are 1.

用于此处的高度优选的阳离子双烷氧基化胺表面活性剂具有下式，

式中R¹为C₁₀-C₁₈烃基及其组合，优选C₁₀、C₁₂、C₁₄烷基及其组合。X为任意方便的阴离子从而提供电荷平衡，优选氯负离子。参照上述阳离子双烷氧基化胺的结构通式，由于在优选化合物中，R¹衍生自(椰油)C₁₂-C₁₄烷基部分脂肪酸，因此R²为甲基，ApR³和A’qR⁴各自为单乙氧基。Highly preferred cationic bisalkoxylated amine surfactants for use herein have the formula,

In the formula, R¹ is a C₁₀ -C₁₈ hydrocarbon group and combinations thereof, preferably C₁₀ , C₁₂ , C₁₄ alkyl groups and combinations thereof. X is any convenient anion to provide charge balance, preferably a chloride anion. With reference to the above general structural formula of the cationic bis-alkoxylated amines, since in the preferred compounds^R is derived from (coconut) C₁₂ -C₁₄ alkyl partial fatty acid, R² is methyl, ApR³ and A' qR⁴ are each monoethoxy.

用于此处的其它阳离子双烷氧基化胺表面活性剂包括具有下式的化合物，

式中R¹为C₁₀-C₁₈烃基，优选C₁₀-C₁₄烷基，独立的p为1至约3，q为1至约3，R²为C₁-C₃烷基，优选甲基，X为阴离子，尤其氯负离子或溴负离子。Other cationic bisalkoxylated amine surfactants useful herein include compounds having the formula,

In the formula, R¹ is C₁₀ -C₁₈ hydrocarbon group, preferably C₁₀ -C₁₄ alkyl group, independently p is 1 to about 3, q is 1 to about 3, R² is C₁ -C₃ alkyl group, preferably methyl base, X is an anion, especially a chloride anion or a bromide anion.

前述类型的其它化合物包括那些其中的乙氧基(CH₂CH₂O)单元(EO)被丁氧基、异丙氧基[CH(CH₃)CH₂O]和[CH₂CH(CH₃)O]单元(i-Pr)或正丙氧基(Pr)，或EO和/或Pr和/或i-Pr单元的组合置换的化合物。所述组分的其它成分和含有所述组分的组合物Other compounds of the foregoing type include those in which the ethoxy (CH₂ CH₂ O) units (EO) are replaced by butoxy, isopropoxy [CH(CH₃ )CH₂ O] and [CH₂ CH(CH₃ ) O] unit (i-Pr) or n-propoxy (Pr), or a compound replaced by a combination of EO and/or Pr and/or i-Pr units. Other components of the components and compositions containing the components

所述组分可以含有其它成分。优选这些成分为常用于此后所述的衣物用洗涤剂或衣物用软化剂的组分。The components may contain other ingredients. These ingredients are preferably components commonly used in laundry detergents or laundry softeners described hereinafter.

本发明的织物软化组分可以存在于洗涤剂组合物或软化组合物中。优选这些组合物为固体，其存在形式为颗粒、挤出物、薄片、块状或片状。The fabric softening component of the present invention may be present in a detergent composition or a softening composition. Preferably, these compositions are solid and are present in the form of granules, extrudates, flakes, blocks or flakes.

所述组合物可以用于自动洗涤或手洗。所述组合物也可以适于预处理或浸泡，或用于主要洗涤后的漂洗或调理织物。The composition can be used for automatic washing or hand washing. The composition may also be suitable for pretreatment or soaking, or for rinsing or conditioning fabrics after a main wash.

本发明的所述组合物也可以含有其它洗涤剂组分。这些其它组分的精确性质及其添加水平将取决于所述组合物或组分的物理形式以及所用洗涤操作的精确性质。The compositions of the present invention may also contain other detergent ingredients. The precise nature of these other components and the level at which they are added will depend on the physical form of the composition or component and the precise nature of the laundering operation employed.

优选本发明组合物含有一种或多种其它洗涤剂组分，所述组分选自如上所述的其它表面活性剂、漂白剂、漂白催化剂、碱体系、其它助洗剂、其它有机聚合物、酶、抑泡剂、皂、钙皂、分散剂、污垢悬浮剂和抗再沉积剂、去污剂、香料、增白剂、光漂白剂和其它的缓蚀剂。Preferably the compositions of the present invention contain one or more other detergent ingredients selected from other surfactants, bleaches, bleach catalysts, alkaline systems, other builders, other organic polymers as described above , enzymes, foam suppressors, soaps, calcium soaps, dispersants, soil suspending and anti-redeposition agents, detergents, perfumes, brighteners, photobleaches and other corrosion inhibitors.

高度优选的其它成分为去污聚合物，尤其聚酯或多糖或其衍生物、纤维素基聚合物(包括羧甲基纤维素、纤维素醚或酯或胺或酰胺改性的纤维素)，包封的香料、泡腾源(优选基于碳酸盐和酸化合物，尤其柠檬酸、苹果酸或马来酸)、膦酸盐助洗剂、染料迁移抑制剂以及加工助剂如水溶助长剂。此处将对这些成分作更详细的描述。Highly preferred further ingredients are soil release polymers, especially polyesters or polysaccharides or derivatives thereof, cellulose based polymers including carboxymethyl cellulose, cellulose ether or ester or amine or amide modified cellulose, Encapsulated perfumes, effervescent sources (preferably based on carbonates and acid compounds, especially citric, malic or maleic acid), phosphonate builders, dye transfer inhibitors and processing aids such as hydrotropes. These ingredients are described in more detail here.

可高度优选包括有羧甲基纤维素化合物(其水平为所述组合物重量的至少0.5％或甚至0.75％或甚至1％)，或者包括或还包括水平为所述组合物重量的至少0.5％或甚至0.75％或甚至1％的多糖。It may be highly preferred to include carboxymethylcellulose compound at a level of at least 0.5% or even 0.75% or even 1% by weight of the composition, or to include or also include at a level of at least 0.5% by weight of the composition Or even 0.75% or even 1% polysaccharides.

可以优选所述组合物含有阳离子软化剂。高度优选的水不溶性季胺化合物具有两个C₁₂-C₂₄烷基或链烯基链，任选被各种官能团如-OH、-O-、-CONH-、-COO-等取代。It may be preferred that the composition contains a cationic softener. Highly preferred water-insoluble quaternary ammonium compounds have two C₁₂ -C₂₄ alkyl or alkenyl chains, optionally substituted with various functional groups such as -OH, -O-, -CONH-, -COO-, and the like.

众所周知的基本不溶于水的季铵化合物具有式R₁R₂R₃R₄NX，式中R₁和R₂代表具有约12-24个碳原子的烃基；R₃和R₄代表含有1至约4个碳原子的烃基；X为阴离子，优选选自卤化物、甲基硫酸根和乙基硫酸根。这些季化软化剂的代表性例子包括二牛油基二甲基氯化铵、甲基硫酸二牛油基二甲基铵、双十六基二甲基氯化铵、二(氢化牛油烷基)二甲基氯化铵、双十八基二甲基氯化铵、双二十烷基二甲基氯化铵、双二十二烷基二甲基氯化铵、甲基硫酸二(氢化牛油基)二甲基铵、双十六烷基二乙基氯化铵、二(椰油烷基)二甲基氯化铵。优选二牛油基二甲基氯化铵、二(氢化牛油烷基)二甲基氯化铵、甲基硫酸二(椰油烷基)二甲基铵。Well-known substantially water-insoluble quaternary ammonium compounds have the formula R₁ R₂ R₃ R₄ NX, wherein R₁ and R₂ represent hydrocarbon groups having about 12-24 carbon atoms; R₃ and R₄ represent A hydrocarbyl group of about 4 carbon atoms; X is an anion, preferably selected from the group consisting of halides, methylsulfate and ethylsulfate. Representative examples of these quaternary softeners include ditallowyldimethylammonium chloride, ditallowyldimethylammonium methylsulfate, dihexadecyldimethylammonium chloride, di(hydrogenated tallow base) dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dieicosyl dimethyl ammonium chloride, dieicosyl dimethyl ammonium chloride, methyl sulfate di( Hydrogenated Tallow) Dimethyl Ammonium, Dicetyl Diethyl Ammonium Chloride, Di(cocoyl) Dimethyl Ammonium Chloride. Preference is given to ditallowdimethylammonium chloride, di(hydrogenated tallowalkyl)dimethylammonium chloride, di(cocoalkyl)dimethylammonium methylsulfate.

此处还合适的有美国专利号4127489(以参考形式并入本文)的咪唑鎓织物软化剂。此处所用术语“织物软化剂”不包括在pH为约6下在20℃的水中的溶解性大于10克/升的阳离子洗涤活性材料。Also suitable herein are the imidazolium fabric softeners of US Patent No. 4,127,489 (incorporated herein by reference). The term "fabric softener" as used herein does not include cationic detergent active materials having a solubility in water at 20°C at a pH of about 6 of greater than 10 grams per liter.

尤其优选的有二牛油基甲基胺。它的商品有来自AKZONV的ArmeenM2HT、来自FARBWERKEHOECHST的Genamin SH301以及来自CECACOMPANY的NoramM2SH。过氧化氢合物漂白剂Especially preferred is ditallowylmethylamine. Its products include ArmeenM2HT from AKZONV, Genamin SH301 from FARBWERKEHOECHST and NoramM2SH from CECACOMPANY. perhydrate bleach

所述组分或组合物的一种优选的其它组分为过氧化氢合物漂白剂如金属过硼酸盐、金属过碳酸盐(尤其钠盐)。过硼酸盐可以为单水合或四水合。过碳酸钠对应式2Na₂CO₃.3H₂O₂并且其商品为结晶固体形式。A preferred further component of the component or composition is a perhydrate bleach such as metal perborates, metal percarbonates (especially sodium salts). Perborate may be monohydrated or tetrahydrated. Sodium percarbonate corresponds_to the formula_{2Na2CO3.3H2O2} and is commercially available as_a crystalline_solid .

过氧单过硫酸钾、钠为用于此处洗涤剂组分的另一种任选的无机过氧化氢合物盐。有机过氧酸漂白剂体系Potassium, sodium peroxymonopersulfate is another optional inorganic perhydrate salt for use in the detergent components herein. Organic Peroxyacid Bleach System

所述组合物或组分的一种优选特征为有机过氧酸漂白剂体系。在一个优选例子中，所述漂白剂体系包括过氧化氢源和有机过氧酸漂白剂前体化合物。通过所述前体与过氧化氢源的原位反应生产有机过氧酸。优选的过氧化氢源包括无机过氧化氢合物漂白剂如要求保护的发明中的过硼酸盐漂白剂。在另一个优选的例子中，将预形成的有机过氧酸直接加入所述组合物中。另一种方案为含有与预形成有机过氧酸结合的过氧化氢源和有机过氧酸前体的混合物的组合物。过氧酸漂白剂前体A preferred feature of the composition or component is an organic peroxyacid bleach system. In a preferred example, the bleach system comprises a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. Organic peroxyacids are produced by in situ reaction of said precursors with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches such as perborate bleaches of the claimed invention. In another preferred example, a preformed organic peroxyacid is added directly to the composition. Another approach is a composition comprising a mixture of a hydrogen peroxide source and an organic peroxyacid precursor in combination with a preformed organic peroxyacid. Peroxyacid Bleach Precursors

过氧酸漂白剂前体是在过水解(perhydrolysis)反应中与过氧化氢反应生成过氧酸的化合物。通常过氧酸漂白剂前体可以表示为

式中L为离去基团，X基本上可以为任意官能团，这样在过水解中生成的过氧酸的结构为

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to form peroxyacids. Usually peroxyacid bleach precursors can be expressed as

In the formula, L is a leaving group, and X can be any functional group substantially, so the structure of the peroxyacid generated in perhydrolysis is

过氧酸漂白剂前体化合物的优选加入水平为所述洗涤剂组合物的0.5-20％(重量)，更优选1-15％(重量)，最优选1.5-10％(重量)。Peroxyacid bleach precursor compounds are preferably incorporated at levels of 0.5-20% by weight of the detergent composition, more preferably 1-15% by weight, most preferably 1.5-10% by weight.

适合的过氧酸漂白剂前体化合物通常含有一个或多个N-或O-酰基基团，可以广泛选择其前体类型。适合的类型包括咪唑和肟的酸酐、酯、酰亚胺、内酰胺和酰化衍生物。属于这些类型的有用材料的例子公开于GB-A-1586789中。适合的酯公开于GB-A-836988、864798、1147871、2143231和EP-A-0170386中。离去基团Suitable peroxyacid bleach precursor compounds generally contain one or more N- or O-acyl groups and there can be a wide choice of precursor types. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials of these types are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. leaving group

离去基团(此后用L基团表示)必须对在最优时间段(如洗涤循环)内进行的过水解反应具有足够的活性。但是，如果L活性太强，这种活化剂将难以稳定地用于漂白组合物中。The leaving group (hereinafter denoted by the L group) must be sufficiently reactive for the perhydrolysis reaction to take place within an optimal time period (eg wash cycle). However, if L is too active, the activator will be difficult to use stably in bleaching compositions.

优选的L基团选自：和

和

及其混合物，式中R¹为含有1-14个碳原子的烷基、芳基或烷芳基，R³为含有1-8个碳原子的烷基链，R⁴为H或R³。Y为H或加溶基。R¹、R³和R⁴的任一个可基本上被下面的任意官能团所取代，这些官能团包括如烷基、羟基、烷氧基、卤素、胺、亚硝酰基、酰胺和铵或烷基铵基团。Preferred L groups are selected from: and

and

and mixtures thereof, wherein R¹ is an alkyl, aryl or alkaryl group containing 1-14 carbon atoms, R³ is an alkyl chain containing 1-8 carbon atoms, and R⁴ is H or R³ . Y is H or a solubilizing group. Any of R¹ , R³ and R⁴ may be substantially substituted with any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl, amide, and ammonium or alkyl ammonium group.

优选的加溶基团为-SO₃^-M⁺、-CO₂^-M⁺、-SO₄^-M⁺、-N⁺(R³)₄X^-和O←N(R³)₃并且最优选-SO₃^-M⁺和-CO₂^-M⁺，式中R³为含有1-4个碳原子的烷基链，M为提供漂白活化剂溶解性的阳离子，X为提供漂白活化剂溶解性的阴离子。优选M为碱金属、铵或取代铵阳离子，最优选钠和钾，X为卤素负离子、氢氧根、甲基硫酸根或乙酸根阴离子。烷基过羧酸漂白剂前体Preferred solubilizing groups are -SO₃^- M⁺ , -CO₂^- M⁺ , -SO₄^- M⁺ , -N⁺ (R³ )₄ X^- and O←N(R³ )₃ and most preferably -SO₃^- M⁺ and -CO₂^- M⁺ , where R³ is an alkyl chain containing 1-4 carbon atoms, M is a cation that provides solubility for bleach activators, and X is a cation that provides solubility for bleach activators of anions. Preferably M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methylsulfate or acetate anion. Alkyl percarboxylic acid bleach precursor

烷基过羧酸漂白剂前体在过水解中形成过羧酸。优选的这类前体在过水解反应中提供过乙酸。Alkyl percarboxylic acid bleach precursors form percarboxylic acids in perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis reaction.

优选酰亚胺类型的烷基过羧酸前体化合物包括N，N，N¹，N¹四乙酰基亚烷基二胺，其中亚烷基含有1-6个碳原子，特别是亚烷基含有1、2和6个碳原子的那些化合物。尤其优选四乙酰基乙二胺(TAED)。优选TAED不存在于本发明的附聚颗粒中，但优选存在于包括所述颗粒的洗涤剂组合物中。Preferred alkyl percarboxylic acid precursor compounds of the imide type include N,N,N¹ ,N¹ tetraacetylalkylenediamines wherein the alkylene group contains 1 to 6 carbon atoms, especially the alkylene group Those compounds containing 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is especially preferred. Preferably TAED is absent from the agglomerated particles of the present invention, but is preferably present in detergent compositions comprising said particles.

其它优选的烷基过羧酸前体包括3，5，5-三甲基己酰氧基苯磺酸钠(异-NOBS)、壬酰氧基苯磺酸钠(NOBS)、乙酰氧基苯磺酸钠(ABS)和五乙酰基葡萄糖。酰胺取代的烷基过氧酸前体Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), acetoxybenzene Sodium Sulfonate (ABS) and Pentaacetyl Glucose. Amide Substituted Alkyl Peroxyacid Precursors

酰胺取代的烷基过氧酸前体化合物在此处适用，其包括具有以下通式的那些化合物：或

Amide substituted alkyl peroxyacid precursor compounds are suitable for use herein and include those compounds having the general formula: or

式中R¹为具有约1至约14个碳原子的烷基，R²为含有约1至14个碳原子的亚烷基，R⁵为H或含有1-10个碳原子的烷基，L基本上可为任何离去基团。这种类型的酰胺取代的漂白活化剂化合物描述于EP-A-0170386。过苯甲酸前体In the formula, R^is an alkyl group having about 1 to about 14 carbon atoms,^R is an alkylene group having about 1 to 14 carbon atoms^, R is H or an alkyl group having 1 to 10 carbon atoms, L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Precursor of perbenzoic acid

过苯甲酸前体化合物在过水解中提供过苯甲酸。适合的O-酰化过苯甲酸前体化合物包括取代和未取代的苯甲酰氧基苯磺酸盐，山梨醇、葡萄糖以及所有糖与苯甲酰化试剂的苯甲酰化产物，以及酰亚胺类型的那些化合物，包括N-苯甲酰琥珀酰亚胺、四苯甲酰基乙二胺和N-苯甲酰取代的脲。适合的咪唑型过苯甲酸前体包括N-苯甲酰咪唑和N-苯甲酰苯并咪唑。其它有用的含N-酰基的过苯甲酸前体包括N-苯甲酰吡咯烷酮、二苯甲酰牛磺酸和苯甲酰基焦谷氨酸。预形成的有机过氧酸Perbenzoic acid precursor compounds provide perbenzoic acid in perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates, sorbitol, glucose, and benzoylation products of all sugars with benzoylating reagents, and acyl Those compounds of the imine type include N-benzoylsuccinimide, tetrabenzoylethylenediamine, and N-benzoyl-substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamate. preformed organic peroxyacids

所述有机过氧酸漂白剂体系可以含有(除了有机过氧酸漂白剂前体化合物或作为其替代品)有机过氧酸漂白剂前体化合物(预形成的疏水有机过氧酸)，通常其水平为0.05-20％(重量)，更优选1-10％(重量)。The organic peroxyacid bleach system may contain (in addition to or as a substitute for the organic peroxyacid bleach precursor compound) an organic peroxyacid bleach precursor compound (pre-formed hydrophobic organic peroxyacid), usually the The level is 0.05-20% by weight, more preferably 1-10% by weight.

一类优选的疏水有机过氧酸化合物为酰胺取代的化合物，其具有以下通式，

或

式中R¹为具有1-14个碳原子的芳基或烷芳基，R²为含有1-14个碳原子的亚烷基、亚芳基和烷亚芳基，R⁵为H或含有1-10个碳原子的烷基、芳基或烷芳基。优选R¹含有约6至12个碳原子。优选R²含有约4至8个碳原子。R¹可以为直链或支链烷基、取代的芳基或含有支化、取代或两者的烷芳基，其可以源于合成源或天然源(包括如牛油)。R²可以有类似的结构变化。R²可以包括烷基、芳基，其中所述R²也可以含有卤素、氮、硫或其它典型的取代基或有机化合物。优选R⁵为H或甲基。R¹和R⁵不应含有超过18的总碳原子数。这类酰胺取代的漂白活化化合物描述于EP-A-0170386。这类试剂的合适的例子包括(6-辛基氨基)-6-氧代-己酸、(6-壬基氨基)-6-氧代-己酸、(6-癸基氨基)-6-氧代-己酸、单过氧邻苯二甲酸镁六水合物、间氯过苯甲酸的镁盐、4-壬基氨基-4-氧代过氧丁酸和二过氧十二烷二酸。这些漂白剂公开于US.4,483,781、U.S.4,634,551、EP 0,133,354、U.S.4,412,934和EP0,170,386。对于本发明目的而言,优选的疏水预形成过氧酸漂白剂化合物为单壬基酰氨过氧羧酸。A preferred class of hydrophobic organic peroxyacid compounds are amide substituted compounds having the general formula,

or

In the formula,^R is an aryl or alkaryl group with 1-14 carbon atoms,^R is an alkylene, arylene and alkarylene group with^1-14 carbon atoms, R is H or contains Alkyl, aryl or alkaryl of 1-10 carbon atoms. Preferably^R1 contains about 6 to 12 carbon atoms. Preferably^R2 contains about 4 to 8 carbon atoms.^R1 can be straight or branched chain alkyl, substituted aryl, or alkaryl containing branching, substitution, or both, which can be derived from synthetic or natural sources including, for example, tallow.^R2 can have similar structural changes. R² may include an alkyl group or an aryl group, wherein the R² may also contain halogen, nitrogen, sulfur or other typical substituents or organic compounds. Preferably R⁵ is H or methyl. R¹ and R⁵ should not contain more than 18 total carbon atoms. Amide substituted bleach activating compounds of this type are described in EP-A-0170386. Suitable examples of such reagents include (6-octylamino)-6-oxo-hexanoic acid, (6-nonylamino)-6-oxo-hexanoic acid, (6-decylamino)-6- Oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate, magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecanedioic acid . These bleaching agents are disclosed in US 4,483,781, US 4,634,551, EP 0,133,354, US 4,412,934 and EP 0,170,386. A preferred hydrophobic preformed peroxyacid bleach compound for the purposes of the present invention is monononylamidoperoxycarboxylic acid.

其它合适的有机过氧酸包括具有不超过7个碳原子的二过氧烷二酸，如二过氧十二双酸、二过氧十四烷二酸和二过氧十六烷二酸。Other suitable organic peroxyacids include diperoxyalkanedioic acids having not more than 7 carbon atoms, such as diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecandioic acid.

其它合适的有机过氧酸包括公开于WO95/032175中的二氨基过氧酸，其具有下面的通式：

Other suitable organic peroxyacids include the diaminoperoxyacids disclosed in WO95/032175, which have the general formula:

式中R选自C₁-C₁₂亚烷基、C₅-C₁₂亚环烷基、C₆-C₁₂亚芳基及其组合；In the formula, R is selected from C₁ -C₁₂ alkylene, C₅ -C₁₂ cycloalkylene, C₆ -C₁₂ arylene and combinations thereof;

R¹和R²独立选自H、C₁-C₁₆烷基和C₆-C₁₂芳基和可以与R³和两个氮一起形成C₃-C₁₂环的基团；R³选自C₁-C₁₂亚烷基、C₅-C₁₂亚环烷基和C₆-C₁₂亚芳基；分别选择n和n’为一整数，使其和为1；分别选择m和m’为一整数，使其和为1；R¹ and R² are independently selected from H, C₁ -C₁₆ alkyl and C₆ -C₁₂ aryl and groups that can form a C₃ -C₁₂ ring together with R³ and two nitrogens; R³ is selected from C₁ -C₁₂ alkylene, C₅ -C₁₂ cycloalkylene and C₆ -C₁₂ arylene; respectively select n and n' as an integer so that the sum is 1; respectively select m and m' is an integer such that its sum is 1;

M选自H、碱金属、碱土金属、铵、链烷醇铵阳离子和自由基及其组合。M is selected from the group consisting of H, alkali metals, alkaline earth metals, ammonium, alkanolammonium cations and free radicals, and combinations thereof.

其它合适的有机过氧酸包括公开于WO95/16673的酰氨基过氧酸，其具有下面的通式：Other suitable organic peroxyacids include the amidoperoxyacids disclosed in WO95/16673, which have the general formula:

X-Ar-CO-NY-R(Z)-CO-OOHX-Ar-CO-NY-R(Z)-CO-OOH

式中X代表氢或配伍的取代基，Ar为芳基，R代表(CH₂)_n，式中n＝2或3，Y和Z分别独立代表选自氢或烷基或芳基或烷芳基或者被配伍的取代基取代的芳基，条件是如果n＝3时，Y和Z的至少一个不为氢。优选苯核上的取代基X为氢或间位或对位取代基，所述取代基选自卤素(通常为氯原子)或一些非释放非干扰基团如烷基(可方便地高达C6如甲基、乙基或丙基)。或者，X可以代表具有下式的仲酰氨过羧酸取代基：In the formula, X represents hydrogen or a compatible substituent, Ar is an aryl group, R represents (CH₂ )_n , where n=2 or 3, Y and Z independently represent hydrogen or alkyl or aryl or alkaryl or aryl substituted by a compatible substituent, provided that if n=3, at least one of Y and Z is not hydrogen. Preferably the substituent X on the benzene nucleus is hydrogen or a meta-position or a para-position substituent selected from halogen (usually a chlorine atom) or some non-releasing non-interfering groups such as alkyl (conveniently up to C6 such as methyl, ethyl or propyl). Alternatively, X may represent a secondary amidopercarboxylic acid substituent having the formula:

-CO-NY-R(Z)-CO-OOH-CO-NY-R(Z)-CO-OOH

式中R、Y、Z和n定义如上。In the formula, R, Y, Z and n are as defined above.

MOOC-R¹CO-NR²-R³-NR⁴-CO-R⁵COOOMMOOC-R¹ CO-NR² -R³ -NR⁴ -CO-R⁵ COOOM

式中R¹选自C₁-C₁₂亚烷基、C₅-C₁₂亚环烷基、C₆-C₁₂亚芳基及其组合；In the formula, R¹ is selected from C₁ -C₁₂ alkylene, C₅ -C₁₂ cycloalkylene, C₆ -C₁₂ arylene and combinations thereof;

此处高度优选邻苯二甲酰氨基过氧酸(PAP)。漂白催化剂Phthalylaminoperoxyacids (PAP) are highly preferred here. bleach catalyst

所述组合物或组分可以包括含有过渡金属漂白催化剂。Said compositions or components may comprise transition metal bleach catalysts.

一类合适的漂白催化剂为含有具有定义漂白活性的过渡金属阳离子如铜、铁或锰阳离子，具有微弱或不具有漂白催化活性的辅助金属阳离子如锌或铝阳离子以及对催化和辅助金属阳离子具有定义稳定常数的螯合剂，尤其乙二胺四乙酸、乙二胺四(亚甲基膦酸)及其水溶性盐。这些催化剂公开于美国专利4,430,243。A class of suitable bleach catalysts are those containing transition metal cations such as copper, iron or manganese cations with defined bleach activity, auxiliary metal cations such as zinc or aluminum cations with weak or no bleach catalytic activity and defined catalytic and auxiliary metal cations Stable constant chelating agents, especially ethylenediaminetetraacetic acid, ethylenediaminetetrakis(methylenephosphonic acid) and their water-soluble salts. These catalysts are disclosed in US Patent 4,430,243.

其它类型的漂白催化剂包括公开于美国专利5,246,621和美国专利5,244,594中的锰基络合物。这些催化剂的优选例子包括Mn^IV₂(u-O)₃(1，4，7-三甲基-1，4，7-三氮杂环壬烷)₂-(PF₆)₂；Mn^III₂(u-O)₁(u-OAc)₂(1，4，7-三甲基-1，4，7-三氮杂环壬烷)₂-(C1O₄)₂；Mn^IV₄(u-O)₆(1，4，7-三氮杂环壬烷)₄-(C1O₄)₂；Mn^IIIMn^IV₄(u-O)₁(u-OAc)₂(1，4，7-三甲基-1，4，7-三氮杂环壬烷)₂-(C1O₄)₃及其混合物。其它漂白催化剂公开于欧洲专利申请公布号549,272。适用于此的其它配体包括1，5，9-三甲基-1，5，9-三氮杂环十二烷、2-甲基-1，4，7-三氮杂环壬烷、2-甲基-1，4，7-三氮杂环壬烷、1，2，4，7-四甲基-1，4，7-三氮杂环壬烷及其混合物。Other types of bleach catalysts include the manganese-based complexes disclosed in US Patent 5,246,621 and US Patent 5,244,594. Preferred examples of these catalysts include Mn^IV₂ (uO)₃ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(PF₆ )₂ ; Mn^III₂ (uO )₁ (u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(C1O₄ )₂ ; Mn^IV₄ (uO)₆ (1, 4,7-triazacyclononane)₄ -(C1O₄ )₂ ; Mn^III Mn^IV₄ (uO)₁ (u-OAc)₂ (1,4,7-trimethyl-1,4,7 -triazacyclononane)₂ -(C1O₄ )₃ and mixtures thereof. Other bleach catalysts are disclosed in European Patent Application Publication No. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-Methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

此处适用的漂白催化剂也可以选用于本发明。合适的漂白催化剂的例子参见美国专利4,246,612和美国专利5,227,084。还参见美国专利5,194,416,其提及单核锰(IV)络合物如Mn(1，4，7-三甲基-1，4，7-三氮杂环壬烷)(OCH₃)₃(PF₆)。Bleach catalysts suitable for use herein may also be selected for use in the present invention. Examples of suitable bleach catalysts are found in US Patent 4,246,612 and US Patent 5,227,084. See also U.S. Patent 5,194,416, which mentions mononuclear manganese(IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(_OCH3 )₃ ( PF₆ ).

公开于美国专利5,114,606的另一类合适的漂白催化剂为具有一配体的锰(III)和/或(IV)的水溶性络合物，所述配体为具有至少三个连续C-OH官能团的非羧酸盐的多羟基化合物。优选的配体包括山梨醇、艾杜醇、卫矛醇、甘露糖醇、木糖醇(xylithol)、阿拉伯醇、福寿糖醇、内消旋-赤藓醇、内消旋肌醇、乳糖及其混合物。Another class of suitable bleach catalysts disclosed in U.S. Pat. No. 5,114,606 are water-soluble complexes of manganese (III) and/or (IV) with a ligand having at least three consecutive C-OH functional groups of non-carboxylate polyols. Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylithol, arabitol, adolitol, meso-erythritol, meso-inositol, lactose and its mixture.

美国专利5,114,611提及一种包括具有一个非(大)环的配体的过渡金属(包括锰、钴、铁或铜)的络合物。所述配体具有下式：

US Patent 5,114,611 mentions a complex of transition metals including manganese, cobalt, iron or copper comprising ligands with one non-(macro)ring. The ligand has the formula:

式中R¹、R²、R³和R⁴可以分别选自H、取代烷基和芳基，使得各个R¹-N＝C-R²和R³-C＝N-R⁴形成五元或六元环。可以进一步取代所述环。B为选自O、S、CR⁵R⁶、NR⁷和C＝O的桥基，其中R⁵、R⁶和R⁷可分别为H、烷基或芳基(包括取代或未取代基团)。优选的配体包括吡啶、哒嗪、嘧啶、吡嗪、咪唑、吡唑和三唑环。任选所述环可以被各种取代基如烷基、芳基、烷氧基、卤化物和硝基所取代。尤其优选配体2，2’-双吡啶胺。优选的漂白催化剂包含钴、铜、锰、铁、-双吡啶基甲烷和-双吡啶胺络合物。高度优选的催化剂包括Co(2，2’-双吡啶胺)Cl₂、二(异硫氰酸根合)双吡啶胺-钴(II)、三(二吡啶胺)-高氯酸钴(II)、Co(2，2-双吡啶胺)₂O₂ClO₄、双-(2，2’-双吡啶胺)高氯酸铜(II)、三(二-2-吡啶胺)高氯酸铁(II)及其混合物。In the formula, R¹ , R² , R³ and R⁴ can be selected from H, substituted alkyl and aryl respectively, so that each R¹ -N=CR² and R³ -C=NR⁴ forms a five-membered or six-membered ring . The rings may be further substituted. B is a bridging group selected from O, S, CR⁵ R⁶ , NR⁷ and C=O, wherein R⁵ , R⁶ and R⁷ can be H, alkyl or aryl (including substituted or unsubstituted groups ). Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally the ring may be substituted with various substituents such as alkyl, aryl, alkoxy, halide and nitro. Particular preference is given to the ligand 2,2'-bispyridylamine. Preferred bleach catalysts comprise cobalt, copper, manganese, iron, -bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bipyridylamine)_Cl2 , bis(isothiocyanato)bipyridylamine-cobalt(II), tris(bipyridylamine)-cobalt(II) perchlorate , Co(2,2-bispyridylamine)₂ O₂ ClO₄ , bis-(2,2'-bispyridylamine) copper (II) perchlorate, tris(bis-2-pyridylamine) ferric perchlorate (II) and mixtures thereof.

其它例子包括与四-N-配位物和双-N-配位物配体进行络合的双核锰，其包括N₄Mn^III(u-O)₂Mn^IVN₄)⁺和[Bipy₂Mn^III(u-O)₂Mn^IVbipy₂]-(ClO₄)₃。Other examples include binuclear manganese complexed with tetra-N-coordinate and bi-N-coordinate ligands, including N₄ Mn^III (uO)₂ Mn^IV N₄ )⁺ and [Bipy₂ Mn^III (uO)₂ Mn^IV bipy₂ ]-(ClO₄ )₃ .

其它漂白催化剂描述于如欧洲专利申请公布号408,131(钴络合物催化剂)、欧洲专利申请公布号384,503和306,089(金属卟啉催化剂)、U.S.4,728,455(锰/多配位物配体催化剂)、U.S.4,711,748和欧洲专利申请公布号224,952(在硅铝酸盐催化剂上吸收的锰)、U.S.4,601,845(承载了锰盐和锌盐或镁盐的硅铝酸盐载体)、U.S.4,626,373(锰/配体催化剂)、U.S.4,119,557(铁络合物催化剂)、德国专利说明书2,054,019(钴螯合物催化剂)、加拿大专利866,191(含过渡金属的盐)、U.S.4,430,243(具有锰阳离子和非催化的金属阳离子的螯合剂)以及U.S.4,728,455(葡萄糖酸锰催化剂)。Other bleach catalysts are described, for example, in European Patent Application Publication No. 408,131 (cobalt complex catalysts), European Patent Application Publication Nos. 384,503 and 306,089 (metalloporphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalysts), U.S. 4,711,748 and European Patent Application Publication Nos. 224,952 (manganese absorbed on aluminosilicate catalysts), U.S. 4,601,845 (aluminosilicate supports loaded with manganese and zinc or magnesium salts), U.S. 4,626,373 (manganese/ligand catalyst ), U.S.4,119,557 (iron complex catalyst), German patent specification 2,054,019 (cobalt chelate catalyst), Canadian patent 866,191 (transition metal-containing salt), U.S.4,430,243 (chelating agent with manganese cation and non-catalytic metal cation ) and U.S. 4,728,455 (manganese gluconate catalyst).

通常以催化有效量将所述漂白催化剂用于此处的组合物和方法中。“催化有效量”是指不管在何种比较测试条件下均足以改进漂白和从目标基材上除去污渍和色斑的量。根据所用的洗涤类型和使用者的习惯变化所述测试条件。在洗衣操作中，一些使用者选择使用热水，另一些使用温水或者甚至冷水。当然，漂白催化剂的催化性能将受这种因素的影响，并且可以适当地调节用于全配方洗涤剂和漂白组合物中所用的漂白催化剂的水平。实际上(不受限制)，可以调节此处的组合物和方法从而提供在含水洗涤液中约至少千万分之一份的活性漂白催化剂物质，并优选提供在洗涤液中约1ppm至约200ppm的催化剂物质。为了进一步说明这一点，在40℃和pH为10，在采用过硼酸盐和漂白剂前体的欧洲条件下，约3微摩尔的锰催化剂是有效的。在美国条件下，可能需要增加浓度3-5倍从而获得相同的结果。重金属离子螯合剂The bleach catalysts are generally used in the compositions and methods herein in catalytically effective amounts. By "catalytically effective amount" is meant an amount sufficient to improve bleaching and stain and stain removal from the target substrate regardless of the comparative test conditions. The test conditions were varied according to the type of laundering used and the habits of the user. In laundry operations, some users choose to use hot water, others use warm or even cold water. Of course, the catalytic performance of the bleach catalyst will be influenced by such factors, and the level of bleach catalyst used in fully formulated detergent and bleach compositions can be adjusted appropriately. In practice (without limitation), the compositions and methods herein can be adjusted to provide about at least one part per million active bleach catalyst species in the aqueous wash liquor, and preferably about 1 ppm to about 200 ppm in the wash liquor. catalyst substance. To further illustrate this point, at 40°C and pH 10, under European conditions using perborate and bleach precursors, about 3 micromolar manganese catalyst was effective. Under US conditions, it may be necessary to increase the concentration by a factor of 3-5 to obtain the same result. Heavy metal ion chelating agent

本发明组合物或组分优选含有作为任选组分的重金属离子螯合剂。此处重金属离子螯合剂是指充当重金属离子螯合剂的组分。这些组分还可具有钙和镁的螯合能力，但优选它们对结合重金属离子如铁、锰和铜具有选择性。The compositions or components of the present invention preferably contain, as an optional ingredient, a heavy metal ion sequestrant. A heavy metal ion sequestrant here refers to a component that acts as a heavy metal ion sequestrant. These components may also have calcium and magnesium chelating capacity, but preferably they are selective for binding heavy metal ions such as iron, manganese and copper.

重金属离子螯合剂通常的存在量为所述组合物或组分重量的0.005-10％，优选0.1-5％，更优选0.25-7.5％，最优选0.3-2％。Heavy metal ion sequestrants are typically present at 0.005-10%, preferably 0.1-5%, more preferably 0.25-7.5%, most preferably 0.3-2%, by weight of the composition or component.

此处适用的重金属离子螯合剂包括有机膦酸盐如氨基亚烷基聚(亚烷基膦酸盐)、碱金属乙烷1-羟基二膦酸盐和次氮基亚丙基膦酸盐。Heavy metal ion sequestrants useful herein include organic phosphonates such as aminoalkylene poly(alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates and nitrilopropylene phosphonates.

在上面化合物中，优选的重金属离子螯合剂为二亚乙基三胺五(亚甲基膦酸盐)、乙二胺三(亚甲基膦酸盐)、己二胺四(亚甲基膦酸盐)和羟基-亚乙基1，1-二膦酸盐、1，1-羟己烷二膦酸和1，1-羟乙烷二亚甲基膦酸。Among the above compounds, preferred heavy metal ion chelating agents are diethylene triamine penta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) salt) and hydroxy-ethylene 1,1-diphosphonate, 1,1-hydroxyhexanediphosphonic acid and 1,1-hydroxyethane dimethylenephosphonic acid.

此处适用的其它适合的重金属离子螯合剂包括次氮基三乙酸和多氨基羧酸如乙二氨基四乙酸、乙二胺二丁二酸、乙二胺二戊二酸、2-羟基丙二胺二丁二酸或其任意盐。Other suitable heavy metal ion sequestrants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropanedi Amine disuccinic acid or any salt thereof.

此处适用的其它适合的重金属离子螯合剂为亚氨基二乙酸衍生物如2-羟乙基二乙酸或甘油基亚氨基二乙酸(描述于EP-A-317,542和EP-A-399,133)。描述于EP-A-516,102的亚氨基二乙酸-N-2-羟丙基磺酸和天冬氨酸N-羧甲基N-2-羟丙基-3-磺酸螯合剂也适用于此。描述于EP-A-509,382的β-丙氨酸-N，N’-二乙酸、天冬氨酸-N，N’-二乙酸、天冬氨酸-N-单乙酸和亚氨基二丁二酸螯合剂也是适合的。Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid (described in EP-A-317,542 and EP-A-399,133). The iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelating agents described in EP-A-516,102 are also suitable here . β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodibutylene, described in EP-A-509,382 Acid sequestrants are also suitable.

EP-A-476,257描述了适合的以氨基为基础的螯合剂。EP-A-510,331描述了由胶原蛋白、角蛋白或酪蛋白衍生而来的适合的螯合剂。EP-A-528,859描述了适合的烷基亚氨基二乙酸螯合剂。吡啶二羧酸和2-膦酰丁烷-1，2，4-三羧酸也是适合的。甘氨酰胺-N，N’-二丁二酸(GADS)、乙二胺-N-N’-二戊二酸(EDDG)和2-羟基丙二胺-N-N’-二丁二酸(HPDDS)也是适合的。EP-A-476,257 describes suitable amino-based chelating agents. EP-A-510,331 describes suitable chelating agents derived from collagen, keratin or casein. EP-A-528,859 describes suitable alkyliminodiacetic acid sequestrants. Also suitable are dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Glycinamide-N,N'-disuccinic acid (GADS), Ethylenediamine-N-N'-diglutaric acid (EDDG), and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) is also suitable.

尤其优选二亚乙基三胺五乙酸、乙二胺-N，N’-二丁二酸(EDDS)和1，1-羟乙烷二膦酸或其碱金属盐、碱土金属盐、铵盐或取代铵盐，或其混合物。酶Especially preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N,N'-disuccinic acid (EDDS) and 1,1-hydroxyethanediphosphonic acid or their alkali metal, alkaline earth metal, ammonium salts or substituted ammonium salts, or mixtures thereof. enzyme

用于此处组分或组合物的另一类优选的成分是一种或多种添加的酶。Another preferred class of ingredients for use in the components or compositions herein is one or more additional enzymes.

优选添加的酶材料包括常规加入洗涤剂组合物中的商业供应的脂酶、角质素酶、淀粉酶、中性和碱性蛋白酶、纤维素酶、endolase、酯酶、果胶酶、乳糖酶和过氧化物酶。适合的酶在美国专利3,519,570和3,533,139中进行了讨论。Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidase. Suitable enzymes are discussed in US Patent Nos. 3,519,570 and 3,533,139.

优选的商品蛋白酶包括由Novo IndustriesA/S(丹麦)以Alcalase、Savinase、Primase、Durazym和Esperase的商品名销售的蛋白酶、由Gist-Brocades以Maxatase、Maxacal和Maxapem的商品名销售的蛋白酶、由Genencor International销售的的蛋白酶以及由Solvay Enzymes以Opticlean和Optimase的商品名出售的那些蛋白酶。可以加入本发明组合物的蛋白酶可以以所述组合物重量的0.0001-4％的活性酶的水平加入到本发明的组合物中。Preferred commercial proteases include those sold under the trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), the proteases sold under the trade names Maxatase, Maxacal and Maxapem by Gist-Brocades, the proteases sold by Genencor International and those proteases sold by Solvay Enzymes under the tradenames Opticlean and Optimase. Proteases that can be added to the compositions of the invention can be added to the compositions of the invention at a level of 0.0001-4% active enzyme by weight of the composition.

优选的淀粉酶包括如由地衣芽孢杆菌(B licheniformis)的特定菌株获得的α-淀粉酶，其更详细内容描述于GB-1,269,839(Novo)。优选的商品淀粉酶包括如由Gist-Brocades以Rapidase的商品名销售的那些、由NovoIndustriesA/S以Termamyl，Duramyl和BAN的商品名出售的那些淀粉酶。高度优选的淀粉酶可以为描述于PCT/US9703635和WO95/26397和WO96/23873的那些淀粉酶。Preferred amylases include alpha-amylases such as those obtained from a particular strain of Bacillus licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercial amylases include those sold under the tradename Rapidase by Gist-Brocades, those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Highly preferred amylases may be those described in PCT/US9703635 and WO95/26397 and WO96/23873.

淀粉酶可以以0.0001-2％(重量)的活性酶水平加入本发明的组合物中。Amylases may be added to the compositions of the present invention at active enzyme levels of 0.0001-2% by weight.

脂解酶可以以0.0001-2％(重量)，优选0.001-1％(重量)，最优选0.001-0.5％(重量)的活性脂解酶的水平存在。The lipolytic enzyme may be present at a level of 0.0001-2% by weight, preferably 0.001-1% by weight, most preferably 0.001-0.5% by weight of active lipolytic enzyme.

脂酶可以是源于真菌或细菌，通过如由Humicola sp.，Thermomyces sp.或Pseudomonas sp.菌株生产获得。来自这些菌株的化学或基因改性突变体的脂酶也适用于此。优选脂酶衍生自类产碱假单胞菌(Pseudomonas pseudoalcaligenes)，其描述于授权的欧洲专利EP-B-0218272。Lipases may be of fungal or bacterial origin, eg produced by Humicola sp., Thermomyces sp. or Pseudomonas sp. strains. Lipases from chemically or genetically modified mutants of these strains are also suitable for use here. Preferably the lipase is derived from Pseudomonas pseudoalcaligenes as described in granted European patent EP-B-0218272.

此处另一种优选的脂酶通过克隆来自Humicola lanuginosa的基因并且在Aspergillus oryza(宿主)内进行表达获得(描述于欧洲专利申请EP-A-0258 068)，其由Novo Industri A/S，Bagsvaerd，Denmark以Lipolase的商品名获得商业供应。这种脂酶也描述于1989年3月7日授权予Huge-Jensen等的美国专利4,810,414。添加的有机聚合物Another preferred lipase here is obtained by cloning the gene from Humicola lanuginosa and expressing it in Aspergillus oryza (host) (described in European Patent Application EP-A-0258 068) from Novo Industri A/S, Bagsvaerd , Denmark is commercially available under the tradename Lipolase. This lipase is also described in US Patent 4,810,414, issued March 7,1989 to Huge-Jensen et al. Added organic polymer

有机聚合物为此处组合物或组分的优选添加组分，并且优选以任何颗粒组分的组分的形式存在，其中所述聚合物可以用于将颗粒组分相互粘合在一起。此处的有机聚合物是指通常用作洗涤剂组合物的分散剂、抗再沉积剂或去污剂的基本上任意聚合有机化合物。Organic polymers are a preferred additional component of the compositions or components herein, and are preferably present as a component of any particulate component where the polymer can serve to bind the particulate components to one another. Organic polymer here refers to essentially any polymeric organic compound commonly used as a dispersant, antiredeposition agent or soil release agent in detergent compositions.

通常加入本发明洗涤剂组合物的有机聚合物的水平为所述组合物或组分重量的0.01-30％，优选0.1-15％，最优选0.5-10％。Organic polymers are typically incorporated into the detergent compositions of the present invention at a level of from 0.01 to 30%, preferably from 0.1 to 15%, most preferably from 0.5 to 10% by weight of the composition or component.

有机聚合物的例子包括水溶性有机均聚或共聚多元羧酸或它们的盐，其中所述多元羧酸包括被不超过两个碳原子相互分开的至少两个羧基。后面类型的聚合物公开于GB-A-1,596,756。这些盐的例子为具有1000-5000的重均分子量(MWt)的聚丙烯酸酯以及它们与马来酸酐的共聚物，这些共聚物的分子量为2000-100,000，尤其40,000-80,000。Examples of organic polymers include water-soluble organic homo- or co-polymeric polycarboxylic acids or their salts, wherein the polycarboxylic acids include at least two carboxyl groups separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of these salts are polyacrylates having a weight average molecular weight (MWt) of 1000-5000 and their copolymers with maleic anhydride, these copolymers having a molecular weight of 2000-100,000, especially 40,000-80,000.

聚氨基化合物适用于此，它们包括如公开于EP-A-305282、EP-A-305283和EP-A-351629的由天冬氨酸衍生而来的那些物质。Polyamino compounds are suitable for use herein and include those derived from aspartic acid as disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

含有选自马来酸、丙烯酸、聚天冬氨酸和乙烯醇单体的三元共聚物，尤其平均分子量为5,000-10,000的那些共聚物也适用于此。Terpolymers containing monomers selected from the group consisting of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5,000-10,000 are also suitable for use herein.

适于加入此处洗涤剂组合物的其它有机聚合物包括纤维素衍生物如甲基纤维素、羧甲基纤维素、羟丙基甲基纤维素和羟乙基纤维素。Other organic polymers suitable for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

其它适用的有机聚合物为聚乙二醇，尤其分子量为1000-10000，更优选为2000-8000，最优选约4000的那些聚乙二醇。Other suitable organic polymers are polyethylene glycols, especially those having a molecular weight of 1000-10000, more preferably 2000-8000, most preferably about 4000.

聚环氧乙烷为优选的添加组分，尤其与此处的粘土一起作为保湿剂存在于颗粒中，优选也与蜡或油相结合。Polyethylene oxide is a preferred added component, especially in combination with the clay herein as humectant in the granules, preferably also in combination with waxes or oils.

此处高度优选的聚合组分为根据Scheibel等人的美国专利4,968,451和Gosselink等人的美国专利5,415,807，尤其根据美国专利申请号60/051517的棉织品和非棉织品去污聚合物。Highly preferred polymeric components herein are cotton and non-cotton soil release polymers according to Scheibel et al. US Patent No. 4,968,451 and Gosselink et al. US Patent No. 5,415,807, especially according to US Patent Application No. 60/051517.

此处使用的优选粘土分散剂/抗再沉积剂的另一类有机化合物可以为下式的乙氧基化阳离子单胺和二胺，式中X为非离子基团，选自H、C₁-C₄烷基或羟烷基酯或醚基及其组合，a为0-20，优选0-4(如亚乙基、亚丙基、六亚甲基)，b为1或0；对于阳离子单胺(b＝0)而言，n至少为16，通常范围为20-35；对于阳离子二胺(b＝1)而言，n至少为约12，通常范围为约12至42。Another class of organic compounds of the preferred clay dispersants/anti-redeposition agents for use herein may be ethoxylated cationic monoamines and diamines of the formula, In the formula, X is a non-ionic group selected from H, C₁ -C₄ alkyl or hydroxyalkyl esters or ether groups and combinations thereof, a is 0-20, preferably 0-4 (such as ethylene, propylene group, hexamethylene), b is 1 or 0; for cationic monoamines (b=0), n is at least 16, usually in the range of 20-35; for cationic diamines (b=1), n is at least about 12 and typically ranges from about 12 to 42.

此处所用的其它分散剂/再沉积剂描述于EP-B-011965和美国专利4,659,802和美国专利4,664,848。抑泡体系Other dispersants/redeposition agents useful herein are described in EP-B-011965 and US Patents 4,659,802 and 4,664,848. Antifoam system

当配制机洗组合物时，此处组分和洗涤剂组合物可以含有抑泡体系，其存在水平为所述组合物或组分重量的0.01-15％，优选0.02-10％，最优选0.05-3％。When formulating machine wash compositions, the components and detergent compositions herein may contain a suds suppressing system present at a level of 0.01-15%, preferably 0.02-10%, most preferably 0.05% by weight of the composition or component. -3%.

适用于此的抑泡体系可以基本上包括任意已知的消泡化合物，包括如硅酮消泡剂和2-烷基alcanol消泡化合物。Foam suppressing systems suitable for use herein can comprise essentially any known antifoam compound including, for example, silicone antifoams and 2-alkyl alcanol antifoam compounds.

此处的消泡化合物是指任何能够用于如抑制由洗涤剂组合物溶液产生(尤其在搅拌溶液的情况下)的泡沫的化合物或这些化合物的混合物。By antifoam compound is meant herein any compound or mixture of compounds which can be used, for example, to suppress foam arising from a solution of a detergent composition, especially when the solution is agitated.

用于此处的尤其优选的消泡化合物为此处定义作为任意消泡化合物的包括硅酮组分的硅酮消泡化合物。这些硅酮消泡化合物通常也含有二氧化硅组分。此处所用和工业上通用的术语“硅酮”包括含有硅氧烷单元和不同类型烃基的各种较高分子量聚合物。优选硅酮消泡化合物为硅氧烷，尤其具有三甲代甲硅烷基端基封闭单元的聚二甲基硅氧烷。Particularly preferred antifoam compounds for use herein are silicone antifoam compounds including a silicone component defined herein as optional antifoam compounds. These silicone antifoam compounds usually also contain a silica component. The term "silicone" as used herein and commonly used in the industry includes various higher molecular weight polymers containing siloxane units and hydrocarbyl groups of different types. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having trimethylsilyl end-blocking units.

其它适合的消泡化合物包括单羧基脂肪酸及其可溶性盐。这些材料描述于1960年9月27日授权予Wayne St.John的美国专利2,954,347。用作抑泡剂的单羧基脂肪酸及其盐的烃链通常具有10-24个碳原子，优选12-18个碳原子。适合的盐包括碱金属盐如钠、钾和锂盐以及铵盐和链烷醇铵盐。Other suitable antifoam compounds include monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The hydrocarbon chains of the monocarboxylic fatty acids and their salts used as suds suppressors generally have 10-24 carbon atoms, preferably 12-18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium, as well as ammonium and alkanolammonium salts.

其它适合的消泡化合物包括如高分子量的脂肪酯(如脂肪酸三甘油酯)、一价醇的脂肪酸酯、脂族C₁₈-C₄₀酮(如硬脂酮)N-烷基化氨基三嗪如三至六烷基三聚氰胺或二至四烷基二胺氯化三嗪，它们是氰尿酰氯与含有1-24个碳原子的二摩尔或三摩尔伯或仲胺形成的产物、环氧丙烷、双硬脂酸酰胺和单硬脂基二碱金属(如钠、钾、锂)磷酸盐和磷酸酯。Other suitable antifoam compounds include, for example, high molecular weight fatty esters (such as fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈ -C₄₀ ketones (such as stearyl ketone), N-alkylated amino triglycerides, Azines such as tri to hexaalkyl melamines or di to tetraalkyl diamine triazine chlorides, which are products of cyanuric chloride with two or three moles of primary or secondary amines containing 1 to 24 carbon atoms, epoxy Propane, bisstearamide and monostearyl dialkali metal (eg sodium, potassium, lithium) phosphates and phosphate esters.

优选的抑泡体系包括：Preferred suds suppressor systems include:

(a)消泡化合物，优选硅酮消泡化合物，最优选硅酮消泡化合物，其包括以下组合：(a) Antifoam compounds, preferably silicone antifoam compounds, most preferably silicone antifoam compounds, comprising combinations of:

(i)聚二甲基硅氧烷，其水平为硅酮消泡化合物重量的50-99％，优选75-95％；和(i) Dimethicone at a level of 50-99%, preferably 75-95%, by weight of the silicone antifoam compound; and

(ii)二氧化硅，其水平为硅酮/二氧化硅消泡化合物重量的1-50％，优选5-25％；(ii) silica at a level of 1-50%, preferably 5-25% by weight of the silicone/silica antifoam compound;

其中所述二氧化硅/硅酮消泡化合物的加入水平为5-50％，优选10-40％(重量)；Wherein said silica/silicone antifoam compound is added at a level of 5-50%, preferably 10-40% by weight;

(b)分散剂化合物，最优选包括硅酮二元醇的耙形(rake)共聚物，聚氧化烯的量为72-78％，环氧乙烷与环氧丙烷之比为1∶0.9至1∶1.1，其水平为0.5-10％，优选1-10％(重量)；尤其优选的这类硅酮二元醇耙形共聚物为DCO544，购自DOW Corning的名为DCO544的商品；(b) a dispersant compound, most preferably comprising a rake copolymer of silicone diol, in an amount of polyoxyalkylene of 72-78%, in a ratio of ethylene oxide to propylene oxide of 1:0.9 to 1:1.1 at a level of 0.5-10%, preferably 1-10% by weight; an especially preferred type of silicone diol rake copolymer of this type is DCO544, commercially available under the name DCO544 from DOW Corning;

(c)惰性载体流体化合物，最优选含有乙氧基化程度为5-50，优选8-15的C₁₆-C₁₈乙氧基化醇，其水平为5-80％，优选10-70％(重量)；(c) an inert carrier fluid compound, most preferably containing a_C16 -_C18 ethoxylated alcohol with a degree of ethoxylation of 5-50, preferably 8-15, at a level of 5-80%, preferably 10-70% (weight);

高度优选的颗粒抑泡体系描述于EP-A-0210731并且包括硅酮消泡化合物和熔点范围为50-85℃的有机载体材料，其中所述有机载体材料包括甘油单酯和具有12-20个碳原子的脂肪酸，EP-A-0210721公开了其它优选的颗粒抑泡体系，其中有机载体材料为熔点45℃-80℃并且其碳链含有12-20个碳原子的脂肪酸或醇，或其混合物。A highly preferred granular antifoam system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50-85°C, wherein the organic carrier material comprises a monoglyceride and has 12-20 Fatty acids with carbon atoms, EP-A-0210721 discloses other preferred granular antifoam systems, wherein the organic carrier material is a fatty acid or alcohol with a melting point of 45°C-80°C and its carbon chain contains 12-20 carbon atoms, or a mixture thereof .

其它高度优选的抑泡体系包括聚二甲基硅氧烷或硅酮混合物，如聚二甲基硅氧烷、硅铝酸盐和多元羧酸聚合物如laic和丙烯酸的共聚物。Other highly preferred suds suppressing systems include polydimethylsiloxanes or silicone blends such as polydimethylsiloxanes, aluminosilicates and polycarboxylic acid polymers such as copolymers of laic and acrylic acid.

也高度优选存在皂。聚合染料迁移抑制剂It is also highly preferred that soap is present. polymeric dye transfer inhibitor

此处的组分或组合物也可以包括0.01-10％，优选0.05-0.5％(重量)的聚合染料迁移抑制剂。The components or compositions herein may also include 0.01-10%, preferably 0.05-0.5%, by weight, of a polymeric dye transfer inhibiting agent.

聚合染料迁移抑制剂优选选自聚胺N-氧化物聚合物，N-乙烯基吡咯烷酮与N-乙烯基咪唑的共聚物、聚乙烯基吡咯烷酮聚合物或其组合，由此这些聚合物可以是交联聚合物。荧光增白剂The polymeric dye transfer inhibitors are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof whereby these polymers can be cross-linked joint polymer. Fluorescent whitening agent

此处的组分和组合物均优选含有为所述组分重量的约0.05-5％，更优选0.07-3％或者甚至0.1-2.5％或者，为所述组合物重量的约0.05-5％，更优选0.1-3％或者甚至0.12-2.5％的某些类型的亲水荧光增白剂。The components and compositions herein each preferably contain from about 0.05-5% by weight of the component, more preferably 0.07-3% or even 0.1-2.5% or, alternatively, from about 0.05-5% by weight of the composition , more preferably 0.1-3% or even 0.12-2.5% of certain types of hydrophilic optical brighteners.

此处适用的亲水荧光增白剂包括那些具有以下结构式的化合物。

式中R₁选自苯胺基、N-2-双-羟乙基和NH-2-羟乙基；R₂选自N-2-双-羟乙基、N-2-羟乙基-N-甲基氨基、吗啉基、氯和氨基；M为成盐阳离子如钠或钾。Hydrophilic optical brighteners suitable for use herein include those compounds having the following structural formulas.

In the formula, R₁ is selected from aniline, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N - methylamino, morpholino, chlorine and amino; M is a salt-forming cation such as sodium or potassium.

在上式中，当R₁为苯胺基，R₂为N-2-双-羟乙基，M为阳离子如钠时，所述增白剂为4，4’-双[(4-苯胺基-6-(N-2-双-羟乙基)-s-三嗪-2-基)氨基]-2，2’-茋二磺酸和二钠盐。这种具体的增白剂由Ciba-GeigyCorporation以Tinopal-UNPA-GX的商品名出售。Tinopal-CBS-X和Tinopal-UNPA-GX是此处洗涤剂组合物适用的优选亲水荧光增白剂。In the above formula, when R₁ is an anilino group, R₂ is N-2-bis-hydroxyethyl, and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4-anilino -6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid and disodium salt. This particular brightener is sold under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-CBS-X and Tinopal-UNPA-GX are preferred hydrophilic optical brighteners for detergent compositions herein.

在上式中，当R₁为苯胺基，R₂为N-2-羟乙基-N-2-甲氨基和M为阳离子如钠时，所述增白剂为4，4’-双[(4-苯胺基-6-(N-2-双-羟乙基-N-甲基氨基)-s-三嗪-2-基)-氨基]2，2’-茋二磺酸二钠盐。这种具体的增白剂由Ciba-Geigy Corporation以Tinopal-5BM-GX的商品名出售。In the above formula, when R₁ is anilino, R₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the whitening agent is 4,4'-bis[ (4-anilino-6-(N-2-bis-hydroxyethyl-N-methylamino)-s-triazin-2-yl)-amino]2,2'-stilbene disulfonic acid disodium salt . This particular brightener is sold under the tradename Tinopal-5BM-GX by Ciba-Geigy Corporation.

在上式中，当R₁为苯胺基，R₂为吗啉基和M为阳离子如钠时，所述增白剂为4，4’-双[(4-苯胺基-6-吗啉基-s-三嗪-2-基)氨基]2，2’-茋二磺酸钠盐。这种具体的增白剂由Ciba-Geigy Corporation以Tinopal-DMS-X和Tinopal AMS-GX的商品名出售。聚合去污剂In the above formula, when_R1 is anilino,_R2 is morpholino and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4-anilino-6-morpholino -s-triazin-2-yl)amino]2,2'-stilbene disulfonic acid sodium salt. Such specific brighteners are sold under the tradenames Tinopal-DMS-X and Tinopal AMS-GX by Ciba-Geigy Corporation. polymeric detergent

聚合去污剂(此后称为“SRA”)可以任选用于本发明的组分或组合物中。如果使用，通常包括0.01-10.0％，一般为0.1-5％，优选0.2-3.0％(重量)的SRA。Polymeric soil release agents (hereinafter "SRA") may optionally be used in the components or compositions of the present invention. If used, typically 0.01-10.0%, typically 0.1-5%, preferably 0.2-3.0% by weight of SRA is included.

优选的SRA通常具有亲水部分和疏水部分，亲水部分使疏水纤维如聚酯和尼龙的表面亲水化，疏水部分沉积在疏水纤维上面并且在完成洗涤和漂洗循环中保持粘附其上，由此充当亲水部分的锚。这使得用SRA处理的污垢在后续洗涤程序中更易于被清除。Preferred SRAs typically have a hydrophilic portion that hydrophilizes the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic portion that deposits on the hydrophobic fibers and remains adhered to them throughout the wash and rinse cycle, Thereby acting as an anchor for the hydrophilic part. This makes soils treated with SRA easier to remove in subsequent wash cycles.

优选的SRA包括低聚对苯二甲酸酯，一般通过通常采用金属催化剂如醇钛(IV)的至少一种酯交换反应/低聚反应来制备。这些酯可以采用其它单体制备，这些单体能够在一、二、三、四或更多个位置加入酯结构，当然没有形成紧密交联的总结构。Preferred SRAs include oligomeric terephthalates, typically prepared by at least one transesterification/oligomerization reaction, usually using a metal catalyst such as titanium(IV) alkoxide. These esters can be prepared using other monomers capable of incorporating the ester structure at one, two, three, four or more positions, without, of course, forming a tightly cross-linked overall structure.

适合的SRA包括含有对苯二甲酰基和氧亚烷基氧重复单元的低聚酯主链的基本直链酯低聚物的磺化产物和与主链共价相连的烯丙基衍生物磺化封端部分(如描述于1990年11月6日授权予J.J.Scheibel和E.P.Gosselink的美国专利4,968,451)。这些酯低聚物可以由以下方法制备：(a)乙氧基化烯丙醇；(b)在二级酯交换反应/低聚反应程序中，使(a)产物与对苯二甲酸二甲酯(“DMT”)和1，2-丙二醇(“PG”)反应；和(c)在水中使(b)产物与偏亚硫酸氢钠反应。其它SRA包括1987年12月8日授权予Gosselink等人的U.S.4,711,730中的非离子封端的1，2-亚丙基/聚氧乙烯对苯二甲酸酯聚酯，例如通过聚(乙二醇)甲醚、DMT、PG和聚(乙二醇)(“PEG”)的酯交换/低聚反应生产的那些物质。SRA的其它例子包括：1988年1月26日授权予Gosselink等人的美国专利4,721,580的部分或全部阴离子封端的低聚酯，如乙二醇(“EG”)、PG、DMT和3，6-二氧杂-8-羟基辛烷磺酸钠；1987年10月27日授权予Gosselink的U.S.4,702,857中的非离子封端的嵌段聚酯低聚物，如由DMT、甲基(Me)-封端的PEG和EG和/或PG，或DMT、EG和/或PG的组合，甲基封端的PEG和二甲基-5-磺基间苯二甲酸钠生产的嵌段低聚物；以及1989年10月31日授权予Maldonado，Gosselink等人的U.S.4,877,896中的阴离子，尤其磺基芳酰基封端的对苯二甲酸酯，后者为用于洗衣和织物调理产品的典型SRA，一个例子是由间磺基苯甲酸单钠盐、PG和DMT，任选但优选进一步包括加入的PEG(如PEG 3400)制备的酯组合物。Suitable SRAs include the sulfonation products of substantially linear ester oligomers with terephthaloyl and oxyalkyleneoxy repeating units in the oligoester backbone and allyl derivatives of sulfonium covalently attached to the backbone. Ol capping moieties (as described in US Patent 4,968,451 issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink). These ester oligomers can be prepared by (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate in a secondary transesterification/oligomerization procedure reacting an ester ("DMT") and 1,2-propanediol ("PG"); and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRAs include non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters in U.S. 4,711,730 issued December 8, 1987 to Gosselink et al. ) methyl ether, DMT, PG, and poly(ethylene glycol) ("PEG") transesterification/oligomerization of those produced. Other examples of SRAs include: partially or fully anionically terminated oligoesters such as ethylene glycol ("EG"), PG, DMT, and 3,6- Sodium dioxa-8-hydroxyoctane sulfonate; non-ionically terminated block polyester oligomers such as DMT, methyl (Me)-capped Terminated PEG and EG and/or PG, or a combination of DMT, EG and/or PG, block oligomers produced from methyl-terminated PEG and sodium dimethyl-5-sulfoisophthalate; and 1989 10 Anions in U.S. 4,877,896, issued March 31 to Maldonado, Gosselink et al., especially sulfoaroyl-terminated terephthalates, which are typical SRAs used in laundry and fabric conditioning products. An ester composition prepared from sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG such as PEG 3400.

SRA也包括：对苯二甲酸乙二醇酯或对苯二甲酸丙二醇酯与聚环氧乙烷或聚环氧丙烷对苯二甲酸酯的简单嵌段共聚物，可以参见1976年5月25日授权予Hays的U.S.3,959,230和1975年7月8日授权予Basadur的U.S.3,893,929；纤维素衍生物如来自Dow的以METHOCEL提供的羟基醚纤维素聚合物；C₁-C₄烷基纤维素和C₄羟烷基纤维素，参见1976年12月28日授权予Nicol等人的U.S.4,000,093；以及甲基纤维素醚，其中每个无水葡萄糖单元的平均取代度(甲基)为约1.6至2.3，在20℃下测得的2％水溶液的溶液粘度为约80至120厘泊。这些材料以METOLOSESM100和METOLOSESM200获得供应，它们是由Shin-etsu Kagaku Kogyo KK生产的甲基纤维素醚的商品名。也高度优选多糖聚合物。SRA also includes: simple block copolymers of ethylene or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see May 25, 1976 US 3,959,230 issued to Hays on July 8 and US 3,893,929 issued to Basadur on July 8, 1975; Cellulose derivatives such as hydroxyether cellulose polymers from Dow available as METHOCEL; C₁ -C₄ alkyl fibers and C₄ hydroxyalkyl cellulose, see US 4,000,093, issued December 28, 1976 to Nicol et al; and methyl cellulose ethers, wherein the average degree of substitution (methyl) per anhydroglucose unit is About 1.6 to 2.3, the solution viscosity of a 2% aqueous solution measured at 20°C is about 80 to 120 centipoise. These materials are available as METOLOSESM100 and METOLOSESM200, which are trade names of methyl cellulose ethers produced by Shin-etsu Kagaku Kogyo KK. Polysaccharide polymers are also highly preferred.

其它类型的SRA包括：(I)采用二异氰酸酯偶联剂连接聚合酯结构的非离子对苯二甲酸酯，参见Violland等人的U.S.4,201,824和Lagasse等人的U.S.4,240,918；和(II)具有羧酸酯端基的SRA，通过将1，2，4-苯三酸酐加入已知的SRA中从而将封端的羟基转化为1，2，4-苯三酸酯制备。就适当选择催化剂而言，1，2，4-苯三酸酐通过1，2，4-苯三酸酐的孤立羧酸的酯，而不是通过打开酸酐键来形成与聚合物末端的键合。非离子或阴离子的SRA可以用作原料，条件是它们具有可以酯化的羟基端基。参见Tung等人的U.S.4,525,524。其它类型包括：(III)氨基甲酸酯连接的阴离子对苯二甲酸酯基SRA变体，参见Violland等人的U.S.4201,824。其它任选组分Other types of SRAs include: (I) nonionic terephthalate esters using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824 to Violland et al. and U.S. 4,240,918 to Lagasse et al.; Ester-terminated SRAs were prepared by adding trimellitic anhydride to known SRAs to convert the capped hydroxyl groups to trimellitic esters. With proper selection of the catalyst, the trimellitic anhydride forms linkages to the polymer ends through the ester of the isolated carboxylic acid of the trimellitic anhydride rather than by opening the anhydride linkage. Nonionic or anionic SRAs can be used as starting materials, provided they have hydroxyl end groups that can be esterified. See U.S. 4,525,524 to Tung et al. Other types include: (III) urethane-linked anionic terephthalate-based SRA variants, see U.S. 4,201,824 to Violland et al. other optional components

适合于包括在本发明组合物或组分中的其它任选成分包括香料、色料和代替硫酸盐填料盐(filer salt)的填料盐。Other optional ingredients suitable for inclusion in the compositions or components of the present invention include fragrances, colors and filler salts in place of sulfate filler salts.

也可优选与碳酸盐、少量(如少于约20％(重量))的中和剂、缓冲剂、相调节剂(phase regulants)、水溶助长剂、酶稳定剂、多酸、泡沫调节剂、遮光剂、抗氧化剂、杀菌剂、光漂白剂、斑饰剂和染料(如1981年授权予Barrat等人的美国专利4,285,841中所述的那些物质，在此加入本文以作参考)一起存在。组合物的形式It may also be preferred to mix with carbonates, small amounts (such as less than about 20% (by weight)) of neutralizing agents, buffers, phase regulators (phase regulators), hydrotropes, enzyme stabilizers, polyacids, foam regulators , sunscreens, antioxidants, bactericides, photobleaches, speckling agents, and dyes (such as those described in US Patent 4,285,841 issued to Barrat et al. in 1981, incorporated herein by reference). form of composition

本发明的组合物可以通过各种方法来生产，这些方法包括包括在所述洗涤剂组分中的各种化合物的干混、附聚、压制或喷雾干燥或者这些技术的组合。The compositions of the present invention may be produced by various methods including dry blending, agglomeration, compression or spray drying of the various compounds included in the detergent components or combinations of these techniques.

此处组合物可以采用包括液体的各种物理形式，但优选固体形式如片状、薄片、锭剂和块状，优选颗粒形式。The compositions herein may take a variety of physical forms including liquids, but solid forms such as tablets, flakes, lozenges and bars are preferred, and granular forms are preferred.

本发明组合物也可以用于漂白添加组合物(例如包括氯漂白剂)中或与漂白添加组合物结合使用。The compositions of the present invention may also be used in or in combination with bleach adjunct compositions, eg comprising chlorine bleach.

此处的洗涤剂组合物，尤其衣物用洗涤剂的堆积密度为280克/升-200克/升，或者优选300克/升或甚至350克/升或420克/升至2000克/升或优选1500克/升或者100克/升或甚至到700克/升。氯基漂白剂The detergent compositions herein, especially laundry detergents, have a bulk density of 280 g/l to 200 g/l, or preferably 300 g/l or even 350 g/l or 420 g/l to 2000 g/l or Preferably 1500 g/l or 100 g/l or even up to 700 g/l. Chlorine Bleach

所述洗涤剂组合物可以含有作为其它组分的氯基漂白剂。但是由于优选本发明的洗涤剂组合物为固体，大多数液体氯基漂白剂将不适合这些洗涤剂组合物并且只有颗粒或粉末氯基漂白剂是适合的。The detergent compositions may contain, as an additional ingredient, chlorine-based bleaches. However, since it is preferred that the detergent compositions of the present invention be solid, most liquid chlorine-based bleaches will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches are suitable.

或者，可以将所述洗涤剂组合物配制成与氯基漂白剂相容的，由此确保氯基漂白剂可以在洗涤过程的开始或过程中由使用者加入洗涤剂组合物中。Alternatively, the detergent composition can be formulated to be chlorine-based bleach compatible, thereby ensuring that chlorine-based bleach can be added to the detergent composition by the user at the beginning or during the wash cycle.

氯基漂白剂可以在水溶液中形成次氯酸盐。次氯酸盐离子的化学表达式为OCl^-。Chlorine-based bleaches can form hypochlorite in aqueous solutions. The chemical expression for the hypochlorite ion is OCl⁻ .

这些在水溶液中生成次氯酸盐的漂白剂包括碱金属和碱土金属次氯酸盐、次氯酸盐的加成产物、氯胺、氯亚胺、氯醛甲酰胺和chlorimides。这类化合物的具体例子包括次氯酸钠、次氯酸钾、单碱式次氯酸钙、二碱式次氯酸镁、氯化磷酸三钠十二水合物、二氯异氰尿酸钾、二氯异氰尿酸钠、二氯异氰尿酸钠二水合物、三氯氰尿酸、1，3-二氯-5，5-二甲基乙内酰脲、N-氯磺酰胺、氯胺T、二氯胺T、氯胺B和二氯胺B。用于本发明的组合物的优选漂白剂为次氯酸钠、次氯酸钾或其混合物。优选的氯基漂白剂可以为Triclosan(商品名)。These hypochlorite-forming bleaches in aqueous solution include alkali and alkaline earth metal hypochlorites, addition products of hypochlorites, chloramines, chlorimines, chloral carboxamides and chlorimides. Specific examples of such compounds include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, dichloroisocyanuric acid Sodium, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfonamide, chloramine T, dichloramine T , Chloramine B and Dichloramine B. Preferred bleaches for use in the compositions of the present invention are sodium hypochlorite, potassium hypochlorite or mixtures thereof. A preferred chlorine-based bleach may be Triclosan (trade name).

大多数上述产生次氯酸盐的漂白剂可以固体或浓缩形式获得供应并在制备本发明的组合物时溶解于水。上述材料的一些以水溶液的形式获得供应。衣物洗涤法Most of the above hypochlorite-generating bleaches are available in solid or concentrated form and are dissolved in water in preparing the compositions of the present invention. Some of the above materials are available as aqueous solutions. laundry method

此处的机器洗衣法通常包括在洗衣机内用其中溶解和分散有效量的本发明机洗洗涤剂组合物的洗涤水溶液处理染污衣物。有效量的洗涤剂组合物是指将10克至300克产品溶于或分散于5至65升洗涤溶液中，这种有效量是通常用于常规机洗法洗衣的典型的产品剂量和洗涤溶液体积。Machine laundering herein generally involves treating soiled garments in a washing machine with an aqueous wash solution in which is dissolved and dispersed an effective amount of the machine detergent composition of the present invention. An effective amount of the detergent composition means that 10 grams to 300 grams of product is dissolved or dispersed in 5 to 65 liters of wash solution, which effective amount is a typical dosage of product and wash solution usually used in conventional machine laundry volume.

此处的组合物可用于常规的洗衣机和低水填充洗衣机(low-waterfill machines)。The compositions herein can be used in conventional washing machines and low-waterfill machines.

一个优选的使用方面为手洗组合物。在另一个优选方面所述洗涤剂组合物为预处理或浸泡组合物，用于预处理或浸泡染污和沾污的织物。One preferred use aspect is a hand wash composition. In another preferred aspect the detergent composition is a pretreatment or soaking composition for pretreating or soaking soiled and soiled fabrics.

在实施例中使用的缩写Abbreviations used in the examples

在洗涤剂组合物中，标注的缩写组分具有下面的含义。LAS           直链C_11-13烷基苯磺酸钠TAS           牛油烷基硫酸钠C_xyS         C_1x-C_1y烷基硫酸钠C₄₆SAS       C₁₄-C₁₆仲(2，3)烷基硫酸钠C_xyE_zS      与z摩尔环氧乙烷缩合的C_1x-C_1y烷基硫酸钠C_xyE_z       与平均z摩尔环氧乙烷缩合的C_1x-C_1y基本直链的伯In detergent compositions, the indicated abbreviated components have the following meanings. LAS linear C_11-13 sodium alkylbenzene sulfonate TAS tallow alkyl sodium C_xy S C_1x -C_1y alkyl sodium C₄₆ SAS C₁₄ -C₁₆ secondary (2,3) alkyl sodium C_xy E_z S C_1x -C_1y sodium alkyl sulfate condensed with z moles of ethylene oxide C_xy E_z C_1x -C_1y essentially linear primary condensed with z moles of ethylene oxide

       醇QAS      R².N⁺(CH₃)₂(C₂H₄OH)，R²＝C₁₂-C₁₄QAS1     R².N⁺(CH₃)₂(C₂H₄OH)，R²＝C₈-C₁₁SADS     式2-(R).C₄H₇-1，4-(SO₄-)₂的C₁₄-C₂₂烷基二硫酸钠Alcohol QAS R² .N⁺ (CH₃ )₂ (C₂ H₄ OH), R² =C₁₂ -C₁₄ QAS1 R² .N⁺ (CH₃ )₂ (C₂ H₄ OH), R² = C₈ -C₁₁ SADS Sodium C₁₄ -C₂₂ Alkyl Disulfate of Formula 2-(R).C₄ H₇ -1,4-(SO₄ -)₂

     盐，式中R＝C₁₀-C₁₈SADE2S   式2-(R).C₄H₇-1，4-(SO₄-)₂的C₁₄-C₂₂烷基二硫酸钠与Salt, where R=C₁₀ -C₁₈ SADE2S formula 2-(R).C₄ H₇ -1,4-(SO₄ -)₂ C₁₄ -C₂₂ alkyl sodium sulfate and

     z摩尔环氧乙烷的缩合物，式中R＝C₁₀-C₁₈MES      C₁₈脂肪酸的x-磺基甲酯APA      C₈-C₁₀酰氨基丙基二甲胺皂       衍生自牛油和椰油脂肪酸的80/20混合物的直链烷Condensate of z moles of ethylene oxide where R = C₁₀ -C₁₈ MES x-sulfomethyl ester of C₁₈ fatty acid APA C₈ -C₁₀ amidopropyl dimethylamine soap derived from tallow and coconut Linear alkanes of 80/20 mixture of oleic fatty acids

     基羧酸钠STS      甲苯磺酸钠CFAA     C₁₂-C₁₄(椰油)烷基N-甲基葡糖酰胺TFAA     C₁₆-C₁₈烷基N-甲基葡糖酰胺TPKFA    C₁₆-C₁₈拔顶全切取馏分脂肪酸STPP     无水三聚磷酸钠TSPP     焦磷酸四钠ZeoliteA  式Na₁₂(AlO₂SiO₂)₁₂.27H₂O的水合硅铝酸钠，粒径Sodium Carboxylate STS Sodium Toluene Sulfonate CFAA C₁₂ -C₁₄ (Coco) Alkyl N-Methyl Glucamide TFAA C₁₆ -C₁₈ Alkyl N-Methyl Glucamide TPKFA C₁₆ -C₁₈ Pull Top Whole Cut Fatty Acid STPP Sodium Tripolyphosphate Anhydrous TSPP Tetrasodium Pyrophosphate ZeoliteA Hydrated Sodium Aluminosilicate of Formula Na₁₂ (AlO₂ SiO₂ )₁₂ .27H₂ O, Particle Size

      为0.1-10微米(基于无水物表达重量)NaSKS-6   式δ-Na₂Si₂O₅的晶体层状硅酸盐柠檬酸    无水柠檬酸硼酸盐    硼酸钠碳酸盐    粒径分布为200微米至900微米的无水碳酸钠碳酸氢盐  粒径分布为400微米至1200微米的无水碳酸氢钠硅酸盐    无定形硅酸钠(SiO₂∶Na₂O＝2.0∶1)硫酸盐    无水硫酸钠硫酸镁    无水硫酸镁柠檬酸盐  二水合柠檬酸三钠，活度为86.4％，粒径分布为4250.1-10 microns (weight_{expressed on anhydrous basis) NaSKS-6 Crystalline layered silicate of the formula δ-Na2Si2O5Citricacid} anhydrous citrate borate Sodium borate carbonate Particle size distribution is Anhydrous sodium bicarbonate from 200 microns to 900 microns Anhydrous sodium bicarbonate silicate with particle size distribution from 400 microns to 1200 microns Amorphous sodium silicate (_SiO2 :_Na2O =2.0:1) sulfate Sodium Sulfate Anhydrous Magnesium Sulfate Anhydrous Magnesium Sulfate Citrate Trisodium Citrate Dihydrate, 86.4% activity, 425 particle size distribution

       微米-850微米MA/AA      1∶4的马来酸/丙烯酸共聚物，平均分子量为约70,000MA/AA(1)   4∶6的马来酸/丙烯酸共聚物，平均分子量为约10,000AA         平均分子量为4,500的聚丙烯酸钠聚合物CMC        羧甲基纤维素钠纤维素醚   聚合度为650的甲基纤维素醚，购自Shin EtsuMicron-850 micron MA/AA 1:4 maleic/acrylic acid copolymer with an average molecular weight of about 70,000MA/AA(1) 4:6 maleic/acrylic acid copolymer with an average molecular weight of about 10,000AA Average molecular weight Sodium polyacrylate polymer CMC of 4,500 Sodium carboxymethyl cellulose cellulose ether Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu

       Chemicals蛋白酶     蛋白水解酶，具有3.3％(重量)的活性酶，由NOVO  Chemicals proteases   Proteolytic enzymes with 3.3% (wt) active enzyme by NOVO

       IndustriesA/S以Savinase的商品名出售蛋白酶I    蛋白水解酶，具有4％(重量)的活性酶，描述于WOIndustries A/S sells Protease I proteolytic enzyme with 4% by weight of active enzyme under the trade name of Savinase, described in WO

       95/10591，由Genencor Int.Inc.出售Alcalase   蛋白水解酶，具有5.3％(重量)的活性酶，由NOVO95/10591, sold by Genencor Int. Inc. Alcalase proteolytic enzyme with 5.3% by weight active enzyme, sold by NOVO

       IndustriesA/S出售纤维素酶   纤维素水解酶，具有0.23％(重量)的活性酶，由Industries A/S sells cellulase cellulolytic enzymes with 0.23% by weight of active enzyme, produced by

       NOVOIndustriesA/S以Carezyme的商品名出售淀粉酶     淀粉水解酶，具有1.6％(重量)的活性酶，由NOVONOVO Industries A/S sells amylase under the tradename Carezyme Starch hydrolase with 1.6% by weight of active enzyme, supplied by NOVO

       IndustriesA/S以Termamy 120T的商品名出售淀粉酶II   公开于PCT/US9703635的淀粉水解酶脂酶       脂肪水解酶，具有2.0％(重量)的活性酶，由NOVOIndustries A/S sells Amylase II under the tradename Termamy 120T Starch hydrolase lipase disclosed in PCT/US9703635 Lipase lipase with 2.0% by weight of active enzyme supplied by NOVO

       Industries A/S以Lipolase的商品名出售脂酶II     脂肪水解酶，具有2.0％(重量)的活性酶，由NOVOIndustries A/S sells Lipase II lipohydrolase under the tradename Lipolase with 2.0% by weight of active enzyme, supplied by NOVO

       Industries A/S以Lipolase Ultra的商品名出售Endolase   内切葡聚糖酶，具有1.5％(重量)的活性酶，由NOVOIndustries A/S sells Endolase endoglucanase under the tradename Lipolase Ultra with 1.5% by weight of active enzyme, supplied by NOVO

       IndustriedA/S出售PB4        标式NaBO₂₃H₂O.H₂O₂的过硼酸钠四水合物PB1        标式NaBO₂.H₂O₂的无水过硼酸钠漂白剂过碳酸盐   标式2Na₂CO₃.3H₂O₂的过碳酸钠DOBS       钠盐形式的癸酰氧基苯磺酸盐DPDA        二过氧十二烷二酸NOBS        钠盐形式的壬酰氧基苯磺酸盐NACA-OBS    (6-壬酰胺基己酰基)氧基苯磺酸盐LOBS        钠盐形式的十二碳酰氧基苯磺酸盐DOBS        钠盐形式的癸酰氧基苯磺酸盐DOBA        癸酰氧基苯甲酸TAED        四乙酰基乙二胺DTPA        二亚乙基三胺五乙酸DTPMP       二亚乙基三胺五(亚甲基膦酸盐)，由Monsanto以Industrial A/S sells PB4 Sodium perborate tetrahydrate with the formula NaBO₂₃ H₂ OH₂ O₂ PB1 Anhydrous sodium perborate bleach with the formula NaBO₂ .H₂ O₂ Percarbonate with the formula 2Na₂ CO₃ .3H₂ O₂ Sodium percarbonate DOBS Sodium salt of decanoyloxybenzenesulfonate DPDA Diperoxydodecanedioic acid NOBS Sodium salt of nonanoyloxybenzenesulfonate NACA-OBS (6- Nonamidocaproyl)oxybenzenesulfonate LOBS sodium salt dodecanoyloxybenzenesulfonate DOBS sodium decanoyloxybenzenesulfonate DOBA decanoyloxybenzoic acid TAED tetraacetyl ethylenediamine DTPA diethylenetriaminepentaacetic acid DTPMP diethylenetriaminepenta(methylene phosphonate) from Monsanto

        Dequest 2060的商品名出售EDDS        乙二胺-N，N’-二丁二酸，钠盐形式的(S，S)异构体光活化剂    包囊在漂白剂(1)糊精可溶性聚合物中的磺化酞菁锌光活化剂    包囊在漂白剂(2)糊精可溶性聚合物中的磺化酞菁铝增白剂1     4，4’-双(2-磺基苯乙烯基)联苯二钠增白剂2     4，4’-双(4-苯胺基-6-吗啉并-1.3.5-三嗪-2-基)氨基)茋-Sold under the trade name Dequest 2060 EDDS Ethylenediamine-N,N'-disuccinic acid, sodium salt form of (S,S) isomer photoactivator encapsulated in bleach (1) dextrin soluble polymer Sulfonated Zinc Phthalocyanine Photoactivator Sulfonated Aluminum Phthalocyanine Brightener Encapsulated in Bleach (2) Dextrin Soluble Polymer 1 4,4'-Bis(2-Sulfostyryl)biphenyl Disodium Brightener 2 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino)stilbene-

        2∶2’-二磺酸二钠HEDP        1，1-羟基乙烷二膦酸PEG_x       聚乙二醇，分子量为x(通常为4,000)PEO         聚环氧乙烷，平均分子量为50,000TEPAE       四亚乙基五胺乙氧基化物PVI         聚乙烯基咪唑，平均分子量为20,000PVP         聚乙烯基吡咯烷酮聚合物，平均分子量为60,000PVNO        聚乙烯基吡啶N-氧化物聚合物，平均分子量为2: Disodium 2'-Disulfonate HEDP 1,1-Hydroxyethanediphosphonic Acid PEG_x Polyethylene Glycol, Molecular Weight x (typically 4,000) PEO Polyethylene Oxide, Average Molecular Weight 50,000 TEPAE Tetraethylene Ethylpentamine ethoxylate PVI Polyvinylimidazole, average molecular weight 20,000PVP Polyvinylpyrrolidone polymer, average molecular weight 60,000PVNO Polyvinylpyridine N-oxide polymer, average molecular weight

        50,000PVPVI       聚乙烯基吡咯烷酮和乙烯基咪唑的共聚物，平均分50,000 PVPVI Copolymer of polyvinylpyrrolidone and vinylimidazole, average score

        子量为20,000QEA         双((C₂H₅O)(C₂H₄O)_n)(CH₃)-N⁺-C₆H₁₂-N⁺-(CH₃)Quantity is 20,000QEA bis((C₂ H₅ O)(C₂ H₄ O)_n )(CH₃ )-N⁺ -C₆ H₁₂ -N⁺ -(CH₃ )

        双((C₂H₅O)(C₂H₄O))_n，其中n为20-30PEI         聚乙烯亚胺，平均分子量为1800，平均乙氧化度为Bis((C₂ H₅ O)(C₂ H₄ O))_n , where n is 20-30PEI polyethyleneimine, the average molecular weight is 1800, and the average ethoxylation degree is

        每个氮7个乙烯氧残基粘土I       膨润土粘土II      绿土型粘土絮凝剂I     分子量为200,000至400,000的聚环氧乙烷絮凝剂II    分子量为400,000至1,000,000的聚环氧乙烷絮凝剂III   分子量为200,000至400,000的丙烯酰胺和/或丙烯7 ethylene oxide residues per nitrogen Clay I Bentonite clay II Smectite-type clay flocculant I Polyethylene oxide flocculant with a molecular weight of 200,000 to 400,000 II Polyethylene oxide flocculant with a molecular weight of 400,000 to 1,000,000 III Molecular weight 200,000 to 400,000 acrylamide and/or propylene

        酸聚合物SRPI        阴离子封端的聚酯去污聚合物SRPII       多糖去污聚合物SRP1        非离子封端的聚酯SRP2        二乙氧基化聚(对苯二甲酸1，2丙二醇酯)短嵌段聚Acid polymer SRPI Anion-terminated polyester soil release polymer SRPII Polysaccharide soil release polymer SRP1 Non-ion-terminated polyester SRP2 Diethoxylated poly(1,2-propylene glycol terephthalate) short-block poly

        合物硅酮消泡剂  硅氧烷-氧化烯共聚物作为分散剂的聚二甲基硅氧烷  Compound silicone defoamer Polydimethylsiloxane with siloxane-oxyalkylene copolymer as dispersant

        泡沫控制剂，所述泡沫控制剂与所述分散剂之比为A foam control agent, the ratio of the foam control agent to the dispersant is

        10∶1-100∶1遮光剂      水基单苯乙烯胶乳混合物，由BASF      10:1-100: 1 sunscreen agent   Water-based monostyrene latex blend, manufactured by BASF

        Aktiengesellschaft以Lytron 621的商品名出售蜡          石蜡斑饰剂      带色的碳酸盐或有机羧酸/盐Aktiengesellschaft sells waxes under the tradename Lytron 621 Paraffin spotting agents Colored carbonates or organic carboxylic acids/salts

下面为本发明组分(所述组分的重量百分数)。   组分  I   II   III   IV V   VI  VII  VIII    IX  X   XI   XII 粘土I和/或II  10.0   15.0   8.0   7.0 5.0   10.0   20.0  25.0    8.0  10.0   100   15.0 絮凝剂I或II  0.1   0.5   1.0   2.0 2.5   1.0   3.0  0.2    0.1  1.0   0.5   2.0    LAS  10.0   8.0   18.0   20.0 -    -   -   -    30.0   35.0    -   18.0    TAS  2   -   -   - 3.0  6.0    -   -    -   -    -   -  0   C24AS  20  -   4.0  -   10.0   20    -   -   -    -   -   -   MBAS  -  -   -  -   5.0   -    -   -   -    -   12.0   -   C24E7或E9  -  -   -  -   2.0   -    6.0   -   -    2.0   -   -   C24E3或E4  -  -   -  -   2.0   -    -   6.0    -    -   -   2.0     QAS  1.0  -   -  -   -   -    -   2.0    -    4.0   -   -   苹果酸  -  2.0   -  -   2.0   -    -   2.0    -    5.0   -   -   柠檬酸  -  -   4.0  -   -   -    -   -   5.0    -   -   -   碳酸盐  10.0  150   10.0  12.0   4.0   -    20.0   10.0   5.0    5.0   5.0   -   碳酸氢盐  -  -   -  -   6.0   -    -   -   -    -   -   -   沸石A或MAP  15.0  -   -  -   20.0   -    -   -   -    20.0   15.0   5.0   STPP  -  10.0   15.0  30   -   18.0    15.0   20.0   30.0    -   -   5.0   硅酸盐  5.0  10   5.0   7.0   -    -   4.0   2.0    -   5.0   -   SKS-6  2.0  -   -  -   -   -    5.0   -   -   5.0   -   -   MA/AA  1.0  -   -  -   -   -    -   -   -   1.0   1.0   -   硫酸盐  -  -   -  -   -   5.0    -   -   -   -   5.0   -   增白剂  01  0.1   0.05  0.2   0.5   0.3    -   0.1   -   0.8   1.0   -   SRP  -  -   -  -   -   1.5    -   -   -   0.8   -   -   TAED  -  -   5.0  -   -   -    -   -   -    -   -   -   干燥剂#  -  -   2.0  -   2.0   -    -   -   -    -   -   -   HEDP/EDDS  -  -   -  -   0.5   -    -   2.0   1.0    -   -   0.8   STS  0.  0.7   -  -   -   1.0    2.0    -    -    -   2.   -   5   0     CMC   -   -   -   -   -   1.2   -   -   -    -   10   0.5   过碳酸盐   -   -   7.0   -   -   3.0   -   -   -    -   10.0   抑泡剂/皂   0.5   0.5   -   -   0.5   1.0   0.8   0.5   -    -   2.0   -     酶   1.0   -   -   -   -   -   -   1.0   2.0    -   -   -   水分   香料  -   -   1.0   2.0   0.5   -   -   -   0.8    2.0   -   -   PEG4000  -   1.0   -   -   -   1.0   -   -   -    -   -   -The following are the components of the present invention (weight percentages of the components). components I II III IV V VI VII VIII IX x XI XII Clay I and/or II 10.0 15.0 8.0 7.0 5.0 10.0 20.0 25.0 8.0 10.0 100 15.0 Flocculant I or II 0.1 0.5 1.0 2.0 2.5 1.0 3.0 0.2 0.1 1.0 0.5 2.0 LAS 10.0 8.0 18.0 20.0 - - - - 30.0 35.0 - 18.0 TAS 2 - - - 3.0 6.0 - - - - - - 0 C24AS 20 - 4.0 - 10.0 20 - - - - - - MBAS - - - - 5.0 - - - - - 12.0 - C24E7 or E9 - - - - 2.0 - 6.0 - - 2.0 - - C24E3 or E4 - - - - 2.0 - - 6.0 - - - 2.0 QAS 1.0 - - - - - - 2.0 - 4.0 - - malic acid - 2.0 - - 2.0 - - 2.0 - 5.0 - - citric acid - - 4.0 - - - - - 5.0 - - - carbonate 10.0 150 10.0 12.0 4.0 - 20.0 10.0 5.0 5.0 5.0 - Bicarbonates - - - - 6.0 - - - - - - - Zeolite A or MAP 15.0 - - - 20.0 - - - - 20.0 15.0 5.0 STPP - 10.0 15.0 30 - 18.0 15.0 20.0 30.0 - - 5.0 Silicate 5.0 10 5.0 7.0 - - 4.0 2.0 - 5.0 - SKS-6 2.0 - - - - - 5.0 - - 5.0 - - MA/AA 1.0 - - - - - - - - 1.0 1.0 - Sulfate - - - - - 5.0 - - - - 5.0 - brightener 01 0.1 0.05 0.2 0.5 0.3 - 0.1 - 0.8 1.0 - SRP - - - - - 1.5 - - - 0.8 - - TAED - - 5.0 - - - - - - - - - Desiccant# - - 2.0 - 2.0 - - - - - - - HEDP/EDDS - - - - 0.5 - - 2.0 1.0 - - 0.8 STS 0. 0.7 - - - 1.0 2.0 - - - 2. - 5 0 CMC - - - - - 1.2 - - - - 10 0.5 Percarbonate - - 7.0 - - 3.0 - - - - 10.0 Antifoam/Soap 0.5 0.5 - - 0.5 1.0 0.8 0.5 - - 2.0 - enzyme 1.0 - - - - - - 1.0 2.0 - - - moisture spices - - 1.0 2.0 0.5 - - - 0.8 2.0 - - PEG4000 - 1.0 - - - 1.0 - - - - - -

#(过干或无水盐/沸石或过干沸石或二氧化硅)# (overdried or anhydrous salt/zeolite or overdried zeolite or silica)

下面实施例的所有水平均以所述组合物重量百分数计。All levels in the following examples are in percent by weight of the composition.

实施例1Example 1

下面为本发明的片状、块状或颗粒配方的洗涤剂配方。 A  B  C  D 组分I-XII 余量 余量 余量 余量 喷在上面 增白剂 0.02  -  -  0.02  C₄₅E₇或E₉  -  -  2.0  1.0  C₄₅E₃或E₄  -  -  2.0  4.0 香料 0.5  -  0.5  0.2 硅酮消泡剂 0.3  -  -  - 干添加 QEA -  -  -  1.0  HEDP/EDDS 0.3  -  0.5  0.5 硫酸盐 2.0  -  0.5  1.0 碳酸盐 2.0  10. 15.0  12.0 柠檬酸 2.5  -  -  2.0  QAS  - -  0.5  0.5  SKS-6  3.5 -  -  5.0 过碳酸盐  - -  15.0  9.0  PB4  - -  -  3.0  TAED/NOBS  - -  -  5.0  PAP  - -  2.0  - 蛋白酶  1.0 1.0  1.0  1.0 脂酶  - 0.4  -  0.2 淀粉酶  0.2 0.2  0.2  0.4 增白剂  0.05 -  -  0.05 香料  1.0 0.2  0.5  0.3 斑饰剂  1.2 0.5  2.0  - 微量/少量组分至100％The following are detergent formulations for tablet, bar or granular formulations of the present invention. A B C D. Components I-XII margin margin margin margin spray on it brightener 0.02 - - 0.02 C₄₅ E₇ or E₉ - - 2.0 1.0 C₄₅ E₃ or E₄ - - 2.0 4.0 spices 0.5 - 0.5 0.2 Silicone defoamer 0.3 - - - dry addition QEA - - - 1.0 HEDP/EDDS 0.3 - 0.5 0.5 Sulfate 2.0 - 0.5 1.0 carbonate 2.0 10. 15.0 12.0 citric acid 2.5 - - 2.0 QAS - - 0.5 0.5 SKS-6 3.5 - - 5.0 Percarbonate - - 15.0 9.0 PB4 - - - 3.0 TAED/NOBS - - - 5.0 PAP - - 2.0 - protease 1.0 1.0 1.0 1.0 Lipase - 0.4 - 0.2 Amylase 0.2 0.2 0.2 0.4 brightener 0.05 - - 0.05 spices 1.0 0.2 0.5 0.3 Spotting agent 1.2 0.5 2.0 - Trace/Minor Components to 100%

实施例2Example 2

下面为本发明的片状、块状或颗粒配方的洗涤剂配方。 E  F  G  H  I  J 组分I-XII 余量 余量 余量 余量 余量 余量 喷在上面  C₄₅E₇  -  2.0  -  -  2.0  2.0  C₂₅E₉  3.0  -  -  -  -  -  C₂₃E₉  -  -  1.5  2.0  -  2.0 香料  0.3  0.3  0.3  2.0  0.3  0.3 附聚物 C₄₅AS  5.0  5.0  -  2.0  5.0  -  LAS  2.0  2.0  7.0   -  -  8.0  STPP/ZeoliteA  7.5  7.5  7.5  8.0  7.5  7.5 碳酸盐 4.0  4.0  4.0  5.0  4.0  4.0 PEG4000 0.5  0.5  0.5  -  0.5  0.5 微量成分(水等) 2.0  2.0  2.0  2.0  2.0  2.0 干添加 -  -  -  -  -   - 柠檬酸 -  -  -  -  2.0   -  PB4 -  3.0  -  -  -   -  PB1 -  -  4.0  1.0  -   - 过碳酸盐 12.0  -  -  1.0  -  2.0 碳酸盐 - 5.3  20.0  5.0  14.0  24.0  NOBS 0.5  -  0.4  0.3  -  0.6  PAP -  0.9  -  -  0.3   -  TAED 0.6  0.4  0.6  0.3  0.9  0.5 甲基纤维素 0.2  -  -  -  -  0.5  DTPA 0.7  0.5  1.0  0.5  0.5  1.2 斑饰剂 0.3  0.2  2.0  -  0.7  0.5  SKS-6 8.0  -  -  -  -   -  STS -  -  2.0  -  1.0   - 枯烯磺酸 - 1.0  -  -  -  2.0 脂酶 0.2  -  0.2  -  0.2  0.4 纤维素酶 0.2  0.2  0.2  0.3  0.2  0.2 淀粉酶II 0.2  -  0.1  -  0.2   - 蛋白酶 0.5  0.5  0.5  0.3  0.5  0.5  PVPVI -  -  -  -  0.5  0.1  PVP -  -  -  -  0.5   -  PVNO -  -  0.5  0.3  -   -  QEA -  -  -  -  1.0   -  SRP I、II或III 0.2  0.5  0.3  -  0.2   - 硅酮消泡剂 0.2  0.4  0.2  -  0.1   - 硫酸镁 - - 0.2 -  0.2  - 微量/少量成分至100％The following are detergent formulations for tablet, bar or granular formulations of the present invention. E. f G h I J Components I-XII margin margin margin margin margin margin spray on it C₄₅ E₇ - 2.0 - - 2.0 2.0 C₂₅ E₉ 3.0 - - - - - C₂₃ E₉ - - 1.5 2.0 - 2.0 spices 0.3 0.3 0.3 2.0 0.3 0.3 Agglomerates C₄₅ AS 5.0 5.0 - 2.0 5.0 - LAS 2.0 2.0 7.0 - - 8.0 STPP/ZeoliteA 7.5 7.5 7.5 8.0 7.5 7.5 carbonate 4.0 4.0 4.0 5.0 4.0 4.0 PEG4000 0.5 0.5 0.5 - 0.5 0.5 Minor ingredients (water, etc.) 2.0 2.0 2.0 2.0 2.0 2.0 dry addition - - - - - - citric acid - - - - 2.0 - PB4 - 3.0 - - - - PB1 - - 4.0 1.0 - - Percarbonate 12.0 - - 1.0 - 2.0 carbonate - 5.3 20.0 5.0 14.0 24.0 NOBS 0.5 - 0.4 0.3 - 0.6 PAP - 0.9 - - 0.3 - TAED 0.6 0.4 0.6 0.3 0.9 0.5 Methylcellulose 0.2 - - - - 0.5 DTPA 0.7 0.5 1.0 0.5 0.5 1.2 Spotting agent 0.3 0.2 2.0 - 0.7 0.5 SKS-6 8.0 - - - - - STS - - 2.0 - 1.0 - cumenesulfonic acid - 1.0 - - - 2.0 Lipase 0.2 - 0.2 - 0.2 0.4 cellulase 0.2 0.2 0.2 0.3 0.2 0.2 Amylase II 0.2 - 0.1 - 0.2 - protease 0.5 0.5 0.5 0.3 0.5 0.5 PVPVI - - - - 0.5 0.1 pvp - - - - 0.5 - PVNO - - 0.5 0.3 - - QEA - - - - 1.0 - SRP I, II or III 0.2 0.5 0.3 - 0.2 - Silicone defoamer 0.2 0.4 0.2 - 0.1 - magnesium sulfate - - 0.2 - 0.2 - Trace/minor ingredients to 100%

实施例3Example 3

下面为本发明的片状、块状或颗粒配方的洗涤剂配方。 K  L  M  N 组分I-XII 余量 余量 余量 余量 喷在上面 C₂₅E₃或E₄  -  -  -  2.0 C₄₅E₅或E₇  -  -  -  2.0 增白剂/光漂白剂  -  -  0.5  0.5 香料  0.2  0.3  0.3  - 干添加 碳酸盐  5.0  10.0  13.0  5.0 PVPVI/PVNO  0.5  -  0.3  - 蛋白酶  1.0  1.0  1.0  0.5 脂酶  0.4  -  -  0.4 淀粉酶  0.1  -  -  0.1 纤维素酶  0.1  -  -  0.1 DTPA  0.5  0.3  0.5  1.0 PB1  5  3.0  10  4.0 PAP/DOBA  1.0  -  0.4  - TAED  0.5  0.3  0.5  0.6 硫酸盐  4.0  5.0  -  5.0 SRPI、II或III  0.2  0.4  1.0  0.5 消泡剂  -  0.5  -  - 斑饰剂  1.8  0.8  0.7  - 絮凝剂 - - 0.1  0.2 香料(淀粉) - 0.2  0.3  0.5 微量/少量成分至100％The following are detergent formulations for tablet, bar or granular formulations of the present invention. K L m N Components I-XII margin margin margin margin spray on it C₂₅ E₃ or E₄ - - - 2.0 C₄₅ E₅ or E₇ - - - 2.0 Brighteners/Photobleaches - - 0.5 0.5 spices 0.2 0.3 0.3 - dry addition carbonate 5.0 10.0 13.0 5.0 PVPVI/PVNO 0.5 - 0.3 - protease 1.0 1.0 1.0 0.5 Lipase 0.4 - - 0.4 Amylase 0.1 - - 0.1 cellulase 0.1 - - 0.1 DTPA 0.5 0.3 0.5 1.0 PB1 5 3.0 10 4.0 PAP/DOBA 1.0 - 0.4 - TAED 0.5 0.3 0.5 0.6 Sulfate 4.0 5.0 - 5.0 SRPI, II or III 0.2 0.4 1.0 0.5 Defoamer - 0.5 - - Spotting agent 1.8 0.8 0.7 - flocculant - - 0.1 0.2 spices (starch) - 0.2 0.3 0.5 Micro/Minor ingredients to 100%

实施例6Example 6

下面为本发明的片状、块状或颗粒配方的洗涤剂配方。 O  P  Q  R  S 组分I-XII 余量 余量 余量 余量 余量 附聚物 粘土 9.0 - - 蜡 0.5 - - 甘油 0.5 - - 附聚物 LAS 15.0 5.0 5.0 TAS 1.0 硅酸盐 3.0 3.0 4.0 ZeoliteA 8.0 8.0 8.0 碳酸盐 8.0 8.0 4.0 喷在上面 香料 0.3 - -  0.3  0.3 C₄₅E₇或E₉ - -  2.0  2.0 C₂₅E₃或E₄ 2.0 - -  -  2.0 干添加 柠檬酸盐或柠檬酸 2.5 - 2.0  2.5  2.5 粘土I或II - 3.0 3.0  -  - 絮凝剂I或II - - - - - 碳酸氢盐 - 3.0 - - - 碳酸盐 15.0 - - 5.0 11.0  TAED 1.0 2.0 5.0 1.0 - 过硼酸钠或过碳酸钠 6.0 7.0 10.0 6.0 -  SRP I、II或III 0.2 0.1 0.2 0.5 0.3  CMC或非离子纤维素醚 1.0 1.5 0.5  - - 蛋白酶 0.3 1.0 1.0 0.3 0.3 脂酶 - 0.4 0.4 - - 淀粉酶 0.2 0.6 0.6 0.2 0.2 纤维素酶 0.2 0.6 0.6 0.2 0.2 硅酮消泡剂 - 5.0 5.0 - - 香料(淀粉) 0.2 0.3 - - - 斑饰剂 0.5 0.5 0.1 - 1.0 SKS-6(硅酸盐2R) 3.5 - - - 3.5 光漂白剂 0.1 - - 0.1 0.1 皂 0.5 2.5 - 0.5 0.5 硫酸钠 - 3.0 - - - 微量/少量成分至100％ 100.0 100.0 100.0 100.0 100.0 密度(g/l) 850  850 850 850 850The following are detergent formulations for tablet, bar or granular formulations of the present invention. o P Q R S Components I-XII margin margin margin margin margin Agglomerates clay 9.0 - - wax 0.5 - - glycerin 0.5 - - Agglomerates LAS 15.0 5.0 5.0 TAS 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 carbonate 8.0 8.0 4.0 spray on it spices 0.3 - - 0.3 0.3 C₄₅ E₇ or E₉ - - 2.0 2.0 C₂₅ E₃ or E₄ 2.0 - - - 2.0 dry addition citrate or citric acid 2.5 - 2.0 2.5 2.5 Clay I or II - 3.0 3.0 - - Flocculant I or II - - - - - Bicarbonates - 3.0 - - - carbonate 15.0 - - 5.0 11.0 TAED 1.0 2.0 5.0 1.0 - Sodium Perborate or Sodium Percarbonate 6.0 7.0 10.0 6.0 - SRP I, II or III 0.2 0.1 0.2 0.5 0.3 CMC or non-ionic cellulose ether 1.0 1.5 0.5 - - protease 0.3 1.0 1.0 0.3 0.3 Lipase - 0.4 0.4 - - Amylase 0.2 0.6 0.6 0.2 0.2 cellulase 0.2 0.6 0.6 0.2 0.2 Silicone defoamer - 5.0 5.0 - - spices (starch) 0.2 0.3 - - - Spotting agent 0.5 0.5 0.1 - 1.0 SKS-6 (silicate 2R) 3.5 - - - 3.5 photobleach 0.1 - - 0.1 0.1 soap 0.5 2.5 - 0.5 0.5 sodium sulfate - 3.0 - - - Trace/minor ingredients to 100% 100.0 100.0 100.0 100.0 100.0 Density (g/l) 850 850 850 850 850

Claims (19)

1. solid fabric softening component, it comprises:

A) a kind of clay;

B) at least 5% surfactant system;

C) solid carrier material of at least 15% weight;

D) a kind of flocculation agent.

2. according to the component of claim 1, wherein said clay and flocculation agent are intimate mixture each other.

3. according to the component of claim 1 or 2, wherein said clay, flocculation agent, surfactant system and solid support material are intimate mixture each other.

4. according to each component in the aforementioned claim, wherein said solid support material comprises silico-aluminate washing assistant and/or phosphate builders, and preferably there is level in it is the 15-60% of described composition weight.

5. according to each component in the aforementioned claim, wherein said solid support material comprises inorganic carbonate, and preferably there is level in it is the 10-60% of described composition weight.

6. according to each component in the aforementioned claim, the level that exists of wherein said surfactant system is 10-70% (weight), and comprises at least a anion sulfoacid salt surfactant or anion sulfate acid salt surfactant.

7. according to each component in the aforementioned claim, wherein said nonionic surfactant system comprises, preferably includes at least a alcohol alcoxylates tensio-active agent, preferably at least two kinds of alcohol alcoxylates tensio-active agents.

8. according to each composition in the aforementioned claim, wherein said flocculation agent comprises that molecular-weight average is 150,000 to 3,000,000 polyethylene oxide.

9. according to each composition in the aforementioned claim, the level that exists of wherein said clay is 5-60% (weight), preferably includes a kind of smectite-type clay.

10. according to each component in the aforementioned claim, comprise the whitening agent of at least 0.1% weight.

11. according to each component in the aforementioned claim, its existence form is spray-dried granules, agglomerate or extrudate.

12. according to each component in the aforementioned claim, it comprises the water of at least 5% (weight).

13., comprise a kind of fabric care agent that is selected from soil release polymer, cellulose polymer compound, dye transfer inhibitor, cationic softening agent or its mixture according to each component in the aforementioned claim.

14., comprise a kind of carbonate and water swellable decomposition agent or can form the acidic cpd that effervescive is preferably carboxylic acid, or its mixture with carbonate reaction according to each component in the aforementioned claim.

15., comprise a kind of clay mixture according to each component in the aforementioned claim.

16. according to each component in the aforementioned claim, wherein said clay, flocculation agent, surfactant system and solid support material are intimate mixture each other.

17. prepare the method for each component in the aforementioned claim, comprise at first mixed clay and flocculation agent formation intimate mixture, the step of mixing described intimate mixture and surfactant system and solid support material then.

18. the method for each component among the preparation claim 3-16, comprise that at first mixed flocculation agent, surfactant system or its part and/or solid support material or its part form intimate mixture, mix intimate mixture and clay and the remainder of the surfactant system of choosing wantonly and/or the remainder of solid support material subsequently.

19. a detergent composition, it comprises among the claim 1-16 each component, and preferred form is a sheet or block or be particulate composition.