CN1268164A - Detergent compositions comprising a specific cellulase and alkyl poly glucoside surfactant - Google Patents
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Abstract
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技术领域Technical field
本发明涉及含有特殊纤维素酶和烷基多葡糖苷表面活性剂的洗衣洗涤剂组合物。The present invention relates to laundry detergent compositions comprising specific cellulases and alkyl polyglucoside surfactants.
发明背景Background of the Invention
现在洗涤剂组合物包括了满足某些特殊需要的活性组分的复杂组合:表面活性剂体系、提供清洁和织物护理效果的酶、漂白剂、助洗剂体系、抑泡剂、污垢悬浮剂、去污剂、荧光增白剂、柔软剂、分散剂、染料转移抑制化合物、磨料、杀菌剂、香料,在近几年中它们的总体性能确实已得到改善。现行的洗涤剂配方通常尤其包括洗涤剂酶和更具体地说纤维素酶。Detergent compositions now include a complex combination of active ingredients for some specific needs: surfactant systems, enzymes to provide cleaning and fabric care benefits, bleaches, builder systems, suds suppressors, soil suspending agents, Detergents, optical brighteners, softeners, dispersants, dye transfer inhibiting compounds, abrasives, bactericides, fragrances, the overall performance of them has indeed improved in recent years. Current detergent formulations often include detergent enzymes and more specifically cellulases among others.
纤维素酶的活性是指其中纤维素纤维或载污体被纤维素酶水解,并取决于纤维素酶的具体功能,它可以是内或外切纤维素酶和各自的半纤维素酶。纤维素结构被解聚或断裂成较小的,因而是更水溶性或可分散的部分。尤其对织物的活性向织物结构提供了清洁、复原、柔软和通常改善的手感特性。Cellulase activity refers to where cellulose fibers or substrates are hydrolyzed by a cellulase, and depending on the specific function of the cellulase, it can be an endo- or exo-cellulase and the respective hemicellulase. The cellulose structure is depolymerized or broken into smaller, and thus more water soluble or dispersible fractions. The activity on fabrics in particular provides cleaning, restoration, softness and generally improved hand properties to the fabric structure.
人们已认识到纤维素分解酶,即纤维素酶在用作织物的织物清洁和粗糙度降低试剂的效能有一段时间;WO89/09259、GB-A-2075028、GB-A-2095275和GB-A-2094826公开了含有纤维素酶以改善洗涤性能的洗涤剂组合物;GB-A-1368599公开了纤维素酶用于降低含棉织物粗糙度的用途;US4435307公开了由Humicola insolens以及其称为ACXI的馏分得到的纤维素分解酶作为降低粗糙度洗涤剂添加剂的用途。Cellulolytic enzymes, i.e. cellulases, have been recognized for some time for their effectiveness as fabric cleaning and roughness reducing agents for fabrics; WO89/09259, GB-A-2075028, GB-A-2095275 and GB-A -2094826 discloses a detergent composition containing cellulase to improve washing performance; GB-A-1368599 discloses the use of cellulase for reducing the roughness of cotton-containing fabrics; Use of a fraction obtained cellulolytic enzyme as a harshness reducing detergent additive.
EP-A-0269168公开了含有纤维素酶的最佳化洗涤剂组合物,它在温和碱性pH范围内配制,并提供了组合的织物洗涤、织物柔软和织物护理性能。EP-A-0269168 discloses optimized detergent compositions containing cellulase enzymes formulated in the mildly alkaline pH range and providing combined fabric washing, fabric softening and fabric care performance.
适用于本发明的特殊纤维素酶在WO91/17244中描述,其中描述了所选择的高比活性单组分酶和其中公开了能够降解纤维素或半纤维素的酶。Specific cellulases suitable for use in the present invention are described in WO 91/17244, which describes selected high specific activity monocomponent enzymes and which discloses enzymes capable of degrading cellulose or hemicellulose.
同样合适的是在WO95/02675中公开的纤维素分解酶,它描述了含有两种纤维素酶组分的洗涤剂组合物:第一种纤维素酶组分具有延迟型的活性并能够去除颗粒污垢,第二种纤维素酶组分含有多个结构域,其包含至少一个连接催化结构域的非催化结构域,并能够澄清颜色,其中至少一种纤维素酶组分是单一组分。所述含酶洗涤剂组合物能够同时提供充分的颜色澄清和去除颗粒污垢,它在有限次数的洗涤周期后,既不损坏,也不部分降解含有纤维素的织物。Also suitable are the cellulolytic enzymes disclosed in WO 95/02675, which describes detergent compositions comprising two cellulase components: a first cellulase component having a delayed type of activity and capable of particle removal Soil, a second cellulase component comprising multiple domains comprising at least one non-catalytic domain linked to a catalytic domain and capable of color clarification, wherein at least one cellulase component is a single component. The enzymatic detergent composition is capable of simultaneously providing sufficient color clarification and removal of particulate soils which neither damages nor partially degrades cellulose-containing fabrics after a limited number of wash cycles.
合适的纤维素酶是1994年9月29日公开的Genencor的WO94/21801中描述的由Trichoderma longibrachiatum得到的EGIII纤维素酶。A suitable cellulase is the EGIII cellulase from Trichoderma longibrachiatum described in WO 94/21801, Genencor, published September 29, 1994.
人们同样已知在洗涤剂配方中发生纤维素酶失活作用,纤维素酶活性损失其中之一是取决于辅助洗涤剂组分的存在,一种类型的辅助洗涤剂组分是表面活性剂。Cellulase inactivation is also known to occur in detergent formulations, one of which is the loss of cellulase activity depending on the presence of co-detergent components, one type of co-detergent components being surfactants.
在文献中和商业实践中已知各种洗涤剂表面活性剂,它们在洗涤剂基体中起两重功能。首先,表面活性剂分子降低了污垢和水相之间的界面张力,从而通过卷起、乳化或增溶机理从表面逐渐除去污渍。阴离子表面活性剂尤其适用于该功能。其次,表面活性剂分子保持污垢悬浮,避免重新沉积在表面上。葡糖苷非离子和阴离子表面活性剂通常用于该用途。Various detersive surfactants are known in the literature and in commercial practice which serve a dual function in the detergent matrix. First, the surfactant molecules lower the interfacial tension between the soil and the water phase, thereby gradually removing the stain from the surface by rolling up, emulsification, or solubilization mechanisms. Anionic surfactants are especially suitable for this function. Second, the surfactant molecules keep the dirt in suspension, avoiding redeposition on the surface. Glucoside nonionic and anionic surfactants are commonly used for this purpose.
事实上,现存的洗衣洗涤剂组合物通常含有非离子表面活性剂,尤其是带有亲水头的非离子表面活性剂。某些商业上可得到的非离子表面活性剂,例如烷基多葡糖苷表面活性剂在结构上类似于棉结构的葡糖苷类型,由于它们即使在低浓度下保持高粘度的能力,因而被认为增强了洗涤性能(Tenside Surf.Det28(1991)6)。In fact, existing laundry detergent compositions often contain nonionic surfactants, especially nonionic surfactants with a hydrophilic head. Certain commercially available nonionic surfactants, such as alkyl polyglucoside surfactants, are structurally similar to the cotton-structured glucoside type and are considered due to their ability to maintain high viscosity even at low concentrations. Enhanced washing performance (Tenside Surf. Det28 (1991) 6).
烷基多葡糖苷表面活性剂已在US3598865、3721633和3772269中公开。这些专利还公开了制备烷基多葡糖苷表面活性剂和含有这些表面活性剂的复配液体洗涤剂组合物的方法。US3219656公开了烷基单葡糖苷,并建议了它们作为其它表面活性剂的泡沫稳定剂的应用。各种多葡糖苷表面活性剂结构和它们的制备方法在US2974134、3640998、3839318、3314936、3346558、4011389和4223129中公开。Alkyl polyglucoside surfactants are disclosed in US3598865, 3721633 and 3772269. These patents also disclose processes for the preparation of alkyl polyglucoside surfactants and formulated liquid detergent compositions containing these surfactants. US3219656 discloses alkyl monoglucosides and suggests their use as foam stabilizers for other surfactants. Various polyglucoside surfactant structures and their methods of preparation are disclosed in US Pat.
在洗涤组合物中烷基多葡糖苷表面活性剂已被公开与若干辅助表面活性剂组合。US4396520公开了含有烷基多糖表面活性剂和钙敏感阴离子洗涤剂辅助表面活性剂的洗涤剂组合物。US4565647公开了含有烷基多糖表面活性剂和硫酸盐、磺酸盐和/或羧酸盐辅助表面活性剂的发泡组合物。US4599188公开了含有烷基多糖表面活性剂、硫酸盐、磺酸盐和/或羧酸盐辅助表面活性剂和酰胺和/或氧化胺辅助增泡剂的发泡组合物。US4732704公开了含有烷基单葡糖苷表面活性剂、硫酸盐或磺酸盐类型的阴离子表面活性剂和脂肪酸烷醇酰胺的手洗餐具洗涤剂组合物。US4839098公开了含有烷基多葡糖苷表面活性剂和磺基琥珀酸二烷基酯的手洗餐具洗涤剂组合物。Alkyl polyglucoside surfactants have been disclosed in combination with several cosurfactants in detergent compositions. US4396520 discloses detergent compositions comprising an alkylpolysaccharide surfactant and a calcium sensitive anionic detergent co-surfactant. US4565647 discloses foaming compositions containing alkyl polysaccharide surfactants and sulphate, sulphonate and/or carboxylate co-surfactants. US4599188 discloses foaming compositions containing alkyl polysaccharide surfactants, sulphate, sulphonate and/or carboxylate co-surfactants and amide and/or amine oxide co-foam boosters. US4732704 discloses hand dishwashing detergent compositions containing alkyl monoglucoside surfactants, anionic surfactants of the sulfate or sulfonate type and fatty acid alkanolamides. US4839098 discloses hand dishwashing detergent compositions containing alkyl polyglucoside surfactants and dialkyl sulfosuccinates.
烷基多葡糖苷表面活性剂还在WO92/19711、WO92/08439、DE4029035、JP3163198、JO3174796、EP216301、EP280143、WO91/13096和WO92/19711中描述。Alkyl polyglucoside surfactants are also described in WO92/19711, WO92/08439, DE4029035, JP3163198, JO3174796, EP216301, EP280143, WO91/13096 and WO92/19711.
鉴于所述,在配制洗涤剂组合物中仍存在的主要技术挑战是满足消费者杰出的洗涤和白度性能效果的需要。In view of the above, the major technical challenge that remains in formulating detergent compositions is to meet consumer demands for outstanding wash and whiteness performance benefits.
我们现在惊奇地发现如下公开类型的烷基多葡糖苷表面活性剂提供了特殊纤维素酶的增效功能。该发现能够在保持相同洗涤性能的同时得到改善的性能或降低的表面活性剂/特殊纤维素酶含量。We have now surprisingly found that alkyl polyglucoside surfactants of the type disclosed below provide a specific cellulase-enhancing function. This discovery enables improved performance or reduced surfactant/special cellulase levels while maintaining the same wash performance.
发明概述Invention Summary
本发明涉及含有特殊纤维素酶和烷基多葡糖苷表面活性剂的洗衣洗涤剂组合物,其提供了杰出的洗涤和白度性能效果。The present invention relates to laundry detergent compositions comprising specific cellulases and alkyl polyglucoside surfactants which provide outstanding cleaning and whiteness performance benefits.
发明的详细描述特殊纤维素酶Detailed Description of the Invention Special Cellulase
本发明的主要组分是特殊纤维素酶,它通常以按总组合物重量计0.0001%-2%,更优选0.0005%-0.05%,最优选0.001%-0.01%纯酶的含量包含在本发明的洗衣洗涤剂组合物中。The main component of the present invention is special cellulase, and it is generally contained in the present invention with the content of 0.0001%-2%, more preferably 0.0005%-0.05%, most preferably 0.001%-0.01% pure enzyme by total composition weight in laundry detergent compositions.
适用于本发明的特殊纤维素酶由真菌菌株得到,优选选自如下生物体:Humicola isolens或Trichoderma longibrachiatum,reseei或viride。特殊纤维素酶的另一特征在于具有4-10的最佳pH和没有纤维素结合结构域(CBD)。术语CBD是指能够将纤维素酶有效结合于纤维素载污体的氨基酸序列。Particular cellulases suitable for use in the present invention are obtained from fungal strains, preferably selected from the following organisms: Humicola isolens or Trichoderma longibrachiatum, reseei or viride. Another feature of the particular cellulase is that it has a pH optimum of 4-10 and lacks a cellulose binding domain (CBD). The term CBD refers to an amino acid sequence capable of effectively binding a cellulase to a cellulose substrate.
我们现在惊奇地发现如下公开类型的烷基多葡糖苷表面活性剂提供了特殊纤维素酶的增效功能。该发现能够在保持相同洗涤性能的同时得到改善的性能或降低的表面活性剂/特殊纤维素酶含量。We have now surprisingly found that alkyl polyglucoside surfactants of the type disclosed below provide a specific cellulase-enhancing function. This discovery enables improved performance or reduced surfactant/special cellulase levels while maintaining the same wash performance.
可适用于本发明的纤维素酶组分的实例是:Examples of cellulase components suitable for use in the present invention are:
内切葡聚糖酶组分,它与由Humicola insolens DSM 1800得到的高纯-50kD内切葡聚糖酶产生的抗体发生免疫反应或它是显示纤维素酶活性的-50kD内切葡聚糖酶的同系物或衍生物;优选的内切葡聚糖酶组分具有PCT专利申请WO91/17244中公开的氨基酸序列,或内切葡聚糖酶组分,它与由尖孢镰孢(Fusarium oxysporum)DSM 2672得到的高纯-50kD(表观分子量,氨基酸组成相当于带有2n糖基化位点的45kD)内切葡聚糖酶产生的抗体发生免疫反应或它是显示纤维素酶活性的-50kD内切葡聚糖酶的同系物或衍生物;优选的内切葡聚糖酶组分具有PCT专利申请WO91/17244中公开的氨基酸序列。更优选的是由近似分子量约50kDa、等电点约5.5和含有415个氨基酸的Humicola insolens,DSM1800得到。Endoglucanase fraction that immunoreacts with antibodies raised from highly purified - 50kD endoglucanase from Humicola insolens DSM 1800 or it is - 50kD endoglucan that exhibits cellulase activity Homologue or derivative of enzyme; Preferred endoglucanase component has the disclosed aminoacid sequence among the PCT patent application WO91/17244, or endoglucanase component, it and by Fusarium oxysporum (Fusarium oxysporum) DSM 2672 obtained high purity - 50kD (apparent molecular weight, amino acid composition is equivalent to 45kD with 2n glycosylation site) endoglucanase immunoreaction or it shows cellulase activity Homologs or derivatives of -50 kD endoglucanase; preferred endoglucanase components have the amino acid sequence disclosed in PCT patent application WO91/17244. More preferred is obtained from Humicola insolens, DSM1800, which has an approximate molecular weight of about 50 kDa, an isoelectric point of about 5.5, and contains 415 amino acids.
内切葡聚糖酶可由已知能够产生纤维素分解酶的微生物,例如腐质霉属、芽孢杆菌属、Trichederma、镰孢属、毁丝霉属(Myceliophtora)、Phanerochaete、裂褶菌属(Schizophyllum)、青霉属、曲霉属和地霉属(Geotricum)得到或分离,和纯化。得到的组分可以是同源或异种的,优选组分是同源的。然而也优选与具有所需性质的高纯纤维素酶组分产生的抗体发生免疫反应的异种组分,和该异种组分由特殊微生物得到的异种组分。Endoglucanases can be obtained from microorganisms known to produce cellulolytic enzymes, such as Humicola, Bacillus, Trichederma, Fusarium, Myceliophtora, Phanerochaete, Schizophyllum ), Penicillium, Aspergillus and Geotricum were obtained or isolated, and purified. The resulting components may be homologous or heterogeneous, preferably the components are homogeneous. However, heterologous fractions immunoreactive with antibodies produced by highly pure cellulase fractions having the desired properties, and heterologous fractions derived from specific microorganisms are also preferred.
例如如WO95/02675中所述,另一种合适内切葡聚糖酶组分具有在其中所附的SEQ ID NO:2或在WO91/17244,附图14A-E中公开的氨基酸序列或具有与所述序列至少60%、优选至少70%,更优选至少75%,更优选至少80%,更优选至少85%,尤其至少90%同源的氨基酸序列的所述内切葡聚糖酶变种。For example, as described in WO95/02675, another suitable endoglucanase component has SEQ ID NO: 2 attached therein or the amino acid sequence disclosed in WO91/17244, accompanying drawings 14A-E or has Said endoglucanase variant with an amino acid sequence at least 60%, preferably at least 70%, more preferably at least 75%, more preferably at least 80%, more preferably at least 85%, especially at least 90% homologous to said sequence .
所述内切葡聚糖酶还可以是与由尖孢镰孢(Fusariumoxysporum)DSM 2672得到的高纯-50kD(表观分子量,氨基酸组成相当于带有2n糖基化位点的45kD)内切葡聚糖酶产生的抗体发生免疫反应的内切葡聚糖酶组分或它是显示纤维素酶活性的-50kD内切葡聚糖酶的同系物或衍生物。优选的内切葡聚糖酶组分具有在WO95/02675中所附的SEQ ID NO:3或在WO91/17244,附图13中公开的氨基酸序列或具有与所述序列至少60%、优选至少70%,更优选75%,更优选至少80%,更优选85%,尤其至少90%同源的氨基酸序列的所述内切葡聚糖酶变种。The endoglucanase can also be an endoglucanase obtained from Fusarium oxysporum (Fusarium oxysporum) DSM 2672 with high purity - 50kD (apparent molecular weight, amino acid composition is equivalent to 45kD with 2n glycosylation sites). The glucanase-generated antibody is immunoreactive to the endoglucanase component or it is a homologue or derivative of the -50kD endoglucanase exhibiting cellulase activity. A preferred endoglucanase component has SEQ ID NO: 3 attached in WO95/02675 or the amino acid sequence disclosed in WO91/17244, accompanying drawing 13 or has at least 60%, preferably at least 70%, more preferably 75%, more preferably at least 80%, more preferably 85%, especially at least 90% homologous amino acid sequence to said endoglucanase variant.
所述内切葡聚糖酶组分组分由米曲霉(Aspergillus oryzae)用含有相应于在WO95/02675中所述的SEQ ID NO:3的氨基酸序列的DNA序列的质粒和使用Taka促进剂和AMG终止剂进行转变后制备,该内切葡聚糖酶可用阳离子色谱法纯化为同质性,具有pl>9。该计算的pl基于氨基酸组成并使用来自Adv.Protein Chem.17,69-165页(1962),C.Tanford.的PHKa值,摩尔消光系数计算为58180。Described endoglucanase component component is made by Aspergillus oryzae (Aspergillus oryzae) with the plasmid containing the DNA sequence corresponding to the aminoacid sequence described in WO95/02675 SEQ ID NO: 3 and using Taka promoter and AMG Prepared after conversion of the terminator, the endoglucanase can be purified to homogeneity with pl > 9 by cationic chromatography. The calculated pl was based on the amino acid composition and using the PHKa value from Adv. Protein Chem. 17, pp. 69-165 (1962), C. Tanford. The molar extinction coefficient was calculated as 58180.
其它合适的纤维素酶是在1994年9月29日公开的WO94/21801,Genencor中描述的由Trichoderma longibrachiatum得到的EGIII。更优选的用于本发明洗衣洗涤剂组合物的纤维素酶是由木霉属(Trichoderma spp)得到的具有22-27kDa近似分子量,7.2-8.0的等电点和5.5-6.0的pH最佳值的纤维素酶。Other suitable cellulases are EGIII from Trichoderma longibrachiatum described in WO 94/21801, Genencor, published September 29, 1994. A more preferred cellulase for use in the laundry detergent compositions of the present invention is obtained from Trichoderma spp having an approximate molecular weight of 22-27 kDa, an isoelectric point of 7.2-8.0 and a pH optimum of 5.5-6.0 of cellulase.
在本发明中,术语“同源”是指由DNA编码的多肽,在某些特殊条件下(例如在5×SSC中预浸泡和在20%甲酰胺、5×Denhardt’s溶液、50mM磷酸钠,pH6.8和50μg变性声处理的牛犊胸腺DNA的溶液中在约40℃预杂交1小时,随后在约40℃下在用100μM ATP补给的相同溶液中杂交18小时)它与用该氨基酸序列编码内切葡聚糖酶的DNA相同的探针杂交。该术语包括通过在天然序列的C和N端的之一或两者加入一个或多个氨基酸残基、在天然序列中在一个或多个位置上取代一个或多个氨基酸残基、在天然氨基酸序列的一端或两端或天然序列中的一个或多个位置上缺失一个或多个氨基酸残基或在天然氨基酸序列的一个或多个位置中插入一个或多个氨基酸残基得到的上述序列的衍生物。In the present invention, the term "homologous" refers to a polypeptide encoded by DNA, which is prepared under certain special conditions (such as presoaking in 5×SSC and in 20% formamide, 5×Denhardt's solution, 50 mM sodium phosphate, pH6 .8 and 50 μg of denatured sonicated calf thymus DNA were prehybridized at about 40° C. for 1 hour, followed by hybridization at about 40° C. in the same solution supplemented with 100 μM ATP) for 18 hours) which is compatible with the endogenous DNA encoded by the amino acid sequence Hybridize with the same probe as the DNA that cleaves the glucanase. The term includes addition of one or more amino acid residues at one or both of the C- and N-termini of the native sequence, substitution of one or more amino acid residues at one or more positions in the native sequence, Derivation of the above sequence obtained by deleting one or more amino acid residues at one or both ends of the natural sequence or at one or more positions in the natural sequence or inserting one or more amino acid residues at one or more positions in the natural amino acid sequence thing.
然而,为工业生产纤维素酶制剂,优选采用重组DNA技术或包含发酵的调节或包含微生物突变的其它技术以确保所需酶活性的超量产生。该方法和技术是本领域中已知的,可以由本领域的技术人员容易地进行。However, for the industrial production of cellulase preparations it is preferred to employ recombinant DNA techniques or other techniques involving modulation of fermentation or involving mutation of microorganisms to ensure overproduction of the desired enzyme activity. Such methods and techniques are known in the art and can be readily performed by those skilled in the art.
上述酶可以是任何合适的来源,例如植物、动物、细菌、真菌和酵母来源。来源还可以是嗜中介态的或嗜极限条件(extremophilic)(嗜冷、嗜热、嗜压、嗜碱、嗜酸、嗜卤素等)。这些酶的纯或不纯的形式都能使用。目前,通常的实践是经蛋白质/基因工程技术改性野生类型的酶以最佳化它们在本发明的洗涤组合物中的性能效率。例如可设计变体以增加酶与该组合物中通常遇到的组分的相容性。此外,可设计变体使得酶变体的最佳pH、漂白剂或螯合剂稳定性、催化活性等能够适应特定的洗涤应用。The aforementioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. The source can also be mesophilic or extremophilic (psychrophilic, thermophilic, barophilic, basophilic, acidophilic, halophilic, etc.). Pure or impure forms of these enzymes can be used. Currently, it is common practice to modify wild-type enzymes via protein/genetic engineering techniques to optimize their performance efficiency in the detergent compositions of the present invention. For example, variants can be designed to increase the compatibility of the enzyme with commonly encountered components of the composition. In addition, variants can be designed such that the optimal pH, bleach or chelator stability, catalytic activity etc. of the enzyme variant can be tailored to a specific wash application.
在漂白剂稳定性的情况下尤其应注意对氧化敏感的氨基酸,和对于表面活性剂相容性应注意表面电荷。这种酶的等电点可通过某些带电荷的氨基酸的取代改性,例如增加等电点会有助于改善与阴离子表面活性剂的相容性。酶的稳定性可进一步通过产生例如附加盐桥和加强钙结合位置以增加螯合剂稳定性改善。葡糖苷表面活性剂:Particular attention should be paid to oxidation-sensitive amino acids in the case of bleach stability, and to the surface charge for surfactant compatibility. The isoelectric point of this enzyme can be modified by the substitution of some charged amino acids, for example, increasing the isoelectric point will help to improve the compatibility with anionic surfactants. Enzyme stability can be further improved by creating, for example, additional salt bridges and strengthening calcium binding sites to increase chelator stability. Glucoside Surfactants:
本发明的洗涤剂组合物含有下式烷基多葡糖苷表面活性剂:Detergent composition of the present invention contains following formula alkyl polyglucoside surfactant:
R-O-Gx其中R是平均C8-C20,优选C8-C16烷基,G是由含有5-6个碳原子的还原糖类得到的部分,优选葡萄糖单元,x是平均1.0-3.0,优选约1.1-1.5,表示烷基多糖表面活性剂的聚合平均程度。ROG x wherein R is an average C 8 -C 20 , preferably C 8 -C 16 alkyl, G is a moiety derived from a reducing sugar containing 5-6 carbon atoms, preferably a glucose unit, x is an average of 1.0-3.0, Preferably about 1.1-1.5, representing the average degree of polymerization of the alkyl polysaccharide surfactant.
对于具体的烷基多糖分子,x可仅假定为整数值。在烷基多葡糖苷表面活性剂的任何物理样品中,它们通常是具有不同x值的分子。物理样品可以x平均值为特征,它可假定非整数值。在说明书中,x的值被认为是平均值。For a particular alkylpolysaccharide molecule, x can only assume integer values. In any physical sample of alkyl polyglucoside surfactants, they are usually molecules with different values of x. Physical samples can be characterized by x-means, which can assume non-integer values. In the specification, the value of x is considered to be an average value.
表面活性剂的多糖亲水部分含有平均约1-约3,优选1.1-约1.5个糖类单元,糖类单元可以是半乳糖苷、葡糖苷、乳糖苷、果糖苷、葡糖基、果糖基、乳糖基和/或半乳糖基单元。这些糖类部分的混合物可用于烷基多糖表面活性剂中。葡糖苷是优选的糖类部分。其它糖类部分将同样地起作用,但由于葡糖苷是优选的糖类部分,其余的公开内容将集中于烷基多葡糖苷表面活性剂。The polysaccharide hydrophilic part of the surfactant contains an average of about 1 to about 3, preferably 1.1 to about 1.5 carbohydrate units, which can be galactoside, glucoside, lactoside, fructoside, glucosyl, fructosyl , lactosyl and/or galactosyl units. Mixtures of these carbohydrate moieties can be used in the alkyl polysaccharide surfactants. Glucosides are the preferred carbohydrate moieties. Other carbohydrate moieties will work equally well, but since glucoside is the preferred carbohydrate moiety, the remainder of the disclosure will focus on alkyl polyglucoside surfactants.
烷基多糖的疏水基团是烷基,它是饱和或不饱和的,支链或非支链的,含有平均约10-约16个碳原子。优选烷基主要是直链饱和C12-C14烷基。The hydrophobic group of the alkylpolysaccharide is the alkyl group, which is saturated or unsaturated, branched or unbranched, containing an average of about 10 to about 16 carbon atoms. Preferred alkyl groups are predominantly linear saturated C 12 -C 14 alkyl groups.
还可用作本发明的表面活性剂体系的非离子表面活性剂的是在1986年1月21日颁布的Llenado的US4565647中公开的烷基多糖,其具有含约6-约30个碳原子,优选约10-约16个碳原子的疏水基团和含有约1.3-约10,优选约1.3-约3,最优选约1.3-约2.7个糖单元的多糖,例如多糖苷亲水基团。可以使用任何含有5或6个碳原子的还原糖类,例如葡萄糖,半乳糖和半乳糖基部分可用于替代葡糖基部分(疏水基选择性地连接在2-、3-、4-等位置,从而得到相对于葡糖苷或半乳糖苷的葡萄糖或半乳糖)。糖间键可在例如附加的糖单元的一个位置和先前的糖单元的2-、3-、4-和/或6-位置之间。Also useful as nonionic surfactants in the surfactant system of the present invention are the alkylpolysaccharides disclosed in US4565647, Llenado, issued January 21, 1986, having carbon atoms of about 6 to about 30, Hydrophobic groups of from about 10 to about 16 carbon atoms are preferred and polysaccharides containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units, such as polyglycoside hydrophilic groups. Any reducing sugar containing 5 or 6 carbon atoms can be used, such as glucose, galactose and galactosyl moieties can be used in place of glucosyl moieties (hydrophobic groups are selectively attached at 2-, 3-, 4-, etc. , so as to obtain glucose or galactose relative to glucoside or galactoside). Intersaccharide linkages may be, for example, between one position of the additional sugar unit and the 2-, 3-, 4- and/or 6-position of the previous sugar unit.
优选的烷基多糖苷具有下式:Preferred alkyl polyglycosides have the formula:
R2O(CnH2nO)t(糖基)x其中R2选自烷基、烷基苯基、羟基烷基、羟基烷基苯基和它们的混合物,其中烷基含有约10-约18,优选约12-约14个碳原子;n是2或3,优选2;t是0-约10,优选0;和x是约1.3-约10,优选约1.3-约3,最优选约1.3-约2.7。糖基优选由葡萄糖得到。为制备这些化合物,首先形成醇或烷基聚乙氧基醇,随后与葡萄糖或葡萄糖源反应形成葡糖苷(连接在1-位)。其它的糖基单元可随后连接在其1-位和先前的糖基单元2-、3-、4-和/或6-位之间,优选主要在2-位。R 2 O(C n H 2n O) t (glycosyl) x wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains about 10- About 18, preferably about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; and x is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably About 1.3-about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl polyethoxy alcohol is first formed and subsequently reacted with glucose or a source of glucose to form the glucoside (attached at the 1-position). Further glycosyl units may subsequently be attached between their 1-position and the previous glycosyl unit 2-, 3-, 4- and/or 6-position, preferably predominantly in the 2-position.
优选的烷基多葡糖苷表面活性剂含有含1-6,优选2-4个α或β吡喃糖苷或呋喃糖苷端基异构体的亲水基团。Preferred alkyl polyglucoside surfactants contain a hydrophilic group comprising 1-6, preferably 2-4 alpha or beta pyranoside or furanoside anomers.
所述烷基多葡糖苷表面活性剂以按总组合物重量计0.1-20%,优选1-10%,更优选2-8%的含量包含在本发明的洗涤剂组合物中。洗涤剂组分The alkyl polyglucoside surfactant is included in the detergent composition of the present invention at a level of 0.1-20%, preferably 1-10%, more preferably 2-8% by weight of the total composition. detergent components
本发明的洗衣洗涤剂组合物还可以含有其它洗涤剂组分。这些附加组分的确切性质和它们的加入量将根据组合物的物理形式和所使用的洗涤操作的性质决定。The laundry detergent compositions of the present invention may also contain other detergent ingredients. The exact nature of these additional ingredients and their level of addition will depend upon the physical form of the composition and the nature of the laundering operation employed.
本发明的洗涤组合物可以是液体、膏状、凝胶、块、片、喷雾剂、泡沫、粉末或颗粒形式,颗粒组合物还可以是“致密”形式,液体组合物还可以是“浓缩”形式。The cleaning composition of the present invention can be in the form of liquid, paste, gel, block, tablet, spray, foam, powder or granules, the granular composition can also be in the form of "compact", and the liquid composition can also be in the form of "concentrated" form.
本发明的组合物可配制成例如手工和机器洗衣洗涤剂组合物,其包括洗衣添加剂组合物和适用于脏织物的浸泡和/或预处理的组合物、漂洗中加入的织物柔软剂组合物。The compositions of the present invention may be formulated, for example, as hand and machine laundry detergent compositions comprising laundry additive compositions and compositions suitable for soaking and/or pretreatment of soiled fabrics, rinse added fabric softener compositions.
本发明的组合物优选同时含有表面活性剂和助洗剂化合物和附加的一种或多种的洗涤剂组分,其优选选自有机聚合物、漂白剂、附加的酶、抑泡剂、分散剂、钙皂分散剂、污垢悬浮剂和抗再沉积剂和腐蚀抑制剂。洗衣组合物还可含有作为附加洗涤剂组分的柔软剂。The compositions of the present invention preferably contain both surfactant and builder compounds and additional one or more detergent ingredients, preferably selected from the group consisting of organic polymers, bleaching agents, additional enzymes, suds suppressors, dispersing agent, lime soap dispersant, soil suspending agent and anti-redeposition agent and corrosion inhibitor. Laundry compositions can also contain softening agents as additional detergent ingredients.
当配制成洗衣洗涤剂组合物时,含有所述特殊纤维素酶和烷基多葡糖苷表面活性剂的该组合物可提供织物洗涤、去污、白度保持、柔软、颜色外观、染料转移抑制和卫生作用。When formulated into a laundry detergent composition, the composition containing said specific cellulase and an alkyl polyglucoside surfactant provides fabric cleaning, stain removal, whiteness maintenance, softness, color appearance, dye transfer inhibition and hygienic effects.
本发明的组合物还可用作洗涤剂添加剂产物。该添加剂产物用来补充或增强常规洗涤剂组合物的性能。The compositions of the present invention are also useful as detergent additive products. The additive products are used to supplement or enhance the performance of conventional detergent compositions.
如果需要,本发明的洗衣洗涤剂组合物的密度在20℃下测定为400-1200克/升,优选600-950克/升组合物。If desired, the laundry detergent compositions of the present invention have a density, measured at 20°C, of 400-1200 g/l, preferably 600-950 g/l composition.
本发明组合物的“致密”形式由密度和,对于组合物,由无机填料盐的量最好地反映;无机填料盐是粉末形式的洗涤剂组合物的常规组分;在常规洗涤剂组合物中,填料盐以大量存在,通常为按总组合物重量计17-35%。The "compact" form of the compositions of the present invention is best reflected by the density and, for the composition, by the amount of inorganic filler salt; inorganic filler salt is a conventional component of detergent compositions in powder form; in conventional detergent compositions In , the filler salt is present in substantial amounts, typically 17-35% by weight of the total composition.
在致密组合物中,填料盐以按组合物重量计不超过总组合物的15%,优选不超过10%,最优选不超过5%的量存在。In compact compositions, the filler salt is present in an amount not exceeding 15%, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition of the total composition.
如本发明的组合物中所述的无机填料盐选自碱金属和碱土金属的硫酸盐和氯化物。The inorganic filler salts as described in the composition of the present invention are selected from alkali metal and alkaline earth metal sulfates and chlorides.
优选的填料盐是硫酸钠。A preferred filler salt is sodium sulfate.
本发明的液体洗涤剂组合物还可以是“浓缩”形式,在该情况下,本发明的液体洗涤剂组合物将含有与常规液体洗涤剂相比较低含量的水。The liquid detergent compositions of the present invention may also be in "concentrated" form, in which case the liquid detergent compositions of the present invention will contain lower levels of water compared to conventional liquid detergents.
浓缩液体洗涤剂的水含量通常优选少于按洗涤剂组合物重量计40%,更优选少于30%,最优选少于20%。附加表面活性剂体系Concentrated liquid detergents generally preferably have a water content of less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition. Additional Surfactant System
除烷基多葡糖苷表面活性剂之外,本发明的洗衣洗涤剂组合物通常含有表面活性剂体系,其中表面活性剂可选自其它非离子和/或阴离子和/或阳离子和/或两性和/或两性离子和/或半极性表面活性剂。The laundry detergent compositions of the present invention generally contain a surfactant system in addition to the alkyl polyglucoside surfactant, wherein the surfactant may be selected from other nonionic and/or anionic and/or cationic and/or amphoteric and /or zwitterionic and/or semi-polar surfactants.
表面活性剂通常以按重量计0.1%-60%的量存在。在本发明的洗衣和漂洗时加入的柔软剂组合物中,更优选加入量为按重量计1%-35%,最优选按重量计1%-25%。Surfactants are typically present in amounts of 0.1% to 60% by weight. In the laundry and rinse softener composition of the present invention, it is more preferably added in an amount of 1%-35% by weight, most preferably 1%-25% by weight.
表面活性剂优选配制成与组合物中存在的酶组分相容。在液体或凝胶组合物中,表面活性剂最优选配制成使其促进,或至少不破坏这些组合物中任何酶的稳定性。The surfactant is preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated so as to promote, or at least not destabilize, any enzymes present in these compositions.
用于本发明的优选表面活性剂体系含有一种或多种本发明描述的用作表面活性剂的非离子和/或阴离子表面活性剂。Preferred surfactant systems for use in the present invention contain one or more nonionic and/or anionic surfactants described herein as surfactants.
烷基苯酚的聚氧乙烯、聚氧丙烯和聚氧丁烯缩合物适合用作本发明表面活性剂体系的非离子表面活性剂,其中优选聚氧乙烯缩合物。这些化合物包括具有含约6-约14个碳原子,优选约8-约14个碳原子的直链或支链构型的烷基的烷基苯酚与烯化氧的缩合产物。在优选实施方案中,环氧乙烷以每摩尔烷基苯酚等于约2-约25摩尔,更优选约3-约15摩尔环氧乙烷的量存在。商业上可得到的这种类型的非离子表面活性剂包括由GAF公司出售的IgepalTM CO-630,由Rohm &Haas公司出售的TritonTM X-45、X-114、X-100和X-102。这些表面活性剂通常称为烷基苯酚烷氧基化物(例如烷基苯酚乙氧基化物)。Polyoxyethylene, polyoxypropylene and polyoxybutylene condensates of alkylphenols are suitable as nonionic surfactants in the surfactant system according to the invention, polyoxyethylene condensates being preferred. These compounds include the condensation products of alkylphenols with alkylene oxides having an alkyl group of about 6 to about 14 carbon atoms, preferably about 8 to about 14 carbon atoms, in a linear or branched configuration. In a preferred embodiment, ethylene oxide is present in an amount equal to about 2 to about 25 moles, more preferably about 3 to about 15 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ™ CO-630 sold by GAF Corporation, Triton ™ X-45, X-114, X-100 and X-102 sold by Rohm & Haas Corporation. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).
伯和仲脂族醇与约1-约25摩尔的环氧乙烷的缩合产物适合用作本发明的非离子表面活性剂体系的非离子表面活性剂。脂族醇的烷基链可以是直链或支链的,伯或仲,通常含有约8-约22个碳原子。优选的是具有含约8-约20个碳原子,更优选含约10-约18个碳原子的烷基的醇与每摩尔醇约2-约10摩尔环氧乙烷的缩合产物。在所述缩合产物中每摩尔醇存在约2-约7摩尔环氧乙烷,最优选2-5摩尔环氧乙烷。商业上可得到的这种类型的非离子表面活性剂的实例包括TergitolTM15-S-9(C11-C15直链醇与9摩尔环氧乙烷的缩合产物)、TergitolTM24-L-6 NMW(具有窄分子量分布的C12-C14伯醇与6摩尔环氧乙烷的缩合产物),均由联合碳化公司出售;NeodolTM45-9(C14-C15直链醇与9摩尔环氧乙烷的缩合产物)、NeodolTM23-3(C12-C13直链醇与3.0摩尔环氧乙烷的缩合产物)、NeodolTM45-7(C14-C15直链醇与7摩尔环氧乙烷的缩合产物)、NeodolTM45-5(C14-C15直链醇与5摩尔环氧乙烷的缩合产物),均由壳牌化学公司出售、KyroTMEOB(C13-C15醇与9摩尔环氧乙烷的缩合产物),由Procter & Gamble公司出售;和Genapol LA 030或050(C12-C14醇与3或5摩尔环氧乙烷的缩合产物),由Hoechst销售。这些产物的优选HLB范围为8-11,最优选8-10。The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having alkyl groups containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with about 2 to about 10 moles of ethylene oxide per mole of alcohol. From about 2 to about 7 moles of ethylene oxide, most preferably from 2 to 5 moles of ethylene oxide, are present in the condensation product per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ™ 15-S-9 (a condensation product of C 11 -C 15 linear alcohols with 9 moles of ethylene oxide), Tergitol ™ 24-L -6 NMW (condensation products of C 12 -C 14 primary alcohols with narrow molecular weight distribution and 6 moles of ethylene oxide), both sold by Union Carbide; Neodol TM 45-9 (C 14 -C 15 linear alcohols with Condensation product of 9 moles of ethylene oxide), Neodol TM 23-3 (condensation product of C 12 -C 13 straight chain alcohol and 3.0 moles of ethylene oxide), Neodol TM 45-7 (C 14 -C 15 straight chain Alcohol Condensation Product with 7 Moles of Ethylene Oxide), Neodol TM 45-5 (Condensation Product of C 14 -C 15 Linear Alcohols with 5 Moles of Ethylene Oxide), both sold by Shell Chemical Company, Kyro TM EOB ( Condensation product of C 13 -C 15 alcohol with 9 moles of ethylene oxide), sold by the company Procter &Gamble; and Genapol LA 030 or 050 (condensation product of C 12 -C 14 alcohol with 3 or 5 moles of ethylene oxide ), marketed by Hoechst. The preferred HLB range for these products is 8-11, most preferably 8-10.
环氧乙烷与通过缩合环氧丙烷与丙二醇形成的疏水基团的缩合产物也适合用作本发明的附加非离子表面活性剂体系。这些化合物的疏水部分优选具有约1500至约1800的分子量,并显示水不溶解性。在该疏水部分中加入聚氧乙烯基团将增加分子总体的水溶解性,产物的液体特征保持至聚氧乙烯含量为缩合产物总重量的约50%,这相当于缩合多达约40摩尔的环氧乙烷。这种类型的化合物的实例包括某些商业上可获得的PlurafacTM LF404和PluronicTM表面活性剂,均由BASF销售。Condensation products of ethylene oxide with hydrophobic groups formed by condensation of propylene oxide with propylene glycol are also suitable for use as an additional nonionic surfactant system in the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. The addition of polyoxyethylene groups to this hydrophobic moiety will increase the overall water solubility of the molecule and the liquid character of the product will remain until the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation of up to about 40 moles of Ethylene oxide. Examples of compounds of this type include certain of the commercially available Plurafac ™ LF404 and Pluronic ™ surfactants, both sold by BASF.
同样适合用作本发明的非离子表面活性剂体系的非离子表面活性剂的是环氧乙烷与通过环氧丙烷和乙二胺反应得到的产物的缩合产物。这些产物的疏水基团由乙二胺和过量环氧丙烷的反应产物组成,通常有约2500至约3000的分子量。该疏水基团与环氧乙烷缩合至使得缩合产物含有按重量计约40%-约80%的聚氧乙烯和具有约5000-约11000的分子量的程度。这种类型的非离子表面活性剂的实例包括某些商业上可获得的TetronicTM化合物,由BASF销售。Also suitable for use as the nonionic surfactant of the nonionic surfactant system according to the invention are the condensation products of ethylene oxide with the product obtained by reacting propylene oxide and ethylenediamine. The hydrophobic groups of these products consist of the reaction product of ethylenediamine and excess propylene oxide and generally have a molecular weight of from about 2500 to about 3000. The hydrophobic group is condensed with ethylene oxide to such an extent that the condensation product contains from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of nonionic surfactants of this type include certain of the commercially available Tetronic ™ compounds, marketed by BASF.
优选用作本发明的表面活性剂体系的非离子表面活性剂是烷基苯酚的聚环氧乙烷缩合物,伯和仲脂族醇与约1-约25摩尔环氧乙烷的缩合产物、烷基多糖和它们的混合物。最优选含有3-15个乙氧基的C8-C14烷基苯酚乙氧基化物和含有2-10个乙氧基的C8-C18醇乙氧基化物(优选C10平均)和它们的混合物。Preferred nonionic surfactants for use in the surfactant system of the present invention are polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, Alkyl polysaccharides and their mixtures. Most preferred are C8 - C14 alkylphenol ethoxylates containing 3-15 ethoxy groups and C8 - C18 alcohol ethoxylates containing 2-10 ethoxy groups (preferably C10 average) and their mixture.
高度优选的非离子表面活性剂是下式的多羟基脂肪酸酰胺表面活性剂:Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:
R2-C(O)-N(R1)-Z其中R1是H,或R1是C1-4烃基、2-羟基乙基、2-羟基丙基或它们的混合物,R2是C5-31烃基,和Z是具有直接连接至少3个羟基的直链烃基链的多羟基烃基,或它们的烷氧基化衍生物。优选R1是甲基,R2是直链C11-15烷基或C16-18烷基或烯基链,例如椰子油烷基或它们的混合物,和Z是由还原糖,例如葡萄糖、果糖、麦芽糖、乳糖在还原氨化反应中得到。R 2 -C(O)-N(R 1 )-Z wherein R 1 is H, or R 1 is C 1-4 hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R 2 is C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain directly attached to at least 3 hydroxyl groups, or an alkoxylated derivative thereof. Preferably R is methyl, R is a straight C 11-15 alkyl or C 16-18 alkyl or alkenyl chain, such as coconut oil alkyl or mixtures thereof, and Z is formed from a reducing sugar such as glucose, Fructose, maltose, and lactose are obtained in reductive amination reactions.
可使用的合适的阴离子表面活性剂是直链烷基苯磺酸盐、烷基酯磺酸盐表面活性剂,其包括C8-C20羧酸(即脂肪酸)的直链酯,它根据“美国油化学会志”,52(1975)第323-329页中的方法用气态三氧化硫磺化。合适的原料将包括由动物脂、棕榈油等得到的天然脂肪物质。Suitable anionic surfactants that can be used are linear alkylbenzene sulfonate, alkyl ester sulfonate surfactants, which include linear esters of C 8 -C 20 carboxylic acids (i.e. fatty acids) according to " Sulfonation with gaseous sulfur trioxide by the method in Journal of the American Oil Chemists' Society, 52 (1975) pp. 323-329. Suitable materials would include natural fatty materials derived from tallow, palm oil, and the like.
尤其用于洗衣应用的优选的烷基酯磺酸盐表面活性剂包括结构式如下的烷基酯磺酸盐表面活性剂:Preferred alkyl ester sulfonate surfactants, especially for laundry applications, include alkyl ester sulfonate surfactants of the formula:
R3-CH(SO3M)-C(O)-OR4其中R3是C8-C20烃基,优选烷基或它们的组合,R4是C1-C6烃基,优选烷基或它们的组合,M是阳离子,它与烷基酯磺酸形成水溶性盐。合适的成盐阳离子包括金属,例如钠、钾和锂,和取代或未取代的铵阳离子,例如单乙醇胺、二乙醇胺和三乙醇胺。优选R3是C10-C16烷基,和R4是甲基、乙基或异丙基。尤其优选的是其中R3是C10-C16烷基的甲基酯磺酸盐。R 3 -CH(SO 3 M)-C(O)-OR 4 wherein R 3 is a C 8 -C 20 hydrocarbon group, preferably an alkyl group or a combination thereof, R 4 is a C 1 -C 6 hydrocarbon group, preferably an alkyl group or Their combination, M is a cation, which forms a water-soluble salt with an alkyl ester sulfonic acid. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably R 3 is C 10 -C 16 alkyl, and R 4 is methyl, ethyl or isopropyl. Especially preferred are methyl ester sulfonates wherein R 3 is C 10 -C 16 alkyl.
其它合适的阴离子表面活性剂包括烷基硫酸盐表面活性剂,它是式ROSO3M的水溶性盐或酸,其中R优选是C10-C24烃基,优选含有C10-C20烷基部分的烷基或羟基烷基,更优选C12-C18烷基或羟基烷基,M是H或阳离子,其可以是碱金属阳离子(例如钠、钾、锂)、或铵或取代的铵(甲基-、二甲基-和三甲基-铵阳离子和季铵阳离子,例如四甲基铵和二甲基哌啶鎓阳离子和由烷基胺,例如乙胺、二乙胺、三乙胺得到的季铵阳离子和它们的混合物等)。对于低洗涤温度(例如低于约50℃),通常优选C12-C16的烷基链,对于较高洗涤温度(例如高于约50℃)优选C16-18烷基链。Other suitable anionic surfactants include alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO 3 M wherein R is preferably a C 10 -C 24 hydrocarbyl, preferably containing a C 10 -C 20 alkyl moiety Alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, M is H or a cation, which can be an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium ( Methyl-, dimethyl- and trimethyl-ammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and alkylamines such as ethylamine, diethylamine, triethylamine obtained quaternary ammonium cations and mixtures thereof, etc.). C12 - C16 alkyl chains are generally preferred for low wash temperatures (eg, below about 50°C), and C16-18 alkyl chains are preferred for higher wash temperatures (eg, above about 50°C).
适用于洗涤用途的其它阴离子表面活性剂也可以包括在本发明的洗涤剂组合物中。它们可以包括皂盐(包括,例如钠、钾、铵和取代的铵盐,例如单-、二-和三乙醇胺盐)、C8-C22伯或仲烷烃磺酸盐、C8-C24烯烃磺酸盐、在GB1082179中描述的通过磺化碱土金属柠檬酸盐的热解产物制备的磺化多羧酸、C8-C24烷基聚乙二醇醚硫酸盐(含有至多10摩尔环氧乙烷);烷基甘油磺酸盐、脂肪酰基甘油磺酸盐、脂肪油酰基甘油硫酸盐、烷基苯酚环氧乙烷醚硫酸盐、石蜡烃磺酸盐、烷基磷酸盐、羟乙磺酸盐,例如,酰基羟乙磺酸盐、N-酰基牛磺酸盐、烷基琥珀酰胺酸盐和磺基琥珀酸盐、磺基琥珀酸盐单酯(尤其是饱和和不饱和C12-C18单酯)和磺基琥珀酸盐二酯(尤其是饱和和不饱和C6-C12二酯)、酰基肌氨酸盐、烷基多糖的硫酸盐,例如烷基多葡糖苷硫酸盐(下文描述的非离子未硫酸化的化合物),支链伯烷基硫酸盐和烷基聚乙氧基羧酸盐,例如式RO(CH2CH2O)k-CH2COO-M+的那些,其中,R是C8-C22烷基,k是1-10整数,M是水溶性的成盐阳离子。树脂酸和氢化树脂酸也是合适的,例如松香、氢化松香、和存在于或由妥尔油得到的树脂酸和氢化树脂酸。Other anionic surfactants suitable for detersive use may also be included in the detergent compositions of the present invention. They may include soap salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), C 8 -C 22 primary or secondary alkane sulfonates, C 8 -C 24 Olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonating pyrolysis products of alkaline earth metal citrates described in GB1082179, C 8 -C 24 alkyl polyglycol ether sulfates (containing up to 10 moles of ring ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkylphenol oxirane ether sulfates, paraffin sulfonates, alkyl phosphates, hydroxyethyl Sulfonates, for example, acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C12 -C 18 monoesters) and sulfosuccinate diesters (especially saturated and unsaturated C 6 -C 12 diesters), acyl sarcosinates, sulfates of alkyl polysaccharides, such as alkyl polyglucoside sulfates Salts (nonionic unsulfated compounds described below), branched primary alkyl sulfates and alkyl polyethoxy carboxylates, such as the formula RO( CH2CH2O ) k - CH2COO - M + wherein, R is a C 8 -C 22 alkyl group, k is an integer of 1-10, and M is a water-soluble salt-forming cation. 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 tall oil.
其它实例在《表面活性剂和洗涤剂》(第I和II卷,Schwartz,Perry和Berch)中描述。各种这类表面活性剂还一般描述在1975年12月30日颁布的Laughlin等的US3929678,第23栏第58行至第29栏第23行中(列为本文参考文献)。Further examples are described in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch). A variety of such surfactants are also generally described in US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 23, line 58 through column 29, line 23 (herein incorporated by reference).
如果包括的话,本发明的洗衣洗涤剂组合物通常含有按重量计约1%-约40%,优选约3%-约20%这类阴离子表面活性剂。If included, the laundry detergent compositions of the present invention will generally contain from about 1% to about 40%, preferably from about 3% to about 20%, by weight of such anionic surfactants.
包括烷基烷氧基化硫酸盐表面活性剂的十分优选的阴离子表面活性剂是式RO(A)mSO3M的水溶性盐或酸,其中R是未取代的C10-C24烷基或含有C10-C24烷基部分的羟基烷基,优选C12-C20烷基或羟基烷基,更优选C12-C18烷基或羟基烷基,A是乙氧基或丙氧基单元,m大于零,通常在约0.5至约6之间,更优选在约0.5至约3之间,M是H或阳离子,其可以是例如金属阳离子(例如钠、钾、锂、钙、镁等)、铵或取代的铵阳离子。本发明仔细考虑烷基乙氧基化硫酸盐和烷基丙氧基化硫酸盐。取代的铵阳离子的具体实例包括甲基-、二甲基-、三甲基-铵阳离子和季铵阳离子,例如四甲基铵和二甲基哌啶鎓阳离子和由烷基胺,例如乙胺、二乙胺、三乙胺,它们的混合物等得到的阳离子等。举例性的表面活性剂是C12-C18烷基聚乙氧基化物(1.0)硫酸盐(C12-C18E(1.0)M)、C12-C18烷基聚乙氧基化物(2.25)硫酸盐(C12-C18E(2.25)M)、C12-C18烷基聚乙氧基化物(3.0)硫酸盐(C12-C18E(3.0)M)和C12-C18烷基聚乙氧基化物(4.0)硫酸盐(C12-C18E(4.0)M),其中M通常选自钠和钾。Highly preferred anionic surfactants including alkyl alkoxylated sulfate surfactants are water soluble salts or acids of the formula RO(A) m SO 3 M where R is an unsubstituted C 10 -C 24 alkyl Or hydroxyalkyl containing C 10 -C 24 alkyl moiety, preferably C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is ethoxy or propoxy m is greater than zero, usually between about 0.5 and about 6, more preferably between about 0.5 and about 3, M is H or a cation, which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cations. The present invention contemplates both alkyl ethoxylated sulfates and alkyl propoxylated sulfates. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as ethylamine , diethylamine, triethylamine, their mixtures, etc. to obtain cations, etc. Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate (C 12 -C 18 E(1.0)M), C 12 -C 18 alkyl polyethoxylate ( 2.25) Sulfate (C 12 -C 18 E(2.25)M), C 12 -C 18 Alkyl Polyethoxylate (3.0) Sulfate (C 12 -C 18 E(3.0)M) and C 12 - C 18 alkyl polyethoxylate (4.0) sulfate (C 12 -C 18 E(4.0)M), where M is typically selected from sodium and potassium.
本发明的洗涤剂组合物还可含有阳离子、两性、两性离子和半极性表面活性剂以及除上文已描述的之外的非离子和/或阴离子表面活性剂。The detergent compositions of the present invention may also contain cationic, amphoteric, zwitterionic and semi-polar surfactants as well as nonionic and/or anionic surfactants other than those already described above.
适用于本发明洗涤组合物的阳离子洗涤表面活性剂是含有一个长链烃基的物质。该阳离子表面活性剂的实例包括铵表面活性剂,例如烷基三甲基铵卤化物,和具有下式的表面活性剂:Cationic detersive surfactants suitable for use in the detergent compositions herein are those which contain a long chain hydrocarbyl group. Examples of the cationic surfactant include ammonium surfactants, such as alkyltrimethylammonium halides, and surfactants having the formula:
[R2(OR3)y][R4(OR3)y]2R5N+X-其中R2是在烷基链中含有约8-约18个碳原子的烷基或烷基苄基,每个R3选自-CH2CH2-、-CH2CH(CH3)-、-CH2CH(CH2OH)-、-CH2CH2CH2-和它们的混合物;每个R4选自C1-C4烷基、C1-C4羟基烷基、由连接两个R4基团形成的苄基环结构、-CH2CHOH-CHOHCOR6CHOHCH2OH,其中R6是任何己糖或分子量低于约1000的己糖聚合物,和当y不是0时,为氢;R5与R4相同或是其中R2加R5的碳原子总数不超过约18的烷基链;每个y是0-约10,y值的总和为0-约15;和X是任何相容的阴离子。[R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N + X - wherein R 2 is an alkyl or alkyl benzyl having from about 8 to about 18 carbon atoms in the alkyl chain Each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 - and mixtures thereof; Each R 4 is selected from C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structure formed by connecting two R 4 groups, -CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH, wherein R 6 is any hexose or hexose polymer having a molecular weight of less than about 1000, and when y is other than 0, hydrogen; R is the same as R or wherein the total number of carbon atoms in R plus R does not exceed about 18 an alkyl chain; each y is from 0 to about 10, the sum of the values of y is from 0 to about 15; and X is any compatible anion.
适用于本发明的季铵表面活性剂具有如下式(I): The quaternary ammonium surfactant suitable for use in the present invention has the following formula (I):
式I其中R1是短链烷基(C6-C10)或如下式(II)的烷基酰氨基烷基: Formula I wherein R is a short-chain alkyl group (C6-C10) or an alkylamidoalkyl group of the following formula (II):
式IIy是2-4,优选3,其中R2是H或C1-C3烷基,其中x是0-4,优选0-2,最优选0,其中R3、R4和R5是相同或不同的,可以是短链烷基(C1-C3)或如下式III的烷氧基化烷基,其中X-是抗衡离子,优选卤化物,例如氯化物或甲基硫酸根, Formula IIy is 2-4, preferably 3, wherein R2 is H or C1-C3 alkyl, wherein x is 0-4, preferably 0-2, most preferably 0, wherein R3, R4 and R5 are identical or different, can is a short chain alkyl group (C1-C3) or an alkoxylated alkyl group of the following formula III, wherein X - is a counterion, preferably a halide, such as chloride or methylsulfate,
式IIIR6是C1-C4和z是1或2。Formula IIIR6 is C 1 -C 4 and z is 1 or 2.
优选的季铵表面活性剂是由式I定义的化合物,其中R1是C8、C10或它们的混合物,x=0,R3,R4=CH3和R5=CH2CH2OH。Preferred quaternary ammonium surfactants are compounds defined by formula I, wherein R 1 is C 8 , C 10 or mixtures thereof, x=0, R 3 , R 4 =CH 3 and R 5 =CH 2 CH 2 OH .
高度优选的阳离子表面活性剂是用于本发明组合物的具有下式的水溶性季铵化合物:Highly preferred cationic surfactants for use in the compositions of the present invention are water-soluble quaternary ammonium compounds having the formula:
R1R2R3R4N+X- (i)其中R1是C8-C16烷基,每个R2、R3和R4分别是C1-C4烷基、C1-C4羟基烷基、苄基和-(C2H4O)xH,其中x是2-5,X是阴离子。R2、R3或R4中不超过一个应是苄基。R 1 R 2 R 3 R 4 N + X - (i) wherein R 1 is C 8 -C 16 alkyl, each of R 2 , R 3 and R 4 is C 1 -C 4 alkyl, C 1 - C 4 hydroxyalkyl, benzyl, and -(C 2 H 4 O) x H, where x is 2-5 and X is an anion. Not more than one of R2 , R3 or R4 shall be benzyl.
R1的优选烷基链长度是C12-C15,尤其是其中烷基是由椰子油或棕榈仁脂肪得到的或由烯烃合成或OXO醇合成方法得到的链长的混合物。R2、R3和R4的优选基团是甲基和羟基乙基,阴离子X可以选自卤化物、甲基硫酸根、乙酸根和磷酸根离子。Preferred alkyl chain lengths for R 1 are C 12 -C 15 , especially mixtures of chain lengths where the alkyl group is derived from coconut oil or palm kernel fat or from olefin synthesis or OXO alcohol synthesis. Preferred groups for R 2 , R 3 and R 4 are methyl and hydroxyethyl, and the anion X may be selected from halide, methylsulfate, acetate and phosphate ions.
用于本发明的合适的式(i)季铵化合物的实例包括:椰子油三甲基铵氯化物或溴化物;椰子油甲基二羟基乙基铵氯化物或溴化物;癸基三乙基铵氯化物;癸基二甲基羟基乙基铵氯化物或溴化物;C12-15二甲基羟基乙基铵氯化物或溴化物;椰子油二甲基羟基乙基铵氯化物或溴化物;十四烷基三甲基铵甲基硫酸盐;十二烷基二甲基苄基铵氯化物或溴化物;十二烷基二甲基(氧乙烯基)4铵氯化物或溴化物;胆碱酯(式(i)化合物,其中R1是CH2-CH2-O-C(O)-C12-14烷基和R2、R3和R4是甲基);二烷基咪唑啉[式(i)化合物]。Examples of suitable quaternary ammonium compounds of formula (i) for use in the present invention include: cocotrimethylammonium chloride or bromide; cocomethyldihydroxyethylammonium chloride or bromide; decyltriethylammonium chloride or bromide; Ammonium Chloride; Decyl Dimethyl Hydroxyethyl Ammonium Chloride or Bromide; C 12-15 Dimethyl Hydroxyethyl Ammonium Chloride or Bromide; Coco Dimethyl Hydroxyethyl Ammonium Chloride or Bromide ; tetradecyl trimethyl ammonium methyl sulfate; dodecyl dimethyl benzyl ammonium chloride or bromide; dodecyl dimethyl (oxyethylene) 4 ammonium chloride or bromide; Choline esters (compounds of formula (i) wherein R 1 is CH 2 -CH 2 -OC(O)-C 12-14 alkyl and R 2 , R 3 and R 4 are methyl); dialkylimidazolines [compound of formula (i)].
用于本发明的其它阳离子表面活性剂还描述在1980年10月14日颁布的Cambre的US4228044和EP000224中。Other cationic surfactants useful in the present invention are also described in US Patent 4,228,044 and EP 000224, Cambre, issued October 14,1980.
典型的阳离子织物柔软组分包括水不溶性季铵织物柔软活性物质,最常用的是二长链烷基链的氯化铵或甲基硫酸盐。Typical cationic fabric softening ingredients include water insoluble quaternary ammonium fabric softening actives, most commonly dilong alkyl chain ammonium chloride or methylsulfate.
其中优选的阳离子柔软剂包括如下:Wherein preferred cationic softener includes as follows:
1)二动物脂二甲基氯化铵(DTDMAC);1) ditallow dimethyl ammonium chloride (DTDMAC);
2)二氢化动物脂二甲基氯化铵;2) dihydrogenated tallow dimethyl ammonium chloride;
3)二氢化动物脂二甲基甲基硫酸铵;3) dihydrogenated tallow dimethyl ammonium methyl sulfate;
4)二硬脂基二甲基氯化铵;4) distearyl dimethyl ammonium chloride;
5)二油基二甲基氯化铵;5) dioleyl dimethyl ammonium chloride;
6)二棕榈基羟基乙基甲基氯化铵;6) dipalmityl hydroxyethyl methyl ammonium chloride;
7)硬脂基苄基二甲基氯化铵;7) stearyl benzyl dimethyl ammonium chloride;
8)动物脂基三甲基氯化铵;8) tallow trimethylammonium chloride;
9)氢化动物脂基三甲基氯化铵;9) Hydrogenated tallow trimethylammonium chloride;
10)C12-14烷基羟基乙基二甲基氯化铵;10) C 12-14 alkyl hydroxyethyl dimethyl ammonium chloride;
11)C12-18烷基二羟基乙基甲基氯化铵;11) C 12-18 alkyl dihydroxyethyl methyl ammonium chloride;
12)二(硬脂酰氧基乙基)二甲基氯化铵(DSOEDMAC);12) Di(stearyloxyethyl)dimethylammonium chloride (DSOEDMAC);
13)二(动物脂氧基乙基)二甲基氯化铵;13) Di(tallowoxyethyl) dimethyl ammonium chloride;
14)二动物脂基咪唑鎓甲基硫酸盐;14) Ditallow imidazolium methyl sulfate;
15)1-(2-动物脂酰氨基乙基)-2-动物脂基咪唑鎓甲基硫酸盐。15) 1-(2-Tallowamidoethyl)-2-tallowimidazolium methylsulfate.
可生物降解的季铵化合物已用作通常使用的二长烷基链氯化铵和甲基硫酸盐的代替物。该季铵化合物含有被官能团,例如羧基间断的长链烷(烯)基,所述物质和含有它们的织物柔软组合物在许多出版物,例如EP-A-0040562和EP-A-0239910中公开。Biodegradable quaternary ammonium compounds have been used as replacements for commonly used dilong alkyl chain ammonium chloride and methylsulfate. The quaternary ammonium compounds contain long chain alk(en)yl groups interrupted by functional groups such as carboxyl groups, said materials and fabric softening compositions containing them are disclosed in a number of publications such as EP-A-0040562 and EP-A-0239910 .
本发明的季铵化合物和胺前体具有如下式(I)或(II):其中Q选自-O-C(O)-、-C(O)-O-、-O-C(O)-O-、-NR4-C(O)-、-C(O)-NR4-;R1是(CH2)n-Q-T2或T3;R2是(CH2)m-Q-T4或T5或R3;R3是C1-C4烷基或C1-C4羟基烷基或H;R4是H或C1-C4烷基或C1-C4羟基烷基;T1、T2、T3、T4和T5独立地是C11-C22烷基或烯基;n和m是1-4的整数;和X-是柔软剂相容的阴离子。The quaternary ammonium compounds and amine precursors of the present invention have the following formula (I) or (II): Wherein Q is selected from -OC(O)-, -C(O)-O-, -OC(O)-O-, -NR 4 -C(O)-, -C(O)-NR 4 -; R 1 is (CH 2 ) n -QT 2 or T 3 ; R 2 is (CH 2 ) m -QT 4 or T 5 or R 3 ; R 3 is C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkane radical or H; R 4 is H or C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl; T 1 , T 2 , T 3 , T 4 and T 5 are independently C 11 -C 22 alkyl Or alkenyl; n and m are integers from 1 to 4; and X - is a softener compatible anion.
与柔软剂相容的阴离子的非限制实例包括氯离子或甲基硫酸根。Non-limiting examples of softener compatible anions include chloride or methylsulfate.
烷基或烯基链T1、T2、T3、T4和T5必须含有至少11个碳原子,优选至少16个碳原子。链可以是直链或支链的。The alkyl or alkenyl chains T 1 , T 2 , T 3 , T 4 and T 5 must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. Chains can be straight or branched.
动物脂是长链烷基和烯基物质的方便和廉价来源。其中T1、T2、T3、T4和T5表示通常动物脂的长链物质混合物的化合物是尤其优选的。Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl species. Compounds in which T 1 , T 2 , T 3 , T 4 and T 5 represent mixtures of long-chain species, usually tallow, are especially preferred.
适用于本发明的含水织物柔软组合物的季铵化合物的具体实例包括:1)N,N-二(动物脂基氧基乙基)-N,N-二甲基氯化铵;2)N,N-二(动物脂基氧基乙基)N-甲基,N-(2-羟基乙基)甲基硫酸盐;3)N,N-二(2-动物脂基氧基-2-氧代乙基)-N,N-二甲基氯化铵;4)N,N-二(2-动物脂基氧基-乙基羰基-氧基乙基)-N,N-二甲基氯化铵;5)N-(2-动物脂基氧基-2-乙基)-N-(2-动物脂基氧基-2-氧代乙基)-N,N-二甲基氯化铵;6)N,N,N-三(动物脂基-氧基-乙基)-N-甲基氯化铵;7)N-(2-动物脂基-氨基-2-氧代乙基)-N-(动物脂基)-N,N-二甲基氯化铵;和8)1,2-二动物脂基氧基-3-三甲基铵丙烷氯化物;和任何上述物质的混合物。Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions of the present invention include: 1) N,N-bis(tallowyloxyethyl)-N,N-dimethylammonium chloride; 2) N , N-bis(tallowyloxyethyl) N-methyl, N-(2-hydroxyethyl) methyl sulfate; 3) N, N-bis(2-tallowyloxy-2- Oxoethyl)-N,N-dimethylammonium chloride; 4) N,N-di(2-tallowyloxy-ethylcarbonyl-oxyethyl)-N,N-dimethyl Ammonium chloride; 5) N-(2-tallowyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxoethyl)-N,N-dimethyl chloride Ammonium chloride; 6) N,N,N-tris(tallowyl-oxyl-ethyl)-N-methylammonium chloride; 7) N-(2-tallowyl-amino-2-oxoethyl base)-N-(tallowyl)-N,N-dimethylammonium chloride; and 8) 1,2-ditallowyloxy-3-trimethylammoniumpropane chloride; and any of the foregoing mixture.
如果包括的话,本发明的洗涤剂组合物通常含有按重量计0.2%-约25%,优选约1%-约8%该阳离子表面活性剂。If included, the detergent compositions herein will generally contain from 0.2% to about 25%, preferably from about 1% to about 8%, by weight of such cationic surfactants.
两性表面活性剂也适用于本发明的洗涤剂组合物中。这些表面活性剂可广义地描述为仲或叔胺的脂族衍生物或杂环仲和叔胺的脂族衍生物,其中脂族基团可以是直链或支链的。脂族取代基之一含有至少约8个碳原子,通常约8-约18个碳原子和至少一个脂族取代基含有阴离子水增溶基团,例如羧基、磺酸根、硫酸根。两性表面活性剂的实例参见1975年12月30日颁布的Laughlin等的US3929678,第19栏第18-35行。Amphoteric surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic group may be straight or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, usually from about 8 to about 18 carbon atoms and at least one of the aliphatic substituents contains an anionic water solubilizing group, eg, carboxy, sulfonate, sulfate. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, lines 18-35, for examples of amphoteric surfactants.
如果包括的话,本发明的洗涤剂组合物通常含有按重量计0.2%-约15%,优选约1%-约10%该两性表面活性剂。If included, the detergent compositions herein will generally contain from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of such amphoteric surfactants.
两性离子表面活性剂也适用于本发明的洗涤剂组合物中。这些表面活性剂可广义地描述为仲和叔胺的衍生物、杂环仲和叔胺的衍生物,或季铵、季鏻或叔锍化合物的衍生物。两性离子表面活性剂的实例参见1975年12月30日颁布的Laughlin等的US3929678,第19栏第38行-22栏48行。Zwitterionic surfactants are also suitable for use in 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. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, line 38-column 22, line 48, for examples of zwitterionic surfactants.
如果包括的话,本发明的洗涤剂组合物通常含有按重量计0.2%-约15%,优选约1%-约10%该两性离子表面活性剂。If included, the detergent compositions herein will generally contain from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of such zwitterionic surfactants.
半极性非离子表面活性剂是特殊种类的非离子表面活性剂,其包括含有一个约10-约18个碳原子的烷基部分和两个选自含有约1-约3个碳原子的烷基和羟基烷基的部分的水溶性氧化胺;含有一个约10-约18个碳原子的烷基和两个选自含有约1-约3个碳原子的烷基和羟基烷基的部分的水溶性氧化膦;和含有一个约10-约18个碳原子的烷基部分和一个选自含有约1-约3个碳原子的烷基和羟基烷基的部分的水溶性亚砜。Semi-polar nonionic surfactants are a special class of nonionic surfactants that include an alkyl moiety containing about 10 to about 18 carbon atoms and two alkyl moieties selected from the group consisting of about 1 to about 3 carbon atoms A water-soluble amine oxide containing part of an alkyl group and a hydroxyalkyl group; containing one alkyl group of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of an alkyl group and a hydroxyalkyl group of about 1 to about 3 carbon atoms water-soluble phosphine oxides; and water-soluble sulfoxides containing an alkyl moiety of about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl groups of about 1 to about 3 carbon atoms.
半极性非离子洗涤剂表面活性剂包括具有下式的氧化胺表面活性剂:其中R3是含有约8-约22个碳原子的烷基、羟基烷基或烷基苯基或其混合物;R4是含有约2-约3个碳原子的亚烷基或羟基亚烷基或它们的混合物;x是0-约3;每个R5是含有约1-约3个碳原子的烷基或羟基烷基或含有约1-约3个环氧乙烷基团的聚氧乙烯基团。R5基团可例如通过氧或氮原子相互连接形成环结构。Semi-polar nonionic detergent surfactants include amine oxide surfactants having the formula: wherein R3 is alkyl, hydroxyalkyl or alkylphenyl or a mixture thereof containing about 8 to about 22 carbon atoms; R4 is alkylene or hydroxyalkylene containing about 2 to about 3 carbon atoms or mixtures thereof; x is 0 to about 3; each R is an alkyl or hydroxyalkyl group containing about 1 to about 3 carbon atoms or a polyoxygen group containing about 1 to about 3 oxirane groups Vinyl group. The R 5 groups may be linked to each other, for example via an oxygen or nitrogen atom, to form a ring structure.
这些氧化胺表面活性剂尤其包括C10-C18烷基二甲基氧化胺和C8-C12烷氧基乙基二羟基乙基氧化胺。These amine oxide surfactants include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxyethyl dihydroxyethyl amine oxides, among others.
如果包括的话,本发明的洗涤剂组合物通常含有按重量计0.2%-约15%,优选约1%-约10%半极性非离子表面活性剂。If included, the detergent compositions herein will generally contain from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of semi-polar nonionic surfactants.
本发明的洗涤剂组合物还含有选自伯或叔胺的辅助表面活性剂。用于本发明的合适的伯胺包括式R1NH2的胺,其中R1是C6-C12,优选C6-C10烷基链或R4X(CH2)n,x是-O-、-C(O)NH-或-NH-,R4是C6-C12烷基链,n是1至5,优选3。R1烷基链可以是直链或支链的,可被至多12个,优选少于5个环氧乙烷部分间断。The detergent compositions of the present invention also contain cosurfactants selected from primary or tertiary amines. Suitable primary amines for use in the present invention include amines of formula R 1 NH 2 , wherein R 1 is a C 6 -C 12 , preferably C 6 -C 10 alkyl chain or R 4 X(CH 2 ) n , x is - O-, -C(O)NH- or -NH-, R 4 is a C 6 -C 12 alkyl chain, n is 1 to 5, preferably 3. The R 1 alkyl chain may be straight or branched and may be interrupted by up to 12, preferably less than 5, ethylene oxide moieties.
本发明上式的优选胺是正烷基胺。用于本发明的合适的胺选自1-己胺、1-辛胺、1-癸烷和十二烷基胺。其它优选的伯胺包括C8-C10氧基丙胺、辛氧基丙胺、2-乙基己氧基丙胺、十二烷基酰氨基丙胺和酰氨基丙胺。Preferred amines of the above formula according to the invention are n-alkylamines. Suitable amines for use in the present invention are selected from 1-hexylamine, 1-octylamine, 1-decane and dodecylamine. Other preferred primary amines include C 8 -C 10 oxypropylamine, octyloxypropylamine, 2-ethylhexyloxypropylamine, dodecylamidopropylamine and amidopropylamine.
用于本发明的合适的叔胺包括具有式R1R2R3N的叔胺,其中R1和R2是C1-C8烷基链或R3是C6-C12,优选C6-C10烷基链或R3是R4X(CH2)n,而X是-O-、-C(O)NH-或-NH-,R4是C4-C12,n是1至5,优选是2-3。R5是H或C1-C2烷基和x是1-6。Suitable tertiary amines for use in the present invention include tertiary amines having the formula R 1 R 2 R 3 N, wherein R 1 and R 2 are C 1 -C 8 alkyl chains or R 3 is C 6 -C 12 , preferably a C 6 -C 10 alkyl chain or R 3 is R 4 X(CH 2 ) n , and X is -O-, -C(O)NH- or -NH-, R 4 is C 4 -C 12 , n is 1 to 5, preferably 2-3. R 5 is H or C 1 -C 2 alkyl and x is 1-6.
R3和R4可以是直链或支链的;R3烷基链可被至多12个,优选少于5个环氧乙烷部分间断。 R3 and R4 may be linear or branched; the R3 alkyl chain may be interrupted by up to 12, preferably less than 5, oxirane moieties.
优选叔胺是R1R2R3N,其中R1是C6-C12烷基链,R2和R3是C1-C3烷基或其中R5是H或甲基和x=1-2。Preferred tertiary amines are R 1 R 2 R 3 N, wherein R 1 is a C 6 -C 12 alkyl chain, R 2 and R 3 are C 1 -C 3 alkyl or wherein R 5 is H or methyl and x=1-2.
同样优选的是下式的酰氨基胺:其中R1是C6-C12烷基;n是2-4,优选n是3;R2和R3是C1-C4。Also preferred are amidoamines of the formula: Wherein R 1 is C 6 -C 12 alkyl; n is 2-4, preferably n is 3; R 2 and R 3 are C 1 -C 4 .
本发明最优选的胺包括1-辛胺、1-己胺、1-癸胺、1-十二烷基胺、C8-C10氧基丙胺、N-椰子油1-3二氨基丙烷、椰子油二甲基胺、十二烷基二甲基胺、十二烷基二(羟基乙基)胺、椰子油二(羟基乙基)胺、2摩尔丙氧基化的十二烷基胺、2摩尔丙氧基化的辛胺、十二烷基酰氨基丙基二甲基胺、C8-10酰氨基丙基二甲基胺和C10酰氨基丙基二甲基胺。The most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C8 - C10 oxypropylamine, N-coco 1-3 diaminopropane, Coco Dimethylamine, Lauryl Dimethylamine, Dodecyl Di(Hydroxyethyl)amine, Coco Di(Hydroxyethyl)amine, 2 Moles Propoxylated Dodecylamine , 2 moles of propoxylated octylamine, lauryl amidopropyl dimethylamine, C 8-10 amidopropyl dimethylamine and C 10 amidopropyl dimethylamine.
用于本发明组合物的最优选的胺是1-己胺、1-辛胺、1-癸烷、1-十二烷基胺。尤其希望是正十二烷基二甲基胺和二羟基乙基椰子油烷基胺和7次乙氧基化的油胺、十二烷基酰氨基丙胺和椰子油酰氨基丙胺。常规洗涤剂酶The most preferred amines for use in the compositions of the present invention are 1-hexylamine, 1-octylamine, 1-decane, 1-dodecylamine. Particularly desirable are n-dodecyldimethylamine and dihydroxyethylcocoalkylamine and 7-times ethoxylated oleylamine, dodecylamidopropylamine and cocoamidopropylamine. Regular Detergent Enzyme
除了本发明特殊纤维素酶之外,洗衣洗涤剂组合物还可含有一种或多种酶,它提供了洗涤性能、织物护理和/或卫生效果。Laundry detergent compositions may contain, in addition to the specific cellulase enzymes of the invention, one or more enzymes which provide detergency, fabric care and/or hygiene benefits.
上述酶包括选自其它的纤维素酶、半纤维素酶、过氧化物酶、蛋白酶、葡糖淀粉酶、淀粉酶、木聚糖酶、脂酶、磷脂酶、酯酶、角质酶、果胶酶、角蛋白酶、还原酶、氧化酶、酚氧化酶、脂肪氧合酶、木质素酶、支链淀粉酶、鞣酸酶、戊聚糖酶、malanases、β-葡聚糖酶、阿拉伯糖苷酶、透明质酶、软骨素酶、漆酶或它们的混合物的酶。The above enzymes include cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, xylanase, lipase, phospholipase, esterase, cutinase, pectin Enzymes, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases , hyaluronase, chondroitinase, laccase, or a mixture thereof.
优选组合是含有常规的适用酶,如蛋白酶、淀粉酶、脂酶、角质酶和/或其它纤维素酶与一种或多种植物细胞壁降解酶结合的混合物的洗衣洗涤剂组合物。本发明的洗衣洗涤剂组合物将优选还含有由Humicola insolens DSM 1800得到的-43kD内切葡聚糖酶。Preferred combinations are laundry detergent compositions containing conventional mixtures of suitable enzymes such as proteases, amylases, lipases, cutinases and/or other cellulases in combination with one or more plant cell wall degrading enzymes. Laundry detergent compositions of the present invention will preferably also contain the -43kD endoglucanase derived from Humicola insolens DSM 1800.
用于本发明的其它纤维素酶包括细菌或真菌纤维素酶。它们优选具有5-12之间的pH最佳值和超过50CEVU(纤维素粘度单位)的活性。合适的纤维素酶在Barbesgoard等的US4435307、J61078384和WO96/02653中描述,它们公开了分别由Humicola insolens、木霉属(Trichoderma)、草根霉属(Thielavia)和孢子丝菌属(Sporotrichum)产生的真菌纤维素酶。EP739982描述了由新的芽孢杆菌种分离的纤维素酶。合适的纤维素酶还公开在GB-A-2075028、GB-A-2095275、DE-OS-2247832和WO95/26398中。Other cellulases useful in the present invention include bacterial or fungal cellulases. They preferably have a pH optimum between 5-12 and an activity in excess of 50 CEVU (Cellulose Viscosity Units). Suitable cellulases are described in US4435307, J61078384 and WO96/02653 by Barbesgoard et al., which disclose cellulase produced by Humicola insolens, Trichoderma, Thielavia and Sporotrichum, respectively. Fungal cellulase. EP739982 describes cellulases isolated from new Bacillus species. Suitable cellulases are also disclosed in GB-A-2075028, GB-A-2095275, DE-OS-2247832 and WO95/26398.
该其它纤维素酶的实例是由Humicola insolens(Humicolagrisea var.thermoidea)的菌株,尤其是腐质霉菌株DSM 1800产生的纤维素酶。其它合适的纤维素酶是由Humicola insolens DSM1800得到的显示纤维素酶活性的-43kD内切葡聚糖酶;优选的内切葡聚糖酶组分具有PCT专利申请WO91/17243中公开的氨基酸序列。尤其合适的纤维素酶是具有颜色护理效果的纤维素酶。这种纤维素酶的实例是在1991年11月6日申请的EP专利申请№91202879.2(Novo)中描述的纤维素酶。Carezyme和Celluzyme(Novo Nordisk A/S)是尤其有用的。还参见WO91/17244和WO91/21801。其它用织物护理和/或洗涤性能的合适的纤维素酶在WO96/34092、WO96/17994和WO95/24471中描述。Examples of such other cellulases are cellulases produced by strains of Humicola insolens (Humicolagrisea var. thermoidea), especially Humicola strain DSM 1800. Another suitable cellulase is a -43kD endoglucanase exhibiting cellulase activity obtained from Humicola insolens DSM1800; a preferred endoglucanase component has the amino acid sequence disclosed in PCT patent application WO91/17243 . Particularly suitable cellulases are cellulases having a color care effect. Examples of such cellulases are the cellulases described in EP patent application No. 91202879.2 (Novo) filed on 06.11.1991. Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or washing performance are described in WO96/34092, WO96/17994 and WO95/24471.
所述其它纤维素酶通常以按洗涤剂组合物重量计0.0001%-2%纯酶的含量加入洗涤剂组合物中。Such other cellulases are typically incorporated into the detergent composition at levels of 0.0001% to 2% pure enzyme by weight of the detergent composition.
过氧化物酶与氧源,例如过碳酸盐、过硼酸盐、过硫酸盐、过氧化氢等和用作漂白增效分子的酚类底物结合使用。它们用于“溶液漂白”,即避免在洗涤操作中由基质除去的染料或颜料转移至在洗涤溶液中的其它基质中。过氧化物酶在现有技术中是已知的,其包括,例如辣根过氧化物酶、木质素酶和卤代过氧化物酶,例如氯和溴代过氧化物酶。含有过氧化物酶的洗涤剂组合物在例如PCT国际申请WO89/099813、WO89/09813和1991年11月6日申请的欧洲专利申请EP91202882.6和1996年2月20日申请的EP№96870013.8中公开。同样合适的是漆酶。Peroxidases are used in combination with oxygen sources such as percarbonate, perborate, persulfate, hydrogen peroxide, etc. and phenolic substrates as bleach boosting molecules. They are used for "solution bleaching", ie to avoid the transfer of dyes or pigments removed from a substrate during washing operations to other substrates in the wash solution. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases, such as chloro- and bromo-peroxidases. Detergent compositions containing peroxidase are e.g. PCT International Applications WO89/099813, WO89/09813 and European Patent Applications EP91202882.6 filed on November 6, 1991 and EP No. 96870013.8 filed on February 20, 1996 public. Also suitable are laccases.
增效剂通常以按总组合物重量计0.1%-5%的含量存在。优选的增效剂是取代的吩噻嗪和吩噁嗪、10-吩噻嗪丙酸(PPT)、10-乙基吩噻嗪-4-羧酸(EPC)、10-吩噁嗪丙酸(POP)和10-甲基吩噁嗪(在WO94/12621中描述)和取代的丁香酸酯(C3-C5取代的烷基丁香酸酯)和苯酚。过碳酸钠或过硼酸钠是优选的过氧化氢源。Builders are typically present at levels of 0.1% to 5% by weight of the total composition. Preferred synergists are substituted phenothiazines and phenoxazines, 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO94/12621) and substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or sodium perborate are preferred sources of hydrogen peroxide.
所上述过氧化物酶通常以按洗涤剂组合物重量计0.0001%-2%纯酶的含量加入洗涤剂组合物中。The above-mentioned peroxidase is usually added to the detergent composition at a content of 0.0001%-2% pure enzyme by weight of the detergent composition.
在本发明中可以包括的其它优选酶包括脂酶,用于洗涤剂用途的合适脂酶包括假单胞菌属的微生物,如GB1372034中所披露的司徒茨氏假单胞菌ATCC 19.154得到的脂酶。合适的脂酶包括与脂酶抗体显示阳性免疫交叉反应的脂酶,它由微生物荧光假单胞菌IAM 1057产生。这种脂酶可由Amano Pharmaceutical Co.Ltd.(Nagoya,日本)得到,商品名为脂酶P“Amano”,下文称为“Amano-P”。其它合适的商品脂酶包括Amano-CES,来自Chromobacter viscosum,如来自ToyoJozo Co.(Tagata,日本)的Chromobacter viscosum var.Lipolyticum NRRLB 3673的脂酶;由U.S.Biochemical Corp.(US)和Disoynth Co.(荷兰)得到的Chromobacter viscosum脂酶;以及由唐菖蒲假单胞菌得到的脂酶。尤其合适的脂酶是脂酶,例如M1LipaseR和LipomaxR(Gist-Brocades)和LipolaseR和LipolaseUltraR(Novo),它们被发现在与本发明的组合物结合使用时是非常有效的。同样合适的是在Novo Nordisk的EP258068、WO92/05249和WO95/22615和Unilever的WO94/03578、WO95/35381和WO96/00292中描述的脂解酶。Other preferred enzymes that may be included in the present invention include lipases. Suitable lipases for detergent use include microorganisms of the genus Pseudomonas, such as the lipid obtained from Pseudomonas stutzeri ATCC 19.154 as disclosed in GB1372034. enzyme. Suitable lipases include those produced by the microorganism Pseudomonas fluorescens IAM 1057 which show positive immunological cross-reactivity with lipase antibodies. This lipase is available from Amano Pharmaceutical Co. Ltd. (Nagoya, Japan) under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES from Chromobacter viscosum, such as Chromobacter viscosum var. Lipolyticum NRRLB 3673 from ToyoJozo Co. (Tagata, Japan); lipase from USBiochemical Corp. (US) and Disoynth Co. (Netherlands). ) from Chromobacter viscosum lipase; and lipase from Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 Lipase R and Lipomax R (Gist-Brocades) and Lipolase R and Lipolase Ultra R (Novo), which have been found to be very effective when used in combination with the compositions of the invention. Also suitable are the lipolytic enzymes described in EP258068, WO92/05249 and WO95/22615 to Novo Nordisk and WO94/03578, WO95/35381 and WO96/00292 to Unilever.
同样合适的是角质酶[EC 3.1.1.50],它被认为是特殊种类的脂酶,即不需要界面活化的脂酶。在洗涤剂组合物中加入角质酶在例如WO-A-88/09367(Genencor);WO90/09446(Plant Genetic System)和WO94/14963和WO94/14964(Unilever)中描述。Also suitable are cutinases [EC 3.1.1.50], which are considered a special class of lipases, i.e. lipases that do not require interfacial activation. The incorporation of cutinases in detergent compositions is described eg in WO-A-88/09367 (Genencor); WO90/09446 (Plant Genetic System) and WO94/14963 and WO94/14964 (Unilever).
脂酶和/或角质酶通常以按洗涤剂组合物重量计0.0001%-2%纯酶的含量加入本发明的洗涤剂组合物中。Lipase and/or cutinase are typically incorporated into the detergent compositions of the present invention at levels of 0.0001% to 2% pure enzyme by weight of the detergent composition.
合适的蛋白酶为得自枯草芽孢杆菌和地衣形芽孢杆菌的特殊菌株的枯草溶菌素(枯草溶菌素BPN和BPN’)。一种合适的蛋白酶由在8-12的整个pH范围具有最大活性的芽孢杆菌属的菌株得到,它由Novo Industries A/S(丹麦)开发,并以ESPERASE销售,以下称为“Novo”。这种酶和类似酶的制备在Novo的GB1243784中描述。其它合适的蛋白酶包括由Novo得到的ALCALASE、DURAZYM和SAVINASE和由Gist-Brocades得到的MAXATASE、MAXACAL、PROPERASE和MAXAPEM(蛋白质工程的Maxacal)。蛋白分解酶还包括改性细菌丝氨酸蛋白酶,例如在1987年4月28日申请的欧洲专利申请序号87303761.8(尤其是17、24和98页)中描述的蛋白酶,它在本文中称为“蛋白酶B”和在1986年10月29日公开的Venegas的EP199404中的蛋白酶,它涉及改性的细菌丝氨酸蛋白分解酶,它在本文中称为“蛋白酶A”。合适的是在本文中称为“蛋白酶C”的蛋白酶,它是由芽孢杆菌属得到的碱性丝氨酸蛋白酶的变种,其中在27位用赖氨酸代替精氨酸,在104位用酪氨酸代替缬氨酸,在123位用丝氨酸代替天冬酰胺和在274位用丙氨酸代替苏氨酸。蛋白酶C在1991年5月16日中公开的EP90915958.4,相应于WO91/06637中描述。基因改性的变种,尤其是蛋白酶C的变种,也包括在本发明中。Suitable proteases are the subtilisins (subtilisins BPN and BPN') obtained from special strains of Bacillus subtilis and Bacillus licheniformis. A suitable protease is obtained from a strain of Bacillus having maximal activity throughout the pH range of 8-12, developed by Novo Industries A/S (Denmark) and marketed as ESPERASE®, hereinafter referred to as "Novo". The preparation of this and similar enzymes is described in GB1243784 to Novo. Other suitable proteases include ALCALASE(R), DURAZYM(R), and SAVINASE(R) from Novo and MAXATASE(R), MAXACAL(R), PROPERASE(R), and MAXAPEM(R) (Maxacal from Protein Engineering) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases, such as those described in European Patent Application Serial No. 87303761.8 filed April 28, 1987 (particularly pages 17, 24 and 98), referred to herein as "Protease B " and the protease in EP199404, Venegas, published October 29, 1986, which relates to a modified bacterial serine proteolytic enzyme, which is referred to herein as "Protease A". Suitable is the protease referred to herein as "Protease C", which is a variant of the alkaline serine protease obtained from Bacillus in which arginine is replaced by lysine at position 27 and tyrosine at position 104 Instead of valine, asparagine was replaced by serine at position 123 and threonine was replaced by alanine at position 274. Protease C is described in EP90915958.4 published on May 16, 1991, corresponding to WO91/06637. Genetically modified variants, especially variants of Protease C, are also included in the present invention.
称为“蛋白酶D”的优选蛋白酶是具有在自然界中未发现的氨基酸序列的羰基水解酶变种,如WO95/10591和1994年10月13日申请的C.Ghosh等的名称为“含有蛋白酶的漂白组合物”(US系列号№08/322677)的专利申请中所述,它通过在上述羰基水解酶中相当于+76位置上用不同氨基酸取代各种氨基酸残基,并优选还结合取代相当于选自根据解淀粉芽孢杆菌枯草溶菌素的编号+99、+101、+103、+104、+107、+123、+27、+105、+109、+126、+128、+135、+156、+166、+195、+197、+204、+206、+210、+216、+217、+218、+222、+260、+265和/或+274位的一种或多种氨基酸残基由前体羰基水解酶得到。A preferred protease called "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, such as WO95/10591 and C. Ghosh et al. Compositions" (US Serial No. 08/322677) by substituting various amino acid residues with different amino acids at positions corresponding to +76 in the above-mentioned carbonyl hydrolases, and preferably in combination with substitutions corresponding to Selected from the numbering according to Bacillus amyloliquefaciens subtilisins +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156 , +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and/or +274 one or more amino acid residues The group is derived from a precursor carbonyl hydrolase.
同样适用于本发明的是在EP251446和WO91/06637中描述的蛋白酶、在WO91/02792中描述的BLAP和在WO95/23221中描述的它们的变种。Also suitable for use in the present invention are the proteases described in EP251446 and WO91/06637, BLAP(R) described in WO91/02792 and their variants described in WO95/23221.
还可参见Novo的WO93/18140A中所描述的由芽孢杆菌属NCIMB40338得到的高pH蛋白酶。Novo的WO92/03529A中描述了包含蛋白酶、一种或多种其它酶和一种可逆蛋白酶抑制剂的加酶洗涤剂。如果需要,可如Procter & Gamble的WO95/07791所述得到具有降低的吸附性和增加的水解性的蛋白酶。Novo的WO94/25583中描述了一种适用于本发明洗涤剂的重组胰蛋白酶状蛋白酶。其它合适的蛋白酶在Unilever的EP516200中描述。See also the high pH protease from Bacillus sp. NCIMB40338 described in WO 93/18140A to Novo. Enzyme detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529A to Novo. If desired, proteases with reduced adsorption and increased hydrolysis can be obtained as described in Procter & Gamble, WO95/07791. A recombinant trypsin-like protease suitable for use in the detergents of the present invention is described in WO 94/25583 to Novo. Other suitable proteases are described in EP516200 to Unilever.
蛋白分解酶以按组合物重量计0.0001%-2%,优选0.001%-0.2%,更优选0.005%-0.1%纯酶的含量加入本发明的洗涤剂组合物中。Proteolytic enzymes are added to the detergent compositions of the present invention at a level of 0.0001%-2%, preferably 0.001%-0.2%, more preferably 0.005%-0.1% pure enzyme by weight of the composition.
可包括淀粉酶(α和/或β)以除去碳水化合物基的污渍。1994年2月3日公开的Novo Nordisk A/S的WO94/02597描述了加入突变种淀粉酶的洗涤组合物。同样参见1995年4月20日公开的Novo NordiskA/S的WO95/10603。已知用于洗涤组合物的其它淀粉酶包括α-和β-淀粉酶。α-淀粉酶在现有技术中是已知的,包括在US5003257、EP252666、WO91/00353、FR2676456、EP285123、EP525610、EP368341和GB1296839(Novo)中描述的淀粉酶。其它合适的淀粉酶是在Genencor的1994年8月18日公开的WO94/18314和1996年2月22日公开的WO96/05295中描述的稳定性增强的淀粉酶和如在WO95/10603中描述的由Novo Nordisk A/S得到的在中间母体中具有附加改性的淀粉酶变种。同样合适的淀粉酶在EP277216、WO95/26397和WO96/23873(均由Novo Nordisk)中描述。Amylases (alpha and/or beta) may be included to remove carbohydrate based stains. WO 94/02597, Novo Nordisk A/S, published February 3, 1994, describes detergent compositions incorporating mutant amylases. See also WO 95/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases known for use in detergent compositions include alpha- and beta-amylases. Alpha-amylases are known in the art and include those described in US5003257, EP252666, WO91/00353, FR2676456, EP285123, EP525610, EP368341 and GB1296839 (Novo). Other suitable amylases are the stability-enhanced amylases described in WO94/18314, published August 18, 1994, and WO96/05295, published February 22, 1996 by Genencor and as described in WO95/10603. Amylase variants with additional modifications in the intermediate parent obtained from Novo Nordisk A/S. Likewise suitable amylases are described in EP277216, WO95/26397 and WO96/23873 (all by Novo Nordisk).
商业α-淀粉酶产物的实例是由Genencor得到的Purafect OxAm和Termamyl、Ban、Fungamyl和Duramyl,均由NovoNordisk A/S丹麦得到。WO95/26397描述了其它合适的淀粉酶:α-淀粉酶,其特征在于,通过Phadebasα-淀粉酶活性试验测定,其在25℃-55℃的温度范围中和在8-10的pH值下具有比Termamyl的比活高至少25%的比活。合适的是在WO96/23873(Novo Nordisk)中描述的上述淀粉酶的变种。在活性水平和热稳定性和较高活性水平结合方面具有改善性质的其它淀粉分解酶在WO95/35382中描述。Examples of commercial alpha-amylase products are Purafect OxAm® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all from NovoNordisk A/S Denmark. WO95/26397 describes other suitable amylases: α-amylases characterized in that they are determined by the Phadebas® α-amylase activity test in the temperature range 25°C-55°C and at a pH value of 8-10 It has a specific activity at least 25% higher than that of Termamyl(R). Suitable are variants of the above amylases described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties in terms of activity level and combination of thermostability and higher activity level are described in WO95/35382.
淀粉分解酶以按组合物重量计0.0001%-2%,优选0.00018%-0.06%,更优选0.00024%-0.048%纯酶的含量加入本发明的洗涤剂组合物中。Amylolytic enzymes are added to the detergent compositions of the present invention at levels of 0.0001%-2%, preferably 0.00018%-0.06%, more preferably 0.00024%-0.048% pure enzyme by weight of the composition.
上述酶可以是任何合适的来源,例如植物、动物、细菌、真菌和酵母来源,来源还可以是嗜中介态的或嗜极限条件(嗜冷、嗜热、嗜压、嗜碱、嗜酸、嗜卤素等)。这些酶的纯或不纯的形式都能使用。目前,通常的实践是经蛋白质/基因工程技术改性野生类型的酶以最佳化它们在本发明的洗涤组合物中的性能效率。例如可设计变体以增加酶与该组合物中通常遇到的组分的相容性。此外,可设计变体使得酶变体的最佳pH、漂白剂或螯合剂稳定性、催化活性等能够适应特定的洗涤应用。The above-mentioned enzymes may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin, and the source may also be mesotropic or extreme conditions (psychrophilic, thermophilic, barophilic, basophilic, acidophilic, halogen, etc.). Pure or impure forms of these enzymes can be used. Currently, it is common practice to modify wild-type enzymes via protein/genetic engineering techniques to optimize their performance efficiency in the detergent compositions of the present invention. For example, variants can be designed to increase the compatibility of the enzyme with commonly encountered components of the composition. In addition, variants can be designed such that the optimal pH, bleach or chelator stability, catalytic activity etc. of the enzyme variant can be tailored to a specific wash application.
在漂白剂稳定性的情况下尤其应注意对氧化敏感的氨基酸,和对于表面活性剂相容性应注意表面电荷。这种酶的等电点可通过某些带电荷的氨基酸的取代改性,例如增加等电点会有助于改善与阴离子表面活性剂的相容性。酶的稳定性可进一步通过产生例如附加盐桥和加强钙结合位置增加螯合剂稳定性而增强。特别必须注意纤维素酶,因为大多数纤维素酶具有单独的结合结构域(CBD)。这种酶的性质可通过这些结构域中的改性改变。Particular attention should be paid to oxidation-sensitive amino acids in the case of bleach stability, and to the surface charge for surfactant compatibility. The isoelectric point of this enzyme can be modified by the substitution of some charged amino acids, for example, increasing the isoelectric point will help to improve the compatibility with anionic surfactants. Enzyme stability can be further enhanced by creating, for example, additional salt bridges and strengthening calcium binding sites to increase chelator stability. Particular attention must be paid to cellulases, since most cellulases have a separate binding domain (CBD). The properties of this enzyme can be altered by modifications in these domains.
所述酶以按洗涤剂组合物重量计0.0001%-2%纯酶的含量加入本发明的洗涤剂组合物中。酶可作为单独的组分(含有一种酶的小球、颗粒、稳定液体等)或作为两种或多种酶的混合物(例如复合颗粒(cogranulate))加入。The enzyme is added to the detergent composition of the present invention at a level of 0.0001% to 2% pure enzyme by weight of the detergent composition. Enzymes can be added as individual components (pellet, granule, stable liquid etc. containing one enzyme) or as a mixture of two or more enzymes (eg cogranulate).
其它可加入的合适洗涤剂组分是酶氧化清除剂,它在1992年1月31日申请的未审欧洲专利申请92870018.6中描述,该酶氧化清除剂的实例是乙氧基化四亚乙基聚胺。Other suitable detergent ingredients that can be added are enzyme oxidation scavengers described in unexamined European patent application 92870018.6 filed on January 31, 1992, examples of which are ethoxylated tetraethylene Polyamine.
Genencor International的WO9307263A和WO9307260A,Novo的WO8908694A和1971年1月5日颁布的McCarty等的US3553139也描述了各种酶物质和它们加入合成洗涤剂组合物中的方法。1978年7月18日颁布的Place等的US4101457和1985年3月26日颁布的Hughes的US4507219进一步对酶进行披露。1981年4月14日颁布的Hora等的US4261868披露了用于液体洗涤配方的酶原料,和它们加入这种配方中的方法。用于洗涤剂的酶可用各种方法加以稳定。1971年8月17日颁布的Gedge等的US3600319和1986年10月29日Venegas的EP199405和EP200586对酶稳定技术进行了披露和列举。酶稳定体系还例如在US3519570中描述。Novo的WO9401532A描述了能够得到蛋白酶、木聚糖酶和纤维素酶的有用的芽孢杆菌属AC13。颜色护理和织物护理效果WO9307263A and WO9307260A to Genencor International, WO8908694A to Novo and US3553139 to McCarty et al., issued January 5, 1971 also describe various enzyme materials and their incorporation into synthetic detergent compositions. Enzymes are further disclosed in US Pat. No. 4,101,457, Place et al., issued July 18, 1978, and US Pat. US Patent 4,261,868, Hora et al., issued April 14, 1981, discloses enzyme materials for use in liquid laundry formulations, and their incorporation into such formulations. Enzymes for use in detergents can be stabilized in a variety of ways. Enzyme stabilization techniques are disclosed and enumerated in US3600319 issued August 17, 1971 by Gedge et al. and EP199405 and EP200586 issued October 29, 1986 by Venegas. Enzyme stabilization systems are also described eg in US3519570. WO9401532A to Novo describes a useful Bacillus sp. AC13 capable of deriving proteases, xylanases and cellulases. Color Care and Fabric Care Effects
还可包括提供颜色护理效果类型的技术。这些技术的实例是用于颜色保护的金属催化剂,该金属催化剂在未审的欧洲专利申请92870181.2中描述。染料固定剂、用于抗皱和改善水吸收能力的聚烯烃分散体、香料和用于颜色护理处理和香料亲和性的氨基官能团聚合物是颜色护理/织物护理技术的其它实例,并在1996年11月7日申请的未审专利申请№96870140.9中描述。Technologies that provide color care effect types may also be included. Examples of these technologies are metal catalysts for color protection which are described in co-pending European patent application 92870181.2. Dye fixatives, polyolefin dispersions for anti-wrinkle and improved water absorption, fragrances and amino-functional polymers for color care treatments and fragrance substantivity are other examples of color care/fabric care technologies and were cited in 1996 Described in unexamined patent application №96870140.9 filed on November 7.
织物柔软剂也可以加入本发明的洗衣洗涤剂组合物中。这些试剂可以是无机或有机类型的。无机柔软剂是例如在GB-A-1400898和US5019292中描述的绿土。有机织物柔软剂包括如GB-A1514276和EP-B0011340中描述的水不溶性叔胺,它们与单C12-C14季铵盐的混合物在EP-B-0026527和EP-B-0026528中公开,和如EP-B-0242919中公开的二长链酰胺。织物柔软体系的其它有用的有机组分包括在EP-A-0299575和0313146中公开的高分子量聚环氧乙烷物质。Fabric softening agents can also be incorporated into the laundry detergent compositions of the present invention. These reagents can be of inorganic or organic type. Inorganic softeners are, for example, smectite clays as described in GB-A-1400898 and US5019292. Organic fabric softeners include water-insoluble tertiary amines as described in GB-A1514276 and EP-B0011340, their mixtures with mono-C12-C14 quaternary ammonium salts are disclosed in EP-B-0026527 and EP-B-0026528, and as described in EP-B-0026528 - Dilong chain amides disclosed in B-0242919. Other useful organic components for fabric softening systems include the high molecular weight polyethylene oxide materials disclosed in EP-A-0299575 and 0313146.
绿土的用量通常在按重量计2%-20%,更优选5%-15%的范围内,该物质作为干混组分加入配方的其余部分中。有机织物柔软剂,例如水不溶性叔胺或二长链酰胺物质以按重量计0.5%-5%,通常1%-3%的用量加入,而高分子量聚环氧乙烷物质和水溶性阳离子物质以按重量计0.1%-2%,通常0.15%-1.5%的用量加入。这些物质通常加入组合物的喷雾干燥部分,虽然在某些情况下它们可更方便地作为干混颗粒加入或作为熔融液体喷洒在组合物的其它固体组分上。漂白剂The amount of smectite clay typically ranges from 2% to 20%, more preferably 5% to 15% by weight, the material being added as a dry blend component to the remainder of the formulation. Organic fabric softeners, such as water-insoluble tertiary amines or dilong-chain amide substances, are added in an amount of 0.5%-5% by weight, usually 1%-3%, while high-molecular-weight polyethylene oxide substances and water-soluble cationic substances It is added in an amount of 0.1%-2%, usually 0.15%-1.5% by weight. These materials are usually added to the spray-dried portion of the composition, although in some cases they may more conveniently be added as dry blended granules or sprayed as a molten liquid onto the other solid components of the composition. bleach
可包含在本发明的洗衣洗涤剂组合物中的其它选择性洗涤剂组分包括漂白剂,例如过氧化氢,颗粒尺寸为400-800微米的PB1、PB4和过碳酸盐。这些漂白剂组分可包括一种或多种氧漂白剂和,根据所选择的漂白剂,一种或多种漂白活化剂。如果存在的话,氧漂白化合物通常以约1%-约25%的含量存在。Other optional detergent ingredients that may be included in the laundry detergent compositions of the present invention include bleaches such as hydrogen peroxide, PB1, PB4 and percarbonates having a particle size of 400-800 microns. These bleach components may include one or more oxygen bleaches and, depending on the bleach chosen, one or more bleach activators. Oxygen bleaching compounds, if present, are typically present at levels from about 1% to about 25%.
用于本发明的漂白剂组分可以是用于洗涤组合物的任何漂白剂,其包括氧漂白剂和其它本领域中已知的漂白剂。适用于本发明的漂白剂可以是活化的或未活化的漂白剂。The bleach component for use in the present invention may be any bleaching agent useful in detergent compositions including oxygen bleaches and others known in the art. Bleaching agents suitable for use in the present invention can be activated or unactivated bleaching agents.
可以使用的一种氧漂白剂包括过羧酸漂白剂和其盐。这类漂白剂的合适的实例包括单过氧邻苯二甲酸镁六水合物、间氯过苯甲酸镁盐、4-壬氨基-4-氧代过氧丁酸和二过氧十二碳烷二酸。该漂白剂在US4483781、US专利申请740446、EP0133354和US4412934中公开。高度优选的漂白剂还包括在US4634551中描述的6-壬氨基-6-氧代过氧己酸。One type of oxygen bleach that can be used includes percarboxylic acid bleaches and salts thereof. Suitable examples of such bleaches include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecane Diacid. Such bleaches are disclosed in US4483781, US Patent Application 740446, EP0133354 and US4412934. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid described in US4634551.
可以使用的另一类漂白剂包括卤素漂白剂。次卤酸盐漂白剂的实例例如包括三氯异氰酸和二氯异氰酸钠和钾和N-氯和N-溴烷烃氨磺酰。该物质通常以按最终产物的重量计0.5-10%,优选按重量计1-5%加入。Another class of bleaches that can be used includes halogen bleaches. Examples of hypohalite bleaches include, for example, sodium and potassium trichloroisocyanates and dichloroisocyanates and N-chloro and N-bromoalkane sulfonamides. This substance is generally added at 0.5-10% by weight of the final product, preferably 1-5% by weight.
过氧化氢释放剂可以与漂白活化剂,例如四乙酰基乙二胺(TAED)、壬酰氧基苯磺酸盐(NOBS,在US4412934中描述)、3,5,-三甲基己酰氧基苯磺酸盐(ISONOBS,在EP120591中描述)或五乙酰基葡萄糖(PAG)或N-壬酰基-6-氨基己酸苯酚磺酸酯(NACA-OBS,在WO94/28106中描述)结合使用,它们被过水解以形成作为活性漂白物质的过酸,得到改善的漂白效果。同样合适的是在未审EP申请91870207.7中公开的酰基化的柠檬酸酯和在Procter & Gamble的未审的专利申请US№60/022786(1996年7月30日申请)和№60/028122(1996年10月15日申请)中公开的下式的不对称无环酰亚胺漂白活化剂:其中R1是C7-C13直链或支链饱和或不饱和烷基,R2是C1-C8直链或支链饱和或不饱和烷基和R3是C1-C4直链或支链饱和或不饱和烷基。Hydrogen peroxide releasing agents can be combined with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US4412934), 3,5,-trimethylhexanoyloxy phenylsulfonate (ISONOBS, described in EP120591) or pentaacetylglucose (PAG) or N-nonanoyl-6-aminocaproic acid phenolsulfonate (NACA-OBS, described in WO94/28106) in combination , which are perhydrolyzed to form peracids as active bleaching substances, resulting in an improved bleaching effect. Also suitable are the acylated citrate esters disclosed in unexamined EP application 91870207.7 and in unexamined patent applications US No. 60/022786 (filed 30 July 1996) and No. 60/028122 ( Unsymmetrical acyclic imide bleach activators of the formula disclosed in the October 15, 1996 application): Wherein R 1 is C 7 -C 13 linear or branched saturated or unsaturated alkyl, R 2 is C 1 -C 8 linear or branched saturated or unsaturated alkyl and R 3 is C 1 -C 4 straight Chain or branched saturated or unsaturated alkyl.
用于本发明的洗涤剂组合物中的有用的漂白剂,包括过氧酸和含有漂白活化剂和过氧漂白化合物的漂白体系,在我们未审的申请USSN08/136626、PCT/US95/07823、WO95/27772、WO95/27773、WO95/27774和WO95/27775中描述。Useful bleaching agents for use in the detergent compositions of the present invention, including peroxyacids and bleaching systems containing bleach activators and peroxygen bleaching compounds, are described in our co-pending applications USSN08/136626, PCT/US95/07823, Described in WO95/27772, WO95/27773, WO95/27774 and WO95/27775.
过氧化氢还可通过加入酶体系(即酶和它们的底物)存在,在洗涤开始或洗涤过程中和/或漂洗过程中,该体系能够产生过氧化氢。该酶体系在1991年10月9日申请的EP专利申请91202655.6中公开。Hydrogen peroxide can also be present by adding an enzymatic system (ie enzymes and their substrates) capable of generating hydrogen peroxide at the beginning of the wash or during the wash and/or rinse. This enzyme system is disclosed in EP patent application 91202655.6 filed on October 9, 1991.
用于漂白剂组合物的含金属催化剂包括含钴催化剂,例如五胺乙酸钴(III)盐和含锰催化剂,例如,在EPA549271、EPA549272、EPA458397、US5246621、EPA458398、US5194416和US5114611中描述的化合物。含有过氧化合物、含锰漂白剂催化剂和螯合剂的漂白组合物在专利申请№94870206.3中描述。大多环刚性配位体的过渡金属配合物是优选的用于本发明的含金属催化剂,它们在Procter &Gamble的1997年3月7日申请的未审专利申请US№60/040629;№60/039915;№60/040 222;№60/040156;№60/040115;№60/038714和№60/039920中描述。Metal-containing catalysts for use in bleach compositions include cobalt-containing catalysts such as cobalt(III) pentaamine acetate and manganese-containing catalysts such as the compounds described in EPA549271, EPA549272, EPA458397, US5246621, EPA458398, US5194416 and US5114611. Bleaching compositions containing peroxygen compounds, manganese-containing bleach catalysts and chelating agents are described in patent application No. 94870206.3. Transition metal complexes of polycyclic rigid ligands are preferred metal-containing catalysts for use in the present invention, as described in unexamined patent applications US No. 60/040629 filed March 7, 1997 by Procter &Gamble; No. 60/039915 ; No. 60/040 222; No. 60/040156; No. 60/040115; No. 60/038714 and No. 60/039920 described.
除氧漂白剂以外的漂白剂在本领域中也是已知的,可用于本发明。一种尤其感兴趣的非氧漂白剂包括光活化漂白剂,例如磺化锌和/或铝酞菁。在洗涤过程中这些物质可沉积在载污体上。在光照射下和在氧气存在下,例如通过将衣服挂在日光中干燥时,磺化锌酞菁被活化,随后载污体被漂白。优选的锌酞菁和光活化漂白方法在US4033718中描述。洗涤剂组合物通常将含有按重量计约0.025%-1.25%磺化锌酞菁。助洗剂体系Bleaching agents other than oxygen bleaching agents are also known in the art and can be used in the present invention. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited on the soil carrier during the washing process. Upon exposure to light and in the presence of oxygen to dry, for example by hanging the clothes in the sun, the sulfonated zinc phthalocyanine is activated and the soil carrier is subsequently bleached. A preferred zinc phthalocyanine and photoactivated bleaching process is described in US4033718. Detergent compositions will generally contain from about 0.025% to 1.25% by weight of sulfonated zinc phthalocyanine. Builder system
本发明的组合物还可含有助洗剂体系。任何常规的助洗剂体系适用于本发明,其包括硅铝酸盐物质、硅酸盐、多羧酸盐、烷基或烯基琥珀酸和脂肪酸、物质,例如乙二胺四乙酸盐、二亚乙基三胺五亚甲基乙酸盐、金属离子螯合剂,例如氨基多膦酸盐,尤其是乙二胺四亚甲基膦酸和二亚乙基三胺五亚甲基膦酸。磷酸盐助洗剂也可用于本发明中。The compositions of the present invention may also contain a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl or alkenyl succinic and fatty acids, materials such as ethylenediaminetetraacetate, Diethylenetriaminepentamethylene acetate, metal ion sequestrants such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid . Phosphate builders are also useful herein.
合适的助洗剂可以是无机离子交换物质,通常是无机水合硅铝酸盐物质,更尤其是水合合成沸石,例如水合沸石A、X、B、HS或MAP。Suitable builders may be inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials, more especially hydrated synthetic zeolites such as hydrated zeolite A, X, B, HS or MAP.
其它合适的无机助洗剂物质是层状硅酸盐,例如SKS-6(Hoechst)。SKS-6是由硅酸钠(Na2Si2O5)组成的结晶层状硅酸盐。Other suitable inorganic builder materials are layered silicates, eg SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate composed of sodium silicate (Na 2 Si 2 O 5 ).
含有一个羧基的合适的多羧酸盐包括在比利时专利831368、821369和821370中公开的乳酸、乙醇酸和它们的醚衍生物。含有两个羧基的多羧酸盐包括琥珀酸、丙二酸、(亚乙二氧基)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和在DE2446686和2446687和US3935257中描述的醚羧酸盐和在比利时专利840623中描述的亚硫酰基羧酸盐。含有三个羧基的多羧酸盐尤其包括水溶性柠檬酸盐、乌头酸盐和柠康酸盐以及琥珀酸盐衍生物,例如在GB1379241中描述的羧基甲氧基琥珀酸盐、在荷兰申请7205873中描述的乳氧基琥珀酸盐和在GB1387447中描述的氧多羧酸盐物质,例如2-氧杂-1,1,3-丙烷三羧酸盐。Suitable polycarboxylates containing one carboxyl group include lactic acid, glycolic acid and their ether derivatives disclosed in Belgian Patents 831368, 821369 and 821370. Polycarboxylates containing two carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, and fumaric acid and ether carboxylates described in DE2446686 and 2446687 and US3935257 and thionyl carboxylates described in Belgian patent 840623. Polycarboxylates containing three carboxyl groups include especially water-soluble citrate, aconitate and citraconic acid salts and succinate derivatives, such as carboxymethoxysuccinate described in GB1379241, application in the Netherlands Lactoxysuccinates described in 7205873 and oxypolycarboxylate materials described in GB1387447, eg 2-oxa-1,1,3-propanetricarboxylate.
含有四个羧基的多羧酸盐包括在GB1261829中公开的氧联二琥珀酸盐、1,1,2,2-乙烷四羧酸盐、1,1,3,3-丙烷四羧酸盐和1,1,2,3-丙烷四羧酸盐。含有磺基取代基的多羧酸盐包括在GB1398421和1398422和US3936448中公开的磺基琥珀酸盐衍生物和在GB1082179中描述的磺化热解柠檬酸盐,而含有膦酰基取代基的多羧酸盐在GB1439000中公开。Polycarboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates disclosed in GB1261829 and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include sulfosuccinate derivatives disclosed in GB1398421 and 1398422 and US3936448 and sulfonated pyrolytic citrates described in GB1082179, while polycarboxylates containing phosphono substituents Salts are disclosed in GB1439000.
脂环和杂环多羧酸盐包括环戊烷-顺,顺,顺-四羧酸盐、环戊二烯(cyclopentadienide)五羧酸盐、2,3,4,5-四氢呋喃-顺,顺,顺-四羧酸盐、2,5-四氢呋喃-顺-二羧酸盐、2,2,5,5-四氢呋喃四羧酸盐、1,2,3,4,5,6-己烷六羧酸盐和多羟基醇,例如山梨糖醇、甘露糖醇和木糖醇的羧甲基衍生物。芳族多羧酸盐包括在GB1425343中公开的苯六甲酸、苯四酸和苯二酸衍生物。Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylate, cyclopentadienide pentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis , cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,2,5,5-tetrahydrofuran tetracarboxylate, 1,2,3,4,5,6-hexane six Carboxylate salts and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and phthalic acid derivatives disclosed in GB1425343.
其中,优选的多羧酸盐是每分子含有至多三个羧基的羟基羧酸盐,更具体是柠檬酸盐。Of these, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
用于本发明组合物的优选助洗剂体系包括水不溶性硅铝酸盐助洗剂,例如沸石A或层状硅酸盐(SKS-6)和水溶性羧酸盐螯合剂,例如柠檬酸的混合物。Preferred builder systems for use in the compositions of the present invention include water-insoluble aluminosilicate builders, such as zeolite A or layered silicate (SKS-6), and water-soluble carboxylate chelating agents, such as citric acid. mixture.
其它优选的助洗剂体系包括水不溶性硅铝酸盐助洗剂,例如沸石A和水溶性羧酸盐螯合剂,例如柠檬酸的混合物。用于本发明的液体洗涤剂组合物的优选助洗剂体系包括皂和多羧酸盐。Other preferred builder systems include mixtures of water-insoluble aluminosilicate builders, such as zeolite A, and water-soluble carboxylate chelating agents, such as citric acid. Preferred builder systems for use in the liquid detergent compositions of the present invention include soaps and polycarboxylates.
可构成部分用于颗粒组合物的助洗剂体系的其它助洗剂物质包括无机物质,例如碱金属碳酸盐、碳酸氢盐、硅酸盐和有机物质,例如有机膦酸盐、氨基聚亚烷基膦酸盐和氨基多羧酸盐。Other builder materials which may form part of the builder system for granular compositions include inorganic materials such as alkali metal carbonates, bicarbonates, silicates and organic materials such as organic phosphonates, aminopolyethylene Alkylphosphonates and aminopolycarboxylates.
其它合适的水溶性有机盐是均或共聚酸或它们的盐,其中多羧酸含有被不超过两个碳原子彼此分开的至少两个羧基。这种类型的聚合物在GB-A-1596756中公开。这种盐的实例是MW2000-5000的聚丙烯酸盐和它们与马来酐的共聚物,该共聚物具有20000-70000,尤其约40000的分子量。Other suitable water-soluble organic salts are homo- or co-polymeric acids or their salts, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1596756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, the copolymers having a molecular weight of 20000-70000, especially about 40000.
洗涤剂助洗剂盐通常以按组合物重量计5%-80%,优选10%-70%,最常见为按重量计30%-60%的量存在。螯合剂Detergent builder salts are generally present in amounts of from 5% to 80%, preferably from 10% to 70%, most often from 30% to 60% by weight of the composition. Chelating agent
本发明洗衣洗涤剂组合物也可选择性地包含一种或多种铁和/或锰螯合剂。这种螯合剂可选自氨基羧酸盐,氨基膦酸盐,多官能团取代的芳香族螯合剂及其混合物,下文将对它们进行定义。尽管不想受理论的限制,但我们认为这些物质的效果部分是因为它们通过形成可溶性螯合物从洗涤液中去除铁和锰离子的优异能力。The laundry detergent compositions of the present invention may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, as defined below. While not wishing to be bound by theory, we believe that the effectiveness of these species is due in part to their excellent ability to remove iron and manganese ions from wash liquors by forming soluble chelates.
可用作选择性的螯合剂的氨基羧酸盐包括乙二胺四乙酸盐,N-羟乙基乙二胺三乙酸盐,次氮基三乙酸盐,乙二胺四丙酸盐,三亚乙基四胺六乙酸盐,二亚乙基三胺五乙酸盐和乙醇二甘氨酸,它们的碱金属,铵,和取代铵盐及其混合物。Amino carboxylates that can be used as optional chelating agents include EDTA, N-hydroxyethyl EDTA, nitrilotriacetate, EDTA , triethylenetetraminehexaacetate, diethylenetriaminepentaacetate, and ethanol diglycine, their alkali metal, ammonium, and substituted ammonium salts, and mixtures thereof.
当允许在洗涤剂组合物中使用至少低含量的总磷时,氨基膦酸盐也适合在本发明组合物中用作螯合剂,它包括乙二胺四(亚甲基膦酸盐),为DEQUEST。该氨基膦酸盐优选不包含多于约6个碳原子的烷基或烯基。Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylene phosphonates), as DEQUEST. The amino phosphonates preferably do not contain alkyl or alkenyl groups of more than about 6 carbon atoms.
多官能团取代的芳香族螯合剂也适合用于本发明组合物。参见1974年5月21日颁布的Connor等的US3812044。优选的酸态的这类化合物为二羟基二磺基苯,如1,2-二羟基-3,5-二磺基苯。Polyfunctionally substituted aromatic chelating agents are also suitable for use in the compositions of the present invention. See US3812044, Connor et al., issued May 21,1974. Preferred compounds of this type in the acid form are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene.
用于本发明的可生物降解的螯合剂优选为乙二胺二琥珀酸盐(“EDDS”),特别是[S,S]异构体,这在1987年11月3日颁布的Hartman和Perkins的US4704233中公开。The preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), particularly the [S, S] isomer, as described in Hartman and Perkins, November 3, 1987. Disclosed in US4704233.
本发明的组合物还可以含有与例如不溶性的助洗剂,例如沸石、层状硅酸盐等一起使用的用作螯合剂或辅助助洗剂的水溶性甲基甘氨酸二乙酸(MGDA)盐(或酸式)。The compositions of the present invention may also contain water-soluble methylglycine diacetic acid (MGDA) salts ( or acid form).
如果使用,这些螯合剂一般为本发明洗涤剂组合物的约0.1%-约15重量%。更加优选的是,如果使用,这些螯合剂为该组合物的约0.1%-约3.0重量%。抑泡剂If utilized, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. Even more preferably, if used, these chelating agents comprise from about 0.1% to about 3.0% by weight of the composition. Foam suppressor
另一选择的组分是抑泡剂,例如聚硅氧烷和二氧化硅-聚硅氧烷混合物。聚硅氧烷通常可表示为烷基化的聚硅氧烷物质,而二氧化硅通常以细粉碎形式使用,例如各种类型的二氧化硅气溶胶、干凝胶和疏水二氧化硅。这些物质可作为微粒加入,其中抑泡剂有利地是在水溶性或水可分散的,非表面活性剂洗涤剂基本上不可渗透的载体中可释放地加入。此外,抑泡剂可溶解或分散在液体载体中,通过喷雾在一种或多种其它组分上加入。Another optional ingredient is a suds suppressor such as silicones and silica-polysiloxane mixtures. Silicones can generally be denoted as alkylated polysiloxane species, while silicas are generally used in finely divided form, eg various types of silica aerosols, xerogels and hydrophobic silicas. These materials can be incorporated as particulates wherein the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, non-surfactant detergent substantially impermeable carrier. Additionally, the suds suppressor can be dissolved or dispersed in the liquid carrier and added by spraying onto one or more of the other ingredients.
优选的聚硅氧烷泡沫控制剂在Bartollota等的US3933672中公开。其它尤其适用的抑泡剂是在1977年4月28日公开的德国专利申请DTOS2646126中描述的自乳化聚硅氧烷抑泡剂。该化合物的实例是DC-544,商业上由Dow Corning得到,它是聚硅氧烷-二醇共聚物。尤其优选的泡沫控制剂是含有聚硅氧烷油和2-烷基链烷醇的混合物的抑泡剂体系。合适的2-烷基-链烷醇是2-丁基辛醇,它在商业上以商品名Isofol 12R得到。Preferred silicone suds control agents are disclosed in US 3,933,672 to Bartollota et al. Other particularly suitable suds suppressors are the self-emulsifying silicone suds suppressors described in German Patent Application DTOS 2646126, published April 28,1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a polysiloxane-diol copolymer. Especially preferred suds control agents are suds suppressor systems comprising a mixture of silicone oils and 2-alkyl alkanols. A suitable 2-alkyl-alkanol is 2-butyloctanol, which is commercially available under the tradename Isofol 12R.
该抑泡剂体系在1992年11月10日申请的未审欧洲专利申请9287 0174.7中描述。This suds suppressor system is described in unexamined European patent application 9287 0174.7, filed November 10, 1992.
尤其优选的聚硅氧烷泡沫控制剂在未审的欧洲专利申请92201649.8中描述,所述组合物可含有与煅制非多孔二氧化硅,例如AerosilR结合的聚硅氧烷/二氧化硅混合物。Particularly preferred silicone suds control agents are described in unexamined European patent application 92201649.8, said compositions may contain a silicone/silica mixture in combination with a fumed non-porous silica such as Aerosil R .
上述抑泡剂通常以按组合物重量计0.001%-2%,优选按重量计0.01%-1%的含量使用。其它The aforementioned suds suppressors are generally used at a level of 0.001% to 2% by weight of the composition, preferably 0.01% to 1% by weight. other
可使用用于洗衣洗涤剂组合物中的其它组分,例如污垢悬浮剂、去污剂、荧光增白剂、磨料、杀菌剂、晦暗抑制剂、着色剂和/或包胶囊或未包胶囊的香料。Other components used in laundry detergent compositions, such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, colorants and/or encapsulated or unencapsulated spices.
尤其合适的包胶囊材料是水溶性胶囊,如GB1464616中所述,它由多糖和多羟基化合物的基质组成。Particularly suitable encapsulating materials are water soluble capsules, as described in GB1464616, which consist of a matrix of polysaccharides and polyols.
其它合适的水溶性包胶囊材料包括如US3455838中所述的由取代的二羧酸的未胶凝化的淀粉酸酯得到的糊精。这些酸酯糊精优选由淀粉,例如软玉米、软高粱、西米、木薯淀粉和马铃薯制备。所述包胶囊材料的合适实例包括由National Starch制备的N-Lok。N-Lok包胶囊材料由改性玉米淀粉和葡萄糖组成。淀粉通过加入单官能团取代基团,例如辛烯基琥珀酸酐改性。Other suitable water-soluble encapsulating materials include dextrins derived from ungelatinized starch esters of substituted dicarboxylic acids as described in US3455838. These ester dextrins are preferably prepared from starches such as soft corn, soft sorghum, sago, tapioca and potato. Suitable examples of such encapsulating materials include N-Lok manufactured by National Starch. N-Lok encapsulating material consists of modified corn starch and dextrose. Starches are modified by adding monofunctional substituent groups such as octenyl succinic anhydride.
本发明合适的抗再沉积和污垢悬浮剂包括纤维素衍生物,例如甲基纤维素、羧甲基纤维素和羟乙基纤维素和多羧酸或其盐的均或共聚物。这种类型的聚合物包括先前提及的作为助洗剂的聚丙烯酸盐和马来酐-丙烯酸共聚物,和马来酐与乙烯、甲基乙烯基醚或甲基丙烯酸的共聚物,马来酐占共聚物的至少20摩尔%。这些物质通常以按重量计0.5%-10%,更优选0.75%-8%,最优选按组合物重量计1%-6%的量使用。Suitable antiredeposition and soil suspension agents herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose and homo- or copolymers of polycarboxylic acids or salts thereof. Polymers of this type include the previously mentioned polyacrylates and maleic anhydride-acrylic acid copolymers as builders, and copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, maleic anhydride The anhydride comprises at least 20 mole percent of the copolymer. These materials are generally used in amounts of 0.5% to 10% by weight, more preferably 0.75% to 8%, most preferably 1% to 6% by weight of the composition.
优选的荧光增白剂是阴离子特征的,其实例是4,4’-双-(2-乙醇氨基-4-苯胺基-s-三嗪-6-基氨基)芪-2:2’二磺酸二钠、4,4’-双-(2-吗啉代-4-苯胺基-s-三嗪-6-基氨基)芪-2:2’二磺酸二钠、4,4’-双-(2,4-二苯胺基-s-三嗪-6-基氨基)芪-2:2’二磺酸二钠、4’,4”-双-(2,4-二苯胺基-s-三嗪-6-基氨基)芪-2-磺酸单钠、4,4’-双-(2-苯胺基-4-(N-甲基-N-2-羟基乙基氨基)-s-三嗪-6-基氨基)芪-2:2’二磺酸二钠、4,4’-双-(4-苯基-2,1,3-三唑-2-基)芪-2:2’二磺酸二钠、4,4’-双-(2-苯胺基-4-(1-甲基-2-羟基乙基氨基)-s-三嗪-6-基氨基)芪-2:2’二磺酸二钠、2-(芪基-4”-(萘并-1’,2’:4,5)-1,2,3-三唑-2”-磺酸钠和4,4’-双(2-磺基苯乙烯基)联苯。高度优选的增白剂是未审的欧洲专利申请95201943.8的具体增白剂。Preferred optical brighteners are anionic in character, an example of which is 4,4'-bis-(2-ethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'disulfo Disodium disulfonate, 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene-2: Disodium 2'disulfonate, 4,4'- Bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2: disodium 2'disulfonate, 4',4"-bis-(2,4-dianilino- s-triazin-6-ylamino)stilbene-2-sulfonic acid monosodium, 4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)- s-triazin-6-ylamino)stilbene-2: disodium 2'disulfonate, 4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)stilbene- 2: Disodium 2'disulfonate, 4,4'-bis-(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene -2: Disodium 2'disulfonate, 2-(stilbene-4"-(naphtho-1',2':4,5)-1,2,3-triazole-2"-sodium sulfonate and 4,4'-bis(2-sulfostyryl)biphenyl. Highly preferred brighteners are the specific brighteners of co-pending European Patent Application 95201943.8.
其它有用的聚合物是聚乙二醇,尤其是分子量为1000-10000,更优选为2000-8000,最优选约4000的聚合物。它们以按重量计0.20%-5%,更优选0.25%-2.5%的量使用。这些聚合物和上文提到的均聚或共聚的多羧酸盐在改善白度保持、织物灰尘沉积和在过渡金属杂质存在下对泥土、蛋白质和可氧化的污垢的洗涤性能方面是有价值的。Other useful polymers are polyethylene glycols, especially polymers having a molecular weight of 1000-10000, more preferably 2000-8000, most preferably about 4000. They are used in amounts of 0.20% to 5%, more preferably 0.25% to 2.5% by weight. These polymers and the homo- or co-polymeric polycarboxylates mentioned above are valuable in improving whiteness retention, fabric dust deposition and wash performance on soil, protein and oxidizable soils in the presence of transition metal impurities of.
用于本发明组合物的去污剂是常规的对苯二甲酸与不同排列方式的乙二醇和/或丙二醇单元的共聚物或三元共聚物。这种聚合物在共同转让的US4116885和4711730和欧洲专利申请公开EP0272033中描述,根据EP-A-0272033,尤其优选的聚合物具有下式:Soil release agents useful in the compositions of the present invention are conventional copolymers or terpolymers of terephthalic acid with different arrangements of ethylene glycol and/or propylene glycol units. Such polymers are described in commonly assigned US4116885 and 4711730 and European Patent Application Publication EP0272033, according to EP-A-0272033 especially preferred polymers have the following formula:
(CH3(PEG)43)0.75(POH)0.25[T-PO)2.8(T-(CH 3 (PEG) 43 ) 0.75 (POH) 0.25 [T-PO) 2.8 (T-
PEG)0.4]T(POH)0.25((PEG)43CH3)0.75其中PEG是-(OC2H4)O-,PO是(OC3H6O)和T是(pcOC6H4CO)。PEG) 0.4 ]T(POH) 0.25 ((PEG) 43 CH 3 ) 0.75 where PEG is -(OC 2 H 4 )O-, PO is (OC 3 H 6 O) and T is (pcOC 6 H 4 CO) .
同样很有用的是改性聚酯,例如对苯二甲酸二甲酯、磺基间苯二甲酸二甲酯、乙二醇和1-2丙二醇的无规共聚物,端基主要由磺基苯甲酸酯和次要由乙二醇和/或丙二醇的单酯组成。目标是得到在两端由磺基苯甲酸酯基团封端的聚合物,在本发明中,大部分本发明的上述共聚物“主要地”由磺基苯甲酸酯封端。然而,某些共聚物将不是完全封端的,因而,它们的端基可由乙二醇和/或丙1-2二醇组成,其“次要地”组成该物质。Also very useful are modified polyesters such as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol, and 1-2 propanediol, the end groups mainly consisting of sulfobenzyl Esters and minors consist of monoesters of ethylene glycol and/or propylene glycol. The aim is to have polymers terminated at both ends by sulfobenzoate groups, and in the present invention most of the above-mentioned copolymers according to the invention are "predominantly" terminated by sulfobenzoate groups. However, some copolymers will not be fully end-capped, thus, their end groups may consist of ethylene glycol and/or propylene 1-2 glycol which "secondarily" makes up the material.
本发明选择的聚酯含有按重量计约46%对苯二甲酸二甲酯、按重量计约16%丙-1,2二醇、按重量计约10%乙二醇、按重量计约13%磺基苯甲酸二甲酯和按重量计约15%磺基间苯二甲酸,其分子量为约3000。聚酯和它们的制备方法在EPA311342中详细描述。The polyester selected for the present invention contains about 46% by weight dimethyl terephthalate, about 16% by weight propane-1,2 glycol, about 10% by weight ethylene glycol, about 13% by weight % dimethyl sulfobenzoate and about 15% by weight sulfoisophthalic acid having a molecular weight of about 3000. Polyesters and their preparation are described in detail in EPA311342.
人们已知在自来水中存在的游离氯迅速地失活洗涤剂组合物中存在的酶。因此,在配方中以按总组合物重量计0.1%以上的含量使用氯清除剂,例如过硼酸盐、硫酸铵、亚硫酸钠或聚乙烯亚胺将在洗涤过程中提供洗涤剂酶的改善的稳定性。含有氯清除剂的组合物在1992年1月31日申请的欧洲专利申请92870018.6中描述。Free chlorine present in tap water is known to rapidly deactivate enzymes present in detergent compositions. Therefore, the use of chlorine scavengers such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine in the formulation at levels above 0.1% by weight of the total composition will provide improved stabilization of the detergent enzymes during the wash process. sex. Compositions containing chlorine scavengers are described in European Patent Application 92870018.6 filed 31 January 1992.
如由聚丙烯酸盐制备的烷氧基化的多羧酸盐用于本发明中以提供附加的去油脂性能。该物质在WO91/08281和PCT90/01815第4页以及以后各页中描述,列为本文参考文献。在化学上这些物质含有每7-8个丙烯酸盐单元一个乙氧基侧链的聚丙烯酸盐。侧链有式-(CH2CH2O)m(CH2)nCH3,其中m是2-3,n是6-12。侧链酯连接于聚丙烯酸盐“骨架”以提供“梳形”聚合物型结构。分子量可变化,但通常为约2000-约50000。该烷氧基化多羧酸盐可占本发明组合物重量的约0.05%-约10%。分散剂Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are useful herein to provide additional grease removal performance. This material is described on pages 4 et seq. of WO91/08281 and PCT90/01815, incorporated herein by reference. Chemically these materials contain polyacrylates with one ethoxy side chain per 7-8 acrylate units. The side chain has the formula -(CH 2 CH 2 O) m (CH 2 ) n CH 3 , where m is 2-3 and n is 6-12. Side chain esters are attached to the polyacrylate "backbone" to provide a "comb" polymer type structure. Molecular weights can vary, but typically range from about 2,000 to about 50,000. The alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the compositions herein. Dispersant
本发明的洗衣洗涤剂组合物还可含有分散剂:合适的水溶性有机盐是均或共聚酸或其盐,其中多羧酸含有被不超过两个碳原子分开的至少两个羧基。The laundry detergent compositions of the present invention may also contain dispersants: Suitable water-soluble organic salts are homo- or co-polymeric acids or salts thereof wherein the polycarboxylic acid contains at least two carboxyl groups separated by not more than two carbon atoms.
这种类型的聚合物在GB-A-1596756中公开。这种盐的实例是MW2000-5000的聚丙烯酸盐和它们与马来酐的共聚物,该共聚物具有1000-100000的分子量。Polymers of this type are disclosed in GB-A-1596756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, the copolymers having a molecular weight of 1000-100000.
尤其是,在本发明的洗衣洗涤剂组合物中可加入按组合物重量计含量为0.5-20%的丙烯酸盐和甲基丙烯酸盐的共聚物,例如分子量为4000的480N。In particular, copolymers of acrylate and methacrylate, such as 480N having a molecular weight of 4000, may be incorporated into the laundry detergent compositions of the present invention at levels of from 0.5% to 20% by weight of the composition.
本发明的组合物可含有钙皂胶溶剂化合物,它具有如下定义的不超过8,优选不超过7,最优选不超过6的钙皂分散能力(LSDP)。钙皂胶溶剂化合物优选以按重量计0%-20%的量存在。The compositions of the present invention may contain a lime soap peptizer compound having a lime soap dispersing power (LSDP) of not more than 8, preferably not more than 7, most preferably not more than 6, as defined below. Lime soap peptizers are preferably present in an amount of 0% to 20% by weight.
钙皂胶溶剂效果的各种测量结果通过钙皂分散剂能力(LSDP)给出,其通过使用在文章H.C.Borghetty和C.A.Bergman,J.Am.Oil.Chem.Soc.第27卷的88-90页中描述的钙皂分散试验测定。该钙皂分散试验方法被本领域中的实践者广泛使用,和例如如下评论文章有关;W.N.Linfield,表面活性剂科学丛书(Surfactant scienceSeries),第7卷,第3页;W.N.Linfield,Tenside surf.det.第27卷,第159-163页(1990)和M.K.Nagarajan,W.F.Masler,Cosmetics and Toiletries,第104卷,71-73页(1989)。LSDP是在333ppm碳酸钙(钙∶镁=3∶2)当量硬度的30ml水中分散由0.025g油酸钠形成的钙皂沉积物所需的分散剂与油酸钠的%重量比。Various measures of the peptizing effect of lime soaps are given by lime soap dispersant power (LSDP), which is obtained by using the paper H.C. Borghetty and C.A. Bergman, J.Am.Oil.Chem.Soc. Determination of the calcium soap dispersion test described on page . This calcium soap dispersion test method is widely used by practitioners in the field and is relevant for example to the following review articles; W.N. Linfield, Surfactant science Series, Vol. 7, p. 3; W.N. Linfield, Tenside surf. det. Vol. 27, pp. 159-163 (1990) and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Vol. 104, pp. 71-73 (1989). LSDP is the % weight ratio of dispersant to sodium oleate required to disperse calcium soap deposits formed by 0.025 g sodium oleate in 30 ml water of 333 ppm calcium carbonate (calcium: magnesium = 3: 2) equivalent hardness.
具有良好钙皂胶溶剂能力的表面活性剂包括某些氧化胺、甜菜碱、磺基甜菜碱、烷基乙氧基硫酸盐和乙氧基化醇。Surfactants with good lime soap peptizing capabilities include certain amine oxides, betaines, sultaines, alkyl ethoxy sulfates and ethoxylated alcohols.
具有LSDP不超过8的用于本发明的表面活性剂的实例包括C16-C18二甲基氧化胺、平均乙氧基化程度为1-5的C12-C18烷基乙氧基硫酸盐,尤其是平均乙氧基化程度为3的C12-C15烷基乙氧基硫酸盐表面活性剂(LSDP=4)和平均乙氧基化程度为12(LSDP=6)或30的C14-C15乙氧基化醇,由BASF GmbH分别以商品名Lutensol A012和Lutensol A030销售。Examples of surfactants useful in the present invention having an LSDP of not more than 8 include C 16 -C 18 dimethyl amine oxide, C 12 -C 18 alkyl ethoxysulfates having an average degree of ethoxylation of 1-5 Salts, especially C 12 -C 15 alkyl ethoxysulfate surfactants with an average degree of ethoxylation of 3 (LSDP=4) and surfactants with an average degree of ethoxylation of 12 (LSDP=6) or 30 C 14 -C 15 ethoxylated alcohols sold under the trade names Lutensol A012 and Lutensol A030, respectively, by BASF GmbH.
适用于本发明的聚合钙皂胶溶剂在M.K.Nagarajan,W.F.Masler的在Cosmetics and Toiletries,第104卷,第71-73页(1989)中的文章中描述。Polymeric calcium soap peptizers suitable for use in the present invention are described in the article by M.K. Nagarajan, W.F. Masler in Cosmetics and Toiletries, Vol. 104, pp. 71-73 (1989).
疏水漂白剂例如4-[N-辛酰基-6-氨基己酰基]苯磺酸盐,4-[N-壬酰基-6-氨基己酰基]苯磺酸盐,4-[N-癸酰基-6-氨基己酰基]苯磺酸盐和它们的混合物和壬酰氧基苯磺酸盐与亲水/疏水漂白剂制剂一起也可用作钙皂胶溶剂化合物。染料转移抑制Hydrophobic bleaches such as 4-[N-octanoyl-6-aminocaproyl]benzenesulfonate, 4-[N-nonanoyl-6-aminocaproyl]benzenesulfonate, 4-[N-decanoyl- 6-aminocaproyl]benzenesulfonate and mixtures thereof and nonanoyloxybenzenesulfonate are also useful as lime soap peptizing compounds with hydrophilic/hydrophobic bleach formulations. dye transfer inhibition
本发明的洗衣洗涤剂组合物还包含抑制在包括有色织物的织物洗涤操作中遇到的溶解和悬浮的染料从一种织物转移到另一种织物的化合物。聚合染料转移抑制剂The laundry detergent compositions of the present invention also comprise compounds which inhibit the transfer of dissolved and suspended dyes from one fabric to another encountered in fabric laundering operations involving colored fabrics. polymeric dye transfer inhibitor
本发明的洗衣洗涤剂组合物还含有按重量计0.001%-10%,优选0.01%-2%,更优选0.05%-1%聚合染料转移抑制剂。在洗衣洗涤剂组合物中加入所述聚合染料转移抑制剂以便抑制带色织物的染料转移至与其一起洗涤的织物上。在洗涤过程中,在从染色织物洗出的短效染料有机会接触其它物品前,该聚合物有配合或吸附该短效染料的能力。The laundry detergent compositions of the present invention also contain from 0.001% to 10%, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. The polymeric dye transfer inhibiting agents are incorporated into laundry detergent compositions to inhibit the transfer of dyes from colored fabrics to fabrics washed therewith. The polymer has the ability to complex or absorb the fugitive dye washed out of the dyed fabric before it has the opportunity to come into contact with other items during the laundering process.
尤其合适的聚合染料转移抑制剂是聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、聚乙烯基吡咯烷酮聚合物、聚乙烯基噁唑烷酮和聚乙烯基咪唑或它们的混合物。Particularly suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinyl imidazoles or their mixtures.
加入该聚合物也提高了本发明的酶的性能。a)聚胺N-氧化物聚合物The addition of this polymer also improves the performance of the enzymes of the invention. a) Polyamine N-oxide polymers
适用的聚胺N-氧化物聚合物含有具有如下结构式的单元:其中P是可聚合的单元,R-N-O基团可与其相连或其中R-N-O基团构成部分可聚合的单元或两者的结合。A是 -O-,-S-,-N-;x是0或1;x是0或1;R是脂族、乙氧基化脂族、芳香族、杂环或脂环基团或其任何组合,N-O基团的氮可与其相连或其中N-O基团的氮是这些基团的一部分。Suitable polyamine N-oxide polymers contain units of the formula: Wherein P is a polymerizable unit to which the RNO group may be attached or wherein the RNO group forms part of the polymerizable unit or a combination of both. A is -O-, -S-, -N-; x is 0 or 1; x is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof , the nitrogen of the NO group may be attached to or wherein the nitrogen of the NO group is part of these groups.
N-O基团可以由如下通式结构表示:其中R1、R2和R3是脂族基团、芳香族、杂环或脂环基团或它们的组合,x或/和y或/和z是0或1,其中N-O基团的氮可与其连接或其中N-O基团的氮构成这些基团的部分。The NO group can be represented by the following general structure: wherein R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z are 0 or 1, wherein the nitrogen of the NO group can be attached to it or wherein the nitrogen of the NO group forms part of these groups.
N-O基团可以是可聚合单元(P)的部分或可与聚合骨架相连或两者的组合。The N-O groups may be part of the polymerizable unit (P) or may be attached to the polymeric backbone or a combination of both.
其中N-O基团构成可聚合单元的部分的合适的聚胺N-氧化物包括聚胺N-氧化物,其中R选自脂族、芳香族、脂环或杂环基团。Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit include polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
一类上述聚胺N-氧化物包括一组聚胺N-氧化物,其中N-O基团的氮构成R-基团的部分。优选的聚胺N-氧化物是其中R是杂环基团,例如吡啶、吡咯、咪唑、吡咯烷、哌啶、喹啉、吖啶和它们的衍生物的化合物。One class of the aforementioned polyamine N-oxides includes a group of polyamine N-oxides in which the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
另一类上述聚胺N-氧化物包括一组聚胺N-氧化物,其中N-O基团的氮连接于R基团。Another class of the aforementioned polyamine N-oxides includes a group of polyamine N-oxides in which the nitrogen of the N-O group is attached to the R group.
其它合适的聚胺N-氧化物是其中N-O基团与可聚合单元连接的聚胺氧化物。Other suitable polyamine N-oxides are polyamine oxides in which the N—O groups are attached to the polymerisable units.
优选类的这些聚胺N-氧化物是具有通式(I)的聚胺N-氧化物,其中R是芳香族、杂环或脂环基团,其中N-O官能团的氮是所述R基团的部分。A preferred class of these polyamine N-oxides are polyamine N-oxides having the general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen of the N-O functional group is the R group part.
这类化合物的实例是聚胺氧化物,其中R是杂环化合物,例如吡啶、吡咯、咪唑和它们的衍生物。Examples of such compounds are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and their derivatives.
另一优选类的聚胺N-氧化物是具有通式(I)的聚胺氧化物,其中R是芳香族、杂环或脂环基团,其中N-O官能团的氮连接于所述R基团。Another preferred class of polyamine N-oxides are polyamine oxides of general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen of the N-O functional group is attached to said R group .
这类化合物的实例是聚胺氧化物,其中R基团可以是芳族的,例如苯基。Examples of such compounds are polyamine oxides, where the R group may be aromatic, eg phenyl.
可以使用任何聚合物骨架只要形成的氧化胺聚合物是水溶性的并具有染料转移抑制性质。合适的聚合骨架的实例是聚乙烯、聚亚烷基、聚酯、聚醚、聚酰胺、聚酰亚胺、聚丙烯酸盐和它们的混合物。Any polymer backbone can be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyethylenes, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.
通常本发明的胺N-氧化物聚合物具有胺与胺N-氧化物的比率为10∶1-1∶1000000。然而,在聚胺氧化物聚合物中存在的氧化胺基团的量可通过合适的共聚或通过合适的N-氧化程度改变。胺与胺N-氧化物的比率优选为2∶3-1∶1000000,更优选为1∶4-1∶1000000,最优选为1∶7-1∶1000000。本发明的聚合物实际上包括无规或嵌段共聚物,其中一个单体类型是胺N-氧化物,而其它单体类型是胺N-氧化物或不是。聚胺N-氧化物的氧化胺单元的PKa<10,优选PKa<7,更优选PKa<6。Typically the amine N-oxide polymers of the present invention have a ratio of amine to amine N-oxide of 10:1 to 1:1,000,000. However, the amount of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or by suitable degree of N-oxidation. The ratio of amine to amine N-oxide is preferably from 2:3 to 1:1000000, more preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present invention actually include random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an amine N-oxide or not. The amine oxide units of the polyamine N-oxides have a PKa<10, preferably a PKa<7, more preferably a PKa<6.
聚胺氧化物可以几乎任何的聚合程度得到,聚合程度不是关键的,只要物质具有所需的水溶性和染料悬浮能力。The polyamine oxides can be obtained in almost any degree of polymerization which is not critical provided the material has the desired water solubility and dye-suspending power.
平均分子量通常为500-1000000;优选1000-50000,更优选2000-30000,最优选3000-20000。b)N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物The average molecular weight is usually 500-1,000,000; preferably 1,000-50,000, more preferably 2,000-30,000, most preferably 3,000-20,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
用于本发明的N-乙烯基咪唑N-乙烯基吡咯烷酮聚合物具有5000-1000000,优选5000-200000的平均分子量。The N-vinylimidazole N-vinylpyrrolidone polymer used in the present invention has an average molecular weight of 5,000-1,000,000, preferably 5,000-200,000.
用于本发明的洗涤剂组合物的高度优选的聚合物包括选自N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物的聚合物,其中所述聚合物具有5000-50000,更优选8000-30000,最优选10000-20000的平均分子量。Highly preferred polymers for use in the detergent compositions of the present invention include polymers selected from N-vinylimidazole N-vinylpyrrolidone copolymers, wherein said polymer has a An average molecular weight of 10,000-20,000 is most preferred.
平均分子量范围通过如Barth H.G.和Mays J.W.《化学分析》113卷,“聚合物表征的现代方法”中所述通过光散射测定。The average molecular weight range is determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis, Vol. 113, "Modern Methods for the Characterization of Polymers".
高度优选的N-乙烯基咪唑N-乙烯吡咯烷酮共聚物具有5000-50000;更优选8000-30000;最优选10000-20000的平均分子量。Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight of 5,000-50,000; more preferably 8,000-30,000; most preferably 10,000-20,000.
以上述平均分子量为特征的N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物提供极好的染料转移抑制性质,而没有不利地影响用其配制的洗涤剂组合物的洗涤性能。The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by the above average molecular weights provide excellent dye transfer inhibiting properties without adversely affecting the cleaning performance of detergent compositions formulated therewith.
本发明的N-乙烯基咪唑N-乙烯基吡咯烷酮共聚物具有N-乙烯基咪唑与N-乙烯基吡咯烷酮的摩尔比为1-0.2,更优选0.8-0.3,最优选0.6-0.4。c)聚乙烯基吡咯烷酮The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1-0.2, more preferably 0.8-0.3, most preferably 0.6-0.4. c) Polyvinylpyrrolidone
本发明的洗涤剂组合物还可以使用平均分子量为约2500-约400000,优选约5000-约200000,更优选约5000-约50000,最优选约5000-约15000的聚乙烯基吡咯烷酮(“PVP”)。合适的聚乙烯基吡咯烷酮在商业上由ISP Corporation,纽约,NY和蒙特利尔,加拿大以产品名PVP K-15(粘度分子量为10000)、PVP K-30(平均分子量40000),PVP K-60(平均分子量160000)和PVP K-90(平均分子量360000)得到。在商业上可由BASF Cooperation得到的其它合适的聚乙烯基吡咯烷酮包括Sokalan HP 165和Sokalan HP 12;在洗涤剂领域中技术人员已知的聚乙烯基吡咯烷酮(参见例如EP-A-262897和EP-A-256696)。d)聚乙烯基噁唑烷酮:The detergent composition of the present invention can also use polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, most preferably from about 5,000 to about 15,000. ). Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight 10000), PVP K-30 (average molecular weight 40000), PVP K-60 (average Molecular weight 160000) and PVP K-90 (average molecular weight 360000). Other suitable polyvinylpyrrolidones commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to those skilled in the detergent field (see e.g. EP-A-262897 and EP-A -256696). d) Polyvinyloxazolidinone:
本发明的洗涤剂组合物也可使用聚乙烯基噁唑烷酮作为聚合染料转移抑制剂,所述聚乙烯基噁唑烷酮具有约2500-约400000,优选约5000-约200000,更优选约5000-约50000,最优选约5000-约15000的平均分子量。e)聚乙烯基咪唑:The detergent compositions of the present invention can also use polyvinyl oxazolidinones having a molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably about Average molecular weight from 5,000 to about 50,000, most preferably from about 5,000 to about 15,000. e) Polyvinylimidazole:
本发明的洗涤剂组合物还可使用聚乙烯基咪唑作为聚合染料转移抑制剂,所述聚乙烯基咪唑具有约2500-约400000,优选约5000-约200000,更优选约5000-约50000,最优选约5000-约15000的平均分子量。f)交联聚合物:The detergent compositions of the present invention may also employ polyvinylimidazole having a value of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 50,000, as a polymeric dye transfer inhibiting agent. Average molecular weights from about 5,000 to about 15,000 are preferred. f) Cross-linked polymers:
交联聚合物是其中骨架相互连接至一定程度的聚合物;这些连接可以是化学或物理性质的,可能在骨架或支链上带有活性基团;交联聚合物在《聚合物科学杂志》22卷,1035-1039页中描述。Cross-linked polymers are polymers in which the backbone is interconnected to some extent; these linkages may be chemical or physical in nature, possibly with reactive groups on the backbone or branches; cross-linked polymers are described in Journal of Polymer Science Described in Vol. 22, pp. 1035-1039.
在一个实施方案中,以这种方式制备交联聚合物使得它们形成三维刚性结构,它能够在由三维结构形成的孔中捕获染料。在另一实施方案中,交联聚合物通过溶胀捕获染料。In one embodiment, the crosslinked polymers are prepared in such a way that they form a three-dimensional rigid structure that is capable of trapping the dye in the pores formed by the three-dimensional structure. In another embodiment, the crosslinked polymer entraps the dye by swelling.
该交联聚合物在未审的专利申请94870213.9中描述。洗涤方法Such crosslinked polymers are described in co-pending patent application 94870213.9. cleaning method
本发明的组合物可用于基本上任何洗涤或清洗方法,其包括浸泡方法、预处理方法和带有可加入单独的漂洗助剂组合物的漂洗步骤的方法。The compositions of the present invention may be used in essentially any washing or cleaning method including soaking methods, pretreatment methods and methods with a rinse step where a separate rinse aid composition may be added.
本发明所述的方法包括将织物以通常和下文所述方式与洗涤溶液接触。The method of the present invention involves contacting the fabrics with a wash solution in the usual manner and as described hereinafter.
本发明的方法通常在洗涤过程中进行。洗涤方法优选在5℃-95℃,尤其在10℃-60℃之间进行,处理溶液的pH优选为7-12。The method of the invention is generally carried out during a wash. The washing method is preferably carried out at 5°C-95°C, especially at 10°C-60°C, and the pH of the treatment solution is preferably 7-12.
如下实施例用于举例说明本发明的组合物,而不是限制或另外定义本发明的范围。The following examples serve to illustrate the compositions of the present invention without limiting or otherwise defining the scope of the invention.
在洗涤剂组合物中,酶的含量以总组合物重量计的纯酶表示,除非另有说明,洗涤剂组分按总组合物重量计表示。缩写的组分符号具有如下含义:LAS :直链C11-13烷基苯磺酸钠TAS :动物脂烷基硫酸钠CxyAS :C1x-C1y烷基硫酸钠CxySAS :C1x-C1y仲(2,3)烷基硫酸钠CxyEz :与平均z摩尔环氧乙烷缩合的C1x-C1y主要为直链的伯醇CxyEzS :与平均z摩尔环氧乙烷缩合的C1x-C1y烷基硫酸钠QAS :R2.N+(CH3)2(C2H4OH),R2=C12-C14QAS1 :R2.N+(CH3)2(C2H4OH),R2=C8-C11APA :C8-10酰氨基丙基二甲基胺皂 :由动物脂和椰子油脂肪酸的80/20混合物得到的直链烷In detergent compositions, enzyme levels are expressed as pure enzyme by weight of the total composition, and detergent components are expressed by weight of the total composition unless otherwise stated. The abbreviated component symbols have the following meanings: LAS: sodium linear C11-13 alkylbenzene sulfonate TAS: sodium tallow alkyl sulfate Cxy AS: C1x - C1y sodium alkylsulfate CxySAS : C1x -C 1y secondary (2,3) sodium alkyl sulfate C xy E z : C 1x -C 1y mainly linear primary alcohols condensed with an average z moles of ethylene oxide C xy E z S : with an average z moles Ethylene oxide condensed C 1x -C 1y sodium alkyl sulfate QAS: R 2 .N + (CH 3 ) 2 (C 2 H 4 OH), R 2 =C 12 -C 14 QAS1 : R 2 .N + (CH 3 ) 2 (C 2 H 4 OH), R 2 =C 8 -C 11 APA: C 8-10 Amidopropyldimethylamine Soap: Obtained from 80/20 mixture of tallow and coconut oil fatty acids straight chain alkanes
基羧酸钠Neodol 45-13:C14-C15直链伯醇乙氧基化物,由Shell Chemical CO销售APG :连接于由葡萄糖单元组成的亲水部分的C8-16脂肪醇基Sodium carboxylate Neodol 45-13: C14 - C15 linear primary alcohol ethoxylate, sold by Shell Chemical CO APG: C8-16 fatty alcohol group attached to a hydrophilic part consisting of glucose units
团的烷基多葡糖苷,聚合程度为1.1-3STS :甲苯磺酸钠CFAA :C12-C14烷基N-甲基葡糖酰胺TFAA :C16-C18烷基N-甲基葡糖酰胺TPKFA :C12-C14拔顶全馏分脂肪酸DEQA :二-(动物脂基-氧基-乙基)二甲基氯化铵DEQA(2) :二-(软-动物脂基氧基乙基)羟基乙基甲基甲基硫酸铵DTDMAMS :二动物脂基二甲基甲基硫酸铵SDASA :比率1∶2的硬脂基二甲基胺∶三压硬脂酸硅酸盐 :无定形硅酸钠(SiO2∶Na2O比率=1.6-3.2)沸石A :式Na12(AlO2SiO2)12.27H2O的水合硅铝酸钠,初级颗粒尺寸Group of alkyl polyglucosides, the degree of polymerization is 1.1-3STS: sodium toluenesulfonate CFAA: C 12 -C 14 alkyl N-methylglucamide TFAA: C 16 -C 18 alkyl N-methylglucose Amide TPKFA: C 12 -C 14 topped whole fraction fatty acid DEQA: Di-(tallow-oxy-ethyl)dimethylammonium chloride DEQA(2): Di-(soft-tallow-oxyethyl Base) Hydroxyethyl methyl ammonium methyl sulfate DTDMAMS: ditallow dimethyl ammonium methyl sulfate SDASA: ratio 1:2 stearyl dimethylamine: triple pressure stearic acid silicate: amorphous Sodium silicate (SiO 2 :Na 2 O ratio = 1.6-3.2) Zeolite A: hydrated sodium aluminosilicate of formula Na 12 (AlO 2 SiO 2 ) 12 .27H 2 O, primary particle size
为0.1-10微米(基于无水基准表示的重量)NaSKS-6 :式δ-Na2Si2O5的结晶层状硅酸盐柠檬酸盐 :柠檬酸三钠二水合物,活性86.4%,颗粒尺寸分布425-0.1-10 microns (weight expressed on anhydrous basis ) NaSKS-6: crystalline layered silicate of formula δ- Na2Si2O5 Citrate: trisodium citrate dihydrate, active 86.4%, Particle Size Distribution 425-
850微米柠檬酸 :无水柠檬酸硼酸盐 :硼酸钠碳酸盐 :无水碳酸钠,颗粒尺寸为200-900微米碳酸氢盐 :无水碳酸氢钠,颗粒尺寸分布为400-1200微米硫酸盐 :无水硫酸钠硫酸镁 :无水硫酸镁STPP :三聚磷酸钠TSPP :焦磷酸四钠MA/AA :4∶1丙烯酸盐/马来酸盐无规共聚物,平均分子量约850 micron citric acid : anhydrous citrate borate : sodium borate carbonate : anhydrous sodium carbonate, particle size 200-900 micron bicarbonate : anhydrous sodium bicarbonate, particle size distribution 400-1200 micron sulfuric acid Salt : Anhydrous Sodium Sulfate Magnesium Sulfate : Anhydrous Magnesium Sulfate STPP : Sodium Tripolyphosphate TSPP : Tetrasodium Pyrophosphate MA/AA : 4:1 Acrylate/Maleate Random Copolymer, Average Molecular Weight Approx.
70000-80000MA/AA1 :6∶4丙烯酸盐/马来酸盐无规共聚物,平均分子量约10000AA :平均分子量为4500的聚丙烯酸钠聚合物PB1 :无水过硼酸钠单水合物,标称式:NaBO2.H2O2PB4 :过硼酸钠四水合物,标称式:NaBO2.3H2O.H2O2过碳酸盐 :无水过碳酸钠,标称式:2Na2CO3.3H2O2NaDCC :二氯异氰脲酸钠TAED :四乙酰基乙二胺NOBS :壬酰氧基苯磺酸盐,钠盐形式NACA-OBS :(6-壬酰氨基己酰基)氧苯磺酸盐DTPA :二亚乙基三胺五乙酸HEDP :1,1-羟基乙烷二膦酸DETPMP :二乙基三胺五(亚甲基)膦酸盐,由孟山都以商品名70000-80000MA/AA1: 6:4 acrylate/maleate random copolymer, average molecular weight about 10000AA: sodium polyacrylate polymer with average molecular weight 4500 PB1: anhydrous sodium perborate monohydrate, nominal formula : NaBO 2 .H 2 O 2 PB4 : Sodium perborate tetrahydrate, nominal formula: NaBO 2 .3H 2 OH 2 O 2 percarbonate : Anhydrous sodium percarbonate, nominal formula: 2Na 2 CO 3 . 3H2O2NaDCC : Sodium Dichloroisocyanurate TAED: Tetraacetylethylenediamine NOBS: Nonanoyloxybenzenesulfonate, sodium salt form NACA-OBS: (6 - Nonanoylaminocaproyl)oxybenzene Sulfonate DTPA: Diethylenetriaminepentaacetic acid HEDP: 1,1-hydroxyethanediphosphonic acid DETPMP: Diethyltriaminepenta(methylene)phosphonate, sold by Monsanto under the trade name
Dequest 2060销售EDDS :乙二胺-N,N’-二琥珀酸,(S,S)异构体,钠盐形式光活化漂白剂 :用糊精可溶的聚合物包胶囊的磺化锌酞菁光活化漂白剂1:用糊精可溶的聚合物包胶囊的磺化铝酞菁蛋白酶 :以商品名Savinase,Alcalase,Durazym(Novo NordiskDequest 2060 sells EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer, sodium salt form Photoactivated Bleach : Sulfonated Zinc Phthalate Encapsulated with Dextrin-Soluble Polymer Cyanine Photoactivated Bleach 1: Sulfonated Aluminum Phthalocyanine Protease Encapsulated with Dextrin-Soluble Polymer: Trade Names Savinase, Alcalase, Durazym (Novo Nordisk
A/S),Maxacal,Maxapem(Gist-Brocades)出售的蛋白分A/S), Maxacal, Maxapem (Gist-Brocades) sold protein fractions
解酶和在专利WO91/06637和/或WO95/10591和/或Lyase and in patents WO91/06637 and/or WO95/10591 and/or
EP251446中描述的蛋白酶淀粉酶 :在WO94/18314,WO96/05295中描述的Genencor出售的Protease amylase described in EP251446: sold by Genencor described in WO94/18314, WO96/05295
Purafact Ox Am的淀粉分解酶;Termamyl、FungamylAmylolytic enzymes from Purafact Ox Am®; Termamyl®, Fungamyl®
和Duramyl,均由Novo Nordisk A/S得到和在and Duramyl®, both obtained from Novo Nordisk A/S and in
WO95/26397中描述的淀粉酶脂酶 :由Novo Nordisk A/S以商品名Lipolase、Lipolase UltraAmylase lipase described in WO95/26397 : sold under the trade names Lipolase, Lipolase Ultra by Novo Nordisk A/S
和由Gist-Brocades以Lipomax销售的脂解酶纤维素酶 :由Novo Nordisk A/S以Endolase销售的纤维素分解酶其它纤维素 :由Novo Nordisk A/S以商品名Carezyme销售的纤维素酶 分解酶CMC :羧甲基纤维素钠PVP :聚乙烯基聚合物,平均分子量为60000。PVNO :聚乙烯基吡啶-N-氧化物,平均分子量为50000。PVPVI :乙烯基咪唑和乙烯基吡咯烷酮共聚物,平均分子量为20000增白剂1 :4,4’-二(2-磺基苯乙烯基)联苯二钠增白剂2 :4,4’-二(4-苯胺基-6-吗啉代-1,3,5-三嗪-2-基)芪-and the lipolytic enzyme marketed as Lipomax by Gist-Brocades Cellulase: a cellulolytic enzyme marketed as Endolase by Novo Nordisk A/S Other Cellulase: a cellulase marketed under the trade name Carezyme by Novo Nordisk A/S Enzyme CMC : Sodium carboxymethyl cellulose PVP : Polyvinyl polymer with an average molecular weight of 60,000. PVNO : Polyvinylpyridine-N-oxide, with an average molecular weight of 50,000. PVPVI : Copolymer of vinylimidazole and vinylpyrrolidone, with an average molecular weight of 20,000 Brightener 1 : 4,4'-bis(2-sulfostyrene)biphenyl disodium Brightener 2 : 4,4'- Bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)stilbene-
2:2’-二磺酸二钠聚硅氧烷消 :含有硅氧烷-氧化烯共聚物作为分散剂的聚二甲基硅氧烷泡剂 泡沫控制剂,所述泡沫控制剂与所述分散剂的比率为2: 2'-disodium disulfonate polysiloxane disinfectant: polydimethylsiloxane foam agent containing siloxane-oxyalkylene copolymer as a dispersant foam control agent, the foam control agent and the The ratio of dispersant is
10∶1-100∶1。抑泡剂 :12%聚硅氧烷/二氧化硅,18%硬脂醇,70%淀粉,颗粒10:1-100:1. Foam suppressor: 12% polysiloxane/silicon dioxide, 18% stearyl alcohol, 70% starch, granules
形式遮光剂 :水基单苯乙烯胶乳混合物,由BASF AktiengesellschaftForm Sunscreen: Water-based monostyrene latex blend by BASF Aktiengesellschaft
以商品名Lytron621销售SRP1 :阴离子封端的聚酯SRP2 :二乙氧基化的聚(对苯二甲酸1,2-亚丙酯)短嵌段聚合物QEA :双((C2H5O)(C2H4O)n)(CH3)-N+-C6H12-N+-(CH3)双((C2H5O)- Marketed under the trade name Lytron 621 SRP1: anion-terminated polyester SRP2: diethoxylated poly(1,2-propylene terephthalate) short block polymer QEA: bis(( C2H5O ) (C 2 H 4 O) n )(CH 3 )-N + -C 6 H 12 -N + -(CH 3 )bis((C 2 H 5 O)-
(C2H4O))n,其中n=20-30PEI :聚乙烯亚胺,平均分子量1800,平均乙氧基化程度为每个(C 2 H 4 O)) n , where n=20-30PEI: Polyethyleneimine, average molecular weight 1800, average ethoxylation degree for each
氮7个乙烯氧基残基SCS :枯烯磺酸钠HMWPEO :高分子量聚环氧乙烷PEGx :聚乙二醇,分子量xPEO :聚环氧乙烷,平均分子量5000TEPAE :四亚乙基五胺乙氧基化物实施例1Nitrogen 7 ethyleneoxy residues SCS : Sodium cumene sulfonate HMWPEO : High molecular weight polyethylene oxide PEGx : Polyethylene glycol, molecular weight xPEO : Polyethylene oxide, average molecular weight 5000 TEPAE : Tetraethylene pentamine Ethoxylate Example 1
制备如下本发明的高密度洗衣洗涤剂组合物:A high density laundry detergent composition of the present invention was prepared as follows:
I II III IV V VILAS 8.0 8.0 8.0 2.0 6.0 6.0TAS - 0.5 - 0.5 1.0 0.1C46(S)AS 2.0 2.5 - - - -C25AS - - - 7.0 4.5 5.5C68AS 1.0 4.0 6.0 - - -C25E5 - - 3.4 8.0 3.6 3.6APG 1.0 1.0 1.0 2.0 1.0 1.0C25E7 3.4 3.4 1.0 - - -C25E3S - - - 2.0 5.0 4.5QAS - 0.8 - - - -QAS 1 - - - 0.8 0.5 1.0沸石A 18.1 18.0 14.1 18.1 20.0 18.1柠檬酸 - - - 2.5 - 2.5碳酸盐 13.0 13.0 27.0 10.0 10.0 13.0Na-SKS-6 - - - 10.0 - 10.0硅酸盐 1.4 1.4 3.0 0.3 0.5 0.3柠檬酸盐 - 1.0 - 3.0 - -硫酸盐 26.1 26.1 26.1 6.0 - -硫酸镁 0.3 - - 0.2 - 0.2MA/AA 0.3 0.3 0.3 4.0 1.0 1.0CMC 0.2 0.2 0.2 0.2 0.4 0.4PB4 9.0 9.0 5.0 - - -过碳酸盐 - - - - 18.0 18.0TAED 1.5 0.4 1.5 - 3.9 4.2NACA-OBS - 2.0 1.0 - - -DETPMP 0.25 0.25 0.25 0.25 - -SRP1 - - - 0.2 - 0.2EDDS - 0.25 0.4 - 0.5 0.5CFAA - 1.0 - 2.0 - -HEDP 0.3 0.3 0.3 0.3 0.4 0.4QEA - - - 0.2 - 0.5纤维素酶 0.005 0.008 0.01 0.05 0.003 0.0005蛋白酶 0.009 0.009 0.01 0.04 0.05 0.03淀粉酶 0.002 0.002 0.002 0.006 0.008 0.008其它纤维素酶 0.0007 - - 0.0007 0.0007 0.0007脂酶 0.006 - - 0.01 0.01 0.01光活化漂白剂 15 15 15 - 20 20(ppm)PVNO/PVPVI - - - 0.1 - -增白剂1 0.09 0.09 0.09 - 0.09 0.09香料 0.3 0.3 0.3 0.4 0.4 0.4聚硅氧烷消泡剂 0.5 0.5 0.5 - 0.3 0.3密度,g/l 850 850 850 850 850 850少量组分/微量组分 最多至II III IV V Vila 8.0 8.0 8.0 2.0 6.0 6.0TAS-0.5-0.5 1.0 0.1C46 (S) AS 2.5------7.0 4.5 5.5C68AS 1.0 6.0---3.4 8.0 3.66 3.6APG 1.0 1.0 1.0 2.0 1.0 1.0C25E7 3.4 3.4 1.0--C25E3S--2.0 5.0 4.5QAS-0.8--qas 1-0.8 0.5 1.0 Burrastone A 18.0 14.1 18.0 18.1 Citric acid---------- 2.5-2.5 carbonate 13.0 13.0 27.0 10.0 10.0 13.0NA-SKS-6--10.0-10.0 silicate 1.4 1.4 3.0 0.5 0.3 Citrate-1.0-3.0-Sulfate 26.1 26.1 6.0--sulfuric acid Magnesium 0.3-0.2-0.2mA/AA 0.3 0.3 0.3 4.0 1.0 1.0cmc 0.2 0.2 0.2 0.4 0.4 9.0 9.0 5.0---18.0 18.0TAed 1.5 0.4 1.5-3.9.2NACA-OBS -2.0 1.0--DetPMP 0.25 0.25 0.25 0.25 -SRP1-0.2 — 0.2edds-0.25 0.4-0.5 0.5CFAA-1.0-2.0 -Hedp 0.3 0.3 0.3 0.4QEA--0.2-0.5 fiberin Enzyme 0.005 0.008 0.01 0.05 0.003 0.0005 protease 0.009 0.009 0.01 0.04 0.05 0.03 amylase 0.002 0.002 0.006 0.008 0.008 Other cellulose enzyme 0.0007-0.0007 0.006-0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.0 (PPM) PVNO/PVPVI--0.1--0.09 0.09 0.09-0.09 0.09 spice 0.3 0.3 0.4 0.4 0.4 polysilicidal foam 0.5 0.5 0.3 0.3 density, G/L 850 850 850 850 850 850 Minor/trace components up to
100%实施例2100% Example 2
制备本发明尤其在欧洲洗衣机条件下使用的颗粒洗衣洗涤剂组合物:Preparation of granular laundry detergent compositions according to the invention for use especially under European washing machine conditions:
I II III IV V VIAPG 1.0 1.0 2.0 2.0 2.0 1.5LAS 5.5 7.5 5.0 5.0 6.0 7.0TAS 1.25 1.9 - 0.8 0.4 0.3C24AS/C25AS - 1.2 3.0 3.0 3.0 2.0C25E3S - 0.8 1.0 1.5 3.0 1.0C45E7 2.25 - - - - 3.0TFAA - - 2.0 - - -C25E5 - 5.5 - - - -QAS 0.8 - - - - -QAS 1 - 0.7 1.0 0.5 1.0 0.7STPP 19.7 - - - - -沸石A - 19.5 25.0 19.5 20.0 17.0Na-SKS-6/柠檬酸 - 10.6 - 10.6 - -(79∶21)Na-SKS-6 - - 9.0 - 10.0 10.0碳酸盐 6.1 21.4 9.0 10.0 10.0 18.0碳酸氢盐 - 2.0 7.0 5.0 - 2.0硅酸盐 6.8 - - 0.3 0.5 -柠檬酸盐 - - 4.0 4.0 - -硫酸盐 39.8 - - 5.0 - 12.0硫酸镁 - - 0.1 0.2 0.2 -MA/AA 0.5 1.6 3.0 4.0 1.0 1.0CMC 0.2 0.4 1.0 1.0 0.4 0.4PB4 5.0 12.7 - - - -过碳酸盐 - - - - 18.0 15.0TAED 0.5 3.1 - - 5.0 -NACA-OBS 1.0 3.5 - - - 2.5DETPMP 0.25 0.2 0.3 0.4 - 0.2HEDP - 0.3 - 0.3 0.3 0.3QEA - - 1.0 1.0 1.0 -纤维素酶 0.0008 0.005 0.006 0.003 0.0003 0.003蛋白酶 0.009 0.03 0.03 0.05 0.05 0.02脂酶 0.003 0.003 0.006 0.006 0.006 0.004其它纤维素酶 0.0006 0.0006 0.0005 0.0005 0.0007 0.0007淀粉酶 0.002 0.002 0.006 0.006 0.01 0.003PVNO/PVPVI - - 0.2 0.2 - -PVP 0.9 1.3 - - - 0.9SRP1 - - 0.2 0.2 0.2 -光活化漂白剂(ppm) 15 27 - - 20 20光活化漂白剂 15 - - - -(1)(ppm)增白剂1 0.08 0.2 - - 0.09 0.15增白剂2 - 0.04 - - - -香料 0.3 0.5 0.4 0.3 0.4 0.3聚硅氧烷消泡剂 0.5 2.4 0.3 0.5 0.3 2.0密度,g/l 750 750 750 750 750 750少量组分/微量组分 最多至I II III IV V VIAPG 1.0 1.0 2.0 2.0 2.0 1.5LAS 5.5 7.5 5.0 5.0 6.0 7.0TAS 1.25 1.9 - 0.8 0.4 0.3C24AS/C25AS - 1.2 3.0 3.0 3.0 2.0C25E3S - 0.8 1.0 1.5 3.0 1.0C45E7 2.25 - - - - 3.0TFAA -2.0--C25E5-5.5---qas 0.8----qas 1 — 0.7 1.0 0.0 0.7stpp 19.7----19.5 25.0 19.5 20.0na-SKS-6/Lemon Acid-10.6-10.6- (79: 21) NA-SKS-6-9.0-10.0 10.0 carbonate 6.1 21.4 9.0 10.0 10.0 18.0 hydrogen-2.0 7.0-2.0 silicate 6.8-0.3 0.5-- Citic acid-4.0 4.0--sulfate 39.8-5.0-12.0 magnesium sulfate-0.2 0.2 -ma/AA 0.5 1.6 3.0 4.0 1.0cmc 0.2 0.4 1.0 1.0 0.4pb4 5.0 12.7---over-carbon-over carbon passing carbon passing carbon passage Acid Salt 0.5 3.1-5.0 -NACA-OBS 1.0 3.5-2.5Detpmp 0.25 0.3 0.2Hedp-0.3 0.3 0.3QEA-1.0 1.0-cellulose enzyme enzyme 0.00.005 0.006 0.003 0.0003 0.003蛋白酶 0.009 0.03 0.03 0.05 0.05 0.02脂酶 0.003 0.003 0.006 0.006 0.006 0.004其它纤维素酶 0.0006 0.0006 0.0005 0.0005 0.0007 0.0007淀粉酶 0.002 0.002 0.006 0.006 0.01 0.003PVNO/PVPVI - - 0.2 0.2 - -PVP 0.9 1.3 - -0.9SRP1-0.2 0.2 0.2-Light activation bleach (PPM) 15 27-20 20 20 light activation bleach 15-- (1) (PPM) white agent 1 0.08 0.2-0.09 0.15 increase white white white white Dose 2-0.04---spice 0.3 0.5 0.4 0.3 0.4 0.3 Polyshiloxane removal agent 0.5 2.4 0.3 0.5 0.3 2.0 density, G/L 750 750 750 750 750 components/trace components up to the most up
100%实施例3100% Example 3
制备如下本发明的尤其用于欧洲洗衣机洗涤条件的洗涤剂组合物。Detergent compositions according to the invention, especially for use in European washing machine washing conditions, are prepared as follows.
I II III IV吹制粉末I I II II III III IV Blowing Powder
LAS 6.0 5.0 11.0 6.0LAS 6.0 5.0 11.0 6.0
TAS 2.0 - - 2.0TAS 2.0 - - - 2.0
沸石A 24.0 - - 20.0Zeolite A 24.0 - - - 20.0
STPP - 27.0 24.0 -STPP - - 27.0 - 24.0 -
硫酸盐 4.0 6.0 13.0 -Sulfates 4.0 6.0 13.0 -
MA/AA 1.0 4.0 6.0 2.0MA/AA 1.0 4.0 6.0 2.0
硅酸盐 1.0 7.0 3.0 3.0Silicate 1.0 7.0 3.0 3.0
CMC 1.0 1.0 0.5 0.6CMC 1.0 1.0 0.5 0.6
增白剂1 0.2 0.2 0.2 0.2Brightener 1 0.2 0.2 0.2 0.2
硅氧烷消泡剂 1.0 1.0 1.0 0.3 Silicone defoamer 1.0 1.0 1.0 0.3
DETPMP 0.4 0.4 0.2 0.4DETPMP 0.4 0.4 0.2 0.4
APG 1.6 1.5 1.0 1.0喷洒液体(SprayOn)APG 1.6 1.5 1.0 1.0 Spray On
增白剂 0.02 - - 0.02
C45E7 - - - 3.0C45E7 - - - - - 3.0
C45E2 2.5 2.5 2.0 -C45E2 2.5 2.5 2.0 -
APG 1.0 1.0 1.0 1.0APG 1.0 1.0 1.0 1.0
香料 0.5 0.3 0.5 0.2Spices 0.5 0.3 0.5 0.2
硅氧烷消泡剂 0.3 0.3 0.3 -干添加剂Silicone defoamer 0.3 0.3 0.3 - dry additive
QEA - - - 1.0QEA - - - - - 1.0
EDDS 0.3 - - -EDDS 0.3 - - -
硫酸盐 2.0 3.0 5.0 10.0Sulfate 2.0 3.0 5.0 10.0
碳酸盐 6.0 13.0 15.0 14.0Carbonate 6.0 13.0 15.0 14.0
柠檬酸 2.5 - - 2.0Citric Acid 2.5 - - - 2.0
QAS1 0.5 - - 0.5
Na-SKS-6 10.0 - - -Na-SKS-6 10.0 - - -
过碳酸盐 18.5 - - -
PB4 - 18.0 10.0 21.5PB4 - 18.0 10.0 21.5
TAED 2.0 2.0 - 2.0TAED 2.0 2.0 - 2.0
NACA-OBS 3.0 2.0 4.0 -NACA-OBS 3.0 2.0 4.0 -
纤维素酶 0.005 0.001 0.006 0.0004Cellulase 0.005 0.001 0.006 0.0004
蛋白酶 0.03 0.03 0.03 0.03Protease 0.03 0.03 0.03 0.03
脂酶 0.008 0.008 0.008 0.004Lipase 0.008 0.008 0.008 0.004
淀粉酶 0.003 0.003 0.003 0.006Amylase 0.003 0.003 0.003 0.006
增白剂1 0.05 - - 0.05Brightener 1 0.05 - - - 0.05
微量和少量组分 最多100%实施例4Trace and Minor Components Up to 100% Example 4
制备如下本发明的颗粒洗涤剂组合物:The granular detergent compositions of the present invention were prepared as follows:
I II III IV V VI吹制粉末I Blowing Powder II II III III IV V V VI Blowing Powder
APG 1.0 1.0 2.0 2.0 - -APG 1.0 1.0 2.0 2.0 - -
LAS 23.0 8.0 7.0 9.0 7.0 7.0LAS 23.0 8.0 7.0 9.0 7.0 7.0
TAS - - - - 1.0 -TAS - - - - - - 1.0 -
C45AS 5.0 5.0 4.0 6.0 - -C45AS 5.0 5.0 4.0 6.0 - -
C45AES - 1.0 1.0 1.0 - -C45AES - 1.0 1.0 1.0 -
C45E35 - - - - 2.0 4.0C45E35 - - - - - - 2.0 4.0
沸石A 10.0 18.0 14.0 12.0 10.0 10.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0
MA/AA - 0.5 - - - 2.0MA/AA - 0.5 - - - - 2.0
MA/AA1 7.0 - - - - -MA/AA1 7.0 - - - - - - - -
AA - 3.0 3.0 2.0 3.0 3.0AA - 3.0 3.0 2.0 3.0 3.0
硫酸盐 5.0 6.3 14.3 11.0 15.0 19.3Sulfate 5.0 6.3 14.3 11.0 15.0 19.3
硅酸盐 10.0 1.0 1.0 1.0 1.0 1.0Silicate 10.0 1.0 1.0 1.0 1.0 1.0
碳酸盐 15.0 20.0 10.0 20.7 8.0 6.0Carbonate 15.0 20.0 10.0 20.7 8.0 6.0
PEG4000 0.4 1.5 1.5 1.0 1.0 1.0PEG4000 0.4 1.5 1.5 1.0 1.0 1.0
DTPA - 0.9 0.5 - - 0.5DTPA - 0.9 0.5 - - 0.5
增白剂2 0.3 0.2 0.3 - 0.1 0.3喷洒液体Brightener 2 0.3 0.2 0.3 - 0.1 0.3 Spray liquid
C45E7 - 2.0 - - 1.0 1.0C45E7 - 2.0 - - - 1.0 1.0
C25E9 3.0 - - - - -C25E9 3.0 - - - - - - -
C23E9 - - 1.5 2 - 2.0C23E9 - - - 1.5 2 - 2.0
APG - - - - 1.0 1.0APG - - - - - - - 1.0 1.0
香料 0.3 0.3 0.3 2.0 0.3 0.3附聚物Fragrance 0.3 0.3 0.3 2.0 0.3 0.3 Agglomerates
C45AS - 5.0 5.0 2.0 - 5.0C45AS - 5.0 5.0 2.0 - 5.0
LAS - 2.0 2.0 - - 2.0LAS - 2.0 2.0 - - - 2.0
沸石A - 7.5 7.5 8.0 - 7.5Zeolite A - 7.5 7.5 8.0 - 7.5
碳酸盐 - 4.0 4.0 5.0 - 4.0Carbonate - 4.0 4.0 5.0 - 4.0
PEG4000 - 0.5 0.5 - - 0.5微量组分(水等) - 2.0 2.0 2.0 - 2.0干添加剂PEG4000 - 0.5 0.5 - - - 0.5 Minor components (water, etc.) - 2.0 2.0 2.0 - - 2.0 Dry additive
QAS - - - - 1.0 -QAS - - - - - - - 1.0 -
柠檬酸 - - - - 2.0 -Citric acid - - - - - - - 2.0 -
PB4 - - - - 12.0 1.0PB4 - - - - - - - 12.0 1.0
PB1 4.0 1.0 3.0 2.0 - -PB1 4.0 1.0 3.0 2.0 - -
过碳酸盐 - - - - 2.0 10.0Percarbonate - - - - - - 2.0 10.0
碳酸盐 - 5.3 1.8 - 4.0 4.0Carbonate - 5.3 1.8 - 4.0 4.0
NOBS 4.0 - 6.0 - - 0.6NOBS 4.0 - 6.0 - 0.6
甲基纤维素 0.2 - - - - -Methylcellulose 0.2 - - - - - - - -
Na-SKS-6 8.0 - - - - -Na-SKS-6 8.0 - - - - - - -
STS - - 2.0 - 1.0 -STS - - - 2.0 - 1.0 -
枯烯磺酸 - 1.0 - - - 2.0cumenesulfonic acid - 1.0 - - - - 2.0
纤维素酶 0.005 0.01 0.0004 0.0005 0.005 0.005Cellulase 0.005 0.01 0.0004 0.0005 0.005 0.005
蛋白酶 0.02 0.02 0.02 0.01 0.02 0.02Protease 0.02 0.02 0.02 0.01 0.02 0.02
脂酶 0.004 - 0.004 - 0.004 0.008Lipase 0.004 - 0.004 - 0.004 0.008
淀粉酶 0.003 - 0.002 - 0.003 -Amylase 0.003 - 0.002 - 0.003 -
其它纤维素酶0.0005 0.0005 0.0005 0.0007 0.0005 0.0005Other cellulase 0.0005 0.0005 0.0005 0.0007 0.0005 0.0005
PVPVI - - - - 0.5 0.1PVPVI - - - - - - - 0.5 0.1
PVP - - - - 0.5 -PVP - - - - - - - 0.5 -
PVNO - - 0.5 0.3 - -PVNO - - - 0.5 0.3 -
QEA - - - - 1.0 -QEA - - - - - - - 1.0 -
SRP1 0.2 0.5 0.3 - 0.2 -SRP1 0.2 0.5 0.3 - 0.2 -
硅氧烷消泡剂 0.2 0.4 0.2 0.4 0.1 -Silicone defoamer 0.2 0.4 0.2 0.4 0.1 -
硫酸镁 - - 0.2 - 0.2 -Magnesium Sulfate - - - 0.2 - - 0.2 -
微量和少量组 最多至Trace and Minor Groups Up to
分 100%实施例5Points 100% Example 5
制备如下本发明的特别用于洗涤带色衣服的不含有漂白剂的洗涤剂组合物:A bleach-free detergent composition according to the invention, especially for washing colored clothes, is prepared as follows:
I II IIII II II III
吹制粉末Blown Powder
沸石A 15.0 15.0 -Zeolite A 15.0 15.0 -
硫酸盐 - 5.0 -Sulphate - 5.0 -
LAS 3.0 3.0 -LAS 3.0 3.0 -
DETPMP 0.4 0.5 -DETPMP 0.4 0.5 -
CMC 0.4 0.4 -CMC 0.4 0.4 -
MA/AA 4.0 4.0 -MA/AA 4.0 4.0 -
附聚物Agglomerates
C45AS - - 11.0C45AS - - - - 11.0
LAS 6.0 5.0 -LAS 6.0 5.0 -
TAS 3.0 2.0 -TAS 3.0 2.0 -
硅酸盐 4.0 4.0 -Silicate 4.0 4.0 -
沸石A 10.0 15.0 13.0Zeolite A 10.0 15.0 13.0
CMC - - 0.5CMC - - - - 0.5
MA/AA - - 2.0MA/AA - - - - 2.0
碳酸盐 9.0 7.0 7.0Carbonate 9.0 7.0 7.0
APG 2.0 2.0 2.0APG 2.0 2.0 2.0
喷淋液体Spray liquid
香料 0.3 0.3 0.5Spices 0.3 0.3 0.5
C45E7 4.0 4.0 4.0C45E7 4.0 4.0 4.0
干添加剂 Dry Additives
MA/AA - - 3.0MA/AA - - - - 3.0
NaSKS-6 - - 12.0NaSKS-6 - - 12.0
柠檬酸盐 10.0 - 8.0Citrate 10.0 - 8.0
碳酸氢盐 7.0 3.0 5.0Bicarbonate 7.0 3.0 5.0
碳酸盐 8.0 5.0 7.0Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5PVPVI/PVNO 0.5 0.5 0.5
纤维素酶 0.005 0.005 0.003 Cellulase
蛋白酶 0.03 0.02 0.05Protease 0.03 0.02 0.05
脂酶 0.008 0.008 0.008Lipase 0.008 0.008 0.008
淀粉酶 0.01 0.01 0.01 Amylase
其它纤维素酶 0.001 0.001 0.001 Other cellulase
硅氧烷消泡剂 5.0 5.0 5.0 Silicone Defoamer
硫酸盐 - 9.0 -Sulfates - - 9.0 -
密度(g/l) 700 700 700Density (g/l) 700 700 700
少量组分和微量组分 最多至100%实施例6Minor and minor components up to 100% Example 6
制备如下本发明的洗涤剂组合物:The following detergent compositions according to the invention were prepared:
I II III IVI II II III III IV
基料颗粒Binder particles
沸石A 30.0 22.0 24.0 10.0Zeolite A 30.0 22.0 24.0 10.0
硫酸盐 10.0 5.0 10.0 7.0Sulfate 10.0 5.0 10.0 7.0
MA/AA 3.0 - - -MA/AA 3.0 - - -
AA - 1.6 2.0 -AA - - 1.6 - 2.0 -
MA/AA1 - 12.0 - 6.0MA/AA1 - 12.0 - 6.0
LAS 14.0 10.0 9.0 20.0LAS 14.0 10.0 9.0 20.0
C45AS 8.0 7.0 9.0 7.0C45AS 8.0 7.0 9.0 7.0
C45AES - 1.0 1.0 -C45AES - 1.0 1.0 -
硅酸盐 - 1.0 0.5 10.0Silicate - 1.0 0.5 10.0
皂 - 2.0 - -Soap - - 2.0 -
增白剂1 0.2 0.2 0.2 0.2Whitening agent 1 0.2 0.2 0.2 0.2
碳酸盐 6.0 9.0 10.0 10.0Carbonate 6.0 9.0 10.0 10.0
PEG4000 - 1.0 1.5 -
DTPA - 0.4 - -DTPA - 0.4 -
喷淋液体Spray liquid
C25E9 - - - 4.0C25E9 - - - - - 4.0
APG 1.0 1.0 1.0 1.0APG 1.0 1.0 1.0 1.0
C23E9 - 1.0 1.5 -C23E9 - 1.0 1.5 -
香料 0.2 0.3 0.3 -干添加剂Fragrances 0.2 0.3 0.3 - Dry Additives
碳酸盐 5.0 10.0 18.0 8.0Carbonate 5.0 10.0 18.0 8.0
PVPVI/PVNO 0.5 - 0.3 -PVPVI/PVNO 0.5 - 0.3 -
纤维素酶 0.0005 0.006 0.0008 0.002 Cellulase 0.0005 0.006 0.0008 0.002
蛋白酶 0.03 0.03 0.03 0.02Protease 0.03 0.03 0.03 0.02
脂酶 0.008 - - 0.008Lipase 0.008 - - - 0.008
淀粉酶 0.002 - - 0.002
其它纤维素酶 0.0002 0.0005 0.0005 0.0002 Other cellulase 0.0002 0.0005 0.0005 0.0002
NOBS - 4.0 - 4.5NOBS - 4.0 - 4.5
PB1 1.0 5.0 1.5 6.0PB1 1.0 5.0 1.5 6.0
硫酸盐 4.0 5.0 - 5.0Sulfates 4.0 5.0 - 5.0
SRP1 - 0.4 - -SRP1 - 0.4 -
抑泡剂 - 0.5 0.5 -
少量组分和微量组分 最多100%实施例7Minor components and trace components up to 100% Example 7
制备如下本发明的颗粒洗涤剂组合物:The granular detergent compositions of the present invention were prepared as follows:
I II IIII II II III III
吹制粉末blown powder
沸石A 20.0 - 15.0Zeolite A 20.0 - 15.0
STPP - 20.0 -
硫酸盐 - - 5.0Sulfates - - - 5.0
碳酸盐 - - 5.0Carbonate - - - - 5.0
TAS - - 1.0TAS - - - - 1.0
LAS 6.0 6.0 6.0LAS 6.0 6.0 6.0
C68AS 2.0 2.0 -C68AS 2.0 2.0 -
硅酸盐 3.0 8.0 -Silicate 3.0 8.0 -
MA/AA 4.0 2.0 2.0MA/AA 4.0 2.0 2.0
CMC 0.6 0.6 0.2CMC 0.6 0.6 0.2
增白剂1 0.2 0.2 0.1Whitening agent 1 0.2 0.2 0.1
DETPMP 0.4 0.4 0.1DETPMP 0.4 0.4 0.1
STS - - 1.0STS - - - - 1.0
喷洒液体Spray liquid
C45E7 4.0 4.0. 3.0C45E7 4.0 4.0. 3.0
APG 1.0 1.0 1.0APG 1.0 1.0 1.0
硅氧烷消泡剂 0.3 0.3 0.1
香料 0.2 0.2 0.3Spices 0.2 0.2 0.3
干添加剂DRY ADDITIVES
QEA - - 1.0QEA - - - - 1.0
碳酸盐 14.0 9.0 10.0Carbonate 14.0 9.0 10.0
PB1 1.5 2.0 -PB1 1.5 2.0 -
PB4 18.5 13.0 13.0PB4 18.5 13.0 13.0
TAED 2.0 2.0 2.0TAED 2.0 2.0 2.0
QAS - - 1.0- - - - - - - - - - - - - - - - - - - - - - - - - - - - - 1.0
光活化漂白剂 15ppm 15ppm 15ppm
Na-SKS-6 - - 3.0Na-SKS-6 - - - 3.0
纤维素酶 0.005 0.0006 0.003
蛋白酶 0.03 0.03 0.007Protease 0.03 0.03 0.007
脂酶 0.004 0.004 0.004
淀粉酶 0.006 0.006 0.003
其它纤维素酶 0.0002 0.0002 0.0005 Other cellulase 0.0002 0.0002 0.0005
硫酸盐 10.0 20.0 5.0Sulfate 10.0 20.0 5.0
密度(g/l) 700 700 700Density (g/l) 700 700 700
微量和少量组分 最多至100%实施例8Trace and Minor Components Up to 100% Example 8
制备本发明如下洗涤剂组合物:The following detergent compositions of the present invention were prepared:
I II IIII II II III
吹制粉末blown powder
沸石A 15.0 15.0 15.0Zeolite A 15.0 15.0 15.0
硫酸盐 - 5.0 -Sulfate - 5.0 -
LAS 3.0 3.0 3.0LAS 3.0 3.0 3.0
QAS - 1.5 1.5
DETPMP 0.4 0.2 0.4DETPMP 0.4 0.2 0.4
EDDS - 0.4 0.2EDDS - 0.4 0.2
CMC 0.4 0.4 0.4CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0附聚物MA/AA 4.0 2.0 2.0 Agglomerates
LAS 5.0 5.0 5.0LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0TAS 2.0 2.0 1.0
硅酸盐 3.0 3.0 4.0Silicate 3.0 3.0 4.0
沸石A 8.0 8.0 8.0Zeolite A 8.0 8.0 8.0
碳酸盐 8.0 8.0 4.0Carbonate 8.0 8.0 4.0
APG 1.1 1.0 1.0喷淋液体APG 1.1 1.0 1.0 spray liquid
香料 0.3 0.3 0.3Spices 0.3 0.3 0.3
C45E7 1.0 1.0 1.0C45E7 1.0 1.0 1.0
C25E3 2.0 - -干添加剂
柠檬酸盐 5.0 - 2.0Citrate 5.0 - 2.0
碳酸氢盐 - 3.0 -Bicarbonate - 3.0 -
碳酸盐 8.0 15.0 10.0Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0TAED 6.0 2.0 5.0
PB1 14.0 7.0 10.0PB1 14.0 7.0 10.0
PEO - - 0.2PEO - - - - 0.2
膨润土 - - 10.0Bentonite - - - - 10.0
纤维素酶 0.005 0.01 0.005
蛋白酶 0.03 0.03 0.03Protease 0.03 0.03 0.03
脂酶 0.008 0.008 0.008
其它纤维素酶 0.001 0.001 0.001 Other cellulase 0.001 0.001 0.001
淀粉酶 0.01 0.01 0.01
硅氧烷消泡剂 5.0 5.0 5.0
硫酸盐 - 30 -Sulfates - 30 -
密度(g/l) 850 850 850Density (g/l) 850 850 850
少量组分和微量组分 最多至100%实施例9Minor and minor components up to 100% Example 9
制备本发明的如下洗涤剂组合物:The following detergent compositions of the present invention were prepared:
I II III IVI I II II III III IV
LAS 18.0 14.0 24.0 20.0LAS 18.0 14.0 24.0 20.0
QAS 0.7 1.0 - 0.7QAS 0.7 1.0 - 0.7
TFAA - 1.0 - -TFAA - 1.0 -
C23E56.5 - 1.0 - -C23E56.5 - 1.0 - -
C45E7 - 1.0 - -C45E7 - 1.0 - -
C45E3S 1.0 2.5 1.0 -C45E3S 1.0 2.5 1.0 -
APG 2.0 2.0 2.0 2.0APG 2.0 2.0 2.0 2.0
STPP 30.0 16.0 28.0 20.0STPP 30.0 16.0 28.0 20.0
硅酸盐 9.0 5.0 9.0 8.0Silicate 9.0 5.0 9.0 8.0
碳酸盐 11.0 7.5 10.0 5.0Carbonate 11.0 7.5 10.0 5.0
碳酸氢盐 - 7.5 - -Bicarbonate - 7.5 - -
PB1 3.0 1.0 - -PB1 3.0 1.0 - -
PB4 - 1.0 - -PB4 - 1.0 - -
NOBS 2.0 1.0 - -NOBS 2.0 1.0 - -
DETPMP - 1.0 - -DETPMP - 1.0 - -
DTPA 0.5 - 0.2 0.3DTPA 0.5 - 0.2 0.3
SRP1 0.3 0.2 - 0.1SRP1 0.3 0.2 - 0.1
MA/AA 1.0 1.5 2.0 0.5MA/AA 1.0 1.5 2.0 0.5
CMC 0.8 0.4 0.4 0.2CMC 0.8 0.4 0.4 0.2
PEI - - 0.4 -PEI - - - - - 0.4 -
硫酸盐 20.0 10.0 20.0 30.0Sulphate 20.0 10.0 20.0 30.0
硫酸镁 0.2 - 0.4 0.9Magnesium Sulfate 0.2 - 0.4 0.9
纤维素酶 0.0005 0.008 0.008 0.005Cellulase 0.0005 0.008 0.008 0.005
蛋白酶 0.03 0.03 0.02 0.02Protease 0.03 0.03 0.02 0.02
淀粉酶 0.008 0.007 - 0.004Amylase 0.008 0.007 - 0.004
脂酶 0.004 - 0.002 -Lipase 0.004 - 0.002 -
其它纤维素酶 0.0003 - - 0.0001Other cellulases 0.0003 - - - 0.0001
光活化漂白剂 30ppm 20ppm - 10ppmPhotoactivated Bleach 30ppm 20ppm - 10ppm
香料 0.3 0.3 0.1 0.2Spice 0.3 0.3 0.1 0.2
增白剂1/2 0.05 0.02 0.08 0.1Brightener 1/2 0.05 0.02 0.08 0.1
微量和少量组分 最多至100%实施例10Trace and Minor Components Up to 100% Example 10
制备如下本发明的液体洗涤剂制剂(含量以重量份数给出,酶用纯酶表示):Prepare the following liquid detergent formulation of the present invention (content is given in parts by weight, and enzyme is expressed with pure enzyme):
I II III IV VLAS 11.5 7.8 - 3.9 -C25E2.5S - 3.0 17.0 - 15.0C45E2.25S 10.5 3.0 - 14.7 -C23E9 - 2.7 1.8 2.0 1.0C23E7 3.2 - - - -APG 1.0 1.0 1.2 1.0 1.0CFAA - - 5.2 - 3.1TPKFA 1.6 - 2.0 0.5 2.0柠檬酸(50%) 6.5 1.2 2.5 4.4 2.5甲酸钙 0.1 0.06 0.1 - -甲酸钠 0.5 0.06 0.1 0.05 0.05SCS 4.0 1.0 3.0 1.2 -硼酸盐 0.6 - 3.0 2.0 2.9氢氧化钠 5.8 2.0 3.5 3.7 2.7乙醇 1.75 1.0 3.6 4.2 2.91,2丙二醇 3.3 2.0 8.0 7.9 5.3单乙醇胺 3.0 1.5 1.3 2.5 0.8TEPAE 1.6 - 1.3 1.2 1.2纤维素酶 0.003 0.003 0.0008 0.0005 0.01蛋白酶 0.03 0.01 0.03 0.02 0.02脂酶 - - 0.002 - -淀粉酶 - - - 0.002 -其它纤维素酶 - - 0.0002 0.0005 0.0001SRP1 0.2 - 0.1 - -DTPA - - 0.3 - -PVNO - - 0.3 - 0.2增白剂1 0.2 0.07 0.1 - -聚硅氧烷消泡剂 0.04 0.02 0.1 0.1 0.1微量组分和水实施例11II III IV VLAS 11 7.8-3.9 -C25E2.5S-3.0 17.0-15.0C45E2.25S 10.5 3.0-14.7 -C23E9-2.7 1.8 1.0C23E7 3.2--APG 1.0 1.0CFAA-5.2-3.1 TPKFA 1.6-2.0 0.5 2.0 Citric acid (50 %) 6.5 1.2 2.5 4.4 2.5 Calcium Tyanate 0.1 0.06 0.1-0.5 0.06 0.05 0.05SCS 4.0 1.0 1.2-Borate 0.6-3.0 2.9 sodium hydroxide 5.8 2.0 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.7 2.7 Ethanol 1.75 1.0 3.6 4.2 2.91, 2 propylene glycol 3.3 2.0 8.0 7.9 5.3 Ethanol 3.0 1.5 1.3 2.5 0.8tepa 1.6-1.3 1.2 1.2 Corteease 0.003 0.0008 0.01 protease 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.0222 0.0222 0.02 0.02 0.0.0 0.03 0.02 0 0.01 0.01 0.03 0.01 0.03 0.03 0.03 0. 0.03 0.03-. Amylorase--0.002-Other cellulose enzyme-0.0002 0.0005 0.0001SRP1 0.2-0.1 -DTPA-0.3 -PVNO-0.3-0.2 whitening agent 1 0.2 0.07 0.1-polysiloxane foam agent 0.04 0.02 0.1 0.1 0.1 Minor components and water Example 11
制备如下本发明的液体洗涤剂制剂(含量以重量份数给出,酶用纯酶表示):Prepare the following liquid detergent formulation of the present invention (content is given in parts by weight, and enzyme is expressed with pure enzyme):
I II III IVI I II II III III IV
LAS 10.0 13.0 9.0 -LAS 10.0 13.0 9.0 -
C25AS 4.0 1.0 2.0 10.0C25AS 4.0 1.0 2.0 10.0
C25E3S 1.0 - - 3.0C25E3S 1.0 - 3.0
C25E7 5.0 7.0 11.0 1.5C25E7 5.0 7.0 11.0 1.5
APG 1.0 2.0 2.0 2.2APG 1.0 2.0 2.0 2.2
TFAA - - - 4.5TFAA - - - - - - 4.5
APA - 1.4 - -APA - 1.4 - -
TPKFA 2.0 - 13.0 7.0TPKFA 2.0 - 13.0 7.0
柠檬酸 2.0 3.0 1.0 1.5Citric acid 2.0 3.0 1.0 1.5
十二碳烯基/十 12.0 10.0 - -Dodecenyl/Ten 12.0 10.0 - -
碳烯基琥珀酸Carbenylsuccinic acid
菜子脂肪酸 4.0 2.0 1.0 -Rapeseed fatty acid 4.0 2.0 1.0 -
乙醇 4.0 4.0 7.0 2.0Ethanol 4.0 4.0 7.0 2.0
1,2丙二醇 4.0 4.0 2.0 7.01,2 Propylene Glycol 4.0 4.0 2.0 7.0
单乙醇胺 - - - 5.0Monoethanolamine - - - - - - 5.0
三乙醇胺 - - 8.0 -Triethanolamine - - - - 8.0 -
TEPAE 0.5 - 0.5 0.2TEPAE 0.5 - 0.5 0.2
DETPMP 1.0 1.0 0.5 1.0DETPMP 1.0 1.0 0.5 1.0
纤维素酶 0.005 0.005 0.01 0.006Cellulase 0.005 0.005 0.01 0.006
蛋白酶 0.02 0.02 0.01 0.008Protease 0.02 0.02 0.01 0.008
脂酶 - 0.002 - 0.002Lipase - 0.002 - 0.002
淀粉酶 0.004 0.004 0.01 0.008Amylase 0.004 0.004 0.01 0.008
其它纤维素酶 - - - 0.002Other cellulases - - - - - - 0.002
SRP2 0.3 - 0.3 0.1SRP2 0.3 - 0.3 0.1
硼酸 0.1 0.2 1.0 2.0Boric acid 0.1 0.2 1.0 2.0
氯化钙 - 0.02 - 0.01Calcium Chloride - 0.02 - 0.01
增白剂1 - 0.4 - -Brightener 1 - 0.4 -
抑泡剂 0.1 0.3 - 0.1Foam suppressant 0.1 0.3 - 0.1
遮光剂 0.5 0.4 - 0.3Sunscreen 0.5 0.4 - 0.3
氢氧化钠最多至 8.0 8.0 7.6 7.7Sodium hydroxide up to 8.0 8.0 7.6 7.7
pHpH
微量组分和水实施例12Minor Components and Water Example 12
制备如下本发明的液体洗涤剂组合物(含量以重量份数给出,酶用纯酶表示):Prepare the following liquid detergent composition of the present invention (content is given in parts by weight, and enzyme is expressed with pure enzyme):
I II III IVLAS 23.0 - - -C25AS - 11.0 16.0 13.0C25E3S - 2.0 2.0 4.0C25E7 - - 4.0 4.0APG 2.0 2.0 2.0 2.0TFAA - 6.0 8.0 8.0APA 3.0 1.0 2.0 -TPKFA - 15.0 11.0 11.0柠檬酸 1.0 1.0 1.0 1.0十二碳烯基/十四碳烯基琥珀酸 15.0 - - -菜子脂肪酸 1.0 - 3.5 -乙醇 7.0 2.0 3.0 2.01,2丙二醇 6.0 8.0 10.0 13.0单乙醇胺 - - 9.0 9.0 TEPAE - - 0.4 0.3DETPMP 2.0 1.2 1.0 -纤维素酶 0.008 0.005 0.005 0.01蛋白酶 0.08 0.02 0.01 0.02脂酶 - - 0.003 0.003淀粉酶 0.04 0.01 0.01 0.01其它纤维素酶 - - 0.004 0.003SRP2 - - 0.2 0.1硼酸 1.0 1.5 2.5 2.5膨润土 4.0 4.0 - -增白剂1 0.1 0.2 0.3 -抑泡剂 0.4 - - -遮光剂 0.8 0.7 - -氢氧化钠最多至pH 8.0 7.5 8.0 8.2微量组分和水实施例13I II III IVLAS 23.0 - - -C25AS - 11.0 16.0 13.0C25E3S - 2.0 2.0 4.0C25E7 - - 4.0 4.0APG 2.0 2.0 2.0 2.0TFAA - 6.0 8.0 8.0APA 3.0 1.0 2.0 -TPKFA - 15.0 11.0 11.0柠檬酸 1.0 1.0 1.0 1.0十Phantarine-based/fourth carbonine-based amber 15.0--cauliflower fatty acid 1.0-3.5-ethanol 7.0 2.0 3.01, 2 propena diol 6.0 8.0 10.0 13.0 single ethanlamine-9.0 TEPAE-0.4 0.3detPMP 2.0 1.0 1.0- Celloinase 0.008 0.005 0.005 0.01 protease 0.08 0.02 0.01 0.02 lipase-0.003 0.003 amylase 0.01 0.01 0.01 Other cellulose enzyme-0.003srp2-0.2 0.1 boric acid 1.5 2.5 2.5 Pensoil 4.0---increase white agent. 1 0.1 0.2 0.3-Foaming agent 0.4---Solite 0.8 0.7--sodium hydroxide up to PH 8.0 7.5 8.0 8.2 trace components and water implementation examples 13
制备如下本发明的液体洗涤剂组合物(含量以重量份数给出,酶用纯酶表示):Prepare the following liquid detergent composition of the present invention (content is given in parts by weight, and enzyme is expressed with pure enzyme):
I III II
LAS 27.6 17.9LAS 27.6 17.9
C45AS 11.8 4.9C45AS 11.8 4.9
C13E8 3.0 3.1C13E8 3.0 3.1
APG 1.9 2.0APG 1.9 2.0
油酸 3.4 2.5Oleic acid 3.4 2.5
柠檬酸 5.4 5.4Citric acid 5.4 5.4
氢氧化钠 0.4 3.6Sodium hydroxide 0.4 3.6
甲酸钙 0.2 0.1Calcium formate 0.2 0.1
甲酸钠 - 0.5Sodium formate - 0.5
乙醇 7.0 -Ethanol 7.0 7.0 -
单乙醇胺 16.5 8.0Monoethanolamine 16.5 8.0
1,2丙二醇 5.9 5.51,2 Propylene Glycol 5.9 5.5
二甲苯磺酸 - 2.4Xylenesulfonic acid - 2.4
TEPAE 1.5 0.8TEPAE 1.5 0.8
蛋白酶 0.05 0.02Protease 0.05 0.02
纤维素酶 0.005 0.005Cellulase 0.005 0.005
PEG - 0.7PEG - 0.7
增白剂2 0.4 0.1Brightener 2 0.4 0.1
香料 0.5 0.3Spices 0.5 0.3
微量组分和水实施例14Minor Components and Water Example 14
制备本发明的如下颗粒织物洗涤剂组合物,它具有“在洗涤过程中柔软”的能力:The following granular fabric detergent compositions according to the present invention are prepared which have the ability to "soften in the wash":
I III II
C45AS - 9.5C45AS - 9.5
LAS 7.1 -LAS 7.1 7.1 -
C68AS 1.3 -C68AS 1.3 1.3 -
C45E7 3.5 -C45E7 3.5 3.5 -
C25E3 - 4.5C25E3 - 4.5
APG 1.0 1.0APG 1.0 1.0
椰子油烷基二甲基羟基乙基氯 1.4 1.0Coconut Alkyl Dimethyl Hydroxyethyl Chloride 1.4 1.0
化铵ammonium chloride
柠檬酸盐 5.0 3.0Citrate 5.0 3.0
Na-SKS-6 - 11.0Na-SKS-6 - 11.0
沸石A 15.0 15.0Zeolite A 15.0 15.0
MA/AA 4.0 4.0MA/AA 4.0 4.0
DETPMP 0.4 0.4DETPMP 0.4 0.4
PB1 15.0 -PB1 15.0 15.0 -
过碳酸盐 - 15.0Percarbonate - 15.0
TAED 5.0 5.0TAED 5.0 5.0
绿土 10.0 10.0Green Soil 10.0 10.0
HMWPEO - 0.1HMWPEO - 0.1
纤维素酶 0.005 0.01Cellulase 0.005 0.01
蛋白酶 0.02 0.01Protease 0.02 0.01
脂酶 0.02 0.01Lipase 0.02 0.01
淀粉酶 0.03 0.005Amylase 0.03 0.005
其它纤维素酶 0.001 -Other cellulases 0.001 -
硅酸盐 3.0 5.0Silicate 3.0 5.0
碳酸盐 10.0 10.0Carbonate 10.0 10.0
抑泡剂 1.0 4.0Foam suppressant 1.0 4.0
CMC 0.2 0.1CMC 0.2 0.1
微量和少量组分 最多至100%实施例15Trace and Minor Components Up to 100% Example 15
制备如下本发明的在漂洗时加入的织物柔软剂组合物:A rinse-in fabric softener composition of the present invention was prepared as follows:
APG 0.5APG 0.5
DEQA(2) 20.0DEQA(2) 20.0
纤维素酶 0.005Cellulase 0.005
其它纤维素酶 0.001Other cellulase 0.001
盐酸 0.03Hydrochloric acid 0.03
消泡剂 0.01Defoamer 0.01
兰色染料 25ppmBlue dye 25ppm
氯化钙 0.20Calcium chloride 0.20
香料 0.90Spices 0.90
微量组分和水 最多至100%实施例16Minor components and water up to 100% Example 16
制备如下本发明的织物柔软剂和干燥器加入的织物调理剂组合物:Fabric softener and dryer added fabric conditioner compositions of the present invention were prepared as follows:
I II III IV VDEQA 2.6 19.0 - - -DEQA(2) - - - - 51.8DTMAMS - - - 26.0 -SDASA - - 70.0 42.0 40.2IV=0的硬脂酸 0.3 - - - -Neodol45-13 - - 13.0 - -盐酸 0.02 0.02 - - -乙醇 - - 1.0 - -糖酶香料 1.0 1.0 0.75 1.0 1.5Glycoperse S-20 - - - - 15.4甘油单硬脂酸酯 - - - 26.0 -琥珀二香叶酯 - - 0.38 - -聚硅氧烷消泡剂 0.01 0.01 - - -电解质 - 0.1 - - -纤维素酶 0.005 0.005 0.008 0.005 0.002APG 0.5 1.0 0.5 0.5 1.0粘土 - - - 3.0 -染料 10ppm 25ppm 0.01 - -水和少量组分 100% 100% - - -实施例17II III IV VDEQA 2.6 19.0--DEQA (2)---51.8dtmams--26.0 -SDASA-70.0 40.2IV = 0 stearic acid 0.3----Neodol45-13.0- 13.0- -On 0.02 0.02---ethanol-1.0 -lase spice 1.0 1.0 0.75 1.0 1.5glycoperse S-20--15.4 Glycerin single-to-26.0-Amber dicer ester-0.38-0.38- -Capyroscopic foaming agent 0.01 0.01--electrolyte-0.1--cellulose enzyme 0.005 0.008 0.005 0.002apg 0.5 1.0 0.5 0.5 1.0 clay--3.0-dye 10PPM 0.01-water and a small number of components 100% 100% - - - -Example 17
制备如下本发明的洗衣条洗涤剂组合物(含量以重量份数给出,酶以纯酶表示):Prepare the following laundry bar detergent composition of the present invention (content is given in parts by weight, and enzyme is represented by pure enzyme):
I II III IV V III VI VLAS - - 17.0 13.0 19.0 6.75 7.8 -C28AS 28.0 11.5 - - - 13.75 10.2 20.5月桂酸钠 2.5 9.0 - - - - - -APG 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0沸石A 2.0 1.25 - - - 1.25 1.25 1.25碳酸盐 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0碳酸钙 27.5 39.0 35.0 - - 40.0 - 40.0硫酸盐 5.0 5.0 3.0 5.0 3.0 - - 5.0TSPP 5.0 - - - - 5.0 2.5 -STPP 5.0 15.0 10.0 - - 7.0 8.0 10.0膨润土 - 10.0 - - 5.0 - - -DETPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7CMC - 1.0 1.0 1.0 1.0 - - 1.0滑石 - - 10.0 15.0 10.0 - - -硅酸盐 - - 4.0 5.0 3.0 - - -PVNO 0.02 0.03 - 0.01 - 0.02 - -MA/AA 0.4 1.0 - - 0.2 0.4 0.5 0.4SRP1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3纤维素酶 0.005 .0005 0.005 0.008 0.005 0.007 0.007 0.01淀粉酶 - - 0.01 - - - 0.002 -蛋白酶 - 0.004 - 0.003 0.003 - - 0.003脂酶 - 0.002 - 0.002 - - - -其它纤维素 - .0003 - - .0003 .0002 - -酶PEO - 0.2 - 0.2 0.3 - - 0.3香料 1.0 0.5 0.3 0.2 0.4 - - 0.4硫酸镁 - - 3.0 3.0 3.0 - - -增白剂 0.15 0.1 0.15 - - - - 0.1光活化漂白 - 15.0 15.0 15.0 15.0 - - 15.0剂(ppm)II III IV Vii Vi VLAS-17.0 13.0 19.0 6.75 7.8 -C28AS 28.0 11.5-13.75 10.2 20.5 May Cinnamin 2.5 9.0-----APG 2.0 2.0 2.0 2.0 2.0 2.0 1.25- -1.25 1.25 1.25 carbonate 20.0 3.0 13.0 8.0 15.0 15.0 10.0 calcium carbonate 27.5 35.0-40.0-40.0 Sulfate 5.0 5.0 3.0-5.0TSPP 5.0-5.0 -Stpp 5.0 10.0-0.0- -7.0 8.0 10.0 Policy-10.0-5.0--Detpmp-0.7 0.6 0.7 0.7 0.7cmc-1.0 1.0 1.0 1.0-1.0 talc- 10.0 15.0 10.0--4.0 5.0 3.0--------4.0 5.0 3.0-------- 4.0 5.0 3.0-- -PVNO 0.02 0.03 - 0.01 - 0.02 - -MA/AA 0.4 1.0 - - 0.2 0.4 0.5 0.4SRP1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3纤维素酶 0.005 .0005 0.005 0.008 0.005 0.007 0.007 0.01淀粉酶 - - 0.01 - - - 0.002-protease-0.004-0.003 0.003-0.003 lipase-0.002-0.002--other cellulose-.0003-.0003 .0002-enzyme PEO-0.2 0.3-0.3 spice 1.0 0.3 0.2 0.2 0.2 0.2 0.2 0.2 0.4-0.4 Magnesium sulfate-3.0 3.0 3.0--increase agent 0.15 0.15--0.1 Light activation bleach-15.0 15.0 15.0-15.0 doses (PPM) (PPM)
Claims (13)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97182370 CN1268164A (en) | 1997-07-11 | 1997-07-11 | Detergent compositions comprising a specific cellulase and alkyl poly glucoside surfactant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97182370 CN1268164A (en) | 1997-07-11 | 1997-07-11 | Detergent compositions comprising a specific cellulase and alkyl poly glucoside surfactant |
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| Publication Number | Publication Date |
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| CN1268164A true CN1268164A (en) | 2000-09-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113825829A (en) * | 2019-05-16 | 2021-12-21 | 联合利华知识产权控股有限公司 | laundry composition |
| US12371635B2 (en) | 2019-05-16 | 2025-07-29 | Conopco, Inc. | Laundry composition |
-
1997
- 1997-07-11 CN CN 97182370 patent/CN1268164A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113825829A (en) * | 2019-05-16 | 2021-12-21 | 联合利华知识产权控股有限公司 | laundry composition |
| US12371635B2 (en) | 2019-05-16 | 2025-07-29 | Conopco, Inc. | Laundry composition |
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