CN105107438A - 包含有益剂的高效胶囊 - Google Patents
包含有益剂的高效胶囊 Download PDFInfo
- Publication number
- CN105107438A CN105107438A CN201510546671.2A CN201510546671A CN105107438A CN 105107438 A CN105107438 A CN 105107438A CN 201510546671 A CN201510546671 A CN 201510546671A CN 105107438 A CN105107438 A CN 105107438A
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- Prior art keywords
- disperse blue
- encapsulation object
- blue
- slurries
- disperse
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- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
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- YKSGNOMLAIJTLT-UHFFFAOYSA-N violanthrone Chemical compound C12=C3C4=CC=C2C2=CC=CC=C2C(=O)C1=CC=C3C1=CC=C2C(=O)C3=CC=CC=C3C3=CC=C4C1=C32 YKSGNOMLAIJTLT-UHFFFAOYSA-N 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229940006486 zinc cation Drugs 0.000 description 1
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Abstract
本发明申请涉及高效颗粒和组合物如包含此类高效颗粒的消费品,以及制备和使用此类高效颗粒和包含此类高效颗粒的组合物的方法。此类高效颗粒和组合物向用此类高效颗粒和组合物处理的部位提供增强的有益剂递送。包封物包含芯和壁,所述壁具有外表面和涂层,并且包封所述芯,所述涂层包含定义的氨基聚合物。
Description
本申请是申请日为2010年11月4日、发明名称为“包含有益剂的高效胶囊”的中国专利申请No.201080049851.5的分案申请。
发明领域
本专利申请涉及高效包封物和组合物如包含此类高效包封物的消费品,以及制备和使用此类高效包封物和包含此类高效包封物的组合物的方法。
发明背景
诸如香料、硅氧烷、蜡、风味剂、维生素和织物软化剂的有益剂是昂贵的,和/或当以高含量用于消费品例如个人护理组合物、清洁组合物和织物护理组合物中时一般是低效的。因此,需要使这些有益剂的效力最大化。实现这种目的的一种方法是改善此类有益剂的递送效率。遗憾的是,很难改善有益剂的递送效率,因为这些试剂可能因试剂的物理或化学特性而损失,或者这些试剂可能与其它组合物组分或要处理的部位不相容。
改善有益剂递送效率的一种方法是包封此类有益剂。虽然该工作可改善有益剂的递送效率,但是仍需要进一步改善递送效率,因为包封有益剂可能在被施用到受关注的部位之前或之后,由于诸如机械或化学交互作用(例如洗涤液和/或漂洗液的作用)和/或电荷交互作用的因素而丧失。在一些应用中,通过用聚合物涂覆包封有益剂改善了包封有益剂的沉积。一般来讲,此类聚合物涂层改善了包封物的沉积。然而,当同时处理多个表面时,例如包含多种织物的一堆衣物,每个表面通常被处理至不同的程度(递送了或多或少的有益剂)。就有益剂为香料的情况而言,洗涤载荷中不同织物上的不同处理程度会造成一些织物上气味过强,而其它织物上气味过弱。申请人认识到,处理不均等问题的根源主要应归于由聚合物沉积助剂驱使的包封物优先沉积。因此,所需要的是在多种不同表面上具有高沉积特征和均匀沉积特征的包封有益剂。
在本专利申请中,申请人公开了包封有益剂和特定类别的含胺聚合物;当混合时,它们在多种不同表面上提供高沉积特征和均匀沉积特征,所述表面为例如毛发、皮肤和多种织物,如棉、高表面棉、涤棉布和聚酯。
发明概述
本专利申请涉及高效包封物和组合物如包含此类高效包封物的消费品,以及制备和使用此类高效包封物和包含此类高效包封物的组合物的方法。
发明详述
定义
如本文所用,“消费品”是指婴儿护理品、美容护理品、织物和家用护理品、家庭护理品、女性护理品、保健护理品、小吃和/或饮料产品或一般旨在以出售形式被使用或消费的装置。此类产品包括但不限于尿布、围兜、擦拭物;涉及处理毛发(人发、狗发和/或猫发)的产品和/或方法,包括漂白、着色、染色、调理、用洗发剂洗发、定型;除臭剂和止汗剂;个人清洁;化妆品;皮肤护理,包括霜膏、洗剂和其它用于消费者使用的局部施用产品,包括精细芳香剂;以及剃刮产品,涉及处理织物、硬质表面和织物区域内的任何其它表面的产品和/或方法,以及家庭护理,包括:空气护理(包括空气清新剂和香味递送体系)、汽车护理、盘碟洗涤、织物护理(包括软化和/或清新)、衣物洗涤去污、衣物洗涤和漂洗添加剂和/或护理、硬质表面清洁和/或处理(包括地板和抽水马桶清洁剂)、以及其它供消费者或机构使用的清洁;涉及卫生纸、面巾纸、手帕纸和/或纸巾的产品和/或方法;棉塞、妇女卫生巾;涉及口腔护理的产品和/或方法,包括牙膏、牙胶、漱口液、牙齿粘合剂、牙齿美白品;非处方保健品,包括咳漱和感冒治疗品、止痛剂、处方药剂、宠物健康和营养品;主要旨在用于习惯性膳食之间或作为膳食伴侣消费的加工食品(非限制性实例包括炸薯片、未经发酵的玉米片、爆米花、脆饼干、玉米片、谷类棒、蔬菜薄片或脆片、混合零食、混合聚会食品、杂粮薄片、薄脆零食、干酪零食、炸猪皮、玉米零食、丸状零食、挤压零食和百吉饼薄片);和咖啡。
如本文所用,术语“清洁和/或处理组合物”是消费品的子集,除非另外指明,其包括美容护理品、织物和家庭护理产品。此类产品包括但不限于处理毛发(人发、狗发和/或猫发)的产品,包括漂白、着色、染色、调理、用洗发剂洗发、定型;除臭剂和止汗剂;个人清洁;化妆品;皮肤护理,包括施用霜膏、洗剂和其它用于消费者使用的局部应用产品,包括精细芳香剂;以及剃刮产品,用于处理织物、硬质表面和织物区域内的任何其它表面的产品,以及家庭护理,包括:空气护理(包括空气清新剂和香味递送体系)、汽车护理、盘碟洗涤、织物护理(包括软化和/或清新)、衣物洗涤去污、衣物洗涤和漂洗添加剂和/或护理、硬质表面清洁和/或处理(包括地板和抽水马桶清洁剂)、颗粒状或粉末状多用途或“重垢型”洗涤剂,尤其是清洁洗涤剂;液体、凝胶或糊剂状的多功能洗涤剂,尤其是所谓的重垢型液体类型;液体精细织物洗涤剂;手洗盘碟洗涤剂或轻垢型盘碟洗涤剂,尤其是高起泡类型的那些;机洗盘碟洗涤剂,包括各种用于家庭和公共机构用途的片剂、颗粒、液体和辅助漂洗类型;液体清洁和消毒剂,包括抗菌手洗型、清洁条皂、漱口水、义齿清洁剂、洁齿剂、汽车或地毯洗涤剂、浴室清洁剂(包括抽水马桶清洁剂);毛发洗涤剂和毛发漂洗剂;沐浴凝胶、精细芳香剂和沐浴液及金属清洁剂;以及清洁辅剂,如漂白添加剂和“去污棒”或预处理类型,负载基质的产品如添加的干燥剂片、干燥和润湿的擦拭物和衬垫、非织造基底和海绵;以及均供消费者和/或机构使用的喷剂和薄雾;和/或涉及口腔护理的方法,包括牙膏、牙胶、漱口液、牙齿粘合剂、牙齿美白品。
如本文所用,术语“织物和/或硬质表面清洁和/或处理组合物”是清洁和处理组合物的子集,除非另外指明,其包括颗粒状或粉末状多用途或“重垢型”洗涤剂,尤其是清洁洗涤剂;液体、凝胶或糊剂状的多功能洗涤剂,尤其是所谓的重垢型液体类型;液体精细织物洗涤剂;手洗盘碟洗涤剂或轻垢型盘碟洗涤剂,尤其是高起泡类型的那些;机洗盘碟洗涤剂,包括各种用于家庭和公共机构用途的片剂、颗粒、液体和辅助漂洗类型;液体清洁和消毒剂,包括抗菌手洗类型、清洁条皂、汽车或地毯洗涤剂、浴室清洁剂(包括抽水马桶清洁剂);以及金属清洁剂、可为液体、固体和/或干燥剂片形式的织物调理产品(包括软化和/或清新);以及清洁助剂,如漂白添加剂和“去污棒”或预处理类型,负载基质的产品如添加的干燥剂片、干燥和润湿的擦拭物和衬垫、非织造基质和海绵;以及喷剂和薄雾。可施用的所有此类产品均可为标准形式、浓缩形式或甚至高浓缩形式。在某些方面中,此类产品甚至于可以是非水性的。
如本文所用,当用于权利要求中时,冠词如“一个”和“一种”被理解为是指一种或多种受权利要求书保护的或所述的物质。
如本文所用,术语“包括”和“包含”是非限制性的。
如本文所用,术语“固体”包括颗粒、粉末、棒状和片剂产品形式。
如本文所用,术语“流体”包括液体、凝胶、糊剂和气体产品形式。
如本文所用,术语“部位”包括纸制品、织物、衣服、硬质表面、毛发和皮肤。
除非另外指明,所有组分或组合物含量均是关于该组分或组合物的活性物质部分,不包括可能存在于这些组分或组合物的市售来源中的杂质,例如残余溶剂或副产物。
除非另外指明,所有百分比和比率均按重量计算。除非另外指明,所有百分比和比率均基于总组合物计算。
应当理解,在整个说明书中给出的每一最大数值限度均包括每一较低数值限度,就像这样的较低数值限度在本文中被明确地写出一样。在本说明书全文中给出的每一最小数值限度将包括每一较高数值限度,就像这样的较高数值限度在本文中被明确地写出一样。在本说明书全文中给出的每一数值范围将包括包含于该较宽数值范围内的每一较窄数值范围,就像这样的较窄数值范围在本文中被明确地写出一样。
高效包封物和包含其的浆液/附聚物
包封物可包含芯、涂层和具有外表面的壁,所述壁包封所述芯,所述涂层涂覆所述壁的外表面,所述涂层可包含一种或多种具有下式的功效聚合物:
其中:
a)其中a和b可为约50-100,000的整数或平均数(实数);
b)每个R1可独立地选自H、CH3、(C=O)H、亚烷基、具有不饱和C-C键的亚烷基、CH2-CROH、(C=O)-NH-R、(C=O)-(CH2)n-OH、(C=O)-R、(CH2)n-E、-(CH2-CH(C=O))n-XR、-(CH2)n-COOH、-(CH2)n-NH2、-CH2)n-(C=O)NH2,指数n可为约0至约24的整数,E可为亲电子基团;R可为饱和或不饱和的烷烃、二烷基甲硅烷氧基、二烷氧基、芳基、烷基化芳基,还可包含选自由下列组成的组的部分:氰基、OH、COOH、NH2、NHR、磺酸酯、硫酸酯、-NH2、季铵化胺、硫醇、醛、烷氧基、吡咯烷酮、吡啶、咪唑、卤化咪唑啉、胍、磷酸酯、单糖、低聚糖或多糖;
c)R2或R3可不存在或存在:
(i)当R3存在时,每个R2可独立地选自由下列组成的组:–NH2、-COO-、-(C=O)-、-O-、-S-、-NH-(C=O)-、-NR1-、二烷基甲硅烷氧基、二烷氧基、亚苯基、萘、亚烷基氧基;并且每个R3可独立地选自与R1相同的基团;
(ii)当R3不存在时,每个R2可独立地选自由下列组成的组:–NH2、-COO-、-(C=O)-、-O-、-S-、-NH-(C=O)-、-NR1-、二烷基甲硅烷氧基、二烷氧基、亚苯基、萘、亚烷基氧基;并且每个R3可独立地选自与R1相同的基团;并且
(iii)当R2不存在时,每个R3可独立地选自与R1相同的基团;
d)所述一种或多种功效聚合物具有约1,000Da至约50,000,000Da,约5,000Da,至约25,000,000Da,约10,000Da至约10,000,000Da,或甚至约340,000Da至约1,500,000Da的平均分子量;就聚乙烯基甲酰胺而言,具有约5%至约95%,约7%至约60%,或甚至约10%至约40%的水解度;和/或具有约1meq/g功效聚合物至约23meq/g功效聚合物,约1.2meq/g功效聚合物至16meq/g功效聚合物,约2meq/g功效聚合物至约10meq/g功效聚合物,或甚至约1meq/g功效聚合物至约4meq/g功效聚合物的电荷密度。
在所述包封物的一个方面,一种或多种功效聚合物选自由下列组成的组:聚乙烯基胺、聚乙烯基甲酰胺和聚烯丙基胺以及它们的共聚物,所述一种或多种功效聚合物可具有:
a)约1,000Da至约50,000,000Da,约5,000Da,至约25,000,000Da,约10,000Da至约10,000,000Da,或甚至约340,000Da至约1,500,000Da的平均分子量;
b)就所述聚乙烯基甲酰胺而言,约5%至约95%,约7%至约60%,或甚至约10%至约40%的水解度;和/或
c)约1meq/g功效聚合物至约23meq/g功效聚合物,约1.2meq/g功效聚合物至16meq/g功效聚合物,约2meq/g功效聚合物至约10meq/g功效聚合物,或甚至约1meq/g功效聚合物至约4meq/g功效聚合物的电荷密度。
在所述包封物的一个方面,所述涂层可包含一种或多种聚乙烯基甲酰胺,所述聚乙烯基甲酰胺可具有:
a)约1,000Da至约50,000,000Da,约5,000Da,至约25,000,000Da,约10,000Da至约10,000,000Da,或甚至约340,000Da至约1,500,000Da的平均分子量;
b)就所述聚乙烯基甲酰胺而言,约5%至约95%,约7%至约60%,或甚至约10%至约40%的水解度;和
c)约1meq/g功效聚合物至约23meq/g功效聚合物,约1.2meq/g功效聚合物至16meq/g功效聚合物,约2meq/g功效聚合物至约10meq/g功效聚合物,或甚至约1meq/g功效聚合物至约4meq/g功效聚合物的电荷密度。在上述方面中,功效聚合物与聚乙烯基甲酰胺同义。
在所述包封物的一个方面,所述包封物可具有约1:200至约1:2,约1:100至约1:4,或甚至约1:80至约1:10的涂层与壁的比率。
在所述包封物的一个方面中:
a)所述芯可包含选自由下列组成的组的材料:香料;增白剂;染料;驱虫剂;硅氧烷;蜡;风味剂;维生素;织物软化剂;护肤剂(在一个方面为石蜡);酶;抗菌剂;漂白剂;感觉剂;以及它们的混合物;
b)所述壁可包含选自由下列组成的组的材料:聚乙烯;聚酰胺;聚苯乙烯;聚异戊二烯;聚碳酸酯;聚酯;聚丙烯酸酯;氨基塑料(在一个方面,所述氨基塑料可包括聚脲、聚氨酯和/或聚脲聚氨酯,在一个方面所述聚脲可包括聚羟甲脲和/或三聚氰胺甲醛);聚烯烃;多糖(在一个方面为藻酸酯(盐)和/或脱乙酰壳多糖);明胶;紫胶;环氧树脂;乙烯基聚合物;水不溶性无机物;硅氧烷;以及它们的混合物。
在所述包封物的一个方面,所述芯可包含香料,并且所述壁可包含三聚氰胺甲醛和/或交联三聚氰胺甲醛。
在所述包封物的一个方面,所述芯可包含香料,并且所述壁可包含三聚氰胺甲醛和/或交联三聚氰胺甲醛、聚(丙烯酸)和聚(丙烯酸-共聚-丙烯酸丁酯)。
在所述包封物的一个方面,所述包封物可包含香料,所述香料可包含一种或多种香料原料,所述香料在重度污垢条件下以及在冷水中提供改善的香料性能。适宜的香料材料可见于美国公布的专利申请2008/0031961A1和2008/0994454A1中。此类香料原料的非限制性列表公开于下表1中。
表1:有用的香料原料
香料微胶囊可混合于香料微胶囊浆液中。
在本发明的上下文中,将香料微胶囊浆液定义为按所述浆液的重量计包含10%至50%香料微胶囊的水分散体。香料微胶囊浆液按所述香料微胶囊浆液的重量计可包含至少20%,更优选至少40%的包封香料成分。
本发明的香料微胶囊浆液可包含水溶性盐,其作为香料微胶囊浆液中的残余杂质存在。该残余杂质可来自香料微胶囊浆液中的购自不同供应商的其它成分。在一个方面,所述香料微胶囊浆液购自供应商。所述供应商可将附加水溶性盐加入到香料微胶囊浆液中以调节香料微胶囊浆液的流变特征和改善浆液在运输和长期贮藏期间的稳定性。
在本发明的上下文中,本文的水溶性盐是指由解离的带正电阳离子和带负电阴离子组成的水溶性离子化合物。在本发明的上下文中,“水溶性”可定义为环境温度和大气压下去除矿物质水中的溶解度。香料微胶囊浆液可包含1mmol/kg至750mmol/kg的水溶性盐。在另一个实施方案中,所述香料微胶囊浆液可包含10mmol/kg至750mmol/kg的水溶性盐。在另一个实施方案中,所述香料微胶囊浆液可包含1至265mmol/kg的水溶性盐。
在一个方面,存在于香料微胶囊浆液中的水溶性盐由多价阳离子与适宜的单原子或多原子阴离子形成,所述多价阳离子选自由下列组成的组:碱土金属、过渡金属或金属阳离子。在另一个实施方案中,所述水溶性盐包含阳离子,所述阳离子选自由下列组成的组:铍、镁、钙、锶、钡、钪、钛、铁、铜、铝、锌、锗、锡。在另一个实施方案中,所述水溶性盐包含阴离子,所述阴离子选自由下列组成的组:氟离子、氯离子、溴离子、碘离子、乙酸根、碳酸根、柠檬酸根、氢氧根、硝酸根、亚磷酸根、磷酸根和硫酸根。在一个实施方案中,所述阴离子为卤素单原子阴离子。
除了本文公开的包封物以外,还公开了可包含功效聚合物涂覆的包封物的浆液,其中所述浆液可具有约-10meV至约+50meV,优选约+2meV至约+40meV,更优选约+5meV至约+25meV,或约-40meV至约+35meV,优选约-38meV至约+25meV,更优选约-35meV至约+10meV的ζ电势。在一个方面,由于所述浆液可获得适宜含量的功效聚合物,因此为包封物一部分的功效聚合物和/或包含所述功效聚合物的包封物可通过使包含包封物的浆液与一种或多种功效聚合物混合而制得。
除了本文公开的包封物以外,还公开了浆液,所述浆液可包含足量的涂覆有功效聚合的包封物,以向所述浆液提供基于总浆液重量约0.05%至约10%,约0.1%至约5%,约0.125%至约2%的功效聚合物。
在一个方面,公开了浆液,所述浆液可包含基于总浆液重量约0.01%至约5%,约0.05%至约2%,或甚至约0.1%至约1%的聚乙烯基甲酰胺,约0%至约5%的MgCl2,约0.1至约3%的MgCl2,约0.2%至约2.5%的MgCl2,约0%至约1%的黄原胶,约0.05%至约0.5%,约0.1%至约0.25%的黄原胶,以及一种或多种涂覆或未涂覆的包封物。
在所述浆液的一个方面,所述聚乙烯基甲酰胺可具有:
a)约1,000Da至约50,000,000Da,约5,000Da,至约25,000,000Da,约10,000Da至约10,000,000Da,或甚至约340,000Da至约1,500,000Da的平均分子量;
b)就所述聚乙烯基甲酰胺而言,约5%至约95%,约7%至约60%,或甚至约10%至约40%的水解度;和
c)约1meq/g聚乙烯基甲酰胺至约23meq/g聚乙烯基甲酰胺,约1.2meq/g聚乙烯基甲酰胺,和16meq/g聚乙烯基甲酰胺,约2meq/g聚乙烯基甲酰胺至约10meq/g聚乙烯基甲酰胺,或甚至约1meq/g聚乙烯基甲酰胺至约4meq/g聚乙烯基甲酰胺的电荷密度。
在一个方面,公开了制备改良浆液的方法,所述方法包括以任何顺序混合包封物、功效聚合物以及任选的稳定体系和任选的生物杀灭剂。在一个方面,所述功效聚合物可包括聚乙烯基甲酰胺,所述稳定体系可包含MgCl2和黄原胶。
在制备改良浆液的所述方法的一个方面,在所述浆液用于产品中之前或用于制备附聚物之前,允许所述包封物与所述功效聚合物紧密接触至少15分钟,至少1小时,或甚至4小时。
在一个方面,可使用本文公开的任何包封物和/或浆液来制备附聚物。
在一个方面,公开了制备附聚物的方法,所述方法包括:
a)混合包封物和/或浆液、增塑剂(在一个方面,增塑剂包含水)和任选的粘合剂和/或螯合剂以形成混合物;
b)使所述混合物与所述隔离剂(在一个方面,隔离剂包含二氧化硅)混合以形成材料;以及
c)从所述材料中移除足量的所述增塑剂以获得产物,所述产物包含基于总产物重量1%至50%的增塑剂。
在一个方面,所述增塑剂包含水。
可转变成本文所公开的高效胶囊的适宜胶囊可根据申请人的教导制得,包括但不限于申请人的实施例、USPA2008/0305982A1和/或USPA2009/0247449A1中的教导。作为另外一种选择,适宜的胶囊可购自AppletonPapersInc.(Appleton,Wisconsin,USA)。
此外,制备上述包封物的材料可得自CPKelcoCorp.(SanDiego,California,USA);BASFAG(Ludwigshafen,Germany);RhodiaCorp.(Cranbury,NewJersey,USA);HerculesCorp.(Wilmington,Delaware,USA);AgriumInc.(Calgary,Alberta,Canada)、ISP(NewJersey,U.S.A.)、AkzoNobel(Chicago,IL,USA);StroeverShellacBremen(Bremen,Germany);DowChemicalCompany(Midland,MI,USA);BayerAG(Leverkusen,Germany);Sigma-AldrichCorp.(St.Louis,Missouri,USA)。
适宜的功效聚合物如聚乙烯酰胺-聚乙烯胺共聚物可通过选择性水解聚乙烯基甲酰胺起始聚合物制得。
适宜的功效聚合物还可通过乙烯基甲酰胺与丙烯酰胺、丙烯酸、丙烯腈、乙烯、丙烯酸钠、丙烯酸甲酯、马来酸酐、乙酸乙烯酯、N-乙烯基吡咯烷的共聚反应而形成。
适宜的功效聚合物或低聚物还可通过乙烯基甲酰胺与质子酸(如甲磺酸)和/或路易斯酸(如三氟化硼)的阳离子聚合反应而形成。
适宜的功效聚合物可得自BASFAG(Ludwigshafen,Germany),并且包括9010和9030。
制备具有涂层的包封物的方法
在一个方面,公开了制备涂覆的包封物的方法,所述方法包括混合包封物与一种或多种功效聚合物。
在一个方面,公开了制备涂覆的包封物的方法,其中当与一种或多种功效聚合物混合时,所述包封物包含于浆液中。
在一个方面,公开了制备涂覆的包封物的方法,其中使足量的功效聚合物与所述浆液混合,以使所述浆液具有基于总浆液重量约0.05%至约10%,约0.1%至约5%,或甚至约0.125%至约2%的所述功效聚合物。
用于制备上述涂覆的包封物的高效聚合物可为本说明书高效包封物与包含其的浆液/附聚物部分中所述的功效聚合物。
消费品
在一个方面,公开了消费品,所述消费品包含任何包封物、本文所公开的包含此类包封物的附聚物和/或浆液。
在所述消费品的一个方面,所述消费品可为清洁和/或处理组合物。
在所述消费品的一个方面,所述消费品可为衣物洗涤剂和/或织物软化剂。
在所述消费品的一个方面,所述消费品可为流体衣物洗涤剂。在一个方面,所述流体衣物洗涤剂可包含基于总流体衣物洗涤剂重量约3%至约80%,约3%至约70%,约5%至约60%,或甚至约8%至约50%的水。
在所述流体洗涤剂的一个方面,所述流体洗涤剂可为液体衣物洗涤剂。
在所述消费品的一个方面,所述消费品可为流体织物软化剂。在一个方面,所述流体织物软化剂可包含基于总流体织物软化剂重量约30%至约90%,约55%至约90%,约65%至约85%,或甚至约70%至约85%的水。
在所述流体织物软化剂的一个方面,所述流体织物软化剂可为液体织物软化剂。
在所述消费品的一个方面,所述消费品可为固体洗涤剂和辅助成分。
在所述消费品的一个方面,所述消费品可为流体美容护理产品,例如洗发剂。在一个方面,所述流体美容护理产品可包含基于总流体美容护理产品重量约30%至约95%,约55%至约90%,或甚至约65%至约85%的水。
在所述消费品的一个方面,所述消费品可为调理剂。
在一个方面,所述消费品可包含足量的浆液和/或包封物,以使所述消费品具有基于总消费品重量约0.0001%至约0.1%,约0.001%至约0.1%,或甚至约0.001%至约0.05%的功效聚合物含量。
在一个方面,所述消费品可包含选自由下列组成的组的材料:阴离子表面活性剂、阳离子表面活性剂、硅氧烷以及它们的混合物,所述消费品还可具有:
a)约100.000:1至约1:1,约25.000:1至约10:1,或甚至约10.000:1至约100:1的阴离子表面活性剂与功效聚合物的比率;
b)约100.000:1至约1:1,约25.000:1至约10:1,或甚至约10.000:1至约100:1的阳离子表面活性剂与功效聚合物的比率;和/或
c)约100.000:1至约1:1,约25.000:1至约10:1,或甚至约10.000:1至约100:1的硅氧烷与功效聚合物的比率。
在一个方面,本文公开的包封物适用于消费品、清洁和处理组合物、以及织物和硬质表面清洁和/或处理组合物、洗涤剂和高度致密的消费品中,包括高度致密的织物和硬质表面清洁和/或处理组合物,例如可为固体或流体的高度致密洗涤剂,所述包封物的含量基于总消费品重量为约0.001%至约20%,约0.01%至约10%,约0.05%至约5%,约0.1%至约2%。
在一个方面,公开了包含辅助成分的消费品,所述辅助成分选自由下列组成的组:聚合物,在一个方面为阳离子聚合物,表面活性剂,助洗剂,螯合剂,光学增白剂,染料转移抑制剂,分散剂,酶,酶稳定剂,催化材料,漂白活化剂,聚合物分散剂,粘土污垢移除/抗再沉积剂,增白剂,染料聚合物缀合物;染料粘土缀合物,抑泡剂,染料,漂白催化剂,附加香料和/或香料递送体系,结构增弹剂,织物软化剂,载体,水溶助长剂,加工助剂,流变改性剂,结构剂,增稠剂,颜料,水以及它们的混合物。
在一个方面,消费品包含辅助成分,所述辅助成分包含流变改性剂、增稠剂和/或结构剂,所述消费品在20sec-1的剪切速率和21℃下具有1至7000cps的高剪切粘度,并且具有大于1000cps,或甚至1000cps至200,000cps的低剪切粘度(在0.5sec-1的剪切速率和21℃下)。在一个方面,就清洁和处理组合物而言,此类流变改性剂在20sec-1和21℃下向含水液体组合物赋予50至3000cps的高剪切粘度,和大于1000cps,或甚至1000cps至200,000cps的低剪切粘度(在0.5sec-1的剪切速率和21℃下)。在一个方面,适宜的流变改性剂、增稠剂和/或结构剂可选自由下列组成的组:聚丙烯酸酯,季铵化聚丙烯酸酯,聚甲基丙烯酸酯,聚酰胺,季铵化聚甲基丙烯酸酯,聚羧酸酯,聚合物树胶如果胶,藻酸酯(盐),阿拉伯半乳聚糖(阿拉伯树胶),角叉菜胶,结冷胶,黄原胶和瓜耳胶,其它非树胶型多糖如结冷胶,以及这些聚合材料的组合,含羟基脂肪酸,脂肪酸酯或脂肪蜡,蓖麻油及其衍生物,氢化蓖麻油衍生物如氢化蓖麻油和氢化蓖麻蜡;以及它们的混合物。
在一个方面,公开了消费品,所述消费品为流体洗涤剂并且包含基于总流体洗涤剂重量小于约80%的水,小于约60%至约2%的水,约45%至约7%的水,约35%至约9%的水。
除了本文公开的包封物以外,某些香料递送体系也可用于上述组合物和/或消费品中。制备此类香料递送体系的方法和制备此类香料递送体系的方法公开于USPA2007/0275866A1中。此类香料递送体系包括:聚合物辅助递送(PAD)、分子辅助递送(MAD)、纤维辅助递送(FAD)、胺辅助递送(AAD)、环糊精递送体系(CD)、淀粉胶囊包封调和物(SEA)、无机载体递送体系(ZIC)、前香料(PP)。此类香料递送体系可用于任何类型的消费品、清洁和/或处理组合物、织物和硬质表面清洁和/或处理组合物、洗涤剂和高度致密洗涤剂的任何组合中。
香料微胶囊
将包封香料成分形式的香料加入到组合物中是有利的,因为香料成分包封能够使香料成分可控地并且均匀地定向释放。香料成分是用于制备香料组合物的单独化合物。香料组合物包含一种或多种香料成分,所述成分类型和数量的选择取决于所期望的最终香味。本发明可包含香料微胶囊。本领域的技术人员熟知的是,与只加入纯香料相比,香料微胶囊在织物处理期间以及穿着过程期间释放香料成分,从而在织物上提供改善的更持久的清新感。经由破坏胶囊壁并且使包封的香料成分扩散的机械应力,触发香料成分的释放。
香料微胶囊包含包围芯的胶囊,所述芯包含香料成分。胶囊可由许多材料制成,但是最优选交联三聚氰胺甲醛。胶囊壁材料可包含适宜的树脂,包括醛与胺的反应产物,适宜的醛包括甲醛。适宜的胺可包括选自由下列组成的组的那些:三聚氰胺、脲、苯胍胺、甘脲以及它们的混合物。适宜的三聚氰胺可包括选自由下列组成的组的那些:羟甲基三聚氰胺、甲基化羟甲基三聚氰胺、亚氨基三聚氰胺以及它们的混合物。适宜的脲可包括选自由下列组成的组的那些:二羟甲基脲、甲基化二羟甲基脲、脲-间苯二酚以及它们的混合物。
在本发明的上下文中,可使用任何适宜的香料成分。本领域的技术人员将识别出适用于香料微胶囊中的相容香料成分,并且将知道如何选择成分的组合来获得所期望的香味。
在一个方面,至少75%、85%或甚至90%的所述香料微胶囊可具有约1微米至约80微米,约5微米至60微米,约10微米至约50微米,或甚至约15微米至约40微米的粒度。
至少75%、85%或甚至90%的所述香料微胶囊可具有约60nm至约250nm,约80nm至约180nm,或甚至约100nm至约160nm的颗粒壁厚。
本发明的液体织物软化组合物按所述液体织物软化组合物的重量计包含0.05%至0.8%的以香料微胶囊形式存在的包封香料成分。该量是确保织物上沉积足量的香料所必需的。香料和香料微胶囊在衣物洗涤过程期间被洗去。因此,重要的是在液体织物软化组合物中具有足量的香料以在考虑到不可避免的损失的情况下,仍在织物上具有足量的沉积。
在一个方面,所述香料微胶囊可被喷雾干燥。
香料微胶囊浆液和附聚物
助剂材料
出于本发明的目的,下文所举例说明的助剂的非限制性列表适用于即用的组合物,并且可期望将其结合到本发明的某些实施方案中,以例如有助于或提高处理待清洁基底的性能,或在含香料、着色剂、染料等的情况下调节组合物的美观性。应当理解,此类助剂是在由申请人的包封物、附聚物和/或浆液所提供的组分之外的。这些附加组分的明确性质及其掺入量将取决于组合物的物理形式以及其所应用的操作的性质。适宜的辅助物质包括但不限于表面活性剂、助洗剂、螯合剂、染料转移抑制剂、分散剂、酶和酶稳定剂、接触催化材料、漂白活化剂、聚合分散剂、粘土污垢移除/抗再沉淀剂、增白剂、抑泡剂、染料、附加香料和香料递送体系、结构弹性剂、织物软化剂、载体、水溶助长剂、加工助剂和/或颜料。除了以下公开内容外,此类其它助剂和用量的合适的实例还存在于美国专利5,576,282、6,306,812B1和6,326,348B1中,所述文献以引用方式并入。
每种辅助成分不是申请人的组合物所必需的。因此,申请人的组合物的某些实施方案不包含一种或多种以下助剂材料:漂白活化剂、表面活性剂、助洗剂、螯合剂、染料转移抑制剂、分散剂、酶和酶稳定剂、催化金属配合物、聚合物分散剂、粘土和污垢移除/抗再沉淀剂、增白剂、抑泡剂、染料、附加的香料和香料递送体系、结构增弹剂、织物软化剂、载体、水溶助长剂、加工助剂和/或颜料。然而,当存在一种或多种助剂时,所述一种或多种助剂可如下详述存在:
表面活性剂-根据本发明所述的组合物可包含一种表面活性剂或表面活性剂体系,其中所述表面活性剂可选自非离子和/或阴离子和/或阳离子表面活性剂和/或两性的和/或两性离子的和/或半极性的非离子表面活性剂。所述表面活性剂的通常含量按所述清洁组合物的重量计为约0.1%,约1%,甚至约5%至约99.9%,至约80%,至约35%,甚至至约30%。
助洗剂-本发明的组合物可包含一种或多种洗涤剂助剂或助洗剂体系。当存在时,所述组合物将通常包含按重量计至少约1%的助洗剂,或约5%或10%至约80%,50%,甚至30%的所述助洗剂。助洗剂包括但不限于多磷酸的碱金属盐、铵盐和链烷醇铵盐,硅酸碱金属盐,碳酸碱土金属和碱金属盐,硅铝酸盐助洗剂,多羧酸盐化合物,醚羟基多羧酸盐,马来酸酐与乙烯或乙烯基甲基醚的共聚物,1,3,5-三羟基苯-2,4,6-三磺酸,和羧甲基苹果酸,多乙酸(如乙二胺四乙酸和氨三乙酸)以及多羧酸(如苯六甲酸、琥珀酸、氧联二琥珀酸、多元马来酸、1,3,5-三苯甲酸、羧甲基苹果酸)的各种碱金属盐、铵盐和取代的铵盐,以及它们的可溶性盐。
螯合剂-本文的组合物还可任选地包含一种或多种铜螯合剂、铁螯合剂和/或锰螯合剂。如果使用螯合剂,这些螯合剂的含量按本文所述组合物的重量计通常为约0.1%至约15%,甚至约3.0%至约15%。
染料转移抑制剂-本发明的组合物还可包含一种或多种染料转移抑制剂。合适的聚合物染料转移抑制剂包括但不限于:聚乙烯吡咯烷酮聚合物、聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、聚乙烯基唑烷酮和聚乙烯基咪唑或它们的混合物。当染料转移抑制剂存在于本发明的组合物中时,其含量按所述清洁组合物的重量计为约0.0001%,约0.01%,约0.05%至约10%,约2%,甚至约1%。
调色剂-荧光光学增白剂发射至少一部分可见光。与之相反,织物调色剂能改变表面颜色,因为它们吸收至少一部分可见光谱。适宜的织物调色剂包括染料、染料-粘土缀合物。适用的染料包括小分子染料和聚合物染料。适宜的小分子染料包括选自由下列组成的组的小分子染料:
(1)下式的三-偶氮直接蓝染料
其中A、B和C萘基环中的至少两个被磺酸根基团取代,C环可在位点5处被NH2或NHPh基团取代,X是由最多2个磺酸根基团取代的苄基或萘基环,其可在位点2处被OH基团取代,也可被NH2或NHPh基团取代。
(2)下式的双-偶氮直接紫染料:
其中Z是H或苯基,A环优选地被甲基和甲氧基基团在箭头所示位点取代,A环也可为萘基环,Y基团是苯基或萘基环,它被硫酸根基团取代,并且可被甲基一取代或甲基二取代。
(3)蓝色或红色酸性染料的化学式
其中X和Y中的至少其中一个必须是芳基。在一个方面,两个芳族基团均可为取代的苄基或萘基,它可被非水增溶的基团取代,例如烷基或烷氧基或芳氧基,X和Y不能被水增溶的基团取代,例如磺酸盐或羧酸盐。在另一方面,X是硝基取代的苄基,Y是苄基。
(4)以下结构的红色酸性染料
其中B是萘基或苄基基团,它可被非水增溶的基团取代,例如烷基或烷氧基或芳氧基,B不能被水增溶的基团取代,例如磺酸根或羧酸根。
(5)重氮基染料的结构
其中X和Y彼此独立,各自为氢、C1-C4烷基或C1-C4-烷氧基,Rα为氢或芳基,Z为C1-C4烷基;C1-C4-烷氧基;卤素;羟基或羧基,n为1或2,并且m为0、1或2,以及它们的相应的盐和它们的混合物
(6)以下结构的三苯甲烷染料
以及它们的混合物。在另一方面中,适宜的小分子染料包括下列小分子染料,此类染料中的一些选自由染料索引(SocietyofDyersandColourists,Bradford,UK)组成的组。1,4-萘二酮、1-[2-[2-[4-[[4-(乙酰氧基)丁基]乙基氨基]-2-甲基苯基]二氮烯基]-5-硝基-3-噻吩基]乙酮、1-羟基-2-(1-萘基偶氮)萘二磺酸离子(2-)、1-羟基-2-[[4-(苯基偶氮)苯基]偶氮]-萘二磺酸离子(2-)、2-[(1E)-[4-[二(3-甲氧基-3-氧丙基)氨基]-2-甲基苯基]偶氮]-5-硝基-3-噻吩甲酸乙酯、2-[[4-[(2-氰基乙基)乙基氨基]苯基]偶氮]-5-(苯基偶氮)-3-噻吩甲腈、2-[2-[4-[(2-氰基乙基)乙基氨基]苯基]二氮烯基]-5-[2-(4-硝基苯基)二氮烯基]-3-噻吩甲腈、2-羟基-1-(1-萘基偶氮)-萘二磺酸离子(2-)、2-羟基-1-[[4-(苯基偶氮)苯基]偶氮]-萘二磺酸离子(2-)、4,4'-[[4-(二甲基氨基)-2,5-环己二烯-1-亚基]亚甲基]二[N,N-二甲基苯胺]、6-羟基-5-[(4-甲氧基苯基)偶氮]-2-萘磺酸一钠盐、6-羟基-5-[(4-甲基苯基)偶氮]-2-萘磺酸一钠盐、7-羟基-8-[[4-(苯基偶氮)苯基]偶氮]-1,3-萘二磺酸离子(2-)、7-羟基-8-[2-(1-萘基)二氮烯基]-1,3-萘二磺酸离子(2-)、8-羟基-7-[2-(1-萘基)二氮烯基]-1,3-萘二磺酸离子(2-)、8-羟基-7-[2-[4-(2-苯基二氮烯基)苯基]二氮烯基]-1,3-萘二磺酸离子(2-)、酸性黑1、酸性黑24、酸性蓝113、酸性蓝15、酸性蓝17、酸性蓝25、酸性蓝29、酸性蓝3、酸性蓝40、酸性蓝45、酸性蓝62、酸性蓝7、酸性蓝75、酸性蓝80、酸性蓝83、酸性蓝9、酸性蓝90、酸性绿27、酸性橙12、酸性橙7、酸性红14、酸性红150、酸性红151、酸性红17、酸性红18、酸性红266、酸性红27、酸性红4、酸性红51、酸性红52、酸性红73、酸性红87、酸性红88、酸性红92、酸性红94、酸性红97、酸性紫15、酸性紫17、酸性紫24、酸性紫43、酸性紫49、碱性蓝159、碱性蓝16、碱性蓝22、碱性蓝3、碱性蓝47、碱性蓝66、碱性蓝75、碱性蓝9、碱性紫1、碱性紫2、碱性紫3、碱性紫4、碱性紫10、碱性紫35、C.I.酸性黑1、C.I.酸性蓝10、C.I.酸性蓝113、C.I.酸性蓝25、C.I.酸性蓝29、C.I.酸性蓝290、C.I.酸性红103、C.I.酸性红150、C.I.酸性红52、C.I.酸性红73、C.I.酸性红88、C.I.酸性红91、C.I.酸性紫17、C.I.酸性紫43、C.I.直接蓝1、C.I.直接蓝120、C.I.直接蓝34、C.I.直接蓝70、C.I.直接蓝71、C.I.直接蓝72、C.I.直接蓝82、C.I.直接紫51、C.I.分散蓝10、C.I.分散蓝100、C.I.分散蓝101、C.I.分散蓝102、C.I.分散蓝106:1、C.I.分散蓝11、C.I.分散蓝12、C.I.分散蓝121、C.I.分散蓝122、C.I.分散蓝124、C.I.分散蓝125、C.I.分散蓝128、C.I.分散蓝130、C.I.分散蓝133、C.I.分散蓝137、C.I.分散蓝138、C.I.分散蓝139、C.I.分散蓝142、C.I.分散蓝146、C.I.分散蓝148、C.I.分散蓝149、C.I.分散蓝165、C.I.分散蓝165:1、C.I.分散蓝165:2、C.I.分散蓝165:3、C.I.分散蓝171、C.I.分散蓝173、C.I.分散蓝174、C.I.分散蓝175、C.I.分散蓝177、C.I.分散蓝183、C.I.分散蓝187、C.I.分散蓝189、C.I.分散蓝193、C.I.分散蓝194、C.I.分散蓝200、C.I.分散蓝201、C.I.分散蓝202、C.I.分散蓝205、C.I.分散蓝206、C.I.分散蓝207、C.I.分散蓝209、C.I.分散蓝21、C.I.分散蓝210、C.I.分散蓝211、C.I.分散蓝212、C.I.分散蓝219、C.I.分散蓝220、C.I.分散蓝222、C.I.分散蓝224、C.I.分散蓝225、C.I.分散蓝248、C.I.分散蓝252、C.I.分散蓝253、C.I.分散蓝254、C.I.分散蓝255、C.I.分散蓝256、C.I.分散蓝257、C.I.分散蓝258、C.I.分散蓝259、C.I.分散蓝260、C.I.分散蓝264、C.I.分散蓝265、C.I.分散蓝266、C.I.分散蓝267、C.I.分散蓝268、C.I.分散蓝269、C.I.分散蓝270、C.I.分散蓝278、C.I.分散蓝279、C.I.分散蓝281、C.I.分散蓝283、C.I.分散蓝284、C.I.分散蓝285、C.I.分散蓝286、C.I.分散蓝287、C.I.分散蓝290、C.I.分散蓝291、C.I.分散蓝294、C.I.分散蓝295、C.I.分散蓝30、C.I.分散蓝301、C.I.分散蓝303、C.I.分散蓝304、C.I.分散蓝305、C.I.分散蓝313、C.I.分散蓝315、C.I.分散蓝316、C.I.分散蓝317、C.I.分散蓝321、C.I.分散蓝322、C.I.分散蓝324、C.I.分散蓝328、C.I.分散蓝33、C.I.分散蓝330、C.I.分散蓝333、C.I.分散蓝335、C.I.分散蓝336、C.I.分散蓝337、C.I.分散蓝338、C.I.分散蓝339、C.I.分散蓝340、C.I.分散蓝341、C.I.分散蓝342、C.I.分散蓝343、C.I.分散蓝344、C.I.分散蓝345、C.I.分散蓝346、C.I.分散蓝351、C.I.分散蓝352、C.I.分散蓝353、C.I.分散蓝355、C.I.分散蓝356、C.I.分散蓝357、C.I.分散蓝358、C.I.分散蓝36、C.I.分散蓝360、C.I.分散蓝366、C.I.分散蓝368、C.I.分散蓝369、C.I.分散蓝371、C.I.分散蓝373、C.I.分散蓝374、C.I.分散蓝375、C.I.分散蓝376、C.I.分散蓝378、C.I.分散蓝38、C.I.分散蓝42、C.I.分散蓝43、C.I.分散蓝44、C.I.分散蓝47、C.I.分散蓝79、C.I.分散蓝79:1、C.I.分散蓝79:2、C.I.分散蓝79:3、C.I.分散蓝82、C.I.分散蓝85、C.I.分散蓝88、C.I.分散蓝90、C.I.分散蓝94、C.I.分散蓝96、C.I.分散紫10、C.I.分散紫100、C.I.分散紫102、C.I.分散紫103、C.I.分散紫104、C.I.分散紫106、C.I.分散紫107、C.I.分散紫12、C.I.分散紫13、C.I.分散紫16、C.I.分散紫2、C.I.分散紫24、C.I.分散紫25、C.I.分散紫3、C.I.分散紫33、C.I.分散紫39、C.I.分散紫42、C.I.分散紫43、C.I.分散紫45、C.I.分散紫48、C.I.分散紫49、C.I.分散紫5、C.I.分散紫50、C.I.分散紫53、C.I.分散紫54、C.I.分散紫55、C.I.分散紫58、C.I.分散紫6、C.I.分散紫60、C.I.分散紫63、C.I.分散紫66、C.I.分散紫69、C.I.分散紫7、C.I.分散紫75、C.I.分散紫76、C.I.分散紫77、C.I.分散紫82、C.I.分散紫86、C.I.分散紫88、C.I.分散紫9、C.I.分散紫91、C.I.分散紫92、C.I.分散紫93、C.I.分散紫93:1、C.I.分散紫94、C.I.分散紫95、C.I.分散紫96、C.I.分散紫97、C.I.分散紫98、C.I.分散紫99、C.I.活性黑5、C.I.活性蓝19、C.I.活性蓝4、C.I.活性红2、C.I.溶剂蓝43、C.I.溶剂蓝43、C.I.溶剂红14、C.I.酸性黑24、C.I.酸性蓝113、C.I.酸性蓝29、C.I.直接紫7、C.I.食品红14、大爱尼克司紫CC、直接蓝1、直接蓝71、直接蓝75、直接蓝78、直接蓝80、直接蓝279、直接紫11、直接紫31、直接紫35、直接紫48、直接紫5、直接紫51、直接紫66、直接紫9、分散蓝106、分散蓝148、分散蓝165、分散蓝3、分散蓝354、分散蓝364、分散蓝367、分散蓝56、分散蓝77、分散蓝79、分散蓝79:1、分散红1、分散红15、分散紫26、分散紫27、分散紫28、分散紫63、分散紫77、EosinY、2,2'-[[4-[(3,5-二硝基-2-噻吩基)偶氮]苯基]亚胺基]双乙醇二乙酸酯(酯)、LumogenF蓝650、LumogenF紫570、N-[2-[2-(3-乙酰基-5-硝基-2-噻吩基)二氮烯基]-5-(二乙基氨基)苯基]乙酰胺、N-[2-[2-(4-氯-3-氰基-5-甲酰基-2-噻吩基)二氮烯基]-5-(二乙基氨基)苯基]乙酰胺、N-[5-[二(2-甲氧基乙基)氨基]-2-[2-(5-硝基-2,1-苯并异噻唑-3-基)二氮烯基]苯基]乙酰胺、N-[5-[二[2-(乙酰氧基)乙基]氨基]-2-[(2-溴-4,6-二硝基苯基)偶氮]苯基]乙酰胺、萘酰亚胺、衍生物、石油炭黑860、焰红染料B、吡唑、玫瑰红、6-羟基-5-(4-异丙基苯基偶氮)-2-萘磺酸钠、溶剂黑3、溶剂蓝14、溶剂蓝35、溶剂蓝58、溶剂蓝59、溶剂红24、溶剂紫13、溶剂紫8、苏丹红380、三苯甲烷和三苯甲烷、它们的衍生物和混合物。
其它适宜的调色剂包括但不限于下述噻吩和噻唑适宜的噻吩可由下列结构来表征:
其中R1和R2可独立地选自:
a)[(CH2CR'HO)x(CH2CR"HO)yH]
其中R’选自由下列组成的组:H、CH3、CH2O(CH2CH2O)zH、以及它们的混合物;其中R”选自由下列组成的组:H、CH2O(CH2CH2O)zH、以及它们的混合物;其中x+y≤5;其中y≥1;并且其中z=0-5
b)R1=烷基、芳基或芳烷基,并且R2=[(CH2CR'HO)x(CH2CR"HO)yH]其中R’选自由下列组成的组:H、CH3、CH2O(CH2CH2O)zH、以及它们的混合物;其中R”选自由下列组成的组:H、CH2O(CH2CH2O)zH、以及它们的混合物;其中x+y≤10;其中y≥1;并且其中z=0-5
c)R1=[CH2CH2(OR3)CH2OR4],并且R2=[CH2CH2(OR3)CH2OR4]其中R3选自由下列组成的组:H、(CH2CH2O)zH、以及它们的混合物;并且其中z=0-10;
其中R4选自由下列组成的组:(C1-C16)烷基、芳基以及它们的混合物;并且
d)其中R1和R2可独立地选自氧化苯乙烯、缩水甘油基甲基醚、异丁基缩水甘油基醚、异丙基缩水甘油基醚、叔丁基缩水甘油基醚、2-乙基己基缩水甘油基醚和缩水甘油基十六烷基醚的氨基加成产物,接着加成1-10个烯化氧单元。
在一个方面,此类噻吩可由下列结构来表征:
其中R’选自由下列组成的组:H、CH3、CH2O(CH2CH2O)zH、以及它们的混合物;其中R”选自由下列组成的组:H、CH2O(CH2CH2O)zH、以及它们的混合物;其中x+y≤5;其中y≥1;并且其中z=0-5
适宜的噻唑染料包括可具有下式(I)的偶氮染料:
其中:
R3和R4可相同或不同,并且彼此独立地为氢、饱和或不饱和的(C1-C22)烷基、被卤素原子取代的(C1-C22)烷基、任选被氧间杂的羟基-(C2-C22)烷基、衍生自环氧乙烷、环氧丙烷或环氧丁烷的聚醚基团、氨基-(C1-C22)烷基、取代或未取代的苯基或苄基、磺酸根、硫酸根或羧酸根封端的(C1-C22)烷基,或基团R3和R4与其余分子一起形成饱和或不饱和的、取代或未取代的杂环或碳环环系,所述环系任选被卤素、硫酸根、磺酸根、磷酸根、硝酸根和羧酸根取代;
X可为可具有下式II的苯酚系列基团或杂环基团或苯胺系列或间甲基苯胺系列;
其中:
R5和R6可相同或不同,并且彼此独立地为直链或支链的饱和或不饱和的(C1-C22)烷基、(C1-C22)烷基醚基团、任选被氧间杂的羟基-(C2-C22)烷基、衍生自环氧乙烷、环氧丙烷、环氧丁烷、缩水甘油基或它们组合的聚醚基团、氨基-(C1-C22)烷基、取代或未取代的苯基或苄基、以直链或支链(C1-C22)烷基、羟基、乙酸根、磺酸根、硫酸根或羧酸根封端的直链或支链(C1-C22)烷基,或R5和R6,或R5和R7,或R6和R7,与氮原子合在一起形成5元至6元环系,所述环系可包含另一个杂原子;或R5和R6,或R5和R7,或R6和R7,与苯环的碳原子合在一起形成任选包含氧或包含氮的五元或六元杂环,所述杂环可被一个或多个(C1-C22)烷基取代;
R7可相同或不同,彼此独立地为氢、卤原子、饱和或不饱和的(C1-C22)烷基、(C1-C22)烷基醚基团、羟基、羟基-(C1-C22)烷基、(C1-C22)烷氧基、氰基、硝基、氨基、(C1-C22)烷基氨基、(C1-C22)二烷基氨基、羧酸基团、C(O)O-(C1-C22)烷基、取代或未取代的C(O)O-苯基;
Q-可为平衡式I化合物总电荷的阴离子,并且指数q可为0或1。适宜的阴离子包括氯、溴、甲酯硫酸根、四氟硼酸根和乙酸根阴离子。
R1可为具有下式(III)的(C1-C22)烷基、烷基芳基或烷基磺酸根基团
其中
R2为氢、甲基、乙基、丙基或羟基;m和p为0至(n-1)的整数,n为1至6的整数,并且m+p=(n-1);
前提条件是式(I)杂环包含至少两个且最多三个杂原子,其中所述杂环含有最多一个硫原子;
在一个方面,适宜的噻唑染料可具有下式IV:
其中R8和R9可相同或不同,并且彼此独立地为饱和或不饱和的(C1-C22)烷基、(C1-C22)烷基、任选被氧间杂的羟基-(C2-C22)烷基、衍生自环氧乙烷、环氧丙烷或环氧丁烷的聚醚基团、氨基-(C1-C22)烷基、取代或未取代的苯基或苄基、以磺酸根、硫酸根或羧酸根封端的(C1-C22)烷基,或R8和R9与氮原子合在一起形成5元至6元环系,所述环系可包含另一个杂原子;或R8或R9可与苯环的碳原子合在一起形成任选包含氧或包含氮的五元或六元杂环,所述杂环可被一个或多个(C1-C22)烷基取代,以及它们的混合物,并且R10为氢或甲基。就式IV而言,Q-如上式I中所述。
在一个方面,适宜的噻唑染料可具有式(V);
其中:
a.)R1可选自支链或非支链的(C1-C22)烷基部分、芳族烷基部分、聚环氧烷部分或具有下式(VI)的部分;
其中
(i)R2可选自氢、甲基、乙基、丙基、乙酸根或羟基部分;m和p可独立地为0至(n-1)的整数,前提条件是n为1至6的整数,并且m+p=(n-1)
(ii)Y可选自羟基、磺酸根、硫酸根、羧酸根或乙酸根部分;
b.)R3和R4:
i.)可独立地选自氢;饱和或不饱和的(C1-C22)烷基部分;羟基-(C2-C22)烷基部分;除了羟基氧以外还包含氧原子的羟基-(C2-C22)烷基部分;聚醚部分;氨基-(C1-C22)烷基部分;取代或未取代的苯基部分;取代或未取代的苄基部分;以磺酸根、硫酸根、乙酸根或羧酸根封端的(C1-C22)烷基部分;或
ii.)当合在一起时可形成饱和或不饱和的杂环或碳环部分;或
iii.)当合在一起时可形成饱和或不饱和的杂环或碳环的部分,所述部分被硫酸根、磺酸根、磷酸根、硝酸根和羧酸根取代;
c.)X可为具有下式VII的部分;
其中:
i.)R5和R6:
(a)可独立地选自氢;饱和或不饱和的(C1-C22)烷基部分;羟基-(C2-C22)烷基部分;除了羟基氧以外还包含氧原子的羟基-(C2-C22)烷基部分;封端或未封端的聚醚部分;氨基-(C1-C22)烷基部分;取代或未取代的苯基部分;取代或未取代的苄基部分;包含封端的C1-C4烷基醚、磺酸根、硫酸根、乙酸根或羧酸根部分的(C1-C22)烷基部分;噻唑部分,或
(b)当合在一起时可形成饱和或不饱和的杂环部分;或
(c)当合在一起时形成饱和或不饱和的杂环部分,所述杂环部分被下列一种或多种取代:烷氧根、硫酸根、磺酸根、磷酸根、硝酸根和/或羧酸根部分;
(d)当与R7、R8、或R7和R8合在一起时,形成一个或多个饱和或不饱和的杂环部分,所述杂环部分任选被下列一种或多种取代:烷氧根、硫酸根、磺酸根、磷酸根、硝酸根和/或羧酸根部分;或
(e)当合在一起时形成噻唑部分;
ii.)R7和R8可独立地选自氢或饱和或不饱和的烷基部分;
d.)Q-可为平衡式I化合物总电荷的阴离子,并且指数q为0或1。适宜的阴离子包括氯、溴、甲酯硫酸根、四氟硼酸根和乙酸根阴离子。
在一个方面,就式V而言:
a.)R1可为甲基部分;
b.)R3和R4可为氢;并且
c.)X可具有下式VIII:
其中
(i)R5和R6可如上式VII所定义;
(ii)R7可为氢或甲基部分;并且
(iii)R8可为氢。
在一个方面,就式VII而言,R5和R6各自独立地包含1至20个亚烷基氧单元,和独立地选自由下列组成的组的部分:氧化苯乙烯、缩水甘油基甲基醚、异丁基缩水甘油基醚、异丙基缩水甘油基醚、叔丁基缩水甘油基醚、2-乙基己基缩水甘油基醚或缩水甘油基十六基醚。
合适的聚合物染料包括选自由下列组成的组的聚合物染料:包含共轭色原体(染料-聚合物缀合物)的聚合物、色原体共聚合进入聚合物主链的聚合物以及它们的混合物。
在另一方面,适宜的聚合物染料选自由下列组成的组:以商品名(Milliken,Spartanburg,SouthCarolina,USA)销售的织物-实体着色剂、由至少一种活性染料形成的染料-聚合物共轭物、以及选自由包含以下部分的聚合物组成的组的聚合物:羟基部分、伯胺部分、仲胺部分、硫醇部分以及它们的混合物。在另一方面,适宜的聚合物染料选自由下列组成的组:(Milliken,Spartanburg,SouthCarolina,USA)紫CT、与活性蓝、活性紫或活性红染料共轭的羟甲基纤维素(CMC)如与C.I.活性蓝19共轭的CMC(由Megazyme(Wicklow,Ireland)以产品名AZO-CM-CELLULOSE,产品代码S-ACMC销售)、以及它们的混合物。
适宜的染料粘土共轭物选自由下列组成的组:包含至少一种阳离子/碱性染料和绿土粘土以及它们的混合物。在另一方面,适宜的染料粘土缀合物选自由下列组成的组:一种阳离子/碱性染料,它选自由下列组成的组:C.I.碱性黄1至108、C.I.碱性橙1至69、C.I.碱性红1至118、C.I.碱性紫1至51、C.I.碱性蓝1至164、C.I.碱性绿1至14、C.I.碱性棕1至23、CI碱性黑1至11以及粘土,所述粘土选自由下列组成的组:蒙脱石粘土、锂蒙脱石粘土、皂石粘土以及它们的混合物。在另一方面,合适的染料粘土共轭物选自由下列组成的组:蒙脱石碱性蓝B7C.I.42595缀合物、蒙脱石碱性蓝B9C.I.52015缀合物、蒙脱石碱性紫V3C.I.42555缀合物、蒙脱石碱性绿G1C.I.42040缀合物、蒙脱石碱性红R1C.I.45160缀合物、蒙脱石C.I.碱性黑2缀合物、锂蒙脱石碱性蓝B7C.I.42595缀合物、锂蒙脱石碱性蓝B9C.I.52015缀合物、锂蒙脱石碱性紫V3C.I.42555缀合物、锂蒙脱石碱性绿G1C.I.42040缀合物、锂蒙脱石碱性红R1C.I.45160缀合物、锂蒙脱石C.I.碱性黑2缀合物、皂碱性蓝B7C.I.42595缀合物、皂碱性蓝B9C.I.52015缀合物、皂碱性紫V3C.I.42555缀合物、皂碱性绿G1C.I.42040缀合物、皂碱性红R1C.I.45160缀合物、皂石C.I.碱性黑2共轭物以及它们的混合物。
适宜的颜料包括选自由下列组成的组的颜料:黄烷士酮、蓝蒽酮、包含1至4个氯原子的氯化蓝蒽酮、皮蒽酮、二氯皮蒽酮、单溴二氯皮蒽酮、二溴二氯皮蒽酮、四溴皮蒽酮、二萘嵌苯-3,4,9,10-四羧酸二酰亚胺酯,其中所述酰亚胺基团可为未取代的或者被C1-C3烷基或苯基或杂环基取代,并且其中苯基和杂环基可另外带有不提供水中溶解度的取代基、吡唑嘧啶羧酸酰胺、蒽酮紫、异蒽酮紫、二嗪颜料、每个分子可包含最多2个氯原子的铜酞菁、多氯铜酞菁或每个分子包含最多14个溴原子的多溴铜酞菁以及它们的混合物。
在另一方面,适宜的颜料选自由下列组成的组:群青蓝(C.I.颜料蓝29)、群青紫(C.I.颜料紫15)、以及它们的混合物。
可以组合使用上述织物调色剂(可使用织物调色剂的任何混合物)。合适的织物调色剂可得自Aldrich,Milwaukee,Wisconsin,USA;CibaSpecialtyChemicals,Basel,Switzerland;BASF,Ludwigshafen,Germany;DaygloColorCorporation,Mumbai,India;OrganicDyestuffsCorp.,EastProvidence,RhodeIsland,USA;Dystar,Frankfurt,Germany;Lanxess,Leverkusen,Germany;Megazyme,Wicklow,Ireland;Clariant,Muttenz,Switzerland;Avecia,Manchester,UK和/或根据本文包含的实例制成。
分散剂-本发明的组合物还可包含分散剂。合适的水溶性有机物是均聚或共聚酸或其盐,其中多元羧酸可包含至少两个彼此相隔不超过两个碳原子的羧基。
酶-组合物可包含一种或多种洗涤剂酶,该酶提供清洁性能和/或织物护理有益效果。合适酶的实施例包括但不限于:半纤维素酶,过氧化物酶、蛋白酶、纤维素酶、木聚糖酶、脂肪酶、磷脂酶、酯酶、角质酶、果胶酶、角质素酶、还原酶、氧化酶、酚氧化酶、脂氧合酶、木素酶、支链淀粉酶、鞣酸酶、戊聚糖酶、麦拉宁酶(melanase)、β-葡聚糖酶、阿拉伯糖酶、透明质酸酶、软骨素酶、漆酶和淀粉酶或它们的混合物。典型的组合是常规可用酶如蛋白酶、脂肪酶、角质酶和/或与淀粉酶结合的纤维素酶的组合。
酶稳定剂-对于用于组合物中的酶,例如洗涤剂可用多种技术来稳定。本发明使用的酶可由最终组合物中存在的钙和/或镁离子水溶性源来稳定,最终组合物将这种离子提供给酶。
催化金属配合物–申请人的组合物可包含催化金属配合物。一类含金属的漂白催化剂是这样的催化剂体系,该体系包含具有确定漂白催化活性的过渡金属阳离子,如铜阳离子、铁阳离子、钛阳离子、钌阳离子、钨阳离子、钼阳离子或锰阳离子;包含具有很低的或者没有漂白催化活性的辅助金属阳离子,如锌阳离子或铝阳离子;以及包含对于催化的和辅助的金属阳离子有确定稳定性常数的螯合剂,尤其是乙二胺四乙酸、乙二胺四(亚甲基膦酸)以及它们的水溶性盐。此类催化剂公开于美国专利4,430,243中。
如果需要,本发明组合物可借助锰化合物进行催化。这些化合物和用量是本领域熟知的,并且包括例如公开于美国专利5,576,282中的锰基催化剂。
可用于本发明的钴漂白催化剂是已知的,并且描述于例如美国专利5,597,936和5,595,967中。此类钴催化剂易于通过已知的方法制备,例如美国专利5,597,936和5,595,967中所提出的方法。
本发明的组合物还可适宜地包含大多环刚性配体(简写为“MRL”)的过渡金属配合物。作为实施项,而不是作为限制,可调节本发明的组合物和清洁方法,使得在含水洗涤介质中提供大约至少一亿分之一的有益剂MRL物质,并且在洗涤液体中可提供约0.005ppm至约25ppm,约0.05ppm至约10ppm,甚至约0.1ppm至约5ppm的MRL
即用的过渡金属漂白催化剂中的适宜过渡金属包括锰、铁和铬。本文适宜的MRL是特殊类型的交联超刚性配体,诸如5,12-二乙基-1,5,8,12-四氮杂双环[6.6.2]十六烷。
通过已知步骤易于制备适宜的过渡金属MRL,例如在WO00/32601和美国专利6,225,464中所提出的。
流变改性剂
本发明的液体组合物可包含流变改性剂。流变改性剂可选自由下列组成的组:非聚合的晶状羟基功能性材料、向所述组合物含水液体基质赋予剪切致稀特征的聚合物流变改性剂。在一个方面,此类流变改性剂在20sec-1的剪切速率和21℃下向含水液体组合物赋予1至7000cps的高剪切粘度,和大于1000cps,或甚至1000cps至200,000cps的低剪切粘度(在0.5sec-1的剪切速率和21℃下)。在一个方面,就清洁和处理组合物而言,此类流变改性剂在20sec-1和21℃下向含水液体组合物赋予50至3000cps的高剪切粘度,和大于1000cps,或甚至1000cps至200,000cps的低剪切粘度(在0.5sec-1的剪切速率和21℃下)。使用得自TAinstruments的AR2000流变仪,采用具有40mm板径和500μm间隙尺寸的钢板锭子,测定如本发明所述的粘度。在20sec-1的高剪切粘度和在0.5sec-1的低剪切粘度可通过在21℃下3分钟时间内由0.1sec-1至25sec-1的对数剪切速率扫描获得。晶状羟基功能性材料在基质中就地结晶时,在整个组合物基质中形成类丝状结构体系的流变改性剂。聚合的流变改性剂优选地选自聚丙烯酸酯、聚合树胶、其它非树胶多糖以及这些聚合材料的组合。
一般来讲,流变改性剂的含量按本文的组合物的重量计为0.01%至1%,优选0.05%至0.75%,更优选0.1%至0.5%。
尤其可用于本发明组合物中的结构化试剂可包括非聚合的(除了常规的烷氧基化以外)晶状羟基功能性材料;当所述材料在基质中就地结晶时,它们可在整个液体基质中形成类丝状结构化体系。这些物质通常可表征为结晶的含羟基脂肪酸、脂肪酸酯或脂肪蜡。在一个方面,流变改性剂包括包含羟基的晶状流变改性剂,包括蓖麻油及其衍生物。在一个方面,流变改性剂包括氢化蓖麻油衍生物如氢化蓖麻油和氢化蓖麻蜡。可商购获得的基于蓖麻油的含羟基晶状流变改性剂包括得自Rheox,Inc.(现为Elementis)的THIXCINTM。
除了上述非聚合的含羟基晶状流变改性剂以外,其它类型的流变改性剂也可用于本文液体洗涤剂组合物中。还可使用向含水液体基质提供剪切致稀特征的聚合材料。
合适的聚合流变改性剂包括聚丙烯酸酯、多糖或多糖衍生物类的那些。通常用作流变改性剂的多糖衍生物包括聚合树胶物质。这些树胶包括果胶、藻酸盐、阿拉伯半乳糖(阿拉伯树胶)、角叉菜胶、结冷胶、黄原胶和瓜耳胶。
如果本文使用聚合流变改性剂,优选的这类物质是结冷胶。结冷胶为杂多糖,通过伊乐假单胞菌ATCC31461发酵制得。结冷胶由CPKelcoU.S.,Inc.以商品名KELCOGEL市售。
另一个供选择的和适宜的流变改性剂包括溶剂与聚羧酸酯聚合物的组合。更具体地讲,所述溶剂可为烷撑二醇。在一个方面,所述溶剂可包括双丙二醇。在一个方面,所述聚羧酸酯聚合物可包括聚丙烯酸酯、聚甲基丙烯酸酯或它们的混合物。在一个方面,溶剂基于总组合物重量可以所述组合物的0.5%至15%,或2%至9%的含量存在。在一个方面,聚羧酸酯聚合物基于总组合物重量可以0.1%至10%,或2%至5%的含量存在。在一个方面,溶剂组分可包括双丙二醇与1,2-丙二醇的混合物。在一个方面,双丙二醇与1,2-丙二醇的比率可为3:1至1:3,或甚至1:1。在一个方面,聚丙烯酸酯可包括不饱和一元或二元酸与(甲基)丙烯酸C1-C30烷基酯的共聚物。在另一方面中,所述流变改性剂可包含不饱和一元或二元酸的聚丙烯酸酯和(甲基)丙烯酸的C1-C30烷基酯。此类共聚物以商品名CarbopolAqua得自NoveonInc。
在不存在流变改性剂并且为了向液体组合物赋予所期望的剪切致稀特征的情况下,液体组合物可通过表面活性剂相化学或凝胶相进行内部结构化。
硅氧烷乳剂
本发明的组合物可包含硅氧烷乳剂。乳液是一种液体(分散相)分散于另一种(连续相)中的混合物。在本发明的上下文中,硅氧烷乳剂还包括粗乳液和微乳液。
在一个实施方案中,本发明的硅氧烷乳剂以水包硅油乳液形式或含35-65(w/w%)范围内的溶剂的水溶液形式加入。在一个实施方案中,本发明的硅氧烷乳剂可为任何硅氧烷乳剂。
在一个实施方案中,硅氧烷乳剂的平均粒度为0.01至2微米,更优选0.2至0.8微米。
所述乳化硅油优选选自由下列组成的组:非离子无氮硅油、氨基官能化硅油以及它们的混合物。
在本发明的一个实施方案中,所述硅氧烷乳剂为氨基官能化硅氧烷,优选氨基聚二甲基硅氧烷。
在本发明优选的实施方案中,硅氧烷乳剂为非离子无氮硅氧烷乳剂,优选选自由下列组成的组:聚二烷基硅氧烷、聚二甲基硅氧烷、烷氧基化硅氧烷、乙氧基化硅氧烷、丙氧基化硅氧烷、乙氧基化丙氧基化硅氧烷、季硅氧烷或它们的衍生物以及它们的混合物。在更优选的实施方案中,所述非离子无氮硅氧烷乳剂选自由下列组成的组:聚二烷基硅氧烷、聚二甲基硅氧烷以及它们的混合物。在一个实施方案中,所述硅氧烷乳剂为聚二甲基硅氧烷。
在该优选实施方案中,其中所述硅氧烷乳剂为聚二甲基硅氧烷,所述聚二甲基硅氧烷具有介于0.0001m2.s-1至0.1m2.s-1之间,优选介于0.0003m2.s-1至0.06m2.s-1之间,更优选介于0.00035m2.s-1至0.012m2.s-1之间的粘度。
适用于含溶剂水溶液中的溶剂可选自由下列组成的组:具有一个或多个游离羟基的C1-C20直链、支链、环状、饱和和/或不饱和醇;胺、链烷醇胺以及它们的混合物。优选的溶剂是一元醇、二元醇、单胺衍生物、甘油、乙二醇以及它们的混合物,如乙醇、丙醇、丙二醇、单乙醇胺、甘油、山梨醇、亚烷基二醇、聚亚烷基二醇以及它们的混合物。最优选的溶剂选自由下列组成的组:1,2-丙二醇、1,3-丙二醇、甘油、乙二醇、二乙二醇以及它们的混合物。
所述乳液包含水溶性乳化剂,所述水溶性乳化剂选自由下列组成的组:可商购获得的乳化剂,包括阳离子乳化剂、阴离子乳化剂、非离子乳化剂或两性离子乳化剂。在本发明优选的实施方案中,所述乳化剂为非离子表面活性剂。
作为另外一种选择,使用硅氧烷乳剂和溶剂的预混物以克服所有成分在整个组合物中完全分散或溶解方面的工艺难题。
在本发明的上下文中,硅氧烷乳剂预混物包括高内相乳液(“HIPE”)。这通过将硅氧烷乳剂如聚二甲基硅氧烷与乳化剂预混形成HIPE来实现,然后将该HIPE混入到所述组合物中,从而达到良好混合,获得均匀混合物。此类HIPE包含至少65重量%,或至少70重量%,或至少74重量%,或至少80重量%;或不大于95重量%的内相(分散相),其中所述内相可包含硅氧烷乳剂。所述内相也可以是没有被预乳化的其它水不溶性织物护理有益剂。通过使用乳化剂来分散所述内相。所述乳化剂的实例包括表面活性剂或表面张力降低聚合物。在一个实施方案中,乳化剂的范围按所述HIPE的重量计为至少0.1%至25%,或1%至10%,或2%至6%。在另一个实施方案中,乳化剂是水溶性的,并且在按去离子水重量计小于0.1%的浓度下,可将水的表面张力降低至小于0.0007N(70达因),或小于0.0006N(60达因),或小于0.0005N(50达因);或等于或大于0.0002N(20达因)。在另一个实施方案中,所述乳化剂是至少部分水不溶性的。
在一个实施方案中,这些外相(连续相)为水,作为另外一种选择,可包含至少一部分水,作为另外一种选择,可几乎不或不包含水。在另一个实施方案中,外相水的含量按HIPE的重量计小于35%,或小于30%,或小于25%;或至少1%。当外相具有低含量的水或无水时,也可使用溶剂来制备非水性HIPE。典型的溶剂包括甘油和丙二醇。
在另一个实施方案中,所述组合物为非浓缩型组合物。在该实施方案中,硅氧烷乳剂至少在初始时是非乳化的,并且可在织物护理组合物自身中乳化。
本发明的组合物可包含硅氧烷乳剂,其用于保持液体织物软化组合物在冻-融循环后以及低温下长期储存后的物理稳定性。
本发明硅氧烷乳剂的含量为0.5%至10%。在另一个实施方案中,本发明硅氧烷乳剂的含量按所述液体织物软化组合物的重量计为0.3%至10%,优选0.3%至5%,并且最优选0.5%至3.0%。
I.非离子无氮硅氧烷乳剂:
在本发明的上下文中,所述硅氧烷乳剂优选选自由下列组成的组:具有式(I)、(II)、(III)的非离子无氮硅氧烷乳剂以及它们的混合物:
R2-(R1)2SiO-[(R1)2SiO]a-[(R1)(R2)SiO]b-Si(R1)2-R2(II);
其中每个R1独立地选自由下列组成的组:具有1至20个碳原子的取代或未取代的直链、支链或环状烷基;具有2至20个碳原子的取代或未取代的直链、支链或环状烯基;具有6至20个碳原子的取代或未取代的芳基;具有7至20个碳原子的取代或未取代的烷基芳基、取代或未取代的芳烷基和取代或未取代的芳基烯基以及它们的混合物;每个R2独立地选自由下列组成的组:具有1至20个碳原子的取代或未取代的直链、支链或环状烷基;具有2至20个碳原子的取代或未取代的直链、支链或环状烯基;具有6至20个碳原子的取代或未取代的芳基;具有7至20个碳原子的取代或未取代的烷基芳基、取代或未取代的芳烷基、取代或未取代的芳基烯基,以及具有下列通式的聚(乙烯氧基/丙烯氧基)共聚物基团;
-(CH2)nO(C2H4O)c(C3H6O)dR3(IV)
聚二烷基硅氧烷、聚二甲基硅氧烷、烷氧基化硅氧烷、季硅氧烷
其中至少一个R2为聚(乙烯氧基/丙烯氧基)共聚物基团(乙氧基化硅氧烷、丙氧基化硅氧烷、乙氧基化丙氧基化硅氧烷乳剂),并且每个R3独立地选自由下列组成的组:氢、具有1至4个碳原子的烷基、乙酰基以及它们的混合物,其中指数w具有一定的值,使得式(I)和(III)的无氮硅氧烷聚合物的粘度介于0.0001m2.s-1(100厘沲)至0.1m2.s-1(100,000厘沲)之间;其中a为1至50;b为1至50;n为1至50;c(所有聚亚烷基氧基侧基)共具有1至100的值;d共为0至14;c+d共具有5至150的值。
所述非离子无氮硅氧烷乳剂更优选选自由下列组成的组:具有上式(II)至(III)的直链非离子无氮硅氧烷乳剂,其中R1选自由下列组成的组:甲基、苯基、苯基烷基以及它们的混合物;其中R2选自由下列组成的组:甲基、苯基、苯基烷基以及它们的混合物;并且选自具有上文定义的通式(IV)的基团以及它们的混合物;其中R3如上文定义,并且其中指数w具有一定的值,使得式(III)无氮硅氧烷乳剂的粘度介于0.0001m2.s-1(100厘沲)至0.1m2.s-1(100,000厘沲)之间;a为1至30,b为1至30,n为3至5,c共为6至100,d共为0至3,并且c+d共为7至100。
所述无氮硅氧烷乳剂最优选选自由下列组成的组:具有上文通式(III)的直链非离子无氮硅氧烷乳剂,其中R1为甲基,即所述硅氧烷乳剂为聚二甲基硅氧烷。在该优选的实施方案中,其中所述硅氧烷乳剂为聚二甲基硅氧烷,指数w具有一定的值,使得聚二甲基硅氧烷具有介于0.0001m2.s-1至0.1m2.s-1之间,优选介于0.0003m2.s-1至0.06m2.s-1之间,更优选介于0.00035m2.s-1至0.012m2.s-1之间的粘度。
II.氨基官能化硅氧烷乳剂:
在本发明的一个实施方案中,所述硅氧烷乳剂为氨基官能化硅氧烷。氨基官能化硅氧烷乳剂是具有下式的物质:
HO[Si(CH3)2-O]x{Si(OH)[(CH2)3-NH-(CH2)2-NH2]O}yH
其中x和y为整数,取决于所述硅氧烷乳剂的粘度。所述氨基官能化硅氧烷乳剂优选具有一定的分子量,使得它表现出0.0005m2.s-1(500厘沲)至0.5m2.s-1(500,000厘沲)的粘度。该物质还被称为“氨基聚二甲基硅氧烷”。
使用方法
本文所公开的某些消费品可被用于清洁或处理部位,特别是表面或织物。典型地,该部位的至少一部分接触申请者的组合物实施方案(其以纯的形式或稀释在液体,例如洗涤液体中),然后可任选洗涤和/或漂洗所述部位。在一个方面,任选洗涤和/或漂洗一个部位,按照本发明或包含所述颗粒的组合物将该颗粒与该部位相接触,然后任选洗涤和/或漂洗该部位。在一个方面,公开了清洁或处理部位的方法,所述方法包括任选洗涤和/或冲洗所述部位,使所述部位接触选自本文公开的组合物及其混合物的组合物,并且任选洗涤和/或冲洗所述部位。就本发明的目的而言,洗涤包括但不限于擦洗和机械搅拌。织物可包括能够在正常消费者使用条件下洗涤或处理的大多数任何类型的织物。可包含所公开组合物的液体可具有约3至约11.5的pH。此类组合物在溶液中通常以约500ppm至约15,000ppm的浓度使用。当洗涤溶剂是水时,水温典型为约5℃至约90℃,并且当所述部位包括织物时,水与织物之比典型为约1:1至约30:1。
测试方法
1.)平均分子量:就本说明书和权利要求的目的而言,根据ASTM方法ASTMD4001-93(2006)测定聚合物的平均分子量。
2.)水解度:就本说明书和权利要求的目的而言,根据美国专利6,132,558第2栏第36行至第5栏第25行中所述的方法测定水解度。
3.)电荷密度:就本说明书和权利要求的目的而言,借助于胶体滴定,测定聚合物的电荷密度,参见D.Horn的“ProgressinColloid&PolymerSci.”65(1978),251-264。
4.)ζ电势:就本说明书和权利要求的目的而言,如下测定ζ电势:
a.)设备:MalvernZetasizer3000
b.)样品制备方法:
(i)将5滴包含受关注包封物的浆液加入到20mL1mMNaCl溶液中以稀释所述浆液。可能需要调节浓度,使得计数率在50至300Kcps的范围内。
(ii)无需过滤,对稀释过的样品测定ζ电势。
(iii)将过滤过的浆液注入到Zetasizer电池中,并且将所述电池插入到设备中。测试温度设为25℃。
(iv)当温度稳定时(通常在3至5分钟内),开始测量。对每个样品而言,进行五次测量。对每一种受关注的浆液取三次样。计算15个读数的平均值。
c.)用于测量的设备设置:
所用样本的参数设置:
材料:三聚氰胺RI1,680,吸光度0.10
分散剂:NaCL1mM
温度:25℃
粘度:0.8900cP
RI:1.330
介电常数:100
F(ka)选择:模型:SmoluchowskiF(ka)1.5
使用分散剂粘度作为样品粘度
电池类型:DTS1060C:透明的一次性Zeta电池
测量:3次测量
d.)结果:以mV为单位,将对受关注浆液测得的15个读数的平均值报导为ζ电势。
实施例
尽管已用具体实施方案来说明和描述了本发明,但对于本领域的技术人员显而易见的是,在不背离本发明的精神和保护范围的情况下可作出许多其它的改变和变型。因此,随附权利要求书中旨在涵盖本发明范围内的所有这些改变和变型。
实施例1:84重量%的芯/16重量%的壁的三聚氰胺甲醛(MF)胶囊
将25g丙烯酸丁酯-丙烯酸共聚物乳化剂(ColloidC351,25%固体,pka4.5至4.7(KemiraChemicals,Inc.Kennesaw,Georgia,U.S.A.))溶解并且混入到200g去离子水中。用氢氧化钠溶液将所述溶液的pH调节至pH4.0。将8g部分地甲基化的羟甲基三聚氰胺树脂(Cymel385,80%固体(CytecIndustriesWestPaterson,NewJersey,U.S.A.))加入到所述乳化剂溶液中。将200g香料油在机械搅拌下加入到先前的混合物中,并且将温度升至50℃。在高速混合直至获得稳定乳液后,将第二溶液和4g硫酸钠盐加入到所述乳液中。此第二溶液包含10g丙烯酸丁酯-丙烯酸共聚物乳化剂(ColloidC351,25%固体,pka4.5-4.7,Kemira)、120g蒸馏水、将pH调节至4.8的氢氧化钠溶液、25g部分甲基化的羟甲基三聚氰胺树脂(Cymel385,80%固体,Cytec)。将此混合物加热至70℃,并且在持续搅拌下保持过夜以完成包封过程。将23g乙酰乙酰胺(Sigma-Aldrich,SaintLouis,Missouri,U.S.A.)加入到悬浮液中。根据780型颗粒计数器分析,获得了30μm的平均胶囊尺寸。
实施例2
制备聚合物涂覆的香料微胶囊的方法
如下制备聚合物涂覆的香料微胶囊:在玻璃广口瓶中称量99g三聚氰胺甲醛香料微胶囊参比浆液(99.75%)和1gLupamin9030(16%活性物质,得自BASF(Ludwigshafen,Germany))。用药匙将两种成分短暂混合。在振荡器中将它们进一步混合过夜。
实施例3
在液体衣物洗涤剂中包含涂层香料微胶囊的方法
称量74.9g不含香料微胶囊的致密型液体洗涤剂,并且加入1.33g聚合物涂覆的香料微胶囊。
用机械搅拌器将所得产物混合1分钟。
实施例4
使用具有R1382附件的Eurostar搅拌器(IKA),以200RPM的恒定速率搅拌9kg实施例2的香料微胶囊浆液等分试样。向所述等分试样中加入500g羧甲基纤维素(CPKelco),同时使用具有如上所述相同附件和速率的Eurostar搅拌器搅拌。将浆液混合共两小时,或直至形成均匀相。
实施例5
将1.28kg沉淀二氧化硅22S(Degussa)加入到F-20桨式搅拌器(Forberg)中。将搅拌器运行初始的5秒以在搅拌器基座上均匀分散二氧化硅。关闭搅拌器,并且将根据实施例4制得的8.25kg糊剂均匀分布在粉末上。然后使搅拌器以120rpm的速率运转总共30秒。接着混合之后,将润湿颗粒倾倒出搅拌器并使用2000微米的筛来筛选以移除粒度过大的颗粒。将穿过筛网的产物按500g一批在CDT0.02流化床烘干机(Niro)中干燥至用KarlFischer测得为20重量%的最终含水量。烘干机在140℃的入口温度和0.68m/s的空气速率下运转。
实施例6-13
下面包括包含所述香料组合物的颗粒状衣物洗涤剂组合物的实施例。
实施例1至19中描述的设备和材料可得自下列公司:IKAWerkeGmbH&Co.KG(Staufen,Germany);CPKelco(Atlanta,UnitedStates);ForbergInternationalAS(Larvik,Norway);DegussaGmbH(Düsseldorf,Germany);NiroA/S(Soeberg,Denmark);BakerPerkinsLtd(Peterborough,UnitedKingdom);NipponShokubai(Tokyo,Japan);BASF(Ludwigshafen,Germany);Braun(Kronberg,Germany);IndustrialChemicalsLimited(Thurrock,UnitedKingdom);Primexehf(Siglufjordur,Iceland);ISPWorldHeadquarters;Polysciences,Inc.(Warrington,Pennsylvania,UnitedStates);CytecIndustriesInc.(NewJersey,UnitedStates);InternationalSpecialtyProducts(Wayne,NewJersey,UnitedStates);P&GChemicalsAmericas(Cincinnati,Ohio,UnitedStates);Sigma-AldrichCorp.(St.Louis,Missouri,UnitedStates);DowChemicalCompany(Midland,MI,USA)。
实施例14-23:织物调理剂
包含本说明书中公开的聚合物涂覆的香料微胶囊的织物调理剂的非限制性实例概括于下表中。
aN,N-二(牛脂酰氧乙基)-N,N-二甲基氯化铵。
b甲基二(牛油酰氨基乙基)2-羟乙基甲酯硫酸铵。
c摩尔比为1.5:1的脂肪酸与甲基二乙醇胺的反应产物,用氯甲烷季铵化,得到摩尔比为1:1的N,N-二(硬脂酰氧乙基)-N,N-二甲基氯化铵和N-(硬脂酰氧乙基)-N-羟乙基-N,N-二甲基氯化铵的混合物。
d以商品名得自NationalStarch的阳离子高直链淀粉玉米淀粉。
f得自BASF的RheovisCDE。
g得自Wacker的SE39
h二亚乙基三胺五醋酸。
i得自RohmandHaasCo的CG。“PPM”为“份每一百万份”。
j戊二醛
k以商品名DC2310得自DowCorningCorp.的硅氧烷消泡剂。
l以商品名E3500由Wacker提供的硅氧烷乳剂
余量
实施例24-29液体衣物洗涤制剂(HDL)
实施例30:洗发剂制剂
本文所公开的量纲和值不旨在被理解为严格地限于所述的精确值。相反,除非另外指明,每个这样的量纲是指所引用的数值和围绕该数值的功能上等同的范围。例如,公开为“40mm”的量纲旨在表示“约40mm”。
在发明详述中引用的所有文献都在相关部分中以引用方式并入本文中;对任何文献的引用不应被解释为承认其是关于本发明的现有技术。当本发明中的术语的任何含义或定义与引入以供参考的文件中术语的任何含义或定义矛盾时,应当服从在本发明中赋予该术语的含义或定义。
尽管已用具体实施方案来说明和描述了本发明,但对于本领域的技术人员显而易见的是,在不背离本发明的精神和保护范围的情况下可作出许多其它的改变和变型。因此,随附权利要求书中旨在涵盖本发明范围内的所有这些改变和变型。
Claims (7)
1.一种包封物,所述包封物包含芯和壁,所述芯包含香料,所述壁包含三聚氰胺甲醛和/或交联三聚氰胺甲醛、聚(丙烯酸)和聚(丙烯酸-共-丙烯酸丁酯);所述壁具有外表面和涂层,所述壁包封所述芯,所述涂层涂覆所述壁的外表面,所述涂层包含一种或多种功效聚合物,其中所述功效聚合物是聚乙烯基甲酰胺,所述功效聚合物具有340,000Da至1,500,000Da的平均分子量;就聚乙烯基甲酰胺而言,具有10%至40%的水解度;和具有1meq/g功效聚合物至16meq/g功效聚合物的电荷密度。
2.如权利要求1所述的包封物,所述包封物具有1:80至1:10的涂层与壁比率。
3.一种浆液,所述浆液包含如权利要求1或2所述的包封物,所述浆液具有+5meV至+25meV或-35meV至+10meV的ζ电势,所述浆液包含足量的所述包封物,以使所述浆液具有基于总浆液重量0.125%至2%的所述功效聚合物。
4.一种附聚物,所述附聚物包含如权利要求1至3中任一项所述的包封物和/或浆液。
5.一种制备如权利要求4所述的附聚物的方法,所述方法包括:
a)混合如权利要求1至3中任一项所述的包封物和/或浆液;增塑剂以形成混合物;
b)使所述混合物与所述隔离剂混合以形成材料,其中所述隔离剂包含二氧化硅;以及
c)从所述材料中移除足量的所述增塑剂以获得产物,所述产物包含基于产物总重量1%至50%的增塑剂。
6.一种消费品,所述消费品包含:选自如权利要求1或2所述的包封物的包封物、如权利要求3所述的浆液;和/或如权利要求4所述的附聚物。
7.如权利要求6所述的消费品,其中所述消费品包含足量的浆液和/或包封物,以使所述消费品具有基于总消费品重量0.001%至0.05%的功效聚合物含量。
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