CN102471735A - 应用织物护理组合物减少皱褶的方法 - Google Patents
应用织物护理组合物减少皱褶的方法 Download PDFInfo
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Abstract
提供一种减少在洗涤衣物上所形成的皱褶的织物调理剂。另外还提供一种减少洗涤衣物上皱褶的发生的方法。
Description
相关申请的交叉参照
本申请要求2009年7月9日提交的美国临时专利申请号61/224,300的优先权,该申请通过引用结合到本文中。
发明背景
在洗涤衣物(laundered garments)时,在洗涤和干燥的步骤中都会形成皱褶(wrinkles)。虽然可以通过熨烫或压制衣物的方式去除皱褶,但是熨烫费工(labor intensive)和费时的(time intensive)。已经多次尝试过在洗涤过程中防止皱褶的形成。众所周知的试图减少皱褶的方法包括在洗衣用洗涤剂或织物软化剂中使用减皱添加剂(wrinkle-reducingadditives)。这样的添加剂包括氨基硅酮(aminosilicones)和固化氨基硅酮(curable aminosilicones)。然而,这些成分中的每一种都有缺陷。例如,氨基硅酮会引起发黄,而固化氨基硅酮需要加热来减少皱褶。
便装物品诸如劳动布牛仔裤需经常洗涤,而用厚重织物诸如劳动布制成的衣物是熨烫起来特别费工而且耗时的。因此,能有对于这样的便装物品不需要熨烫而减少皱褶的方法是高度合意的。需要一种有效并且高效的方法,来消除或减少衣物特别是便装衣物在洗涤并干燥时其上面的皱褶。
发明概述
一种使皱褶减到最少的洗衣方法。所述方法包括在洗涤程序中洗涤衣服、并随后向洗涤的衣服施用织物调理剂的步骤。所述织物调理剂包含脂肪酯季铵和蛋白质-硅酮共聚物,该织物调理剂适于减少具有至少250g/m2(7.5盎司每平方码)和最高600g/m2织物重量的洗涤衣物上的皱褶。理想地,该衣服具有少于40%,优选少于30%的由用缝线缝接的一层以上织物覆盖的其表面积。
本发明在给衣物提供柔软性的同时还提供能使洗涤的衣物皱褶减少或最小化的织物调理剂。所述织物调理剂特别适合于减少由至少250g/m2和最高600g/m2重量的织物制成的衣物上的皱褶。
所述织物调理剂可包含基于所述组合物总重量的0.5%-50%重量的织物软化剂(诸如脂肪酯季铵)和0.1%-2%重量的蛋白质-硅酮共聚物,而所述织物软化剂可以是二酯二牛油二乙基铵盐(diester ditallowdiethyl ammonium salt)或二酯二牛油二甲基铵盐。合意的是,与未用软化组合物洗涤的衣物相比,所述组合物减少洗涤衣物形成的皱褶至少50%,更优选至少60%,甚至更优选至少70%。
发明详述
正如纵贯全文所用的一样,范围被用作描述在该范围之内的每一个值。该范围内的任何值可选作该范围的界限。此外,所有在此引用的参考文献都通过参照其全文结合到本文中。倘若本公开中的定义与引用的参考文献的定义相冲突时,以本公开为准。
除非另外说明,在本说明书中于此及其它地方所表示的所有百分数和数量都应当理解是指重量百分数。所给的数量都是基于所述材料的有效重量,除非另有说明。
所述术语洗涤包括任何清洗织物的方法。一般来说,织物可以用水来清洗,不论是用洗衣机或手洗,或者用干洗组合物清洗,其使用一种无水的溶剂。
所述术语织物调理剂指一种能够调理织物的组合物。该术语包括织物软化剂。织物软化剂包括使织物变柔软的材料。
AI指单酯季胺盐(monoesterquat)、双酯季胺盐(diesterquat),三酯季胺盐(triesterquat)的合并量的有效重量。
本发明提供一种减少洗涤或干燥衣物时可形成的皱褶的方法。该方法包括将衣物与诸如织物调理剂的织物护理组合物相接触的步骤,该组合物包含季铵软化活性剂和蛋白质-硅酮共聚物。该方法特别针对减少由厚重织物所制成衣物的皱褶。适用于本发明所述衣物的厚重织物包括至少250g/m2和最高达600g/m2,优选270g/m2至550g/m2,更优选300g/m2到500g/m2重量的织物。通常,厚重织物通过一种编织模式制得,诸如劳动布、斜纹布、卡其布或帆布。该方法还涉及处理衣物,所述衣物具有由通过缝线缝接的一层以上织物的重叠区域覆盖的少于40%的其表面积。所述缝合的重叠区域优选为5%到30%,且更优选为10%到25%。与不用软化组合物洗涤的衣物相比,该织物软化使由厚重织物制成的衣物洗涤的皱褶形成减少了至少50%,更优选至少60%,甚至更优选至少70%。
所述织物护理组合物,优选是软化组合物,包含了活性阳离子软化剂。适宜的活性阳离子软化剂是脂肪酯季铵化合物。该脂肪酯季铵化合物具有下式:
其中R4代表具有8到22个碳原子的脂肪烃基,R2和R3独立地代表(CH2)s-R5,其中R5代表含有8到22个碳原子的烷氧基羧基、苯甲基、苯基、(C1-C4)-烷基取代的苯基、OH或者H;R1代表(CH2)tR6,其中R6代表苯甲基、苯基、(C1-C4)-烷基取代的苯基、OH或者H;q,s和t各自独立地代表从1到3的整数;和X-是软化剂相容的阴离子,包括卤素例如氯化物,硫酸二甲酯或硫酸乙酯。季铵化合物的合适实例包括二酯二烷基二甲基铵盐,诸如二酯二牛油二甲基氯化铵,和二酯二牛油二甲基硫酸甲酯铵;二酯二烷基二乙基铵盐,诸如二酯二牛油二乙基硫酸甲酯铵,二酯二牛油乙基甲基硫酸甲酯铵,及它们的混合物。适当的季铵化合物还可包含烷醇胺的季铵化单-烃基酯,或三-烃基酯,及它们的混合物。适当的烷醇胺包括三乙醇胺,而适当的季胺化合物包括牛油基(tallowyl)三酯乙醇氯化铵,牛油基三酯乙醇硫酸铵,牛油基单酯二乙醇氯化铵,和牛油基单酯二乙醇硫酸铵。其它带有取代或未取代的烃基的季胺化合物,诸如硬脂酸,棕榈酸,形成带有烷醇胺的酯的肉豆蔻脂肪酸基,也是适当的。所述织物调理剂包含基于所述组合物总重量的1-50%重量,优选为基于所述材料的有效重量的2-35%重量,更优选3-20%重量,甚至更优选6-10%重量,最优选8-9%重量的阳离子软化活性剂。
所述织物调理剂包含蛋白质-硅酮共聚物。如此处所用的术语蛋白质指水解的蛋白质。如此处所用的术语硅酮包括硅烷或硅氧烷。该蛋白质-硅酮共聚物具有键结于蛋白质组分的氨基的硅酮组分。该共聚物可通过将有机官能硅烷(organofunctional silane)或硅氧烷化合物与蛋白质氨基共价键合,形成包括蛋白质-硅酮交联的聚合物分子来制备。蛋白质组分的重均分子量可为500至500,000道尔顿,优选1,000到20,000道尔顿。在EP540357和WO03/078503中公开了典型的适当的蛋白质-硅酮共聚物。
适当的共聚物包括以下通式的共聚物:
其中R是水解蛋白质R-NH2的残基;每个R1独立地是有机官能硅烷HR1-Si(R2’)(R3’)-OH的残基,其中R2’和R3’独立地是甲基,羟基、具有1到6个碳原子的烷氧基;R2和R3各自独立地是甲基,羟基、具有1到6个碳原子的烷氧基或是化学式为(A)或(B)化合物的残基:
其中R、R1、R2和R3各自独立地如上所定义;而n相当于反应的氨基数,优选在1到100的范围之内,每个蛋白质的反应性氨基具有0.1到0.4个硅烷分子。R优选是水解植物蛋白的残基,诸如水解的小麦或马铃薯蛋白质,特别是小麦蛋白质的残基。
R1作为用于和蛋白质组分反应而形成共聚物的有机官能硅烷的残基,其性质取决于该有机官能硅烷中的最初存在的官能团的性质。例如,当有机官能硅烷中的最初存在的官能团是卤化酰基时,R1基团通常包含与蛋白质残基的氮原子直接键合的羧基。同样,当该有机官能硅烷中的最初存在的官能团是磺酰卤时,R1基团通常包含与蛋白质残基的氮原子键合的磺酰基。优选R1基团由含作为该官能团的环氧基的有机官能硅烷的反应而得到。在这种情况下,在最终的共聚物化合物中,R1基团将包含式-CH2-CH(OH)-的部分,其中的亚甲基部分直接与蛋白质残基的氮原子键合。优选R1基团是具有1到10个碳原子的烯基(alkylen group),其可被一个或多个氧原子间断并可被一个或多个选自羟基、卤原子、具有1到6个碳原子的烷基和具有1到6个碳原子的烷氧基的基团取代。适当的R1包括-(CH2)3-O-CH2-CHOH-CH2-,或者-(CH2)3-CH(CH2-CO2H)-CO-。
该聚合物优选地包括式(C)的化合物:
其中R是水解的小麦或马铃薯蛋白的残基;R2和R3各自都不是甲基;和n是1到4,优选是2。用于本发明的适当的蛋白质-硅酮共聚物是市场上可买到的,例如,以商品名COLTIDETMHSi和CRODASONTMW购自禾大化学公司(Croda Chemicals)。COLTIDE HSi是特别合适的。所述织物调理剂包含基于该组合物总重量的0.02-0.5%重量,优选0.03-0.25%重量,更优选0.04-0.2%重量,最优选0.05-0.15%重量的蛋白质-硅酮共聚物。该蛋白质-硅酮共聚物的重量是基于所供给的重量计算的。
在一个实施方案中,所述组合物包含8.3%重量的酯季铵盐(esterquat)和0.45%重量的蛋白质-硅酮共聚物。在另一实施方案中,该组合物包含2.8%重量的酯季铵盐和0.8%重量的蛋白质-硅酮共聚物。在另一实施方案中,该组合物包含6.4%重量的酯季铵盐和0.25%重量的蛋白质-硅酮共聚物。在另一实施方案中,该组合物包含6.4%重量的酯季铵盐和0.45%重量的蛋白质-硅酮共聚物。在另一实施方案中,该组合物包含10.67%重量的酯季铵盐和0.45%重量的蛋白质-硅酮共聚物。
所述织物调理剂可额外地包含增稠剂。适当的增稠剂是可溶于水的交联阳离子乙烯基聚合物,其使用70到300ppm,优选75到200ppm,且最优选80到150ppm水平的双官能乙烯基加成单体(additionmonomer)的交联剂进行交联。这些聚合物在美国专利号4806345中有进一步的描述,而其它可利用的聚合物在WO90/12862中公开。通常,这样的聚合物被制备成油包水乳液,其中该交联聚合物分散在可含有表面活性剂的矿物油中。在制成品与水相接触期间,该乳状液发生转化,使水溶性聚合物膨胀。用于本发明的最优选的增稠剂是季铵丙烯酸盐或季铵甲基丙烯酸盐与丙烯酰胺单体结合的交联共聚物。所需要的依据本发明的增稠剂提供了在储藏时表现出长期稳定性的织物调理剂,该增稠剂还允许存在相对高水平的电解质而不影响该组合物的稳定性。此外,在向其施加剪切力时,该织物调理剂仍然保持稳定。
所述织物调理剂可进一步包括螯形化合物。适当的螯形化合物能够螯合金属离子并以占织物调理剂至少0.001%重量的水平,优选0.001%到0.5%,且更优选0.005%到0.25%重量的水平存在。所述螯形化合物在性质上为酸性的,可以酸的形式或者作为带有适当相反阳离子的复合物/盐的形式存在,诸如碱或碱土金属离子、铵或取代的铵离子或者它们的任何混合物。这样的螯形化合物选自氨基羧酸化合物和有机氨基膦酸化合物,以及它们的混合物。适当的氨基羧酸化合物包括:乙二胺四乙酸(EDTA)、N-羟基乙二胺三乙酸、氨三乙酸(NTA);和二亚乙基三胺五乙酸(DEPTA)。适当的有机氨基膦酸化合物包括:乙二胺四(亚甲基膦酸)(ethylenediamine tetrakis(methylenephosphonicacid));1-羟基乙叉1,1-二膦酸(HEDP);和氨基三(亚甲基膦酸)。
所述织物调理剂可包含组合物的0.01%到3%重量,优选0.05%到2%重量,更优选0.1%到1.5%重量的消泡剂。适当的消泡剂包括任何已知的消泡化合物,包括例如硅酮消泡化合物、醇消泡化合物如2-烷基烷醇消泡化合物、脂肪酸、石蜡消泡化合物,和它们的混合物。于此使用的特别优选的消泡化合物是硅酮消泡化合物,在此定义为任何包含硅酮组分的消泡化合物。这样的硅酮消泡化合物还通常包含二氧化硅组分。该硅酮组分包括硅氧烷单体和各种类型的烃基的各种相对高分子量聚合物,诸如聚有机硅氧烷油,例如聚二甲基-硅氧烷、聚有机硅氧烷油或树脂的分散液或乳液,及聚有机硅氧烷和二氧化硅粒子的组合,其中聚有机硅氧烷被化学吸收到或稠合到二氧化硅上。消泡化合物已经为技术人员所熟知,并且在例如1981年5月5日发表的、授权于Gandolfo等的美国专利号4265779,以及于1990年2月7日由Starch,M.S公布的欧洲专利号89307851.9中公开。其它的硅酮消泡化合物在美国专利号3455839中公开,该专利涉及通过向其中掺入少量聚二钾硅氧烷液体以消去水溶液的泡沫的组合物和方法。硅酮和硅烷化(silanated)二氧化硅的混合物在例如德国专利申请号DOS2124526中描述。适当的硅酮消泡化合物的实例是聚有机硅氧烷及可在Dow Corning,Wacker Chemie和通用电气公司中购买的二氧化硅颗粒的组合。
本发明的织物调理剂可包括任选的用于将材料悬浮于冲洗液中并抑制它们沉淀在洗涤的织物上的分散剂。分散剂在该组合物中的有效利用水平在0%到7%,更优选0.1%到5%,且最优选0.2%到3%重量。适当的分散剂包括非离子型表面活性剂,其包括环氧己烷和任选的氧化丙烯与脂肪醇、脂肪酸、脂肪胺等的加成产物。它们在此被称为乙氧基化脂肪醇、乙氧基化脂肪酸和乙氧基化脂肪胺。在下文中所描述的特别类型的任何乙氧基化材料可用作非离子型表面活性剂。适当的化合物是以下通式的表面活性剂:
R5-Y-(C2H4O)z-C2H4OH
其中R5选自伯、仲及支链烷基和/或酰基和/或酰基烃基;伯、仲及支链烯烃基,以及伯、仲及支链烷基-和烯基取代的酚型烃基(phenolichydrocarbyl groups);所述烯基具有8到20个,优选9到18个碳原子的烃链长度。在此处的乙氧基化非离子型表面活性剂的通式中,Y通常是--O--,--C(O)O--,优选--O--,且其中R5,当存在时,具有在上文中给定的含义,和z是1-30,更优选是7-25。
所述织物调理剂可任选地包含通常包括在织物调理组合物中的组分,诸如香料、表面活性剂浓缩助剂、乳化剂、着色剂、防腐剂、任选的增白剂、天然和/或合成提取剂、荧光剂、水溶助长剂、抗再沉积剂、抗缩剂、抗斑剂、抗腐蚀剂、皱褶传递剂(drape imparting agents)、抗静电剂、熨平助剂(ironing aids)以及它们的混合物。
本发明的织物调理剂高度适合于减少洗涤和干燥衣物时形成的皱褶,优选地适合于厚重织物衣物上,例如便装可以经过洗涤后穿上而不需要费劲地熨烫衣物。
实施例
实施例1:织物软化剂
织物软化剂组合物由下述成分制成。
表1:
软化剂的制备方法
将水加热到65℃,并一边加入膦酸和蛋白质-硅酮共聚物一边搅拌。另外,将季铵化牛油酯铵(quaternized tallow ester ammonium)加热至65℃并同时搅拌。慢慢地将季铵加入到酸-水溶液中并混合10分钟。将混合物冷却至35度并加入乳酸。然后加入增稠剂并同时搅拌。将混合物再次搅拌10分钟。
实施例2:皱褶评估
用自动洗衣机洗涤具有织物重量400到500g/m2的100%纯棉牛仔布和具有织物重量190g/m2的100%纯棉长袖礼服衬衫(dress shirt),在织物软化剂周期中使用实施例1中的组合物2和3。按照市售的织物软化剂使用说明书来定量给予该织物软化组合物。作为对照,洗涤另一组上文描述的衣物而不加本发明的织物处理组合物。从洗衣机中移出衣物并在周围条件下挂干。邀请一个六位评估员的评价小组以目视对经过干燥的衣物评估每件衣物上所形成的皱褶数并对是否还需要对衣服进行熨平提出意见。该目测皱褶评估通过指定1表示最少皱褶数量和3表示最大皱褶数量来进行。表2列举了所有洗过的衣服上给出的数目的总和。
表2:皱褶目测评估
衣服型号 | 组合物2 | 组合物3 | 无织物处理 |
牛仔裤 | 14 | 25 | 21 |
礼服衬衫 | 15 | 18 | 19 |
表3:熨烫的需要(不需要熨烫的回应%)
衣服型号 | 组合物2 | 组合物3 | 无织物处理 |
牛仔裤 | 80% | 0% | 50% |
礼服衬衫 | 0% | 10% | 0% |
如从上述可以看出,本发明的织物护理组合物显著地减少了由厚重织物制成的衣物上所形成的皱褶。织物护理组合物显著地减少了对厚重便装衣物进行熨烫的需要,也显著地减少了费劲的家庭杂务。
实施例3:织物上的皱褶
准备20cm2的方形布样并用自动洗衣机来洗涤,在织物软化剂周期中使用实施例1中的组合物1。作为对照,也洗涤另一组布样但不加本发明的织物处理组合物。在最后的旋转周期之前立即停止洗衣机,并将布样从洗衣机取出。每块布样沿长度方向折叠两次,并用手将水拧去。打开拧过的布样,并抓住该布样的两个角摇动三次。评估每件干燥的布样中以布样中心处6cm2的圆内目测的皱褶数量。对于每个配方,测试每种织物的四十五块布样。表4列举了皱褶的平均数量。
表4:
实施例3
在评估小组试验中评价组合物4到7,所述评估小组具有30到32位对衣物所出现皱褶进行评估的成员。该衣物以5绩点量表进行评估,即1表示没有一点皱褶而5表示非常皱。评估小组成员站立在一间照明良好的房间里距离衣物1.5米左右。下面的结果是这些衣物在不同条件下的平均评级值。洗涤牛仔裤(100%棉)和衬衫(65%聚酯和35%棉)并用组合物4到7处理织物。有192件被评估的牛仔裤和192件被评估的衬衫。一半的牛仔裤和衬衫晾干(92),一半用烘干机烘干(92)。下表中的数据是基于3次下面所述的累积洗衣循环后评估的。更小的数据表明皱褶更少。
在第一次洗涤中,将衣服放在前负荷自动洗衣机中洗涤,使用45公升25℃的100ppm硬水、1.8kg衣服,和30g的来自墨西哥的Axion洗衣用洗涤剂。用不加任何洗涤剂的同样的条件进行第二次洗涤。使用66公升的常温(大约23-25度)的水,2.8kg衣服,42.5g的美国Tide洗涤液,和110ml的组合物4、5、6或7进行第三次洗涤。将衣服放在高处干燥60分钟。
组合物5、6、7都是一样的,除了ColtideTMHSi的蛋白质-硅酮共聚物的水平不一样。在烘干机烘干中,ColtideTMHSi蛋白质-硅酮共聚物的添加减少了衣物上皱褶的数量。
Claims (15)
1.一种用于减少厚重织物衣物在洗涤时产生的皱褶的方法,其包括以下步骤:在洗涤程序中洗涤衣物,并向衣物中施用织物调理剂,该织物调理剂包含脂肪酯季铵,和蛋白质-硅酮共聚物,其中该衣物是由具有至少250g/m2的织物重量的织物制成。
2.根据权利要求1的方法,其中所述织物调理剂包含基于所述组合物总重量的1到50%重量的脂肪酯季铵化合物和0.02到0.5%重量的蛋白质-硅酮共聚物。
3.根据任一项前述权利要求的方法,其中所述织物调理剂被施用于洗过的衣物上。
4.根据任一项前述权利要求的方法,其中所述脂肪酯季铵包括二酯二牛油二乙基铵盐或者二酯二牛油二甲基铵盐。
5.根据任一项前述权利要求的方法,其中与不用所述软化组合物洗涤和干燥的同样的衣物相比,所述软化组合物减少了至少50%的皱褶。
6.根据任一项前述权利要求的方法,其中所述软化组合物包含基于所述组合物总重量的6%到10%重量的脂肪酯季铵化合物,和0.05%到0.15%重量的蛋白质-硅酮共聚物。
7.根据任一项前述权利要求的方法,其中所述洗涤程序包括洗涤步骤和单独的漂洗步骤,且其中蛋白质-硅酮共聚物是在漂洗步骤中施用的。
8.根据权利要求7的方法,其中所述洗涤步骤是通过洗衣机自动进行的而漂洗步骤则是手动进行的。
9.根据权利要求7所述方法,其中所述洗涤程序是在自动洗衣机中进行的,所述自动洗衣机具有洗涤步骤和漂洗步骤,其中织物调理剂是在漂洗步骤中施用的。
10.根据任一项前述权利要求的方法,其还包括在烘干机中干燥厚重织物衣物。
11.一种用于厚重织物衣物的抗皱织物调理剂,其包含:
a)0.5%到50%重量的阳离子软化剂,
b)0.02%到0.5%重量的蛋白质-硅酮共聚物,
c)香料,和
d)水,其中所述软化组合物减少由具有至少250g/m2织物重量的织物制成的衣物上至少50%的皱褶。
12.根据权利要求11的组合物,其中所述软化剂包含脂肪酯季铵化合物。
13.根据权利要求11-12的任一项的组合物,其中所述软化剂包含二酯二牛油二乙基铵盐或二酯二牛油二甲基铵盐。
15.根据权利要求11-14中任一项所述组合物,其中所述软化组合物包含基于该组合物总重量的6%到10%重量的脂肪酯季铵,和0.05到0.15%重量的蛋白质-硅酮共聚物。
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CN114599773A (zh) * | 2019-10-31 | 2022-06-07 | 高露洁-棕榄公司 | 具有改善的微生物稳健性的织物护理组合物及其使用方法 |
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WO2013070655A1 (en) * | 2011-11-11 | 2013-05-16 | The Dial Corporation | Method of increasing the performance of cationic fabric softeners |
GB2499628A (en) * | 2012-02-23 | 2013-08-28 | Mcbride Robert Ltd | Method of producing an aqueous fabric conditioning composition |
WO2017162836A1 (en) | 2016-03-23 | 2017-09-28 | Novozymes A/S | Use of polypeptide having dnase activity for treating fabrics |
BR112019012606A2 (pt) * | 2016-12-29 | 2020-03-03 | Colgate-Palmolive Company | Composições de cuidados domiciliares |
EP3775142A1 (en) * | 2018-03-29 | 2021-02-17 | Unilever Plc. | Use of fabric conditioner composition |
EP4041855A1 (en) * | 2019-10-07 | 2022-08-17 | Unilever IP Holdings B.V. | Fabric softener |
EP4041854A1 (en) * | 2019-10-07 | 2022-08-17 | Unilever IP Holdings B.V. | Fabric softener |
CA3234063A1 (en) * | 2021-10-28 | 2023-05-04 | Rahul PARAKHIA | Fabric care compositions, methods of use for reducing microfiber release from fabrics, and articles exhibiting improved resistance to microfiber release |
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2010
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- 2010-07-08 CA CA2763216A patent/CA2763216A1/en not_active Abandoned
- 2010-07-08 BR BR112012000402A patent/BR112012000402A2/pt not_active IP Right Cessation
- 2010-07-08 AU AU2010271428A patent/AU2010271428B2/en not_active Ceased
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- 2010-07-08 SG SG2011082856A patent/SG175989A1/en unknown
- 2010-07-08 US US13/382,950 patent/US20120246838A1/en not_active Abandoned
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2011
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US20030062507A1 (en) * | 2001-09-10 | 2003-04-03 | The Procter & Gamble Company | Fabric treatment composition and method |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113710786A (zh) * | 2019-04-10 | 2021-11-26 | 联合利华知识产权控股有限公司 | 织物调理剂组合物 |
CN114599773A (zh) * | 2019-10-31 | 2022-06-07 | 高露洁-棕榄公司 | 具有改善的微生物稳健性的织物护理组合物及其使用方法 |
Also Published As
Publication number | Publication date |
---|---|
WO2011005963A1 (en) | 2011-01-13 |
SG175989A1 (en) | 2011-12-29 |
IL216487A0 (en) | 2012-01-31 |
BR112012000402A2 (pt) | 2019-09-24 |
MX2011012490A (es) | 2011-12-14 |
AU2010271428A1 (en) | 2011-12-08 |
EP2451917A1 (en) | 2012-05-16 |
US20120246838A1 (en) | 2012-10-04 |
AU2010271428B2 (en) | 2013-05-02 |
CA2763216A1 (en) | 2011-01-13 |
RU2490320C1 (ru) | 2013-08-20 |
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