CN111417705B - 包含硅酮材料的织物护理组合物 - Google Patents
包含硅酮材料的织物护理组合物 Download PDFInfo
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- CN111417705B CN111417705B CN201880076896.8A CN201880076896A CN111417705B CN 111417705 B CN111417705 B CN 111417705B CN 201880076896 A CN201880076896 A CN 201880076896A CN 111417705 B CN111417705 B CN 111417705B
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- 229940082509 xanthan gum Drugs 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- 229940105296 zinc peroxide Drugs 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- 229940118257 zinc undecylenate Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
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Abstract
公开了织物护理组合物,其任选地在可接受的介质中包含至少一种未固化的硅酮基聚合物和至少一种织物护理成分。还公开了用于制备织物护理组合物的方法和所述织物护理组合物的用途。
Description
本公开涉及织物护理组合物,其任选地在可接受的介质中包含至少一种未固化的硅酮基聚合物和至少一种织物护理成分。还公开了制备织物护理组合物的方法和所述织物护理组合物的用途。
织物护理组合物包括用于护理织物和纤维的织物液体洗涤剂、固体洗涤剂、预清洗处理、织物柔软剂、颜色护理处理等,也就是说,适于施用到纤维、织物或纺织品(例如衣服)以便于改善织物或纺织品的外观或状况的任何产品。
各种硅酮材料可以用于织物护理应用。这些硅酮材料在它们的聚合结构方面、在它们的粘度或稠度方面以及在许多一般性能(如硬度、流动性、粘性、相容性)方面不同。它们可以适于在洗衣机中使用或适于在手清洗/漂洗/染色时使用,并且可以呈液体、糊状物、肥皂、粒状形式和/或可以存在于乳膏、凝胶、泡沫、喷雾或气雾剂中。它们可以呈单相体系、双相或交替多相体系;乳液(例如,水包油、油包水、水包硅酮、硅酮包水);多重乳液(例如,油包水包油、水包硅酮包多元醇、硅酮包水包油)的形式。
织物护理组合物可以用于洗衣过程中,以去除织物或纺织品,特别是衣服和家用织物上的污垢、污渍和异味。然而,洗衣过程涉及苛刻的条件,所述条件通常会导致对织物的损坏(如织物起球、收缩和颜色强度损失和/或颜色清晰度损失。织物软化组合物可以用于洗衣过程中,以防止所洗涤织物中的静电吸附(static cling),并且从而使织物更柔软。颜色护理添加剂是为了保持其颜色的完整性,例如织物的颜色的强度和色度。
使用包含硅酮基材料的织物护理组合物获得的益处可以包括织物软化和/或手感增强、织物保护、防污效果、服装形状保持和/或恢复和/或弹性、易于熨烫、颜色护理、抗磨损、抗起球、硅酮沉积、吸水性、减少和/或去除和/或防止皱纹、织物增强(或调理)或其任意组合。在染色过程中,益处包括色牢度、颜色吸收性、颜色持久性。
本公开涉及包含未固化的硅酮基聚合物的织物护理组合物。特别地,本公开涉及一种织物护理组合物,其任选地在织物护理可接受的介质中包含未固化的硅酮基聚合物;和至少一种织物护理成分;其中未固化的硅酮基聚合物是直链或支链的,具有下式
(R1O)3-x-Si(R2)x-(Z)d-(O)q-(R3 2SiO)N-(SiR3 2-Z)d-Si(R2)y(OR1)3-y
其中:
x是0(零)或1;
y是0、1、2或3,
N是从300至10,000;
d是0或1,q是0或1,并且d+q=1;R1、R2和R3各自独立地是含有1至10个碳的直链烷基;并且
每个Z独立地是
(i)具有从1至12个碳原子的直链或支链亚烷基,所述直链或支链亚烷基可以被一个或多个包含1至20个硅原子的直链或支链硅氧烷基间杂;或者
(ii)基于聚氧化烯基单元的有机链,所述有机链可以被一个或多个包含1至20个硅原子的直链或支链硅氧烷基间杂。
为了本发明的目的,织物护理组合物包括适于施用到纤维、织物或纺织品(例如衣服)的任何产品,以便于改善织物或纺织品的外观或状况。为了举例的目的,织物护理组合物的实例可以包括用于护理织物和纤维的液体洗涤剂、固体洗涤剂、预清洗处理、织物柔软剂、颜色护理处理等。织物护理成分是除了如上文所述的未固化的硅酮基聚合物之外的用于织物护理组合物中的成分,如将在下面进行讨论的。
聚二甲基硅氧烷的分子量与粘度的关系在科学文献中有所描述,例如,至少在Mills,E.,《欧洲聚合物杂志(European Polymer Journal)》,1969年,第5卷,第675-695页。本文中公布的公式可以用于近似计算聚合物的重均分子量(Mw),其中精确度为约10%。多分散指数(PI)是Mw/Mn之比。根据这种关系,可以计算出数均分子量(Mn)。
硅酮聚合物的Mn和Mw也可以由凝胶渗透色谱法(GPC)测定,其中精确度为约10至15%。这种技术是标准技术,并且产生用于Mw(重均)、Mn(数均)和多分散指数(PI)(其中PI=Mw/Mn)的值。
本申请中提供的Mn值已由GPC测定,并且表示所用聚合物的典型值。如果不是由GPC提供,Mn也可以根据基于所述聚合物的动态粘度的计算获得。
如上文所述的未固化的硅酮基聚合物是直链或支链的,具有下式
(R1O)3-x-Si(R2)x-(Z)d-(O)q-(R3 2SiO)N-(SiR3 2-Z)d-Si(R2)y(OR1)3-y
其中:
x是0(零)或1;
y是0、1、2或3,
N是从300至10,000;
d是0或1,q是0或1,并且d+q=1;R1、R2和R3各自独立地是含有1至10个碳的直链烷基;并且
每个Z独立地是
(i)具有从1至12个碳原子的直链或支链亚烷基,所述直链或支链亚烷基可以被一个或多个包含1至20个硅原子的直链或支链硅氧烷基间杂;或者
(ii)基于聚氧化烯基单元的有机链,所述有机链可以被一个或多个包含1至20个硅原子的直链或支链硅氧烷基间杂。
虽然x可以是0或1,但是x优选的是0。虽然y可以是0、1、2或3,但y优选的是0或3或0和3的混合。N是从300至10,000,替代性地为从300至1000,替代性地为从500至1000,替代性地为从600至900。
R1、R2和R3独立地是含有1至10个碳,替代性地从1至3个碳,替代性地甲基或乙基的直链烷基。在一个实施例中,R1=甲基或乙基,
R2=甲基和/或R3=甲基。本文包括具有不同值的x、y和N的聚合物的共混物,特别是其中x是0并且y是0和/或3的共混物。
在Z(以下分别称为Z(i)和Z(ii))的两种选择的情况下,聚合物链可以被一个或多个包含1至20个硅原子的直链或支链硅氧烷基间杂),如果存在的话,直链或支链硅氧烷基将由结构单元-[R5 aSiO(4-a)/2]-构成,其中a可以是从2至4,并且R5是饱和烷基、或苯基或类型–(CbH2b)e-Si-(R2)v(OR1)3-v的烷氧基甲硅烷基片段,其中b是从1至10,e是零或1,并且v是0、1或2。在此类单元中,通常a=2,得到硅氧烷单元的直链基团。然而,当在一个或多个单元中a是零或1时,就会发生分支。
在一个替代性方案中,Z(i)不含有直链或支链硅氧烷基,即Z(i)是具有从1至12个碳原子的直链或支链亚烷基,替代性地Z(i)是具有从1至6个碳原子的直链或支链亚烷基,Z(i)是具有从1至6个碳原子的直链亚烷基,替代性地Z(i)是具有从2至4个碳原子的直链或支链亚烷基。
当Z是Z(ii)时,Z(ii)可以是基于聚氧化烯基单元的有机链,此类聚氧化烯单元优选地包含由重复的氧化烯单元(由平均式(-CnH2n-O-)m示出的(-CnH2n-O-))构成的线性主要氧化烯聚合物,其中n是从2至(包括)4的整数,并且m是至少四的整数。每个聚氧化烯聚合物嵌段的数均分子量可以在约300至约10,000的范围内,但是数均Mn-分子量可以更高。而且,在整个聚氧化烯单体中,氧化烯单元不一定是相同的,但是从单元到单元可以不同。例如,聚氧化烯嵌段可以由氧化乙烯单元(-C2H4-O-);氧丙烯单元(-C3H6-O-);或氧丁烯单元,(-C4H8-O-);或其混合物构成。没有暗示聚乙二醇片段的特定触感和/或块状。
在一个替代性方案中,Z(ii)不含有直链或支链的硅氧烷基,即Z(ii)是由重复的氧化烯单元构成的直链主要氧化烯聚合物。在Z(ii)中,可以提供多个具有从2至6个碳原子的亚烷基中的一个。
相对于织物护理组合物的总重量,织物护理组合物中未固化的硅酮基聚合物的总水平按重量计可以在0.1%至50%变化,替代性地在0.1%至20%变化,替代性地在0.5%至10%变化,替代性地在0.5%至5%变化,替代性地在0.5%至2%变化。
如上文所述的未固化的硅酮基聚合物可以在增量剂的存在下被提供。当使用时,增量剂可以在聚合物制备之前、之后或期间添加,但是它不促进或参与聚合过程。为了易于操作,可以在聚合反应开始之前添加增量剂。提供如本文所述的增量剂以稀释聚合物并且防止其在加工期间(即进一步使用)变得太粘。
增量剂的实例包括
(i)含硅液体(如六甲基二硅氧烷、八甲基三硅氧烷)和其它短链直链硅氧烷(如八甲基三硅氧烷、十甲基四硅氧烷、十二甲基五硅氧烷、十四甲基六硅氧烷、十六烷基七硅氧烷、七甲基-3-{(三甲硅烷基)氧基)}三硅氧烷)、环硅氧烷(如六甲基环三硅氧烷、八甲基环四硅氧烷、十甲基环五硅氧烷、十二甲基环六硅氧烷、进一步的聚二有机硅氧烷(任选地包括芳基官能的硅氧烷,所述芳基官能的硅氧烷具有在25℃下使用布鲁克菲尔德锥板粘度计RV DIII、使用锥板CP-52、在5rpm下测量的从500至12,500mPa.s的粘度;
(ii)有机液体(如乙酸丁酯、烷烃、醇、酮、酯、醚、乙二醇、乙二醇醚、烃、氢氟碳化合物或能够稀释组合物而不会对组分材料中的任何一个产生不利影响的任何其它材料)。烃包括异十二烷、异十六烷、Isopar L(C11-C 13)、Isopar H(C11-C12)、氢化聚癸烯、矿物油,尤其是氢化矿物油或白油、液体聚异丁烯、异链烷烃油或凡士林。醚和酯包括新戊酸异癸酯、新戊二醇庚酸酯、乙二醇二硬脂酸酯、碳酸二辛酯、碳酸二乙基己酯、丙二醇正丁醚、3-乙氧基丙酸乙酯、丙二醇甲醚乙酸酯、十三烷醇新戊酸酯、丙二醇甲醚乙酸酯(PGMEA)、丙二醇甲醚(PGME)、辛基十二烷基新戊酸酯、己二酸二异丁酯、己二酸二异丙酯、丙二醇二辛酸酯/二癸酸酯和棕榈酸辛酯。附加的有机稀释剂包括脂肪、油、脂肪酸和脂肪醇。也可以使用稀释剂的混合物。
未固化的硅酮基聚合物与增量剂的重量比可以是例如100/0至10/90,替代性地70/30至20/80。
织物护理成分包括表面活性材料,如表面活性剂或洗涤剂或乳化剂、增稠剂、水相稳定剂、pH控制剂、防腐剂和杀生物剂、蛋白质或氨基酸以及它们的衍生物、颜料、着色剂、硅酮调理剂、阳离子调理剂、非离子调理剂、疏水调理剂、UV吸收剂、防晒剂、染料、芳香剂或香料、抗氧化剂、去污剂、氧化剂、还原剂、推进剂气体、分散助剂、无机盐、抗细菌剂、抗真菌剂、漂白剂、螯合剂、酶、稀释剂及其混合物。
表面活性材料的实例可以是阴离子的、阳离子的或非离子的,并且包括有机改性的硅酮(如聚二甲基硅酮共聚醇);甘油的氧乙烯化和/或氧丙基化的醚;脂肪醇的氧乙烯化和/或氧丙基化的醚(如ceteareth-30、C12-15 pareth-7);聚乙二醇的脂肪酸酯(如PEG-50硬脂酸酯、PEG-40单硬脂酸酯);糖酯和醚(如蔗糖硬脂酸酯、蔗糖椰油酸酯和山梨醇硬脂酸酯及其混合物);磷酸酯及其盐(如DEA oleth-10磷酸盐);磺基琥珀酸盐(如PEG-5月桂醇柠檬酸酯磺基琥珀酸酯二钠和蓖麻醇酸酰胺MEA磺基琥珀酸酯二钠;烷基醚硫酸盐(如月桂基乙醚硫酸钠);羟乙磺酸盐;甜菜碱衍生物;及其混合物。
非离子表面活性剂的实例包括聚氧乙烯烷基醚、聚氧乙烯脂肪醇、聚氧乙烯烷基酚醚、聚氧乙烯月桂醚(如聚氧乙烯(23)月桂醚、聚氧乙烯(4)月桂醚)、直链烷氧基化醇(包括伯醇烷氧基化物)、直链仲醇烷氧基化物、烷基酚烷氧基化物、烯烃烷氧基化物、支链烷氧基化物,具体的实例包括乙氧基化醇,如乙氧基化三甲基壬醇、C12-C14仲醇乙氧基化物、乙氧基化C10-Guerbet醇、乙氧基化异-C13醇;聚(氧乙烯)-聚(氧丙烯)-聚(氧乙烯)三嵌段共聚物(也称为泊洛沙姆);四官能聚(氧乙烯)-聚(氧丙烯)嵌段共聚物(衍生自环氧丙烷和环氧乙烷向乙二胺(也称为泊洛沙胺)、硅酮聚醚的顺序添加)及其混合物。非离子表面活性剂的进一步的实例包括聚氧乙烯脱水山梨醇单油酸酯、聚氧乙烯烷基酯、聚氧乙烯脱水山梨醇烷基酯、聚乙二醇、聚丙二醇、二甘醇、聚氧化烯取代的硅酮(rake或ABn型)、硅酮烷醇酰胺、硅酮酯、硅酮糖苷以及其混合物。
非离子表面活性剂的进一步的实例包括聚二甲基硅酮共聚醇、多元醇的脂肪酸酯,例如山梨醇或甘油基单-、二-、三-或倍半油酸酯或硬脂酸酯、甘油基或聚乙二醇月桂酸酯;聚乙二醇的脂肪酸酯(聚乙二醇单硬脂酸酯或单月桂酸酯);山梨醇的聚氧乙烯化脂肪酸酯(硬脂酸酯或油酸酯);聚氧乙烯化烷基(月桂基、鲸蜡基、硬脂基或辛基)醚,环氧乙烷与长链脂肪醇或脂肪酸(如C12-16)醇的缩合物、环氧乙烷与胺或酰胺的缩合物、环氧乙烷和环氧丙烷的缩合产物,甘油、蔗糖、山梨醇、脂肪酸烷基醇酰胺的酯、蔗糖酯、氟表面活性剂、脂肪胺氧化物及其混合物。
阳离子表面活性剂的实例包括烷基胺盐、季铵盐、锍盐和鏻盐。
阴离子表面活性剂的实例包括羧酸盐(2-(2-羟烷基氧基)乙酸钠))、氨基酸衍生物(N-酰基谷氨酸盐、N-酰基乙酸盐或酰基肌氨酸盐)、烷基硫酸盐、烷基醚硫酸盐和它们的氧乙烯化衍生物、磺酸盐、羟乙磺酸盐以及N-酰基乙硫代磺酸盐、牛磺酸盐和N-酰基N-甲基牛磺酸盐、磺基磺基琥珀酸酯、烷基硫酸磺基乙酸酯、磷酸酯和烷基磷酸酯、多肽、烷基聚糖苷的阴离子衍生物(酰基-D-半乳糖苷尿酸酯)和脂肪酸皂及其混合物。高级脂肪酸的碱金属盐、胺盐或铵盐、烷芳基磺酸盐(如十二烷基苯磺酸纳、长链脂肪醇磺基硫酸酯、烯烃磺基硫酸酯和烯烃磺基磺酸盐、硫酸化单甘油酯、硫酸酯、磺化乙氧基醇、磺基琥珀酸酯、烷基磺酸酯、磷酸酯、烷基羟乙基磺酸酯、烷基牛磺酸酯、烷基肌氨酸酯及其混合物。
两性或两性离子表面活性剂包括甜菜碱、N-烷基酰胺甜菜碱及其衍生物、蛋白质及其衍生物、甘氨酸衍生物、磺基甜菜碱、烷基多氨基羧酸盐和烷基两性乙酸盐、咪唑啉化合物、烷基氨基酸盐及其混合物。
增稠剂的实例包括丙烯酰胺聚合物和共聚物、丙烯酸酯共聚物及其盐(如聚丙烯酸钠)、黄原胶和衍生物、纤维素胶和纤维素衍生物(如甲基纤维素、甲基羟丙基纤维素、羟丙基纤维素、聚丙烯羟乙基纤维素)、淀粉和淀粉衍生物(如羟乙基直链淀粉和淀粉酶)、聚氧化乙烯、卡波姆、锂蒙脱石和锂蒙脱石衍生物、海藻酸钠、阿拉伯胶、桂皮胶、瓜尔胶和瓜尔胶衍生物、椰油酰胺衍生物、烷基醇、明胶、PEG衍生物、糖类(如果糖、葡萄糖)和糖类衍生物(如聚乙二醇-120甲基葡萄糖二酸酯)及其混合物。
水相稳定剂的实例包括电解质(例如,碱金属盐和碱土金属盐,尤其是钠、钾、钙和镁的氯化物、硼酸盐、柠檬酸盐和硫酸盐,以及水合氯化铝和聚电解质,尤其是透明质酸和透明质酸钠)、多元醇(甘油、丙二醇、丁二醇和山梨醇)、醇(如乙醇和水胶体)及其混合物。
pH控制剂的实例包括任何水溶性酸(如羧酸或无机酸(如盐酸、硫酸和磷酸)、一元羧酸(如乙酸和乳酸)、以及多元羧酸(如琥珀酸、己二酸、柠檬酸及其混合物)。
防腐剂和杀生物剂的实例包括对羟基苯甲酸酯衍生物、乙内酰脲衍生物、氯己定及其衍生物、咪唑烷基脲、苯氧乙醇、银衍生物、水杨酸盐衍生物、三氯生、环吡酮胺、己脒定、氧喹啉以及其衍生物、PVP-碘、锌盐和衍生物(如吡啶硫酮锌)、戊二醛、甲醛、2-溴-2-硝基丙烷-1,3-二醇、5-氯-2-甲基-4-异噻唑啉-3-酮、2-甲基-4-异噻唑啉-3-酮及其混合物。
蛋白质或氨基酸以及它们的衍生物的实例包括从小麦、大豆、大米、玉米、角蛋白、弹性蛋白或蚕丝提取的那些。蛋白质可以呈水解形式,并且它们也可以是季铵化的,如水解弹性蛋白、水解小麦粉、水解蚕丝。蛋白质的实例包括酶,如水解酶、角质酶、氧化酶、转移酶、还原酶、半纤维素酶、酯酶、异构酶、果胶酶、乳糖酶、过氧化物酶、漆酶、过氧化氢酶及其混合物。水解酶的实例包括蛋白酶(细菌、真菌、酸、中性或碱性)、淀粉酶(α或β)、脂肪酶、甘露聚糖酶、纤维素酶、胶原酶、溶菌酶、超氧化物歧化酶、过氧化氢酶及其混合物。
色素或着色剂的实例包括表面处理或未处理的氧化铁、表面处理或未处理的二氧化钛、表面处理或未处理的云母、氧化银、硅酸盐、氧化铬、类胡萝卜素、炭黑、群青、叶绿素衍生物和黄禇石。有机颜料的实例包括芳香烃类型,所述芳香烃类型包括偶氮、靛蓝、三苯基甲烷、蒽醌和黄嘌呤染料,所述黄嘌呤染料被称为D&C和FD&C蓝、棕色、绿色、橙色、红色、黄色等及其混合物。表面处理包括基于卵磷脂、硅酮、硅烷、氟化合物的那些处理。
硅酮调理剂的实例包括硅酮油(如聚二甲基硅酮);硅酮胶(如聚二甲基硅氧醇);硅酮树脂(如三甲基硅氧基硅酸酯、聚丙烯倍半硅酮);硅酮弹性体;烷基甲基硅氧烷;有机改性硅酮油(如氨基封端聚二甲基硅酮、氨基丙基苯基聚三甲基硅酮、苯基聚三甲基硅酮、三甲基五苯基三硅氧烷、硅酮季铵盐-16/缩水甘油氧基聚二甲基硅酮交联聚合物、硅酮季铵盐-16);糖类官能硅氧烷;甲醇官能硅氧烷;硅酮聚醚;硅氧烷共聚物(二乙烯基聚二甲基硅酮/聚二甲基硅酮共聚物);丙烯酸酯或丙烯酸官能硅氧烷;及其混合物或乳液。
阳离子调理剂的实例包括瓜尔胶衍生物(如瓜尔胶的羟丙基三甲基铵衍生物);阳离子纤维素衍生物、阳离子淀粉衍生物;纤维素醚的季氮衍生物;季铵化三乙醇胺酯(酯季铵盐);二甲基二烯丙基氯化铵的均聚物;丙烯酰胺和二甲基二烯丙基氯化铵的共聚物;衍生自丙烯酸或甲基丙烯酸的均聚物或共聚物,所述均聚物或共聚物含有通过酯或酰胺键连接到聚合物上的阳离子氮官能团;与脂肪烷基二甲基铵取代的环氧化物反应的羟乙基纤维素的聚合季铵盐;N,N'-二(2,3-环氧丙基)-哌嗪或哌嗪-双-丙烯酰胺和哌嗪的缩聚产物;和具有季氮官能团的乙烯基吡咯烷酮和丙烯酸酯的共聚物。特定材料包括各种聚季铵盐:聚季铵盐-7、聚季铵盐-8、聚季铵盐-10、聚季铵盐-11和聚季铵盐-23。其它类别的调理剂包括阳离子表面活性剂(如十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十八烷基三甲基氯化铵及其混合物)。在一些情况下,阳离子调理剂也是疏水改性的,如疏水改性的季铵化羟乙基纤维素聚合物;阳离子疏水改性的半乳甘露聚糖醚;及其混合物。
非离子调理剂的实例包括多元醇的脂肪酸偏酯或其酸酐,其中酯的多元醇部分可以是乙二醇、甘油、聚(例如二-、三-、四-、五-、和/或六-)甘油、木糖醇、蔗糖、赤藓糖醇、季戊四醇、山梨醇或脱水山梨醇,并且其中酯的脂肪酸部分衍生自具有从约12至约30个碳原子的脂肪酸,如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸和二十二烷酸。
疏水调理剂的实例包括瓜尔胶衍生物;半乳甘露聚糖胶衍生物;纤维素衍生物;及其混合物。
织物软化化合物的实例包括阳离子和非离子化合物。织物软化化合物的进一步的实例包括聚烷基季铵盐,如二硬脂基二甲基氯化铵、二(硬化牛油烷基)二甲基氯化铵、二棕榈酰羟乙基甲基氯化铵,硬脂酰苄基二甲基氯化铵、N,N-二(塔罗酰氧基乙基)-N-甲基、N-(2-羟乙基)氯化铵;具有一个或多个完全饱和的烷基链的酯连接的季铵材料,及其混合物。
UV吸收剂和防晒剂包括吸收约290至320纳米(UV-B区)之间的紫外线的那些和吸收320至400纳米(UV-A区)范围内的紫外线的那些。
防晒剂的一些实例是氨基苯甲酸、西诺沙酯、甲氧基肉桂酸二乙醇胺、二甘醇三油酸酯、二氧苯并酮、4-[双(羟基丙基)]氨基苯甲酸乙酯、氨基苯甲酸甘油酯、高水杨酸酯、具有二羟基丙酮的指甲花醌、邻氨基苯甲酸薄荷酯、奥克立林、甲氧基肉桂酸乙基己酯、水杨酸辛酯、氧苯酮、二甲基氨基苯甲酸、苯并咪唑磺基硫磺酸、红凡士林、磺异苯酮、二氧化钛、水杨酸三乙醇胺及其混合物。
UV吸收剂的一些实例是醋氨沙洛、尿囊素PABA、苯亚甲基苯酞、二苯甲酮、二苯甲酮1-12、3-亚苄基樟脑、亚苄基樟脑水解的胶原磺酰胺、亚苄基樟脑磺酸、水杨酸苄酯、波尼酮、布米三唑、丁基甲氧基二苯甲酰甲烷、丁基PABA、二氧化铈/二氧化硅、二氧化铈/二氧化硅滑石、西诺沙酯、甲氧基肉桂酸DEA盐、二苯并噁唑萘、二叔丁基羟基苯亚甲基樟脑、棓酰棓酸三油酸酯、二异丙基肉桂酸甲酯、二甲基PABA乙基鲸蜡硬脂基二甲基铵甲苯磺酸盐、二辛基丁酰胺基三嗪酮、二苯基甲酯基乙酰氧基萘并吡喃、双乙基苯基亚氨基三嗪二苯乙烯磺酸钠、二苯乙烯基联苯三氨基三嗪二苯乙烯磺酸钠、二苯乙烯基联苯二磺酸钠、甲酚曲唑、甲酚曲唑三硅氧烷、二羟丙基PABA乙酯、二异丙基肉桂酸乙酯、甲氧基肉桂酸乙酯、PABA乙酯、尿刊酸乙酯、etrocrylene阿魏酸、辛酸二甲氧基肉桂酸甘油酯、甘油对氨基苯甲酸酯(glyceryl PABA)、乙二醇水杨酸酯、胡莫柳酯、对甲氧基肉桂酸异戊酯、异丙苄醇水杨酸酯、异丙基二苯甲酰甲烷、甲氧基肉桂酸异丙酯、薄荷醇邻氨基苯甲酸酯、水杨酸薄荷酯、4-甲基苯亚甲基、樟脑、奥克立林、奥克三唑、辛基二甲基对氨基苯甲酸(octyl dimethylPABA)、甲氧基肉桂酸乙基己酯、丁基辛醇水杨酸酯、乙基己基三嗪酮、PABA、PABA-25PABA、二甲基PABA戊酯、苯基苯并咪唑磺酸、聚丙烯酰胺甲基亚苄基樟脑、甲氧基肉桂酸钾、苯基苯并咪唑磺酸钾、红凡士林、苯并咪唑磺酸钠、尿刊酸钠、苯基苯并咪唑磺酸TEA盐、水杨酸TEA盐、对苯二亚甲基二磷磺酸、二氧化钛、三PABA泛醇、尿刊酸、VA/巴豆酸酯/甲基丙烯酰氧二苯酮-1共聚物及其混合物。
染料通常可以被描述为对被施用的基质具有亲和力的有色物质。染料的实例包括阴离子染料(例如直接染料或酸性染料)、活性染料、非离子染料(例如分散染料)或颜料染料(例如还原染料)。直接染料通常是大的平面的芳香体系,通常用于给棉花染色,例如直接红色80或直接黑色56。活性染料(例如雷玛唑亮蓝和普施安蓝3G)的尺寸是中等的、通常用于具有与纤维反应的端基的棉花和羊毛,所述端基与织物的原子形成共价键。分散染料是用于聚酯的致密的芳香族分子、或尼龙上的深色度,并且包括分散蓝11。还原染料用于棉花,主要是印花和斜纹棉布。水溶性还原形式被原位氧化形成不溶性染料。实例包括还原蓝4。染料的进一步的实例包括可溶性靛蓝、散沫花提取物、1-乙酰氧基-2-甲基萘;5-氨基-4-氯-o-甲酚;5-氨基-2,6-二甲氧基-3-羟基-吡啶;3-氨基-2,6-二甲基苯酚;2-氨基-5-乙基苯酚盐酸盐;5-氨基-4-氟-2-甲基苯酚硫酸酯;4-氨基-2-硝基苯酚;4-氨基-3-硝基苯酚;2-氨基-4-硝基苯酚硫酸酯;间氨基苯酚盐酸盐;对氨基苯酚盐酸盐;间氨基苯酚;邻氨基苯酚;4,6-双(2-羟乙氧基)-间苯二胺盐酸盐;2-氯-5-硝基-N-羟乙基-对苯二胺;2-氯-对苯二胺;3,4-二氨基苯甲酸;4,5-二氨基-1-((4-氯苯基)甲基)-1H-吡唑-硫酸酯;2,3-二氨基二氢吡唑吡唑啉酮甲基硫酸盐;2,6-二氨基吡啶;2,6-二氨基-3-((吡啶-3-基)偶氮)吡啶;二羟基吲哚;二羟基二氢吲哚;N,N-二甲基-对苯二胺;2,6-二甲基-对苯二胺;N,N-二甲基-对苯二胺硫酸盐;直接染料;4-乙氧基-间苯二胺硫酸盐;3-乙基氨基-对甲酚硫酸盐;N-乙基-3-硝基PABA;葡糖酰胺丙基氨丙基聚二甲基硅酮;巴西苏木木材提取物;HC染料;羟乙基-3,4-亚甲二氧基苯胺盐酸盐;羟乙基-2-硝基-对甲苯胺;羟乙基-对苯二胺硫酸盐;2-羟乙基苦氨酸;羟吡啶酮;羟基琥珀酰亚胺基C21-22酸异烷基酯;靛红;欧洲菘蓝叶粉;2-甲氧基甲基-对苯二胺硫酸盐;2-甲氧基-对苯二胺硫酸盐;6-甲氧基-2,3-吡啶二胺盐酸盐;4-甲基苄基4,5-二氨基吡唑硫酸盐;2,2'-亚甲基双4-氨基苯酚;2,2'-亚甲基双-4-氨基苯酚盐酸盐;3,4-亚甲二氧基苯胺;p对苯二胺硫酸盐;苯基甲基吡唑啉酮;N-苯基-对苯二胺盐酸盐;颜料蓝15:1;颜料紫23;颜料黄13;邻苯二酚;邻苯三酚;间苯二酚;苦氨酸钠;对氨基苯磺酸钠;溶剂黄85;溶剂黄172;四氨基嘧啶硫酸盐;四溴酚蓝;2,5,6-三氨基-4-嘧啶醇硫酸盐;1,2,4-三羟基苯;及其混合物。
芳香剂或香料的实例包括己基肉桂醛;茴香醛;2-n-正己基-3-氧代-环戊烷羧酸甲酯;丙位十二内酯;醋酸苯仲乙(基)酯;4-乙酰基-6-叔丁基-1,1-二甲基茚满;广藿香;乳香树脂;劳丹脂;香根草油;苦配巴香脂;冷杉香脂;4-(4-羟基-4-甲基戊基)-3-环己烯-1-甲醛;邻氨基苯甲酸甲酯;香叶醇;乙酸香叶酯;芳樟醇;香茅醇;乙酸松油酯;水杨酸苄酯;2-甲基-3-(对异丙基苯基)-丙醛;异丁酸苯氧乙基酯;雪松醇缩醛;对甲氧苯甲醛;麝香芳香剂;大环酮;大环内酯麝香芳香剂;十三碳二酸乙二醇二酯;及其混合物。
抗氧化剂的实例是乙酰半胱氨酸、熊果苷、抗坏血酸、抗坏血酸多肽、抗坏血酸二棕榈酸酯、抗坏血酸甲基硅烷醇果胶酸酯、抗坏血酸棕榈酸酯、抗坏血酸硬脂酸酯、BHA、对羟基苯甲醚、BHT、叔丁基氢醌、咖啡酸、茶油、壳聚糖抗坏血酸酯、壳聚糖乙醇酸酯、壳聚糖水杨酸酯、绿原酸、半胱氨酸、半胱氨酸盐酸盐、柠檬酸、癸基巯基甲基咪唑、异抗坏血酸、二戊基氢醌、二叔丁基氢醌、二鲸蜡醇硫代二丙酸酯、二环戊二烯/叔丁基甲酚共聚物、棓酰棓酸三油酸酯、二月桂醇硫代二丙酸酯、二肉豆蔻醇硫代二丙酸酯、二油基生育酚甲基硅烷醇、异栎素、地奥司明、抗坏血酸硫酸二钠、芸香亭基硫酸二钠、二硬脂醇硫代二丙酸酯、双十三醇硫代二丙酸酯、十二醇棓酸酯、阿魏酸乙酯、阿魏酸、氢醌、盐酸羟胺、硫酸羟胺、巯基乙酸异辛酯、柠檬酸异丙酯、曲酸、羟基积雪草苷、抗坏血酸镁、抗坏血酸磷酸镁、褪黑激素、甲氧基-PEG-7芸香苷琥珀酸酯、亚甲基二叔丁基甲酚、甲基硅烷醇抗坏血酸、去甲羟基愈创木酸、没食子酸辛酯、苯基巯基乙酸、间苯三酚、抗坏血酸磷酸酯钾、亚硫基二乙酰胺、亚硫酸氢钾、没食子酸丙酯、迷迭香酸、芸香苷、抗坏血酸钠、抗坏血酸/胆甾醇磷酸酯钠、亚硫酸氢钠、异抗坏血酸钠、焦亚硫酸钠、亚硫酸钠、巯基乙酸钠、山梨醇缩糠醛、茶树(Melaleucaaftemifolia)油、二乙烯三胺五乙酸、生育酚乙酸酯、四己基癸醇抗坏血酸酯、四氢二阿魏酰甲烷、生育酚亚油酸酯/油酸酯、硫二甘醇、生育酚琥珀酸酯、亚硫基二乙酸、巯基乙酸、硫羟乳酸、硫代水杨酸、硫代牛磺酸、视黄醇、生育酚聚醚-5、生育酚聚醚-10、生育酚聚醚-12、生育酚聚醚-18、生育酚聚醚-50、生育酚、托可索仑、生育酚亚油酸酯、生育酚烟酸酯、托可醌、邻甲苯基双胍、三(壬基苯基)亚磷酸酯、泛醌、二丁基二硫代氨基甲酸锌及其混合物。
去污剂的实例包括对苯二甲酸酯和聚环氧乙烷或聚环氧丙烷等的共聚物嵌段。
氧化剂的实例是过硫酸铵、过氧化钙、过氧化氢、过氧化镁、过氧化三聚氰胺、溴酸钾、过一硫酸氢钾复合盐、氯酸钾、过硫酸钾、溴酸钠、过碳酸钠、氯酸钠、碘酸钠、过硼酸钠、过硫酸钠、二氧化锶、过氧化锶、过氧化尿素、过氧化锌及其混合物。
还原剂的实例是亚硫酸氢铵、亚硫酸氢铵、巯基乙酸铵、硫代乳酸铵、盐酸半胱氨酸、半胱氨酸、盐酸乙醇胺巯基乙酸、谷胱甘肽、巯基乙酸甘油酯、巯基丙酸甘油酯、氢醌、对羟基苯甲醚、巯基乙酸异辛酯、巯基乙酸镁、巯基丙酸、偏亚硫酸氢钾、亚硫酸氢钾、巯基乙酸钾、亚硫酸氢钠、亚硫酸氢钠、羟基甲烷磺酸钠、偏亚硫酸氢钠、亚硫酸钠、巯基乙酸钠、巯基乙酸锶、超氧化物歧化酶、硫代甘油、巯基乙酸、硫代乳酸、硫代水杨酸、甲醛磺酸锌及其混合物。
推进剂气体的实例包括二氧化碳、氮气、一氧化二氮、挥发性碳氢化合物(如丁烷、异丁烷或丙烷)、以及氯化或氟化碳氢化合物(如二氯二氟甲烷和二氯四氟乙烷或二甲醚);及其混合物。分散助剂可以用于促进组合物在漂洗水中的分散。
分散助剂的实例包括选自由单烷基阳离子季铵化合物、单烷基氧化胺及其混合物组成的群组中的那些。
无机盐的实例包括本领域已知的用于添加到织物柔软剂组合物中的任何无机盐。合适的无机盐的非限制性实例包括:MgI2、MgBr2、MgCl2、Mg(NO3)2、Mg3(PO4)2、Mg2P207、MgS04、硅酸镁、NaI、NaBr、NaCl、NaF、Na3(PO4)、NaSO3、Na2SO4、Na2SO3、NaNO3、NaIO3、Na4P2O7、硅酸钠、偏硅酸钠、四氯铝酸钠、三聚磷酸钠(STPP)、Na2Si307、锆酸钠、CaF2、CaCl2、CaBr2、CaI2、CaSO4、Ca(NO3)2、KI、KBr、KCl、KF、KNO3、KIO3、K2SO4、K2SO3、K3(PO4)、K4(P2O7)、焦亚硫酸钾、焦亚硫酸钾、LiI、LiBr、LiCl、LiF、LiNO3、ALF3、AlCl3、AlBr3、Al2(SO4)3、Al(PO4)、Al(NO3)3、硅酸铝;包括这些盐的水合物、以及包括这些盐或具有混合阳离子的盐(例如,铝矾酸钾AlK(S04)2)以及具有混合阴离子的盐(例如,四氯铝酸钾和四氟铝酸钠)的组合。结合有来自周期表中的IIIa、IVa、Va、VIa、VIIa、VIII、Ib和IIb族的原子序数>13的阳离子的盐也可用于降低稀释。具有来自Ia或IIa族的原子序数>20的阳离子的盐以及具有来自lactinide系或锕系的阳离子的盐及其混合可用于降低稀释粘度。
抗细菌剂的实例包括氯己二烯葡萄糖酸盐、醇、苯扎氯铵、苯扎氯铵、过氧化氢、甲基苯扎氯铵、苯酚、泊洛沙姆188、聚维酮碘及其混合物。
抗真菌剂的实例包括硝酸咪康唑、十一碳烯酸钙、十一碳烯酸、十一碳烯酸锌及其混合物。
漂白剂的实例包括氯漂白剂,如氯、二氧化氯、次氯酸钠、次氯酸钙、氯酸钠;过氧化物漂白剂,如过氧化氢、过碳酸钠、过硼酸钠;还原漂白剂,如连二亚硫酸钠、硼氢化钠;臭氧;及其混合物。
螯合剂(也是络合剂)的实例包括膦酸盐;氨基羧酸化合物(如乙二胺四乙酸(EDTA);N-羟基乙二胺三乙酸;腈三乙酸(NTA);和二乙烯三胺五乙酸(DEPTA));有机氨基膦酸化合物(如乙二胺四(亚甲基膦酸);1-羟基乙烷1,1-二膦酸(HEDP);和氨基三(亚甲基膦酸));及其混合物。
酶的实例包括脂肪酶、纤维素酶、蛋白酶、淀粉酶、甘露聚糖酶、果胶酸裂解酶及其混合物。
稀释剂通常是必要的,以充分降低制剂的粘度,以供应用。织物护理组合物的稀释剂可以是如前所讨论的关于聚合物的增量剂的附加或与所述增量剂相同。实际上,任选地与聚合物组合提供的增量剂可以在最终的织物护理组合物中作为稀释剂型织物护理成分起作用。典型地,任选的稀释织物护理成分可以从此处上文的替代性增量剂的列表中选择。
可以用于织物护理组合物的附加成分包括消泡剂化合物、助洗剂、研磨剂、织物柔软剂、荧光增白剂、土壤悬浮剂、分散剂、染料转移抑制剂、染料螯合剂、固色剂和抗再沉积剂。
相对于织物护理组合物的总重量,织物护理组合物中存在的织物护理成分按重量计累积地以0.01%至99.99%的水平存在。
如上文所述的织物护理可接受的介质包括但不限于水、溶剂、或其混合物和乳液。溶剂包括高度溶于水的低分子量有机溶剂,例如C1至C4一元醇、C2至C5多元醇,包括亚烷基二醇、聚亚烷基二醇、亚烷基碳酸酯及其混合物。典型的溶剂包括乙醇、丙醇、异丙醇、正丁醇、叔丁醇、乙二醇、二甘醇、丙二醇、二丙二醇、甘油、碳酸丙烯酯及其混合物。织物护理可接受的载体的其它合适的实例包括具有低于10mPa.s、替代性地低于5mPa.s、替代性地低于3mPa.s的粘度的短链聚硅氧烷、包含3至12个硅原子、替代性包含4至7个硅原子、替代性地4至6个硅原子的环状聚硅氧烷,或者其共混物、有机矿物油、有机聚酯和上述项中的任何一项的合适共混物。这些材料的粘度可以使用本领域已知的任何方法在25℃下测量,例如配有适用于低粘度的锥板主轴的Wells/BrookfieldTM锥板装置DV3TLVCP或DV2TLVCP或DV1MLVCP,例如CPA-40Z、CPA-41Z、CPA-42Z。详情和范围可从www.brookfieldengineering.com获得。
本文描述的未固化的硅酮基聚合物可以以任何可接受的形式引入到也如本文所述的织物护理组合物中。例如,它可以被提供为纯净的(未稀释的)、被提供为呈稀释形式(例如具有如先前讨论的增量剂)、或者呈乳液形式,它可以通过任何已知的方法制备,例如通过如下面讨论的方法。
包含如上文所述的未固化的硅酮基聚合物的织物护理组合物可以通过多种方法制备。例如,织物护理组合物的成分可以仅仅混合在一起。替代性地,在添加一种或多种织物护理成分之前,未固化的硅酮基聚合物可以首先与可接受的介质(例如,水、溶剂和/或一种或多种稀释剂)混合,以形成溶液、分散体或乳液。在进一步的替代性方案中,可以将如上文所述的未固化的硅酮基聚合物引入包含一种或多种织物护理成分和可接受介质(例如水和/或一种或多种稀释剂)的预成型织物护理组合物中,同时将所得的组合物混合以形成溶液、分散体或乳液。在进一步的替代性方案中,未固化的硅酮基聚合物可以首先与可接受的介质(例如水、溶剂和/或一种或多种稀释剂)混合以形成溶液、分散体或乳液,所述溶液、分散体或乳液可以随后与由一种或多种织物护理成分和可接受的介质(例如水和/或一种或多种溶剂或稀释剂)的溶液、分散体或乳液混合。
在一些情况下,在织物护理可接受的介质中,未固化的硅酮基聚合物与选自阳离子调理剂、疏水调理剂或其混合物的织物护理成分结合使用。
本文描述的未固化的硅酮基聚合物可以以任何可接受的形式引入到也如本文所述的织物护理组合物中。例如,它可以被提供为纯净的(未稀释的)、被提供为呈稀释形式(例如具有如先前讨论的增量剂)、或者呈乳液形式,它可以通过任何已知的方法制备,例如通过如下面讨论的方法。
一种用于在水中制备未固化的硅酮基聚合物的乳液的方法包含以下步骤:
I)形成混合物,所述混合物包含:
A)100重量份如上文所述的未固化的硅酮基聚合物,
B)0.1至50重量份的表面活性剂,
II)将足量的水混入到来自步骤1)的混合物中以形成具有连续相和分散相的乳液,
III)任选地,进一步剪切混合乳液和/或稀释具有连续相的乳液。
对于每100重量份未固化的硅酮基聚合物,在步骤(I)中添加的表面活性剂(如上所述,其是合适的织物护理成分)的量应为0.1至50重量份,替代性地为1至50重量份,替代性地为2至20重量份。
步骤(I)中的混合可以通过本领域中任何合适的方法来完成,以实现乳液的混合。混合可以作为分批、半连续或连续过程进行。混合可以例如使用具有中/低剪切的分批混合装备来进行,所述装备包括易拉罐混合器、双行星混合器、锥形螺杆混合器、带式搅拌器、双臂或西格马型叶片混合器;具有高剪切和高速分散器的分批装备包括由Charles Ross&Sons(纽约)、Hockmeyer Equipment Corp.(新泽西)制造的那些装备;具有高剪切作用的分批装备包括Banbury型(新泽西州的CW Brabender Instruments Inc.公司)和Henschel型(德克萨斯州的Henchel mixers America公司);基于离心力的高剪切混合装备,例如Speed(德国的Hauschild&Co KG公司)。连续混合器/混合机的说明性实例包括单螺杆挤出机、双螺杆和多螺杆挤出机、同向旋转挤出机,如由Krupp Werner&Pfleiderer Corp公司(新泽西州拉姆齐)和Leistritz(新泽西州)制造的那些挤出机;双螺杆反向旋转挤出机、两级挤出机、双转子连续混合器、动态或静态混合器或该装备的组合。
进行步骤(I)的混合的温度和压力并不重要,但通常在环境温度(20至25℃)和压力下进行。通常,在混合过程期间,由于剪切此类高粘度材料时相关联的机械能,混合物的温度将增加。
过程的步骤(II)涉及将水混入到步骤(I)的产物中以形成乳液。典型地,将每100重量份步骤(I)的产物引入5至2000重量份水以形成乳液。利用附加混合以合适的速率将水添加到步骤(I)的产物中,以便与步骤(I)的产物形成乳液。虽然水的这个量可以根据表面活性剂的选择而变化,但通常水的量为每100重量份步骤(I)的产品从0.1至2000份,替代性地每100重量份步骤1的产品从5至500份,或替代性地每100重量份步骤(I)的产品从5至100份。
向步骤(I)的产物中添加水可以以增量部分进行,其中每个增量部分包含少于30重量%的来自步骤(I)的混合物,并且在分散前一增量部分的水之后,将每个增量部分的水连续添加到前一增量部分中,其中添加足够的增量部分的水以与未固化的硅酮基聚合物形成乳液。
步骤(II)中的混合可以通过本领域已知实现高粘度材料混合的任何方法来完成。混合可以作为分批、半连续或连续过程进行。如针对步骤(I)描述的混合方法中的任何一个可以用于实现步骤(II)中的混合。替代性地,步骤(II)中的混合也可以通过本领域已知提供高剪切混合来实现乳液形成的那些技术进行。此类高剪切混合技术的代表包括:均化器、超声振荡器和其它类似的剪切装置。
任选地,可以根据步骤(III)进一步剪切步骤(II)中形成的乳液,以减小粒径和/或提高长期储存稳定性。剪切可以通过以上讨论的混合技术中的任何一个进行。在某些情况下,可能需要在较低的压力或真空下运行步骤(I)至(III)中的一个或几个。
替代性地,未固化的硅酮基聚合物在水中的乳液可以通过以下方法制备:(I)形成混合物,所述混合物包含:
A)100重量份如上文所述的未固化的硅酮基聚合物;
B)任选的稀释剂;
C)0.1至50重量份的表面活性剂,
(II)将足量的水与来自步骤(I)的产物混合,以形成具有连续相和分散相的乳液,
(III)任选地,进一步剪切混合乳液和/或用连续相稀释乳液。
在此替代性方法中,混合和添加条件保持为如针对第一过程所公开的那样。反应条件也如上所讨论。稀释剂可以是如上文所述的稀释剂,但也可以是如上文所述的增量剂。
以上两种方法提供了用于制备织物护理组合物的方法,其中表面活性剂和稀释剂(当存在时)是织物护理成分。然而,以上也可以是部分制备步骤,作为将未固化的硅酮基聚合物引入到组合物的其它成分中的手段。
织物护理组合物可以通过包含以下步骤的方法制备
i.混合如上文所述未固化的硅酮基聚合物
ii.和至少一种织物护理成分,
任选地在可接受的介质的存在下。
未固化的硅酮基聚合物可以以任何合适的形式提供,即它可以呈“纯净”或未稀释形式、呈扩展形式(即在如上所述的具有增量剂的混合物中)或在织物护理可接受的介质的存在下,例如在乳液中。当将上述成分混合在一起时,织物护理组合物可以乳液的形式制备。
本公开的乳液可以是油/水乳液、水/油乳液、多相或三相乳液。可以使用上述混合设备制备乳液。
在一个实施例中,本公开的乳液是油/水乳液。本发明的油/水乳液的特征在于连续水相中分散的(油)相的平均体积粒径。粒径可以通过乳液的激光衍射来确定。合适的激光衍射技术在本领域中是熟知的。粒径从粒径分布(PSD)获得。PSD可以基于体积、表面、长度来测定。体积粒径等于具有与给定粒子相同的体积的球体的直径。术语Dv代表分散的颗粒的平均体积粒径。Dv 0.5是以体积测量的对应于累积颗粒总数的50%的粒径。换句话说,如果Dv 0.5=10μm,则50%的颗粒具有低于10μm的平均体积粒径,并且50%的颗粒具有高于10μm的体积平均粒径。除非另有说明,否则所有平均体积粒径均使用Dv 0.5来计算。
油/水乳液中的分散的硅氧烷颗粒的平均体积粒径可以在0.1μm和150μm之间变化;或者在0.1μm和30μm之间变化;或者在0.2μm和5.0μm之间变化。
在本发明的一个实施例中,组合物可以配制成血清。出于本发明的目的,“血清”被定义为未固化的硅酮基聚合物与至少一种低粘度织物护理可接受载体的共混物,优选地是挥发性载体,例如如上所述的溶剂中的一个,并且还含有至少一种织物护理成分。
织物护理组合物可以通过在最终织物护理组合物的合适相中混合未固化的硅酮基聚合物来制备。
当未固化的硅酮基聚合物以乳液形式使用时,它可以与水相成分混合,并且任选地随后与任选的第二疏水相混合。当有多个相时,不同的相可以随后混合在一起,任选地在加热下混合。
当未固化的硅酮基聚合物以乳液形式使用时,它可以与水相成分混合,并且任选地随后与任选的第二疏水相混合。
当有多个相时,不同的相可以随后混合在一起,任选地在加热下混合。方法可以在范围从15至90℃、替代性地从20至60℃、替代性地在室温(25℃)的范围的温度下,使用简单的螺旋桨式混合器、反向旋转混合器或均化混合器进行。通常不需要特殊的装备或加工条件。根据所制备的组合物的类型,制备方法将是不同的,但是此类方法在本领域中是众所周知的。
包含未固化的硅酮基聚合物的织物护理组合物可以适于在洗衣机中使用或适于当手清洗时使用。根据本发明的织物护理组合物可以呈液体、糊状物、肥皂或粒状形式。织物护理组合物的其它形式包括乳膏、凝胶、泡沫、喷雾剂或气雾剂。织物护理组合物可以呈单相体系、双相或交替多相体系;乳液(例如,水包油、油包水、水包硅酮、硅酮包水);多重乳液(例如,油包水包油、水包硅酮包多元醇、硅酮包水包油)的形式。
为了去除来自织物或纺织品(特别是衣服和家用织物)上的污垢、污渍和异味,洗衣过程是必要的。然而,洗衣过程涉及苛刻的条件,所述条件通常会导致对织物的损坏(如织物起球、收缩和颜色强度损失和/或颜色清晰度损失。
织物软化组合物可以用于洗衣过程中,以防止洗涤织物中的静电吸附,并且从而使织物更柔软。颜色护理添加剂是为了保持其颜色的完整性,例如织物的颜色的强度和色度。
未固化的硅酮基聚合物可以以液体、可倾倒的形式使用,或者可以被制粒/凝聚以结合在固体织物护理组合物中。
当以粒状形式提供时,粒状组合物可以通过结合基础颗粒成分(例如表面活性剂、助洗剂、水等)作为浆料,并将所得的浆料喷雾干燥至低水平的残留水分(5至12%)来制造。在某些情况下,在制粒过程期间可以添加附加的成分,如颜色护理添加剂和芳香剂。
织物护理组合物可以通过将未固化的硅酮基聚合物与织物护理组合物的其它液体成分混合来制备。当为固体时,织物护理组合物可以通过将双模水连续乳液中的粒状形式与进一步的成分混合,或者通过喷雾干燥/凝聚包含未固化的硅酮基聚合物的液体织物护理组合物来制备。
从使用包含未固化的硅酮基聚合物的织物护理组合物获得的益处包括织物软化和/或手感增强、服装形状保持和/或恢复和/或弹性、易于熨烫、颜色护理、抗磨损、抗起球、硅酮沉积、吸水性、减少和/或去除和/或防止皱纹织物增强(或调理)或其任意组合。在染色过程中,益处包括色牢度、颜色吸收性、颜色持久性。
本发明还包含一种通过向其施用根据本发明第一方面的织物护理组合物来处理织物基材和纤维的方法。
一种清洗织物基材和纤维的方法包含以下步骤
i.任选地在可接受的介质的存在下,将如上文所述的未固化的硅酮基聚合物和至少一种织物护理成分混合,
ii.将混合物施用到织物基材和纤维上;
iii.任选地让混合物停留在织物基材和纤维上;
iv.任选地漂洗织物基材和纤维。
一种调理织物基材和纤维的方法包含以下步骤:
i.任选地在可接受的介质的存在下,将如上所述的未固化的硅酮基聚合物和至少一种织物护理成分混合;
ii.将混合物施用到织物基材和纤维上;
iii.任选地让混合物停留在织物基材和纤维上;
iv.任选地漂洗织物基材和纤维。
护理或调理织物基材和纤维的方法的任选静置时间范围可以从10秒至24小时,替代性地从10分钟至12小时,替代性地从10分钟至3小时,替代性地从10分钟至1小时。
在一个实施例中,本发明提供了本发明织物护理组合物用于护理织物基材(即清洁、调理和/或复新织物)的用途。
织物护理组合物可以呈乳膏、凝胶、粉末(自由流动的粉末或压制的粉末)、糊状物、固体、自由倾倒的液体、气雾剂的形式。织物护理组合物可以呈单相体系、双相或交替多相体系;乳液(例如,水包油、油包水、水包硅酮、硅酮包水);多重乳液(例如,油包水包油、水包硅酮包多元醇、硅酮包水包油)的形式。
如上文所述的织物护理组合物可以用于洗衣过程中,以去除织物或纺织品,尤其是衣服和家用织物上的污垢、污渍和异味。然而,洗衣过程涉及苛刻的条件,所述条件通常会导致对织物的损坏(如织物起球、收缩和颜色强度损失和/或颜色清晰度损失。因此,它们可以用作液体洗涤剂、固体洗涤剂、预清洗处理、织物柔软剂、颜色护理处理等,用于护理织物和纤维,也就是说,适于施用到纤维、织物或纺织品(例如衣服)的任何产品,以便于改善织物或纺织品的外观或状况。洗衣过程中的织物软化组合物用于防止洗涤织物中的静电附着,并且从而使织物更柔软。颜色护理护理组合物用于保持其颜色的完整性,例如织物颜色的强度和色度。
因此,从使用包含如上文所述的未固化的硅酮基聚合物的织物护理组合物获得的益处包括织物软化和/或手感增强、服装形状保持和/或恢复和/或弹性、易于熨烫、颜色护理、抗磨损、抗起球、硅酮沉积、吸水性、减少和/或去除和/或防止皱纹织物增强(或调理)或其任意组合。在染色过程中,益处包括色牢度、颜色吸收性、颜色持久性。
织物护理组合物可施用于由动物、植物或合成来源制成的纤维、织物和纺织品上。纤维表面包括各种纺织品和天然纤维。可以用处理组合物处理的纤维或纺织品包括天然纤维,如棉花、蚕丝、亚麻、羊毛、安哥拉羊毛、马海毛、羊绒;再生纤维,如人造丝和醋酸纤维;合成纤维,如聚酯、聚酰胺、聚丙烯腈、聚乙烯和聚丙烯;其组合及共混物。纤维的形式可以包括线、细丝、丝束、纱线、机织物、针织材料、非织造材料、纸、地毯和皮革。
包含本组合物的纤维处理组合物可以在制造纤维或纺织品期间,或随后通过后施用过程施用到纤维和/或纺织品上。施用后,载体(如果有的话)可以从处理组合物中去除,例如通过在环境温度或高温下干燥组合物。施用到纤维和纺织品上的处理组合物的量通常足以在纤维和纺织品上提供基于其干重的0.1至15重量%的组合物,优选地以基于纤维或纺织品干重的0.2至5重量%的量提供。
实例
提供以下实施例来说明本发明的优选实施例。除非另有说明,否则所有配方都是以质量份计,而不是%计,因此总和不一定是100。
表1列出了用于制备这些实例的乳液的成分。比较例1是比较例以及实例1、2和3以及本文所述的实例。在比较例1中,聚合物是三甲基封端的聚二甲基硅氧烷。在实例1至实例3中,聚合物是根据如上所述的未稀释的硅酮聚合物,其中
(R1O)3-x-Si(R2)x-(Z)d-(O)q-(R3 2SiO)N-(SiR3 2-Z)d-Si(R2)y(OR1)3-y
其中:
x是0(零)或1;
y是0、1、2、3,
N是从300至10,000;
d是0或1,q是0或1,并且d+q=1;R1、R2和R3各自独立地是含有1至10个碳的直链烷基;并且
每个Z是乙烯单元
将聚合物和表面活性剂添加到容器中,所述容器适用于与Hauschild混合器型DAC150.1FV一起使用。聚合物和表面活性剂然后使用Hauschild混合器型DAC 150.1FV通过在3500转/分钟(rpm)下混合持续30s而混合至均匀。然后添加转化水,并在3500rpm下剪切1分钟后获得浓乳液。连续添加三次“稀释”水以稀释浓乳液,每次添加后在3500rpm下进行30s的混合步骤。
分散相的粒径(D(v,0.5)和D(v,0.9))在过程结束时使用英国MalvernInstruments Ltd.公司的Malvern Mastersizer 3000仪器进行测量。(关于粒度测定的进一步的信息可以在“粒径分析的基本原理(Basic Principles of Particle SizeAnalytics)”,Dr.Alan Rawle,Malvern Instruments Limited,WR14 1XZ,UK和“Malvern粒径分析仪手册(Manual of Malvern Particle Size Analyser)”中找到。具体参考编号为MNA 0096,Issue1.0,Nov.1994的用户手册。本申请中指示的所有粒径都是根据上述D(v,0.5)和D(v,0.9)的平均粒径。D(v,0.5)是由仪器测定的分散相“颗粒”的、指示50%的分散相颗粒群低于所标识的值,而另50%高于所述值的体积直径。类似地,在D(v,0.9)的情况下,仪器标识了值,其中90%的分散相颗粒群低于所标识的值,而另外10%高于所述值。
表1
然后分析以上制备的乳液,以按照标准方案,使用以下步骤鉴别沉积在标准化棉针织物片(每片50g)的表面上的硅酮的量:
织物预调理
对织物样品进行预调理,以确保之前已经进行的任何处理(例如在制造期间)的残留物至少基本上且优选地完全去除,使得可以合理地预期,在用如上文所述的样品处理之前,织物样品不含硅酮。
将3kg棉针织物片(每片50g)在商用洗衣机中进行预清洗,同时在第一次清洗循环中,在90℃和1400转/分钟(rpm)下添加40g洗涤剂粉末,随后进行六次累积“空白循环”,例如在90℃和1400rpm下不添加洗涤剂。
然后使用上述的比较例1和实例1至3的乳液使用以下步骤清洗和漂洗经过上述的预调理样品:
清洗步骤:
将一升硬度为0dH(1德国硬度(dH)=10mg/L CaO)并且温度为40℃的水引入到2L烧杯中。以使得水中的最终硅酮含量为按重量计0.25%的量添加硅酮乳液。
向该混合物中添加5g液体洗涤剂(5g),并将所得的混合物均匀化。将四片经预调理的棉针织物片引入到烧杯中,并在不搅拌的情况下浸泡持续5分钟的时段。
漂洗步骤
将四片棉针织物片引入到含有一升水(硬度0dH,温度40℃)的2L烧杯中,并且在不搅拌的情况下漂洗持续3分钟的时段。漂洗后,将棉针织物片逐个取出,挤压以排出水,并且然后晾干持续约2至3小时。
在“仅清洗样品”的情况下,织物片没有经历漂洗步骤(排水和漂洗),而是在清洗步骤完成后立即被线干燥持续2至3小时。在样品被清洗和漂洗的情况下,它们经历了上述清洗步骤和漂洗步骤两者。
然后用x射线荧光(XRF)光谱测定沉积在所测试的织物样品上的总硅。这一点很重要,因为这是预测在清洗组合物中使用的情况下到棉织服装的表面上硅酮沉积水平的手段。XRF是一种原子发射方法,在所述方法中,测量样品中由激发的原子发射的X射线的波长和强度。来自X射线管的主要X射线束的照射引起具有样品中存在的元素的离散的能量特性的荧光X射线的发射。因此,人们可以获得每种元素的化学组成和(借助校准曲线)获得所述每种元素的含量。
在上述干燥步骤之后,用稍微潮湿的织物制备XRF杯。在XRF分析之前,将这些杯进一步干燥持续48小时的时段。
X射线荧光分析是使用PANalytical Axios 2.4kW顺序波长色散X射线荧光(WDXRF)光谱仪进行的,所述光谱仪带有Rh端窗口管(75μm的Be端窗口)、24kV和100mA的功率设置、弯曲的InSb111-c晶体(用于超高灵敏度和提高Si分辨率的专用单色仪)、700μm的主准直器、150μm的铍束过滤器、气流检测器和120秒的照射时间。
样品旋转器用于在分析期间旋转样品,并且有助于将样品中任何不均匀性的影响最小化。使用相同的基底织物(相同的组分、编织和厚度)作为基线。光谱仪在氦分析介质中运行(20秒介质冲洗时间)。通过比较从经处理和未处理样品获得的信号,Si Kα线的净荧光强度与沉积在织物样本上的硅酮聚合物的量有关。
在上述线干燥步骤之后,用稍微潮湿的织物制备XRF杯。
将每种织物材料切割成方形样本,以装入标准的40mm直径尺寸的XRF杯,并且然后将所述方形样本用于封闭杯,而不是原来的薄膜样品支撑件。
织物样品首先由珠子抓住并在所有接触点保持拉紧,并且然后暂时拉伸,直到珠子最终锁定在单元颈部。如果织物支撑件正确地定位,则它没有褶皱且拉紧。在制备XRF杯期间,首先要防止织物样品接触和污染。对于每个样品,在XRF杯中制备四个样品,表2中的结果是平均值。
测定了来自“清洗、漂洗、干燥”(在表2中称为“WRD”)和“仅清洗”(在表2中称为“WO”)实验的XRF Si信号之间的值的差异,并在表2中表示为百分比。值越高,沉积在织物上的硅酮量就越高。单位Kcps是每秒千次。
表2
可以看出,与比较例1相比,实例1、2和3观察到更好的沉积。
Claims (13)
1.一种织物护理组合物,其在织物护理可接受的介质中包含未固化的硅酮基聚合物;和至少一种织物护理成分;其中所述未固化的硅酮基聚合物是直链或支链的,具有下式
(R1O)3-x-Si(R2)x-(Z)d-(O)q-(R3 2SiO)N-(SiR3 2-Z)d - Si(R2)y(OR1)3-y
其中:
x是0或1;
y是0、1、2、3,
N是从300至10,000;
d是0或1,q是0或1,并且d + q = 1;R1、R2和R3各自独立地是含有1至10个碳的直链烷基;并且
每个Z独立地是
(i)具有从1至12个碳原子的直链或支链亚烷基,所述直链或支链亚烷基可以被一个或多个包含1至20个硅原子的直链或支链硅氧烷基间杂;或者
(ii)基于聚氧化烯基单元的有机链,所述有机链可以被一个或多个包含1至20个硅原子的直链或支链硅氧烷基间杂。
2.根据权利要求1所述的织物护理组合物,其中y是0、3。
3.根据权利要求1或2所述的织物护理组合物,其中所述未固化的硅酮基聚合物呈纯净且未稀释形式、呈稀释形式或者呈乳液形式。
4.根据权利要求1或2所述的织物护理组合物,其中所述织物护理成分选自表面活性剂,乳化剂,增稠剂、水相稳定剂、pH控制剂、防腐剂、蛋白质或氨基酸以及它们的衍生物、着色剂、硅酮调理剂、阳离子调理剂、非离子调理剂、疏水调理剂、UV吸收剂、防晒剂、芳香剂或香料、抗氧化剂、去污剂、氧化剂、还原剂、推进剂气体、分散助剂、无机盐、抗细菌剂、抗真菌剂、漂白剂、螯合剂、酶、消泡剂化合物、助洗剂、研磨剂、织物柔软剂、荧光增白剂、污垢悬浮剂、分散剂、染料转移抑制剂、抗再沉积剂、脂肪醇、颜色护理添加剂、熨烫剂、悬浮剂以及其混合物。
5.根据权利要求1或2所述的织物护理组合物,其中所述织物护理成分选自阳离子调理剂、非离子调理剂、疏水调理剂以及其混合物。
6.根据权利要求1或2所述的织物护理组合物,所述织物护理组合物呈液体、糊状物、肥皂、粒状形式、乳膏、凝胶、泡沫或气雾剂的形式。
7.根据权利要求1所述的织物护理组合物,其呈单相体系、双相、多相体系;乳液的形式。
8.根据权利要求7所述的织物护理组合物,其中所述乳液是水包油、油包水、水包硅酮、硅酮包水;或者是多重乳液。
9.根据权利要求8所述的织物护理组合物,其中所述多重乳液是油包水包油、水包硅酮包多元醇、或硅酮包水包油。
10.一种制备根据权利要求1至6中任一项所述的织物护理组合物的方法,其包含以下步骤
i. 将如权利要求1中限定的未固化的硅酮基聚合物和至少一种织物护理成分混合;
ii.任选地在可接受的介质的存在下。
11.一种用于处理织物基材和纤维的方法,其包含以下步骤
i. 任选地在可接受的介质的存在下,将如权利要求1中限定的未固化的硅酮基聚合物和至少一种织物护理成分混合以形成混合物,
ii.将所述混合物施用到所述织物基材和纤维上;
iii.任选地让所述混合物停留在所述织物基材和纤维上;
iv.任选地漂洗所述织物基材和纤维。
12.一种调理织物基材和纤维的方法,其包含以下步骤
i. 任选地在可接受的介质的存在下,将如权利要求1中限定的未固化的硅酮基聚合物和至少一种织物护理成分混合以形成混合物,
ii.将所述混合物施用到所述织物基材和纤维上;
iii. 任选地让所述混合物停留在所述织物基材和纤维上;
iv. 任选地漂洗所述织物基材和纤维。
13.使用一种根据权利要求1至5中任一项所述的织物护理组合物用于护理织物基材和纤维。
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CN1681911A (zh) * | 2002-09-05 | 2005-10-12 | 宝洁公司 | 结构化液体织物护理组合物 |
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WO2012119940A1 (en) * | 2011-03-04 | 2012-09-13 | Dow Corning Corporation | Organosiloxane compositions |
WO2017085296A1 (en) * | 2015-11-20 | 2017-05-26 | Dow Corning Corporation | Room temperature curable compositions |
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EP3728539A1 (en) | 2020-10-28 |
US20200339915A1 (en) | 2020-10-29 |
CN111417705A (zh) | 2020-07-14 |
US11359167B2 (en) | 2022-06-14 |
WO2019126014A1 (en) | 2019-06-27 |
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