CN103547663B - 去污剂组合物 - Google Patents
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Abstract
液体水性去污剂组合物,包括作为增稠剂和助悬剂的含有一个或多个乙酰乙酰基或氰基乙酰基的交联的碱性可溶胀聚丙烯酸酯。
Description
技术领域
本发明涉及液体水性去污剂组合物,包括作为增稠剂和助悬剂的含有一个或多个乙酰乙酰基或氰基乙酰基的交联的碱性可溶胀聚丙烯酸酯。
在表面活性剂和电解质存在的情况下,交联的含有一个或多个乙酰乙酰基或氰基乙酰基的碱性可溶胀聚丙烯酸酯具有高增稠能力,提供均匀和澄清溶液并且有出色的悬浮性质表现。
背景技术
已知在去污剂和化妆品工业中经常遇到的一个技术问题是得到含有表面活性剂、电解质和可能的分散固体颗粒的稳定黏稠均匀的制剂。
使用的增稠剂应该开发其增稠的能力而不负面地改变制剂的其他性质。
通常,还要求增稠剂控制组合物的整体流变,包括屈服应力值。
在液体去污剂水性组合物的领域中,增稠剂通常选自交联的聚丙烯酸和交联的丙烯酸共聚物(属于交联的碱性可溶胀聚丙烯酸酯种类)、瓜耳胶及其衍生物、淀粉及其衍生物、交联的聚氧乙烯、羧甲基纤维素、部分水解的交联的水可溶胀聚合物如部分水解的聚丙烯酰胺、缔合性聚氨酯。
通常优选部分中和为钠盐的交联的聚丙烯酸和交联的丙烯酸共聚物。
在专门的文献中,报道了很多方法来调节不同制剂的流变性质,包括在中性和碱性pH下用作增稠剂的交联的丙烯酸共聚物的使用。
作为示例,我们引用:
-GB870,994,其揭示了在水性乳液中的甲基丙烯酸和丙烯酸C1-C4烷基酯(C1-C4alkylacrylate)的共聚物;
-EP13836,其描述了基于(甲基)丙烯酸、C1-C4(甲基)丙烯酸酯、包括聚氧乙烯单元的选择的(甲基)丙烯酸酯、和任选的多烯键式不饱和单体的增稠剂,据称这些增稠剂对电解质的敏感性低于不使用选择的(甲基)丙烯酸酯制备的现有技术合成的增稠剂;
-US4,529,773和US4,138,381,其描述了包括缔合性单体的碱溶性乳液丙烯酸类聚合物及其使用方法;
-US6,140,438,其描述了在特定交联剂存在下,通过丙烯酸类单体聚合得到的具有高增稠性和悬浮性质的交联的丙烯酸类聚合物;
-EP1272159,其描述了一般不含(如含有低于约1重量%)的缔合性单体的交联的丙烯酸酯共聚物的使用。
发明内容
按照本发明制备的液体水性去污剂组合物包括:
i)0.2-10重量%、优选0.5-8重量%的增稠剂,其是通过以下聚合得到的交联的碱性可溶胀聚丙烯酸酯:
a)20-70重量%、优选20-50重量%的含有羧基的单烯键式不饱和单体;
b)20-70重量%、优选40-70重量%的(甲基)丙烯酸酯;
c)0.05-3重量%、优选0.1-2重量%的含有一个或多个乙酰乙酰基或氰基乙酰基的不饱和单体;
d)0.01-3重量%、优选0.02-1重量%的多烯键式不饱和单体;
e)0-10重量%的非离子型丙烯酸类缔合性单体;
ii)5-60重量%、优选5-20重量%的去污剂组分,其包括至少一种选自阴离子型表面活性剂、两性表面活性剂、阳离子型表面活性剂、两性离子表面活性剂、非离子型表面活性剂及其混合物的化合物。
上述交联的碱性可溶胀聚丙烯酸酯已证明在电解质和表面活性剂存在下有效发挥增稠剂的作用并且与现有技术中交联的碱性可溶胀聚丙烯酸酯相比具有改进的悬浮和增稠性质。
因此,本发明的另一个目标是上述交联的碱性可溶胀丙烯酸酯用于增稠液体水性去污剂组合物的应用,所述组合物包括5-60重量%、优选5-20重量%的上述去污剂组分。
发明详述
“去污剂组合物”表示通常用于个人洗护(个人护理去污剂,如香波和皮肤和身体清洁剂)和家用或重型(heavyduty)洗护(家用和重型洗护去污剂,如洗衣去污剂、洗盘去污剂、家用清洁剂、轻型去污剂和工业去污剂)的产品。
制备本发明的增稠剂的关键点是在单体之间存在含有一个或多个乙酰乙酰基或氰基乙酰基的不饱和单体。
乙酰乙酰基和氰基乙酰基分别具有化学式-CO-CH2-COCH3和-CO-CH2-CN。
有用的含有一个或多个乙酰乙酰基或氰基乙酰基的不饱和单体的示例是(甲基)丙烯酸乙酰乙酰氧基烷基酯、乙酰乙酸烯丙酯、乙酰乙酸乙烯酯、不饱和乙酰乙酰胺、氰基乙酸烯丙基酯(allylcyanoacetate)。
优选的含有一个或多个乙酰乙酰基或氰基乙酰基的不饱和单体是含有一个或多个乙酰乙酰基的不饱和单体。
更优选地含有一个或多个乙酰乙酰基的不饱和单体是(甲基)丙烯酸乙酰乙酰氧基烷基酯,具体是化学式为CH2=CR-CO-O-R1-O-CO-CH2-CO-CH3的(甲基)丙烯酸乙酰乙酰氧基烷基酯,其中R是H或CH3并且R1是C2-C4的直链或支链亚烷基。
最优选地,含有一个或多个乙酰乙酰基的不饱和单体是甲基丙烯酸乙酰乙酰氧基乙基酯,如化学式为CH2=CR-CO-O-R1-O-CO-CH2-CO-CH3的(甲基)丙烯酸乙酰乙酰氧基烷基酯,其中R是CH3并且R1是亚乙基。
甲基丙烯酸乙酰乙酰氧基乙基酯有一个反应活性的亚甲基基团,其在聚合物合成后可用于交联和改性聚合物。
已知反应活性的亚甲基基团能与三聚氰胺、异氰酸酯、迈克尔反应性双键(Michaelreactivedoublebond)、醛反应。
除了反应活性的亚甲基之外,(甲基)丙烯酸乙酰乙酰氧基烷基酯还含有一个反应活性的羰基,其也经过对于树脂交联或改性有用的反应。
乙酰乙酰基化聚合物的羰基处于烯醇和酮之间的平衡形式:烯醇化使得乙酰乙酰基化聚合物与以下金属的多价阳离子螯合,如锌、锡、铝、铜、锆,以及与胺和二胺的反应。
由于这个特殊的化学性质,发现甲基丙烯酸乙酰乙酰氧基乙基酯可用作制备用于涂料、塑料和粘合剂应用的反应后可交联的聚合物的丙烯酸类单体。
如示例,US5,516,453描述了含有活性亚甲基官能组分和活性亚甲基反应活性组分的稳定的环境固化单一成分(one-pack)组合物,其可用作涂料、粘合剂和浸渍剂并且能在多种基材上使用,如木材、水泥和混凝土、织物、金属、陶瓷、塑料。
除了含有反应活性亚甲基的不饱和单体,还通过一个或多个含有羧基的单烯键式不饱和单体、一个或多个(甲基)丙烯酸酯、一个或多个多烯键式不饱和单体、以及可能的一个或多个非离子型丙烯酸类缔合性单体的共聚得到本发明的交联的碱性可溶胀聚丙烯酸酯。
丙烯酸、甲基丙烯酸、衣康酸及其混合物是所述含有羧基的单烯键式不饱和单体的示例,其可用于制备本发明的交联的碱性可溶胀聚丙烯酸酯。
甲基丙烯酸是优选的含有羧基的单烯键式不饱和单体。
有用的(甲基)丙烯酸酯是C1-C40(甲基)丙烯酸烷基酯(C1-C40(meth)acrylicacidalkylester),如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯及其混合物。
优选的(甲基)丙烯酸酯是丙烯酸乙酯。
添加多烯键式不饱和单体用作聚合物交联剂,是制备本发明增稠剂的另一个关键点。
多烯键式不饱和单体可以是任意已知的多官能衍生物,其已知与(甲基)丙烯酸单体发生自由基聚合。
在有用的多烯键式不饱和单体中,我们引用马来酸二烯丙酯、甲基丙烯酸烯丙酯、邻苯二甲酸二烯丙酯、N-亚甲基双丙烯酰胺、季戊四醇醚聚丙烯酸酯(pentaerithritoletherpolyacrylates)、氰尿酸三烯丙酯(triallylcianurate)。
非离子型丙烯酸类缔合性单体可以选自(甲基)丙烯酸的C8-C30烷基酯、烷基芳基酯或聚乙二醇的多环烃基单醚的酯,其中所述聚乙二醇具有至少2个氧乙烯单元,优选具有10-40个氧乙烯单元,以及具有多至70个氧乙烯单元,该酯具有通式H2C=C(R)-CO-O(CH2CH2O)n-R’,其中
R是H或CH3,优选后者,
n至少为2,并且优选具有至少10的平均值,多至40-60或甚至多至70等等,并且R’是疏水性基团,例如:烷基,烷基芳基,或具有8-30个碳原子、优选16-18个碳原子、或更优选平均具有12-18个碳原子的多环烷基。
除了a)-e)以外的其他可用于聚合的不饱和单体是,例如,其他非离子型丙烯酸类单体、单烯键式不饱和单体(可能含有一个磺酸基)、阳离子型丙烯酸类单体。
其他可用的不饱和单体的非限制性的示例是乙酸乙烯酯、苯乙烯、氯乙烯、偏二氯乙烯、丙烯腈、(甲基)丙烯酰胺、N,N,-二甲基(甲基)丙烯酰胺、叔丁基-(甲基)丙烯酰胺、乙烯基磺酸钠、2-丙烯酰氨基-2-甲基丙磺酸。
但是,通过在聚合中仅仅使用a)-e)的单体,就得到了交联的碱性可溶胀聚丙烯酸酯在水性去污剂组合物中出色的增稠和悬浮性能。
本发明的交联的碱性可溶胀聚丙烯酸酯也能够通过以下方式间接得到:在含有羟基的不饱和单体存在下,单体a)、b)、d)与可能的e)反应,以及得到的聚合物和市售的乙酰乙酸叔丁酯的合成后反应。
交联的碱性可溶胀聚丙烯酸酯具有在水中pH7.5下高的粘度,如粘度(轴6,RVT,20rpm,1.0重量%和20℃下)为至少500mPa*s。
本发明的液体水性去污剂组合物的去污剂组分由阴离子型表面活性剂、两性表面活性剂、阳离子型表面活性剂、非离子型表面活性剂、两性离子表面活性剂及其混合物制成。
优选地,本发明的液体水性去污剂组合物的去污剂组分包含阴离子型表面活性剂。
按照本发明的实施方式,本发明的液体水性去污剂组合物的去污剂组分包括阴离子型表面活性剂。
阴离子型表面活性剂包括烷基和烷基醚硫酸盐;烷基磺酸盐;烷基和烷基醚磷酸盐;烷基或烷基醚磺基琥珀酸盐以及烷基和烷基醚羧酸盐或烷基聚糖苷的阴离子衍生物,如烷基聚聚糖苷的柠檬酸酯、酒石酸酯或磺基琥珀酸酯。
能够在本发明的组合物中使用的两性表面活性剂是广泛描述为脂族季铵化合物的衍生物,其中脂族取代基中的一个含有阴离子水溶性基团,如羧酸基团、磺酸基团、硫酸基团等。两性表面活性剂的示例包括椰油酰两性羧基丙酸酯(cocoamphocarboxypropionate)、椰油酰两性羧基丙酸(cocoamphocarboxypropionicacid)、椰油酰两性乙酸酯(cocoamphoacetate)、椰油酰两性二乙酸酯(cocoamphodiacetate)、月桂酰两性乙酸钠(sodiumlauroamphoacetate)。
在本发明的组合物中有用的阳离子型表面活性剂含有氨基或季铵亲水部分,其在溶于本发明的水性组合物中时带正电。阳离子型表面活性剂的示例是长链烷基三甲基氯化铵、长链烷基苄基二甲基氯化铵、盐酸烷基胺(alkylaminehydrochloride)、乙酸烷基胺、二(长链烷基)二甲基溴化铵。
非离子型表面活性剂能够广泛定义为含有一个疏水部分和一个非离子亲水部分的化合物。疏水部分的示例可以是烷基、烷基芳族和芳基芳族。亲水部分的示例是聚氧化烯、胺氧化物和烷醇酰胺。非离子型表面活性剂的示例是烷氧基化脂族醇或烷氧基化脂肪酸、烷氧基化二苯乙烯基苯酚和烷氧基化三苯乙烯基苯酚(alkoxylateddi-andtri-stirylphenols)、多羟基脂肪酸酰胺、糖酯和聚酯、烷氧基化糖酯、去水山梨糖醇和烷氧基化去水山梨糖醇脂肪酸酯。其他非离子型乳化剂的示例包括烷基聚糖苷,如椰油酰聚糖苷(cocopolyglucosides)。
两性离子表面活性剂的示例包括烷基甜菜碱和酰氨基甜菜碱、磺基甜菜碱、甘氨酸烷基酯(alkylglycinate)和羧基甘氨酸烷基酯(alkylcarboxyglycinate)。
令人惊讶的是,含有反应活性亚甲基的本发明的交联的碱性可溶胀聚丙烯酸酯在存在表面活性剂的情况下,在水中显示出增强的粘度。有大范围的表面活性剂和用量都是有效的。
虽然现有技术已知,在存在表面活性剂的情况下,在交联的碱性可溶胀聚丙烯酸酯中引入特定缔合性单体可能增强增稠性能,但是在向含有本发明的增稠剂的水性体系中加入表面活性剂之后所观察到的增稠的显著增强与聚合物中的非离子型丙烯酸类缔合性单体的存在无关。
对于现有技术的类似的不含乙酰乙酰基或氰基乙酰基的交联的碱性可溶胀聚丙烯酸酯,没有观察到同样方式的该现象。
不仅如此,已发现甚至很小量的含有反应活性亚甲基的单体显著改善了水性去污剂组合物的悬浮性质。
按照本发明的一种优选实施方式,为了增强增稠剂的悬浮性质,在聚合中使用0.1-0.5重量%的含有一个或多个乙酰乙酰基或氰基乙酰基的不饱和单体,还有1.0-2.0重量%的非离子型缔合性单体。
较佳地,本发明的水性液体去污剂组合物中增稠剂的反应活性亚甲基在存在几种常规的去污剂组合物添加剂如防腐剂(具体是甲醛或甲醛供体)和多价金属阳离子的情况下,可以进一步向聚合物提供可调的增粘性质。
在聚合物和添加剂中反应活性亚甲基的量和种类可用于调节最终水性液体组合物的粘度,这可由本领域技术人员通过少量实验容易地确定。
本发明的交联的碱性可溶胀聚丙烯酸酯可以任意常规方式制备,例如,通过沉淀聚合、悬浮液和溶液聚合、乳液聚合。通常本发明的交联的碱性可溶胀聚丙烯酸酯通过乳液聚合制备。
乳液聚合技术是本领域众所周知的,例如参见美国专利第4,325,856号;第4,654,397号;以及第4,814,373号。在乳液聚合中可以使用常规的表面活性剂,例如阴离子型和/或非离子型乳化剂,如碱金属或铵的烷基硫酸盐、烷基磺酸、脂肪酸,以及乙氧基化的烷基苯酚。以全部单体的重量为基准计,表面活性剂的用量通常为0.1-6重量%。可以使用热引发法或氧化还原引发法。可以采用常规的自由基引发剂,例如:过氧化氢,叔丁基过氧化氢或叔戊基过氧化氢,碱金属或铵的过硫酸盐,和偶氮引发剂如4,4′-偶氮二(4-氰基戊酸)、和2,2′-偶氮二异丁腈(“AIBN”),以全部单体的重量为基准计,所述自由基引发剂的含量通常为0.01-3.0重量%。使用相同引发剂和合适还原剂(例如甲醛合次硫酸氢钠、连二亚硫酸钠、异抗环血酸、硫酸羟胺和亚硫酸氢钠)的组合的氧化还原体系可以类似的含量使用,任选地与金属离子如铁和铜组合,任选地还包含金属的络合剂。可以使用硫醇之类的链转移剂,以降低聚合物的分子量。单体混合物可以以纯的形式加入,或者以水乳液的形式加入。所述单体混合物可以一次性加入或多次加入,或在反应过程中使用均匀或变化的组合物连续加入。乳液聚合过程可使用预先形成的晶种乳液聚合物,例如,通过向反应釜加入5%(以全部单体为基准计)的单体混合物并使其提前反应。可以使用减少残留单体的技术,例如,使反应混合物经蒸汽汽提、保持时间、和另外的自由基源。
本发明的交联的碱性可溶胀聚丙烯酸酯通常以酸形式、乳液形式或固态形式提供;由于其含有酸性基团,它们需要被中和成盐的形式以在水性去污剂组合物中产生最佳的粘度增加。
通常,洗衣去污剂和很多家用清洁剂具有中性-碱性的pH值;结果是本发明的水性去污剂组合物通常可通过用酸性乳液简单稀释交联的碱性可溶胀聚丙烯酸酯或通过在接近中性或碱性的水性溶液中溶解固态的交联的碱性可溶胀聚丙烯酸酯,同时伴随着加入去污剂组分和任意最优成分制备。
表面活性剂是所述水性去污剂组合物的必需成分,可以在交联的碱性可溶胀聚丙烯酸酯之后或之前加入所述表面活性剂,但是优选在交联的碱性可溶胀聚丙烯酸酯之后加入;如果需要,为了中和交联的碱性可溶胀聚丙烯酸酯,通常使用高扩散的碱性物质,如氢氧化钠或氢氧化钾、乙醇胺、氨等。
然后,在合适的时间或方式下,在对粘度水平没有显著损害的情况下,通常可用弱有机酸,如柠檬酸、水杨酸等,使得到的增稠的组合物的pH下降。
本发明的液体水性去污剂组合物的另外成分为本领域熟知,例如,可以选自香水、染料、珠光剂、遮光剂、酶、防腐剂、消毒剂、抗再沉积助剂、沸石助洗剂、磷酸盐助洗剂、抗微生物添加剂、起泡剂、消泡剂、湿润剂、调节剂、去污物剂(soilreleaseagent)、增亮剂、溶剂和pH缓冲剂。
实施例1-6
实施例1-6的增稠的液体水性洗涤剂组合物按照下面的步骤制备。
通过乳液聚合并且在去离子水中以2.7重量%a.m.分散来制备交联的碱性可溶胀聚丙烯酸酯乳液。然后加入去污剂组分(10.7重量%a.m.)并且在搅拌后通过加入NaOH调节pH至6.6-6.8。通过搅拌约30分钟进一步混合溶液,并且在测量粘度之前静置过夜。
表1a描述了在实施例1-6中使用的去污剂组分的名称和化学组成,而表1b描述两种测试的交联的碱性可溶胀聚丙烯酸酯的单体组成(PAC1和PAC2);单体的量以重量份数(pbw)计。
实施例1和4-6的去污剂组分购自Zschimmer和Schwarz公司(Zschimmer&Schwarz),而实施例2和3的去污剂组分购自LambertiSpA公司(LambertiSpA)。
表1a-去污剂组分
表1b-聚丙烯酸酯
单体 | PAC1* | PAC2 |
丙烯酸乙酯(pbw) | 62 | 62 |
甲基丙烯酸(pbw) | 38 | 38 |
甲基丙烯酸乙酰乙酰氧基乙基酯(pbw) | - | 1.00 |
马来酸二烯丙酯(pbw) | 0.05 | 0.05 |
*比较例
这些得到的增稠的液体水性去污剂组合物在25℃下用ModelLVT粘度计在说明的轴速下测量粘度,结果如表2和表3(BV)所示。
组合物的假塑性由Brookfield屈服应力值(BYV)测量,其通过下面的公式计算:
BYV=(BV0.5rpm-BV1rpm)/100
BYV如表2和表3所示。
表2-BV(mPa*s)和BYV
*比较例
表3-BV(mPa*s)和BYV
*比较例
实施例7
实施例7的增稠的液体水性洗涤剂组合物按照下面的步骤制备。
通过乳液聚合并且在去离子水中以2.7重量%a.m.分散和以2.25重量%a.m.分散来制备交联的碱性可溶胀聚丙烯酸酯。加入去污剂组分(10.7重量%a.m.的月桂醇聚醚硫酸钠和2.4重量%a.m.的椰油酰氨基丙基甜菜碱(CocoamidopropylBetaine))并混合,然后通过加入NaOH将pH调节至6.6-6.8。搅拌约30分钟混合溶液并且在测量粘度之前静置过夜。
测试四个具有表4中所示的单体组合物(PAC3、PAC4、PAC5、PAC6)的交联的碱性可溶胀聚丙烯酸酯;单体的量以重量份表示(pbw)。
表4-聚丙烯酸酯
*比较例
由此得到的增稠的液体水性去污剂组合物在25℃下用ModelLVT粘度计在说明的轴速下测量粘度(BV,mpa*s)和BYV并且结果如表5(2.7重量%聚丙烯酸酯a.m.)和表6(2.25重量%聚丙烯酸酯a.m.)所示。
含有PAC3、PAC4和PAC5的增稠的液体水性去污剂组合物是未着色的和透明澄清的,而含有PAC6的增稠的液体水性去污剂组合物具有淡蓝色反射。
表5-BV(mPa*s)和BYV(2.7重量%a.m.)
*比较例
表6-BV(mPa*s)和BYV(2.25重量%a.m.)
*比较例
应该注意的是剪切速率,如本文所述的轴速(rpm),在粘度测量中是重要的参数,按照本发明的所有组合物都是显著假塑性的,或剪切稀化的。
该行为和相关的BYV反映了组合物的悬浮性质,其是显著改善的。
实施例8
实施例8的增稠的液体水性洗涤剂组合物按照下面的步骤制备。
通过乳液聚合并且在去离子水中以1.5重量%a.m.分散来制备交联的碱性可溶胀聚丙烯酸酯(PAC4)。
加入去污剂组分(10.7重量%a.m.的月桂醇聚醚硫酸钠和2.4重量%a.m.的椰油酰氨基丙基甜菜碱(CocoamidopropylBetaine))并混合,然后加入NaOH将pH调节至6.6-6.8。
加入在表7中所示量的电解质(NaCl)(重量%)。
搅拌约30分钟混合溶液并且在测量粘度之前静置过夜。
测试具有不同量的NaCl的五种组合物。
由此得到的增稠的液体水性去污剂组合物在25℃下用ModelLVT粘度计在说明的轴速下测量粘度(BV,mPa*s)并且结果如表7所示。所有的组合物都是完美的无色和澄清。
表7-BV(mPa*s)(1.5重量%a.m.)
Claims (13)
1.液体水性去污剂组合物,所述组合物包括:
i)0.2-10重量%的增稠剂,所述增稠剂是交联的碱性可溶胀聚丙烯酸酯,其通过下面物质聚合得到:
a)20-70重量%的含有羧基的单烯键式不饱和单体,其选自丙烯酸和甲基丙烯酸;
b)20-70重量%的(甲基)丙烯酸酯,其选自(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯及其混合物;
c)0.05-3重量%的含有一个或多个乙酰乙酰基的化学式(I)的不饱和单体:
其中R是H或CH3而R1是C2-C4直链或支链亚烷基;
d)0.01-3重量%的多烯键式不饱和单体;
e)0-10重量%的非离子型丙烯酸类缔合性单体,其选自C8-C30烷基、烷基芳基或聚乙二醇的多环烃基单醚的(甲基)丙烯酸酯,其中所述聚乙二醇具有至少2个氧乙烯单元并且具有多至70个氧乙烯单元;
ii)5-60重量%的去污剂组分,其包括至少一种选自阴离子型表面活性剂、两性表面活性剂、阳离子型表面活性剂、两性离子型表面活性剂、非离子型表面活性剂及其混合物的化合物。
2.如权利要求1所述的液体水性去污剂组合物,其特征在于,所述组合物包括:
i)0.5-8重量%的增稠剂,所述增稠剂是交联的碱性可溶胀聚丙烯酸酯,其通过下面物质聚合得到:
a)20-50重量%的含有羧基的单烯键式不饱和单体;
b)40-70重量%的(甲基)丙烯酸酯;
c)0.1-2重量%的化学式(I)的不饱和单体;
d)0.02-1重量%的多烯键式不饱和单体;
e)0-10重量%的非离子型丙烯酸类缔合性单体;
ii)5-20重量%的去污剂组分。
3.如权利要求2所述的液体水性去污剂组合物,其特征在于,化学式(I)中R是CH3而且R1是亚乙基。
4.如权利要求3所述的液体水性去污剂组合物,其特征在于,所述含有羧基的单烯键式不饱和单体是甲基丙烯酸并且所述(甲基)丙烯酸酯是丙烯酸乙酯。
5.如权利要求1所述的液体水性去污剂组合物,其特征在于,所述交联的碱性可溶胀聚丙烯酸酯通过下述物质聚合获得:
a)20-70重量%的含有羧基的单烯键式不饱和单体;
b)20-70重量%的(甲基)丙烯酸酯;
c)0.1-0.5重量%的化学式(I)的不饱和单体;
d)0.01-3重量%的多烯键式不饱和单体;
e)1.0-2.0重量%的非离子型丙烯酸类缔合性单体,其选自C8-C30烷基、烷基芳基或聚乙二醇的多环烃基单醚的(甲基)丙烯酸酯,其中所述聚乙二醇具有至少2个氧乙烯单元并且具有多至70个氧乙烯单元。
6.一种交联的碱性可溶胀聚丙烯酸酯的应用,所述交联的碱性可溶胀聚丙烯酸酯通过下述物质聚合获得:
a)20-70重量%的含有羧基的单烯键式不饱和单体,其选自丙烯酸和甲基丙烯酸;
b)20-70重量%的(甲基)丙烯酸酯,其选自(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯及其混合物;
c)0.05-3重量%的含有一个或多个乙酰乙酰基的化学式(I)的不饱和单体:
其中R是H或CH3而R1是C2-C4直链或支链亚烷基;
d)0.01-3重量%的多烯键式不饱和单体;
e)0-10重量%的非离子型丙烯酸类缔合性单体,
其用于增稠液体水性去污剂组合物,所述组合物包括5-60重量%的去污剂组分,其包括至少一种选自阴离子型表面活性剂、两性表面活性剂、阳离子型表面活性剂、两性离子型表面活性剂和非离子型表面活性剂及其混合物的化合物。
7.如权利要求6中所述的交联的碱性可溶胀聚丙烯酸酯的应用,所述交联的碱性可溶胀聚丙烯酸酯通过下述物质聚合获得:
a)20-50重量%的含有羧基的单烯键式不饱和单体;
b)40-70重量%的(甲基)丙烯酸酯;
c)0.1-2重量%的化学式(I)的不饱和单体;
d)0.02-1重量%的多烯键式不饱和单体;
e)0-10重量%的非离子型丙烯酸类缔合性单体,
用于增稠液体水性去污剂组合物,所述组合物包括5-20重量%的去污剂组分。
8.如权利要求6所述的应用,其特征在于,化学式(I)中R是CH3而且R1是亚乙基。
9.如权利要求6所述的应用,其特征在于,所述含有羧基的单烯键式不饱和单体是甲基丙烯酸并且所述(甲基)丙烯酸酯是丙烯酸乙酯。
10.如权利要求6所述的应用,其特征在于,所述的交联的碱性可溶胀聚丙烯酸酯通过下述物质聚合获得:
a)20-70重量%的含有羧基的单烯键式不饱和单体;
b)20-70重量%的(甲基)丙烯酸酯;
c)0.1-0.5重量%的化学式(I)的不饱和单体;
d)0.01-3重量%的多烯键式不饱和单体;
e)1.0-2.0重量%的非离子型丙烯酸类缔合性单体。
11.如权利要求6-10中任一项所述的应用,其特征在于,所述液体水性去污剂组合物是个人护理去污剂。
12.如权利要求6-10中任一项所述的应用,其特征在于,所述液体水性去污剂组合物是家用去污剂。
13.如权利要求6-10中任一项所述的应用,其特征在于,所述液体水性去污剂组合物是重型去污剂。
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IT000008A ITVA20110008A1 (it) | 2011-03-25 | 2011-03-25 | Composizioni detergenti |
ITVA2011A000008 | 2011-03-25 | ||
PCT/EP2011/063187 WO2011117427A2 (en) | 2011-03-25 | 2011-08-01 | Detergent compositions |
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EP (2) | EP2688999B1 (zh) |
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CN (2) | CN103547663B (zh) |
BR (2) | BR112013021506A2 (zh) |
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Families Citing this family (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2716664A4 (en) * | 2011-05-24 | 2014-12-10 | Sumitomo Seika Chemicals | COPOLYMER ON (METH) ACRYLIC ACID BASE |
BR112014026429B1 (pt) | 2012-04-23 | 2022-02-01 | Unilever Ip Holdings B.V. | Composição detergente líquida isotrópica aquosa externamente estruturada |
BR112015012098B1 (pt) * | 2012-11-29 | 2019-10-01 | Unilever N.V. | Composição aquosa e método cosmético não-terapêutico de tratamento do cabelo |
BR112015012153B8 (pt) * | 2012-11-29 | 2019-12-03 | Unilever Nv | composição aquosa para cuidado dos cabelos e uso de um copolímero |
GB2508672A (en) * | 2012-12-10 | 2014-06-11 | Scott Bader Co | Method for making a thickener |
FR3000085B1 (fr) * | 2012-12-20 | 2016-06-10 | Coatex Sas | Agent polymerique pour obtenir une composition aqueuse stable comprenant des particules en suspension |
US9693935B2 (en) * | 2013-01-13 | 2017-07-04 | Sarah McCoy | Personal care solid granules that sustain essential oils and or plant herbal extracts that emulsify in hot water creating therapeutic solution |
CN105143423B (zh) * | 2013-04-29 | 2018-05-29 | 荷兰联合利华有限公司 | 增稠液体洗涤剂组合物的方法 |
DE102014104255A1 (de) * | 2014-03-26 | 2015-10-01 | Beiersdorf Ag | Öl in Wasser-Emulsionen mit einem Gehalt an 4-Hydroxyacetophenon und anionischen Emulgatoren |
CN104069052B (zh) * | 2014-05-12 | 2016-10-05 | 陈来成 | 一种仿蛋壳膜功效的q弹记忆面膜霜及其制备方法 |
KR20160001102A (ko) * | 2014-06-26 | 2016-01-06 | 이호규 | 그라비올라 한방 추출물을 포함하는 모발 화장료 조성물 |
FR3030307B1 (fr) * | 2014-12-23 | 2016-12-09 | Coatex Sas | Polymere multiphasique a titre d'agent epaississant et suspensif |
CN107106435A (zh) * | 2014-12-24 | 2017-08-29 | 莱雅公司 | 化妆品冲洗式皮肤护理组合物和使用其的化妆方法 |
WO2016120851A1 (en) * | 2015-01-30 | 2016-08-04 | Lonza Ltd. | Hair treatment composition |
CN107257849B (zh) | 2015-03-02 | 2019-09-27 | 荷兰联合利华有限公司 | 具有减少的染料转移性能的组合物 |
WO2016139133A1 (en) | 2015-03-02 | 2016-09-09 | Unilever Plc | Perfumed fluid cleaning fluids |
MX2017010507A (es) | 2015-03-02 | 2017-12-14 | Unilever Nv | Metodo para separar ramnolipidos de un caldo de fermentacion. |
US9775346B1 (en) | 2016-04-01 | 2017-10-03 | Roger Wilson | Hand sanitizer composition and method of manufacture |
US10561698B2 (en) | 2015-04-01 | 2020-02-18 | Roger Wilson | Hand sanitizer composition and method of manufacture |
US9937118B2 (en) * | 2016-06-21 | 2018-04-10 | Johnson & Johnson Consumer Inc. | Clear suspending personal care cleansing compositions |
BR112018001974B1 (pt) * | 2015-08-07 | 2021-06-29 | Rohm And Haas Company | Composição para cuidados pessoais, e, métodos para clareamento do tom de pele e para melhorar a dispersão da luz visível de uma composição |
KR102453888B1 (ko) * | 2015-09-30 | 2022-10-11 | (주)아모레퍼시픽 | 성형이 가능한 모발 케어용 조성물 |
CN107789217A (zh) * | 2016-09-06 | 2018-03-13 | 上海家化联合股份有限公司 | 清洁剂组合物和用途 |
JP7041067B2 (ja) * | 2016-10-19 | 2022-03-23 | 株式会社 資生堂 | 洗浄剤組成物 |
US11028679B1 (en) | 2017-01-24 | 2021-06-08 | Devon Energy Corporation | Systems and methods for controlling fracturing operations using monitor well pressure |
US11365617B1 (en) | 2017-01-24 | 2022-06-21 | Devon Energy Corporation | Systems and methods for controlling fracturing operations using monitor well pressure |
JP7082138B2 (ja) | 2017-04-26 | 2022-06-07 | ザ プロクター アンド ギャンブル カンパニー | 増粘ポリマーを含む組成物 |
US20200199801A1 (en) | 2017-06-09 | 2020-06-25 | Conopco, Inc., D/B/A Unilever | Laundry liquid dispensing system |
EP3459872A1 (en) | 2017-09-22 | 2019-03-27 | Unilever PLC | Consumer packaging with fabric treatment fluid |
IT201900003841A1 (it) * | 2019-03-15 | 2020-09-15 | Lamberti Spa | Composizioni per la cura della persona |
ES1258595Y (es) * | 2020-09-28 | 2021-03-12 | Laboratorios Vinfer S A | Formulacion de limpieza acida |
US11859490B2 (en) | 2021-08-19 | 2024-01-02 | Devon Energy Corporation | Systems and methods for monitoring fracturing operations using monitor well flow |
WO2023229957A1 (en) * | 2022-05-24 | 2023-11-30 | Dow Global Technologies Llc | Aqueous detergent formulation |
CN115851384A (zh) * | 2022-11-25 | 2023-03-28 | 浙江理工大学 | 一种丝素蛋白-聚天冬氨酸-十二烷基葡糖苷磺基琥珀酸二钠清洁剂的制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4529773A (en) * | 1982-03-17 | 1985-07-16 | David Witiak | Alkali-soluble emulsion polymers in acidic surfactant compositions |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT580324A (zh) | 1956-11-21 | |||
US4138381A (en) | 1975-04-14 | 1979-02-06 | E. I. Du Pont De Nemours And Company | Polymeric thickeners, processes for their preparation and uses thereof |
CA1188043A (en) | 1978-12-29 | 1985-05-28 | Ching-Jen Chang | Methacrylic acid emulsion copolymers for thickening purposes |
US4325856A (en) | 1980-01-02 | 1982-04-20 | The Dow Chemical Company | Sequential emulsion polymerization process |
JPS5943069B2 (ja) * | 1980-09-26 | 1984-10-19 | 日本合成化学工業株式会社 | 木材用接着剤 |
DE3443964A1 (de) | 1984-12-01 | 1986-06-12 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von polymer-dispersionen, die blockfeste filme bilden |
US4814373A (en) | 1984-12-20 | 1989-03-21 | Rohm And Haas Company | Modified latex polymer composition |
US5516453A (en) | 1993-02-19 | 1996-05-14 | Rohm And Haas Company | Stable ambient-curing composition |
GB9408748D0 (en) * | 1994-05-03 | 1994-06-22 | Zeneca Resins Bv | Production of aqueous polymer compositions |
EP0708119A1 (en) * | 1994-10-21 | 1996-04-24 | Air Products And Chemicals, Inc. | Self-crosslinking, aqueous absorbent polymer compositions |
JP3641110B2 (ja) | 1997-08-20 | 2005-04-20 | 株式会社メニコン | 軟質眼内レンズ用材料 |
AU5644400A (en) * | 1999-09-24 | 2001-03-29 | Rohm And Haas Company | Pellet compositions |
US6635702B1 (en) | 2000-04-11 | 2003-10-21 | Noveon Ip Holdings Corp. | Stable aqueous surfactant compositions |
EP1371679B1 (en) * | 2002-06-14 | 2008-04-09 | Rohm And Haas Company | Aqueous composition containing polymeric nanoparticles |
CN1812774B (zh) * | 2003-06-24 | 2010-06-16 | 尼普洛外用药品株式会社 | 医疗用经皮吸收胶带制剂用非水性粘结剂和医疗用经皮吸收胶带制剂及其制备方法 |
US20050131176A1 (en) * | 2003-12-10 | 2005-06-16 | Cheng-Le Zhao | Process for production of polymer dispersions containing an acetoacetate moiety |
US20050132500A1 (en) * | 2003-12-22 | 2005-06-23 | Basf Aktiengesellschaft | Composition for impregnation of fibers, fabrics and nettings imparting a protective activity against pests |
US7205271B2 (en) * | 2004-10-14 | 2007-04-17 | Isp Investments Inc. | Rheology modifier/hair styling resin |
-
2011
- 2011-03-25 IT IT000008A patent/ITVA20110008A1/it unknown
- 2011-08-01 BR BR112013021506A patent/BR112013021506A2/pt not_active IP Right Cessation
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-
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Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4529773A (en) * | 1982-03-17 | 1985-07-16 | David Witiak | Alkali-soluble emulsion polymers in acidic surfactant compositions |
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BR112013021506A2 (pt) | 2016-10-18 |
EP2689000A1 (en) | 2014-01-29 |
CN103547663A (zh) | 2014-01-29 |
KR101808892B1 (ko) | 2017-12-13 |
US20140017184A1 (en) | 2014-01-16 |
KR20140010135A (ko) | 2014-01-23 |
KR20140050598A (ko) | 2014-04-29 |
WO2012130644A1 (en) | 2012-10-04 |
WO2011117427A2 (en) | 2011-09-29 |
CN103459580A (zh) | 2013-12-18 |
CN103459580B (zh) | 2016-02-17 |
JP2014508788A (ja) | 2014-04-10 |
WO2011117427A3 (en) | 2012-04-05 |
EP2689000B1 (en) | 2016-03-16 |
ITVA20110027A1 (it) | 2011-12-28 |
ITVA20110008A1 (it) | 2012-09-26 |
JP5922755B2 (ja) | 2016-05-24 |
BR112013021509A2 (pt) | 2016-11-01 |
EP2688999A2 (en) | 2014-01-29 |
US20140018284A1 (en) | 2014-01-16 |
EP2688999B1 (en) | 2016-02-24 |
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