CN109715879A - 用于纺织织物整理的不含氟的水性分散体 - Google Patents
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Abstract
一种不含含氟化学物质的水性分散体,其包含:(A)至少一种通过以下单体聚合获得的共聚物:a)至少一种不含氟的(甲基)丙烯酸C16‑C18醇酯,b)至少一种不含氟的(甲基)丙烯酸C18‑C22醇酯,c)至少一种选自氯乙烯和偏二氯乙烯的单体,和任选地d)至少一种选自(甲基)丙烯酸2‑羟基乙酯和(甲基)丙烯酸3‑氯‑2‑羟基乙酯的单体,(B)至少一种选自具有55℃至75℃的熔化范围的石蜡和具有25℃至55℃的熔化范围的硅蜡的组分,(C)至少一种表面活性剂,和(D)水,其中共聚物(A)的单体a)和b)是不同的,和共聚物(A)不含任何苯乙烯或α‑甲基苯乙烯的聚合单元,该水性分散体可用于天然和合成纺织织物的整理以赋予所述织物优异的防水性。
Description
本发明涉及一种包含基于两种不同的长烃链(甲基)丙烯酸酯的共聚物、蜡组分和表面活性剂的水性分散体、所述共聚物的制备和使用所述共聚物的水性分散体处理纺织织物的方法。根据本发明的水性分散体不含含氟化学物质并赋予天然和合成纺织织物防水性。
在过去数年中,很多国家致力于通过节约自然资源并降低对气候有害的物质的排放而改善环境质量。政府提供资金以支持产业实现这些目标。消费者寻求根据最高生态学标准生产的环保纺织产品。品牌和零售商将这些需要转化成实际需求,并且纺织品制造商继续通过投资现代化设备并选择环保化学物质而改善它们的生产优势。
已知通过采用包含特定化学成分的水性分散体处理织物赋予纺织织物例如织造物、针织物或非织造物某些性能,例如防水性。通过使用含氟产品作为此类化学成分来实现纺织品的防水性。然而,含氟产品昂贵并且它们的使用由于化学品的开发规章制度而受到限制。或者,已经提出包含石蜡和丙稀酸类聚合物的水性体系来获得纺织品的防水性。此类体系例如记载于EP1424433A2和WO2010115496A1中。在WO2010115496A1中公开的水性分散体包含石蜡和由(甲基)丙烯酸酯和苯乙烯或α-甲基苯乙烯获得的共聚物。
现有技术的组合物不满足当下期望的全部要求,例如不同织物(特别是由合成纤维制成的织物)的优异的防水性。
本发明的目的是提供甚至在长期存放后仍然具有高稳定性的组合物,其不含任何含氟化学物质或苯乙烯类,并且为包括含聚酯织物在内的全部纺织织物提供优异的防水性。本发明还提供一种在所述织物上获得优异的防水性的方法。
因此,本发明涉及一种不含含氟化学物质的水性分散体,其包含:
(A) 至少一种通过以下单体聚合获得的共聚物:
a) 至少一种不含氟的(甲基)丙烯酸C16-C18醇酯,
b) 至少一种不含氟的(甲基)丙烯酸C18-C22醇酯,
c) 至少一种选自氯乙烯和偏二氯乙烯的单体,和任选地
d) 至少一种选自(甲基)丙烯酸2-羟基乙酯和(甲基)丙烯酸3-氯-2-羟基乙酯的单体,
(B) 至少一种选自具有55℃至75℃的熔化范围的石蜡和具有25℃至55℃的熔化范围的硅蜡的蜡,
(C) 至少一种表面活性剂,和
(D) 水,其中
共聚物(A)的单体a)和b)是不同的,和
共聚物(A)不含任何苯乙烯或α-甲基苯乙烯的聚合单元。
本文上下文中的术语“不含氟”是指各个化合物不含任何氟烷基。
根据本发明的水性分散体既不含任何含氟化学物质也不含苯乙烯类。它们也不含任何N-羟甲基化合物。N-羟甲基化合物可能释放不期望量的甲醛到大气气氛中。因此,本发明进一步限定制备用于纺织品应用的水性分散体中使用的可能对健康和环境有害的成分的数量。
至少一种共聚物(A)的单体a)为至少一种,例如一种、两种或三种(甲基)丙烯酸的线性或支化C16-C18醇酯。考虑此类(甲基)丙烯酸的线性或支化C16-C18醇酯,例如甲基丙烯酸十六烷基酯、甲基丙烯酸十七烷基酯、甲基丙烯酸十八烷基酯、丙烯酸十六烷基酯、丙烯酸十七烷基酯和丙烯酸十八烷基酯、或至少两种不同的(甲基)丙烯酸C16-C18醇酯的混合物,例如甲基丙烯酸十六烷基酯和甲基丙烯酸十八烷基酯的混合物,其可作为工业级甲基丙烯酸硬脂酯(CAS:90551 -83-0)商购。
至少一种共聚物(A)的单体b)为至少一种,例如一种、两种或三种(甲基)丙烯酸的线性或支化C18-C22醇酯。考虑此类(甲基)丙烯酸的线性或支化C18-C22醇酯,例如甲基丙烯酸十八烷基酯、甲基丙烯酸二十烷基酯、甲基丙烯酸二十二烷基酯、丙烯酸十八烷基酯、丙烯酸二十烷基酯、丙烯酸二十二烷基酯、或至少两种不同的(甲基)丙烯酸C18-C22醇酯的混合物,例如甲基丙烯酸十八烷基酯、甲基丙烯酸二十烷基酯和甲基丙烯酸二十二烷基酯的混合物,其可作为工业级甲基丙烯酸山嵛酯(CAS:90551 -86-3)商购。
共聚物(A)的单体a)和b)是不同的,即单体a)和单体b)由于醇的链长而不同,例如单体a)和单体b)不能分别为同一C18醇的(甲基)丙烯酸酯。然而,单体a)和b)能够各自包含同一醇例如C18醇的(甲基)丙烯酸酯,无论是单体a)或单体b)或单体a)和b),都为至少两种(甲基)丙烯酸酯的混合物,其中所述至少两种(甲基)丙烯酸酯中只有一种为同一醇例如C18醇的酯。因此,单体a)可以为甲基丙烯酸十六烷基酯和甲基丙烯酸十八烷基酯的混合物,单体b)可以为甲基丙烯酸十八烷基酯、甲基丙烯酸二十烷基酯和甲基丙烯酸二十二烷基酯的混合物。
单体a)或单体b)各自为丙烯酸酯或甲基丙烯酸酯,或丙烯酸酯和甲基丙烯酸酯以某一摩尔比例如1:1、1.5:1或1:1.5的混合物。
共聚物(A)的单体a)和单体b)为可商购的或能够通过一般已知的方法制备。
在一个实施方案中,所述至少一种用于制备至少一种共聚物(A)的(甲基)丙烯酸酯a)和b)包含饱和醇,即所述至少一种(甲基)丙烯酸酯a)和b)不含具有碳-碳多键的不饱和醇。
所述至少一种选自氯乙烯和偏二氯乙烯的单体c)为可商购的。
所述至少一种选自(甲基)丙烯酸2-羟基乙酯和(甲基)丙烯酸3-氯-2-羟基乙酯的单体d)在制备至少一种共聚物(A)中不是严格需要的,但可以用于改善合成纺织织物的效果水平。
所述至少一种共聚物(A)通过a)至少一种(甲基)丙烯酸C16-C18醇酯、b)至少一种(甲基)丙烯酸C18-C22醇酯、c)至少一种选自氯乙烯和偏二氯乙烯的单体和任选地d)至少一种选自(甲基)丙烯酸2-羟基乙酯和(甲基)丙烯酸3-氯-2-羟基乙酯的单体的聚合获得。除了单体a)、b)、c)和任选地d)之外,其他合适的单体也可以用于聚合反应中,只要这些单体不劣化通过本发明实现的有利效果。令人惊讶地,苯乙烯或α-甲基苯乙烯不是制备至少一种共聚物(A)以实现有利效果所必要的,并因此可以省去。优选地,所述至少一种共聚物(A)通过单体a)、b)、c)和任选地d)而不使用任何其他单体聚合获得,即至少一种共聚物(A)有利地由单体a)、b)、c)和任选地d)构成。
所述至少一种共聚物(A)能够通过以下本领域中一般已知的方法由单体a)、b)、c)和任选地d)制备。典型地,通过使用自由基聚合引发剂进行共聚作为自由基聚合。出于本发明的目的,所使用的自由基聚合引发剂包括偶氮化合物,例如分别来自DuPont或WAKO PureChemical Industries的Vazo 56或Wako V-50(CAS:2997-92-4)。基于单体a)、b)、c)和任选地d)的总重量,以通常已知的量例如2.5重量%至5重量%施加自由基聚合引发剂。
所述至少一种共聚物(A)获自以下物质的彼此聚合
20重量%至50重量%,优选30重量%至40重量%的单体a),
20重量%至50重量%,优选30重量%至40重量%的单体b),
10重量%至40重量%,优选20重量%至30重量%的单体c),
0重量%至10重量%,优选0重量%至5重量%的单体d),基于聚合反应中使用的单体a)、b)、c)和d)的总重量计,聚合反应中使用的单体a)、b)、c)和d)的总量为100重量%。
共聚物(A)是新颖的。因此,本发明还涉及由以下物质彼此聚合获得的共聚物(A):
a) 至少一种不含氟的(甲基)丙烯酸C16-C18醇酯,
b) 至少一种不含氟的(甲基)丙烯酸C18-C22醇酯,
c) 至少一种选自氯乙烯和偏二氯乙烯的单体,和任选地
d) 至少一种选自(甲基)丙烯酸2-羟基乙酯和(甲基)丙烯酸3-氯-2-羟基乙酯的单体,其中适用于上文给出的含义和参数选择。
所述至少一种蜡组分(B)选自具有55℃至75℃的熔化范围的石蜡和具有25℃至55℃的熔化范围的硅蜡。具有这些范围之外的熔化范围的石蜡和硅蜡不是非常适合根据本发明的分散体。具有比上述更低熔化范围的石蜡和硅蜡没有为采用水性分散体处理的纺织品提供期望的关于防水性的效果水平。它们还导致经处理的纺织品部分降低的清洗耐久性。具有比上述更高的熔化范围的石蜡和硅蜡可能导致纺织品的可接受的防水性和清洗耐久性,但导致这些水性分散体具有提高的粘度,从而这些分散体的可加工性变得不足够。
此外,然后分散体更昂贵和更不方便制造。合适的石蜡是已知的并例如记载于"Rompp Chemie-Lexikon, 第9版, Georg-Thieme-Verlag, Stuttgart - New York, 章节抬头"Paraffin"和"Wachse"中。合适的硅蜡例如为含烷基侧链的聚硅氧烷。用于本发明分散体的至少一种蜡(B)是可商购的,例如作为合适的石蜡的Sasol Wax GmbH的Sasolwax7040和作为合适的硅蜡的Siltech Corporation的Silwax D222。
如果石蜡用作所述至少一种组分(B),则根据本发明的水性分散体合适地包含例如20至60重量%,优选30至50重量%,特别是35至45重量%的组分(A),和40至80重量%,优选50至70重量%,特别是55至65重量%的具有55℃至75℃的熔化范围的石蜡作为组分(B),基于水性分散体中的组分(A)和组分(B)的总重量计,组分(A)和(B)总计为100重量%。
如果硅蜡用作所述至少一种组分(B),则根据本发明的水性分散体合适地包含例如60至95重量%,优选70至90重量%,特别是75至85重量%的组分(A),和5至40重量%,优选10至30重量%,特别是15至25重量%的具有25℃至55℃的熔化范围的硅蜡作为组分(B),基于水性分散体中的组分(A)和组分(B)的总重量计,组分(A)和(B)总计为100重量%。
所述至少一种表面活性剂(C)为确保分散体稳定性的分散剂或分散剂混合物。可用的分散剂包括已知的商购表面活性化合物,例如非离子型乙氧基化化合物,例如乙氧基化醇或乙氧基化羧酸、阳离子型表面活性剂,例如季铵盐、或脂肪胺。合适地,脂肪胺与合适的酸例如有机酸如乙酸组合施加。
优选地,所述至少一种表面活性剂(C)为脂肪胺、或脂肪醇乙氧基化物、或脂肪胺和脂肪醇乙氧基化物的表面活性剂混合物。合适的脂肪胺例如为C12-C22烷基二甲基胺,例如月桂基二甲基胺、十四烷基二甲基胺、十六烷基二甲基胺、二甲基椰油胺(dimethylcoconut amine)、十八烷基二甲基胺、二十二烷基二甲基胺,特别是十八烷基二甲基胺。合适的脂肪胺为可商购的。合适的脂肪醇乙氧基化物为支化或未支化的。合适的支化的仲醇乙氧基化物例如为聚乙二醇三甲基壬基醚,例如来自Dow的Tergitol TMN-10。
基于分散体的总重量计,本发明的分散体包含0.5重量%至3重量%的至少一种表面活性剂(C)。优选地,基于分散体的总重量计,脂肪胺以0.5重量%至2重量%的量施加。本发明的水性分散体具有非常高的稳定性。
根据本发明的水性分散体能够在一步法或两步法中制备。
在本发明的一个实施方案中,如果该蜡(B)为石蜡,应用两步法。因此,通过在容器中将蜡加热至比其熔点大约高20℃制备石蜡(B)的水性分散体。合适地,添加少量合适溶剂,例如二丙二醇。分开制备至少一种表面活性剂(C)的热水性混合物并使用Turrax在搅拌下添加至熔融蜡中,其随后进行高压分散,例如在250 bar和85至90℃下进行。在分开的容器中,通过混合至少一种表面活性剂(C)、单体a)、b)和任选地d)和温水制备共聚物(A)的水性分散体。通过例如在250 bar和50至60℃下高压分散所述混合物获得分散体。将所述分散体冷却至室温,添加聚合引发剂和单体c),并在例如55至65℃的温度下进行聚合数个小时。合并石蜡(B)的水性分散体和共聚物(A)的水性分散体以获得稳定的水性分散体。
在本发明的另一个实施方案中,如果该蜡(B)为硅蜡,应用一步法。因此,通过使用Turrax在搅拌下向容器添加至少一种表面活性剂(C)、适当地少量合适溶剂例如二丙二醇、硅蜡(B)、单体a)、b)和任选地d)和温水制备水性分散体。通过在例如250 bar和50至60℃下高压分散所述混合物获得分散体。将该分散体冷却至室温,添加聚合引发剂和单体c),并在例如55至65℃的温度下进行聚合数个小时以获得稳定的水性分散体。
如果期望的话,可以将已知用作纺织品处理组合物的组分的进一步成分添加至本发明的所得水性分散体。
可以通过以下的一般性常规方法例如通过填补、随后干燥和在需要时在例如90至190℃,优选100至180℃的温度下固化进行纺织织物的处理。在某一实施方案中,在100℃下进行低温固化。在另一实施方案中,在150℃下进行固化。采用根据本发明的水性分散体处理的纺织织物例如为棉、聚酯或棉-聚酯共混物。通常,此类织物为织造物、针织物或非织造物。
根据本发明的分散体特别用于赋予天然和合成纺织织物防水性。令人惊讶地,甚至在合成纺织织物,例如聚酯织物或棉和聚酯的混合织物上实现期望的防水效果水平。可以通过使将本发明的水性分散体与用于防油和水的产品的增量剂(例如PHOBOL® XAN增量剂(Huntsman Corp))组合使用而改善效果水平。采用根据本发明的水性分散体处理的纺织织物特别适合外套。
以下实施例用于示例本发明。除非另外指出,否则温度以摄氏度提供,份为重量份和百分比涉及重量百分比。重量份以千克对升的比率与体积份相关。
化学物质:
• 十八烷基二甲基胺(CAS: 124-28-7)
• Tergitol TMN-10:> 87 %聚乙二醇三甲基壬基醚(CAS: 60828-78-6)
• 二丙二醇(CAS:25265-71-8)
• 乙酸(CAS:64-19-7)
• 在大致70℃ 下熔化的Paraffin 2222或Sasolwax 7040(CAS:8002-74-2;64742-51-4)
• Silwax D222,熔化范围为34至42℃(CAS:73891-93-7)
• 甲基丙烯酸山嵛酯1822 (BEMA 1822) (CAS:90551-86-3)
• 甲基丙烯酸硬脂酯(MA 16-18) (CAS:90551-83-0)
• 甲基丙烯酸2-羟基乙酯(CAS:868-77-9)
• 偏二氯乙烯(CAS:75-35-4)
• Wako V 50:2,2'-偶氮双(2-甲基丙脒)二盐酸盐(CAS:2997-92-4)
• 用于防油和水的产品的PHOBOL® XAN增量剂。
实施例1:
a) 向容器装填2.2份十八烷基二甲基胺、1.1份Tergitol TMN-10、6.6份二丙二醇和2.0份乙酸(60%)。向这个混合物中添加15.0份甲基丙烯酸山嵛酯、15.0份甲基丙烯酸硬脂酯和0.7份甲基丙烯酸2-羟基乙酯和最后110份温水。采用Turrax搅拌该混合物大约1分钟,随后在250 bar的压力和50至60℃的温度下将其高压分散以获得稳定乳液。将所获得的乳液冷却至大约20℃的温度。在4.6份水和12.0份偏二氯乙烯中添加0.4份Wako V 50之后,在氮气气氛中在65℃下进行聚合大约8小时。获得152份水性共聚物分散体(在120℃ 下干燥90分钟之后,40.6份产品)。
b) 在容器中,60.0份Paraffin 2222或Sasolwax 7040在大约90℃的温度下熔化。将10.0份二丙二醇添加至所获得的石蜡的热熔体中。在搅拌下用3.4份十八烷基二甲基胺、1.6份Tergitol TMN-10和4.0份乙酸(60%)和最后200份热水装填分开的容器。在搅拌下将所得混合物添加至熔融蜡中。
随后,用Turrax搅拌所得混合物大约1分钟,其随后在250 bar的压力和85至90℃的温度下高压分散以获得265份稳定分散体。
根据本发明的水性分散体通过混合56.3份由步骤a)获得的分散体和155.8份由步骤b)获得的分散体获得。
实施例2:
向容器装填2.2份十八烷基二甲基胺、1.1份Tergitol TMN- 10、6.6份二丙二醇和2.0份乙酸(60%)。向这个混合物中添加8.5份硅蜡、15.0份甲基丙烯酸山嵛酯、15.0份甲基丙烯酸硬脂酯和0.7份甲基丙烯酸2-羟基乙酯和最后110份温水。采用Turrax搅拌该混合物大约1分钟,随后在250 bar的压力和50至60℃的温度下将其高压分散以获得稳定乳液。将所获得的乳液冷却至大约20℃的温度。在4.5份水和12.0份偏二氯乙烯中添加0.5份Wako V 50之后,在氮气气氛中在65℃下进行聚合大约8小时。获得155份根据本发明的水性分散体(在120℃ 下干燥90分钟之后,47.3份产品)。
以下实施例记载采用按照实施例1和2制备的分散体处理不同的纺织织物。
应用实施例(整理):
聚酯:采用含1 g/l的60%乙酸、5 g/l润湿剂(INVADINE® PBN)和40 g/l (80 g/l)的实施例1的分散体或实施例2的分散体的液体填补织造的100%聚酯织物(液体吸收率59%)。
棉-聚酯共混物:在轧染机(pad-mangle)中采用含1 g/l 的60%乙酸、5 g/l的润湿剂(INVADINE® PBN)和40 g/l (80 g/l)的实施例1的分散体或实施例2的分散体的液体处理织造织物(液体吸收率51 %)。
棉:在轧染机中采用含1 g/l 的60%乙酸、5 g/l的润湿剂(INVADINE® PBN)和40g/l (80 g/l)的实施例1的分散体或实施例2的分散体的液体处理织造棉织物(100%)(液体吸收率69 %)。
使用水性处理组合物(其除了上述成分之外还含有5 g/l (10 g/l)的PHOBOL®XAN增量剂)重复上文的应用实施例。
在填补之后,在110℃下干燥织物(棉、聚酯和棉-聚酯共混物)10分钟,然后在150℃下固化5分钟。
对按照应用实施例获得的经整理的织物施以以下测试:
(I) 按照AATCC 22-2005,ISO 4920 (EN 24 920)进行的喷雾测试
(II) 按照DIN EN 29865,ISO 9865进行的Bundesmann测试。
测试结果总结于下表1至3中。
表1:聚酯织物的结果
a) 40 g/l的实施例1(Ex1)或实施例2(Ex2)的分散体
b) 80 g/l的实施例1(Ex1)或实施例2(Ex2)的分散体
c) 5 g/l的PHOBOL® XAN增量剂
d) 10 g/l的PHOBOL® XAN增量剂
e) 织物整理之后的初始等级
f) 在经整理的织物20 x洗涤和清洗,20 x 7A LTD(清洗烘干(laundy tumble dry))之后的等级。
表2:棉-聚酯共混织物的结果
a)至f)如表1下方定义。
表3:棉织物的结果
a)至f)如表1下方定义。
Claims (8)
1.一种不含含氟化学物质的水性分散体,其包含:
(A) 至少一种通过以下单体聚合获得的共聚物:
a) 至少一种不含氟的(甲基)丙烯酸C16-C18醇酯,
b) 至少一种不含氟的(甲基)丙烯酸C18-C22醇酯,
c) 至少一种选自氯乙烯和偏二氯乙烯的单体,和任选地
d) 至少一种选自(甲基)丙烯酸2-羟基乙酯和(甲基)丙烯酸3-氯-2-羟基乙酯的单体,
(B) 至少一种选自具有55℃至75℃的熔化范围的石蜡和具有25℃至55℃的熔化范围的硅蜡的组分,
(C) 至少一种表面活性剂,和
(D) 水,其中
共聚物(A)的单体a)和b)是不同的,和
共聚物(A)不含任何苯乙烯或α-甲基苯乙烯的聚合单元。
2.根据权利要求1所述的水性分散体,其包含
20至60重量%的组分(A),和
40至80重量%的具有55℃至75℃的熔化范围的石蜡作为组分(B),
基于水性分散体中的组分(A)和组分(B)的总重量计。
3.根据权利要求1所述的水性分散体,其包含
60至95重量%的组分(A),和
5至40重量%的具有25℃至55℃的熔化范围的硅蜡作为组分(B),
基于水性分散体中的组分(A)和组分(B)的总重量计。
4.根据权利要求1至3任一项所述的水性分散体,其中所述至少一种共聚物(A)获自以下物质的彼此聚合
20重量%至50重量%,优选30重量%至40重量%的单体a),
20重量%至50重量%,优选30重量%至40重量%的单体b),
10重量%至40重量%,优选20重量%至30重量%的单体c),
0重量%至10重量%,优选0重量%至5重量%的单体d),基于聚合反应中使用的单体a)、b)、c)和d)的总重量计。
5.根据权利要求1至4任一项所述的水性分散体,其中所述至少一种表面活性剂为脂肪胺、或脂肪醇乙氧基化物、或脂肪胺和脂肪醇乙氧基化物的表面活性剂混合物。
6.一种处理纺织织物的方法,其包括向纺织织物施加根据权利要求1至5任一项所述的水性分散体。
7.根据权利要求6所述的方法,其中所述纺织织物为棉、聚酯或棉-聚酯共混织物。
8.一种通过以下单体聚合获得的共聚物:
a) 至少一种不含氟的(甲基)丙烯酸C16-C18醇酯,
b) 至少一种不含氟的(甲基)丙烯酸C18-C22醇酯,
c) 至少一种选自氯乙烯和偏二氯乙烯的单体,和任选地
d) 至少一种选自(甲基)丙烯酸2-羟基乙酯和(甲基)丙烯酸3-氯-2-羟基乙酯的单体。
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PCT/EP2017/072766 WO2018054712A1 (en) | 2016-09-23 | 2017-09-11 | Fluorine-free aqueous dispersions for the finishing of textile fabrics |
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KR102513179B1 (ko) | 2018-02-20 | 2023-03-24 | 다이킨 고교 가부시키가이샤 | 표면 처리제 |
JP7469845B2 (ja) * | 2018-09-14 | 2024-04-17 | 日華化学株式会社 | 繊維用撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法 |
TWI825185B (zh) * | 2018-09-28 | 2023-12-11 | 日商大金工業股份有限公司 | 非氟鏈段共聚物 |
JP7252757B2 (ja) * | 2018-12-27 | 2023-04-05 | 日華化学株式会社 | 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法 |
CN111500066A (zh) * | 2019-01-30 | 2020-08-07 | 大金工业株式会社 | 拨水性柔软剂 |
US20230037578A1 (en) * | 2019-12-24 | 2023-02-09 | Mitsui Chemicals, Inc. | Water repellent composition, method for producing water repellent composition, and fiber product |
JP2021143292A (ja) * | 2020-03-12 | 2021-09-24 | 日華化学株式会社 | 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法 |
CN111944102B (zh) * | 2020-08-20 | 2022-04-26 | 北京中纺化工股份有限公司 | 一种提高剥离强度的纺织添加剂 |
US20240068158A1 (en) | 2021-03-15 | 2024-02-29 | Dow Silicones Corporation | Silicone - (meth)acrylate copolymer formulation and processes for preparation and use thereof |
JP2022169275A (ja) * | 2021-04-27 | 2022-11-09 | ダイキン工業株式会社 | 分散液 |
WO2023019044A1 (en) | 2021-08-10 | 2023-02-16 | Dow Silicones Corporation | Silicone-(meth)acrylate copolymer emulsion formulation for textile treatment |
WO2023086692A1 (en) | 2021-11-10 | 2023-05-19 | Dow Silicones Corporation | Textile treatment emulsion formulation including a silicone - (meth)acrylate copolymer and a silicone additive |
JP7307788B1 (ja) | 2021-12-28 | 2023-07-12 | 日華化学株式会社 | 撥水剤組成物及びその製造方法、並びに撥水性繊維製品及びその製造方法 |
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US20200017616A1 (en) | 2020-01-16 |
JP2019534908A (ja) | 2019-12-05 |
BR112019003705A2 (pt) | 2019-05-28 |
MX2019002695A (es) | 2019-05-20 |
ES2870972T3 (es) | 2021-10-28 |
KR20190052117A (ko) | 2019-05-15 |
US10844151B2 (en) | 2020-11-24 |
PT3516105T (pt) | 2021-06-11 |
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WO2018054712A1 (en) | 2018-03-29 |
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