CN107532034A - 可固化水性组合物 - Google Patents
可固化水性组合物 Download PDFInfo
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- CN107532034A CN107532034A CN201580079972.7A CN201580079972A CN107532034A CN 107532034 A CN107532034 A CN 107532034A CN 201580079972 A CN201580079972 A CN 201580079972A CN 107532034 A CN107532034 A CN 107532034A
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- aqueous compositions
- polymer
- curable aqueous
- crosslinking agent
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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Abstract
本发明提供一种包括(共)聚合物和环氧交联剂的可固化水性组合物。所述(共)聚合物以(共)聚合单元的形式包括,按所述(共)聚合物的总单体计,按干重计0.05%至10%的具有至少两个羧酸基的烯属不饱和酸性单体,并且所述环氧交联剂是具有至少两个反应性环氧乙烷基的脂肪族化合物。其另外提供用于形成经过处理的衬底的方法和由所述方法形成的衬底。
Description
技术领域
本发明涉及可固化水性组合物、使用所述可固化水性组合物形成经过处理的柔性衬底的方法和如此处理的衬底。
背景技术
柔性衬底,如纸、纺织织物和非纺织织物,常常通过用聚合粘合剂处理来加固或加强以便安置于衬底内或衬底上。这类聚合粘合剂在本领域中可被称为可固化水性组合物。经过处理的衬底在干燥的、浸水的(湿)或浸有异丙醇(IPA)的状态下的拉伸强度是反映可固化水性组合物品质的最重要的特性之一。当经可固化水性组合物处理的衬底具有较高干燥、湿或IPA拉伸强度时,它通常具有改良的特性,包含弹性、抗裂性、干洗耐性、耐洗性、撕裂强度和折叠耐力。
在许多情况下,可固化水性组合物是以基本上热塑性或基本上非交联的状态存在,使得在可固化水性溶液或分散液已经接触衬底之后可能出现流动、渗透、成膜等等。为了增强经过处理的衬底的特性,常常期望一旦可固化水性组合物到达它的最终位置便进行交联或同时进行干燥过程。许多常规交联剂如共聚N-羟甲基丙烯酰胺(NMA)和添加的脲/甲醛树脂本身含有或释放甲醛。另外,含有NMA的可固化水性组合物在受热时释放更多甲醛。
因此期望提供一种具有良好拉伸强度的环境友好型可固化水性组合物。
发明内容
本发明提供一种包括(共)聚合物和环氧交联剂的可固化水性组合物。(共)聚合物以(共)聚合单元的形式包括,按(共)聚合物的总单体计,按干重计0.05%至10%的具有至少两个羧酸基的烯属不饱和酸性单体。环氧交联剂是具有至少两个反应性环氧乙烷基的脂肪族化合物。
本发明另外提供形成经过处理的衬底的方法,包括以下步骤:i)形成包括(共)聚合物和环氧交联剂的可固化水性组合物,所述(共)聚合物以(共)聚合单元的形式包括,按(共)聚合物的总单体计,按干重计0.05%至10%的具有至少两个羧酸基的烯属不饱和酸性单体,并且所述环氧交联剂是具有至少两个反应性环氧乙烷基的脂肪族化合物;ii)将柔性衬底与可固化水性组合物接触;和iii)在80℃至250℃温度下加热可固化水性组合物。本发明另外提供由以上方法形成的衬底。
具体实施方式
出于描述本发明组合物中成分的目的,所有包括圆括号的短语指示所包含的带圆括号的物质以及其不带圆括号的物质中的任一者或两者。例如,短语“(共)聚合物”包含聚合物、共聚物以及其混合物;并且短语“(甲基)丙烯酸酯”意指丙烯酸酯、甲基丙烯酸酯以及其混合物。
可固化水性组合物包括(共)聚合物和环氧交联剂。
(共)聚合物
本发明的可固化水性组合物包括(共)聚合物或(共)聚合物的冷掺合物。在本文中短语“可固化”意指能够发生足以改变已施加有效量的聚合粘合剂的柔性衬底的特性的结构或形态变化,如共价化学反应、离子相互作用或簇合、改善的对衬底的粘附力、相转化或逆转和氢键结。在本文中(共)聚合物是通过水性乳液或溶液聚合过程中的烯属不饱和单体的加成聚合制备的(共)聚合物;本文中(共)聚合物的冷掺合物是两种或更多种乳液或溶液(共)聚合物的混合物。在本文中“水性组合物”意指连续相是水或主要包含水但也包含可与水混溶的溶剂的混合物的组合物。在本文中“可固化组合物”是在某一程度上经历化学过程,如在加入的能量的作用下(最典型地是加热)形成共价键,的可固化组合物。
(共)聚合物以(共)聚合单元的形式包括,按(共)聚合物的总单体计,按干重计0.05%至10%,优选地2%至8%,并且更优选地4%至6%的具有至少两个羧酸基的烯属不饱和酸性单体。适合的具有至少两个羧酸基的烯属不饱和酸性单体的实例包含:伊康酸、反丁烯二酸、顺丁烯二酸、乌头酸、它们的盐以及其混合物。优选地,烯属不饱和酸性单体具有两个羧酸基。
(共)聚合物另外包括,按(共)聚合物的总单体计,按干重计至多99.95%,优选地75%至98%,并且更优选地90%至95%的一种或多种其它(共)聚合烯属不饱和单体。适合的其它(共)聚合烯属不饱和单体的实例包含:(甲基)丙烯酸酯单体,包含:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、脲基官能性(甲基)丙烯酸酯和(甲基)丙烯酸的乙酰乙酸酯、乙酰胺或氰基乙酸酯;苯乙烯或取代苯乙烯;乙烯基甲苯;丁二烯;乙酸乙烯酯或其它乙烯基酯;乙烯基单体,如氯乙烯、偏氯乙烯和N-乙烯基吡咯酮;和(甲基)丙烯腈。优选地,不包括在聚合时或后续加工期间可能产生甲醛的单体,如N-醇(甲基)丙烯酰胺。
在一些实施例中,(共)聚合物另外包括,按(共)聚合物的总单体计,按干重计小于5%,优选地小于2%,并且更优选地小于1%的(共)聚合多烯属不饱和单体。多烯属不饱和单体包含:(甲基)丙烯酸烯丙酯、邻苯二甲酸二烯丙酯、1,4-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,2-乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯和二乙烯基苯。
可固化水性组合物可能包括至少两种不同(共)聚合物。对于两种或更多种乳液或溶液聚合物的混合物,具有至少两个羧酸基的(共)聚合烯属不饱和酸性单体的含量应由(共)聚合物的总体组成确定而不考虑其中(共)聚合物的数目。
用于制备水性乳液或溶液(共)聚合物的乳液或溶液聚合技术在所属领域中是众所周知的,并且至少在美国专利第4,325,856号、第4,654,397号、第5,314,943号和第4,814,373号中公开。常规表面活性剂可用作阴离子和/或非离子乳化剂,如碱金属烷基硫酸盐或铵烷基硫酸盐、烷基磺酸、脂肪酸和乙氧基化烷基酚。按总单体的干重计,所用表面活性剂的量通常是按干重计0.1%至6%。可使用热引发方法或氧化还原引发方法。可以使用常规自由基引发剂,并且适合实例包含过氧化氢、叔丁基过氧化氢、叔戊基过氧化氢、铵和碱金属过硫酸盐,典型地以按总单体的干重计,按干重计0.01%至3.0%的含量。可以类似含量使用结合有适合还原剂,如连二亚硫酸钠、异抗坏血酸和亚硫酸氢钠,的使用相同引发剂的氧化还原体系,任选地组合金属离子如铁和铜,任选地另外包含金属络合剂。可使用链转移剂,如硫醇,来调整(共)聚合物的分子量。单体混合物可以无掺杂的添加或以水中乳液的形式添加。在反应期间,单体混合物可使用均匀或变化的组合物以单次添加或以多次添加或连续地添加。在任一阶段之前、期间或之后可添加其它成分,如自由基引发剂、氧化剂、还原剂、链转移剂、中和剂、表面活性剂和分散剂。可以采用产生多峰粒度分布的方法,如公开于美国专利第4,384,056号和第4,539,361号中的方法。
在另一实施例中,水性乳液(共)聚合物可通过多阶段乳液聚合方法制备,其中至少两个组成不同的阶段以依次形式聚合。这类方法通常导致形成至少两种互不相容的聚合物组合物,从而导致在聚合物粒子内形成至少两个相。这类粒子由两个或更多个各种几何结构的相构成,如芯/壳或芯/皮粒子、壳相不完全包裹芯的芯/壳粒子、多个芯的芯/壳粒子和互穿网状粒子。多阶段乳液聚合物的每个阶段可含有选自上文中针对乳液聚合物所公开的那些单体、表面活性剂和链转移剂。对于多阶段乳液聚合物,共聚二甲酸单体含量应由乳液聚合物的总体组成确定而不考虑其中阶段或相的数目。用于制备这类多阶段乳液聚合物的聚合技术在所属领域中是众所周知的,并且公开于美国专利第4,325,856号、第4,654,397号和第4,814,373号中。
(共)聚合物的玻璃转化温度(Tg)是-65℃至150℃,优选地-55℃至65℃,并且更优选地-35℃至40℃。在本文中聚合物的Tg使用福克斯方程式(Fox equation)计算(T.G.Fox,《美国物理学会通报(Bull.Am.Physics Soc.)》,第1卷,第3期,123页(1956)),也就是说,对于计算单体M1和单体M2的共聚物的Tg,
1/Tg(计算)=w(M1)/Tg(M1)+w(M2)/Tg(M2),
其中Tg(计算)是计算的共聚物的玻璃转化温度,w(M1)是共聚物中单体M1的重量分数,w(M2)是共聚物中单体M2的重量分数,Tg(M1)是M1的均聚物的玻璃转化温度,并且Tg(M2)是M2的均聚物的玻璃转化温度,而且所有温度均以绝对温度单位(K),它可由等式T(℃)=T(K)-273.15转换成摄氏度(℃)。
均聚物的玻璃转化温度可例如见于“聚合物手册(Polymer Handbook)”,由J.Brandrup和E.H.Immergut编,国际科学出版社(Interscience Publishers)。
(共)聚合物粒子的平均粒径典型地是30纳米到500纳米,优选地60纳米至150纳米,如由Brookhaven Instrument公司,Holtsville,NY提供的Brookhaven BI-90型粒径分析仪测量。
环氧交联剂
环氧交联剂是具有至少两个反应性环氧乙烷基的脂肪族化合物。适合的环氧交联剂的实例包含:表氯醇与脂肪族多元醇的反应产物缩水甘油醚和表氯醇与脂肪族二羧酸的反应产物缩水甘油酯。适合的脂肪族多元醇的实例包含单体多元醇和聚合多元醇。适合的单体多元醇的实例包含乙二醇、甘油、1,4-丁二醇、1,6-己二醇、季戊四醇以及其混合物。适合的聚合多元醇的实例包含聚二醇,如聚乙二醇(PEG)、聚丙二醇(PPG)、聚丁二醇(PBG);聚二醇共聚物;以及其混合物。优选地,脂肪族多元醇是聚乙二醇(PEG)、聚丙二醇(PPG)、其共聚物以及其混合物。更优选地,多元醇是聚丙二醇(PPG)。适合的脂肪族二羧酸的实例包含己二酸、戊二酸、壬二酸以及其混合物。按(共)聚合物的总干重计,环氧乙烷基的重量%是,按干重计0.23%至10%,优选地0.5%至5%,并且更优选地1%至2.5%。
环氧交联剂的粘度小于10000mPa.s,优选地小于3000mPa.s,并且更优选地小于1000mPa.s。
适用于本发明中的环氧交联剂和这类环氧树脂的制备公开于,例如Lee,H.和Neville,K.,《环氧树脂手册(Handbook of Epoxy Resins)》,McGraw-Hill图书公司,纽约(New York),1967,第2章,第2-1至2-27页,所述文献以引用的方式并入本文中。
其它成分
可固化水性组合物可能另外含有常规处理成分,如乳化剂、颜料、填充剂或增量剂、防迁移辅助物、固化剂、聚结剂、表面活性剂、杀生物剂、塑化剂、有机硅烷、抗起泡剂、防腐剂、着色剂、蜡、其它聚合物和抗氧化剂。
使用可固化水性组合物处理衬底的方法
在本发明的另一方面中,提供形成经过处理的衬底的方法,包括以下步骤:a)形成本发明的可固化水性组合物;b)将柔性衬底与可固化水性组合物接触;和c)在80℃至250℃温度下加热可固化水性组合物。
适合的柔性衬底的实例包含:纸、皮革、纺织织物和非纺织织物、毯和垫或其它纤维的组合物和纤维。包含纤维的衬底可包含:棉、如聚酯和人造丝的合成纤维、玻璃以及其混合物。
使用常规施加技术,如空气或无空气喷雾、浸染、浸透、滚涂、帘幕式涂覆和印刷,将柔性衬底与可固化水性组合物接触。.
将可固化水性组合物在80℃至200℃,优选地100℃至170℃,并且更优选地125℃至150℃温度下加热一段足以达到可接受的固化水平的时间,如1分钟至10分钟,优选地2分钟至5分钟的时间。干燥和固化功能可在两个或更多个分开的步骤中进行。例如,可将组合物先在一温度下加热并且持续足以基本上干燥但不基本上固化组合物的时间,并且随后在较高温度下再次加热和/或持续一段更长的时间来进行固化。这种程序,称作“B阶段化”,可用于提供经过粘合剂处理的非纺织,例如以卷的形式,它可在后续阶段被固化,与固化过程并行地形成或成型为特定构形或不形成或成型为特定构形。
经过处理的衬底
在本发明的另一方面中,提供由本发明的方法形成的经过处理的衬底。
在本说明书中,除非另外规定,否则每个优选技术方案和更优选技术方案中的技术特点可彼此组合来形成新技术方案。为了简洁,申请人省略对这些组合的描述。然而,所有通过组合这些技术特点而获得的技术方案应被视为明确地逐字地被描述在本说明书中。
实例
I.原材料
所使用的缩写:PPG=聚丙二醇;IPA=异丙醇;DI水=去离子水;EA=丙烯酸乙酯;EHA=丙烯酸2-乙基己酯;BA=丙烯酸丁酯;Sty=苯乙烯;IA=伊康酸;AA=丙烯酸;MAA=甲基丙烯酸;和NMA=n-羟甲基丙烯酰胺。
D.E.R.TM732是具有至少两个反应性环氧乙烷基的脂肪族环氧树脂,可购自陶氏化学公司(The Dow Chemical Company)。它的环氧化物当量重量(epoxide equivalentweight;EEW)是310-330gr/eq,并且粘度是25℃下60-70mPa.s。
D.E.R.TM736是具有至少两个反应性环氧乙烷基的脂肪族环氧树脂,可购自陶氏化学公司(The Dow Chemical Company)。它的环氧化物当量重量(EEW)是175-205gr/eq,并且粘度是25℃下30-60mPa.s。
D.E.R.TM331是由表氯醇和双酚A反应得来的液态环氧树脂,可购自陶氏化学公司(The Dow Chemical Company)。它的环氧化物当量重量(EEW)是182-192gr/eq,并且粘度是25℃下11000-14000mPa.s。
TRITONTMX 100是陶氏化学公司(The Dow Chemical Company)的表面活性剂。
II.测试方法
1.膜制备和杨氏模量测试
将每个可固化水性组合物(按干重计4g)放入内径93mm的培养皿中,并且在恰当搅拌下用13.33g DI水稀释。将培养皿在室温下在调平表面上放置4天无振动。随后从培养皿中去除干燥膜。所有膜均约0.5至0.6mm厚。在测试之前,将膜在150℃下固化3min。将固化膜切成22mm×5mm,并且通过Instron 5943拉力测试仪测试它的杨氏模量。
2.经过处理的非纺织衬底和拉伸强度测试
将一张WHATMANTM4级滤纸(28cm×46cm,Whatman有限公司)浸入200mL可固化水性组合物中。用Mathis浸轧机浸染经过处理的衬底,并且随后在设计的条件(120℃下3分钟或150℃下3分钟)下干燥并固化。将可固化组合物在纸上的附加控制在28%与32%之间。将固化衬底切成1吋×5吋的碎片,其中5吋方向是纸的横向。在干燥(未经处理)、湿(浸没在中0.1%TRITONTMX 100溶液中30分钟之后)和“IPA”(浸没在异丙醇中30分钟之后)处理下用Instron 5943拉力测试仪测试试样的拉伸强度。湿强度反映可固化水性组合物在水中的耐性并且IPA强度反映可固化水性组合物在溶剂中的耐性。强度越高,可固化水性组合物的效能越好。
III.实验实例
1.聚合物乳液的制备
将710g DI水和65.6g十二烷基硫酸钠添加至氮气下的3升玻璃反应器中,在环境温度下保持30分钟并且随后加热至57℃。随后将通过在槽中伴随着恰当搅拌添加585g DI水、2.85g碳酸钠、4.1g十二烷基苯磺酸钠、729g BA、126g Sty、31.5g AA和15g IA制得的66g单体乳液1(ME1)和15g DI水添加至反应器中。两分钟之后,在56℃温度下添加5g0.15%水性硫酸铁七水合物的溶液、3.33g过硫酸铵在20g DI水中的溶液和0.17g硫酸氢钠在20g DI水中的溶液。在接下来的两分钟观测到放热至61.5℃,并且同时开始其余ME1和0.88g亚硫酸氢钠在60g DI水中的溶液的加成。温度保持在56.5℃至61.5℃进行加成126分钟的时间。随后添加30g DI水。适当时,尤其在二阶段聚合中,随后将通过在槽中伴随着适当搅拌添加65g DI水、1.0g十二烷基苯磺酸钠、2.5g AA、101g Sty制得的单体乳液2(ME2)添加到反应器中,并且另外添加0.69g 70%叔丁基过氧化氢溶液在5g DI水中的溶液和0.46g异抗坏血酸在5g DI水中的溶液。一段55分钟的时间之后,在此期间温度从58℃下降至49℃,添加1.0g叔丁基过氧化氢在10g DI水中的溶液和0.7g异抗坏血酸在10g DI水中的溶液。十五分钟之后,当温度降低至47℃时,添加1.0g叔丁基过氧化氢在10g DI水中的溶液和0.7g异抗坏血酸在10g DI水中的溶液。
根据以上方法利用二阶段聚合制备聚合物乳液1(PE1)。
聚合物乳液2(PE2)是根据以上方法利用一阶段聚合制备,只不过它的ME1包括650g DI水、16.5g十二烷基硫酸钠、950g EA和50g IA。
聚合物乳液3(PE3)是根据以上方法利用一阶段聚合制备,只不过它的ME1包括650g DI水、16.5g十二烷基硫酸钠、750g EA、200g EHA和50g IA。
聚合物乳液4(PE4)是根据以上方法利用一阶段聚合制备,只不过它的ME1包括650g DI水、16.5g十二烷基硫酸钠、750g EA、200g EHA、45g AA和5g IA。
聚合物乳液5(PE5)是根据以上方法利用一阶段聚合制备,只不过它的ME1包括650g DI水、16.5g十二烷基硫酸钠、750g EA、200g EHA和50g AA。
聚合物乳液6(PE6)是根据以上方法利用一阶段聚合制备,只不过它的ME1包括650g DI水、16.5g十二烷基硫酸钠、963g EA和37g NMA。
2.可固化水性组合物和比较可固化水性组合物(比较)的制备
将每个聚合物乳液和交联剂恰当地搅拌30min,得到可固化水性组合物。详细技术信息进一步描述在表1和表2中。
IV.结果
表1
可固化水性组合物 | 比较组合物1 | 比较组合物2 | 组合物1 | 组合物2 |
聚合物乳液 | PE1 | PE1 | PE1 | PE1 |
IA含量* | 1.5% | 1.5% | 1.5% | 1.5% |
环氧交联剂* | - | 3%D.E.R.331 | 3%D.E.R.736 | 6%D.E.R.736 |
环氧乙烷基* | - | 1.2% | 1.2% | 2.4% |
杨氏模量 | 0.26MPa | 0.60MPa | 1.56MPa | 2.15MPa |
*按以(共)聚合物的总干重计的干重%计。
如表1中所显示,比较组合物1是不包括环氧交联剂的比较可固化水性组合物,并且比较组合物2是包括芳香族环氧交联剂的比较可固化水性组合物,它不具有脂肪链。相比于本发明可固化水性组合物1和2中每一个,两个比较组合物皆显示较差杨氏模量。
对两个本发明实例,可固化水性组合物1和2,的观测支持:与可固化水性组合物1相比,具有较高环氧乙烷基含量的可固化水性组合物2显示更具改善的杨氏模量。
表2
可固化水性组合物 | 聚合物乳液 | 环氧交联剂 | IA* | 环氧乙烷基# |
比较3 | PE6 | - | - | - |
比较4 | PE2 | - | 5% | - |
比较5 | PE5 | - | - | - |
比较6 | PE4 | - | 0.5% | - |
比较7 | PE5 | D.E.R.736 | - | 1.4% |
比较8 | PE3 | - | 5% | - |
3 | PE2 | D.E.R.732 | 5% | 1.4% |
4 | PE2 | D.E.R.736 | 5% | 2.3% |
5 | PE3 | D.E.R.736 | 5% | 1.4% |
6 | PE4 | D.E.R.736 | 0.5% | 1.4% |
7 | PE3 | D.E.R.736 | 5% | 0.23% |
8 | PE3 | D.E.R.736 | 5% | 5.1% |
*按以(共)聚合物的总单体计的干重%计。
#按以(共)聚合物的总干重计的干重%计。
表3
*阈值意指可接受的效能值。
表2和表3是比较可固化水性组合物(比较)3至8和本发明可固化水性组合物3至8的拉伸强度结果。
本发明可固化水性组合物3和4包括适当量的聚合IA和环氧交联剂(环氧乙烷基含量),并且相比于不包括聚合IA和环氧交联剂(环氧乙烷基含量)的比较可固化水性组合物3的拉伸强度以及不包括环氧交联剂(环氧乙烷基含量)的比较可固化水性组合物4的拉伸强度,具有改善的拉伸强度(固化温度120℃或150℃)。
本发明可固化水性组合物5包括适当量的聚合IA和环氧交联剂(环氧乙烷基含量),并且相比于不包括聚合IA和环氧交联剂(环氧乙烷基含量)的比较可固化水性组合物5的拉伸强度,具有改善的拉伸强度(固化温度150℃)。
本发明可固化水性组合物6包括适当量的聚合IA和环氧交联剂(环氧乙烷基含量),并且相比于包括适当量的仅聚合IA或环氧交联剂(环氧乙烷基含量)的比较可固化水性组合物6和7的拉伸强度,具有改善的拉伸强度(固化温度150℃)。
本发明可固化水性组合物7和8包括适当量的聚合IA和环氧交联剂(环氧乙烷基含量),并且相比于包括仅适当量的聚合IA的比较可固化水性组合物8的拉伸强度,具有改善的拉伸强度(固化温度150℃)。
Claims (15)
1.一种可固化水性组合物,包括(共)聚合物和环氧交联剂,其中所述(共)聚合物以(共)聚合单元的形式包括,按所述(共)聚合物的总单体计,按干重计0.05%至10%的具有至少两个羧酸基的烯属不饱和酸性单体,并且所述环氧交联剂是具有至少两个反应性环氧乙烷基的脂肪族化合物。
2.根据权利要求1所述的可固化水性组合物,其中所述具有至少两个羧酸基的烯属不饱和酸性单体选自伊康酸、反丁烯二酸、顺丁烯二酸、乌头酸、它们的盐以及其混合物。
3.根据权利要求1所述的可固化水性组合物,其中所述烯属不饱和酸性单体具有两个羧酸基。
4.根据权利要求1所述的可固化水性组合物,其中所述(共)聚合物另外包括,按所述(共)聚合物的总单体计,按干重计至多99.95%的一种或多种其它(共)聚合烯属不饱和单体。
5.根据权利要求1所述的可固化水性组合物,其中所述(共)聚合物另外包括,按所述(共)聚合物的总单体计,按干重计小于5%的(共)聚合多烯属不饱和单体。
6.根据权利要求1所述的可固化水性组合物,其中所述(共)聚合物不包括在聚合时或后续加工期间产生甲醛的单体。
7.根据权利要求1所述的可固化水性组合物,其中所述(共)聚合物不包括N-醇(甲基)丙烯酰胺。
8.根据权利要求1所述的可固化水性组合物,其中所述环氧乙烷基在所述环氧交联剂中以按所述(共)聚合物的总干重计,按干重计0.23%至10%的范围内存在。
9.根据权利要求1所述的可固化水性组合物,其中所述环氧交联剂选自表氯醇与脂肪族多元醇的反应产物缩水甘油醚和表氯醇与脂肪族二羧酸的反应产物缩水甘油酯。
10.根据权利要求9所述的可固化水性组合物,其中所述脂肪族多元醇选自单体多元醇和聚合多元醇。
11.根据权利要求10所述的可固化水性组合物,其中所述脂肪族多元醇选自聚乙二醇、聚丙二醇、它们的共聚物以及其混合物。
12.根据权利要求1所述的可固化水性组合物,其中所述环氧交联剂的粘度小于10000mPa.s。
13.一种用于形成经过处理的衬底的方法,包括以下步骤:
i)形成包括(共)聚合物和环氧交联剂的可固化水性组合物,其中所述(共)聚合物以(共)聚合单元的形式包括,按所述(共)聚合物的总单体计,按干重计0.05%至10%的具有至少两个羧酸基的烯属不饱和酸性单体,所述环氧交联剂是具有至少两个反应性环氧乙烷基的脂肪族化合物;
ii)将柔性衬底与所述可固化水性组合物接触;和
iii)将所述可固化水性组合物在80℃至250℃的温度下加热。
14.根据权利要求13所述的方法,其中所述柔性衬底是纺织或非纺织纤维。
15.一种衬底,由根据权利要求13所述的方法形成。
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2015
- 2015-05-19 CN CN201580079972.7A patent/CN107532034B/zh active Active
- 2015-05-19 EP EP15892171.8A patent/EP3298091B1/en active Active
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- 2015-05-19 JP JP2017560159A patent/JP6709234B2/ja active Active
- 2015-05-19 US US15/574,906 patent/US10870776B2/en active Active
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- 2015-05-19 BR BR112017024119-6A patent/BR112017024119B1/pt active IP Right Grant
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2016
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US3926891A (en) * | 1974-03-13 | 1975-12-16 | Dow Chemical Co | Method for making a crosslinkable aqueous solution which is useful to form soft, water-swellable polyacrylate articles |
JP2002173871A (ja) * | 2000-12-06 | 2002-06-21 | Nippon Carbide Ind Co Inc | 繊維加工用架橋型樹脂水性分散液。 |
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MX2017014448A (es) | 2018-04-20 |
EP3298091A1 (en) | 2018-03-28 |
TW201641625A (zh) | 2016-12-01 |
CN107532034B (zh) | 2021-10-29 |
JP6709234B2 (ja) | 2020-06-10 |
RU2690348C1 (ru) | 2019-05-31 |
US10870776B2 (en) | 2020-12-22 |
TWI793060B (zh) | 2023-02-21 |
BR112017024119B1 (pt) | 2022-09-06 |
BR112017024119A2 (zh) | 2018-07-31 |
JP2018521157A (ja) | 2018-08-02 |
WO2016183792A1 (en) | 2016-11-24 |
AR104536A1 (es) | 2017-07-26 |
EP3298091A4 (en) | 2019-01-02 |
US20180163079A1 (en) | 2018-06-14 |
EP3298091B1 (en) | 2022-12-28 |
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