CN108368406B - 不含甲醛的可固化调配物 - Google Patents
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Abstract
一种可固化水性调配物,包含:a)乳液聚合物,具有0.1到20重量%酸单体;b)含恶唑啉的聚合物;以及c)水性丙烯酸聚合物分散体,具有40到100重量%酸单体并且重均分子量在2000到500000范围内。
Description
技术领域
本发明涉及用于纺织品和非纺织应用的粘合剂。
背景技术
纺织品和非纺织应用中使用的传统粘合剂含有N-羟甲基丙烯酰胺(NMA)作为官能单体,使固化后的粘合剂具有出色的耐水性(湿强度)和耐溶剂性(异丙醇强度)。然而,含NMA的粘合剂在加热时会释放甲醛。过去使用的一种解决方案是基于衣康酸的不含甲醛的交联技术。这一技术在固化后具有良好的耐水性和耐溶剂性,但欠缺含NMA粘合剂的优异特性。因此,需要一种不含甲醛却也具有相当特性的***。
发明内容
本发明的一个方面是一种可固化水性调配物,包含以下组分、由以下组分或基本上由以下组分组成:a)乳液聚合物,具有0.1到20重量%的酸单体,b)含恶唑啉的聚合物;以及c)水性丙烯酸聚合物分散体,具有40到100重量%酸单体并且重均分子量在2000到500000范围内。
具体实施方式
本发明提供一种形成水性可固化调配物的方法。
如本文所用,“水性”是指其中连续相为水的组合物或在替代方案中,主要包括水但也任选地包括与水混溶的溶剂、杀生物剂、润滑剂、缓冲剂、螯合剂和表面活性剂以及其它成分的混合物。
本文中的“纺织”是指通常呈片状或网状形式的纤维的织物状组织,其通过使沿一个方向穿过的长线与其它成直角地交织而形成。
本文中通过“非纺织”意指并非织造或编织材料的通常呈片状或网状形式的纤维的织物状组织。非纺织衬底包括纸;非纺织织物;毡和垫;或纤维的其它组织。非纺织衬底可包括:纤维素纤维,如棉、人造丝和木浆;合成纤维,如聚酯、玻璃和尼龙;双组分纤维;以及其混合物。它可通过所属领域中已知的方法形成,例如湿法成网、气流成网、纺粘成网、熔纺成网以及水缠绕成网。
所述可固化水性调配物包含以下组分、由以下组分或基本上由以下组分组成:a)乳液聚合物,具有0.1到20重量%的酸单体,b)含恶唑啉的聚合物;以及c)水性丙烯酸聚合物分散体,其具有40到100重量%酸单体并且重均分子量在2000到500000范围内。
组分A-乳液聚合物
水性非纺织粘合剂包括乳液聚合物;即,在水性乳液聚合工艺中通过烯系不饱和单体的自由基聚合制备的聚合物。以乳液聚合物的重量计,乳液聚合物包括0.1重量%到20重量%酸性单体作为共聚单元。本文包括并公开0.1重量%与20重量%之间的所有范围;例如酸单体的重量百分比可从下限0.1、5、7或10到上限12、15、18或20。
乳液聚合物还具有5000到500000的重均分子量。本文包括并公开5000与500000之间的任何和所有范围,例如,乳液聚合物可具有50000到400000或100000到300000的重均分子量。
酸单体可包括一元酸单体和二元酸单体。一元酸单体包括例如羧酸单体,例如丙烯酸、甲基丙烯酸、巴豆酸、衣康酸单甲酯、反丁烯二酸单甲酯、反丁烯二酸单丁酯。二元酸单体的实例包括但不限于衣康酸、反丁烯二酸、顺丁烯二酸;包括其酸酐、盐以及其混合物。
乳液聚合物还包括至少一种其它共聚的烯系不饱和单体,例如(甲基)丙烯酸酯单体,包括(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、脲基官能的(甲基)丙烯酸酯和乙酰乙酸酯、(甲基)丙烯酸的乙酰胺或氰基乙酸酯;苯乙烯或经取代的苯乙烯;乙烯基甲苯;丁二烯;乙酸乙烯酯或其它乙烯酯;乙烯基单体,如氯乙烯、偏二氯乙烯;以及(甲基)丙烯腈。如在整个本公开中所使用的后接另一术语如(甲基)丙烯酸酯或(甲基)丙烯酰胺等使用的术语“(甲基)”分别是指丙烯酸酯和甲基丙烯酸酯或丙烯酰胺和甲基丙烯酰胺两者。也可以使用具有不同组成的乳液聚合物的混合物。
以干燥固体计,乳液聚合物在调配物中以80到99.8重量%的范围存在。在各种其它实施例中,乳液聚合物可以以82到99.8重量%的范围存在,在各种其它实施例中,可以以85到99.8重量%存在。
组分B-含恶唑啉的聚合物
调配物还包含至少一种含恶唑啉的聚合物作为交联剂。在各种实施例中,含唑啉的聚合物可通过使用所属领域技术人员已知的任何合适的聚合方法在水性介质中进行可加成聚合的恶唑啉与至少一种烯系不饱和单体(例如以上所列举的那些)。的溶液聚合反应或乳液聚合来制备。在各种实施例中,发生加成聚合反应。
在各种实施例中,含恶唑啉的聚合物具有下式所示的结构:
其中R1、R2、R3以及R4独立地表示氢原子、卤素原子、烷基、芳烷基、苯基、经取代的苯基,并且R5表示具有可加成聚合的不饱和键的非环状有机基团。在一些实施例中,含恶唑啉的聚合物具有2-恶唑啉基团。
含恶唑啉的聚合物的实例包括但不限于乙烯基恶唑啉,如2-乙烯基-2-恶唑啉、2-乙烯基-4-甲基-2-恶唑啉、2-乙烯基-5-甲基-2-恶唑啉、2-异丙烯基-2-恶唑啉、2-异丙烯基-4-甲基-2-恶唑啉、2-异丙烯基-5-乙基-2-恶唑啉、2-异丙烯基-4-羟甲基-4-乙基-2-恶唑啉、2-(I-十六烷基乙烯基)-4,4-双(硬酯酰氧基甲基)-2-恶唑啉、2-(I-二十烷基乙烯基)-4,4-双(羟甲基)-2-恶唑啉、2-异丙烯基-4,4-双(羟甲基)-2-恶唑啉、2-异丙烯基-4,4-双(甲基)-2-恶唑啉。
以干燥固体计,含恶唑啉的聚合物在调配物中通常以0.1到10重量%的范围存在。在各种其它实施例中,含恶唑啉的聚合物可以以1到8重量%的范围存在,并且在各种其它实施例中,以3到7重量%存在。
组分C-水性丙烯酸聚合物分散体
调配物还包括水性丙烯酸聚合物分散体。水性丙烯酸聚合物分散体具有40到100重量%的酸基团。在各种其它实施例中,分散体可以具有50到95重量%的酸基团,并且在各种其它实施例中,具有65到80重量%的酸基团。水性丙烯酸聚合物分散体还具有在2000到500000的范围内的重均分子量。在各种其它实施例中,分散体可以具有50000到400000的重均分子量,并且在各种其它实施例中,可具有100000到350000的重均分子量。
水性丙烯酸聚合物分散体也可以由上文列出的任何烯系不饱和单体形成。
以干燥固体计,水性丙烯酸聚合物分散体在调配物中通常以0.1到10重量%的范围存在。在各种其它实施例中,分散体可以以1到8重量%的范围存在,在各种其它实施例中,以3到7重量%存在。
任选组分
水性非纺织粘合剂还可包括常规处理组分,例如乳化剂、颜料、填充剂或增量剂、抗迁移助剂、聚结剂、表面活性剂、杀生物剂、增塑剂、有机硅烷、消泡剂、腐蚀抑制剂、着色剂、蜡、其它聚合物以及抗氧化剂。
用于制备乳液聚合物的乳液聚合技术在所属领域中是众所周知的,例如如美国专利第4,325,856号;第4,654,397号;以及第4,814,373号中所公开。在各种实施例中,取决于引发过程(例如热或氧化还原),在室温到100℃的反应温度下进行乳液聚合。可使用常规表面活性剂,例如阴离子和/或非离子乳化剂,如烷基硫酸碱金属盐或铵盐、烷基磺酸、脂肪酸、可共聚表面活性剂以及氧乙基化烷基酚。优选的为阴离子乳化剂。以单体的重量计,所用表面活性剂的量通常为0.1重量%到6重量%。可使用热引发方法或氧化还原引发方法。可使用常规自由基引发剂,例如过氧化氢、叔丁基氢过氧化物、叔戊基氢过氧化物、过硫酸铵和/或碱金属盐以及水溶性偶氮化合物,如偶氮双氰戊酸,以总单体的重量计,通常呈0.01重量%到3.0重量%的含量。在一个实施例中,以总单体的重量计,引发剂以0.5重量%到1.5重量%的范围存在。可以按类似的含量使用采用与合适的还原剂(如甲醛次硫酸钠(sodium sulfoxylate formaldehyde)、连二亚硫酸钠、异抗坏血酸、硫酸羟胺以及亚硫酸氢钠)偶合的相同引发剂的氧化还原***,任选地与例如铁和铜等金属离子组合,任选地另外包括金属络合剂。可使用如硫醇等链转移剂降低聚合物的分子量。在乳液聚合中,可以添加纯单体混合物或呈水中的乳液形式的单体混合物。在反应时间段内,单体混合物可使用均一或变化的组成以单次添加或多次添加或连续添加。可在任一阶段之前、期间或之后添加其它成分,例如自由基引发剂、氧化剂、还原剂、链转移剂、中和剂、表面活性剂以及分散剂。在各种实施例中,乳液聚合物可通过多阶段乳液聚合过程制备,其中组成上不同的至少两个阶段以依序方式聚合。最终聚合物的分子量在以上分子量范围内。在一些实施例中,随后可将含恶唑啉的聚合物和水性丙烯酸聚合物分散体在搅拌或搅动下加入到乳液聚合物中。
乳液聚合物粒子的平均粒径通常为30纳米到1000纳米,优选100纳米到200纳米,如通过由纽约州霍尔茨维尔的美国布鲁克海文仪器公司(Brookhaven Instrument Corp.,Holtsville,NY)供应的Brookhaven BI-90型粒径分析仪所测量。
纺织或非纺织衬底与可固化水性调配物接触。通常,以干燥重量计,以百分比表示的调配物与接触衬底的比率(也称为重量增加%(%add-on))为1%到40%,优选地15%到35%,根据衬底的强度和期望的最终用途进行选择。使用常规施加技术,例如空气或无空气喷涂、浸染、浸透、滚涂、帘涂、凹版印刷等使衬底与可固化水性调配物接触。衬底可与可固化水性调配物接触,以便在一个或两个表面处或附近、或在整个结构中均匀分布或不均匀分布地提供粘合剂。还预期,当期望图案化分布时,可固化水性调配物可以非均匀方式施加于一个或两个表面。
在用于形成含有本发明可固化水性调配物的衬底的方法中,将已经与可固化水性调配物接触过的衬底加热到120℃到220℃、优选140℃到180℃的温度,持续足以实现固化的一段时间。
除了纺织和非纺织应用之外,本发明可固化水性调配物还可用于制造压敏粘着剂和层压粘着剂。
实例
所用缩写:
IPA:异丙醇
DI水:去离子水
CD:横向
固体含量
BA:丙烯酸丁酯
Sty:苯乙烯
IA:衣康酸
AA:丙烯酸
DS-4:十二烷基苯磺酸钠,一种表面活性剂
TR-407:基于NMA技术与甲醛(HCHO)的目前商用产品
SWX1116(A):SC为45%的具有于聚合物中49Sty/46BA/3AA/2IA的乳液
EPOCROS WS500(B):来自Nippon Shokubai的具有恶唑啉基团的溶液聚合物,SC为40%并且恶唑啉含量为4.5毫摩尔/克固体
Leukotan 1084(C1):来自陶氏化学公司(The Dow Chemical Company)的水溶液聚合物,其具有100%AA并且SC为28%
ASE60(C2):来自陶氏化学公司的乳液聚合物,其具有40%AA并且SC为28%
TRITONTM X-100:来自陶氏化学公司的表面活性剂
来自Whatman Ltd.的WHATMANTM#4纸
本发明实例1和2与比较实例1和2
根据表1和2中的配方,将上述原料在适当搅动下调配30分钟以获得可固化水性组合物。
表1:样品配方.
*括号()内的数值为在调配物中的固体比率
表2:样品配方.
水 | SWX1116(A) | EPOCROS WS500(B) | Leukotan1084(C1) | |
比较2b | 200 | 100 | ||
本发明3 | 192.75 | 80(80%)* | 11.25(10%) | 16(10%) |
本发明4 | 199.93 | 99.8(99.8%)* | 0.11(0.1%) | 0.16(0.1%) |
本发明5 | 198.69 | 89.9(89.9%) | 11.25(10%) | 0.16(0.1%) |
本发明6 | 193.99 | 89.9(89.9%) | 0.11(0.1%) | 16(10%) |
*括号()内的数值为在调配物中的固体比率
将一张28cm×46cm的WHATMANTM纸浸入200mL经调配的乳液中。处理后的衬底用Mathis浸染机浸染,然后干燥并在150℃下固化3分钟。对于表1,纸上聚合物的量控制在28%到32%之间,对于表2,控制在15%到16%之间。将固化衬底切成1英寸×4英寸的片,其中4英寸方向是纸的横向(CD)。在干(未经处理)、湿(在0.1%Triton X-100/水溶液中浸泡30分钟后)以及IPA(在异丙醇中30分钟后)处理下测试样品的拉伸强度。湿强度反映粘合剂对水的耐受性,并且IPA强度反映粘合剂在溶剂中的耐受性。数据显示于表3和4中。
表3:样品的应用测试.
含HCHO的 | 描述 | 干强度 | 湿强度 | IPA强度 | |
比较1 | Y | 16.23 | 9.15 | 6.72 | |
比较2a | N | A | 16.12 | 6.72 | 3.48 |
比较3 | N | A+B | 16.12 | 7.42 | 6.9 |
比较4 | N | A+B+酸 | 16.02 | 7.39 | 6.63 |
比较5 | N | A+C1 | 16.9 | 6.83 | 4.49 |
比较6 | N | A+C2 | 16.47 | 6.9 | 3.05 |
本发明1 | N | A+B+C1 | 16.56 | 8.59 | 6.94 |
本发明2 | N | A+B+C2 | 16.18 | 8.13 | 6.2 |
表3中的结果显示:
●强度值越高,性能越好。
●除比较1外,所有实例都不含HCHO。
●比较1是基于含有HCHO的NMA技术,并且显示出最佳的整体性能。
●比较3显示出比比较2a更好的IPA强度。
●比较4具有低分子量酸,并且性能没有比比较3提高。
●比较5、6具有高酸性聚合物(C),并且总体性能没有比不含恶唑啉的聚合物的比较2a提高。
表4:样品的应用测试.
干强度 | 湿强度 | IPA强度 | |
比较2b | 9.37 | 3.51 | 2.25 |
本发明3 | 9.34 | 3.02 | 4.74 |
本发明4 | 9.60 | 3.98 | 2.80 |
本发明5 | 9.84 | 4.13 | 4.56 |
本发明6 | 9.83 | 3.26 | 3.81 |
概述:
·相比于比较2b,本发明实例4和5显示,湿强度提高大于10%并且IPA强度的提高为至少20%。
·相比于比较2b,本发明实例3和6显示,湿强度有小于15%的降低但是IPA强度的增加大于65%。
·比较发明实例4和6,发现如果组分C从0.1%增加到10%,则IPA强度将从2.8增加到3.81。
Claims (2)
1.一种使用可固化水性调配物来形成固化衬底的方法,所述可固化水性调配物包含:a)乳液聚合物,具有5到20重量%酸单体,以所述乳液聚合物的重量计;b)含恶唑啉的聚合物;以及c)水性丙烯酸聚合物分散体,具有40到100重量%酸单体并且重均分子量在2000到500000范围内;
所述方法包含:
a)使纺织或非纺织衬底与所述可固化水性调配物接触以形成接触衬底;和
b)将接触后非纺织衬底加热到120℃到220℃的温度以形成所述固化衬底。
2. 一种产品,包含:
a)粘合剂,包含可固化水性调配物,其中所述可固化水性调配物包含:a)乳液聚合物,具有5到20重量%酸单体,以所述乳液聚合物的重量计;b)含恶唑啉的聚合物;以及c)水性丙烯酸聚合物分散体,具有40到100重量%酸单体并且重均分子量在2000到500000范围内;和
b)纺织或非纺织衬底,其中所述衬底是使纺织或非纺织衬底与所述可固化水性调配物接触而形成的接触衬底。
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