CN117241944A - 具有改善的粘结强度和热密封性能的粘合剂组合物 - Google Patents
具有改善的粘结强度和热密封性能的粘合剂组合物 Download PDFInfo
- Publication number
- CN117241944A CN117241944A CN202180091891.4A CN202180091891A CN117241944A CN 117241944 A CN117241944 A CN 117241944A CN 202180091891 A CN202180091891 A CN 202180091891A CN 117241944 A CN117241944 A CN 117241944A
- Authority
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- China
- Prior art keywords
- adhesive composition
- maleic anhydride
- structural units
- emulsion polymer
- anhydride copolymer
- Prior art date
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- 229920001577 copolymer Polymers 0.000 claims abstract description 35
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- 125000005907 alkyl ester group Chemical group 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
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- 239000004971 Cross linker Substances 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
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Classifications
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
- C08F222/08—Maleic anhydride with vinyl aromatic monomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
本发明提供了一种粘合剂组合物,其包含:(A)丙烯酸类乳液聚合物;(B)乙烯基芳族单体‑马来酸酐共聚物,其中基于粘合剂组合物的总固体重量计,(B)乙烯基芳族单体‑马来酸酐共聚物以0.1重量%至6.5重量%的量存在。该粘合剂组合物在粘结强度和/或热密封性能方面提供改进的性能。
Description
技术领域
本公开涉及粘合剂组合物。更具体地,本公开涉及粘合剂组合物、包含所述粘合剂组合物的制品以及制备所述制品的方法。该粘合剂组合物在粘结强度和/或热密封性能方面提供改进的性能。
背景技术
粘合剂组合物可用于广泛多种目的。例如,粘合剂组合物用于将诸如聚乙烯、聚丙烯、聚酯、聚酰胺、金属、纸或玻璃纸的基材粘结在一起以形成复合膜,即层合物。粘合剂在不同的层合最终用途应用中的使用通常是已知的。例如,粘合剂可以用于制造包装工业中使用(尤其用于食品包装)的膜/膜和膜/箔层合物。用于层合应用的粘合剂或“层合粘合剂”通常可分为三类:基于溶剂的、基于水的和无溶剂的。
数年来,许多水基层合粘合剂已经被开发用于膜/膜(箔)层合。然而,对于更广泛的应用,水基层合粘合剂也受到性能缺点的限制。现有技术中的水基层合粘合剂倾向于表现出对基于箔的层合结构的低粘结强度和/或差的热密封性能。因此希望开发一种在粘结强度和/或热密封性能方面具有改进性能的粘合剂组合物。
发明内容
在一个方面,本公开提供了一种粘合剂组合物,该粘合剂组合物包含:
(A)丙烯酸类乳液聚合物;以及
(B)乙烯基芳族单体-马来酸酐共聚物,
其中基于所述粘合剂组合物的总固体重量计,(B)乙烯基芳族单体-马来酸酐共聚物以0.1重量%至6.5重量%的量存在。
在另一方面,本公开提供了一种使用所描述的粘合剂组合物生产层合体的方法,该方法包括:
(a)提供如上所述的粘合剂组合物;
(b)将所述粘合剂组合物施加于基材的表面的第一部分上以形成所述粘合剂组合物的层;
(d)使基材的表面的第二部分与所述粘合剂组合物的层接触,使得所述粘合剂组合物的层夹置于所述第一部分与所述第二部分之间;以及
(e)干燥所述粘合剂组合物或使其干燥。
在另一方面,本公开提供了一种层合体,其通过使用如本文所述的生产层合体的方法制备。
在另一方面,本公开提供了一种层合体,该层合体包括基材的表面的第一部分,如本文所述的粘合剂组合物的层,以及同一基材或不同基材的表面的第二部分,其中该粘合剂组合物的层夹置于第一部分与第二部分之间并且与该第一部分和该第二部分接触。
在另一个方面,本公开提供了乙烯基芳族单体-马来酸酐共聚物用于改善包含丙烯酸类乳液聚合物的粘合剂组合物的粘结强度和/或热密封性能的用途。优选地,基于粘合剂组合物的总固体重量计,乙烯基芳族单体-马来酸酐共聚物以0.1重量%至6重量%的量存在。
具体实施方式
除非另外定义,否则本文所用的所有技术和科学术语具有与本发明所属领域中的普通技术人员通常所理解相同的含义。此外,本文所提及的所有公开案、专利申请、专利以及其他参考文献均以引用的方式并入。
如本文所公开,“和/或”意指“和、或作为替代方案”。除非另外指明,否则所有范围均包括端值。
除非另有说明,否则如本文所公开,本文提及的所有百分比均按重量计,并且温度以℃为单位。
本文中的“水性”组合物或分散体意指分散在水性介质中的颗粒。本文中的“水性介质”是指水和按介质的重量计的0重量%至30重量%的水混溶性化合物,例如,醇、二醇、二醇醚、二醇酯或它们的混合物。
如本文所用,“玻璃化转变温度”或“Tg”可通过各种技术测量,包括例如差示扫描量热法(“DSC”)或通过使用Fox公式进行的计算。本文所报告的Tg的特定值是使用Fox公式计算的值(T.G.Fox,《美国物理学会公报(Bull.Am.Physics Soc.)》,第1卷,第3期,第123页(1956))。例如,用于计算单体M1和M2的共聚物的Tg,
其中Tg(经计算的)是针对共聚物计算的玻璃化转变温度,w(M1)是共聚物中的单体M1的重量分数,w(M2)是共聚物中的单体M2的重量分数,Tg(M1)是单体M1的均聚物的玻璃化转变温度,并且Tg(M2)是单体M2的均聚物的玻璃化转变温度;所有温度以K为单位。均聚物的玻璃转化温度可见于例如由J.Brandrup和E.H.Immergut编辑的“《聚合物手册(PolymerHandbook)》”,国际科学出版社(Interscience Publishers)。
命名单体的“结构单元”(也被称为“聚合单元”)是指聚合后单体的残余物,即,聚合单体或呈聚合形式的单体。例如,甲基丙烯酸甲酯的结构单元如下所示:其中虚线表示结构单元与聚合物主链的附接点。
粘合剂组合物
根据本公开的粘合剂组合物包含(A)丙烯酸类乳液聚合物;和(B)乙烯基芳族单体-马来酸酐共聚物,其中基于所述粘合剂组合物的总固体重量计,(B)乙烯基芳族单体-马来酸酐共聚物以0.1重量%至6.5重量%的量存在。
粘合剂组合物优选是水基的。
更优选地,粘合剂组合物是单组分水基粘合剂组合物。
丙烯酸类乳液聚合物
本发明的丙烯酸类乳液聚合物可以包含(a)一种或多种烯键式不饱和离子单体的结构单元。本文中的术语“离子单体”是指在pH=1-14之间带有离子电荷的单体。合适的烯键式不饱和离子单体的示例包括α,β-烯键式不饱和羧酸,其包括含酸性单体,如甲基丙烯酸、丙烯酸、衣康酸、顺丁烯二酸或富马酸;苯乙烯磺酸钠(SSS)、乙烯基磺酸钠(SVS)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、2-丙烯酰胺基-2-甲基-1-丙磺酸的钠盐、2-丙烯酰胺基-2-甲基-1-丙烷磺酸的铵盐;烯丙醚磺酸的钠盐;(甲基)丙烯酸磷烷基酯,如(甲基)丙烯酸磷酸乙酯、(甲基)丙烯酸磷酸丙酯、(甲基)丙烯酸磷酸丁酯、它们的盐和它们的混合物;CH2=C(Rp1)-C(O)-O-(Rp2O)p-P(O)(OH)2,其中Rp1=H或CH3,Rp2=烷基,并且p=1-10,诸如SIPOMER PAM-100、SIPOMER PAM-200和SIPOMER PAM-300,均购自苏威公司(Solvay);(甲基)丙烯酸磷烷氧基酯,诸如磷乙二醇(甲基)丙烯酸酯、磷二乙二醇(甲基)丙烯酸酯、磷三乙二醇(甲基)丙烯酸酯、磷丙二醇(甲基)丙烯酸酯、磷二丙二醇(甲基)丙烯酸酯、磷三丙二醇(甲基)丙烯酸酯、烯丙基醚磷酸酯、乙烯基膦酸、它们的盐或它们的混合物。优选的烯键式不饱和离子单体为甲基丙烯酸磷酸乙酯(PEM)、丙烯酸(AA)、甲基丙烯酸(MAA)或它们的混合物。基于乳液聚合物的重量计,本发明的丙烯酸类乳液聚合物可包含按重量计0.1%或更多、0.3%或更多、0.5%或更多、0.75%或更多或甚至1%或更多,并且同时8%或更少、7%或更少、6%或更少、5%或更少、4.5%或更少、4%或更少、3.8%或更少、3.5%或更少或甚至3.3%或更少的烯键式不饱和离子单体的结构单元。
本发明的丙烯酸类乳液聚合物可包含(b)一种或多种烯键式不饱和非离子单体的结构单元,其可以是单烯键式或多烯键式不饱和单体。本文中的术语“非离子单体”是指在pH=1-14之间不带有离子电荷的单体。合适的单烯键式不饱和非离子单体可包括例如乙烯基芳族单体、(甲基)丙烯酸C1-C20-烷基酯、丙烯腈(AN)、(甲基)丙烯酰胺或它们的混合物。(甲基)丙烯酸C1-C20烷基酯是指含有具有1至20个碳原子的烷基的(甲基)丙烯酸的烷基酯。(甲基)丙烯酸C1-C20烷基酯可包括(甲基)丙烯酸C1-C3烷基酯、(甲基)丙烯酸环烷基酯和不同于(甲基)丙烯酸环烷基酯的(甲基)丙烯酸C4-C20烷基酯。合适的(甲基)丙烯酸烷基酯的示例包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯;(甲基)丙烯酸环烷基酯,诸如(甲基)丙烯酸环己酯、(甲基)丙烯酸甲基环己酯、(甲基)丙烯酸二氢二环戊二烯基酯、(甲基)丙烯酸三甲基环己酯和丙烯酸叔丁基(甲基)环己酯;羟基官能团(甲基)丙烯酸烷基酯,诸如甲基丙烯酸羟乙酯和甲基丙烯酸羟丙酯;(甲基)丙烯酸缩水甘油酯;或者它们的混合物。乙烯基芳族单体可包括苯乙烯,取代的苯乙烯诸如α-甲基苯乙烯、反式-β-甲基苯乙烯、2,4-二甲基苯乙烯、乙基苯乙烯、丁基苯乙烯、对甲氧基苯乙烯;邻-甲氧基苯乙烯、间-甲氧基苯乙烯和对-甲氧基苯乙烯;以及对-三氟甲基苯乙烯;或者它们的混合物。优选的单烯键式不饱和非离子单体包括甲基丙烯酸甲酯、苯乙烯、甲基丙烯酸环己酯、丙烯酸2-乙基己酯、丙烯酸丁酯或它们的混合物。优选的单烯键式不饱和非离子单体包括甲基丙烯酸甲酯、丙烯酸甲酯、苯乙烯、甲基丙烯酸丁酯、丙烯酸丁酯或它们的混合物。可调节烯键式不饱和非离子单体的结构单元的含量以得到具有所需汉森溶解度参数的所得乳液聚合物。例如,基于乳液聚合物的重量计,该乳液聚合物可包含按重量计优选35%或更多、36%或更多或甚至37%或更多,并且同时45%或更少、44%或更少或甚至43%或更少的量的丙烯酸丁酯的结构单元;以及30%或更多、31%或更多、32%或更多、33%或更多或甚至34%或更多,并且同时50%或更少、49%或更少、48%或更少、46%或更少或甚至45%或更少的量的苯乙烯的结构单元。另选地,基于乳液聚合物的重量计,该乳液聚合物可包含按重量计优选30%或更多、31%或更多或甚至32%或更多,并且同时40%或更少、39%或更少或甚至38%或更少的量的丙烯酸2-乙基己酯的结构单元;以及30重量%或更多、31重量%或更多、32重量%或更多、33重量%或更多或甚至34重量%或更多,并且同时39.5重量%或更少、39重量%或更少、38重量%或更少或甚至37重量%或更少的量的苯乙烯的结构单元。基于乳液聚合物的重量计,该乳液聚合物可包含按重量计小于19%的丙烯腈的结构单元,例如,小于15%、小于10%、小于5%、小于1%或甚至0%的丙烯腈的结构单元。可用于本发明的多烯键式不饱和非离子单体包括二烯键式不饱和单体、三烯键式不饱和单体、四烯键式不饱和单体或更高的多官能烯键式不饱和单体。合适的多烯键式不饱和单体可包含例如(甲基)丙烯酸烯丙酯、二乙烯基苯、二甲基丙烯酸乙二醇酯、二甲基丙烯酸丁二醇酯或它们的混合物。基于乳液聚合物的重量计,该乳液聚合物可包含按重量计0重量%至3.0重量%、0.05重量%至0.8重量%或0.1重量%至0.5重量%的多烯键式不饱和非离子单体的结构单元。
基于乳液聚合物的重量计,丙烯酸类乳液聚合物包含按重量计,
30%至50%的乙烯基芳族单体的结构单元,
50%至70%的(甲基)丙烯酸C1-C20烷基酯的结构单元,和
0.1%至8%的(甲基)丙烯酸的结构单元。
另选地,基于乳液聚合物的重量计,丙烯酸类乳液聚合物包含按重量计,
30%至50%的苯乙烯的结构单元,
50%至70%的丙烯酸丁酯的结构单元,和
0.1%至8%的丙烯酸的结构单元。
丙烯酸类乳液聚合物中的结构单元的总浓度等于100%。可选择上述单体的类型和水平,以使所提供的乳液聚合物具有适合于不同应用的玻璃化转变温度(Tg)。丙烯酸类乳液聚合物可具有在-20℃至60℃、-15℃至50℃、-10℃至30℃或-5℃至20℃范围内的Tg。乳液聚合物的Tg值可通过各种技术来测量,包括差示扫描量热法(DSC)或通过使用Fox方程来计算。
可用于本发明的丙烯酸类乳液聚合物可通过上文所述的单体的自由基聚合、优选乳液聚合来制备。用于制备丙烯酸共聚物的单体的总重量浓度等于100%。单体可以纯净地或以在水中的乳液形式添加;或者在制备丙烯酸共聚物的反应时间段内以一种或多种添加形式或连续、线性或非线性地添加。适用于聚合过程的温度可低于100℃,在30℃至95℃范围内或在50℃至90℃范围内。
在制备乳液聚合物的过程中,可以使用自由基引发剂。聚合过程可为热引发或氧化还原引发的乳液聚合。合适的自由基引发剂的示例包括过氧化氢、叔丁基过氧化氢、氢过氧化枯烯、铵和/或碱金属过硫酸盐、过硼酸钠、过磷酸和其盐;高锰酸钾和过氧二硫酸的铵或碱金属盐。基于用于制备乳液聚合物的单体的总重量计,自由基引发剂通常可以0.01重量%至3.0重量%的水平使用。在聚合方法中,可使用包含上述引发剂和合适的还原剂的氧化还原体系。合适的还原剂的示例包括甲醛次硫酸氢钠、抗坏血酸、异抗坏血酸、含硫的酸的碱金属盐和铵盐,如亚硫酸钠、亚硫酸氢盐、硫代硫酸盐、次硫酸盐、硫化物、氢硫化物或连二亚硫酸盐,甲亚磺酸(formadinesulfinic acid)、丙酮亚硫酸氢盐、乙醇酸、羟基甲磺酸、乙醛酸水合物、乳酸、甘油酸、苹果酸、酒石酸和前述酸的盐。铁、铜、锰、银、铂、钒、镍、铬、钯或钴的金属盐可用于催化氧化还原反应。可任选地使用金属螯合剂。
在制备乳液聚合物的过程中,可使用链转移剂。合适的链转移剂的示例包含3-巯基丙酸、巯基丙酸甲酯、巯基丙酸丁酯、正十二烷基硫醇、苯硫醇、壬二酸烷基硫醇或它们的混合物。链转移剂可以有效量使用,以控制乳液聚合物的分子量。基于用于制备乳液聚合物的单体的总重量计,链转移剂可以0重量%至3重量%、0.01重量%至1重量%或0.1重量%至0.3重量%的量存在。
在制备乳液聚合物的过程中,可使用表面活性剂。表面活性剂可在单体聚合之前、期间或之后添加,或在它们的组合添加。合适的附加表面活性剂的示例包括烷基、芳基或烷基芳基硫酸盐、磺酸盐或磷酸盐的碱金属或铵盐;烷基磺酸;磺基琥珀酸盐;脂肪酸;可聚合表面活性剂;乙氧基化醇或酚;以及它们的混合物。基于乳液聚合物的干重计,附加表面活性剂在不损害水性聚合物分散体的性能的情况下应以例如,0至1.5重量%、0.1重量%至1重量%、0.2重量%至0.8重量%或0.3重量%至0.6重量%的量使用。
通过中和,可将所得水性乳液聚合物分散体的pH值控制为至少5,例如,6至10或6.5至9。中和可通过添加一种或多种可以导致多级聚合物颗粒的离子或潜在离子基团的部分或完全中和的碱来进行。合适的碱的示例包括氨;碱金属或碱土金属化合物,如氢氧化钠、氢氧化钾、氢氧化钙、氧化锌、氧化镁、碳酸钠;伯胺、仲胺和叔胺,诸如三乙胺、乙胺、丙胺、单异丙胺、单丁胺、己胺、乙醇胺、二乙胺、二甲胺、二-正丙胺、三丁胺、三乙醇胺、二甲氧基乙基胺、2-乙氧基乙胺、3-乙氧基丙胺、二甲基乙醇胺、二异丙醇胺、吗啉、乙二胺、2-二乙基氨基乙胺、2,3-二氨基丙烷、1,2-丙二胺、新戊二胺、二甲基氨基丙胺、己二胺、4,9-二氧杂十二烷-1,12-二胺、聚乙烯亚胺或聚乙烯胺;氢氧化铝;或者它们的混合物。
可用于本发明的乳液聚合物的粒度可为50纳米(nm)至500nm、80nm至200nm或90nm至150nm。本文中的粒度是指Z平均大小,并且可通过Brookhaven BI-90Plus粒度分析仪来测量。
乙烯基芳族单体-马来酸酐共聚物
本公开的乙烯基芳族单体-马来酸酐共聚物可包含(a)一种或多种乙烯基芳族单体的结构单元。乙烯基芳族单体可包括苯乙烯,取代的苯乙烯诸如α-甲基苯乙烯、反式-β-甲基苯乙烯、2,4-二甲基苯乙烯、乙基苯乙烯、丁基苯乙烯、对甲氧基苯乙烯;邻-甲氧基苯乙烯、间-甲氧基苯乙烯和对-甲氧基苯乙烯;以及对-三氟甲基苯乙烯;或者它们的混合物。基于乙烯基芳族单体-马来酸酐共聚物的重量计,本发明的乙烯基芳族单体-马来酸酐共聚物可以包含按重量计20%或更多、30%或更多、或甚至40%或更多,并且同时99%或更少、90%或更少、80%或更少、70%或更少、或甚至60%或更少的乙烯基芳族单体的结构单元。
本公开的乙烯基芳族单体-马来酸酐共聚物可以包含(b)马来酸酐的结构单元。基于乙烯基芳族单体-马来酸酐共聚物的重量计,本发明的乙烯基芳族单体-马来酸酐共聚物可以包含按重量计5%或更多、10%或更多、20%或更多、30%或更多、或甚至40%或更多,并且同时80%或更少、70%或更少、或甚至60%或更少的马来酸酐的结构单元。
本公开的乙烯基芳族单体-马来酸酐共聚物可以通过胺诸如氨或二甲基丙二胺进行酰亚胺化。该共聚物的酰亚胺化程度可以在50%和100%之间。这些酰亚胺化的乙烯基芳族单体-马来酸酐共聚物也可从克雷威利公司(Cray Valley)以名称SMA X10000i、SMAX2000i、SMA X3000i、SMA X4000i和SMA 3000H商购获得。
本发明优选的乙烯基芳族单体-马来酸酐共聚物是苯乙烯和马来酸酐的共聚物(SMA)。优选地,苯乙烯与马来酸酐的比率为1/1至6/1,优选为2/1至4/1。
乙烯基芳族单体-马来酸酐共聚物的数量分子量在500和20,000之间,优选在2,000和5,000之间。
该乙烯基芳族单体-马来酸酐共聚物可通过任何已知方法制备,例如根据US 3,444,151 A中描述的方法。
基于粘合剂组合物的总固体重量计,乙烯基芳族单体-马来酸酐共聚物(B)以0.1重量%或更多、0.5重量%或更多、0.8重量%或更多、1.0重量%或更多、1.2重量%或更多、1.5重量%或更多,并且同时6.5重量%或更少、6.0重量%或更少,或5.5重量%或更少、5.0重量%或更少、4.5重量%或更少的量存在。
任选组分
根据本公开的粘合剂组合物可任选地包含一种或多种选自异氰酸酯交联剂、流变改性剂、消泡剂、硅烷和其它添加剂的组分。
一种或多种异氰酸酯交联剂
根据本公开的粘合剂组合物可任选地包含异氰酸酯交联剂。该异氰酸酯交联剂包括异氰酸酯单体、多异氰酸酯、异氰酸酯加合物以及混合物、或碳二亚胺。
在本公开的粘合剂组合物中,基于粘合剂组合物的总固体重量计,异氰酸酯交联剂可以以0.1重量%至20重量%,优选1重量%至15重量%,更优选1重量%至8重量%,并且还更优选3重量%至7重量%的量存在。
流变改性剂
根据本公开的粘合剂组合物还可包含流变改性剂。流变改性剂可包括(不限于)非离子氨基甲酸酯聚合物、纤维素、纤维素醚、聚乙二醇、淀粉醚、聚乙烯醇、聚酰亚胺、胶状物、面粉和其混合物。流变改性剂优选地选自非缔合型增稠剂,如纤维素醚。
基于粘合剂组合物的总固体重量计,流变改性剂可以一般为0.1重量%至5.0重量%、0.2重量%至3重量%、或0.5重量%至2.0重量%或0.4重量%至1.0重量%的量存在。
消泡剂
根据本公开的粘合剂组合物还可包含一种或多种消泡剂。本文中的“消泡剂”是指减少泡沫并且阻止泡沫形成的化学添加剂。消泡剂可为基于硅氧烷的消泡剂、基于矿物油的消泡剂、基于环氧乙烷/环氧丙烷的消泡剂或它们的混合物。适合的市售消泡剂包括例如均可购自迪高(TEGO)的TEGO Airex902W和TEGO Foamex 1488聚醚硅氧烷共聚物乳液、可购自毕克(BYK)的BYK-024硅酮消泡剂、可购自诺普科公司(NOPCO)的NOPCO NXZ消泡剂或其混合物。按粘合剂组合物的总固体重量计,消泡剂可以一般为0.01%至2%、0.02%到1.5%、或0.04%至0.5%或0.04%至0.1%的量存在。
硅烷
对于一些应用,需要具有高粘度(例如>20,000cP)和高固体含量(例如>70%)的粘合剂组合物。在这些情况下,为了提供足够的适用期,将限制NCO交联剂的载荷,并将硅烷用作添加剂来补偿NCO交联剂,因此会提供充足的适用期和粘合性能两者。根据本公开的硅烷可以是环氧官能硅烷。
可用于本发明的环氧官能硅烷化合物通常为具有环氧基团的饱和烷氧基化硅烷。环氧官能硅烷化合物可具有至少一个可水解硅烷基团。优选的环氧官能硅烷化合物具有通式(I):
其中每个R3独立地表示具有1至6个碳原子的烷基基团;每个OR3基团独立地表示具有1至6个碳原子的烷氧基基团,包括例如甲氧基、乙氧基或它们的组合;R4表示分子量为200或更少的二价有机基团,优选R4为C1-C10、C1-C5或C1-C3亚烷基基团;R5表示氢原子,或具有1至20个碳原子的烷基、芳基或芳烷基基团;并且q为1、2或3。适合的环氧官能硅烷化合物的实例包括3-缩水甘油基氧丙基三甲氧基硅烷、3-缩水甘油基氧丙基三乙氧基硅烷、3-缩水甘油基氧丙基甲基二乙氧基硅烷、3-缩水甘油基氧丙基甲基二甲氧基硅烷或其混合物。可商购的环氧官能硅烷化合物可包括来自迈图高性能材料公司的Silquest A-187γ-缩水甘油基氧丙基三甲氧基硅烷。
按粘合剂组合物的总固体重量计,可用于本公开中的环氧官能硅烷可以0或更多、0.05%或更多、0.1%或更多、0.15%或更多、0.2%或更多、0.25%或更多、0.3%或更多或甚至0.35%或更多,以及同时5%或更少、4%或更少、3%或更少、2.5%或更少、2%或更少、1.5%或更少、1.2%或更少、1%或更少、0.8%或更少或甚至0.5%或更少的组合量存在。
其他添加剂
除上述组分以外,本发明的粘合剂组合物还可包含以下添加剂中的任一种或组合:分散剂、缓冲剂、中和剂、保湿剂、防霉剂、杀生物剂、着色剂、流动剂、抗氧化剂、塑化剂、调平剂、触变剂、粘合促进剂和研磨媒剂。如果存在,那么基于粘合剂组合物的总固体重量计,这些添加剂可以0重量%至5重量%、或0.1重量%至3重量%或0.5重量%至1.5重量%的组合量存在。
本发明的粘合剂组合物可以用粘合剂领域已知的技术制备,该技术包括将丙烯酸类乳液聚合物与乙烯基芳族单体-马来酸酐共聚物和如上所述的其它任选组分混合。可以任何顺序混合粘合剂组合物中的组分,以提供本发明的粘合剂组合物。还可将上述任选的组分中的任一者在混合期间或之前添加至组合物,以形成粘合剂组合物。
本公开还提供了一种通过使用如本文所描述的粘合剂组合物来生产层合体的方法,该方法包括:
(a)提供如上所述的粘合剂组合物;
(b)将所述粘合剂组合物施加于基材的表面的第一部分上以形成所述粘合剂组合物的层;
(c)使基材的表面的第二部分与所述粘合剂组合物的层接触,使得所述粘合剂组合物的层夹置于所述第一部分与所述第二部分之间;以及
(d)干燥所述粘合剂组合物或使其干燥。
在一些实施方案中,该方法可包括将粘合剂组合物施加于基材(例如,膜)的表面的第一部分上以形成粘合剂组合物的层。如本文所用,“基材表面的第一部分”可指部分或整个表面。在一些实施方案中,表面的第一部分可以是表面的一部分或整个表面。在一些实施方案中,粘合剂组合物的涂布量可为0.5g/m2至5.0g/m2、0.5g/m2至4.0g/m2、0.5g/m2至3.0g/m2、0.5g/m2至2.0g/m2、0.5g/m2至1.0g/m2、0.8g/m2至4.0g/m2、0.8g/m2至3.0g/m2、1.0g/m2至3.0g/m2、1.5g/m2至3.0g/m2、或1.5g/m2至2.0g/m2。在一些实施方案中,基材可由选自由聚乙烯、聚丙烯、聚酯、聚酰胺、金属、纸、玻璃纸和它们的组合组成的群组的材料制得。在一些实施方案中,基材可以是膜的形式。
“膜”可以指具有0.5mm或更小的厚度的材料层。在一些实施方案中,膜可以是在一个维度上为0.5mm或更小并且在其他两个维度上都为1cm或更大的结构。在一些实施方案中,聚合物膜是由聚合物或聚合物的混合物制得的膜。在一些实施方案中,施加至膜的粘合剂组合物的层的厚度为1μm至5μm。合适的膜包括纸、织造和非织造织物、金属箔、聚合物,以及金属涂布的聚合物。膜任选地具有用油墨印刷图像的表面;油墨可以与粘合剂组合物接触。在一些实施方案中,膜是聚合物膜和金属涂布的聚合物膜,更优选的是聚合物膜。聚合物膜可以是PE或PET膜。
在一些实施方案中,该方法可包括使基材(例如,膜)的表面的第二部分与粘合剂组合物的层接触,使得可固化混合物的层置于第一部分和第二部分之间以形成层合体。如本文所用,“基材的表面的第二部分”可指部分或整个表面。一般来讲,第二部分不同于如上所述的第一部分。在一些实施方案中,第一部分和第二部分可以是在相同或不同表面上的部分。在一些实施方案中,第一部分和第二部分可以是相同或不同基材的相同或不同表面的部分。在一些实施方案中,表面的第一部分可以是表面的一部分或整个表面。在一些实施方案中,表面的第二部分可以是表面的一部分或整个表面。
在一些实施方案中,该方法可包括干燥粘合剂组合物或使其干燥。在一些实施方案中,层合体可经受压力,例如通过穿过可加热或可不加热的轧辊。在一些实施方案中,可将层合体加热(例如,在30℃至90℃,例如30℃至60℃的温度下)以加速干燥过程。
在另一方面,本公开提供了一种通过使用如本文所述的生产固化的层合体的方法制备的层合体。
在另一方面,本公开提供了一种层合体,该层合体包括基材的表面的第一部分,如本文所述的粘合剂组合物的层,以及同一基材或不同基材的表面的第二部分,其中该粘合剂组合物的层夹置于第一部分与第二部分之间并且与该第一部分和该第二部分接触。
实施例
现在将在以下实施例中描述本发明的一些实施方案,其中所有的份数和百分比都是按重量计,除非另有说明。然而,本公开的范围当然不限于这些实施例中所述的配方。相反,实施例仅仅是为了说明本公开。
1.原材料
下表1中列出了实施例中使用的原材料的信息。
表1:原材料
2.制备程序:
根据表2中所列出的配方制备样品。称量ROBONDTML-80D和SMA-3000H并在玻璃反应器中小心地混合,然后将其放入25℃的水浴中。开启旋转器并将旋转速度控制在50RM并监测整个过程。0.5小时后,将产物加入100ml HDPE瓶中。
表2:粘合剂组合物配方
注:基于粘合剂组合物的总固体重量计,通过SMA-3000H的干重测量的SMA-3000H(%)。
3.涂布和层合过程:
在SDC Labo-Combi 400机器中进行涂布和层合过程。在整个层合过程中,层合速度保持在100m/min的速度。涂布量为1.8-2.0g/m2。然后在测试前使层合膜在室温(23℃-25℃)下或在烘箱中固化。
4.测试方法:
T剥离(90°)粘结强度(手动辅助型T剥离)
在干燥后,将层合膜切割成15mm宽的条带,用于在Instron 5943机器中以250mm/min夹头速度进行T剥离测试。对三个条带进行测试以取平均值。在测试期间,用手指轻轻拉动每个条带的尾部,以确保尾部与剥离方向保持90度。
热密封强度:
在可购自布鲁格公司(Brugger Company)的HSG-C热密封机中在140℃的密封温度和300N的压力下将层合物热密封1秒,然后冷却并且切割成15mm宽的条带,以用于使用可购自英斯特朗公司(Instron Corporation)的5940系列单柱台式系统在250mm/min的夹头速度下进行热密封强度测试。每个样品测试三个条带并计算平均值。结果以N/15mm为单位。
5.性能评价结果
粘结强度(BS)和热密封强度(HS)特性总结于表3中。结果表明,使用SMA-3000H将改善PET/PE和箔/PE的粘结强度和热密封强度。然而,当SMA-3000H的含量增加至5.08干重%时,PET/PE和箔/PE的粘结强度开始降低。当SMA-3000H的含量进一步增加至6.67%时,粘结强度甚至变得低于原始ROBONDTML-80D的性能。
表3
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Claims (11)
1.一种粘合剂组合物,所述粘合剂组合物包含:
(A)丙烯酸类乳液聚合物;以及
(B)乙烯基芳族单体-马来酸酐共聚物,
其中基于所述粘合剂组合物的总固体重量计,(B)乙烯基芳族单体-马来酸酐共聚物以0.1重量%至6.5重量%的量存在。
2.根据权利要求1所述的粘合剂组合物,其中所述丙烯酸类乳液聚合物包含(a)一种或多种烯键式不饱和离子单体的结构单元和(b)一种或多种烯键式不饱和非离子单体的结构单元。
3.根据权利要求1所述的粘合剂组合物,其中基于所述乳液聚合物的重量计,所述丙烯酸类乳液聚合物包含按重量计
30%至50%的乙烯基芳族单体的结构单元,
50%至70%的(甲基)丙烯酸C1-C20烷基酯的结构单元,和
0.1%至8%的(甲基)丙烯酸的结构单元。
4.根据权利要求1所述的粘合剂组合物,其中所述乙烯基芳族单体-马来酸酐共聚物包含(a)一种或多种乙烯基芳族单体的结构单元和(b)马来酸酐的结构单元。
5.根据权利要求1所述的粘合剂组合物,其中基于所述粘合剂组合物的总固体重量计,所述乙烯基芳族单体-马来酸酐共聚物(B)以0.5重量%或更多,并且同时以6.0重量%或更少的量存在。
6.根据权利要求1所述的粘合剂组合物,其中所述粘合剂组合物是单组分水基粘合剂组合物。
7.一种使用所述粘合剂组合物生产层合体的方法,所述方法包括:
(a)提供根据权利要求1至6中任一项所述的粘合剂组合物;
(b)将所述粘合剂组合物施加于基材的表面的第一部分上以形成所述粘合剂组合物的层;
(d)使基材的表面的第二部分与所述粘合剂组合物的所述层接触,使得所述粘合剂组合物的所述层夹置于所述第一部分与所述第二部分之间;以及
(e)干燥所述粘合剂组合物或使其干燥。
8.一种层合体,所述层合体通过使用根据权利要求7所述的生产层合体的方法制备。
9.一种层合体,所述层合体包括基材的表面的第一部分、根据权利要求1至6中任一项所述的粘合剂组合物的层以及同一或不同基材的表面的第二部分,其中所述粘合剂组合物的所述层夹置于所述第一部分与所述第二部分之间并且与所述第一部分和所述第二部分接触。
10.乙烯基芳族单体-马来酸酐共聚物用于改善包含丙烯酸类乳液聚合物的粘合剂组合物的粘结强度和/或热密封性能的用途。
11.根据权利要求10所述的用途,其中基于所述粘合剂组合物的总固体重量计,所述乙烯基芳族单体-马来酸酐共聚物以0.1重量%至6重量%的量存在。
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