CN113825782B - 粘合剂组合物 - Google Patents

粘合剂组合物 Download PDF

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CN113825782B
CN113825782B CN201980096107.1A CN201980096107A CN113825782B CN 113825782 B CN113825782 B CN 113825782B CN 201980096107 A CN201980096107 A CN 201980096107A CN 113825782 B CN113825782 B CN 113825782B
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adhesive composition
component
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CN113825782A (zh
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白晨艳
陈红宇
T·施密特
余英丰
董海军
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Dow Global Technologies LLC
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Abstract

一种粘合剂组合物,包括以下反应混合物:(A)至少一种含异氰酸酯的组分;(B)至少一种多元醇组分;(C)共聚结晶潜伏催化剂;上述粘合剂组合物的制备方法;以及使用上述粘合剂组合物制成的层压结构。

Description

粘合剂组合物
技术领域
本发明涉及一种粘合剂组合物;更具体地,本发明涉及一种聚氨酯粘合剂组合物,其含有起潜伏催化剂作用的共聚结晶聚合物。
背景技术
无溶剂聚氨酯(PU)粘合剂通常由两种组分配制而成,称为双组分(2K)体系;其中,2K体系的第一种组分是异氰酸酯预聚物,2K体系的第二种组分是多元醇。就在施加所得混合物之前将两种组分混合在一起。当两种组分混合时,异氰酸酯预聚物的异氰酸酯(NCO)基团和多元醇的羟基(OH)基团之间发生化学反应。该反应导致粘合剂的粘度增加,并最终导致粘合剂固化。
在粘合剂制剂或组合物的粘度增加到粘度增加不再允许粘合剂涂覆到基材上之前的时间段通常被称为粘合剂的“适用期(pot life)”。具有长适用期的粘合剂对于改进操作和工艺灵活性是可取的;并且还需要具有较快固化速度的粘合剂,以尽快达到所需的最终性能,以便粘合剂可以用于生产层压板,并且层压板可以在生产过程中快速进入分切或制袋阶段。通常,将催化剂加入粘合剂组合物中以加速组合物的固化。然而,迄今已知的包含已知催化剂的粘合剂组合物:(1)具有良好的适用期和缓慢的固化速度;或者(2)固化速度快,适用期短;但是已知的催化剂并没有表现出良好的适用期和快速的固化速度。
因此需要提供一种具有快速固化速度和长适用期的粘合剂组合物。
发明内容
本发明涉及一种用于制备层压结构的层压粘合剂。在一个优选实施方式中,粘合剂组合物包括以下反应混合物:(A)至少一种含异氰酸酯的组分;(B)至少一种多元醇组分;和(C)共聚结晶潜伏催化剂。在一个优选实施方式中,共聚结晶潜伏催化剂包括以下反应产物:(a)至少一种结晶丙烯酸酯单体;(b)至少一种含锡催化剂组分;(c)至少一名引发剂;(d)至少一种链转移剂;(e)任选地,至少一种溶剂。
本发明的粘合剂组合物的一些优点包括:(1)表现出优异适用期的粘合剂组合物;(2)含有催化剂的粘合剂组合物,其中该催化剂可以在低活化温度(例如,低于80℃)下活化以开始粘合剂组合物的固化并且其中催化剂不会损害粘合剂组合物的适用期;(3)粘合剂组合物,其含有简单的反应组分以改进粘合剂组合物的处理。
具体实施方式
关于催化剂,“潜伏”在本文中是指催化剂在某些条件下,例如操作温度下不催化反应,而在其他不同条件下(例如通过升高反应温度),催化剂确实开始催化相同的反应。
“热潜伏催化剂”是在将催化剂加热到第二高温(例如,40℃)之前在第一低温(例如,在25℃的室温)下不处于其活性状态的催化剂。
关于双组分聚氨酯粘合剂组合物,“适用期(pot life)”在本文中是指粘合剂组合物的粘度增加到粘合剂组合物不再适合涂敷到基材上之前的时间段。
在一个广泛的实施方式中,本发明的粘合剂制剂或组合物可包括以下反应混合物:(A)至少一种含异氰酸酯基团的组分;(B)至少一种多元醇组分(或含羟基的组分);(C)共聚结晶潜伏催化剂。在一优选实施方式中,粘合剂组合物可为无溶剂2K PU体系,但本发明不限于这种2K体系。其他添加剂和组分可用于形成本发明的粘合剂组合物。
可用于本发明粘合剂组合物的含异氰酸酯基团的组分(组分(A))可包括例如至少一种每个分子具有两个或更多个异氰酸酯基团的组分。在一种实施方式中,组分(A)可包括一种或多种异氰酸酯官能化聚氨酯预聚物。聚氨酯预聚物可以是如下组分,例如由多元醇组分(或其他活性氢官能化组分)与至少一种具有至少两个官能度的异氰酸酯反应产生的组分。上述反应可以在无溶剂下或在如乙酸乙酯、丙酮、甲乙酮及其混合物的溶剂存在下进行。聚氨酯预聚物不仅可以包括具有较低分子量的组分,例如由多元醇与过量多异氰酸酯的反应形成的组分,还可以包括低聚组分聚合组分。
本发明中使用的组分A的分子量通常在一个实施方式中为500克/摩尔(g/mol)至30,000g/mol,在另一个实施方式中为600g/mol至15,000g/mol,在再一个实施方式中为700g/mol至10,000g/mol。除非另有说明,以上基于聚合物的分子量是指数均分子量(Mn)。
通常,上述合适的多异氰酸酯可以包括例如脂肪族或芳族多异氰酸酯;在一个优选实施方式中,本发明使用芳族多异氰酸酯。例如,4,4′-二苯基甲烷二异氰酸酯(MDI)或其异构体;甲苯二异氰酸酯(TDI)或其异构体;或聚合二苯甲烷二异氰酸酯可用作本发明中的多异氰酸酯。在一个优选实施方式中,MDI单体用于本发明。
通常,上述合适的多元醇组分可包括例如聚醚多元醇、聚酯多元醇、生物基多元醇及其混合物。合适的聚醚多元醇可包括,但不限于例如环氧乙烷、环氧丙烷、四氢呋喃、环氧丁烷的加聚产物,以及它们的共加成和接枝产物,以及通过多元醇或其混合物的缩合获得的聚醚多元醇。适用于本发明的聚醚多元醇的实例可包括但不限于聚丙二醇(PPG)、聚乙二醇(PEG)、聚丁二醇、聚四亚甲基醚二醇(PTMEG)及其混合物。聚醚多元醇的分子量可以在一个实施方式中为300g/mol至3,000g/mol,在另一个实施方式中为350g/mol至2,500g/mol,在再一个实施方式中为400g/mol至2,200g/mol。
可用于本发明的聚酯多元醇组分是双官能团或三官能团醇与二羧酸和/或三羧酸的缩聚产物。醇的实例可包括乙二醇、二甘醇、新戊二醇、己二醇、丁二醇、丙二醇、甘油、三羟甲基丙烷及其混合物。特别合适的醇可包括例如已二醇、乙二醇、二甘醇、新戊二醇及其两种或更多种的混合物。酸的实例可包括己二酸、琥珀酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸及其混合物。特别合适的酸可以是间苯二甲酸、己二酸及其混合物。聚醚多元醇的分子量可以在一个实施方式为600g/mol至10,000g/mol,在另一个实施方式中为700g/mol至8,000g/mol,在再一个实施方式中为800g/mol至3,000g/mol。
可用于本发明的生物基多元醇可包括例如一种或多种生物基多元醇,例如蓖麻油或其他类似的生物基多元醇。在一个实施方式中,生物基多元醇具有至少1.5且至多4的羟基官能度,即生物基多元醇的羟基官能度可为1.5≤f≤4。
多元醇组分,即组分(B),可以是一种或多种组分的溶液、混合物或掺合物,包括例如:至少一种聚醚多元醇组分和/或聚酯多元醇组分、生物基多元醇或它们的混合物。可用于本发明的粘合剂组合物中的多元醇组分可包括,例如上述聚醚多元醇、聚酯多元醇和生物基多元醇中的任一种或任意组合或两种或更多种。例如,适用根据本公开的用途的聚醚多元醇可以是环氧乙烷、环氧丙烷、四氢呋喃、环氧丁烷的加聚产物,以及它们的共加成和接枝产物,以及通过多元醇和其混合物的缩合获得的聚醚多元醇。适用于本发明的聚醚多元醇的实例可包括但不限于PPG、PEG、聚丁二醇和PTMEG。
聚酯多元醇组分可以是双官能团或三官能团醇与二羧酸和/或三羧酸的缩聚产物。醇的实例可包括乙二醇、二甘醇、新戊二醇、己二醇、丁二醇、丙二醇、甘油或三羟甲基丙烷。在一个优选实施方式中,合适的醇可以是己二醇、乙二醇、二甘醇、新戊二醇及其两种或更多种的混合物。酸的实例可以是己二酸、琥珀酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸及其混合物。本发明中使用的特别合适的酸是间苯二甲酸、己二酸及其混合物。在一个实施方式中,的分子量在一个实施方式中可以为600g/mol至10,000g/mol,在另一个实施方式中可以为700g/mol至8,000g/mol,在又一个实施方式中可以为800g/mol至6,000g/mol。
如上所述,当使用生物基多元醇时,可用于本发明的生物基多元醇可包括例如一种或多种生物基多元醇,例如蓖麻油或其他类似的生物基多元醇。并且,在一个实施方式中,生物基多元醇具有至少1.5且至多4的羟基官能度,即生物基多元醇的羟基官能度可为1.5≤f≤4。
对于本发明的粘合剂组合物,异氰酸酯组分(A)与多元醇组分(B)的重量比在一个实施方式中可以为1∶2至3∶1,在另一个实施方式中可以为1∶1至2∶1,在又一个实施方式中可以为2∶1至1∶3。
用于制备本发明粘合剂组合物的共聚结晶潜伏催化剂组分(C)可以是Lucy Bai等人于2019年4月18日提交的共同未决中国专利申请号PCT/CN2019/083167中描述的任何一种或多种共聚结晶潜伏催化剂。例如,在一个实施方式中,共聚结晶潜伏催化剂包括以下反应产物:(a)至少一种结晶单体组分,如结晶丙烯酸酯单体,例如结晶丙烯酸十八烷基酯(例如,可从Scientific Polymer购得的18AA),其形成结晶聚合物;(b)至少一种可共聚的潜伏催化剂组分,如含锡催化剂组分(例如,马来酸二丁基锡[DBTM]),其可以接枝到结晶聚合物主链上以形成催化剂接枝的结晶聚合物潜伏催化剂;(c)至少一种引发剂,例如2,2′-偶氮二异丁腈(AIBN);(d)至少一种链转移剂,例如十二烷基硫醇(DDM);(e)任选地,至少一种溶剂,例如甲苯。
通常,共聚结晶潜伏催化剂组分(C)可以例如使用共聚方法制备,其中催化剂组分(例如DBTM)接枝到结晶聚合物主链上以形成催化剂接枝的结晶聚合物潜伏催化剂组合物。然后可以将接枝的潜伏催化剂组分(C)与异氰酸酯组分(A)和多元醇组分(B)组合以制备本发明的粘合剂组合物。
制备共聚结晶潜伏催化剂组分(C)的一个实施方式包括以下共聚方法:将可共聚的潜潜伏催化剂组分例如含锡的潜伏催化剂组分(例如DBTM)与结晶单体化合物例如结晶丙烯酸十八烷基酯(例如,18AA)聚合以将潜伏催化剂固定到结晶聚合物主链上,从而形成共聚结晶潜伏催化剂结构。例如,在一个优选实施方式中,用于形成这种催化剂结构的共聚方法为如下方案(I)所示的催化剂结构:
有利地,接枝聚合物中的潜伏催化剂在粘合剂组合物的第一操作温度期间保持无活性(失活),该第一操作温度低于结晶聚合物的熔点。此后,当粘合剂组合物经受高于结晶聚合物熔点的第二固化温度(即高于操作温度的温度)时,催化剂被活化(即,当温度升高到固化条件时,催化剂可以通过加热活化),然后活化加速了粘合剂组合物中组分之间的反应以进行固化。在潜伏催化剂在第一操作温度下保持失活期间,未观察到对粘合剂组合物的适用期的显着损害。
用于制备本发明的粘合剂组合物的共聚结晶潜伏催化剂组分(C)的量可例如在一个实施方式中为0.001wt%至10wt%,在另一个实施方式中为0.005wt%至8wt%,在再一个实施方式中为0.01wt%至6wt%。
尽管本发明的粘合剂组合物涉及双组分体系,但本发明的粘合剂组合物可以与多种任选的添加剂一起配制以实现特定功能的性能,同时保持所得粘合剂产品的优异益处/特性。除了共聚结晶潜伏催化剂、异氰酸酯组分和多元醇组分之外,本发明的粘合剂组合物还可以包括一种或多种本领域已知的用于它们的用途或功能的任选组分。例如,可用于组合物中的一些任选的组分或添加剂可包括:溶剂,例如乙酸乙酯、丙酮和酮及其混合物;粘合促进剂,例如硅烷、环氧树脂、酚醛树脂及其混合物;增链剂,例如甘油、三羟甲基丙烷、二甘醇、丙二醇、2-甲基-1,3-丙二醇及其混合物。
在一个优选实施方式中,可以将聚氨酯粘合剂的任选组分、组分(D)加入到第二多元醇组分(B)中。一般地,基于组合物中的组分的总重量,2K粘合剂组合物中的任选添加剂组分(C)的量在一个实施方式中可以在0wt%至20wt%的范围内;在另一个实施方式中可以在0.01wt%至10wt%的范围内;在再一个实施方案中可以在1wt%至5wt%的范围内。
在一般实施方式中,制备本发明的粘合剂组合物的方法包括共混、混合或掺合的步骤:(A)含异氰酸酯基团的组分;(B)上述聚合物组分;(C)上述共聚结晶潜伏催化剂;(D)任何其他所需的任选组分。
例如,组分(A)至(D)可以在上文所讨论的期望浓度下并在一个实施方式中在约25℃到约45℃的温度下混合在一起;在另一个实施方式中,在约30℃到约40℃下混合在一起。组分的混合顺序并不严格,并且可以将两种或更多种组分混合在一起,然后添加其余组分。可以通过任何已知的混合工艺和设备将粘合剂组合物组分混合在一起。
通常,组分(A)和(B)是彼此分开制备的;并且每种组分都储存在单独的容器中。粘合剂组合物的潜伏催化剂、组分(C)和其他组分或任选的添加剂可以作为第二组分(B)的一部分存在。用于储存每种组分的合适容器可以是例如鼓、小圆桶、袋、桶、罐、筒或管。在施加粘合剂组合物之前,将两种组分分开储存并仅在施加期间或就在施加之前彼此混合。
一旦制备了本发明的粘合剂组合物,共聚结晶催化剂在操作温度下保持失活,直到粘合剂组合物已被使用或应用到两个基材上以将两个基材粘合在一起;并且直到粘合剂组合物准备好在升高的温度下固化。本发明的粘合剂组合物可以表现出几种有利的性能,例如与不添加共聚结晶催化剂的粘合剂相比几乎不破坏适用期);与不添加共聚结晶催化剂的粘合剂相比,粘合强度发展快速,如通过常规T剥离试验测量的)。
例如,与不添加共聚结晶催化剂的粘合剂相比,粘合剂组合物的适用期可以相同或最大缩短5分钟(min)。粘合剂组合物的适用期通过跟踪粘合剂组合物在特定温度(例如,30℃)下的粘度变化并记录粘合剂组合物达到3,000毫帕秒(mPa.s)粘度所需的时间来测量。
通过上述方法制备的本发明的粘合剂组合物表现出的一些其他有利特性可以包括结合强度发展快速,使用5940系列单立柱测试系统(可从英斯特朗集团(InstronCorporation)购得)在250毫米每分钟(mm/min)十字头速度下用15毫米(mm)宽条带使用T型剥离测试来测试结合强度。T型剥离测试的结果以牛顿每15毫米(N/15mm)为单位。T型剥离测试结果的相对较高的值表明更好的粘合强度。
在一个广泛的实施方式中,本发明的粘合剂组合物可用于将至少两个基材(例如,至少第一基材和至少第二基材)粘合在一起以形成层状层压结构,其中应用粘合剂组合物并且使其位于两个基材之间。
第一基材和第二基材可以由相同或不同的材料制成。合适的材料包括纸、织造和非织造织物、金属箔、聚合物、金属涂敷的聚合物及其混合物。该材料任选地可以具有在其上用墨水印刷图像的表面;并且油墨可以与粘合剂组合物接触。在一些实施方式中,该材料可包括聚合物膜和金属涂覆的聚合物膜。在优选实施方式中,该材料包括聚合物膜,例如聚对苯二甲酸乙二醇酯(PET)、聚乙烯(PE)及其混合物。
层压板可以由层压领域的技术人员通过熟知的层压工艺制备,例如,典型的诺德美克(Nordmeccanica)无溶剂机器或典型的干层压机可用于本发明。
根据本发明制造的层压制品可用于多种应用,包括例如用于生产干燥食品包装、重型包装和液体小袋包装;以及生产自立袋包装和任何其他包装。
实施例
提供以下实例以另外详细地说明本发明,但不应解释为限制权利要求的范围。除非另外指示,否则所有份数和百分比都按重量计。
下面在本发明实施例(Inv.Ex.)和比较例(Comp.Ex.)中使用的各种术语和命名和原材料(或成分)在下表I中进行了解释。
表I-原材料
共聚结晶催化剂的合成
根据以下方法在甲苯溶液中制备共聚结晶催化剂:结晶丙烯酸酯单体、DBTM、引发剂AIBN、扩链剂和甲苯在缓慢搅拌下混合在一起。然后,在连续搅拌下将所得混合物的温度升至60℃至80℃的温度;并将混合物的温度在60℃至80℃下保持24小时。此后,停止搅拌混合物并冷却。将所得共聚物沉淀到甲醇中,并将沉淀物放入40℃真空烘箱中24小时以溶出任何残留溶剂。在上述溶出步骤之后获得最终的共聚催化剂。
四种催化剂样品Cat.1-Cat.4使用上述共聚结晶催化剂的合成方法制备。在制备的每个催化剂样品中,DBTM浓度和丙烯酸酯单体类型都发生了变化;并且得到的每一种所得共聚物都显示出结晶温度和熔化温度。表II中描述了四种催化剂样品,即Cat.1-Cat.4。
表II-共聚结晶催化剂
*“Cat.”用作“催化剂”的缩写。
实施例1-4与比较例A和B
应用性能评估2K无溶剂(SL)PU粘合剂与共聚结晶催化剂
将表II中描述的四种共聚结晶催化剂中的每一种加入到双组分(2k)无溶剂(SL)聚氨酯(PU)粘合剂组合物中以形成本发明的粘合剂组合物;并评估粘合剂组合物的性能。评估粘合剂组合物的适用期和粘合强度发展性能。将含有表II中描述的共聚结晶催化剂Cat.1-4的本发明粘合剂组合物(本发明实施例1-4)的性能结果(适用期和粘合强度发展)分别与以下进行比较:(1)不存在共聚结晶催化剂的2k SL PU粘合剂组合物(比较例A),和(2)含有纯DBTM的2k SL PU粘合剂组合物,它是一种非共聚结晶催化剂(比较例B);表III中描述了性能结果。
从表III中的结果可以看出,与没有共聚结晶粘合剂的催化剂(比较例A)相比,本发明的2k SL PU粘合剂(本发明实施例1-4)在30℃的操作温度下显示出可比的适用期。然而,与没有共聚结晶催化剂的粘合剂(比较例A)相比,含有共聚结晶催化剂的2k SL PU粘合剂在50℃下固化90分钟后表现出更高的粘合强度。从表III中的结果可以得出结论,具有共聚结晶催化剂的本发明粘合剂组合物的粘合强度发展快速并且当粘合剂组合物包含共聚结晶催化剂时不会损害粘合剂组合物的适用期。
另一方面,与本发明的2k SL PU粘合剂(本发明实施例1-4)相比,具有非共聚催化剂(纯DBTM)的2k SL PU粘合剂(比较例B)与本发明的2k SL PU粘合剂(本发明实施例1-4)相比显示出更短的适用期。此外,与没有催化剂的粘合剂(比较例A)相比,含有DBTM的2k SLPU粘合剂的适用期要短得多,这表示含有纯DBTM的粘合剂组合物(比较例B)没有表现出任何潜伏。然而,具有纯DBTM的2k SL PU粘合剂(比较例B)的粘合强度分别类似于本发明的具有共聚结晶催化剂(Cat.1-4)的2k SL PU粘合剂(本发明实施例1-4)的粘合强度。而且,具有纯DBTM的2k SL PU(比较例B)比没有催化剂的粘合剂(比较例A)的粘合强度高。
表III
*适用期是指在30℃下达到3,000mPa.s的时间。
**粘合强度(BS)对于PET/PE40是在50℃下固化90分钟后。

Claims (10)

1.一种包含以下各项的反应混合物的粘合剂组合物:
(A)至少一种含异氰酸酯的组分;
(B)至少一种多元醇组分;以及
(C)至少一种共聚的结晶潜伏催化剂,其包含以下各者的反应产物:(a)至少一种结晶丙烯酸酯单体,其形成结晶聚合物,其中所述结晶丙烯酸酯单体选自丙烯酸十八烷基酯、甲基丙烯酸十八烷基酯、丙烯酸二十二烷基酯、甲基丙烯酸二十二烷基酯及其混合物;(b)至少一种可共聚的催化剂组分,其接枝到结晶聚合物主链上以形成催化剂接枝的结晶聚合物潜伏催化剂,其中所述可共聚的催化剂组分是马来酸二丁基锡DBTM;(c)至少一种引发剂;(d)至少一种链转移剂;(e)任选地,至少一种溶剂。
2.根据权利要求1所述的粘合剂组合物,其中,与不含共聚结晶潜伏催化剂组分(C)的粘合剂组合物相比,所述粘合剂组合物的适用期相同或最大缩短5分钟,所述适用期是通过跟踪所述粘合剂组合物在30℃至40°的温度下的粘度变化并记录所述粘合剂组合物达到3,000毫帕秒粘度所需的时间测量的。
3.根据权利要求1所述的粘合剂组合物,其中,与不含共聚结晶潜伏催化剂组分(C)的粘合剂组合物相比,所述粘合剂组合物在50℃至60℃的温度下具有更快的粘合强度发展,所述粘合强度发展是通过T型剥离测试测量的。
4.根据权利要求1所述的粘合剂组合物,其中,所述至少一种含异氰酸酯的组分(A)的浓度为10重量%至78重量%。
5.根据权利要求1所述的粘合剂组合物,其中,所述至少一种多元醇组分(B)的浓度为20重量%至88重量%。
6.根据权利要求1所述的粘合剂组合物,其中,所述至少一种共聚结晶潜伏催化剂组分(C)的浓度为0.01重量%至10重量%。
7.根据权利要求1所述的粘合剂组合物,其中,所述共聚结晶潜伏催化剂组分(C)的熔点为45℃至60℃;并且其中,所述共聚结晶潜伏催化剂组分(C)的结晶温度为40℃至55℃。
8.一种制备粘合剂组合物的方法,包括混合:
(A)至少一种含异氰酸酯的组分;
(B)至少一种多元醇组分;以及
(C)共聚结晶潜伏催化剂,其包含以下各者的反应产物:(a)至少一种结晶丙烯酸酯单体,其形成结晶聚合物,其中所述结晶丙烯酸酯单体选自丙烯酸十八烷基酯、甲基丙烯酸十八烷基酯、丙烯酸二十二烷基酯、甲基丙烯酸二十二烷基酯及其混合物;(b)至少一种可共聚的催化剂组分,其接枝到结晶聚合物主链上以形成催化剂接枝的结晶聚合物潜伏催化剂,其中所述可共聚的催化剂组分是马来酸二丁基锡DBTM;(c)至少一种引发剂;(d)至少一种链转移剂;和(e)任选地,至少一种溶剂。
9.一种用于制造层压结构的方法,其包括以下步骤:
(I)提供至少第一基材和至少第二基材;
(II)将权利要求1所述的粘合剂组合物应用到所述至少第一基材或所述至少第二基材的一个表面的至少一部分以形成设置在所述第一或第二基材上的粘合剂膜层;
(III)将第一基材和第二基材与粘合剂接触以形成层状层压结构;其中,所述粘合剂设置在所述第一和第二基材之间;和
(IV)加热所述层状层压结构以固化所述粘合剂组合物,从而形成粘合的层压结构。
10.一种通过根据权利要求9所述的方法制造的层压结构。
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