CN113966182A - 湿气固化型热熔黏合剂组合物、黏合体、及衣物 - Google Patents

湿气固化型热熔黏合剂组合物、黏合体、及衣物 Download PDF

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CN113966182A
CN113966182A CN201980095751.7A CN201980095751A CN113966182A CN 113966182 A CN113966182 A CN 113966182A CN 201980095751 A CN201980095751 A CN 201980095751A CN 113966182 A CN113966182 A CN 113966182A
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moisture
urethane prepolymer
curable hot
melt adhesive
adhesive composition
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CN113966182B (zh
Inventor
曲淑杰
小宫聪一郎
今井卓也
马笼和幸
龟井淳一
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Resonac Holdings Corp
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Showa Denko KK
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Abstract

本发明公开一种湿气固化型热熔黏合剂组合物。该湿气固化型热熔黏合剂组合物含有：氨基甲酸酯预聚物，其包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有2个以上的异氰酸酯基；及氨基甲酸酯预聚物的改性体，其包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有1个以上的由蓖麻油一元醇所改性的异氰酸酯基。

Description

湿气固化型热熔黏合剂组合物、黏合体、及衣物
技术领域
本发明是涉及一种湿气固化型热熔黏合剂组合物、黏合体、及衣物。
背景技术
热熔黏合剂由于为无溶剂型的黏合剂，因此对环境及人体的负担较少，且由于能够在短时间内黏合，因此为适合提高生产性的黏合剂。热熔黏合剂能够大致区分为下述2种：以热塑性树脂作为主成分的热熔黏合剂；及以反应性树脂作为主成分的热熔黏合剂。以反应性树脂作为主成分的热熔黏着剂，主要是利用一种氨基甲酸酯(urethane)预聚物，其末端具有异氰酸酯基。以氨基甲酸酯预聚物作为主成分的反应性热熔黏合剂，在涂布后，通过黏合剂本身的冷却固化，即能够在短时间内显现某种程度的黏合强度。然后，通过氨基甲酸酯预聚物的末端异氰酸酯基与湿气(空气中的水分或黏附体(黏附体，adherend)表面的水分)进行反应而高分子量化并产生交联，由此形成固化物并显现耐热性。具有这样的性质的反应性热熔黏合剂，称为湿气固化型热熔黏合剂。因此，以氨基甲酸酯预聚物作为主成分的湿气固化型热熔黏合剂，有在加热时仍会显示良好的黏合强度的倾向。
近年来，湿气固化型热熔黏合剂，也逐渐用于衣物、尿布等的材料即布、纸等。此外，正在接连地开发穿戴式制品，而对于除了黏合性以外还具有较高的伸缩性的黏合剂的需求正在提高。这样的用途中所使用的湿气固化型热熔黏合剂，已揭示例如：专利文献1、2中所记载的黏合剂。
以往技术文献
专利文献
专利文献1：日本特开平10-088097号公报
专利文献2：日本特开2017-020037号公报
发明内容
发明要解决的技术课题
然而，习知的湿气固化型热熔黏合剂，在伸缩性方面并不充分，而尚有改善的空间。
本发明是鉴于上述情况而完成的，主要目的在于提供一种湿气固化型热熔黏合剂组合物，其能够形成一种具有优异的伸缩性的固化物。
用于解决技术课题的手段
本发明的一方式提供一种湿气固化型热熔黏合剂组合物，其含有：氨基甲酸酯预聚物，其包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有2个以上的异氰酸酯基；及氨基甲酸酯预聚物的改性体，其包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有1个以上的由蓖麻油一元醇所改性的异氰酸酯基。若通过这样的湿气固化型热熔黏合剂组合物，则能够形成一种具有优异的伸缩性的固化物。其理由尚不明确，但本发明人等认为：氨基甲酸酯预聚物的改性体的分子末端即源自蓖麻油一元醇的部分(残基)具有可挠性及润滑性，且分子末端能够自由运动会有助于显现优异的伸缩性。
氨基甲酸酯预聚物中的多元醇及氨基甲酸酯预聚物的改性体中的多元醇，可包含非晶性聚酯多元醇及结晶性聚酯多元醇。
湿气固化型热熔黏合剂组合物，可用于将选自布及纸中的多个黏附体相互贴合。此处，黏附体的组合可为：布与布、纸与纸、或布与纸。
本发明进一步涉及一种组合物的应用，其是作为湿气固化型热熔黏合剂、或用以制造湿气固化型热熔黏合剂，该组合物含有上述氨基甲酸酯预聚物及上述氨基甲酸酯预聚物的改性体，该湿气固化型热熔黏合剂是用于将选自布及纸中的多种黏附体相互贴合。
本发明的另一方式提供一种黏合体，其具备：第1黏附体；第2黏附体；及黏合剂层，其是用以将第1黏附体与第2黏附体相互黏合，并且，黏合剂层含有上述湿气固化型热熔黏合剂组合物的固化物。
本发明的另一方式提供一种衣物，其具备上述黏合体，并且，第1黏附体及第2黏附体为布。衣物可为无缝制衣物。
发明效果
根据本发明，能够提供一种湿气固化型热熔黏合剂组合物，其能够形成一种具有优异的伸缩性的固化物。此外，根据本发明，能够提供一种黏合体，其使用了这样的湿气固化型热熔黏合剂组合物。并且，根据本发明，能够提供一种衣物，其具备这样的黏合体。
附图说明
图1是显示制作一实施方式的黏合体的步骤的概略图，图1的(a)、(b)、(c)及(d)是显示各步骤的概略图。
具体实施方式
以下，详细说明本发明的实施方式。但是，本发明并不受下述实施方式所限定。
本说明书中，“多元醇”是意指分子内具有2个以上的羟基的化合物。
本说明书中，“多异氰酸酯”是意指分子内具有2个以上的异氰酸酯基的化合物。
[湿气固化型热熔黏合剂组合物]
一实施方式的湿气固化型热熔黏合剂组合物，含有：氨基甲酸酯预聚物，其包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有2个以上的异氰酸酯基；及氨基甲酸酯预聚物的改性体，其包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有1个以上的由蓖麻油一元醇所改性的异氰酸酯基。湿气固化型热熔黏合剂组合物，一般能够通过化学反应来高分子量化而显现黏合性等。氨基甲酸酯预聚物，因会通过与湿气进行反应来高分子量化而固化(形成固化物)，因此能够作为湿气固化型热熔黏合剂的主成分而发挥作用。另一方面，我们推测：氨基甲酸酯预聚物的改性体主要是对提高伸缩性产生作用。
<氨基甲酸酯预聚物>
氨基甲酸酯预聚物，包括包含源自多元醇((a)成分)的结构单元及源自多异氰酸酯((b)成分)的结构单元的聚合链，且具有2个以上的异氰酸酯基。换言之，氨基甲酸酯预聚物为多元醇与多异氰酸酯的反应物，并且，具有2个以上的异氰酸酯基来作为聚合链的主链的末端基或侧链基。再者，氨基甲酸酯预聚物是意指不具有由后述蓖麻油一元醇所改性的异氰酸酯基的化合物，而氨基甲酸酯预聚物的概念是不包含后述氨基甲酸酯预聚物的改性体。本实施方式的黏合剂组合物，通过含有这样的氨基甲酸酯预聚物，即能够在湿气固化后显现优异的黏合强度。
(a)成分：多元醇
(a)成分只要为具有2个以上的羟基的化合物，则能够无特别限制地使用。(a)成分可为具有2个羟基的化合物(二醇)。从更加提高黏合强度的观点来看，多元醇可包含聚酯多元醇。(a)成分可进一步包含聚醚多元醇。这样的氨基甲酸酯预聚物能够包括包含源自聚酯多元醇的结构单元、源自聚醚多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链。
通过聚合链包含源自聚酯多元醇的结构单元，即能够调整黏合剂组合物的固化时间及粘度。聚酯多元醇能够使用一种化合物，其是通过多元醇与多元羧酸的缩聚反应来产生。聚酯多元醇可为例如下述的缩聚物：多元醇，其具有2～15个碳原子，且具有2或3个羟基；及多元羧酸，其具有2～14个碳原子(包含羧基中的碳原子)，且具有2～6个羧基。
聚酯多元醇可为由二醇与二羧酸所产生的直链聚酯二醇，可为由三醇与二羧酸产生的分枝聚酯三醇。此外，分枝聚酯三醇也能够通过二醇与三羧酸的反应来获得。
作为多元醇，例如可以举出乙二醇、1,2-丙二醇、1,3-丙二醇、丁二醇的各异构物、戊二醇的各异构物、己二醇的各异构物、2,2-二甲基-1,3-丙二醇、2-甲基丙二醇、2,4,4-三甲基-1,6-己二醇、2,2,4-三甲基-1,6-己二醇、1,4-环己烷二醇、1,4-环己烷二甲醇等脂肪族或脂环族二醇；4,4’-二羟基二苯基丙烷、双酚A、双酚F、焦儿茶酚、间苯二酚、氢醌等芳香族二醇等。多元醇可单独使用1种，也可组合使用2种以上这些之中，优选脂肪族二醇，更优选具有2～6个碳原子的脂肪族二醇。
作为多元羧酸，例如可以举出邻苯二甲酸、间苯二甲酸、对苯二甲酸、1,2,4-苯三甲酸等芳香族多元羧酸；马来酸、富马酸、乌头酸、1,2,3-丙烷三甲酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、环己烷-1,2-二甲酸、1,4-环己烷二烯-1,2-二甲酸等脂肪族或脂环族多元羧酸等。多元羧酸可单独使用1种，且也可组合使用2种以上。
也能够使用羧酸酐、羧基的一部分由酯化而成的化合物等多元羧酸衍生物，来取代上述多元羧酸。作为多元羧酸衍生物例如可以举出十二烷基马来酸、十八烯基马来酸等。
聚酯多元醇可为非晶性聚酯多元醇((a-1)成分)，也可为结晶性聚酯多元醇((a-2)成分)。此处，非晶性及结晶性的判断能够在25℃的状态下判断。本说明书中，非晶性聚酯多元醇是意指在25℃为非结晶的聚酯多元醇，结晶性聚酯多元醇是意指在25℃为结晶的聚酯多元醇。氨基甲酸酯预聚物中的多元醇及后述氨基甲酸酯预聚物的改性体中的多元醇，优选为包含(a-1)成分及(a-2)成分双方。
从粘度与黏合力之间的平衡的观点来看，(a-1)成分的数目平均分子量可为1000～4000或1500～2500。再者，本说明书中，数目平均分子量是通过凝胶渗透层析法(GPC)来测定，并以标准聚苯乙烯来换算而得的值。GPC的测定能够在下述条件下进行。
管柱：“Gelpack GLA130-S”、“Gelpack GLA150-S”及“Gelpack GLA160-S”(ShowaDenko Materials Co.,Ltd.制，高效液相层析法(HPLC)用填充管柱)
洗脱液：四氢呋喃
流量：1.0mL/分钟
管柱温度：40℃
检测器：折射率检测器(RI)
(a-1)成分能够直接使用市售物。作为(a-1)成分的市售物，例如可以举出一种非晶性聚酯多元醇，其是以己二酸及间苯二甲酸以及乙二醇及新戊二醇作为主成分(羟基数为2，数目平均分子量为2000)；一种非晶性聚酯多元醇，其是以壬二酸及间苯二甲酸以及乙二醇及新戊二醇作为主成分(羟基数为2，数目平均分子量为2000)等。这些可单独使用1种，也可组合使用2种以上。
以(a)成分总量作为基准计，(a-1)成分的含量可为5～90质量％、10～80质量％、或30～70质量％。
从粘度与黏合力之间的平衡的观点来看，(a-2)成分的数目平均分子量可为3000～8000或3000～6000。
(a-2)成分能够直接使用市售物。作为(a-2)成分的市售物，例如可以举出一种结晶性聚酯多元醇，其是以己二酸及1,6-己二醇作为主成分(羟基数为2，数目平均分子量为5000)；一种结晶性聚酯多元醇，其是以己二酸以及乙二醇及1,4-丁二醇作为主成分(羟基数为2，数目平均分子量为2000)等。这些可单独使用1种，也可组合使用2种以上。
以(a)成分总量作为基准计，(a-2)成分的含量可为10～70质量％、20～60质量％、或35～60质量％。
(a)成分，除了(a-1)成分及(a-2)成分以外，还可进一步包含聚醚多元醇((a-3)成分)。从粘度与黏合力之间的平衡的观点来看，(a-3)成分的数目平均分子量可为1000～4000或1000～2000。
(a-3)成分能够直接使用市售物。作为(a-3)成分的市售物，例如可以举出PEG4000S(SANYO CHEMICAL INDUSTRIES,LTD.制)、EXCENOL2020(AGC Inc.制)等。这些可单独使用1种，也可组合使用2种以上。
以(a)成分总量作为基准计，(a-3)成分的含量可为1～40质量％、3～20质量％、或3～10质量％。
(a)成分，除了(a-1)成分～(a-3)成分以外，还可进一步包含(a-1)成分～(a-3)成分以外的其它多元醇。作为其它多元醇，例如可以举出聚丙烯酸酯多元醇、聚碳酸酯多元醇、聚硅氧烷多元醇、聚异戊二烯多元醇、聚烯烃多元醇等。其它多元醇可单独使用1种，也可组合使用2种以上。
(b)成分：多异氰酸酯
(b)成分只要具有2个以上的异氰酸酯基的化合物，则能够无特别限制地使用。(b)成分可为具有2个异氰酸酯基的化合物(二异氰酸酯)。作为(b)成分，例如可以举出二苯基甲烷二异氰酸酯、二甲基二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、二甲苯二异氰酸酯、对苯二异氰酸酯等芳香族异氰酸酯；二环己基甲烷二异氰酸酯、异佛酮二异氰酸酯等脂环族异氰酸酯；六亚甲基二异氰酸酯等脂肪族异氰酸酯等。从反应性及黏合性的观点来看，(b)成分优选为包含芳香族二异氰酸酯，更优选为包含二苯基甲烷二异氰酸酯。(b)成分可单独使用1种，也可组合使用2种以上。
氨基甲酸酯预聚物能够以下述方式合成：使多元醇与多异氰酸酯进行反应。氨基甲酸酯预聚物包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有2个以上的异氰酸酯基。当合成这样的氨基甲酸酯预聚物时，多异氰酸酯的异氰酸酯基(NCO)相对于多元醇的羟基(OH)的当量比(多异氰酸酯的异氰酸酯基(NCO)当量/多元醇的羟基(OH)当量，NCO/OH)可为1.1以上，可为1.1～2.1。若NCO/OH为1.1以上，则有氨基甲酸酯预聚物具有2个以上的异氰酸酯基并且能够抑制氨基甲酸酯预聚物的粘度上升而更加提高操作性的倾向。若NCO/OH为2.1以下，则有在进行黏合剂组合物的湿气固化反应不容易发生起泡而容易抑制黏合强度降低的倾向。
当合成氨基甲酸酯预聚物时使多元醇与多异氰酸酯进行反应的温度及时间无特别限定，可为例如：85～120℃，0.1分钟～48小时。
<氨基甲酸酯预聚物的改性体>
氨基甲酸酯预聚物的改性体，包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有1个以上的由蓖麻油一元醇所改性的异氰酸酯基。换言之，氨基甲酸酯预聚物的改性体为氨基甲酸酯预聚物与蓖麻油一元醇的反应物，并且具有1个以上的由蓖麻油一元醇所改性的异氰酸酯基来作为聚合链的主链的末端基或侧链基。本实施方式的黏合剂组合物，通过含有这样的氨基甲酸酯预聚物的改性体，即能够在湿气固化后显现优异的伸缩性。例如：当氨基甲酸酯预聚物为二醇与二异氰酸酯的反应物时，以聚合链的主链的末端基的形式存在的异氰酸酯基的数目为2个。我们推测：若此氨基甲酸酯预聚物由蓖麻油一元醇所改性，则至少其中一个异氰酸酯基被改性，因此氨基甲酸酯预聚物的改性体与湿气之间的反应点会减少，而会较氨基甲酸酯预聚物更加抑制高分子量化。
氨基甲酸酯预聚物的改性体中，用以构成改性前的氨基甲酸酯预聚物的多元醇及多异氰酸酯的种类、含量等，可与上述氨基甲酸酯预聚物中的例示相同。多元醇可包含非晶性聚酯多元醇及结晶性聚酯多元醇。氨基甲酸酯预聚物的改性体中的改性前的氨基甲酸酯预聚物，可与本实施方式的湿气固化型热熔黏合剂组合物中所含的氨基甲酸酯预聚物相同或不同，从合成的观点来看，可相同。
(c)成分：蓖麻油一元醇
(c)成分为一种一元醇，其具有源自蓖麻油脂肪酸(蓖麻酸)的基及1个羟基，该蓖麻油脂肪酸是使蓖麻油水解而获得。(c)成分可为例如蓖麻酸的二酸甘油酯。(c)成分可单独使用1种，也可组合使用2种以上。
(c)成分能够直接使用市售物。作为(c)成分的市售物，例如可以举出URIC H-31(ITOH OIL CHEMICALS CO.,LTD.制)等。
氨基甲酸酯预聚物的改性体能够以下述方式合成：使氨基甲酸酯预聚物与(c)成分进行反应。换言之，氨基甲酸酯预聚物的改性体为氨基甲酸酯预聚物与(c)成分的反应物，并且为氨基甲酸酯预聚物中的至少1个异氰酸酯基由(c)成分的羟基所改性的化合物。当合成氨基甲酸酯预聚物的改性体时，使氨基甲酸酯预聚物与(c)成分进行反应的温度及时间无特别限制，可为例如：85～120℃，0.1分钟～48小时。再者，该反应中可进行减压脱泡。
从促进氨基甲酸酯预聚物固化而使更高的黏合强度显现的观点来看，湿气固化型热熔黏合剂组合物可进一步含有触媒。作为触媒，例如可以举出月桂酸二丁锡、硫辛酸二丁酯、二甲基环己基胺、二甲基苯甲基胺、三辛基胺等。以湿气固化型热熔黏合剂组合物的总量作为基准计，触媒的含量可为0.001～0.5质量％。
从提高所形成的黏合剂层的橡胶弹性而更加提高耐冲击性的观点来看，湿气固化型热熔黏合剂组合物可进一步含有热塑性聚合物。作为热塑性聚合物，例如可以举出聚氨酯、乙烯系共聚物、丙烯系共聚物、氯乙烯系共聚物、丙烯酸系共聚物、苯乙烯-共轭二烯嵌段共聚物等。以湿气固化型热熔黏合剂组合物的总量作为基准计，热塑性弹性体的含量可为0.1～50质量％。
从对所形成的黏合剂层赋予更加牢固的黏合性的观点来看，湿气固化型热熔黏合剂组合物可进一步含有增黏树脂。作为增黏树脂，例如可以举出松香树脂、松香酯树脂、氢化松香酯树脂、萜烯树脂、萜烯酚树脂、氢化萜烯树脂、石油树脂、氢化石油树脂、香豆酮树脂、酮树脂、苯乙烯树脂、改性苯乙烯树脂、二甲苯树脂、环氧树脂等。以湿气固化型热熔黏合剂组合物的总量作为基准计，增黏树脂的含量可为0.1～50质量％。
湿气固化型热熔黏合剂组合物可因应需要来进一步含有其它成分。作为其它成分，例如可以举出抗氧化剂、颜料、紫外线吸收剂、界面活性剂、难燃剂、填充剂、光显色剂、热显色防止剂、香料、显影剂、热交联剂等。以湿气固化型热熔黏合剂组合物的总量作为基准计，其它成分的含量可为0.001～10质量％。
湿气固化型热熔黏合剂组合物能够通过一种方法来制造，该方法具备：使多元醇与多异氰酸酯进行反应而获得氨基甲酸酯预聚物的步骤，该氨基甲酸酯预聚物包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有2个以上的异氰酸酯基；及使所获得的氨基甲酸酯预聚物的一部分与蓖麻油一元醇进行反应(在所获得的氨基甲酸酯预聚物中添加蓖麻油一元醇而使氨基甲酸酯预聚物的一部分改性)，而获得包含氨基甲酸酯预聚物及氨基甲酸酯预聚物的改性体的混合物的步骤。当为这样的制造方法时，氨基甲酸酯预聚物与氨基甲酸酯预聚物的改性体的改性前的氨基甲酸酯预聚物能够相同。以氨基甲酸酯预聚物中的(a)成分总量作为基准计，(c)成分的添加量可为0.5～5质量％。
当使氨基甲酸酯预聚物的一部分与蓖麻油一元醇进行反应(在所获得的氨基甲酸酯预聚物中添加蓖麻油一元醇而使氨基甲酸酯预聚物的一部分改性)时，(c)成分的羟基(OH)相对于氨基甲酸酯预聚物的异氰酸酯基(NCO)的当量比((c)成分的羟基(OH)当量/氨基甲酸酯预聚物的异氰酸酯基(NCO)当量，OH/NCO)可为例如：0.5以下、0.3以下、或0.15以下，可为例如0.01以上。若OH/NCO为0.5以下，则有能够获得充分的黏合强度的倾向，
湿气固化型热熔黏合剂组合物也能够通过例如一种方法来制造，该方法具备：分别个别合成氨基甲酸酯预聚物及氨基甲酸酯预聚物的改性体的步骤；及将所合成的氨基甲酸酯预聚物与所合成的氨基甲酸酯预聚物混合的步骤。当为这样的制造方法时，会有氨基甲酸酯预聚物与氨基甲酸酯预聚物的改性体的改性前的氨基甲酸酯预聚物相同的情形及不同的情形。
湿气固化型热熔黏合剂组合物(固化前的湿气固化型热熔黏合剂组合物)在120℃時的粘度，可为0.01Pa·s以上、0.05Pa·s以上、0.1Pa·s以上、0.5Pa·s以上、1Pa·s以上、或2Pa·s以上，可为100Pa·s以下、80Pa·s以下、60Pa·s以下、50Pa·s以下、30Pa·s以下、或20Pa·s以下。利用120℃时的粘度在上述范围内，当使用分配器等来涂布时的操作性良好。本说明书中，湿气固化型热熔黏合剂组合物(固化前的湿气固化型热熔黏合剂组合物)在120℃时的粘度，是意指通过实施例中所记载的方法来测定的值。
湿气固化型热熔黏合剂组合物因黏合剂组合物中所含的氨基甲酸酯预聚物的异氰酸酯基会与空气中的水分或黏附体(黏附体)表面的水分进行反应，因此例如：通过在温度23℃、50％RH(相对湿度)放置(熟成)24小时而高分子量化并产生交联，由此形成黏合剂组合物的固化物。黏附体彼此会经由所形成的黏合剂组合物的固化物来黏合。
使用湿气固化型热熔黏合剂组合物来将黏附体彼此压合并使黏合剂组合物固化而获得黏合体，在该黏合体所测定的黏合强度(湿气固化型热熔黏合剂组合物的固化后的黏合强度)可为1N/4mm以上、3N/4mm以上、或5N/4mm以上。固化后的黏合强度的上限无特别限制，可为30N/4mm以下。再者，本说明书中，固化后的黏合强度是意指通过实施例中所记载的方法来测定的值。换言之，固化后的黏合强度是意指黏合体中的湿气固化型热熔黏合剂组合物的固化后的黏合强度，该黏合体是通过使用湿气固化型热熔黏合剂组合物来在120℃将黏附体彼此压合而获得层叠体后，在23℃、50％RH(相对湿度)放置(熟成)24小时而获得。
从柔软性的观点来看，湿气固化型热熔黏合剂组合物的固化后的拉伸弹性模量(湿气固化型热熔黏合剂组合物的固化物的拉伸弹性模量)可为0.01MPa以上、0.05MPa以上、0.1MPa以上、0.5MPa以上、1MPa以上、5MPa以上、10MPa以上、或15MPa以上，可为45MPa以下、40MPa以下、35MPa以下、或30MPa以下。当用于衣服或穿戴式制品时，拉伸弹性模量在上述范围内，即能够更加减少穿着时的不适感。再者，本说明书中，固化后的拉伸弹性模量，是意指通过实施例中所记载的方法来测定的值。换言之，固化后的拉伸弹性模量是意指固化物的弹性模量，该固化物是通过将湿气固化型热熔黏合剂组合物在23℃、50％RH(相对湿度)放置(熟成)24小时来使其固化而获得。
湿气固化型热熔黏合剂组合物的固化后的延伸率可为900％以上、1000％以上、或1100％以上。再者，本说明书中，固化后的延伸率是意指通过实施例中所记载的方法来测定的值。换言之，固化后的延伸率是意指固化物的延伸率，该固化物是通过将湿气固化型热熔黏合剂组合物在23℃、50％RH(相对湿度)放置(熟成)24小时来使其固化而获得。
湿气固化型热熔黏合剂组合物能够通过例如下述方式来使用：在60～130℃熔融后，涂布于黏附体。涂布方法无特别限制，例如可以举出使用下述涂布装置的方法：棒涂布器、模具涂布器、辊涂布器、喷雾器等。当涂布于小型零件等狭小的部位时，分配器较适合。湿气固化型热熔黏合剂组合物的涂布图案能够适当设定，例如可以举出圆点(dot)状、直线状、锯齿状、面状、曲线状等的涂布图案。
黏附体无特别限制，可为例如布或纸。湿气固化型热熔黏合剂组合物能够合适地用于将选自布及纸中的多个黏附体相互贴合。此处，黏附体的组合可为：布与布、纸与纸、或布与纸。
湿气固化型热熔黏合剂组合物可形成为薄膜状来使用。这样的黏合剂薄膜能够通过下述方式来形成：将湿气固化型热熔黏合剂组合物涂布于PET(聚对苯二甲酸乙二酯)薄膜等支撑薄膜上。湿气固化型热熔黏合剂薄膜的厚度可为10μm以上、20μm以上、或30μm以上，可为300μm以下、250μm以下、或200μm以下。若湿气固化型热熔黏合剂薄膜变厚，则能够保证黏合性，若湿气固化型热熔黏合剂薄膜变薄，则有更容易确保伸缩性的倾向。
湿气固化型热熔黏合剂组合物能够合适地用于：衣服等衣物(服饰商品)、护具、背包、钱包、内部装潢、各种盖体、框体、穿戴式机器等。
[黏合体]
一实施方式的黏合体，其具备：第1黏附体；第2黏附体；及黏合剂层，其是用以将第1黏附体与第2黏附体相互黏合；并且，黏合剂层含有上述湿气固化型热熔黏合剂组合物的固化物。作为具备黏合体的物品，例如可以举出衣物(特别是无缝制衣物)。
第1黏附体及第2黏附体的例示，能够与上述黏附体中的例示相同。换言之，第1黏附体及第2黏附体可为布或纸。第1黏附体与第2黏附体的组合可为：布与布、纸与纸、或布与纸。当具备黏合体的物品为衣物时，第1黏附体及第2黏附体可为布。
黏合体能够通过例如一种方法来制造，该方法具备：通过使上述湿气固化型热熔黏合剂组合物熔融，并涂布于第1黏附体，来形成黏合剂层的步骤；通过将第2黏附体配置于黏合剂层上，并将第2黏附体压合，来获得层叠体的步骤；及通过使所获得的层叠体中的黏合剂层固化，来获得黏合体的步骤。作为使黏合剂层固化的方法，例如可以举出在空气中放置(熟成)(例如在23℃24小时)的方法等。黏合体中的黏合剂层，能够含有湿气固化型热熔黏合剂组合物的固化物。
作为将第2黏附体压合的方法，例如可以举出使用加压辊等来压合的方法。
图1是显示制作一实施方式的黏合体的步骤的概略图，图1的(a)、(b)、(c)及(d)是显示各步骤的概略图。以下，参照图1来说明黏合体的制作步骤，该黏合体使用了布即伸缩性布料来作为第1黏附体及第2黏附体。
首先，以沿着夹具10的方式设置伸缩性布料1(参照图1的(a))。然后，将本实施方式的湿气固化型热熔黏合剂组合物涂布于伸缩性布料1的规定部分，而形成黏合剂层4(参照图1的(b))。夹具10的材质及形状无特别限定，能够因应目的来适当选择。黏合剂组合物的涂布可使用例如分配器来进行。然后，将伸缩性布料2配置于黏合剂层4上，并一面使用辊等来从伸缩性布料2的上方施加压力，一面隔着黏合剂层4来将伸缩性布料1与伸缩性布料2贴合，而获得层叠体20(参照图1的(c)及(d))。然后，通过将层叠体20放置(熟成)，即能够使层叠体20中的黏合剂层4湿气固化，而获得伸缩性布料的黏合体(伸缩性布料的衣物，更详细而言为伸缩性布料的无缝制衣物)。黏合体中的黏合剂层4含有湿气固化型热熔黏合剂组合物的固化物。
图1的(b)中，也可将预先形成于脱模性基材上的湿气固化型热熔黏合剂组合物的黏合剂薄膜，转印至伸缩性布料1上，而形成黏合剂层4。此外，也可将黏合剂层设置于伸缩性布料2侧后，与伸缩性布料1贴合。
[衣物]
一实施方式的衣物具备上述黏合体。此时，第1黏附体及第2黏附体为布。衣物可为无缝制衣物。
实施例
以下，列举实施例来更具体说明本发明。但是，本发明并不受这些实施例所限定。
(实施例1～4及比较例1)
<湿气固化型热熔黏合剂组合物的制备>
使用表1表示的种类及质量份的多元醇、多异氰酸酯、及蓖麻油一元醇。相对于预先通过真空干燥机进行脱水处理的多元醇，以使多异氰酸酯的异氰酸酯基相对于多元醇的羟基的当量比((NCO)当量/(OH)当量)成为表1中表示的数值的方式加入多异氰酸酯，并混合直到成为均匀为止。在110℃使其进行反应1小时，由此获得氨基甲酸酯预聚物。如表1所示，由于(NCO)当量/(OH)当量大于1，因此我们推测：所获得的氨基甲酸酯预聚物具有包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链、及与该聚合链键结的2个以上的异氰酸酯基。然后，对所获得的氨基甲酸酯预聚物，加入表1中表示的质量份的蓖麻油一元醇，并进一步在110℃减压脱泡搅拌1小时，由此获得湿气固化型热熔黏合剂组合物。我们推测：由蓖麻油一元醇的添加量来看，湿气固化型热熔黏合剂组合物为一种混合物，其包含：氨基甲酸酯预聚物，其具有2个以上的异氰酸酯基；及氨基甲酸酯预聚物的改性体，其具有1个以上的由蓖麻油一元醇所改性的异氰酸酯基。
表1中表示的各成分的详细内容是如下所述。
·多元醇(a)
(a-1-1)非晶性聚酯多元醇：一种非晶性聚酯多元醇，其是以己二酸及间苯二甲酸以及乙二醇及新戊二醇作为主成分，羟基数为2，数目平均分子量为2000
(a-2-1)结晶性聚酯多元醇：一种结晶性聚酯多元醇，其是以己二酸及乙二醇以及1,4-丁二醇作为主成分，羟基数为2，数目平均分子量为2000
(a-2-2)结晶性聚酯多元醇：一种结晶性聚酯多元醇，其是以己二酸及1,6-己二醇作为主成分，羟基数为2，数目平均分子量为5000
(a-3-1)聚醚多元醇：AGC Inc.制，商品名为EXCENOL2020，数目平均分子量为2000，羟基数为2
·多异氰酸酯(b)
(b-1)二苯基甲烷二异氰酸酯：Nippon Polyurethane Industry Co.,Ltd.制，商品名为Millionate MT，异氰酸酯基数为2
·蓖麻油一元醇(c)
(c-1)蓖麻油一元醇：ITOH OIL CHEMICALS CO.,LTD.制，商品名为URICH-31，羟基数为1
<固化前的粘度>
使用BH-HH型少量旋转粘度计(TOKI SANGYO CO.,LTD.制)，在转子4号、样品量15g、120℃的条件下测定实施例1～4及比较例1的固化前的湿气固化型热熔黏合剂组合物的粘度。结果是如表1所示。
<固化后的黏合强度>
在120℃使实施例1～4及比较例1的湿气固化型热熔黏合剂组合物熔融后，使用分配器来涂布于伸缩性布料(使用下述线来编织而成的布料，该线是以使用耐纶来将聚氨酯包围的方式进行而形成，厚度为520μm)上。然后，将相同的伸缩性布料配置于所涂布的黏合剂组合物上，并在60℃将由黏合剂组合物所构成的层的厚度压合直到100μm为止，由此获得层叠体。在23℃、50％RH将上述层叠体放置24小时，而使由黏合剂组合物所构成的层固化，由此制作黏合体。使用拉伸测试机(Shimadzu Corporation.制，商品名：Autograph AGS-X)，在测定温度25℃、拉伸速度100mm/分钟的条件下通过T型剥离强度测试来测定黏合体的黏合强度，并求出湿气固化型热熔黏合剂组合物的固化后的黏合强度。结果是如表1所示。
<固化后的拉伸弹性模量及固化后的延伸率>
准备2片隔离薄膜。在120℃使实施例1～4及比较例1的湿气固化型热熔黏合剂组合物熔融后，涂布于1片隔离薄膜上，并以另1片隔离薄膜来将湿气固化型热熔黏合剂组合物夹入后，使用低压加压测试机(稻冈铸造所有限公司制)，在加压温度100℃、加压压力400kPa的条件下加压至100μm的厚度，由此获得由湿气固化型热熔黏合剂组合物所构成的黏合剂薄膜。在23℃、50％RH将所获得的黏合剂薄膜放置24小时而使其固化，而获得黏合剂薄膜的固化物。使用Dumbbell Cutter(DUMBBELL CO.,LTD.制)，来将所获得的黏合剂薄膜的固化物冲切成Dumbbell 1号的形状，并将隔离薄膜剥离后，设为测定样品。拉伸弹性模量及延伸率是使用Autograph AGS-X(Shimadzu Corporation.制)，在测定温度23℃、拉伸速度10mm/分钟、夹头间距离40mm的条件下进行测定。拉伸弹性模量是由拉伸初期阶段的应力-应变曲线的斜率求出。延伸率是通过下述方法来求出。以拉伸速度100mm/分钟来使测定样品伸长。测定下述长度：测定前的样品长度、及伸长直到断裂为止时的长度，并分别设为L1及L2。通过将测得的L1及L2代入下述式中来算出。各个结果是如表1所示。
延伸率(％)＝L2/L1×100
[表1]
Figure BDA0003318806340000151
与不含氨基甲酸酯预聚物的改性体的比较例1的湿气固化型热熔黏合剂组合物相比，含有氨基甲酸酯预聚物的改性体的实施例1～4的湿气固化型热熔黏合剂组合物的拉伸弹性模量更低，而延伸率更大。由上述结果能够确认：本发明的湿气固化型热熔黏合剂组合物，能够形成一种具有优异的伸缩性的固化物。
符号说明
1,2-伸缩性布料，4-黏合剂层，10-夹具，20-层叠体。

Claims (5)

1.一种湿气固化型热熔黏合剂组合物，其含有：
氨基甲酸酯预聚物，其包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有2个以上的异氰酸酯基；及
氨基甲酸酯预聚物的改性体，其包括包含源自多元醇的结构单元及源自多异氰酸酯的结构单元的聚合链，且具有1个以上的由蓖麻油一元醇所改性的异氰酸酯基。
2.根据权利要求1所述的湿气固化型热熔黏合剂组合物，其中，
所述氨基甲酸酯预聚物中的多元醇及所述氨基甲酸酯预聚物的改性体中的多元醇，包含非晶性聚酯多元醇及结晶性聚酯多元醇。
3.根据权利要求1或2所述的湿气固化型热熔黏合剂组合物，其用于将选自布及纸中的多个黏附体相互贴合。
4.一种黏合体，其具备：
第1黏附体；
第2黏附体；及
黏合剂层，其将所述第1黏附体与所述第2黏附体相互黏合；
所述黏合剂层含有权利要求1或2所述的湿气固化型热熔黏合剂组合物的固化物。
5.一种衣物，其具备：
权利要求4所述的黏合体，
所述第1黏附体及所述第2黏附体为布。
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