TW202106841A - 濕氣硬化型熱熔黏著劑組成物、黏著體、及衣類 - Google Patents

濕氣硬化型熱熔黏著劑組成物、黏著體、及衣類 Download PDF

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TW202106841A
TW202106841A TW108146549A TW108146549A TW202106841A TW 202106841 A TW202106841 A TW 202106841A TW 108146549 A TW108146549 A TW 108146549A TW 108146549 A TW108146549 A TW 108146549A TW 202106841 A TW202106841 A TW 202106841A
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Taiwan
Prior art keywords
moisture
urethane prepolymer
adhesive composition
melt adhesive
adherend
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TW108146549A
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English (en)
Inventor
曲淑杰
小宮聰一郎
今井卓也
馬籠和幸
龜井淳一
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日商日立化成股份有限公司
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Publication of TW202106841A publication Critical patent/TW202106841A/zh

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Abstract

揭示一種濕氣硬化型熱熔黏著劑組成物。該濕氣硬化型熱熔黏著劑組成物，其含有：胺酯預聚物，其包含下述聚合鏈且具有2個以上的異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元；及，胺酯預聚物的改質體，其包含下述聚合鏈且具有1個以上的經蓖麻油一元醇所改質之異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元。

Description

濕氣硬化型熱熔黏著劑組成物、黏著體、及衣類
本發明是有關一種濕氣硬化型熱熔黏著劑組成物、黏著體、及衣類。
熱熔黏著劑由於為無溶劑型的黏著劑，故對環境及人體的負擔較少，且由於能夠在短時間內黏著，故為適合提高生產性的黏著劑。熱熔黏著劑能夠大致區分為下述2種：以熱塑性樹脂作為主成分之熱熔黏著劑；及，以反應性樹脂作為主成分之熱熔黏著劑。以反應性樹脂作為主成分之熱熔黏著劑，主要是利用一種胺酯(urethane)預聚物，其末端具有異氰酸酯基。以胺酯預聚物作為主成分之反應性熱熔黏著劑，在塗佈後，藉由黏著劑本身的冷卻固化，即能夠在短時間內顯現某種程度的黏著強度。然後，藉由胺酯預聚物的末端異氰酸酯基與濕氣(空氣中的水分或被黏著體(黏附體，adherend)表面的水分)進行反應而高分子量化並產生交聯，藉此形成硬化物並顯現耐熱性。具有這樣的性質的反應性熱熔黏著劑，稱為濕氣硬化型熱熔黏著劑。因此，以胺酯預聚物作為主成分之濕氣硬化型熱熔黏著劑，有在加熱時仍會顯示良好的黏著強度的傾向。
近年來，濕氣硬化型熱熔黏著劑，亦逐漸用於衣類、尿布等的材料亦即布、紙等。此外，正在接連地開發穿戴式製品，而對於除了黏著性以外還具有較高的伸縮性的黏著劑的需求正在提高。這樣的用途中所使用的濕氣硬化型熱熔黏著劑，已揭示例如：專利文獻1、2中所記載的黏著劑。 [先前技術文獻] (專利文獻)
專利文獻1：日本特開平10-088097號公報 專利文獻2：日本特開2017-020037號公報
[發明所欲解決的問題] 然而，習知的濕氣硬化型熱熔黏著劑，在伸縮性方面並不充分，而尚有改善的空間。
本發明是鑒於這樣實際情況而研創，主要目的在於提供一種濕氣硬化型熱熔黏著劑組成物，其能夠形成一種具有優異的伸縮性的硬化物。 [解決問題的技術手段]
本發明的一態樣提供一種濕氣硬化型熱熔黏著劑組成物，其含有：胺酯預聚物，其包含下述聚合鏈且具有2個以上的異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元；及，胺酯預聚物的改質體，其包含下述聚合鏈且具有1個以上的經蓖麻油一元醇所改質之異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元。若藉由這樣的濕氣硬化型熱熔黏著劑組成物，則能夠形成一種具有優異的伸縮性的硬化物。其理由尚不明確，但本發明人等認為：胺酯預聚物的改質體的分子末端亦即源自蓖麻油一元醇的部分(殘基)具有可撓性及潤滑性，且分子末端能夠自由運動會有助於顯現優異的伸縮性。
胺酯預聚物中的多元醇及胺酯預聚物的改質體中的多元醇，可包含非晶性聚酯多元醇及結晶性聚酯多元醇。
濕氣硬化型熱熔黏著劑組成物，可用於將從布及紙之中選出的複數個被黏著體相互貼合。此處，被黏著體的組合可為：布與布、紙與紙、或布與紙。
本發明進一步有關一種組成物的應用，其是作為濕氣硬化型熱熔黏著劑、或用以製造濕氣硬化型熱熔黏著劑，該組成物含有上述胺酯預聚物及上述胺酯預聚物的改質體，該濕氣硬化型熱熔黏著劑是用於將從布及紙之中選出的複數種被黏著體相互貼合。
本發明的其它一態樣提供一種黏著體，其具備：第1被黏著體；第2被黏著體；及，黏著劑層，其是用以將第1被黏著體與第2被黏著體相互黏著，並且，黏著劑層含有上述濕氣硬化型熱熔黏著劑組成物的硬化物。
本發明的其它一態樣提供一種衣類，其具備上述黏著體，並且，第1被黏著體及第2被黏著體為布。衣類可為無縫製衣類。 [功效]
根據本發明，能夠提供一種濕氣硬化型熱熔黏著劑組成物，其能夠形成一種具有優異的伸縮性的硬化物。此外，根據本發明，能夠提供一種黏著體，其使用了這樣的濕氣硬化型熱熔黏著劑組成物。並且，根據本發明，能夠提供一種衣類，其具備這樣的黏著體。
以下，詳細說明本發明的實施方式。但是，本發明並不受下述實施形態所限定。
本說明書中，「多元醇」是意指分子內具有2個以上的羥基之化合物。
本說明書中，「多異氰酸酯」是意指分子內具有2個以上的異氰酸酯基之化合物。
[濕氣硬化型熱熔黏著劑組成物] 一實施形態的濕氣硬化型熱熔黏著劑組成物，含有：胺酯預聚物，其包含下述聚合鏈且具有2個以上的異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元；及，胺酯預聚物的改質體，其包含下述聚合鏈且具有1個以上的經蓖麻油一元醇所改質之異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元。濕氣硬化型熱熔黏著劑組成物，一般能夠藉由化學反應來高分子量化而顯現黏著性等。胺酯預聚物，因會藉由與濕氣進行反應來高分子量化而硬化(形成硬化物)，因此能夠作為濕氣硬化型熱熔黏著劑的主成分而發揮作用。另一方面，我們推測：胺酯預聚物的改質體主要是對提高伸縮性產生作用。
>胺酯預聚物> 胺酯預聚物，包含下述聚合鏈且具有2個以上的異氰酸酯基，該聚合鏈包含源自多元醇((a)成分)的結構單元及源自多異氰酸酯((b)成分)的結構單元。換言之，胺酯預聚物為多元醇與多異氰酸酯的反應物，並且，具有2個以上的異氰酸酯基來作為聚合鏈的主鏈的末端基或側鏈基。再者，胺酯預聚物是意指不具有經後述蓖麻油一元醇所改質之異氰酸酯基之化合物，而胺酯預聚物的概念是不包含後述胺酯預聚物的改質體。本實施形態的黏著劑組成物，藉由含有這樣的胺酯預聚物，即能夠在濕氣硬化後顯現優異的黏著強度。
(a)成分：多元醇 (a)成分只要為具有2個以上的羥基之化合物，則能夠無特別限制地使用。(a)成分可為具有2個羥基之化合物(二醇)。從更加提高黏著強度的觀點來看，多元醇可包含聚酯多元醇。(a)成分可進一步包含聚醚多元醇。這樣的胺酯預聚物能夠包含下述聚合鏈，該聚合鏈包含源自聚酯多元醇的結構單元、源自聚醚多元醇的結構單元及源自多異氰酸酯的結構單元。
藉由聚合鏈包含源自聚酯多元醇的結構單元，即能夠調整黏著劑組成物的固化時間及黏度。聚酯多元醇能夠使用一種化合物，其是藉由多元醇與多元羧酸的縮聚反應來產生。聚酯多元醇可為例如下述的縮聚物：多元醇，其具有2～15個碳原子，且具有2或3個羥基；及，多元羧酸，其具有2～14個碳原子(包含羧基中的碳原子)，且具有2～6個羧基。
聚酯多元醇可為由二醇與二羧酸所產生的直鏈聚酯二醇，可為由三醇與二羧酸產生的分枝聚酯三醇。此外，分枝聚酯三醇亦能夠藉由二醇與三羧酸的反應來獲得。
作為多元醇，可舉例如：乙二醇、1,2-丙二醇、丁二醇的各異構物、戊二醇的各異構物、己二醇的各異構物、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-環己烷二醇、1,4-環己烷二甲醇等脂肪族或脂環族二醇；4,4’-二羥基二苯基丙烷、雙酚A、雙酚F、焦兒茶酚、間苯二酚、氫醌等芳香族二醇等。多元醇可單獨使用1種，亦可組合使用2種以上。此等之中，以脂肪族二醇為佳，以具有2～6個碳原子之脂肪族二醇較佳。
作為多元羧酸，可舉例如：鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,4-苯三甲酸等芳香族多元羧酸；馬來酸、富馬酸、烏頭酸、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、環己烷-1,2-二甲酸、1,4-環己烷二烯-1,2-二甲酸等脂肪族或脂環族多元羧酸等。多元羧酸可單獨使用1種，且亦可組合使用2種以上。
亦能夠使用羧酸酐、羧基的一部分經酯化而成之化合物等多元羧酸衍生物，來取代上述多元羧酸。作為多元羧酸衍生物可舉例如：十二烷基馬來酸、十八烯基馬來酸等。
聚酯多元醇可為非晶性聚酯多元醇((a-1)成分)，亦可為結晶性聚酯多元醇((a-2)成分)。此處，非晶性及結晶性的判斷能夠在25℃的狀態下判斷。本說明書中，非晶性聚酯多元醇是意指在25℃為非結晶的聚酯多元醇，結晶性聚酯多元醇是意指在25℃為結晶的聚酯多元醇。胺酯預聚物中的多元醇及後述胺酯預聚物的改質體中的多元醇，較佳是包含(a-1)成分及(a-2)成分雙方。
從黏度與黏著力之間的平衡的觀點來看，(a-1)成分的數目平均分子量可為1000～4000或1500～2500。再者，本說明書中，數目平均分子量是藉由凝膠滲透層析法(GPC)來測定，並以標準聚苯乙烯來換算而得的值。GPC的測定能夠在下述條件下進行。
管柱：「Gelpack GLA130-S」、「Gelpack GLA150-S」及「Gelpack GLA160-S」(日立化成股份有限公司製，高效液相層析法(HPLC)用填充管柱) 溶析液：四氫呋喃 流量：1.0 mL/分鐘 管柱溫度：40℃ 偵測器：折射率偵測器(RI)
(a-1)成分能夠直接使用市售物。作為(a-1)成分的市售物，可舉例如：一種非晶性聚酯多元醇，其是以己二酸及間苯二甲酸以及乙二醇及新戊二醇作為主成分(羥基數為2，數目平均分子量為2000)；一種非晶性聚酯多元醇，其是以壬二酸及間苯二甲酸以及乙二醇及新戊二醇作為主成分(羥基數為2，數目平均分子量為2000)等。此等可單獨使用1種，亦可組合使用2種以上。
以(a)成分總量作為基準計，(a-1)成分的含量可為5～90質量％、10～80質量％、或30～70質量％。
從黏度與黏著力之間的平衡的觀點來看，(a-2)成分的數目平均分子量可為3000～8000或3000～6000。
(a-2)成分能夠直接使用市售物。作為(a-2)成分的市售物，可舉例如：一種結晶性聚酯多元醇，其是以己二酸及1,6-己二醇作為主成分(羥基數為2，數目平均分子量為5000)；一種結晶性聚酯多元醇，其是以己二酸以及乙二醇及1,4-丁二醇作為主成分(羥基數為2，數目平均分子量為2000)等。此等可單獨使用1種，亦可組合使用2種以上。
以(a)成分總量作為基準計，(a-2)成分的含量可為10～70質量％、20～60質量％、或35～60質量％。
(a)成分，除了(a-1)成分及(a-2)成分以外，還可進一步包含聚醚多元醇((a-3)成分)。從黏度與黏著力之間的平衡的觀點來看，(a-3)成分的數目平均分子量可為1000～4000或1000～2000。
(a-3)成分能夠直接使用市售物。作為(a-3)成分的市售物，可舉例如：PEG4000S(三洋化成工業股份有限公司製)、EXCENOL2020(旭硝子股份有限公司製)等。此等可單獨使用1種，且亦可組合使用2種以上。
以(a)成分總量作為基準計，(a-3)成分的含量可為1～40質量％、3～20質量％、或3～10質量％。
(a)成分，除了(a-1)成分～(a-3)成分以外，還可進一步包含(a-1)成分～(a-3)成分以外的其它多元醇。作為其它多元醇，可舉例如：聚丙烯酸酯多元醇、聚碳酸酯多元醇、聚矽氧烷多元醇、聚異戊二烯多元醇、聚烯烴多元醇等。其它多元醇可單獨使用1種，亦可組合使用2種以上。
(b)成分：多異氰酸酯 (b)成分只要具有2個以上的異氰酸酯基之化合物，則能夠無特別限制地使用。(b)成分可為具有2個異氰酸酯基之化合物(二異氰酸酯)。作為(b)成分，可舉例如：二苯基甲烷二異氰酸酯、二甲基二苯基甲烷二異氰酸酯、甲苯二異氰酸酯、二甲苯二異氰酸酯、對苯二異氰酸酯等芳香族異氰酸酯；二環己基甲烷二異氰酸酯、異佛酮二異氰酸酯等脂環族異氰酸酯；六亞甲基二異氰酸酯等脂肪族異氰酸酯等。從反應性及黏著性的觀點來看，(b)成分較佳是包含芳香族二異氰酸酯，更佳是包含二苯基甲烷二異氰酸酯。(b)成分可單獨使用1種，亦可組合使用2種以上。
胺酯預聚物能夠以下述方式合成：使多元醇與多異氰酸酯進行反應。胺酯預聚物包含下述聚合鏈且具有2個以上的異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元。當合成這樣的胺酯預聚物時，多異氰酸酯的異氰酸酯基(NCO)相對於多元醇的羥基(OH)的當量比(多異氰酸酯的異氰酸酯基(NCO)當量/多元醇的羥基(OH)當量，NCO/OH)可為1.1以上，可為1.1～2.1。若NCO/OH為1.1以上，則有胺酯預聚物具有2個以上的異氰酸酯基並且能夠抑制胺酯預聚物的黏度上升而更加提高操作性的傾向。若NCO/OH為2.1以下，則有在進行黏著劑組成物的濕氣硬化反應不容易發生起泡而容易抑制黏著強度降低的傾向。
當合成胺酯預聚物時使多元醇與多異氰酸酯進行反應的溫度及時間無特別限定，可為例如：85～120℃，0.1分鐘～48小時。
>胺酯預聚物的改質體> 胺酯預聚物的改質體，包含下述聚合鏈且具有1個以上的經蓖麻油一元醇所改質之異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元。換言之，胺酯預聚物的改質體為胺酯預聚物與蓖麻油一元醇的反應物，並且具有1個以上的經蓖麻油一元醇所改質之異氰酸酯基來作為聚合鏈的主鏈的末端基或側鏈基。本實施形態的黏著劑組成物，藉由含有這樣的胺酯預聚物的改質體，即能夠在濕氣硬化後顯現優異的伸縮性。例如：當胺酯預聚物為二醇與二異氰酸酯的反應物時，以聚合鏈的主鏈的末端基的形式存在的異氰酸酯基的數目為2個。我們推測：若此胺酯預聚物經蓖麻油一元醇所改質，則至少其中一個異氰酸酯基會經改質，故胺酯預聚物的改質體與濕氣之間的反應點會減少，而會較胺酯預聚物更加抑制高分子量化。
胺酯預聚物的改質體中，用以構成改質前的胺酯預聚物的多元醇及多異氰酸酯的種類、含量等，可與上述胺酯預聚物中的例示相同。多元醇可包含非晶性聚酯多元醇及結晶性聚酯多元醇。胺酯預聚物的改質體中的改質前的胺酯預聚物，可與本實施形態的濕氣硬化型熱熔黏著劑組成物中所含的胺酯預聚物相同或不同，從合成的觀點來看，可相同。
(c)成分：蓖麻油一元醇 (c)成分為一種一元醇，其具有源自蓖麻油脂肪酸(蓖麻酸)的基及1個羥基，該蓖麻油脂肪酸是使蓖麻油水解而獲得。(c)成分可為例如蓖麻酸的二酸甘油酯。(c)成分可單獨使用1種，亦可組合使用2種以上。
(c)成分能夠直接使用市售物。作為(c)成分的市售物，可舉例如：URIC H-31(伊藤製油股份有限公司製)等。
胺酯預聚物的改質體能夠以下述方式合成：使胺酯預聚物與(c)成分進行反應。換言之，胺酯預聚物的改質體為胺酯預聚物與(c)成分的反應物，並且為胺酯預聚物中的至少1個異氰酸酯基經(c)成分的羥基所改質之化合物。當合成胺酯預聚物的改質體時，使胺酯預聚物與(c)成分進行反應的溫度及時間無特別限制，可為例如：85～120℃，0.1分鐘～48小時。再者，該反應中可進行減壓脫泡。
從促進胺酯預聚物硬化而使更高的黏著強度顯現的觀點來看，濕氣硬化型熱熔黏著劑組成物可進一步含有觸媒。作為觸媒，可舉例如：月桂酸二丁錫、硫辛酸二丁酯、二甲基環己基胺、二甲基苯甲基胺、三辛基胺等。以濕氣硬化型熱熔黏著劑組成物的總量作為基準計，觸媒的含量可為0.001～0.5質量％。
從提高所形成的黏著劑層的橡膠彈性而更加提高耐衝擊性的觀點來看，濕氣硬化型熱熔黏著劑組成物可進一步含有熱塑性聚合物。作為熱塑性聚合物，可舉例如：聚胺酯、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-共軛二烯嵌段共聚物等。以濕氣硬化型熱熔黏著劑組成物的總量作為基準計，熱塑性彈性體的含量可為0.1～50質量％。
從對所形成的黏著劑層賦予更加牢固的黏著性的觀點來看，濕氣硬化型熱熔黏著劑組成物可進一步含有增黏樹脂。作為增黏樹脂，可舉例如：松香樹脂、松香酯樹脂、氫化松香酯樹脂、萜烯樹脂、萜烯酚樹脂、氫化萜烯樹脂、石油樹脂、氫化石油樹脂、香豆酮樹脂、酮樹脂、苯乙烯樹脂、改質苯乙烯樹脂、二甲苯樹脂、環氧樹脂等。以濕氣硬化型熱熔黏著劑組成物的總量作為基準計，增黏樹脂的含量可為0.1～50質量％。
濕氣硬化型熱熔黏著劑組成物可因應需要來進一步含有其它成分。作為其它成分，可舉例如：抗氧化劑、顏料、紫外線吸收劑、界面活性劑、難燃劑、填充劑、光顯色劑、熱顯色防止劑、香料、顯影劑、熱交聯劑等。以濕氣硬化型熱熔黏著劑組成物的總量作為基準計，其它成分的含量可為0.001～10質量％。
濕氣硬化型熱熔黏著劑組成物能夠藉由一種方法來製造，該方法具備：使多元醇與多異氰酸酯進行反應而獲得胺酯預聚物的步驟，該胺酯預聚物包含下述聚合鏈且具有2個以上的異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元；及，使所獲得的胺酯預聚物的一部分與蓖麻油一元醇進行反應(在所獲得的胺酯預聚物中添加蓖麻油一元醇而使胺酯預聚物的一部分改質)，而獲得包含胺酯預聚物及胺酯預聚物的改質體之混合物的步驟。當為這樣的製造方法時，胺酯預聚物與胺酯預聚物的改質體的改質前的胺酯預聚物能夠相同。以胺酯預聚物中的(a)成分總量作為基準計，(c)成分的添加量可為0.5～5質量％。
當使胺酯預聚物的一部分與蓖麻油一元醇進行反應(在所獲得的胺酯預聚物中添加蓖麻油一元醇而使胺酯預聚物的一部分改質)時，(c)成分的羥基(OH)相對於胺酯預聚物的異氰酸酯基(NCO)的當量比((c)成分的羥基(OH)當量/胺酯預聚物的異氰酸酯基(NCO)當量，OH/NCO)可為例如：0.5以下、0.3以下、或0.15以下，可為例如0.01以上。若OH/NCO為0.5以下，則有能夠獲得充分的黏著強度的傾向，
濕氣硬化型熱熔黏著劑組成物亦能夠藉由例如一種方法來製造，該方法具備：分別個別合成胺酯預聚物及胺酯預聚物的改質體的步驟；及，將所合成的胺酯預聚物與胺酯預聚物的改質體混合的步驟。當為這樣的製造方法時，會有胺酯預聚物與胺酯預聚物的改質體的改質前的胺酯預聚物相同的情形及不同的情形。
濕氣硬化型熱熔黏著劑組成物(硬化前的濕氣硬化型熱熔黏著劑組成物)在120℃時的黏度，可為0.01 Pa・s以上、0.05 Pa・s以上、0.1 Pa・s以上、0.5 Pa・s以上、1 Pa・s以上、或2 Pa・s以上，可為100 Pa・s以下、80 Pa・s以下、60 Pa・s以下、50 Pa・s以下、30 Pa・s以下、或20 Pa・s以下。利用120℃時的黏度在上述範圍內，當使用分配器等來塗佈時的操作性良好。本說明書中，濕氣硬化型熱熔黏著劑組成物(硬化前的濕氣硬化型熱熔黏著劑組成物)在120℃時的黏度，是意指藉由實施例中所記載的方法來測定的值。
濕氣硬化型熱熔黏著劑組成物因黏著劑組成物中所含的胺酯預聚物的異氰酸酯基會與空氣中的水分或被黏著體(黏附體)表面的水分進行反應，因此例如：藉由在溫度23℃、50％RH(相對濕度)放置(熟成)24小時而高分子量化並產生交聯，藉此形成黏著劑組成物的硬化物。被黏著體彼此會經由所形成的黏著劑組成物的硬化物來黏著。
使用濕氣硬化型熱熔黏著劑組成物來將被黏著體彼此壓合並使黏著劑組成物硬化而獲得黏著體，在該黏著體所測定的黏著強度(濕氣硬化型熱熔黏著劑組成物的硬化後的黏著強度)可為1 N/4 mm以上、3 N/4 mm以上、或5 N/4 mm以上。硬化後的黏著強度的上限無特別限制，可為30 N/4 mm以下。再者，本說明書中，硬化後的黏著強度是意指藉由實施例中所記載的方法來測定的值。換言之，硬化後的黏著強度是意指黏著體中的濕氣硬化型熱熔黏著劑組成物的硬化後的黏著強度，該黏著體是藉由使用濕氣硬化型熱熔黏著劑組成物來在120℃將被黏著體彼此壓合而獲得積層體後，在23℃、50％RH(相對濕度)放置(熟成)24小時而獲得。
從柔軟性的觀點來看，濕氣硬化型熱熔黏著劑組成物的硬化後的拉伸彈性模數(濕氣硬化型熱熔黏著劑組成物的硬化物的拉伸彈性模數)可為0.01 MPa以上、0.05 MPa以上、0.1 MPa以上、0.5 MPa以上、1 MPa以上、5 MPa以上、10 MPa以上、或15 MPa以上，可為45 MPa以下、40 MPa以下、35 MPa以下、或30 MPa以下。當用於衣服或穿戴式製品時，拉伸彈性模數在上述範圍內，即能夠更加減少穿著時的不適感。再者，本說明書中，硬化後的拉伸彈性模數，是意指藉由實施例中所記載的方法來測定的值。換言之，硬化後的拉伸彈性模數是意指硬化物的彈性模數，該硬化物是藉由將濕氣硬化型熱熔黏著劑組成物在23℃、50％RH(相對濕度)放置(熟成)24小時來使其硬化而獲得。
濕氣硬化型熱熔黏著劑組成物的硬化後的延伸率可為900％以上、1000％以上、或1100％以上。再者，本說明書中，硬化後的延伸率是意指藉由實施例中所記載的方法來測定的值。換言之，硬化後的延伸率是意指硬化物的延伸率，該硬化物是藉由將濕氣硬化型熱熔黏著劑組成物在23℃、50％RH(相對濕度)放置(熟成)24小時來使其硬化而獲得。
濕氣硬化型熱熔黏著劑組成物能夠藉由例如下述方式來使用：在60～130℃熔融後，塗佈於被黏著體。塗佈方法無特別限制，可舉例如使用下述塗佈裝置的方法：棒塗佈器、模具塗佈器、輥塗佈器、噴霧器等。當塗佈於小型零件等狹小的部位時，分配器較適合。濕氣硬化型熱熔黏著劑組成物的塗佈圖案能夠適當設定，可舉例如：圓點(dot)狀、直線狀、鋸齒狀、面狀、曲線狀等的塗佈圖案。
被黏著體無特別限制，可為例如布或紙。濕氣硬化型熱熔黏著劑組成物能夠合適地用於將從布及紙之中選出的複數個被黏著體相互貼合。此處，被黏著體的組合可為：布與布、紙與紙、或布與紙。
濕氣硬化型熱熔黏著劑組成物可形成為薄膜狀來使用。這樣的黏著劑薄膜能夠藉由下述方式來形成：將濕氣硬化型熱熔黏著劑組成物塗佈於PET(聚對苯二甲酸乙二酯)薄膜等支撐薄膜上。濕氣硬化型熱熔黏著劑薄膜的厚度可為10 μm以上、20 μm以上、或30 μm以上，可為300 μm以下、250 μm以下、或200 μm以下。若濕氣硬化型熱熔黏著劑薄膜變厚，則能夠保證黏著性，若濕氣硬化型熱熔黏著劑薄膜變薄，則有更容易確保伸縮性的傾向。
濕氣硬化型熱熔黏著劑組成物能夠合適地用於：衣服等衣類(服飾商品)、護具、背包、錢包、內部裝潢、各種蓋體、框體、穿戴式機器等。
[黏著體] 一實施形態的黏著體，其具備：第1被黏著體；第2被黏著體；及，黏著劑層，其是用以將第1被黏著體與第2被黏著體相互黏著；並且，黏著劑層含有上述濕氣硬化型熱熔黏著劑組成物的硬化物。作為具備黏著體之物品，可舉例如：衣類(特別是無縫製衣類)。
第1被黏著體及第2被黏著體的例示，能夠與上述被黏著體中的例示相同。換言之，第1被黏著體及第2被黏著體可為布或紙。第1被黏著體與第2被黏著體的組合可為：布與布、紙與紙、或布與紙。當具備黏著體之物品為衣類時，第1被黏著體及第2被黏著體可為布。
黏著體能夠藉由例如一種方法來製造，該方法具備：藉由使上述濕氣硬化型熱熔黏著劑組成物熔融，並塗佈於第1被黏著體，來形成黏著劑層的步驟；藉由將第2被黏著體配置於黏著劑層上，並將第2被黏著體壓合，來獲得積層體的步驟；及，藉由使所獲得的積層體中的黏著劑層硬化，來獲得黏著體的步驟。作為使黏著劑層硬化的方法，可舉例如：在空氣中放置(熟成)(例如在23℃24小時)的方法等。黏著體中的黏著劑層，能夠含有濕氣硬化型熱熔黏著劑組成物的硬化物。
作為將第2被黏著體壓合的方法，可舉例如：使用加壓輥等來壓合的方法。
第1圖是顯示製作一實施形態的黏著體的步驟的概略圖，第1圖(a)、(b)、(c)及(d)是顯示各步驟的概略圖。以下，參照第1圖來說明黏著體的製作步驟，該黏著體使用了布亦即伸縮性布料來作為第1被黏著體及第2被黏著體。
首先，以沿著治具10的方式設置伸縮性布料1(參照第1圖的(a))。然後，將本實施形態的濕氣硬化型熱熔黏著劑組成物塗佈於伸縮性布料1的規定部分，而形成黏著劑層4(參照第1圖的(b))。治具10的材質及形狀無特別限定，能夠因應目的來適當選擇。黏著劑組成物的塗佈可使用例如分配器來進行。然後，將伸縮性布料2配置於黏著劑層4上，並一面使用輥等來從伸縮性布料2的上方施加壓力，一面隔著黏著劑層4來將伸縮性布料1與伸縮性布料2貼合，而獲得積層體20(參照第1圖的(c)及(d))。然後，藉由將積層體20放置(熟成)，即能夠使積層體20中的黏著劑層4濕氣硬化，而獲得伸縮性布料的黏著體(伸縮性布料的衣類，更詳細而言為伸縮性布料的無縫製衣類)。黏著體中的黏著劑層4含有濕氣硬化型熱熔黏著劑組成物的硬化物。
第1圖的(b)中，亦可將預先形成於脫模性基材上的濕氣硬化型熱熔黏著劑組成物的黏著劑薄膜，轉印至伸縮性布料1上，而形成黏著劑層4。此外，亦可將黏著劑層設置於伸縮性布料2側後，與伸縮性布料1貼合。
[衣類] 一實施形態的衣類具備上述黏著體。此時，第1被黏著體及第2被黏著體為布。衣類可為無縫製衣類。 [實施例]
以下，列舉實施例來更具體說明本發明。但是，本發明並不受此等實施例所限定。
(實施例1～4及比較例1) >濕氣硬化型熱熔黏著劑組成物的調製> 使用表1表示的種類及質量份的多元醇、多異氰酸酯、及蓖麻油一元醇。對預先經藉由真空乾燥機來進行脫水處理的多元醇，以使多異氰酸酯的異氰酸酯基相對於多元醇的羥基的當量比((NCO)當量/(OH)當量)成為表1中表示的數值的方式加入多異氰酸酯，並混合直到成為均勻為止。在110℃使其進行反應1小時，藉此獲得胺酯預聚物。如表1所示，由於(NCO)當量/(OH)當量大於1，因此我們推測：所獲得的胺酯預聚物具有下述聚合鏈及與該聚合鏈鍵結的2個以上的異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元。然後，對所獲得的胺酯預聚物，加入表1中表示的質量份的蓖麻油一元醇，並進一步在110℃減壓脫泡攪拌1小時，藉此獲得濕氣硬化型熱熔黏著劑組成物。我們推測：由蓖麻油一元醇的添加量來看，濕氣硬化型熱熔黏著劑組成物為一種混合物，其包含：胺酯預聚物，其具有2個以上的異氰酸酯基；及，胺酯預聚物的改質體，其具有1個以上的經蓖麻油一元醇所改質之異氰酸酯基。
表1中表示的各成分的詳細內容是如下所述。 ・多元醇(a) (a-1-1)非晶性聚酯多元醇：一種非晶性聚酯多元醇，其是以己二酸及間苯二甲酸以及乙二醇及新戊二醇作為主成分，羥基數為2，數目平均分子量為2000 (a-2-1)結晶性聚酯多元醇：一種結晶性聚酯多元醇，其是以己二酸及乙二醇以及1,4-丁二醇作為主成分，羥基數為2，數目平均分子量為2000 (a-2-2)結晶性聚酯多元醇：一種結晶性聚酯多元醇，其是以己二酸及1,6-己二醇作為主成分，羥基數為2，數目平均分子量為5000 (a-3-1)聚醚多元醇：旭硝子股份有限公司製，商品名為EXCENOL2020，數目平均分子量為2000，羥基數為2 ・多異氰酸酯(b) (b-1)二苯基甲烷二異氰酸酯：日本聚胺酯工業股份有限公司製，商品名為Millionate MT，異氰酸酯基數為2 ・蓖麻油一元醇(c) (c-1)蓖麻油一元醇：伊藤製油股份有限公司製，商品名為URICH-31，羥基數為1
>硬化前的黏度> 使用BH-HH型少量旋轉黏度計(東機產業股份有限公司製)，在轉子4號、樣品量15 g、120℃的條件下測定實施例1～4及比較例1的硬化前的濕氣硬化型熱熔黏著劑組成物的黏度。結果是如表1所示。
>硬化後的黏著強度> 在120℃使實施例1～4及比較例1的濕氣硬化型熱熔黏著劑組成物熔融後，使用分配器來塗佈於伸縮性布料(使用下述線來編織而成的布料，該線是以使用耐綸來將胺酯包圍的方式進行而形成，厚度為520 μm)上。然後，將相同的伸縮性布料配置於所塗佈的黏著劑組成物上，並在60℃將由黏著劑組成物所構成的層的厚度壓合直到100 μm為止，藉此獲得積層體。在23℃、50％RH將上述積層體放置24小時，而使由黏著劑組成物所構成的層硬化，藉此製作黏著體。使用拉伸測試機(島津製作所股份有限公司製，商品名：Autograph AGS-X)，在測定溫度25℃、拉伸速度100 mm/分鐘的條件下藉由T型剝離強度測試來測定黏著體的黏著強度，並求出濕氣硬化型熱熔黏著劑組成物的硬化後的黏著強度。結果是如表1所示。
>硬化後的拉伸彈性模數及硬化後的延伸率> 準備2片隔離膜。在120℃使實施例1～4及比較例1的濕氣硬化型熱熔黏著劑組成物熔融後，塗佈於1片隔離膜上，並以另1片隔離膜來將濕氣硬化型熱熔黏著劑組成物夾入後，使用低壓加壓測試機(稻岡鑄造所有限公司製)，在加壓溫度100℃、加壓壓力400 kPa的條件下加壓至100 μm的厚度，藉此獲得由濕氣硬化型熱熔黏著劑組成物所構成的黏著劑薄膜。在23℃、50％RH將所獲得的黏著劑薄膜放置24小時而使其硬化，而獲得黏著劑薄膜的硬化物。使用Dumbbell Cutter(DUMBBELL股份有限公司製)，來將所獲得的黏著劑薄膜的硬化物衝切成Dumbbell 1號的形狀，並將隔離膜剝離後，設為測定樣品。拉伸彈性模數及延伸率是使用Autograph AGS-X(島津製作所股份有限公司製)，在測定溫度23℃、拉伸速度10 mm/分鐘、夾頭間距離40 mm的條件下進行測定。拉伸彈性模數是由拉伸初期階段的應力-應變曲線的斜率求出。延伸率是藉由下述方法來求出。以拉伸速度100 mm/分鐘來使測定樣品伸長。測定下述長度：測定前的樣品長度、及伸長直到斷裂為止時的長度，並分別設為L1及L2。藉由將測得的L1及L2代入下述式中來算出。各個結果是如表1所示。 延伸率(％)＝L2/L1×100
[表1]
Figure 02_image001
實施例1～4的濕氣硬化型熱熔黏著劑組成物含有胺酯預聚物的改質體，比較例1的濕氣硬化型熱熔黏著劑組成物不含胺酯預聚物的改質體，相較於比較例1的濕氣硬化型熱熔黏著劑組成物，實施例1～4的濕氣硬化型熱熔黏著劑組成物的抗張彈性模數更低，而延伸率更大。由上述結果能夠確認：本發明的濕氣硬化型熱熔黏著劑組成物，能夠形成一種具有優異的伸縮性的硬化物。
1,2:伸縮性布料 4:黏著劑層 10:治具 20:積層體
第1圖是顯示製作一實施形態的黏著體的步驟的概略圖，第1圖(a)、(b)、(c)及(d)是顯示各步驟的概略圖。
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Claims (5)

  1. 一種濕氣硬化型熱熔黏著劑組成物，其含有： 胺酯預聚物，其包含下述聚合鏈且具有2個以上的異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元；及， 胺酯預聚物的改質體，其包含下述聚合鏈且具有1個以上的經蓖麻油一元醇所改質之異氰酸酯基，該聚合鏈包含源自多元醇的結構單元及源自多異氰酸酯的結構單元。
  2. 如請求項1所述之濕氣硬化型熱熔黏著劑組成物，其中，前述胺酯預聚物中的多元醇及前述胺酯預聚物的改質體中的多元醇，包含非晶性聚酯多元醇及結晶性聚酯多元醇。
  3. 如請求項1或2所述之濕氣硬化型熱熔黏著劑組成物，其是用於將從布及紙之中選出的複數個被黏著體相互貼合。
  4. 一種黏著體，其具備： 第1被黏著體； 第2被黏著體；及， 黏著劑層，其是用以將前述第1被黏著體與前述第2被黏著體相互黏著； 並且，前述黏著劑層含有請求項1或2所述之濕氣硬化型熱熔黏著劑組成物的硬化物。
  5. 一種衣類，其具備請求項4所述之黏著體，並且，前述第1被黏著體及前述第2被黏著體為布。
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