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TWI796450B - 接著劑、積層薄膜、及積層薄膜之製造方法 - Google Patents

接著劑、積層薄膜、及積層薄膜之製造方法 Download PDF

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Publication number
TWI796450B
TWI796450B TW108108581A TW108108581A TWI796450B TW I796450 B TWI796450 B TW I796450B TW 108108581 A TW108108581 A TW 108108581A TW 108108581 A TW108108581 A TW 108108581A TW I796450 B TWI796450 B TW I796450B
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Taiwan
Prior art keywords
polyol
adhesive
polyisocyanate
composition
laminated film
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TW108108581A
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English (en)
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TW201940638A (zh
Inventor
大久保智雄
高橋茂和
富田大樹
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日商迪愛生股份有限公司
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Abstract

一種接著劑，其係以含有多異氰酸酯(A)的多異氰酸酯組成物(X)、與含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)的多元醇組成物(Y)為必要成分；一種使用該接著劑之積層薄膜；及一種積層薄膜之製造方法，其係具有使被塗布至一方的基材之含有多異氰酸酯(A)的多異氰酸酯組成物(X)，與被塗布至另一方的基材之含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)的多元醇組成物(Y)接觸而進行壓接的二液分別塗布步驟。

Description

接著劑、積層薄膜、及積層薄膜之製造方法
本發明係關於二液型接著劑、及使用該接著劑積層各種薄膜而成之積層薄膜。更詳而言之，係關於積層用接著劑，其能在無溶劑下使用，且用於將各種塑膠薄膜、金屬蒸鍍薄膜、鋁箔等積層，而製造主要使用於食品、醫藥品、洗劑等的包裝材料之積層薄膜時。
聚胺甲酸酯樹脂由於與基材的密合性、柔軟性優異之點而被廣泛使用作為軟包裝材用積層接著劑，利用由多異氰酸酯與多元醇的反應所形成之胺甲酸酯樹脂系接著劑而貼合的積層薄膜，被用作為食品、醫藥品、洗劑等的包裝材料。
以往，係以將溶解於有機溶劑的接著劑塗敷至薄膜，在通過烘箱的過程中使有機溶劑揮發，貼合另一片薄膜貼合的乾式積層方式為主流，但是近年，從環境負荷的減低及作業環境的改善之觀點，不含有機溶劑的二液型之無溶劑型積層接著劑(亦稱為二液型接著劑、反應性接著劑)的需要正不斷提高。
二液型之無溶劑型積層接著劑，為了在積層後進行多異氰酸酯組成物與多元醇組成物的反應，而必須進行熟成步驟。熟成的溫度、時間係由使用的接著 劑而定，但通常在25~50℃進行1~5天，被要求不加熱(25℃前後)且熟成時間的短縮。
作為不加熱而在25℃前後能夠短時間熟成的方法，使用胺觸媒為眾所周知的。然而，胺觸媒其本身亦與多異氰酸酯的反應性高，會在接著劑塗膜中形成低分子量的三次元交聯物。因此，會使接著劑塗膜脆弱，且有使熱封強度、積層強度劣化的傾向。
作為無溶劑型積層接著劑之以不加熱在25℃前後的短時間熟成而能顯現熱封強度、積層強度的方法，已知一種二液分別塗布型胺甲酸酯系接著劑，其係組合了以於分子兩末端具有異氰酸酯基之化合物為主要成分的在常溫為液狀之無溶劑型A劑，與以於分子兩末端具有胺基之化合物為主要成分的在常溫為液狀的無溶劑型B劑(參照例如專利文獻1)。又，亦已知使前述無溶劑型B劑進一步含有分子內具有三級胺的化合物及黏著性賦予樹脂者(參照例如專利文獻2)、或以分子內具有羥基的化合物為主要成分且進一步使用三級胺化合物及/或有機錫化合物者(參照例如專利文獻3)。
然而，任何方法都有以不加熱在25℃前後的短時間熟成得不到期望的熱封強度、積層強度的問題。
先前技術文獻 專利文獻
專利文獻1 日本特開2003-171641號公報
專利文獻2 日本特開2003-171642號公報
專利文獻3 日本特開2003-171643號公報
本發明所欲解決之課題，在於提供以低溫、短時間熟成而顯現優異的熱封強度、積層強度之無溶劑型的二液型接著劑。
本發明人等專心研究，發現以含有多異氰酸酯(A)的多異氰酸酯組成物(X)、與含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)的多元醇組成物(Y)為必要成分之無溶劑型的二液型接著劑，以在25℃前後的短時間熟成而會顯現優異的熱封強度、積層強度，終至完成了本發明。
亦即，本發明提供一種接著劑，其係以含有多異氰酸酯(A)的多異氰酸酯組成物(X)、與含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)的多元醇組成物(Y)為必要成分。
又，本發明提供一種積層薄膜，其係在第一基材薄膜與第二基材薄膜之間具有經硬化的接著劑之積層薄膜，而前述接著劑為前述記載的接著劑。
又，本發明提供一種積層薄膜之製造方法，其係在對基材塗布有前述記載之接著劑的積層薄膜之製造方法中，具有下列步驟：使被塗布至一方的基材之含有多異氰酸酯(A)的多異氰酸酯組成物(X)，與被塗布至另一方的基材之含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)的多元醇組成物(Y)接觸而進行壓接的二液分別塗布步驟。
本發明的無溶劑型之二液型接著劑，由於以在25℃前後的短時間熟成而會顯現優異的熱封強度、積層強度，所以使用了該接著劑之積層薄膜係生產性優異。
用以實施發明之形態 (接著劑)
本發明的接著劑係以含有多異氰酸酯(A)的多異氰酸酯組成物(X)、與含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)的多元醇組成物(Y)為必要成分。
(多異氰酸酯(A))
本發明中使用的多異氰酸酯(A)，並未特別限定，可使用眾所周知者。可列舉例如甲苯二異氰酸酯、2,4’二苯基甲烷二異氰酸酯(以下有記載MDI的情形)、2,2’MDI、4,4’MDI、1,5-萘二異氰酸酯、三苯基甲烷三異氰酸酯、苯二甲基二異氰酸酯等的在分子構造內具有芳香族構造的多異氰酸酯、此等多異氰酸酯的NCO基的一部分被碳二亞胺改質的化合物；源自此等多異氰酸酯的脲甲酸酯(allophanate)化合物；異佛酮二異氰酸酯、4,4’-亞甲基雙(環己基異氰酸酯)、1,3-(異氰酸酯甲基)環己烷等的在分子構造內具有脂環式構造的多異氰酸酯；1,6-六亞甲基二異氰酸酯、離胺酸二異氰酸酯、三甲基 六亞甲基二異氰酸酯等的直鏈狀脂肪族多異氰酸酯、及此脲甲酸酯化合物；此等多異氰酸酯的三聚異氰酸酯體；源自此等多異氰酸酯的脲甲酸酯體；源自此等多異氰酸酯的縮二脲體；被三羥甲基丙烷改質的加成物；前述的各種多異氰酸酯與多元醇成分的反應生成物之多異氰酸酯等。
又，特別在本發明中，從可藉由使在分子構造內具有芳香族構造的多異氰酸酯與前述直鏈狀脂肪族多異氰酸酯一起和多元醇成分反應，而對積層物賦予可撓性且提高實際包裝性之點而言為較佳。在此情形下，直鏈狀脂肪族多異氰酸酯，可在與多元醇成分中的羥基反應時，一面形成胺甲酸酯鍵或脲甲酸酯鍵，並同時導入多異氰酸酯(A)中。在併用前述具有芳香族構造的多異氰酸酯與前述直鏈狀脂肪族多異氰酸酯的情形，從低黏度化之點而言，較佳為彼等的使用比例以質量基準計[具有芳香族構造的多異氰酸酯/直鏈狀脂肪族多異氰酸酯]為99/1~70/30的比例。
特別是從能夠在25℃前後的短時間熟成之點而言，針對作為多異氰酸酯製造時的原料使用的異氰酸酯單體，較佳為4,4’MDI的比率占全原料中的38%以上。
此處，前述的多異氰酸酯與多元醇成分的反應比例，從接著劑的黏度成為適當範圍且塗敷性成為良好之點，或者從接著劑塗膜的凝集力之點而言，較佳為異氰酸酯基與多元醇成分中的羥基之當量比[異氰酸酯基/羥基]在1.5~5.0的範圍。
又，作為與前述在分子構造內具有脂環式構造或芳香族構造的多異氰酸酯進行反應的多元醇成分，具體而言，可列舉乙二醇、丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇、新戊二醇、甲基戊二醇、二甲基丁二醇、丁基乙基丙二醇、二乙二醇、三乙二醇、四乙二醇、二丙二醇、三丙二醇、雙羥基乙氧基苯等的鏈狀脂肪族二醇；1,4-環己二醇、1,4-環己烷二甲醇等的脂環式二醇；丙三醇、三羥甲基丙烷、新戊四醇等的3官能或4官能的脂肪族醇；雙酚A、雙酚F、氫化雙酚A、氫化雙酚F等的雙酚；二聚物二醇；在前述二醇、3官能或4官能的脂肪族醇等的聚合起始劑的存在下加成聚合環氧乙烷、環氧丙烷、環氧丁烷、氧化苯乙烯、表氯醇、四氫呋喃、環己烯等的環氧烷之聚醚多元醇；為藉由丙內酯、丁內酯、ε-己內酯、σ-戊內酯、β-甲基-σ-戊內酯等之環狀酯化合物的開環聚合反應所得之聚酯，與前述二醇或3官能或是4官能的脂肪族醇的反應物之聚酯多元醇(1)；使前述鏈狀脂肪族二醇、脂環式二醇、二聚物二醇、雙酚或前述聚醚多元醇等的多元醇，與多元羧酸反應所得之聚酯多元醇(2)：使前述3官能或4官能的脂肪族醇，與多元羧酸反應所得之聚酯多元醇(3)；使2官能型多元醇、前述3官能或4官能的脂肪族醇、及多元羧酸反應所得之聚酯多元醇(4)；為二羥甲基丙酸、篦麻油脂肪酸等的羥基酸的聚合物之聚酯多元醇(5)；前述聚酯多元醇(1)、(2)、(3)、(4)、(5)與聚醚多元醇的混合物；為篦麻油、脫水 篦麻油、篦麻油的氫化物之蓖麻硬化油、篦麻油的環氧烷5~50莫耳加成物等的篦麻油系多元醇等。
此處，就前述聚酯多元醇(2)、(3)或(4)的製造所使用的多元羧酸而言，可列舉例如琥珀酸、己二酸、壬二酸、癸二酸、十二烷二羧酸、馬來酸酐、富馬酸等的非環狀脂肪族二羧酸；1,3-環戊烷二羧酸、1,4-環己烷二羧酸等的脂環式二羧酸；對苯二甲酸、間苯二甲酸、苯二甲酸、1,4-萘二羧酸、2,5-萘二羧酸、2,6-萘二羧酸、萘二甲酸、聯苯基二羧酸、1,2-雙(苯氧基)乙烷-p,p’-二羧酸等的芳香族系二羧酸；此等脂肪族或芳香族二羧酸的酐或是酯形成性衍生物；對羥基苯甲酸、對(2-羥基乙氧基)苯甲酸及此等二羥基羧酸的酯形成性衍生物、二聚物酸等的多元酸類。
此等多元醇成分之中，從濕潤性之點而言，特別較佳為藉由以前述聚醚多元醇為必要成分，使其與前述多異氰酸酯反應所得之多異氰酸酯。
從縮短熟成時間，且同時能確保適當的實際包裝性之點而言，上述的多異氰酸酯(A)較佳為重量平均分子量(Mw)在3,000~10,000的範圍，更佳為在500~5,000的範圍。
又，從成為適當的樹脂黏度且塗敷性優異之點而言，較佳為利用滴定法(使用二-正丁基胺)的異氰酸酯含有率為5~20質量%者。
(多元醇組成物(Y)具有複數個羥基的三級胺化合物(B))
在本發明中，多元醇組成物(Y)含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)。
在前述具有複數個羥基的三級胺化合物(B)中，羥基必須具有2個以上，較佳為具有2~6個。又三級胺基具有1個以上即可，但較佳為具有1~2個。
具體而言，可列舉聚丙二醇乙二胺醚、三(1,2-聚丙二醇)胺、N-乙基二乙醇胺、N-甲基-N-羥基乙基-N-羥基乙氧基乙基胺、五羥基丙基二伸乙三胺、肆羥基丙基乙二胺、N,N,N’,N’-肆(2-羥基丙基)乙二胺等。
具有複數個羥基的三級胺化合物(B)可使用市售品。就市售品而言，可列舉ADEKA股份有限公司製的EDP300、國都化工公司製的ED-500、TE-360等。
前述多元醇(C)、與前述具有複數個羥基的三級胺化合物(B)的摻合比例，較佳為作為質量比[(C)/(B)]以成為100/5~100/70之比例的方式摻合，更佳係100/10~100/70的比例。在此範圍中，可作成硬化性更快速的接著劑。
在本發明中，使用含有前述多元醇(C)與具有複數個羥基的三級胺化合物(B)之多元醇組成物(Y)，為何硬化性會變得快速尚不明確，但推斷如下。
一般具有複數個羥基的三級胺可成為具有自催化作用的多元醇，但由於三級胺與羥基為接近的構造，而推斷催化作用更顯著地起作用。推斷因此而硬化性變快。
在本發明中，三級胺化合物(B)具有的羥基，較佳為第二級或第三級。藉由為第二級或第三級，而可維持二液混合後的可用時間(使用期限)，又，即使在分別塗布二液的步驟中，也不妨礙壓接後的多異氰酸酯組成物(X)與多元醇組成物(Y)的混層。
(多元醇組成物(Y)多元醇(C))
在本發明中使用的多元醇(C)，可列舉例如乙二醇、丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇、新戊二醇、甲基戊二醇、二甲基丁二醇、丁基乙基丙二醇、二乙二醇、三乙二醇、四乙二醇、二丙二醇、三丙二醇、雙羥基乙氧基苯、1,4-環己二醇、1,4-環己烷二甲醇、三乙二醇等的二醇；丙三醇、三羥甲基丙烷、新戊四醇等的3官能或4官能的脂肪族醇；雙酚A、雙酚F、氫化雙酚A、氫化雙酚F等的雙酚；二聚物二醇；前述二醇、3官能或4官能的脂肪族醇等的在聚合起始劑的存在下加成聚合環氧乙烷、環氧丙烷、環氧丁烷、氧化苯乙烯、表氯醇、四氫呋喃、環己烯等的環氧烷之聚醚多元醇；將該聚醚多元醇進一步以前述芳香族或脂肪族多異氰酸酯高分子量化之聚醚胺甲酸酯多元醇；為藉由丙內酯、丁內酯、ε-己內酯、σ-戊內酯、β-甲基-σ-戊內酯等之環狀酯化合物的開環聚合反應所得之聚酯與前述二醇、丙三醇、三羥甲基丙烷、新戊四醇等的多元醇的反應物之聚酯多元醇(1)； 使前述二醇、二聚物二醇、或前述雙酚等的2官能型多元醇，與多元羧酸反應所得之聚酯多元醇(2)；使前述3官能或4官能的脂肪族醇，與多元羧酸反應所得之聚酯多元醇(3)；使2官能型多元醇、前述3官能或4官能的脂肪族醇、及多元羧酸反應所得之聚酯多元醇(4)；二羥甲基丙酸、篦麻油脂肪酸等的羥基酸的聚合物之聚酯多元醇(5)；使前述聚酯多元醇(1)~(5)、前述聚醚多元醇、及芳香族或是脂肪族多異氰酸酯反應所得之聚酯聚醚多元醇；將前述聚酯多元醇(1)~(5)以芳香族或是脂肪族多異氰酸酯高分子量化所得之聚酯聚胺甲酸酯多元醇；聚酯多元醇(1)~(5)與聚醚多元醇的混合物；篦麻油、脫水篦麻油、為篦麻油的氫化物之蓖麻硬化油、篦麻油的環氧烷5~50莫耳加成物等的篦麻油系多元醇等。使用的多元醇(C)的重量平均分子量(Mw)較佳為400~5000。
此處，就多元羧酸而言，可列舉例如琥珀酸、己二酸、壬二酸、癸二酸、十二烷二羧酸、馬來酸酐、富馬酸、1,3-環戊烷二羧酸、1,4-環己烷二羧酸等的脂肪族二羧酸；對苯二甲酸、間苯二甲酸、1,4-萘二羧酸、2,5-萘二羧酸、2,6-萘二羧酸、萘二甲酸、聯苯基二羧酸、1,2-雙(苯氧基)乙烷-p,p’-二羧酸等的芳香族二羧酸；及此等脂肪族或二羧酸的酐或酯形成性衍生物；對羥基苯甲酸、對(2-羥基乙氧基)苯甲酸及此等二羥基羧酸的酯形成性衍生物、二聚物酸等的多元酸類。
(多元醇組成物(Y)脂肪族環狀醯胺化合物(D))
前述脂肪族環狀醯胺化合物(D)，可列舉例如δ-戊內醯胺、ε-己內醯胺、ω-庚內醯胺、η-辛內醯胺、β-丙內醯胺等。尤其此等之中，從低分子化學物質之洗析量減低的效果優異之點而言，較佳為ε-己內醯胺。其摻合量較佳為每100質量份的多元醇(C)，以0.1~5.5質量份的範圍混合脂肪族環狀醯胺化合物。又，更佳為每100質量份的多元醇組成物(Y)，以0.1~5質量份的範圍混合脂肪族環狀醯胺化合物。
此處使用的脂肪族環狀醯胺化合物(D)，可列舉例如δ-戊內醯胺、ε-己內醯胺、ω-庚內醯胺、η-辛內醯胺、β-丙內醯胺等。此等之中，從低分子化學物質之洗析量減低的效果優異之點而言，較佳為ε-己內醯胺。又，其摻合量較佳為每100質量份的多元醇(C)，以0.1~5.5質量份的範圍混合脂肪族環狀醯胺化合物。又，較佳為每100質量份的多元醇組成物(Y)，以0.1~5質量份的範圍混合脂肪族環狀醯胺化合物(D)。
(胺價)
在本發明的接著劑中，前述接著劑所含有的胺價較佳在0.5~40mgKOH/g的範圍。
此處所謂的胺價，係指相對於要中和試料1g所需要的HCl量而為當量之KOH的毫克數，並無特別限制，可使用眾所周知的方法算出。具體而言，較佳可列舉例如以下所示的方法。
胺化合物的化學構造可進一步按照需要，在知道平均分子量等的情形，從下述的計算式算出。
胺基(mgKOH/g)=(每1分子的胺基的數/平均分子量)×56.1×1000
又，在胺化合物的化學構造或平均分子量等不明的情形，可利用眾所周知的胺價測定方法測定，例如，就胺價的測定方法而言，可列舉依照JIS-K7237-1995進行測定的方法。
若胺價在該範圍，則可一面確保實際包裝性且同時得到更優異的硬化性。胺價，其中又較佳在1.5~35mgKOH/g的範圍，更佳在1.5~25mgKOH/g的範圍。
(溶劑)
本發明的接著劑係藉由異氰酸酯基與羥基的化學反應而硬化的接著劑，可作為無溶劑型的接著劑使用。此外本發明中所謂的無溶劑型之接著劑的「溶劑」，係指能夠溶解本發明中使用的多異氰酸酯(A)或多元醇(C)之溶解性高的有機溶劑，所謂的「無溶劑」係指不含此等溶解性高的有機溶劑。所謂溶解性高的有機溶劑，具體而言，可列舉甲苯、二甲苯、二氯甲烷、四氫呋喃、甲醇、乙醇、異丙醇、乙酸甲酯、乙酸乙酯、乙酸正丁酯、丙酮、甲基乙基酮(MEK)、環己酮、甲苯、二甲苯、正己烷、環己烷等。其中，又已知甲苯、二甲苯、二氯甲烷、四氫呋喃、乙酸甲酯、乙酸乙酯為溶解性特別高的有機溶劑。
另一方面，本發明的接著劑在有低黏度等之要求的情形，可按照所期望的黏度，而適當以前述溶解性高的有機溶劑稀釋而使用。在該情形，可稀釋多異氰酸酯組成物(X)或多元醇組成物(Y)中的任一者，亦可稀釋兩者。就在這種情形使用的有機溶劑而言，可列舉例如甲醇、乙醇、異丙醇、乙酸甲酯、乙酸乙酯、乙酸正丁酯、丙酮、甲基乙基酮(MEK)、環己酮、甲苯、二甲苯、正己烷、環己烷等。此等之中，從溶解性之點而言，較佳為乙酸乙酯或甲基乙基酮(MEK)，特佳為乙酸乙酯。有機溶劑的使用量取決於所需的黏度，但大多以大約20~50質量%的範圍使用。
在本發明的接著劑中，前述多異氰酸酯組成物(X)與前述多元醇組成物(Y)的摻合比例，從接著強度、熱封時的耐熱性優異之點而言，較佳為前述多異氰酸酯(A)中的異氰酸酯基、與前述多元醇(C)中的羥基之當量比〔異氰酸酯基/羥基〕在0.6~5.0的範圍，從成為此等性能變得顯著者之點而言，特佳係在1.0~3.5的範圍。
本發明的接著劑可依照需要而併用顏料。就此情形可使用的顏料而言，並未特別限定，可列舉例如，塗料原料便覽1970年度版(日本塗料工業協會)所記載的體質顏料、白顏料、黑顏料、灰色顏料、紅色顏料、茶色顏料、綠色顏料、藍顏料、金屬粉顏料、發光顏料、真珠色顏料等的有機顏料、無機顏料，以及塑膠顏料等。就此等著色劑的具體例而言，有揭示各式各樣者，就有 機顏料而言，可列舉例如聯苯胺黃、漢薩黃、色淀紅4R等的、各種的不溶性偶氮顏料；色淀紅C、胭脂紅6B、棗紅10等的溶性偶氮顏料；酞花藍藍、酞花藍綠等的各種(銅)酞花藍系顏料；玫瑰紅淀、甲基紫色淀等各種的鹼性染色色淀；喹啉色淀、堅牢天藍等各種的媒染染料系顏料；蒽醌系顏料、硫靛系顏料、苝酮系顏料等各種的建染染料系顏料；新喀希阿紅(Shin Cassia Red)B等各種的喹吖酮系顏料；二
Figure 108108581-A0202-12-0014-3
紫等各種的二
Figure 108108581-A0202-12-0014-4
系顏料；固美透(Cromophtal)等各種的縮合偶氮顏料；苯胺黑等。
就無機顏料而言，可列舉例如如同鉻黃、鉻酸鋅、鉬鉻橘等各種的鉻酸鹽；普魯士藍等各種的亞鐵氰化合物；氧化鈦、鋅白、棕黃(Mapico Yellow)、氧化鐵、印度紅、氧化鉻綠、氧化鋯等各種的金屬氧化物；鎘黃、鎘紅、硫化汞等各種的硫化物或硒化物；硫酸鋇、硫酸鉛等各種的硫酸鹽；矽酸鈣、群青等各種的矽酸鹽；碳酸鈣、碳酸鎂等各種的碳酸鹽；鈷紫、錳紫等各種的磷酸鹽；鋁粉、金粉、銀粉、銅粉、青銅粉、黃銅粉等各種的金屬粉末顏料；此等金屬的薄片顏料、雲母．薄片顏料；被覆有金屬氧化物之形態的雲母．薄片顏料、雲母狀氧化鐵顏料等的金屬顏料、珠光顏料；石墨、碳黑等。
就體質顏料而言，可列舉例如沈降性硫酸鋇、白堊、沈降碳酸鈣、碳酸氫鈣、方解石、氧化鋁白、矽石、含水微粉矽石(白碳)、超微粉無水矽石(Aerosol)、矽砂(矽石砂)、滑石、沈降性碳酸鎂、皂土、黏土、高嶺土、黃土等。
再者，就塑膠顏料而言，可列舉例如，DIC(股)製「GRANDEUR PP-1000」、「PP-2000S」等。
就本發明中使用的顏料而言，由於耐久性、耐侯性、設計性優異，而較佳為作為白色顏料的氧化鈦、鋅白等的無機氧化物、作為黑色顏料的碳黑。
本發明中使用的顏料的質量比例，係相對於多異氰酸酯組成物(X)及多元醇(C)的合計100質量份為1~400質量份，其中由於黏合性、耐黏連性等優異而更佳為10~300質量份。
本發明的接著劑中亦可使用接著促進劑。接著促進劑可列舉矽烷偶合劑、鈦酸酯系偶合劑、鋁系等的偶合劑、環氧樹脂。
就矽烷偶合劑而言，可列舉例如，γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)-γ-胺基丙基三甲基二甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷等的胺基矽烷；β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷等的環氧矽烷；乙烯基參(β-甲氧基乙氧基)矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷等的乙烯基矽烷；六甲基二矽氮烷、γ-巰基丙基三甲氧基矽烷等。
就鈦酸酯系偶合劑而言，可列舉例如，四異丙氧基鈦、四-正丁氧基鈦、鈦酸丁酯二聚物、鈦酸四硬脂酯、乙醯丙酮鈦、乳酸鈦、四辛二醇鈦酸酯、乳酸鈦、四硬脂氧基鈦等。
又，就鋁系偶合劑而言，可列舉例如，乙醯烷氧基鋁二異丙醇等。
就環氧樹脂而言，可列舉一般市售的表雙型(Epi-bis-type)、酚醛清漆型、β-甲基表氯醇型、環狀環氧乙烷型、縮水甘油醚型、縮水甘油酯型、聚乙二醇醚型、乙二醇醚型、環氧化脂肪酸酯型、多元羧酸酯型、胺基縮水甘油基型、間苯二酚型等的各種環氧樹脂。
本發明的接著劑中，如有必要的話，亦可含有前述以外的其他添加劑。就添加劑而言，可列舉例如調平劑；膠體狀矽石、氧化鋁溶膠等的無機微粒子；聚甲基丙烯酸甲酯系的有機微粒子；消泡劑；流掛性防止劑；濕潤分散劑；黏性調整劑；紫外線吸收劑；金屬惰性化劑；過氧化物分解劑；阻燃劑；補強劑；塑化劑；潤滑劑；防銹劑；螢光性增白劑；無機系熱線吸收劑；防火劑；抗靜電劑；脫水劑等。
此等顏料、接著促進劑、添加劑，可混合在多異氰酸酯組成物(X)或多元醇組成物(Y)之任一方的成分，或者作為第3成分而在塗敷時摻合使用。
(製造方法)
本發明的積層薄膜可使用眾所周知的方法獲得。可列舉例如將為本發明的接著劑之含有多異氰酸酯(A)的多異氰酸酯組成物(X)、與含有含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)的多元醇組成物(Y)事先混合後，塗布至第一塑膠薄膜， 接著在塗布面積層第二塑膠薄膜，使該接著劑層硬化而獲得之方法(製造方法1)；或藉由將前述多異氰酸酯組成物(X)、與前述多元醇組成物(Y)分別塗布至第一塑膠薄膜及第二塑膠薄膜後，使該塗布面接觸並壓接之二液分別塗布步驟，而積層第一塑膠薄膜與第二塑膠薄膜，使該接著劑層硬化而獲得之方法(製法方法2)。
其中在本發明中，若以製造方法2，亦即具有：使被塗布至一方的基材之含有多異氰酸酯(A)的多異氰酸酯組成物(X)、與被塗布至另一方的基材之含有含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)的多元醇組成物(Y)接觸而進行壓接的二液分別塗布步驟之方法(亦稱為分別塗敷)進行，則本發明的接著劑的效果之優異的硬化性可最大限度地發揮而較佳。
(製造方法1)
就前述製造方法1的例子而言，可列舉將預先混合了前述多異氰酸酯組成物(X)、與前述多元醇組成物(Y)之本發明的接著劑，例如，以輥塗機塗敷方式塗布至第一塑膠薄膜，接著，不經歷乾燥步驟，而貼合其他基材的方法。
塗敷條件只要為塗敷設備適合的條件，可使用任何條件，但通常在輥塗機中，較佳係於加熱至25℃~120℃左右的狀態下，以本發明的接著劑之黏度成為2500mPa．s以下的狀態進行塗敷。更佳的黏度範圍係2000mPa．s 以下。又塗布量較佳以0.5~5.0g/m2，更佳以1.0~4.0g/m2左右使用。
(製造方法2)
就前述製造方法2之所謂的分別塗敷的例子而言，在本發明的接著劑中，將前述多異氰酸酯組成物(X)、與前述多元醇組成物(Y)分別塗布至第一塑膠薄膜及第二塑膠薄膜。此時，例如在第一塑膠薄膜塗布前述多異氰酸酯組成物(X)的情形，係在第二塑膠薄膜塗布前述多元醇組成物(Y)。又也可以反過來。然後藉由貼合兩基材，而A劑與B劑接觸並使其壓接而開始反應，藉此而硬化會快速進行，且同時無需如通常的二液混合型接著劑的二液混合，因此沒有必要擔心二液混合後的可用時間(使用期限)，且作業性優異。壓接方法較佳為利用乾式積層(Dry lamination)而貼合的方法，積層輥的溫度較佳係在室溫~120℃左右，壓力較佳係3~300kg/cm2左右。如此進行而可得到軟包裝薄膜。
分別塗敷的情形，為了更有效率的進行貼合後的前述多異氰酸酯組成物(X)、與前述多元醇組成物(Y)的混層，較佳為以更低黏度進行塗敷。具體而言，較佳係以黏度1000mPa．S以下進行塗敷。又多異氰酸酯組成物(X)、與前述多元醇組成物(Y)的塗布量，較佳為分別以0.5~3.0g/m2，更佳為以0.5~2.0g/m2左右使用。
在任一種方法中，使用本發明的接著劑之情形，積層之後，於常溫或加熱下，接著劑會在3~24小時內硬化，顯現實用物性。
就此處使用的第一塑膠薄膜而言，可列舉PET(聚乙烯聚對苯二甲酸乙二酯)薄膜、耐綸薄膜(以下簡稱為『OPA薄膜』)、OPP(二軸延伸聚丙烯)薄膜、各種蒸鍍薄膜等的基底薄膜、鋁箔等，又，就前述其他基材而言，可列舉CPP(無延伸聚丙烯)薄膜、LLDPE(直鏈低密度聚乙烯)薄膜等的密封膠薄膜。
如此進行所得之積層薄膜，在工業上可作為軟包裝薄膜、軟包裝材料(包裝的形式係藉由裝入內容物所形成的包裝)等填充洗劑、藥劑之包裝材料使用。就具體的用途而言，作為洗劑、藥劑，可列舉洗滌用液體洗劑、廚房用液體洗劑、浴用液體洗劑、浴用液體肥皂、液體洗髮乳、液體護髮乳等。
使用本發明的接著劑所製造的包裝材料，洗劑、藥劑等的內容物的填充時是當然的，而即使在填充後的時間經過後，也不會發生分層等的積層構成體的剝離，具有優異的黏合性、內容物耐性。
〔實施例〕 (製造例1[多異氰酸酯(A-1)的合成])
在具備攪拌機、溫度計、氮氣導入管的燒瓶中，將36.5份的4,4-MDI、1份的六亞甲基二異氰酸酯的三聚異氰酸酯體進料至反應容器內，在氮氣下攪拌，加熱至60 ℃。將4.3份的數量平均分子量430的3官能丙二醇(旭硝子股份有限公司製，EXCENOL 430)、53.2份的數量平均分子量2000的2官能丙二醇(三井化學聚胺甲酸酯股份有限公司製，ACTCALL D-2000)分數次滴下，攪拌5~6小時，使胺甲酸酯化反應結束。
接著，將5.0份的聚合物型MDI(BASF INOAC聚胺甲酸酯股份有限公司製，製品名：Lupranate M20S)投入至反應容器內。所得之多異氰酸酯的NCO基含有率為10.5%，在40℃中的熔融黏度為1500mPa.s。以下將該多異氰酸酯簡稱為「A-1」。
此外，使用的聚合物型MDI，由於是環狀MDI與4,4-MDI以60/40構成，所以「A-1」所含有的4,4-MDI的比率成為38.5%。
(實施例1~4及比較例1~2)
關於多異氰酸酯組成物，係使用「A-1」。關於多元醇組成物，係使用依照表1的摻合所作成的B1~B6。將評價結果記載於表2。進行下述的各種評價。
(積層薄膜之製造方法)
就積層薄膜之製造方法而言，係以製造方式(1)及製造方式(2)進行。
(製造方式1)
將依照表2記載的配比而調整的多異氰酸酯組成物(X)與多元醇組成物(Y)混合之接著劑，在調整後於薄膜A以塗布量成為固體成分2.0g/m2左右的方式塗布接著劑，並以積層機貼合此薄膜A的塗布面與薄膜B，而製作熱封強度、積層強度測定用的積層薄膜。
(製造方式2)
依照表2記載的配比分別調整多異氰酸酯組成物(X)與多元醇組成物(Y)，分別將多異氰酸酯組成物(X)塗布至薄膜A、多元醇組成物(Y)塗布至薄膜B後，以壓送輥(壓送輥溫度：50℃)壓接薄膜A與薄膜B彼此的塗布面，而製作塑膠薄膜積層體。多異氰酸酯組成物(X)與多元醇組成物(Y)各自的塗布量，係依照表1、表2記載的多異氰酸酯組成物(X)與多元醇組成物(Y)的質量比，使合計成為2.0g/m2。加工速度為30m/min。
(評價方法) (熱封強度)
使用耐綸薄膜(以下簡稱為OPA薄膜)作為薄膜A、使用直鏈低密度聚乙烯薄膜(以下簡稱為LLDPE薄膜)作為薄膜B，依照製造方式(1)、製造方式(2)而製作熱封強度測定用的積層薄膜。製作的積層薄膜係LLDPE面相對，而且從OPA薄膜側使用寬1cm的熱封條進行壓接使其熔融接著。此時的熱封條件為180度、0.1bar、1秒。將熱封部切斷成15mm寬，並測定熱封強度。以 300mm/min的速度測定。熱封強度的單位為N/15mm。熟成溫度設為25度。為了比較熟成時間的短縮程度而製作積層薄膜，評價在1、3、5、24小時後的熱封強度。評價係5階段評價且進行如下。
5：50以上
4：40~49
3：30~39
2：20~29
1：0~19
(積層強度)
與熱封強度評價同樣，以OPA薄膜與LLDPE薄膜的積層物來評價積層強度。以300mm/min的速度，用T型剝離評價。積層強度的測定單位為N/15mm。為1、3、5、24小時後的積層強度，評價係5階段評價且進行如下。
5：3以上
4：2.1~3.0
3：1.1~2.0
2：0.5~1.0
1：0.5以下
Figure 108108581-A0202-12-0023-1
表1中的縮寫係如下所示。
‧PPG-1000：聚丙二醇(三井化學聚胺甲酸酯股份有限公司製，數量平均分子量約1,000，羥基價112mgKOH/g，40℃熔融黏度150mPa．s)
‧PPG-2000：聚丙二醇(三井化學聚胺甲酸酯股份有限公司製，數量平均分子量約2,000，羥基價56mgKOH/g，40℃熔融黏度150mPa．s)
‧篦麻油：純化篦麻油(伊藤製油股份有限公司製，羥基價160.5mgKOH/g，40℃熔融黏度250mPa．s)
‧TEA：三乙基胺(DAICEL股份有限公司製)
‧DEA：二乙基胺(DAICEL股份有限公司製)
‧EDP300：N,N,N’,N’-肆(2-羥基丙基)乙二胺
‧ED-500：聚丙二醇乙二胺醚
‧TE-360：三(1,2-聚丙二醇)胺
‧ε己內醯胺：2-側氧基六亞甲基亞胺(關東化學股份有限公司製)
‧δ-戊內醯胺：四氫-2H-哌喃-2-酮(關東化學股份有限公司製)
‧β-丙內酯：2-氧雜環丁烷酮(關東化學股份有限公司製)
‧OFS-6040：3-環氧丙氧基丙基三甲氧基矽烷(Toray Dowconing股份有限公司製)
‧KBM903：3-胺基丙基三乙氧基矽烷(信越化學工業股份有限公司製)
Figure 108108581-A0202-12-0024-2
表2中，h表示小時。
由以上的結果可知，本案的接著劑由於含有具有複數個羥基的三級胺化合物(B)與脂肪族環狀醯胺化合物(D)，所以熱封強度與積層強度均從較早的時間顯現。
相對於此，比較例1為不含有具有複數個羥基的三級胺化合物(B)的例子，但是熱封強度與積層強度明顯為低。
比較例2為僅添加不含有羥基的胺化合物之組成，與比較例1、2同樣地熱封強度與積層強度低。

Claims (5)

  1. 一種二液型接著劑，其特徵係以含有多異氰酸酯(A)的多異氰酸酯組成物(X)、與含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)的多元醇組成物(Y)為必要成分；使該多異氰酸酯組成物(X)為100時，該多元醇組成物(Y)的質量比在10~150的範圍；該二液型接著劑的胺價在0.5~40mgKOH/g的範圍。
  2. 如請求項1之二液型接著劑，其中該多元醇(C)為聚酯多元醇、聚酯胺甲酸酯多元醇、或聚醚胺甲酸酯多元醇、或聚醚多元醇或篦麻油系多元醇。
  3. 如請求項1之二液型接著劑，其中該脂肪族環狀醯胺化合物(D)係選自包含δ-戊內醯胺、ε-己內醯胺、ω-庚內醯胺、η-辛內醯胺、β-丙內醯胺之群組。
  4. 一種積層薄膜，其係在第一基材薄膜與第二基材薄膜之間具有經硬化的接著劑之積層薄膜，其特徵係該接著劑為如請求項1至3中任一項之二液型接著劑。
  5. 一種積層薄膜之製造方法，其係對基材塗布有如請求項1至3中任一項之二液型接著劑的積層薄膜之製造方法，其特徵係具有使被塗布至一方的基材之含有多異氰酸酯(A)的多異氰酸酯組成物(X)，與被塗布至另一方的基材之含有具有複數個羥基的三級胺化合物(B)、多元醇(C)、及脂肪族環狀醯胺化合物(D)的多元醇組成物(Y)接觸而進行壓接的二液分別塗布步驟。
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