CN111886313B - 粘接剂、层叠膜和层叠膜的制造方法 - Google Patents

粘接剂、层叠膜和层叠膜的制造方法 Download PDF

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CN111886313B
CN111886313B CN201980020790.0A CN201980020790A CN111886313B CN 111886313 B CN111886313 B CN 111886313B CN 201980020790 A CN201980020790 A CN 201980020790A CN 111886313 B CN111886313 B CN 111886313B
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polyol
adhesive
polyisocyanate
composition
laminated film
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CN111886313A (zh
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大久保智雄
高桥茂和
富田大树
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DIC Corp
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Abstract

本发明涉及粘接剂、使用该粘接剂的层叠膜、以及层叠膜的制造方法，上述粘接剂将聚异氰酸酯组合物(X)和多元醇组合物(Y)作为必需成分，上述聚异氰酸酯组合物(X)包含聚异氰酸酯(A)，上述多元醇组合物(Y)含有具有多个羟基的叔胺化合物(B)、多元醇(C)和脂肪族环状酰胺化合物(D)，上述层叠膜的制造方法具有二液分别涂布工序，其中，在一个基材上涂布的聚异氰酸酯组合物(X)与在另一个基材上涂布的多元醇组合物(Y)接触而进行压接，上述聚异氰酸酯组合物(X)包含聚异氰酸酯(A)，上述多元醇组合物(Y)含有具有多个羟基的叔胺化合物(B)、多元醇(C)和脂肪族环状酰胺化合物(D)。

Description

粘接剂、层叠膜和层叠膜的制造方法
技术领域
本发明涉及二液型粘接剂、以及使用该粘接剂将各种膜层压而成的层叠膜。更详细而言，本发明涉及可在无溶剂的情况下使用，层压各种塑料膜、金属蒸镀膜、铝箔等，制造主要用于食品、医药品、清洗剂等的包装材料的层叠膜时使用的层压用粘接剂。
背景技术
从与基材的密合性、柔软性优异的观点出发，聚氨酯树脂作为软包装材料用层压粘接剂被广泛使用，通过由聚异氰酸酯与多元醇的反应形成的聚氨酯树脂系粘接剂贴合而成的层压膜被用作食品、医药品、清洗剂等的包装材料。
以往，将溶解于有机溶剂的粘接剂涂布于膜，在通过烘箱的过程中使有机溶剂挥发，贴合其它膜的干式层压方式为主流，但近年，从环境负荷的降低和作业环境的改善的观点出发，不含有有机溶剂的二液型的无溶剂型层压粘接剂(也称为二液型粘接剂、反应性粘接剂)的需求日益提高。
二液型的无溶剂型层压粘接剂在层压后进行聚异氰酸酯组合物与多元醇组合物的反应，因此需要熟化工序。熟化的温度、时间也取决于使用的粘接剂，通常在25～50℃进行1～5天，要求不加热(25℃左右)且缩短熟化时间。
作为不加热而能够在25℃左右进行短时间熟化的方法，使用胺催化剂是公知的。但是，胺催化剂其本身与聚异氰酸酯的反应性高，在粘接剂涂膜中形成低分子量的三维交联物。由此，存在使粘接剂涂膜脆弱，使热封强度、层压强度劣化的趋势。
作为无溶剂型层压粘接剂的不加热且在25℃左右的短时间熟化能显现热封强度、层压强度的方法，已知以下二液分别涂布型氨基甲酸酯系粘接剂，上述二液分别涂布型氨基甲酸酯系粘接剂是将以分子两末端具有异氰酸酯基的化合物为主成分的常温下液态的无溶剂型A剂和以分子两末端具有氨基的化合物为主成分的常温下液态的无溶剂型B剂组合而得到的(例如参照专利文献1)。另外，还已知在上述无溶剂型B剂中进一步含有分子内具有叔胺的化合物和增粘树脂的物质(例如参照专利文献2)，以分子内具有羟基的化合物为主成分，进而使用叔胺化合物和/或有机锡化合物的物质(例如参照专利文献3)。
但是，所有方法都存在不加热且在25℃左右的短时间熟化中无法得到期望的热封强度、层压强度的问题。
现有技术文献
专利文献
专利文献1：日本特开2003-171641号公报
专利文献2：日本特开2003-171642号公报
专利文献3：日本特开2003-171643号公报
发明内容
(发明要解决的课题)
本发明要解决的课题在于提供在低温、短时间熟化中显现出优异的热封强度、层压强度的无溶剂型的二液型粘接剂。
(用于解决课题的技术方案)
本发明人等进行深入研究，发现将聚异氰酸酯组合物(X)和多元醇组合物(Y)作为必需成分的无溶剂型的二液型粘接剂在25℃左右的短时间熟化中显现出优异的热封强度、层压强度，其中，上述聚异氰酸酯组合物(X)含有聚异氰酸酯(A)，上述多元醇组合物(Y)含有具有多个羟基的叔胺化合物(B)、多元醇(C)和脂肪族环状酰胺化合物(D)，从而完成本发明。
即，本发明提供一种粘接剂，其将聚异氰酸酯组合物(X)和多元醇组合物(Y)作为必需成分，上述聚异氰酸酯组合物(X)包含聚异氰酸酯(A)，上述多元醇组合物(Y)含有具有多个羟基的叔胺化合物(B)、多元醇(C)和脂肪族环状酰胺化合物(D)。
另外，本发明提供一种层叠膜，其具有在第一基材膜与第二基材膜之间固化的粘接剂，上述粘接剂为上述记载的粘接剂。
另外，本发明提供一种层叠膜的制造方法，在基材上涂布有上述记载的粘接剂的层叠膜的制造方法，上述层叠膜的制造方法具有二液分别涂布工序，其中，涂布在一个基材上的聚异氰酸酯组合物(X)与涂布在另一个基材上的多元醇组合物(Y)接触而进行压接，上述聚异氰酸酯组合物(X)包含聚异氰酸酯(A)，上述多元醇组合物(Y)含有具有多个羟基的叔胺化合物(B)、多元醇(C)和脂肪族环状酰胺化合物(D)。
本发明的无溶剂型的二液型胶粘剂在25℃左右的短时间熟化中显现出优异的热封强度、层压强度，因此使用该粘接剂的层叠膜的生产率优异。
具体实施方式
(粘接剂)
本发明的粘接剂将聚异氰酸酯组合物(X)和多元醇组合物(Y)作为必需成分，上述聚异氰酸酯组合物(X)包含聚异氰酸酯(A)，上述多元醇组合物(Y)含有具有多个羟基的叔胺化合物(B)、多元醇(C)和脂肪族环状酰胺化合物(D)。
(聚异氰酸酯(A))
本发明中使用的聚异氰酸酯(A)没有特别限定，可使用公知的化合物。例如，甲苯二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯(以下有时记载为MDI)、2,2’MDI、4,4’MDI、1,5-萘二异氰酸酯、三苯基甲烷三异氰酸酯、苯二甲基二异氰酸酯等分子结构内具有芳香族结构的聚异氰酸酯、利用碳二亚胺(Carbodiimide)将这些聚异氰酸酯的NCO基的一部分改性而成的化合物；来自这些聚异氰酸酯的脲基甲酸酯(allophanate)化合物；异佛尔酮二异氰酸酯、4,4’-亚甲基双(环己基异氰酸酯)、1,3-(异氰酸根合甲基)环己烷等分子结构内具有脂环式结构的聚异氰酸酯；1,6-六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、三甲基六亚甲基二异氰酸酯等直链状脂肪族聚异氰酸酯、及其脲基甲酸酯化合物；这些聚异氰酸酯的异氰脲酸酯体；来自这些聚异氰酸酯的脲基甲酸酯体；来自这些聚异氰酸酯的缩二脲体；三羟甲基丙烷改性的加合物；作为上述各种的聚异氰酸酯与多元醇成分的反应生成物的聚异氰酸酯等。
另外，特别是在本发明中，从通过使上述直链状脂肪族聚异氰酸酯与分子结构内具有芳香族结构的聚异氰酸酯一起与多元醇成分反应，可对层压物赋予挠性并提高实际包装性的的出发，优选。此时，直链状脂肪族聚异氰酸酯在与多元醇成分中的羟基反应时可在形成氨基甲酸酯键或脲基甲酸酯键的同时导入聚异氰酸酯(A)中。在并用上述具有芳香族结构的聚异氰酸酯和上述直链状脂肪族聚异氰酸酯的情况下，从低粘度化的观点出发，它们的使用比例，以质量基准计，[具有芳香族结构的聚异氰酸酯/直链状脂肪族聚异氰酸酯]优选为99/1～70/30的比例。
特别是从能够进行在25℃左右的短时间熟化的观点出发，对于作为聚异氰酸酯的制造时的原料使用的异氰酸酯单体，优选4,4’MDI的比率占全部原料中的38％以上。
在此，从胶粘剂的粘度成为适当范围而涂布性变得良好的观点或胶粘剂涂膜的凝聚力的观点出发，上述聚异氰酸酯与多元醇成分的反应比例，以异氰酸酯基与多元醇成分中的羟基的当量比[异氰酸酯基/羟基]计，优选为1.5～5.0的范围。
此外，作为与上述分子结构内具有脂环式结构或芳香族结构的聚异氰酸酯反应的多元醇成分，具体而言，可举出乙二醇、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、双羟基乙氧基苯等链状脂肪族二醇；1,4-环己二醇、1,4-环己烷二甲醇等脂环式二醇；甘油、三羟甲基丙烷、季戊四醇等3官能或4官能的脂肪族醇；双酚A、双酚F、氢化双酚A、氢化双酚F等双酚；二聚体二醇；在上述二醇、3官能或4官能的脂肪族醇等的聚合引发剂的存在下加成聚合环氧乙烷、环氧丙烷、环氧丁烷、氧化苯乙烯、表氯醇、四氢呋喃、环己稀等环氧烷而成的聚醚多元醇；通过丙内酯、丁内酯、ε-己内酯、σ-戊内酯、β-甲基-σ-戊内酯等环状酯化合物的开环聚合反应而得到的聚酯与上述二醇或3官能或4官能的脂肪族醇的反应物即聚酯多元醇(1)；使上述链状脂肪族二醇、脂环式二醇、二聚体二醇、双酚或上述聚醚多元醇等多元醇与多元羧酸反应而得到的聚酯多元醇(2)：使上述3官能或4官能的脂肪族醇与多元羧酸反应而得到的聚酯多元醇(3)；使2官能型多元醇与上述3官能或4官能的脂肪族醇与多元羧酸反应而得到的聚酯多元醇(4)；作为二羟甲基丙酸、蓖麻油脂肪酸等羟基酸的聚合物的聚酯多元醇(5)；上述聚酯多元醇(1)、(2)、(3)、(4)、(5)与聚醚多元醇的混合物；作为蓖麻油、脱水蓖麻油、蓖麻油的氢化物的蓖麻硬化油、蓖麻油的环氧烷5～50摩尔加成物等蓖麻油系多元醇等。
此处，作为上述聚酯多元醇(2)、(3)或(4)的制造中使用的多元羧酸，例如可举出琥珀酸、己二酸、壬二酸、癸二酸、十二烷二酸、马来酸酐、富马酸等非环状脂肪族二酸；1,3-环戊烷二酸、1,4-环己烷二酸等脂环式二酸；对苯二甲酸、间苯二甲酸、邻苯二甲酸、1,4-萘二酸、2,5-萘二酸、2,6-萘二酸、萘二酸、联苯二酸、1,2-双(苯氧基)乙烷-p,p’-二酸等芳香族系二酸；这些脂肪族或芳香族二酸的酸酐或酯形成性衍生物；对羟基苯甲酸、对-(2-羟基乙氧基)苯甲酸以及它们的二羟基羧酸的酯形成性衍生物、二聚酸等多元酸类。
这些多元醇成分中，从润湿性的观点考虑，特别优选为以上述聚醚多元醇为必需成分，通过使其与上述聚异氰酸酯反应而得到的聚异氰酸酯。
从缩短熟化时间的同时确保适当的实际包装性的观点出发，上述聚异氰酸酯(A)的重均分子量(Mw)优选为3000～10000的范围，更优选为500～5000的范围。
另外，从成为适当的树脂粘度且涂布性优异的观点出发，基于滴定法(使用二正丁基胺)的异氰酸酯含有率优选为5～20质量％。
(多元醇组合物(Y)具有多个羟基的叔胺化合物(B))
本发明中多元醇组合物(Y)含有具有多个羟基的叔胺化合物(B)、多元醇(C)和脂肪族环状酰胺化合物(D)。
上述具有多个羟基的叔胺化合物(B)中，必须具有2个以上羟基，优选具有2～6个羟基。另外，叔氨基只要具有1个以上即可，优选具有1～2个。
具体而言，可举出聚丙二醇乙二胺醚、三(1,2-聚丙二醇)胺、N-乙基二乙醇胺、N-甲基-N-羟基乙基-N-羟基乙氧基乙基胺、五(羟基丙基)二亚乙基三胺、四(羟基丙基)乙二胺、N,N,N’,N’-四(2-羟基丙基)乙二胺等。
具有多个羟基的叔胺化合物(B)可以使用市售品。作为市售品，可举出株式会社ADEKA制造的EDP300、国都化工公司制造的ED-500、TE-360等。
上述多元醇(C)与上述具有多个羟基的叔胺化合物(B)的配合比例优选配合以质量比[(C)/(B)]计成为100/5～100/70的比例，更优选为100/10～100/70的比例。在该范围内，可制成固化性更高的粘接剂。
在本发明中，通过使用含有上述多元醇(C)和具有多个羟基的叔胺化合物(B)的多元醇组合物(Y)，虽然固化性变快的原因尚不确定，但推测如下。
通常具有多个羟基的叔胺可成为具有自催化作用的多元醇，但推测由于叔胺与羟基处于接近的结构，因此催化作用更显著发挥作用。由此推测固化性变快。
在本发明中，叔胺化合物(B)具有的羟基优选为仲羟基或叔羟基。通过为仲羟基或叔羟基，可维持二液混合后的可使用时间(适用期)，另外，在分别涂布二液的工序中，也不会阻碍压接后的聚异氰酸酯组合物(X)与多元醇组合物(Y)的混层。
(多元醇组合物(Y)多元醇(C))
本发明中使用的多元醇(C)，例如可举出乙二醇、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、双羟基乙氧基苯、1,4-环己二醇、1,4-环己烷二甲醇、
三乙二醇等二醇；甘油、三羟甲基丙烷、季戊四醇等3官能或4官能的脂肪族醇；双酚A、双酚F、氢化双酚A、氢化双酚F等双酚；
二聚体二醇；在上述二醇、3官能或4官能的脂肪族醇等的聚合引发剂的存在下加成聚合环氧乙烷、环氧丙烷、环氧丁烷、氧化苯乙烯、表氯醇、四氢呋喃、环己稀等环氧烷而成的聚醚多元醇；进一步利用上述芳香族或脂肪族聚异氰酸酯将该聚醚多元醇高分子量化而成的聚醚聚氨酯多元醇；通过丙内酯、丁内酯、ε-己内酯、σ-戊内酯、β-甲基-σ-戊内酯等环状酯化合物的开环聚合反应而得到的聚酯与上述二醇、甘油、三羟甲基丙烷、季戊四醇等多元醇的反应物即聚酯多元醇(1)；
使上述二醇、二聚体二醇或上述双酚等2官能型多元醇与多元羧酸反应而得到的聚酯多元醇(2)：
使上述3官能或4官能的脂肪族醇与多元羧酸反应而得到的聚酯多元醇(3)；使2官能型多元醇与上述3官能或4官能的脂肪族醇与多元羧酸反应而得到的聚酯多元醇(4)；作为二羟甲基丙酸、蓖麻油脂肪酸等羟基酸的聚合物的聚酯多元醇(5)；使上述聚酯多元醇(1)～(5)与上述聚醚多元醇与芳香族或脂肪族聚异氰酸酯反应而得到的聚酯聚醚多元醇；利用芳香族或脂肪族聚异氰酸酯将上述聚酯多元醇(1)～(5)高分子量化而得到的聚酯聚氨酯多元醇；聚酯多元醇(1)～(5)与聚醚多元醇的混合物；作为蓖麻油、脱水蓖麻油、蓖麻油的氢化物的蓖麻硬化油、蓖麻油的环氧烷5～50摩尔加成物等蓖麻油系多元醇等。使用的多元醇(C)的重均分子量(Mw)优选为400～5000。
此处，作为多元羧酸，例如可举出琥珀酸、己二酸、壬二酸、癸二酸、十二烷二酸、马来酸酐、富马酸、1,3-环戊烷二酸、1,4-环己烷二酸等脂肪族二酸；对苯二甲酸、间苯二甲酸、1,4-萘二酸、2,5-萘二酸、2,6-萘二酸、萘二酸、联苯二酸、1,2-双(苯氧基)乙烷-p,p’-二酸等芳香族二酸；以及这些脂肪族或二羧酸的酸酐或酯形成性衍生物；对羟基苯甲酸、对-(2-羟基乙氧基)苯甲酸以及它们的二羟基羧酸的酯形成性衍生物、二聚酸等多元酸类
(多元醇组合物(Y)脂肪族环状酰胺化合物(D))
上述脂肪族环状酰胺化合物(D)例如可举出δ-戊内酰胺、ε-己内酰胺、ω-庚内酰胺、η-辛内酰胺和β-丙内酰胺。其中，从降低低分子化学物质的溶出量的效果优异的观点出发，优选为ε-己内酰胺。相对于多元醇(C)100质量份，其配合量优选在0.1～5.5质量份的范围内混合脂肪族环状酰胺化合物。另外，相对于多元醇组合物(Y)100质量份，优选在0.1～5质量份的范围内混合脂肪族环状酰胺化合物。
在此使用的脂肪族环状酰胺化合物(D)例如可举出δ-戊内酰胺、ε-己内酰胺、ω-庚内酰胺、η-辛内酰胺、β-丙内酰胺等。其中，从降低低分子化学物质的溶出量的效果优异的方面出发，优选为ε-己内酰胺。另外，相对于多元醇(C)100质量份，其配合量优选在0.1～5.5质量份的范围内混合脂肪族环状酰胺化合物。另外，相对于多元醇组合物(Y)100质量份，优选在0.1～5质量份的范围内混合脂肪族环状酰胺化合物(D)。
(胺值)
在本发明的粘合剂中，上述粘合剂中所包含的胺值优选为0.5～40mgKOH/g的范围。
此处所谓的胺值是指相对于中和1g试样所需要的HCl量为当量的KOH的毫克数，没有特别限制，可使用公知的方法算出。具体而言，例如可优选举出以下所示的方法。
在已知胺化合物的化学结构以及根据需要的平均分子量等的情况下，可由以下计算式算出。
[数学式1]
胺值(mgKOH/g)
＝(每1分子的氨基的数量/平均分子量)×56.1×1000
另外，胺化合物的化学结构、平均分子量等不明的情况下，可通过公知的胺值的测定方法进行测定，例如，作为胺值的测定方法，可举出按照JIS-K7237-1995测定的方法。
如果胺值在该范围内，则可在确保实际包装性的同时得到更优异的固化性。其中胺值优选为1.5～35mgKOH/g的范围，更优选为1.5～25mgKOH/g的范围。
(溶剂)
本发明的粘接剂是通过异氰酸酯基与羟基的化学反应而固化的粘接剂，可作为无溶剂型粘接剂使用。应予说明，本发明中所谓的无溶剂型粘接剂的“溶剂”是指能够溶解本发明中使用的聚异氰酸酯(A)、多元醇(C)的溶解性高的有机溶剂，“无溶剂”是指不包含这些溶解性高的有机溶剂。作为溶解性高的有机溶剂，具体而言，可举出甲苯、二甲苯、二氯甲烷、四氢呋喃、甲醇、乙醇、异丙醇、乙酸甲酯、乙酸乙酯、乙酸正丁酯、丙酮、甲基乙基酮(MEK)、环己酮、甲苯(toluol)、二甲苯(xylol)、正己烷、环己烷等。其中，作为溶解性特别高的有机溶剂，已知有甲苯、二甲苯、二氯甲烷、四氢呋喃、乙酸甲酯、乙酸乙酯。
另一方面，本发明的粘接剂在具有低粘度等要求的情况下，可以根据期望的粘度适当利用上述溶解性高的有机溶剂稀释而使用。在该情况下，可以将聚异氰酸酯组合物(X)或多元醇组合物(Y)中的任一者稀释，也可以将两者稀释。作为在这种情况下使用的有机溶剂，例如可举出甲醇、乙醇、异丙醇、乙酸甲酯、乙酸乙酯、乙酸正丁酯、丙酮、甲基乙基酮(MEK)、环己酮、甲苯(toluol)、二甲苯(xylol)、正己烷和环己烷。其中，从溶解性的观点出发，优选为乙酸乙酯、甲基乙基酮(MEK)，特别优选为乙酸乙酯。有机溶剂的使用量取决于所需要的粘度，大多在约20～50质量％的范围内使用。
在本发明的粘接剂中，从粘接强度、热封时的耐热性优异的观点出发，上述聚异氰酸酯组合物(X)与上述多元醇组合物(Y)的配合比例，以上述聚异氰酸酯(A)中的异氰酸酯基与上述多元醇(C)中的羟基的当量比〔异氰酸酯基/羟基〕计，优选为0.6～5.0的范围，从这些性能变得显著的观点出发，特别优选为1.0～3.5的范围。
本发明的粘接剂可以根据需要并用颜料。作为此时可使用的颜料，没有特别限定，例如可举出涂料原料便览1970年度版(日本涂料工业会编)记载的体质颜料、白颜料、黑颜料、灰色颜料、红色颜料、茶色颜料、绿色颜料、蓝色颜料、金属粉颜料、发光颜料、珍珠色颜料等有机颜料、无机颜料、以及塑料颜料等。作为这些着色剂的具体例，可举出各种着色剂，作为有机颜料，例如可举出联苯胺黄、汉撒黄、色淀红4R等各种不溶性偶氮颜料；色淀红C、胭脂红6B、枣红10等可溶性偶氮颜料；酞菁蓝、酞菁绿等各种(铜)酞菁系颜料；罗丹明色淀、甲基紫色淀等各种碱性染色色淀；喹啉色淀、坚牢天蓝(Fast Sky Blue)等各种媒染染料系颜料；蒽醌系颜料、硫靛系颜料、芘酮系颜料(Perinone)等各种建染染料系颜料；(ShinCassia Red)B等各种喹吖啶酮系颜料；二噁嗪紫等各种二噁嗪系颜料；克劳莫夫塔尔(Cromophtal)等各种缩合偶氮颜料；苯胺黑等。
作为无机颜料，例如可举出如铬黄(lead chromate)、铬酸锌、钼铬橙等之类的各种铬酸盐；普鲁士蓝等各种亚铁氰化物；氧化钛、氧化锌、玛皮珂黄(Mapico Yellow)、氧化铁、铁红、氧化铬绿、氧化锆等各种金属氧化物；镉黄、镉红、硫化汞等各种硫化物或硒化物；硫酸钡、硫酸铅等各种硫酸盐；硅酸钙、群青等各种硅酸盐；碳酸钙、碳酸镁等各种碳酸盐；钴紫、锰紫等各种磷酸盐；铝粉、金粉、银粉、铜粉、青铜粉、黄铜粉等各种金属粉末颜料；这些金属的薄片颜料、云母·薄片颜料；被覆有金属氧化物的形态的云母·薄片颜料、云母状氧化铁颜料等金属颜料、珠光颜料；石墨、炭黑等。
作为体质颜料，例如可举出沉降性硫酸钡、胡粉、沉降碳酸钙、碳酸氢钙、冷水石、氧化铝白、二氧化硅、含水微粉二氧化硅(白炭)、超微粉无水二氧化硅(AEROSIL)、硅砂(二氧化硅砂)、滑石、沉降性碳酸镁、膨润土、粘土、高岭土、黄土等。
此外，作为塑料颜料，例如可举出DIC株式会社制造“Grandeur PP-1000”、“PP-2000S”等。
作为本发明中使用的颜料，从耐久性、耐候性、设计性优异的观点出发，更优选作为白色颜料的氧化钛、氧化锌等无机氧化物、作为黑色颜料的炭黑。
相对于聚异氰酸酯组合物(X)和多元醇(C)的合计100质量份，本发明中使用的颜料的质量比例优选为1～400质量份，其中，从粘接性、耐黏连性等优异的观点出发，更优选为10～300质量份。
本发明的粘接剂也可使用粘接促进剂。作为粘接促进剂，可举出硅烷偶联剂、钛酸酯类偶联剂、铝系等偶联剂、环氧树脂。
作为硅烷偶联剂，例如可举出γ-氨基丙基三乙氧基硅烷、γ-氨基丙基三甲氧基硅烷、N-β(氨基乙基)-γ-氨基丙基三甲氧基硅烷、N-β(氨基乙基)-γ-氨基丙基三甲基二甲氧基硅烷、N-苯基-γ-氨基丙基三甲氧基硅烷等氨基硅烷；β-(3,4-环氧环己基)乙基三甲氧基硅烷、γ-环氧丙氧基丙基三甲氧基硅烷、γ-环氧丙氧基丙基三乙氧基硅烷等环氧硅烷；乙烯基三(β-甲氧基乙氧基)硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷等乙烯基硅烷；六甲基二硅氮烷、γ-巯基丙基三甲氧基硅烷等。
作为钛酸酯系偶联剂，例如可举出四异丙氧基钛、四正丁氧基钛、丁基钛酸酯二聚物、四硬脂基钛酸酯、乙酰丙酮钛、乳酸钛、四辛基二醇钛酸酯、乳酸钛、四硬脂氧基钛(Tetrastearyloxy Titan)等。
另外，作为铝系偶联剂，例如可举出乙酰烷氧基二异丙醇铝(acetoalcoxyaluminumdiisopropylate)等
作为环氧树脂，可举出通常市售的表双型(Epi-Bis-type)、线性酚醛清漆型、β-甲基表氯醇型、环状环氧乙烷型、缩水甘油醚型、缩水甘油酯型、聚二醇醚型、二醇醚型、环氧化脂肪酸酯型、多元羧酸酯型、氨基缩水甘油基型、间苯二酚型等各种环氧树脂。
在本发明的粘接剂中，如果需要，也可以含有上述以外的其它添加剂。作为添加剂，例如可举出流平剂；胶体状二氧化硅、氧化铝溶胶等无机微粒；聚甲基丙烯酸甲酯系有机微粒；消泡剂；流挂性抑制剂；湿润分散剂；粘性调节剂；紫外线吸收剂；金属钝化剂；过氧化物分解剂；阻燃剂；增强剂；增塑剂；润滑剂；防锈剂；荧光性增白剂；无机系热射线吸收剂；防火剂；防静电剂；脱水剂等。
这些颜料、粘接促进剂、添加剂可与聚异氰酸酯组合物(X)或多元醇组合物(Y)中的任一者的成分混合，或者作为第三成分在涂布时配合使用。
(制造方法)
本发明的层叠膜可通过公知的方法得到。例如可举出以下方法，将本发明的粘接剂即包含聚异氰酸酯(A)的聚异氰酸酯组合物(X)、和含有具有多个羟基的叔胺化合物(B)、多元醇(C)和脂肪族环状酰胺化合物(D)的多元醇组合物(Y)预先混合后，涂布于第一塑料膜，接着在涂布面层叠第二塑料膜，使该粘接剂层固化而得到的方法(制造方法1)；通过将上述聚异氰酸酯组合物(X)和上述多元醇组合物(Y)分别涂布于第一塑料膜和第二塑料膜后，使该涂布面接触并压接的二液分别涂布工序，使第一塑料膜和第二塑料膜层叠，使该粘接剂层固化而得到的方法(制法方法2)。
其中，在本发明中，制造方法2，即，在进行具有二液分别涂布工序的方法(也称为分别涂布)时，能够最大限度地发挥作为本发明的粘接剂的效果的优异的固化性，因而优选。上述二液分别涂布工序为：在一个基材上涂布的包含聚异氰酸酯(A)的聚异氰酸酯组合物(X)与在另一个基材上涂布的含有具有多个羟基的叔胺化合物(B)、多元醇(C)和脂肪族环状酰胺化合物(D)的多元醇组合物(Y)接触而进行压接。
(制造方法1)
作为上述制造方法1的示例，可举出将预先混合有上述聚异氰酸酯组合物(X)和上述多元醇组合物(Y)的本发明的粘接剂，例如以辊涂机涂布方式涂布于第一塑料膜，接着，不经过干燥工序而贴合其它基材的方法。
涂布条件只要是符合涂布设备的条件则可以在任意的条件下使用，在通常的辊涂机中，优选在加热至25℃～120℃左右的状态下，在使本发明的粘接剂的粘度为2500mPa·s以下的状态下进行涂布。应予说明，优选的粘度范围为2000mPa·s以下。另外，涂布量以优选为0.5～5.0g/m2，更优选为1.0～4.0g/m2左右使用即可。
(制造方法2)
作为上述制造方法2，即，所谓的分别涂布的示例，在本发明的粘接剂中，将上述聚异氰酸酯组合物(X)和上述多元醇组合物(Y)分别涂布于第一塑料膜和第二塑料膜。此时，例如在第一塑料膜上涂布上述聚异氰酸酯组合物(X)的情况下，在第二塑料膜上涂布上述多元醇组合物(Y)。另外，也可以反过来。然后，通过将两个基材贴合，A剂与B剂接触、压接而开始反应，由此迅速进行固化，并且不需要通常的二液混合型粘接剂那样的二液的混合，因此不需要担心二液混合后的可使用时间(适用期)，作业性优异。压接方法优选为通过干式层压(干式层叠法)进行贴合的方法，层压辊的温度优选为室温～120℃左右，压力优选为3～300kg/cm2左右。如此可得到软包装膜。
在分别涂布的情况下，为了更有效地进行贴合后的上述聚异氰酸酯组合物(X)与上述多元醇组合物(Y)的混层，优选以更低粘度进行涂布。具体而言，优选以粘度为1000mPa·S以下进行涂布。另外，聚异氰酸酯组合物(X)与上述多元醇组合物(Y)的涂布量分别优选以0.5～3.0g/m2，更优选以0.5～2.0g/m2左右使用。
无论是哪种方法，在使用本发明的粘接剂的情况下，在层压后，在常温或加热下，粘接剂在3～24小时固化，表现出实用物性。
作为在此使用的第一塑料膜，可举出PET(聚对苯二甲酸乙二醇酯)膜、尼龙膜(以下简写为“OPA膜”)、OPP(双轴拉伸聚丙烯)膜、各种蒸镀膜等基膜或铝箔等，另外，作为上述其它基材，可举出CPP(未拉伸聚丙烯)膜、LLDPE(直链低密度聚乙烯)膜等密封胶膜。
如此得到的层叠膜在工业上可作为软包装膜、软包装材料(包装的形式是通过放入内容物而形成的包装)等、填充清洗剂、药剂的包装材料使用。作为具体用途，作为清洗剂、药剂，可举出洗涤用液体清洗剂、厨房用液体清洗剂、沐浴用液体清洗剂、沐浴用液体皂、液体洗发水、液体护发素等。
使用本发明的粘接剂制造的包装材料在填充清洗剂、药剂等内容物时自不必说，在填充后经过时间后，也不会发生分层等层压结构体的剥离，具有优异的粘接性、内容物耐性。
实施例
(制造例1[聚异氰酸酯(A-1)的合成])
在具备搅拌机、温度计、氮气导入管的烧瓶中，将4,4-MDI 36.5份、六亚甲基二异氰酸酯的脲酸酯体1份装入反应容器内，在氮气下进行搅拌，加热至60℃。将数均分子量430的3官能丙二醇(旭硝子株式会社制造，EXCENOL 430)4.3份、数均分子量2000的2官能丙二醇(三井化学聚氨酯株式会社制造，ACTCOL D-2000)53.2份分数次滴加，搅拌5～6小时，使氨基甲酸酯化反应结束。接着，将聚合MDI 5.0份(BASF INOAC聚氨酯株式会社制造产品名：Lupranate M20S)投入反应容器内。得到的聚异氰酸酯的NCO基含有率为10.5％、40℃下的熔融粘度为1500mPa·s，以下将该聚异氰酸酯简写为“A-1”。
应予说明，使用的聚合MDI由环状MDI和4,4-MDI以60/40构成，因此“A-1”所包含的4,4-MDI的比率为38.5％。
(实施例1～4和比较例1～2)
聚异氰酸酯组合物使用“A-1”。多元醇组合物使用按照表1的配合制作的B1～B6。将评价结果记载于表2。进行下述各种评价。
(层叠膜的制造方法)
作为层叠膜的制造方法，通过制造方式(1)和制造方式(2)进行。
(制造方式1)
将按照表2记载的配合调整的聚异氰酸酯组合物(X)和多元醇组合物(Y)混合而成的粘接剂以涂布量成为固体成分2.0g/m2左右的方式涂布于调整后膜A，利用层压机使该膜A的涂布面与膜B贴合，制作热封强度、层压强度测定用层叠膜。
(制造方式2)
按照表2记载的配合分别调整聚异氰酸酯组合物(X)和多元醇组合物(Y)，将聚异氰酸酯组合物(X)涂布于膜A，将多元醇组合物(Y)涂布于膜B后，利用夹持辊(夹持辊温度：50℃)将膜A与膜B的相互的涂布面压接，制作塑料膜层叠体。聚异氰酸酯组合物(X)和多元醇组合物(Y)各自的涂布量按照表1、表2记载的聚异氰酸酯组合物(X)和多元醇组合物(Y)的质量比，合计为2.0g/m2。加工速度为30m/min。
(评价方法)
(热封强度)
使用尼龙膜(以下简称为OPA膜)作为膜A，使用直链低密度聚乙烯膜(以下简称为LLDPE膜)作为膜B，按照制造方式(1)、制造方式(2)制作热封强度测定用层压膜。制作的层压膜在面向LLDPE面的基础上，使用1cm宽度的热封棒从OPA膜侧进行压制，使其熔化粘接。此时的热封条件为180度、0.1bar、1秒。将热封部切断为15mm宽度，测定热封强度。以300mm/min的速度进行测定。热封强度的单位为N/15mm。熟化温度设为25度。为了比较熟化时间的缩短程度，制作层压膜，评价1、3、5、24小时后的热封强度。评价按照5个等级评价按照以下方式进行。
5：50以上
4：40～49
3：30～39
2：20～29
1：0～19
(层压强度)
与热封强度评价相同，利用OPA膜和LLDPE膜的层压物评价层压强度。以300mm/min的速度通过T型剥离进行评价。层压强度的测定单位为N/15mm。评价1、3、5、24小时后的层压强度，评价以5个等级评价按照以下方式进行。
5：3以上
4：2.1～3.0
3：1.1～2.0
2：0.5～1.0
1：0.5以下
[表1]
Figure BDA0002692103600000171
表1中的缩写如以下所示。
·PPG-1000：聚丙二醇(三井化学聚氨酯株式会社制造，数均分子量约1000，羟基值112mgKOH/g，40℃熔融粘度150mPa·s)
·PPG-2000：聚丙二醇(三井化学聚氨酯株式会社制造，数均分子量约2000，羟基值56mgKOH/g，40℃熔融粘度150mPa·s)
·蓖麻油：精制蓖麻油(伊藤制油株式会社制造，羟基值160.5mgKOH/g，40℃熔融粘度250mPa·s)
·TEA：三乙胺(株式会社Daicel制造)
·DEA：二乙胺(株式会社Daicel制造)
·EDP300：N,N,N’,N’-四(2-羟基丙基)乙二胺
·ED-500：聚丙二醇乙二胺醚
·TE-360：三(1,2-聚丙二醇)胺
·ε己内酰胺：2-氧代六亚甲基亚胺(关东化学株式会社制造)
·δ-戊内酰胺：四氢-2H-吡喃-2-酮(关东化学株式会社制造)
·β-丙内酯：2-氧杂环丁酮(关东化学株式会社制造)
·OFS-6040：3-缩水甘油基氧基丙基三甲氧基硅烷(Dow Corning Toray株式会社制造)
·KBM903：3-氨基丙基三乙氧基硅烷(信越化学工业株式会社制造)
[表2]
Figure BDA0002692103600000191
表2中，h表示时间。
根据以上结果可知，本申请的粘接剂含有具有多个羟基的叔胺化合物(B)和脂肪族环状酰胺化合物(D)，因此热封强度和层压强度均从较早的时间开始显现。
与此相对，比较例1为不含有具有多个羟基的叔胺化合物(B)的示例，但热封强度和层压强度显著低。
比较例2是仅添加不具有羟基的胺化合物的组成，与比较例1、2相同，热封强度和层压强度低。

Claims (6)

1.一种二液型粘接剂，其特征在于，
将聚异氰酸酯组合物（X）和多元醇组合物（Y）作为必需成分，
所述聚异氰酸酯组合物（X）包含聚异氰酸酯（A），
所述多元醇组合物（Y）含有具有多个羟基的叔胺化合物（B）、多元醇（C）和脂肪族环状酰胺化合物（D），
所述羟基为仲羟基或叔羟基，
所述多元醇（C）为选自由聚酯多元醇、聚酯聚氨酯多元醇、聚醚聚氨酯多元醇、聚醚多元醇和蓖麻油系多元醇组成的组中的至少一种，
所述二液型粘接剂在常温或加热下固化。
2.根据权利要求1所述的二液型粘接剂，其中，所述粘接剂的胺值为0.5～40mgKOH/g的范围。
3.根据权利要求1～2中任一项所述的二液型粘接剂，其中，所述脂肪族环状酰胺化合物（D）选自δ-戊内酰胺、ε-己内酰胺、ω-庚内酰胺、η-辛内酰胺、β-丙内酰胺。
4.根据权利要求1～2中任一项所述的二液型粘接剂，其中，将所述聚异氰酸酯组合物（X）设为100时的所述多元醇组合物（Y）的质量比为10～150的范围。
5.一种层叠膜，其特征在于，具有在第一基材膜与第二基材膜之间固化的粘接剂，所述粘接剂为权利要求1～4中任一项所述的二液型粘接剂。
6.一种层叠膜的制造方法，其特征在于，所述层叠膜在基材上涂布有权利要求1所述的二液型粘接剂，所述层叠膜的制造方法具有二液分别涂布工序，其中，使涂布在一个基材上的聚异氰酸酯组合物（X）与涂布在另一个基材上的多元醇组合物（Y）接触而进行压接，
所述聚异氰酸酯组合物（X）包含聚异氰酸酯（A），所述多元醇组合物（Y）含有具有多个羟基的叔胺化合物（B）、多元醇（C）和脂肪族环状酰胺化合物（D），
所述羟基为仲羟基或叔羟基，
所述多元醇（C）为选自由聚酯多元醇、聚酯聚氨酯多元醇、聚醚聚氨酯多元醇、聚醚多元醇和蓖麻油系多元醇组成的组中的至少一种，
所述二液型粘接剂在常温或加热下固化。
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