CN108728033B - 粘着剂及使用其的粘着片、层叠体、显示装置 - Google Patents
粘着剂及使用其的粘着片、层叠体、显示装置 Download PDFInfo
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- CN108728033B CN108728033B CN201810599555.0A CN201810599555A CN108728033B CN 108728033 B CN108728033 B CN 108728033B CN 201810599555 A CN201810599555 A CN 201810599555A CN 108728033 B CN108728033 B CN 108728033B
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Classifications
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
本发明提供一种可形成剥离线残留的问题得到解决的、平滑性高的粘着层的粘着剂及使用其的粘着片、层叠体、显示装置。本发明的粘着剂包含:作为多元醇(a)与聚异氰酸酯(b)的反应物的含羟基的氨基甲酸酯预聚物(A)、异氰酸酯硬化剂(B)以及多官能多元醇(F),所述氨基甲酸酯预聚物(A)的分子量分散度为1.5以上且未满4,所述多官能多元醇(F)的一分子中的羟基数为3以上,且在分子末端具有一级羟基。
Description
技术领域
本发明涉及一种粘着剂及使用其的粘着片、层叠体、显示装置。
背景技术
液晶显示器(liquid crystal display,LCD)、有机电致发光显示器(organicelectroluminescence display,OELD)等平板显示器(flat panel display)、将该平板显示器与触摸屏(touch pannel)组合而成的触摸屏显示器等显示装置广泛用于电视(television,TV)、个人计算机(personal computer,PC)、便携式信息终端等中。
自从前以来,作为保护显示装置中使用的光学构件免受刮伤或尘埃附着等的影响的表面保护片,广泛使用在基材片上形成有粘着层的粘着片。
表面保护片的粘着层通常大多情况下使用包含丙烯酸树脂或氨基甲酸酯树脂的粘着剂。其中,包含氨基甲酸酯树脂的粘着剂(以下,称为氨基甲酸酯粘着剂)对于以玻璃为代表的各种被粘合体而言具有适度的粘着力,且再剥离性优异,因此在粘着层中使用。
且说,近年来,比以前更加要求表面保护片的生产性提高,因此要求宽幅下的涂敷适应性优异的粘着剂。但是,若欲以宽幅的涂敷机涂敷粘着剂,则存在如下问题:由于干燥烘箱中的温风的接触方式的不同(干燥不均)而难以获得均匀的涂膜,从而导致在基材上容易产生粘着剂的微小的凝聚物等。
另外,在将粘着片贴附于被粘合体时,在贴附对准失败的情况下,需要暂时剥离粘着片并重新贴合的作业。该情况下,若在剥离步骤中中途中断剥离,则存在如下问题:在剥离的界限位置粘着层出现线(条)(剥离线残留),而无法再利用所述粘着片。
专利文献1中揭示了一种粘着剂及使用其的粘着片,所述粘着剂包含:使多元醇(a)的羟基与聚异氰酸酯(b)的异氰酸酯基以NCO/OH=0.5~0.9的摩尔比反应而得的分子量分散度4~12的氨基甲酸酯预聚物(A)、多官能多元醇(B)及异氰酸酯硬化剂(C)。
[现有技术文献]
[专利文献]
[专利文献1]日本专利特开2016-176068号公报
发明内容
[发明所要解决的课题]
专利文献1中揭示的粘着剂在对被粘合体的润湿性、对曲面的密接性、再剥离性的方面优异。但是,存在如上所述那样的以宽幅涂敷粘着剂时的外观不良、产生剥离线残留的问题。
本发明是鉴于所述背景而成者,其目的在于提供一种可形成剥离线残留的问题得到解决的、平滑性高的粘着层的粘着剂及使用其的粘着片、层叠体、显示装置。
[解决课题的技术手段]
本发明人等人为了解决所述课题而反复进行努力研究的结果,发现利用以下所示的实施方式可解决所述课题,从而完成了本发明。
[1]:一种粘着剂,其包含:作为多元醇(a)与聚异氰酸酯(b)的反应物的含羟基的氨基甲酸酯预聚物(A)、异氰酸酯硬化剂(B)以及多官能多元醇(F),
所述氨基甲酸酯预聚物(A)的分子量分散度为1.5以上且未满4,
所述多官能多元醇(F)的一分子中的羟基数为3以上,且在分子末端具有一级羟基。
[2]:根据[1]所述的粘着剂,其中所述多元醇(a)包含选自由聚醚多元醇、聚酯多元醇及聚丁二烯改性多元醇所组成的群组中的一种以上。
[3]:根据[1]或[2]所述的粘着剂,其中相对于所述氨基甲酸酯预聚物(A)100质量份而包含2质量份~50质量份的所述多官能多元醇(F)。
[4]:根据[1]~[3]中任一项所述的粘着剂,其包含塑化剂(C)。
[5]:根据[1]~[4]中任一项所述的粘着剂,其还包含抗氧化剂(D)。
[6]:根据[1]~[5]中任一项所述的粘着剂,其还包含抗静电剂(E)。
[7]:一种粘着片,其包括:基材、以及作为根据[1]~[6]中任一项所述的粘着剂的硬化物的粘着层。
[8]:一种层叠体,其包括:选自由透明导电膜、玻璃、丙烯酸板、聚碳酸酯板及烯烃板所组成的群组中的构件;以及根据[7]所述的粘着片。
[9]:一种显示装置,其包括根据[8]所述的层叠体。
[发明的效果]
根据本发明,可提供一种可形成剥离线残留的问题得到解决的、平滑性高的粘着层的粘着剂及使用其的粘着片、层叠体、显示装置。
具体实施方式
在本发明的说明前对用语进行定义。本说明书中,所谓被粘合体是指贴附粘着胶带的对象。本说明书中,所谓分子量分散度是重量平均分子量除以数量平均分子量而得的数值,成为分子量分布的标准。本说明书中,所谓粘着片包括:基材、及包含粘着剂的硬化物的粘着层。本说明书中,“胶带”、“膜”及“片”具有相同含义。本说明书中,主成分是指多种调配的成分中调配量最多的成分。
本说明书中,只要未特别注明,则“分子量”是指数量平均分子量(Mn)。再者,“Mn”是通过凝胶渗透色谱法(Gel Permeation Chromatography,GPC)测定所求出的聚苯乙烯换算的数量平均分子量。
本实施方式的粘着剂包含:作为聚异氰酸酯(b)与多元醇(a)的反应物的含羟基的氨基甲酸酯预聚物(A)(以下,也称为氨基甲酸酯预聚物(A))、异氰酸酯硬化剂(B)以及多官能多元醇(F)。氨基甲酸酯预聚物(A)的分子量分散度为1.5以上且未满4。另外,多官能多元醇(F)的一分子中的羟基数为3以上,且在分子末端具有一级羟基。
通过将氨基甲酸酯预聚物(A)设为较狭小的分子量分散度、即将分子量分散度设为1.5以上且未满4,本发明人意外发现可削减利用少量的交联而成为凝聚物的高分子量成分,可形成适合于甚至连微小的缺点都不允许的近年来的要求水平的粘着层。
本实施方式的粘着剂例如可用于具有平坦部或曲面部的液晶显示器(LCD)、有机电致发光显示器(OELD)等显示器、使用了该显示器的触摸屏中。另外,可广泛地用于搭载了所述显示器或触摸屏的移动电话、智能手机、平板终端的便携式终端、计算机等电子机器的表面保护用途。
本实施方式的粘着剂的被粘合体材质并不限定于玻璃,例如可例示聚烯烃、金、银、铜、氧化铟锡(Indium tin oxide,ITO)等。本实施方式的粘着剂尤其适合于保护容易受损的材质的被粘合体。
作为本实施方式的粘着剂的具体的用途,并不限定于显示器,例如可用于窗玻璃、发光二极管(Light Emitting Diode,LED)、车辆、配线等所有的构件、层叠体。另外,还可用于构件的制造步骤中的保护、以及制造后的制品。再者,本发明的粘着剂当然可用于表面保护用途以外的用途。
(含羟基的氨基甲酸酯预聚物(A))
含羟基的氨基甲酸酯预聚物(A)是使一种以上的聚异氰酸酯(b)与一种以上的多元醇(a)进行反应而得的反应物。所述“反应物”是指多元醇(a)与聚异氰酸酯(b)的反应产物。聚异氰酸酯(b)优选为在一分子中具有两个异氰酸酯基的二官能异氰酸酯(b1)(也称为二异氰酸酯)。另外,多元醇(a)优选为在一分子中具有两个以上的羟基的多元醇(a1)。聚异氰酸酯(b)的异氰酸酯基(isocyanate基)以少于多元醇(a)的羟基的摩尔比(NCO/OH比)使用。由此,可获得具有羟基的氨基甲酸酯预聚物(A)。氨基甲酸酯反应优选为使用用以促进反应的催化剂。共聚反应中视需要可使用溶媒。
含羟基的氨基甲酸酯预聚物(A)可单独或并用两种以上。
<多元醇(a)>
多元醇(a)是具有两个以上的羟基的化合物。多元醇(a)优选为聚醚多元醇、聚酯多元醇、聚丁二烯改性多元醇,聚碳酸酯多元醇、蓖麻油多元醇等多元醇,更优选为聚醚多元醇、聚酯多元醇、聚丁二烯改性多元醇。
为了实现粘着层的适度的凝聚力及粘着力,本实施方式中使用的多元醇(a)也可并用两种以上。优选为并用具有两个羟基的多元醇与具有三个以上的羟基的多元醇。另外,在并用具有三个以上的羟基的多元醇的情况下,优选为将NCO/OH比控制在0.80以下。
作为聚醚多元醇,例如可列举将一分子中具有两个以上活性氢的含活性氢的化合物用作引发剂,并使一种以上的氧杂环丙烷化合物进行加成聚合而得的反应物。
含活性氢的化合物优选为含羟基的化合物及胺等。
作为含羟基的化合物,例如可列举:乙二醇(Ethylene Glycol,EG)、丙二醇(Propylene Glycol,PG)、1,4-丁二醇、新戊二醇、丁基乙基戊二醇等含二官能活性氢的化合物;甘油、三羟甲基丙烷等含三官能活性氢的化合物;季戊四醇等含四官能活性氢的化合物等。
作为胺,例如可列举:N-氨基乙基乙醇胺、异佛尔酮二胺、亚二甲苯基二胺等含二官能活性氢的化合物;三乙醇胺等含三官能活性氢的化合物;乙二胺、芳香族二胺等含四官能活性氢的化合物;二乙三胺等含五官能活性氢的化合物等。
作为氧杂环丙烷化合物,例如可列举:环氧乙烷(Ethylene oxide,EO)、环氧丙烷(Propylene oxide,PO)、及环氧丁烷(Butylene oxide,BO)等环氧烷(Alkylene oxide,AO);四氢呋喃(Tetrahy drofuran,THF)等。
聚醚多元醇优选为在分子内具有源自含活性氢的化合物的亚烷氧基(将所述多元醇也称为“聚氧化烯基多元醇”)。作为构成聚氧化烯基多元醇的含羟基的化合物,优选为聚乙二醇、聚丙二醇及聚四亚甲基二醇等聚醚多元醇,尤其优选为结晶性低、容易显现出柔软性的聚丙二醇。
聚醚多元醇的数量平均分子量(Mn)并无特别限制,就容易显现出透明性或柔软性的方面而言,优选为200~6,000,更优选为400~4,000,进而优选为600~4,000。通过将Mn设为200以上,而容易进行氨基甲酸酯预聚物(A)合成时的反应控制。另外,通过将Mn设为6,000以下,容易将氨基甲酸酯预聚物(A)的凝聚力调整为适度的范围。
聚酯多元醇例如优选为使一种以上的多元醇成分与一种以上的酸成分进行酯化反应而得的化合物(酯化物)、或者对内酯进行开环聚合而合成的化合物(开环聚合物)等。
内酯例如可列举:聚己内酯、聚(β-甲基-γ-戊内酯)及聚戊内酯等。
多元醇成分例如除了所述含活性氢的化合物以外,可列举:二乙二醇、1,3-丁二醇、3-甲基-1,5-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、1,2-己二醇、1,6-己二醇、2-乙基-1,3-己二醇、1,8-辛二醇、1,9-壬二醇、2-甲基-1,8-辛二醇、1,8-癸二醇、十八烷二醇、己三醇等。
酸成分例如可列举:丁二酸、甲基丁二酸、己二酸、庚二酸、壬二酸、癸二酸、1,12-十二烷二酸、1,14-十四烷二酸、二聚物酸、2-甲基-1,4-环己烷二羧酸、2-乙基-1,4-环己烷二羧酸、对苯二甲酸、间苯二甲酸、邻苯二甲酸、1,4-萘二羧酸及4,4′-联苯二羧酸、三聚物酸及这些的酸酐等。
聚酯多元醇的数量平均分子量(Mn)优选为200~8,000,更优选为500~6,000,进而优选为500~4,000,尤其优选为500~3,000。通过将Mn设为200以上,而容易进行氨基甲酸酯预聚物(A)合成时的反应控制。另外,通过将Mn设为6,000以下,容易将氨基甲酸酯预聚物(A)的凝聚力调整为适度的范围。
聚丁二烯改性多元醇例如具有两个以上的羟基末端,具有1,2-乙烯基部位、1,4-顺式部位、1,4-反式部位或这些经氢化的结构,且为直链状或分支状的聚丁二烯。
聚丁二烯改性多元醇的数量平均分子量(Mn)优选为200~6,000,更优选为500~6,000,进而优选为500~4,000,尤其优选为500~3,000。通过将Mn设为200以上,而容易进行氨基甲酸酯预聚物(A)合成时的反应控制。另外,通过将Mn设为6,000以下,容易将氨基甲酸酯预聚物(A)的凝聚力调整为适度的范围。
对聚丁二烯改性多元醇进行氢化的程度优选为在进行氢化前所存在的双键部位全部经氢化,但本发明中,也可残存少量双键部位。
作为所述以外的其他多元醇,例如可列举聚碳酸酯多元醇、蓖麻油多元醇等。其他多元醇优选为与聚醚多元醇或聚酯多元醇并用使用。其他多元醇的数量平均分子量(Mn)为200~8,000左右。
再者,若多元醇(a)含有羧基、磺基等酸性官能基,则有时会腐蚀被粘合体,因此优选为使用不含酸性官能基的多元醇。
<聚异氰酸酯(b)>
聚异氰酸酯(b)例如可使用芳香族聚异氰酸酯、脂肪族聚异氰酸酯、芳香脂肪族聚异氰酸酯以及脂环族聚异氰酸酯等公知的聚异氰酸酯。
作为芳香族聚异氰酸酯,例如可列举:1,3-亚苯基二异氰酸酯、4,4′-二苯基二异氰酸酯、1,4-亚苯基二异氰酸酯、4,4′-二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4′-甲苯胺二异氰酸酯、2,4,6-三异氰酸酯甲苯、1,3,5-三异氰酸酯苯、联大茴香胺二异氰酸酯、4,4′-二苯基醚二异氰酸酯、及4,4′,4″-三苯基甲烷三异氰酸酯等。
作为脂肪族聚异氰酸酯,例如可列举:三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、五亚甲基二异氰酸酯、1,2-亚丙基二异氰酸酯、2,3-亚丁基二异氰酸酯、1,3-亚丁基二异氰酸酯、十二亚甲基二异氰酸酯、以及2,4,4-三甲基六亚甲基二异氰酸酯等。
作为芳香脂肪族聚异氰酸酯,例如可列举:ω,ω′-二异氰酸酯-1,3-二甲基苯、ω,ω′-二异氰酸酯-1,4-二甲基苯、ω,ω′-二异氰酸酯-1,4-二乙基苯、1,4-四甲基二甲苯二异氰酸酯、及1,3-四甲基二甲苯二异氰酸酯等。
作为脂环族聚异氰酸酯,例如可列举:3-异氰酸酯甲基-3,5,5-三甲基环己基异氰酸酯、1,3-环戊烷二异氰酸酯、1,3-环己烷二异氰酸酯、1,4-环己烷二异氰酸酯、甲基-2,4-环己烷二异氰酸酯、甲基-2,6-环己烷二异氰酸酯、4,4′-亚甲基双(环己基异氰酸酯)、1,4-双(异氰酸酯甲基)环己烷、以及1,4-双(异氰酸酯甲基)环己烷等。
也可使用对所述二异氰酸酯进行了改性的三异氰酸酯。三异氰酸酯例如可列举所述二异氰酸酯的三羟甲基丙烷加合物、缩二脲(biuret)体、及三聚体(该三聚体包含异三聚氰酸酯环)等。
聚异氰酸酯(b)在这些中尤其优选为4,4′-二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、及3-异氰酸酯甲基-3,5,5-三甲基环己基异氰酸酯(异佛尔酮二异氰酸酯)等。
聚异氰酸酯(b)可单独或使用两种以上。
<催化剂>
催化剂例如优选为三级胺系化合物及有机金属系化合物等。
三级胺系化合物例如可列举:三乙胺、三乙二胺、以及1,8-二氮杂双环[5.4.0]-十一碳烯-7(1,8-Diazabicyclo[5.4.0]-undecene-7,DBU)等。
有机金属系化合物优选为锡系化合物及非锡系化合物等。
锡系化合物例如可列举:二丁基二氯化锡、二丁基氧化锡、二丁基二溴化锡、二马来酸二丁基锡(dibutyltin dimaleate)、二月桂酸二丁基锡(dibutyltin dilaurate,DBTDL)、二乙酸二丁基锡、二丁基硫化锡、三丁基硫化锡、三丁基氧化锡、乙酸三丁基锡、三乙基乙醇锡(triethyltin ethoxide)、三丁基乙醇锡(tributyltin ethoxide)、二辛基氧化锡、三丁基氯化锡、三氯乙酸三丁基锡、及2-乙基己酸锡等。
非锡系化合物例如可列举:二丁基二氯化钛、钛酸四丁酯、及丁氧基三氯化钛等钛系化合物;油酸铅、2-乙基己酸铅、苯甲酸铅、及环烷酸铅等铅系化合物;2-乙基己酸铁及乙酰丙酮铁等铁系化合物;苯甲酸钴及2-乙基己酸钴等钴系化合物;环烷酸锌及2-乙基己酸锌等锌系化合物;环烷酸锆等锆系化合物。
催化剂可单独或使用两种以上。
催化剂优选为相对于聚异氰酸酯(b)与多元醇(a)的合计100质量份而使用0.01质量份~1.0质量份。
<溶剂>
氨基甲酸酯预聚物(A)的制造中视需要可使用一种以上的溶剂。溶剂例如可列举:丙酮、甲基乙基酮等酮系溶剂;乙酸乙酯等酯系溶剂;甲苯、二甲苯等烃系溶剂等。这些中,就氨基甲酸酯预聚物(A)的溶解性及溶剂的沸点等方面而言,优选为酯系溶剂、烃系溶剂等。
<氨基甲酸酯预聚物(A)的制造方法>
氨基甲酸酯预聚物(A)的制造方法并无特别限制,可利用块状聚合法及溶液聚合法等公知的聚合方法来加以制造。
制造方法的顺序,例如可列举:
(顺序1)将一种以上的聚异氰酸酯(b)、一种以上的多元醇(a)、视需要一种以上的催化剂、及视需要一种以上的溶剂一并投入至烧瓶中的顺序;
(顺序2)将一种以上的多元醇(a)、视需要一种以上的催化剂、及视需要一种以上的溶剂投入至烧瓶中,并向其中通过滴加而添加一种以上的聚异氰酸酯(b)的顺序。
这些中,为了使原料中的低分子成分优先反应且使分子量分散度变狭小,以及就反应控制容易的方面而言,优选为所述顺序2。
在使用催化剂的情况下,反应温度优选为未满100℃,更优选为85℃~95℃。若使反应温度未满100℃,则可抑制氨基甲酸酯反应以外的副反应,因此容易获得所需的树脂。在不使用催化剂的情况下,反应温度优选为100℃以上,更优选为110℃以上。
关于制造氨基甲酸酯预聚物(A)时的聚异氰酸酯(b)的异氰酸酯基(NCO)及多元醇(a)的羟基(OH),就NCO/OH的摩尔比而言,优选为0.3~0.95,更优选为0.4~0.90,进而优选为0.5~0.80。若NCO/OH比为所述范围内,则可形成具有适度的分子链的氨基甲酸酯预聚物(A),因此润湿性及生产性进一步提高。
当在合成时使用催化剂的情况下,优选为使所述催化剂惰性化。反应停止剂例如只要调配乙酰丙酮等即可。
反应停止剂可单独或使用两种以上。
氨基甲酸酯预聚物(A)的重量平均分子量(Mw)优选为10,000~200,000,更优选为30,000~180,000,进而优选为30,000~150,000。通过使重量平均分子量(Mw)为所述范围内,可抑制高分子量成分的生成,且确保涂膜平滑性。
氨基甲酸酯预聚物(A)的分子量分散度的下限值为1.5以上,优选为1.8以上,进而优选为2.0以上。另外,上限值未满4,优选为3.6以下,更优选为3以下。通过使氨基甲酸酯预聚物(A)的分子量分散度为所述范围内,本发明人意外发现可获得能够形成剥离线残留的问题得到解决的、平滑性高的粘着层的粘着剂。
(异氰酸酯硬化剂(B))
异氰酸酯硬化剂(B)是具有多个异氰酸酯基的公知的化合物。异氰酸酯硬化剂(B)优选为所述聚异氰酸酯(b),其中更优选为芳香族聚异氰酸酯、脂肪族聚异氰酸酯、芳香脂肪族聚异氰酸酯及脂环族聚异氰酸酯、以及这些的三羟甲基丙烷加合物、以及这些的缩二脲体、以及作为这些的三聚体的三官能异氰酸酯等。
异氰酸酯硬化剂(B)可单独或使用两种以上。
异氰酸酯硬化剂(B)的调配量优选为相对于氨基甲酸酯预聚物(A)100质量份而为0.1质量份以上且30质量份以下,更优选为1质量份~25质量份,进而优选为3质量份~20质量份,尤其优选为5质量份~15质量份。若调配适量的异氰酸酯硬化剂(B),则容易获得适度的粘着力、凝聚力及耐剥离线性。
(塑化剂(C))
本发明的粘着剂可还包含塑化剂(C)。通过包含塑化剂(C),粘着层相对于被粘合体的润湿性进一步提高。就与其他成分的相容性等观点而言,塑化剂(C)优选为碳数8~30的脂肪酸酯或磷酸酯等。
碳数8~30的脂肪酸酯例如可列举:碳数6~18的一元酸或多元酸与碳数18以下的分支醇的酯、碳数14~18的不饱和脂肪酸或分支酸与四价以下的醇的酯、碳数6~18的一元酸或多元酸与聚亚烷基二醇的酯、利用过氧化物等对不饱和部位进行环氧化而得的脂肪酸酯等。
作为碳数6~18的一元酸或多元酸与碳数18以下的分支醇的酯,例如可列举:月桂酸异硬脂基酯、肉豆蔻酸异丙酯、肉豆蔻酸异鲸蜡酯、肉豆蔻酸辛基十二烷基酯、棕榈酸异硬脂基酯、硬脂酸异鲸蜡酯、油酸辛基十二烷基酯、己二酸二异硬脂基酯、癸二酸二异鲸蜡酯、偏苯三甲酸三油烯基酯、及偏苯三甲酸三异鲸蜡酯等。
构成碳数14~18的不饱和脂肪酸或分支酸与四价以下的醇的酯的、碳数14~18的不饱和脂肪酸及分支酸与四价以下的醇可例示以下的化合物。碳数14~18的不饱和脂肪酸或分支酸例如可列举:肉豆蔻油酸、油酸、亚麻油酸、次亚麻油酸、异棕榈酸、异硬脂酸等。作为四价以下的醇,可列举:乙二醇、丙二醇、甘油、三羟甲基丙烷、季戊四醇、山梨醇酐等。
作为碳数6~18的一元酸或多元酸与聚亚烷基二醇的酯,可列举:二己基酸聚乙二醇、二-2-乙基己基酸聚乙二醇、二月桂酸聚乙二醇、二油酸聚乙二醇、及己二酸二聚乙二醇甲醚等。
利用过氧化物等对不饱和部位进行环氧化而得的脂肪酸酯例如可列举环氧化大豆油、环氧化亚麻籽油、环氧化棉籽油等环氧化油脂或对碳数8~18的不饱和脂肪酸进行环氧化而得的化合物、与碳数1~6的直链醇或分支醇的酯化合物等。
磷酸酯例如可列举亚磷酸或磷酸、与碳数2~18的直链醇或分支醇的酯化合物。
塑化剂(C)可单独或使用两种以上。
就润湿速度提高等观点而言,塑化剂(C)的数量平均分子量(Mn)优选为300~1000,更优选为300~900,进而优选为350~850。
塑化剂(C)的调配量优选为相对于氨基甲酸酯预聚物(A)100质量份而为0.1质量份~100质量份,更优选为1质量份~80质量份,进而优选为10质量份~50质量份。若调配适量的塑化剂(C),则润湿性进一步提高。
(抗氧化剂(D))
本实施方式的粘着剂可还包含抗氧化剂(D)。若包含抗氧化剂(D),则可抑制氨基甲酸酯预聚物(A)的热劣化。
抗氧化剂优选为酚系抗氧化剂及胺系抗氧化剂等自由基链抑制剂、以及硫系抗氧化剂或磷系抗氧化剂等。更优选为酚系抗氧化剂。
酚系抗氧化剂例如可列举:2,6-二-叔丁基-对甲酚、丁基化羟基苯甲醚、2,6-二-叔丁基-4-乙基苯酚、以及β-(3,5-二-叔丁基-4-羟基苯基)丙酸硬脂酯等单酚系抗氧化剂;
2,2′-亚甲基双(4-甲基-6-叔丁基苯酚)、2,2′-亚甲基双(4-乙基-6-叔丁基苯酚)、4,4′-硫代双(3-甲基-6-叔丁基苯酚)、4,4′-亚丁基双(3-甲基-6-叔丁基苯酚)、以及3,9-双[1,1-二甲基-2-[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]2,4,8,10-四氧杂螺[5,5]十一烷等双酚系抗氧化剂;
1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二-叔丁基-4-羟基苄基)苯、四-[亚甲基-3-(3′,5′-二-叔丁基-4′-羟基苯基)丙酸酯]甲烷、双[3,3′-双-(4′-羟基-3′-叔丁基苯基)丁酸]乙二醇酯、以及1,3,5-三(3′,5′-二-叔丁基-4′-羟基苄基)-S-三嗪-2,4,6-(1H,3H,5H)三酮、生育酚等高分子型酚系抗氧化剂等。
硫系抗氧化剂例如可列举:3,3′-硫代二丙酸二月桂基酯、3,3′-硫代二丙酸二-十四烷基酯、以及3,3′-硫代二丙酸二硬脂基酯等。
磷系抗氧化剂例如可列举:亚磷酸三苯基酯、亚磷酸二苯基异癸基酯、以及亚磷酸苯基二异癸基酯等。
抗氧化剂(D)可单独或使用两种以上。
抗氧化剂(D)的调配量优选为相对于氨基甲酸酯预聚物(A)100质量份而为0.01质量份~10质量份,更优选为0.1质量份~5质量份。
(抗静电剂(E))
本实施方式的粘着剂可还包含抗静电剂(E)。若包含抗静电剂(E),则容易抑制剥离粘着片时的静电放电,例如容易防止显示器等中组入的零件等的破损。
抗静电剂例如可列举:无机盐、离子性液体、表面活性剂等。这些中,优选为离子性液体。再者,“离子性液体”也称为常温溶融盐,在25℃下显示液体的性状。
无机盐例如可列举:氯化钠、氯化钾、氯化锂、过氯酸锂、氯化铵、氯酸钾、氯化铝、氯化铜、氯化亚铁、氯化铁、硫酸铵、硝酸钾、硝酸钠、碳酸钠及硫氰酸钠等。
离子性液体是阳离子与阴离子的盐,阳离子例如优选为咪唑离子、吡啶离子、铵离子等。
包含咪唑离子的离子性液体例如可列举:1-乙基-3-甲基咪唑双(三氟甲基磺酰基)酰亚胺、1,3-二甲基咪唑双(三氟甲基磺酰基)酰亚胺及1-丁基-3-甲基咪唑双(三氟甲基磺酰基)咪唑等。
包含吡啶离子的离子性液体例如可列举:1-甲基吡啶双(三氟甲基磺酰基)酰亚胺、1-丁基吡啶双(三氟甲基磺酰基)酰亚胺、1-己基吡啶双(三氟甲基磺酰基)酰亚胺、1-辛基吡啶双(三氟甲基磺酰基)酰亚胺、1-己基-4-甲基吡啶双(三氟甲基磺酰基)酰亚胺、1-己基-4-甲基吡啶六氟磷酸盐、1-辛基-4-甲基吡啶双(三氟甲基磺酰基)酰亚胺、1-辛基-4-甲基吡啶双(氟磺酰基)酰亚胺、1-甲基吡啶双(全氟乙基磺酰基)酰亚胺及1-甲基吡啶双(全氟丁基磺酰基)酰亚胺等。
包含铵离子的离子性液体例如可列举:三甲基庚基铵双(三氟甲烷磺酰基)酰亚胺、N,N-二乙基-N-甲基-N-丙基铵双(三氟甲烷磺酰基)酰亚胺、N,N-二乙基-N-甲基-N-戊基铵双(三氟甲烷磺酰基)酰亚胺、N,N-二乙基-N-甲基-N-庚基铵双(三氟甲烷磺酰基)酰亚胺及三-正丁基甲基铵双三氟甲烷磺酰亚胺等。
除此以外,可适宜使用阳离子为吡咯烷盐、鏻盐及锍盐等的公知的离子性液体。
表面活性剂可分类为非离子性、阴离子性、阳离子性、及两性类型。
非离子性类型例如可列举:甘油脂肪酸酯、聚氧化烯基烷基醚、聚氧乙烯烷基苯基醚、聚氧乙烯烷基胺、聚氧乙烯烷基胺脂肪酸酯、脂肪酸二乙醇酰胺、聚醚酯酰胺型、环氧乙烷-表氯醇型、及聚醚酯型等。
阴离子性类型例如可列举:烷基磺酸盐、烷基苯磺酸盐、磷酸烷基酯、及聚苯乙烯磺酸型等。
阳离子性类型例如可列举:四烷基铵盐、三烷基苄基铵盐、及含四级铵盐基的丙烯酸酯聚合物型等。
两性类型例如可列举:烷基甜菜碱及烷基咪唑甜菜碱、高级烷基氨基丙酸盐等氨基酸型两性表面活性剂、高级烷基二甲基甜菜碱、及高级烷基二羟基乙基甜菜碱等甜菜碱型两性表面活性剂等。
抗静电剂(E)可单独或使用两种以上。
抗静电剂(E)的调配量优选为相对于氨基甲酸酯预聚物(A)100质量份而为0.01质量份~10质量份,更优选为0.03质量份~5质量份。
(多官能多元醇(F))
本实施方式中,多官能多元醇(F)和氨基甲酸酯预聚物(A)一起与异氰酸酯硬化剂(B)反应,而形成在粘着剂层的交联结构中交联密度高的链段。所述交联密度高的链段由于在即将进行反应前的分子量低,因此发挥如下效果:表面配向性优异,使涂膜表面牢固,从而减少剥离线残留。
多官能多元醇(F)可使用所述说明的多元醇(a)中一分子中的羟基数为3以上,且在分子末端具有一级羟基的多元醇。
多官能多元醇(F)的一分子中的羟基数为3以上。通过将一分子中的羟基数设为3以上,可在涂膜表面适当地调整交联密度高的链段,因此剥离线残留进一步减少。
多官能多元醇(F)在分子末端具有一级羟基。若分子末端的羟基为一级,则与异氰酸酯硬化剂(B)的反应优先于氨基甲酸酯预聚物(A),可抑制氨基甲酸酯预聚物(A)的高分子量成分与异氰酸酯硬化剂(B)的反应所引起的涂膜平滑性的劣化。
多官能多元醇(F)优选为相对于氨基甲酸酯预聚物(A)100质量份而包含2质量份~50质量份,更优选为5质量份~30质量份。通过包含2质量份~50质量份的多官能多元醇(F),可在涂膜表面适当地调整交联密度高的链段的比例,因此剥离线残留进一步减少。
多官能多元醇(F)可使用所述多元醇(a)中所列举中一分子中的羟基数为3以上,且在分子末端具有一级羟基者。尤其优选为聚酯多元醇或聚醚多元醇。
多官能多元醇(F)的数量平均分子量(Mn)优选为500~6,000的范围者,进而优选为1,000~5,000。若为500以上,则可抑制与异氰酸酯硬化剂(B)局部地反应的微凝胶的生成,若为6,000以下,则通过减小交联间分子量,可抑制剥离线残留。
(溶剂)
作为溶剂,可使用所述氨基甲酸酯预聚物(A)的制造时可使用的溶剂,但优选为酯系溶剂、烃系溶剂等。溶剂可单独或使用两种以上。
(任意成分)
本实施方式的粘着剂只要为可解决课题的范围内,则可视需要包含任意成分。任意成分可列举:树脂、填充剂、金属粉、颜料、箔状物、软化剂、紫外线吸收剂、光稳定剂、表面润滑剂、流平剂、防腐蚀剂、耐热稳定剂、聚合抑制剂、消泡剂、以及润滑剂等。
填充剂例如可列举:滑石、碳酸钙、氧化钛等。
紫外线吸收剂例如可列举:二苯甲酮系紫外线吸收剂、苯并三唑系紫外线吸收剂、水杨酸系紫外线吸收剂、草酰苯胺系紫外线吸收剂、氰基丙烯酸酯系紫外线吸收剂、及三嗪系紫外线吸收剂等。
二苯甲酮系紫外线吸收剂例如可列举;2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-辛氧基二苯甲酮、2-羟基-4-十二烷氧基二苯甲酮、2,2′-二羟基-4-二甲氧基二苯甲酮、2,2′-二羟基-4,4′-二甲氧基二苯甲酮、2-羟基-4-甲氧基-5-磺基二苯甲酮、及双(2-甲氧基-4-羟基-5-苯甲酰基苯基、)甲烷等。
苯并三唑系紫外线吸收剂例如可列举:2-(2′-羟基-5′-甲基苯基)苯并三唑、2-(2′-羟基-5′-叔丁基苯基)苯并三唑、2-(2′-羟基-3′,5′-二-叔丁基苯基)苯并三唑、2-(2′-羟基-3′-叔丁基-5′-甲基苯基)-5-氯苯并三唑、2-(2′-羟基-3′,5′-二-叔丁基苯基)5-氯苯并三唑、2-(2′-羟基-3′,5′-二-叔戊基苯基)苯并三唑、2-(2′-羟基-4′-辛氧基苯基)苯并三唑、2-[2′-羟基-3′-(3″,4″,5″,6″-四氢邻苯二甲酸酰亚胺甲基)-5′-甲基苯基]苯并三唑、2,2′-亚甲基双[4-(1,1,3,3-四甲基丁基)-6-(2H-苯并三唑-2-基)苯酚]、及[2(2′-羟基-5′-甲基丙烯酰氧基苯基)-2H-苯并三唑]等。
水杨酸系紫外线吸收剂例如可列举:水杨酸苯酯、水杨酸对-叔丁基苯酯、及水杨酸对辛基苯酯等。
氰基丙烯酸酯系紫外线吸收剂例如可列举:2-乙基己基-2-氰基-3,3′-二苯基丙烯酸酯及乙基-2-氰基-3,3′-二苯基丙烯酸酯等。
光稳定剂例如可列举受阻胺系光稳定剂、紫外线稳定剂等。
受阻胺系光稳定剂例如可列举:[双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯]、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯及甲基1,2,2,6,6-五甲基-4-哌啶基癸二酸酯等。
紫外线稳定剂例如可列举:镍双(辛基苯基)硫化物、[2,2′-硫代双(4-叔辛基酚盐)]-正丁基胺镍、镍复合体-3,5-二-叔丁基-4-羟基苄基-磷酸单乙醇盐、镍-二丁基二硫代氨基甲酸酯、苯甲酸酯类型的猝灭剂、及镍-二丁基二硫代氨基甲酸酯等。
流平剂可列举丙烯酸系流平剂、氟系流平剂、硅系流平剂等。若列举流平剂的市售品,则丙烯酸系流平剂例如可列举:珀利弗洛(Polyflow)No.36、珀利弗洛(Polyflow)No.56、珀利弗洛(Polyflow)No.85HF、珀利弗洛(Polyflow)No.99C(均为共荣社化学公司制造)等。氟系流平剂例如可列举美佳法(Megafac)F470N、美佳法(Megafac)F556(均为DIC公司制造)等。硅系流平剂例如可列举格蓝迪(grandic)PC4100(DIC公司制造)等。
[粘着片]
本实施方式的粘着片包括基材、以及作为粘着剂的硬化物的粘着层。粘着层可形成于基材的单面或两面。再者,关于粘着层的与基材不接触的面,为了防止异物的附着,通常直至即将使用前利用剥离片保护。
基材可并无限制地使用柔软的片及板材。基材可列举:塑料、纸及金属箔、以及将这些层叠的基材等。
对于基材的与粘着层接触的面,为了提高密接性,例如可预先进行电晕放电处理等干式处理或锚涂剂(anchor coating agent)涂布等湿式处理的异接着处理。
基材的塑料例如可列举:聚对苯二甲酸乙二酯(polyethylene terephthalate,PET)、聚萘二甲酸乙二酯(Polyethylene Naphthalate,PEN)等酯系树脂;聚乙烯(polyethylene,PE)、聚丙烯(polypropylene,PP)及环烯烃聚合物(Cycio OlefinsPolymer,COP)等烯烃系树脂;聚氯乙烯等乙烯系树脂;尼龙66等酰胺系树脂;氨基甲酸酯系树脂(包含发泡体)等。
基材的厚度通常为10μm~300μm左右。另外,基材使用聚氨基甲酸酯片(包含发泡体)时的厚度通常为20μm~50,000μm左右。纸例如可列举普通纸、涂被纸、以及铜版纸等。金属箔例如可列举铝箔、铜箔等。
剥离片可使用在塑料或纸等的表面上实施了硅酮系剥离剂等的公知的剥离处理的公知的剥离片。
粘着片的制造方法例如可列举如下方法:在基材的表面上涂敷粘着剂,形成涂敷层,继而对涂敷层进行干燥及硬化而形成粘着层。加热及干燥温度通常为60℃~150℃左右。粘着层的厚度通常为0.1μm~200μm左右。
涂布方法例如可列举辊涂机(roll coater)法、缺角轮涂布机(comma coater)法、模涂机(die coater)法、反向涂布机(reverse coater)法、丝网印制(silk screen)法、以及凹版涂布机(gravure coater)法等公知的方法。
另外,可列举如下方法:与所述方法相反地,在剥离片的表面上涂敷粘着剂而形成涂敷层,继而对涂敷层进行干燥及硬化而形成包含本实施方式的粘着剂的硬化物的粘着层,最后,在粘着层的露出面上贴合基材。若利用所述方法贴合剥离片来代替基材,则可获得剥离片/粘着层/剥离片的流延粘着片。
[层叠体]
本实施方式的层叠体至少具有构件、以及本实施方式的粘着片。构件并无特别限定,但适宜的是选自由透明导电膜、玻璃、丙烯酸板、聚碳酸酯板及烯烃板所组成的群组中的构件。
[显示装置]
本实施方式的显示装置具备所述层叠体。
[实施例1]
以下,通过实施例对本发明加以更详细的说明。再者,本发明的实施方式当然并不限定于实施例。以下,“份”是指“质量份”,“%”是指“质量%”。
[重量平均分子量(Mw)及数量平均分子量(Mn)的测定]
重量平均分子量(Mw)及数量平均分子量(Mn)是利用凝胶渗透色谱(GPC)法进行测定。测定条件如下所述。再者,Mw及Mn均为聚苯乙烯换算值。
<测定条件>
装置:岛津卓越(SHIMADZU Prominence)(岛津制作所公司制造)、管柱:将三根索得克斯(SHODEX)LF-804(昭和电工公司制造)串联连接
检测器:示差折射率检测器
溶媒:四氢呋喃(Tetrahydrofuran,THF)
流速:0.5mL/min
溶媒温度:40℃
试样浓度:0.1%
试样注入量:100μL
[材料]
所使用的材料如下所述。
<多元醇(a)>
(a1):P510(“可乐丽多元醇(Kuraray Polyol)P-510”、聚酯多元醇、Mn500、羟基数2、一级羟基、可乐丽(Kuraray)公司制造)
(a2):P1010(“可乐丽多元醇(Kuraray Polyol)P-1010”、聚酯多元醇、Mn1000、羟基数2、一级羟基、可乐丽(Kuraray)公司制造)
(a3):P2010(“可乐丽多元醇(Kuraray Polyol)P-2010”、聚酯多元醇、Mn2000、羟基数2、一级羟基、可乐丽(Kuraray)公司制造)
(a4):P3199(“普利拉斯(priprast)3199”、聚酯多元醇、Mn2000、羟基数2、一级羟基、禾大(CRODA)公司制造)
(a5):PP1000(“苏尼克(Sannix)PP-1000”、聚氧丙烯二醇、Mn1000、羟基数2、二级羟基、三洋化成工业公司制造)
(a6):PP2000(“苏尼克(Sannix)PP-2000”、聚氧丙烯二醇、Mn2000、羟基数2、二级羟基、三洋化成工业公司制造)
(a7):PP4000(“苏尼克(Sannix)PP-4000”、聚氧丙烯二醇、Mn4000、羟基数2、二级羟基、三洋化成工业公司制造)
(a8):GI1000(“倪索(NISSO)-PB GI-1000”、两末端羟基氢化聚丁二烯、Mn1500、羟基数2、一级羟基、日本曹达公司制造)
(a9):GI3000(“倪索(NISSO)-PB GI-3000”、两末端羟基氢化聚丁二烯、Mn3100、羟基数2、一级羟基、日本曹达公司制造)
(a10):HLBH P2000(“卡索(Krasol)(注册商标)HLBH P2000”、末端羟基改性液状聚丁二烯、Mn2000、羟基数1.95、一级羟基、克雷威利(CRAY VALLEY)公司制造)
(a11):F3010(“可乐丽多元醇(Kuraray Polyol)F-3010”、聚酯多元醇、Mn3000、羟基数3、一级羟基、可乐丽(Kuraray)公司制造)
(a12):AM302(“艾迪科聚醚(Adeka polyether)AM-302”、甘油PO/EO多元醇、Mn3000、羟基数3、一级羟基、艾迪科(ADEKA)公司制造)
(a13):R45HTLO(“保利博德(Poly bd)(注册商标)R45HTLO”、末端羟基改性液状聚丁二烯、Mn2800、羟基数3、一级羟基克雷威利(CRAY VALLEY)公司制造)
(a14):GP3000(“苏尼克(Sannix)GP-3000”、甘油/聚氧丙烯二醇、Mn3000、羟基数3、二级羟基、三洋化成工业公司制造)
<聚异氰酸酯(b)>
(b1):HDI(六亚甲基二异氰酸酯,住化科思创聚氨酯(Sumika CovestroUrethane)公司制造的“德斯莫杜尔(Desmodur)H”)、
(b2):IPDI(异佛尔酮二异氰酸酯,住化科思创聚氨酯(Sumika CovestroUrethane)公司制造的“德斯莫杜尔(Desmodur)I”)、
(b3):TDI(甲苯二异氰酸酯、东曹公司制造的“库洛特(CORONATE)T-65”)。
<异氰酸酯硬化剂(B)>
(B1):HDI加合物(“苏米都(Sumidur)HT”、六亚甲基二异氰酸酯的三羟甲基丙烷加合物,住化科思创聚氨酯(Sumika Covestro Urethane)公司制造)
(B2):HDI脲酸酯(nurate)(“苏米都(Sumidur)N3300”、六亚甲基二异氰酸酯的脲酸酯体,住化科思创聚氨酯(Sumika Covestro Urethane)公司制造)
(B3):HDI缩二脲(“苏米都(Sumidur)N3200”、六亚甲基二异氰酸酯的缩二脲体住化科思创聚氨酯(Sumika Covestro Urethane)公司制造)
<多官能多元醇(F)>
将与所述(a11)~(a13)相同者分别作为多官能多元醇(F1)~多官能多元醇(F3)而使用。
<并非多官能多元醇(F)的多官能多元醇(F′)>
将与所述(a14)相同者作为多官能多元醇(F4)而使用。
<塑化剂(C)>
(C1):M182A(“友信达(unistar)M182A”、油酸甲酯、日油公司制造)
(C2):W262(“莫赛泽(Monocizer)W262”、醚酯系塑化剂、DIC公司制造)
(C3):D55(“艾迪科赛泽(ADEKACIZER)D-55”、环氧化脂肪酸烷基酯、艾迪科(ADEKA)公司制造)
(C4):TOP(“TOP”、三(2-乙基己基)磷酸酯、大八工业化学公司制造)
<抗氧化剂(D)>
(D1):Irg1010(“易加乐斯(Irganox)1010”、季戊四醇四[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]、酚系抗氧化剂、巴斯夫(BASF)公司制造)
<抗静电剂(E)>
(E1):FSI-铵盐(三-正丁基甲基铵·双三氟甲烷磺酰胺)
(E2):FSI-锂盐(锂·双三氟甲烷磺酰胺)
[氨基甲酸酯预聚物(A)的合成例]
(合成例1)
在具备搅拌机、回流冷却管、氮气导入管、温度计、滴加漏斗的四口烧瓶中投入可乐丽多元醇(Kuraray Polyol)P-510(二官能聚酯多元醇、可乐丽(Kuraray)公司制造)1000份、六亚甲基二异氰酸酯300份、甲苯557份、作为催化剂的二辛基二月桂酸锡0.1份,缓缓升温至100℃,进行2小时反应。在确认到IR图表的NCO特性吸收(2,270cm-1)消失后,冷却至25℃,在加入乙酰丙酮13份后,结束反应。所述氨基甲酸酯预聚物(A1)的Mw为31,000,分子量分散度为1.8。
(合成例2~合成例23)
除了将实施例1的材料及调配比变更为表1所示以外,通过与合成例1同样地进行,而分别获得各合成例2~合成例22的氨基甲酸酯预聚物(A)、以及并非氨基甲酸酯预聚物(A)的合成例23的氨基甲酸酯预聚物(A′)。将所得的氨基甲酸酯预聚物(A)及氨基甲酸酯预聚物(A′)的Mw与分子量分散度示于表1中。再者,表中所具有的原料的调配量为不挥发成分换算,无特别说明的数值的单位为“份”。
(实施例1)
调配合成例1中所得的氨基甲酸酯预聚物(A1)100份、异氰酸酯硬化剂(B1)10份、抗氧化剂(D1)0.5份、多官能多元醇(F1)=(a11)10份及溶剂的乙酸乙酯100份,利用分散机进行搅拌,而获得粘着剂。再者,除溶剂以外的各材料的使用量表示不挥发成分换算值[份]。
基材准备厚度50μm的聚对苯二甲酸乙二酯(PET)(“露米勒(Lumirror)T-60”、东丽公司制造)。使用缺角轮涂布机(comma coater)(注册商标),以涂敷速度3m/min、宽度30cm且以干燥后的厚度成为12μm的方式将所获得的粘着剂涂敷于所述基材上而形成涂敷层。
其次,使用干燥烘箱,将所形成的涂敷层在100℃、1分钟的条件下干燥,形成粘着层。在所述粘着层上贴合厚度38μm的市售的剥离片,进而在23℃-50%RH的条件下进行1周养护,由此获得粘着片。
(实施例2~实施例42、比较例1~比较例3)
除了将实施例1的材料及调配比变更为表2~表4所示以外,通过与实施例1同样地进行,而分别获得实施例2~实施例42、比较例1~比较例3的粘着剂及粘着片。
[评价项目及评价方法]
所得的粘着剂及粘着片的评价项目及评价方法如下所述。
(耐剥离线性)
以宽度50mm、长度100mm的大小准备所得的粘着胶带并作为测定试样。继而,在23℃、50%RH的环境下,剥下剥离衬垫,将露出的粘着层贴附于玻璃板上,使2kg辊往返一次并压接,而制作层叠体。在一分钟后,在剥离了一半贴合面积的时间点暂时中断剥离,在所述状态下静止10秒后,完全剥离粘着胶带。在暗室内透过明亮的光,目视评价中途停止剥离所产生的粘着层的线(中断剥离所产生的痕迹)的残留情况。评价基准如下所述。
◎:完全未观察到线。优良。
○:观察到线的一部分。良好。
△:轻微地观察到线的整体。可实用。
×:清楚地观察到线。无法实用。
(涂膜平滑性)
除了将实施例1的涂敷速度变为30m/min、宽度变为150cm以外,与实施例同样地进行而制作粘着片,评价高速涂敷下的缺点数。评价是以每1m2评价目视可确认到的大小的凝聚物的数量(缺点数)。
◎:0个。优良。
○:1个。良好。
△:2个以上且3个以下。可实用。
×:4个以上。无法实用。
[表1]
表1(继续)
表1(继续)
[表4]
Claims (9)
1.一种粘着剂,其特征在于,包含:作为多元醇(a)与聚异氰酸酯(b)的反应物的含羟基的氨基甲酸酯预聚物(A)、异氰酸酯硬化剂(B)以及多官能多元醇(F),
所述氨基甲酸酯预聚物(A)的分子量分散度为1.5以上且未满4,
所述多官能多元醇(F)的一分子中的羟基数为3以上,且在分子末端具有一级羟基。
2.根据权利要求1所述的粘着剂,其特征在于:所述多元醇(a)包含选自由聚醚多元醇、聚酯多元醇及聚丁二烯改性多元醇所组成的群组中的一种以上。
3.根据权利要求1或2所述的粘着剂,其特征在于:相对于所述氨基甲酸酯预聚物(A)100质量份而包含2质量份~50质量份的所述多官能多元醇(F)。
4.根据权利要求1或2所述的粘着剂,其特征在于:还包含塑化剂(C)。
5.根据权利要求1或2所述的粘着剂,其特征在于:还包含抗氧化剂(D)。
6.根据权利要求1或2所述的粘着剂,其特征在于:还包含抗静电剂(E)。
7.一种粘着片,其特征在于,包括:基材、以及作为根据权利要求1至6中任一项所述的粘着剂的硬化物的粘着层。
8.一种层叠体,其特征在于包括:选自由透明导电膜、玻璃、丙烯酸板、聚碳酸酯板及烯烃板所组成的群组中的构件;以及根据权利要求7所述的粘着片。
9.一种显示装置,其特征在于,包括根据权利要求8所述的层叠体。
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JP7030269B2 (ja) * | 2018-03-28 | 2022-03-07 | 東洋インキScホールディングス株式会社 | 粘着剤および粘着シート |
CN111936592B (zh) * | 2018-04-06 | 2022-06-10 | Dic株式会社 | 氨基甲酸酯粘合剂和粘合片 |
JP7122228B2 (ja) * | 2018-11-06 | 2022-08-19 | ライオン・スペシャリティ・ケミカルズ株式会社 | 粘着剤、粘着シート、粘着シートの製造方法、および画像表示装置 |
JP6769503B2 (ja) * | 2019-02-22 | 2020-10-14 | 東洋インキScホールディングス株式会社 | 粘着剤、および粘着シートとその使用方法 |
WO2020175220A1 (ja) * | 2019-02-28 | 2020-09-03 | Agc株式会社 | ウレタンプレポリマー、粘着剤、貼付材、粘着テープ、ウェアラブルデバイス及びウェアラブルデバイスキット |
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JP6795079B1 (ja) * | 2019-12-03 | 2020-12-02 | 東洋インキScホールディングス株式会社 | 粘着組成物および粘着シート |
CN110951436A (zh) * | 2019-12-09 | 2020-04-03 | 深圳盛得莱防静电设备有限公司 | 一种防静电胶及其制备方法 |
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