CN105555897B - 粘接剂及发光装置 - Google Patents

粘接剂及发光装置 Download PDF

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Publication number
CN105555897B
CN105555897B CN201480050394.XA CN201480050394A CN105555897B CN 105555897 B CN105555897 B CN 105555897B CN 201480050394 A CN201480050394 A CN 201480050394A CN 105555897 B CN105555897 B CN 105555897B
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acrylic resin
acid
evaluated
conduction
epoxide
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CN105555897A (zh
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青木正治
蟹泽士行
波木秀次
小山太一
石神明
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Dexerials Corp
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Dexerials Corp
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
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    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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Abstract

一种粘接剂，其含有环氧化合物、阳离子催化剂以及丙烯酸类树脂，所述丙烯酸类树脂包含丙烯酸和具有羟基的丙烯酸酯。丙烯酸类树脂中的丙烯酸与环氧化合物反应而生成丙烯酸类树脂的岛与环氧化合物的海的连接，并且使氧化膜的表面粗糙而加强其与环氧化合物的海的固着效果。此外，丙烯酸类树脂中的具有羟基的丙烯酸酯通过羟基的极性而获得对于布线的静电粘接力。通过如此以丙烯酸类树脂的岛和环氧化合物的海的固化物整体对氧化膜进行粘接，可获得优异的粘接力。

Description

粘接剂及发光装置
技术领域
本发明涉及对电子部件之间进行电连接的粘接剂，特别涉及连接LED(LightEmitting Diode，发光二级管)等发光元件与布线基板的粘接剂、以及连接有发光元件和布线基板的发光装置。
背景技术
作为将LED等芯片部件安装于电路基板的方法，广泛采用的是，使用使导电性颗粒分散到环氧类粘接剂中并成形为薄膜状的各向异性导电薄膜(ACF：AnisortropicConductive Film)进行倒装芯片安装的方法(例如参见专利文献1、2)。根据该方法，芯片部件与电路基板之间的电连接可由各向异性导电薄膜的导电性颗粒实现，因此能够缩短连接工艺，能够提高生产效率。
现有技术文献
专利文献
专利文献1：日本特开2010-24301号公报
专利文献2：日本特开2012-186322号公报
发明内容
发明要解决的问题
在近年来的LED产品中，有的为了低成本化而使用将电路基板的布线的金属从Au、Ag变更为Al、Cu的基板，在PET(聚对苯二甲酸乙二醇酯、Polyethylene terephthalate)基材上形成有ITO(铟锡氧化物、Indium Tin Oxide)布线的透明基板。
然而，由于在Al、Cu等的金属布线、ITO布线的表面形成有钝化、氧化覆膜等氧化膜，因此以现有的环氧类粘接剂难以粘接。
本发明用于解决上述现有技术中的问题，其目的在于提供对氧化膜具有优异的粘接性的粘接剂以及使用其的发光装置。
用于解决问题的方案
为了解决上述问题，本发明的粘接剂的特征在于，其含有阳离子催化剂、重均分子量为50000～900000的丙烯酸类树脂、以及脂环式环氧化合物或氢化环氧化合物，前述丙烯酸类树脂包含0.5～10wt％的丙烯酸和0.5～10wt％的具有羟基的丙烯酸酯。
此外，本发明的发光装置的特征在于，其具备：具有由铝形成的布线图案的基板、形成在前述布线图案的电极上的各向异性导电膜、以及安装在前述各向异性导电膜上的发光元件，前述各向异性导电膜为各向异性导电粘接剂的固化物，所述各向异性导电粘接剂含有阳离子催化剂、重均分子量为50000～900000的丙烯酸类树脂、导电性颗粒、以及脂环式环氧化合物或氢化环氧化合物，前述丙烯酸类树脂包含0.5～10wt％的丙烯酸和0.5～10wt％的具有羟基的丙烯酸酯。
此外，本发明的发光装置的特征在于，其具备：具有由透明导电膜形成的布线图案的透明基板、形成在前述布线图案的电极上的各向异性导电膜、以及安装在前述各向异性导电膜上的发光元件，前述各向异性导电膜为各向异性导电粘接剂的固化物，所述各向异性导电粘接剂含有阳离子催化剂、重均分子量为50000～900000的丙烯酸类树脂、导电性颗粒、以及脂环式环氧化合物或氢化环氧化合物，前述丙烯酸类树脂包含0.5～10wt％的丙烯酸和0.5～10wt％的具有羟基的丙烯酸酯。
发明的效果
根据本发明，通过配混包含丙烯酸和具有羟基的丙烯酸酯的丙烯酸类树脂，能够以固化物整体对氧化膜进行粘接，能够获得优异的粘接力。
附图说明
图1是示出以环氧化合物为海并以丙烯酸类树脂为岛时的海岛模型的剖视图。
图2是示出发光装置的一个例子的剖视图。
图3是示出90度剥离强度试验的概要的剖视图。
图4是用于说明LED安装样品的制作工序的图。
图5是示出模头剪切强度试验的概要的剖视图。
具体实施方式
以下，对于本发明的实施方式(以下称为本实施方式)，边参照附图边按下述顺序进行详细说明。需要说明的是，自不用说，本发明并不限定于以下实施方式，在不脱离本发明的要旨的范围内可以进行各种变更。此外，附图是示意性的，各尺寸的比率等有时会与实际不同。具体的尺寸等应斟酌以下说明进行判断。此外，自不用说，在附图相互之间包括彼此的尺寸关系、比率不同的部分。
1.粘接剂
2.发光装置
3.实施例
<1.粘接剂>
本发明所应用的粘接剂含有阳离子催化剂、重均分子量为50000～900000的丙烯酸类树脂、以及脂环式环氧化合物或氢化环氧化合物，丙烯酸类树脂包含0.5～10wt％的丙烯酸和0.5～10wt％的具有羟基的丙烯酸酯。
图1是示出在粘接剂与氧化膜的界面处以环氧化合物为海、以丙烯酸类树脂为岛时的海岛模型的剖视图。该海岛模型是示出分散在环氧化合物的海12中的丙烯酸类树脂的岛13连接在布线11的氧化膜11a上的状态的固化物模型。
在该固化物模型中，丙烯酸类树脂中的丙烯酸与环氧化合物反应，生成丙烯酸类树脂的岛13与环氧化合物的海12的连接，并且使氧化膜11a的表面粗糙而加强其与环氧化合物的海12的固着效果。此外，丙烯酸类树脂中的具有羟基的丙烯酸酯通过羟基的极性而获得对于布线11的静电粘接力。通过如此以丙烯酸类树脂的岛13和环氧化合物的海12的固化物整体对氧化膜11a进行粘接，能够获得优异的粘接力。
作为脂环式环氧化合物，优选列举出分子内具有2个以上环氧基的物质。脂环式环氧化合物可以是液态，也可以是固态。具体可列举出：3,4-环氧环己烯基甲基-3’,4’-环氧环己烯羧酸酯、缩水甘油基六氢双酚A等。这些当中，从能够确保固化物具有适于LED元件的安装等的光透过性、且快速固化性也优异的角度来看，优选使用3,4-环氧环己烯基甲基-3’,4’-环氧环己烯羧酸酯。
作为氢化环氧化合物，可以使用上面说的脂环式环氧化合物的氢化物、双酚A型、双酚F型等公知的氢化环氧化合物。
脂环式环氧化合物、氢化环氧化合物可以单独使用，也可以并用2种以上。此外，在不损害本发明的效果的情况下，可以在这些环氧化合物的基础上并用其它环氧化合物。例如可列举出：使双酚A、双酚F、双酚S、四甲基双酚A、二芳基双酚A、氢醌、儿茶酚、间苯二酚、甲酚、四溴双酚A、三羟基联苯、二苯甲酮、双间苯二酚、双酚六氟丙酮、四甲基双酚A、四甲基双酚F、三(羟基苯基)甲烷、联二甲苯酚、苯酚酚醛清漆、甲酚酚醛清漆等多元酚与表氯醇反应而得的缩水甘油醚；使甘油、新戊二醇、乙二醇、丙二醇、丁二醇、己二醇、聚乙二醇、聚丙二醇等脂肪族多元醇与表氯醇反应而得的聚缩水甘油醚；使对羟基苯甲酸、β-羟基萘甲酸这种羟基羧酸与表氯醇反应而得的缩水甘油醚酯；由邻苯二甲酸、甲基邻苯二甲酸、间苯二甲酸、对苯二甲酸、四氢邻苯二甲酸、桥亚甲基四氢邻苯二甲酸、桥亚甲基六氢邻苯二甲酸、偏苯三酸、聚合脂肪酸这种聚羧酸得到的聚缩水甘油酯；由氨基苯酚、氨基烷基酚得到的缩水甘油基氨基缩水甘油醚；由氨基苯甲酸得到的缩水甘油基氨基缩水甘油酯；由苯胺、甲苯胺、三溴苯胺、苯二甲基二胺、二氨基环己烷、双氨基甲基环己烷、4,4’-二氨基二苯基甲烷、4,4’-二氨基二苯基砜等得到的缩水甘油胺；环氧化聚烯烃等公知的环氧树脂类。
作为阳离子催化剂，例如可列举出：铝螯合物类潜伏性固化剂、咪唑类潜伏性固化剂、锍类潜伏性固化剂等潜伏性阳离子固化剂。这些当中，优选使用速固化性优异的铝螯合物类潜伏性固化剂。
阳离子催化剂的含量过少时会失去反应性，过多时存在粘接剂的产品寿命缩短的倾向，因此相对于环氧化合物100重量份，优选为0.1～30质量份，更优选为0.5～20质量份。
丙烯酸类树脂的重均分子量为50000～900000。在图1所示的固化物模型中，丙烯酸类树脂的重均分子量显示与丙烯酸类树脂的岛13的大小相关，通过使丙烯酸类树脂的重均分子量为50000～900000，可以使大小适度的丙烯酸类树脂的岛13与氧化膜11a接触。丙烯酸类树脂的重均分子量小于50000时，丙烯酸类树脂的岛13与氧化膜11a的接触面积减小，无法获得提高粘接力的效果。此外，丙烯酸类树脂的重均分子量超过900000时，丙烯酸类树脂的岛13增大，称不上以丙烯酸类树脂的岛13和环氧化合物的海12的固化物整体对氧化膜11a进行粘接的状态，粘接力降低。
此外，丙烯酸类树脂含有0.5～10wt％的丙烯酸，更优选含有1～5wt％。通过使丙烯酸类树脂中含有0.5～10wt％的丙烯酸，通过其与环氧化合物的反应而产生丙烯酸类树脂的岛13与环氧化合物的海12的连接，并且使氧化膜11a的表面粗糙而使其与环氧化合物的海12的固着效果加强。
此外，丙烯酸类树脂包含0.5～10wt％的具有羟基的丙烯酸酯，更优选包含1～5wt％。通过使丙烯酸类树脂中包含0.5～10wt％的具有羟基的丙烯酸酯，通过羟基的极性而获得对于布线11的静电粘接力。
作为具有羟基的丙烯酸酯，可列举出：甲基丙烯酸2-羟乙酯、甲基丙烯酸2-羟丙酯、丙烯酸2-羟乙酯、丙烯酸2-羟丙酯等，可以使用选自由这些丙烯酸酯组成的组中的1种以上丙烯酸酯。这些当中，优选使用对氧化膜的粘接性优异的甲基丙烯酸2-羟乙酯。
此外，丙烯酸类树脂除了丙烯酸和具有羟基的丙烯酸酯以外还包含不具有羟基的丙烯酸酯。作为不具有羟基的丙烯酸酯，可列举出：丙烯酸丁酯、丙烯酸乙酯、丙烯腈等。优选丙烯酸类树脂含有选自这些丙烯酸丁酯、丙烯酸乙酯、丙烯腈中的1种以上丙烯酸酯。
此外，丙烯酸类树脂的含量相对于环氧化合物100质量份优选为1～10质量份，更优选为1～5质量份。通过使丙烯酸类树脂的含量相对于环氧化合物100质量份为1～10质量份，可以得到使丙烯酸类树脂12的岛以良好的密度分散在环氧树脂13的海中的固化物。
此外，对于本发明所应用的粘接剂，作为其它成分，可以为了提高与无机材料的界面处的粘接性而进一步含有硅烷偶联剂。作为硅烷偶联剂，可列举出：环氧类、甲基丙烯酰氧基类、氨基类、乙烯基类、巯基·硫醚类、脲基类等，它们可以单独使用，也可以组合使用2种以上。这些当中，本实施方式优选使用环氧系硅烷偶联剂。
此外，粘接剂可以为了控制流动性、提高颗粒捕捉率而含有无机填料。作为无机填料，没有特别限定，可以使用二氧化硅、滑石、氧化钛、碳酸钙、氧化镁等。这种无机填料可以根据缓和由粘接剂连接的连接结构体的应力的目的而适当使用。此外，可以配混热塑性树脂、橡胶成分等柔软剂等。
根据这种粘接剂，对于铝等难粘接金属，能够获得高的粘接力。
此外，粘接剂可以是含有导电性颗粒的各向异性导电粘接剂。作为导电性颗粒，可以使用公知的导电性颗粒。例如可列举出：镍、铁、铜、铝、锡、铅、铬、钴、银、金等各种金属、金属合金的颗粒，在金属氧化物、碳、石墨、玻璃、陶瓷、塑料等颗粒的表面涂布有金属的颗粒，进一步在这些颗粒的表面涂布有绝缘膜的颗粒等。为在树脂颗粒的表面涂布有金属的颗粒时，作为树脂颗粒，例如可以使用环氧树脂、酚醛树脂、丙烯酸类树脂、丙烯腈·苯乙烯(AS)树脂、苯并胍胺树脂、二乙烯苯类树脂、苯乙烯类树脂等的颗粒。
作为导电性颗粒的平均粒径，通常为1～10μm，更优选为2～6μm。此外，从连接可靠性和绝缘可靠性的角度来看，粘接剂成分中的导电性颗粒的平均颗粒密度优选为1000～100000个/mm2，更优选为30000～80000个/mm2。
根据这种各向异性导电粘接剂，对于具有氧化膜的铝布线、ITO布线，能够获得优异的连接可靠性。
<2.发光装置>
接着，对应用了本发明的发光装置进行说明。图2是示出发光装置的一个例子的剖视图。发光装置具备：具有布线图案22的基板21、形成在布线图案22的电极上的各向异性导电膜30、以及安装在各向异性导电膜30上的发光元件23，各向异性导电膜30由前述的各向异性导电粘接剂的固化物形成。该发光装置通过在基板21上的布线图案22与连接用凸块26之间涂布前述的各向异性导电粘接剂、对基板21和发光元件23进行倒装芯片安装来得到，所述连接用凸块26分别形成于作为发光元件23的LED元件的n电极24和p电极25。
本实施方式中，通过使用前述的各向异性导电粘接剂，能够适宜地使用具有由铝形成的布线图案的基板。由此，能够实现LED产品的低成本化。
此外，能够适宜地使用具有由ITO等的透明导电膜形成的布线图案的透明基板。由此，例如能够将LED安装于在PET(聚对苯二甲酸乙二醇酯)基材上形成有ITO(铟锡氧化物)布线的透明基板。
需要说明的是，可以根据需要而以被覆LED元件23整体的方式用透明模塑树脂进行封装。此外，可以在LED元件23上设置光反射层。此外，作为发光元件，除了LED元件以外还可以在不损害本发明的效果的范围内使用公知的发光元件。
<3.实施例>
实施例
以下，对本发明的实施例进行说明。本实施例中，制作各种各向异性导电粘接剂，对颜色、全反射率和剥离强度进行了评价。此外，使用各向异性导电粘接剂在基板上搭载LED芯片来制作LED安装样品，对模头剪切强度和导通电阻进行了评价。需要说明的是，本发明并不限定于这些实施例。
[颜色的评价]
将各向异性导电粘接剂以厚度达到100μm的方式涂布在由陶瓷形成的白色板上，以180℃加热30秒而使其固化。对于所得固化物，使用色度计测定白色度(JIS P 8148)。将白色度为70％以上的评价为“白色”，白色度小于70％时，通过目视评价颜色。
[全反射率的测定]
将各向异性导电粘接剂以厚度达到100μm的方式涂布于由陶瓷形成的白色板上，以180℃加热30秒而使其固化。对于所得固化物，使用分光光度计(株式会社岛津制作所制造UV3100)以硫酸钡为标准测定对波长460nm的光的全反射率(镜面反射和漫反射)。此外，对于100℃、1000h的条件的耐热试验后的固化物，也测定对波长460nm的光的全反射率。需要说明的是，光反射率在实用上理想的是超过30％。
[剥离强度的测定]
将各向异性导电粘接剂以厚度达到100μm的方式涂布于由陶瓷形成的白色板上，在180℃-1.5N-30秒的条件下热压接1.5mm×10mm的铝片，制得接合体。
如图3所示，使用TENSILON，以拉伸速度50mm/秒沿90°Y轴方向剥离接合体的铝片42，测定其剥离所需的剥离强度的最大值。
[LED安装样品的制作]
如图4所示，制得LED安装样品。将多个50μm间距的布线基板(50μm Al布线-25μmPI(聚酰亚胺)层-50μm Al基座)51排列在工作台上，在各布线基板51上涂布约10μg的各向异性导电粘接剂50。在各向异性导电粘接剂50上搭载Cree公司制造的LED芯片(商品名：DA3547、最大额定值：150mA、尺寸：0.35mm×0.46mm)5，使用热加压工具53进行倒装芯片安装，得到LED安装样品。
此外，实施例5中，作为布线基板，使用形成有50μm间距的ITO布线的布线基板(50μm ITO布线-25μm PI(聚酰亚胺)层-50μm Al基座)。
[模头剪切强度的测定]
如图5所示，使用模头剪切测试仪，在工具54的剪切速度20μm/秒、25℃的条件下测定各LED安装样品的接合强度。
[导通电阻的评价]
测定各LED安装样品的初始、冷热循环试验(TCT)后、100℃-1000小时的环境试验后、以及60℃-90％RH-500小时的环境试验后的导通电阻。冷热循环试验将以使LED安装样品在-40℃和100℃的气氛中各暴露30分钟作为1个循环的冷热循环进行100、500、1000个循环，分别测定导通电阻。导通电阻的评价中，测定If＝50mA时的Vf值，Vf值自试验成绩表的Vf值起上升的部分小于5％的情况评价为“○”，为5％以上的情况评价为“×”。
[综合评价]
各向异性导电粘接剂的颜色为白色、初始和100℃-1000h的环境试验后的全反射率为70％以上、初始和60℃-90％RH-500小时的环境试验后的剥离强度为2.0N以上、初始和60℃-90％RH-500小时的环境试验后的模头剪切强度为5.0N以上、以及导通性评价全部为“○”的评价为“○”，除此之外评价为“×”。
[实施例1]
在由脂环式环氧化合物(品名：CELLOXIDE 2021P、Daicel Chemical Industries,Ltd.制造)100质量份、潜伏性阳离子固化剂(铝螯合物类潜伏性固化剂)5质量份、丙烯酸类树脂(丙烯酸丁酯(BA)：15％、丙烯酸乙酯(EA)：63％、丙烯腈(AN)：20％、丙烯酸(AA)：1wt％、甲基丙烯酸2-羟乙酯(HEMA)：1wt％、重均分子量Mw：70万)3质量份构成的粘接剂中，分散导电性颗粒(品名：AUL704、积水化学工业株式会社制造)10质量份，制得各向异性导电粘接剂。此外，LED安装样品的制作中的固化条件设定为180℃-1.5N-30秒。
表1示出实施例1的各项评价结果。各向异性导电粘接剂的颜色为白色，初始的全反射率为75％，100℃-1000h的环境试验后的全反射率为74％。此外，初始的剥离强度为4.0N，60℃-90％RH-500小时的环境试验后的剥离强度为4.1N。此外，LED安装样品的初始的模头剪切强度为8.5N，60℃-90％RH-500小时的环境试验后的模头剪切强度为5.3N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为○，500个循环后的导通性评价为○，1000个循环后的导通性评价为○，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为○。因此，综合评价为○。
[实施例2]
作为丙烯酸类树脂使用重均分子量Mw为50万的树脂，除此之外与实施例1同样制作各向异性导电粘接剂，得到LED安装样品。
表1示出实施例2的各评价结果。各向异性导电粘接剂的颜色为白色，初始的全反射率为73％，100℃-1000h的环境试验后的全反射率为73％。此外，初始的剥离强度为3.1N，60℃-90％RH-500小时的环境试验后的剥离强度为2.9N。此外，LED安装样品的初始的模头剪切强度为7.8N，60℃-90％RH-500小时的环境试验后的模头剪切强度为7.6N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为○，500个循环后的导通性评价为○，1000个循环后的导通性评价为○，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为○。因此，综合评价为○。
[实施例3]
作为丙烯酸类树脂使用重均分子量Mw为20万的树脂，除此之外与实施例1同样制作各向异性导电粘接剂，得到LED安装样品。
表1示出实施例3的各项评价结果。各向异性导电粘接剂的颜色为白色，初始的全反射率为75％，100℃-1000h的环境试验后的全反射率为74％。此外，初始的剥离强度为3.5N，60℃-90％RH-500小时的环境试验后的剥离强度为3.1N。此外，LED安装样品的初始的模头剪切强度为7.5N，60℃-90％RH-500小时的环境试验后的模头剪切强度为7.6N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为○，500个循环后的导通性评价为○，1000个循环后的导通性评价为○，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为○。因此，综合评价为○。
[实施例4]
作为丙烯酸类树脂使用重均分子量Mw为5万的树脂，除此之外与实施例1同样制作各向异性导电粘接剂，得到LED安装样品。
表1示出实施例4的各项评价结果。各向异性导电粘接剂的颜色为白色，初始的全反射率为71％，100℃-1000h的环境试验后的全反射率为71％。此外，初始的剥离强度为3.8N，60℃-90％RH-500小时的环境试验后的剥离强度为3.3N。此外，LED安装样品的初始的模头剪切强度为6.9N，60℃-90％RH-500小时的环境试验后的模头剪切强度为7.1N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为○，500个循环后的导通性评价为○，1000个循环后的导通性评价为○，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为○。因此，综合评价为○。
[实施例5]
作为布线基板，使用形成有50μm间距的ITO布线的布线基板(50μm ITO布线-25μmPI(聚酰亚胺)层-50μm Al基座)，除此之外与实施例1同样制得LED安装样品。
表1示出实施例5的各项评价结果。各向异性导电粘接剂的颜色为白色，初始的全反射率为75％，100℃-1000h的环境试验后的全反射率为74％。此外，LED安装样品的模头剪切强度的测定时在ITO与基板的界面处发生破坏，粘接剂与ITO的粘接强度为良好。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为○，500个循环后的导通性评价为○，1000个循环后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为○。因此，综合评价为○。
[比较例1]
使用重均分子量Mw为20万并且丙烯酸(AA)的含量为0wt％的丙烯酸类树脂(BA：15％、EA：64％、AN：20％、AA：0wt％、HEMA：1wt％、Mw：20万)，除此之外与实施例1同样制作各向异性导电粘接剂，得到LED安装样品。
表1示出比较例1的各项评价结果。各向异性导电粘接剂的颜色为白色，初始的全反射率为73％，100℃-1000h的环境试验后的全反射率为72％。此外，初始的剥离强度为0.9N，60℃-90％RH-500小时的环境试验后的剥离强度为1.1N。此外，LED安装样品的初始的模头剪切强度为6.1N，60℃-90％RH-500小时的环境试验后的模头剪切强度为5.3N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为○，500个循环后的导通性评价为×，1000个循环后的导通性评价为×，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为○。因此，综合评价为×。
[比较例2]
使用重均分子量Mw为20万、丙烯酸(AA)的含量为0wt％并且甲基丙烯酸2-羟乙酯(HEMA)的含量为0wt％的丙烯酸类树脂(BA：15％、EA：65％、AN：20％、AA：0wt％、HEMA：0wt％、Mw：20万)，除此之外与实施例1同样制作各向异性导电粘接剂，得到LED安装样品。
表1示出比较例2的各项评价结果。各向异性导电粘接剂的颜色为白色，初始的全反射率为74％，100℃-1000h的环境试验后的全反射率为74％。此外，初始的剥离强度小于0.5N，60℃-90％RH-500小时的环境试验后的剥离强度小于0.5N。此外，LED安装样品的初始的模头剪切强度为4.5N，60℃-90％RH-500小时的环境试验后的模头剪切强度为3.9N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为○，500个循环后的导通性评价为×，1000个循环后的导通性评价为×，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为○。因此，综合评价为×。
[比较例3]
在由脂环式环氧化合物(品名：CELLOXIDE 2021P、Daicel Chemical Industries,Ltd.制造)50质量份、酸酐固化剂(甲基六氢邻苯二甲酸酐)40质量份、丙烯酸类树脂(BA：15％、EA：63％、AN：20％、AA：1wt％、HEMA：1wt％、Mw：70万)3质量份构成的粘接剂中，分散导电性颗粒(品名：AUL704、积水化学工业株式会社制造)10质量份，制得各向异性导电粘接剂。此外，LED安装样品的制作中的固化条件设定为230℃-1.5N-30秒。
表1示出比较例3的各项评价结果。各向异性导电粘接剂的颜色为白色，初始的全反射率为75％，100℃-1000h的环境试验后的全反射率为75％。此外，初始的剥离强度为1.6N，60℃-90％RH-500小时的环境试验后的剥离强度为1.3N。此外，LED安装样品的初始的模头剪切强度为7.2N，60℃-90％RH-500小时的环境试验后的模头剪切强度为6.3N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为×，500个循环后的导通性评价为×，1000个循环后的导通性评价为×，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为×。因此，综合评价为×。
[比较例4]
使用重均分子量Mw为20万、丙烯酸(AA)的含量为0wt％并且甲基丙烯酸2-羟乙酯(HEMA)的含量为0wt％的丙烯酸类树脂(BA：15％、EA：65％、AN：20％、AA：0wt％、HEMA：0wt％、Mw：20万)，除此之外与比较例3同样制作各向异性导电粘接剂，制得LED安装样品。
表1示出比较例4的各项评价结果。各向异性导电粘接剂的颜色为白色，初始的全反射率为77％，100℃-1000h的环境试验后的全反射率为77％。此外，初始的剥离强度小于0.5N，60℃-90％RH-500小时的环境试验后的剥离强度小于0.5N。此外，LED安装样品的初始的模头剪切强度为3.8N，60℃-90％RH-500小时的环境试验后的模头剪切强度为3.2N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为×、500个循环后的导通性评价为×，1000个循环后的导通性评价为×，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为×。因此，综合评价为×。
[比较例5]
使用环烯烃100质量份代替脂环式环氧化合物，除此之外与实施例1同样制作各向异性导电粘接剂，得到LED安装样品。此外，LED安装样品的制作中的固化条件设定为180℃-1.5N-240秒。
表1示出比较例5的各项评价结果。各向异性导电粘接剂的颜色为黄色，初始的全反射率为61％，100℃-1000h的环境试验后的全反射率为32％。此外，初始的剥离强度为1.2N，60℃-90％RH-500小时的环境试验后的剥离强度为1.4N。此外，LED安装样品的初始的模头剪切强度为7.2N，60℃-90％RH-500小时的环境试验后的模头剪切强度为6.5N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为×，500个循环后的导通性评价为×，1000个循环后的导通性评价为×，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为○。因此，综合评价为×。
[比较例6]
使用双酚F型环氧化合物代替脂环式环氧化合物，使用阴离子固化剂(胺类固化剂)代替潜伏性阳离子固化剂，未配混丙烯酸类树脂，除此之外与实施例1同样制作各向异性导电粘接剂，得到LED安装样品。此外，LED安装样品的制作中的固化条件设定为150℃-1.5N-30秒。
表1示出比较例6的各项评价结果。各向异性导电粘接剂的颜色为黄色，初始的全反射率为58％，100℃-1000h的环境试验后的全反射率为15％。此外，初始的剥离强度为1.4N，60℃-90％RH-500小时的环境试验后的剥离强度小于0.1N。此外，LED安装样品的初始的模头剪切强度为6.8N，60℃-90％RH-500小时的环境试验后的模头剪切强度为1.1N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为○，500个循环后的导通性评价为×，1000个循环后的导通性评价为×，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为×。因此，综合评价为×。
[比较例7]
配混丙烯酸类树脂(BA：15％、EA：63％、AN：20％、AA：1wt％、HEMA：1wt％、Mw：70万)3质量份，除此之外与比较例6同样制作各向异性导电粘接剂，制得LED安装样品。
表1示出比较例7的各项评价结果。各向异性导电粘接剂的颜色为黄色，初始的全反射率为53％，100℃-1000h的环境试验后的全反射率为11％。此外，初始的剥离强度为2.5N，60℃-90％RH-500小时的环境试验后的剥离强度小于0.1N。此外，LED安装样品的初始的模头剪切强度为7.1N，60℃-90％RH-500小时的环境试验后的模头剪切强度为0.4N。此外，LED安装样品的初始的导通性评价为○，冷热循环试验的100个循环后的导通性评价为○，500个循环后的导通性评价为○，1000个循环后的导通性评价为×，100℃-1000小时的环境试验后的导通性评价为○，并且60℃-90％RH-500小时的环境试验后的导通性评价为×。因此，综合评价为×。
[表1]
比较例1、2在丙烯酸类树脂中不含丙烯酸(AA)和甲基丙烯酸2-羟乙酯(HEMA)，因此对铝的粘接力低，导通可靠性也低。
此外，比较例3、4中，由于作为固化剂使用了酸酐，因此60℃-90％RH-500小时的环境试验后的导通可靠性低。此外，比较例3与比较例4的比较和比较例1、2与实施例的比较同样可知：使用具有AA、HEMA的丙烯酸类树脂的例子较好。
此外，比较例5中，由于作为主剂使用了环烯烃，因此反应慢，至固化为止较费时。此外，由于树脂自身的颜色、由双键导致的变色而未能保持白色。进而，导通可靠性也低。
比较例6、7中，通过胺类固化剂的极性效果而对铝具有粘接力，但不耐湿度，60℃-90％RH-500小时的环境试验后的导通可靠性低。此外，由于胺的变色导致白色度低。
另一方面，实施例1～5由于配混有脂环式环氧化合物、潜伏性阳离子固化剂以及具有丙烯酸(AA)和甲基丙烯酸2-羟乙酯(HEMA)的丙烯酸类树脂，因此具有光学用途的特性，进而，对于具有氧化膜的铝、ITO布线，成功获得了高的粘接力和优异的导通可靠性。
附图标记说明
11布线；12环氧化合物的海；13丙烯酸类树脂的岛；21基板；22布线图案；23发光元件；24n电极；25p电极；26凸块；30各向异性导电膜；50各向异性导电粘接剂；51布线基板；52LED芯片；53加热工具；54工具

Claims (8)

1.一种粘接剂，其含有阳离子催化剂、重均分子量为50000～900000的丙烯酸类树脂、以及脂环式环氧化合物或氢化环氧化合物，
所述丙烯酸类树脂包含0.5～10wt％的丙烯酸以及0.5～10wt％的具有羟基的丙烯酸酯，所述丙烯酸类树脂中的丙烯酸与所述环氧化合物反应，生成丙烯酸类树脂的岛与环氧化合物的海。
2.根据权利要求1所述的粘接剂，其中，所述丙烯酸类树脂的含量相对于所述环氧化合物100质量份为1～10质量份。
3.根据权利要求1或2所述的粘接剂，其中，所述具有羟基的丙烯酸酯为选自由甲基丙烯酸2-羟乙酯、甲基丙烯酸2-羟丙酯、丙烯酸2-羟乙酯、丙烯酸2-羟丙酯组成的组中的1种以上。
4.根据权利要求1或2所述的粘接剂，其中，所述丙烯酸类树脂含有选自丙烯酸丁酯、丙烯酸乙酯、丙烯腈中的1种以上。
5.根据权利要求1或2所述的粘接剂，其中，所述阳离子催化剂为铝螯合物类潜伏性固化剂。
6.根据权利要求1或2所述的粘接剂，其含有导电性颗粒。
7.一种发光装置，其具备：
具有由铝形成的布线图案的基板、
形成在所述布线图案的电极上的各向异性导电膜、以及
安装在所述各向异性导电膜上的发光元件，
所述各向异性导电膜为各向异性导电粘接剂的固化物，所述各向异性导电粘接剂含有阳离子催化剂、重均分子量为50000～900000的丙烯酸类树脂、导电性颗粒、以及脂环式环氧化合物或氢化环氧化合物，所述丙烯酸类树脂包含0.5～10wt％的丙烯酸和0.5～10wt％的具有羟基的丙烯酸酯，所述丙烯酸类树脂中的丙烯酸与所述环氧化合物反应，生成丙烯酸类树脂的岛与环氧化合物的海。
8.一种发光装置，其具备：
具有由透明导电膜形成的布线图案的透明基板、
形成在所述布线图案的电极上的各向异性导电膜、以及
安装在所述各向异性导电膜上的发光元件，
所述各向异性导电膜为各向异性导电粘接剂的固化物，所述各向异性导电粘接剂含有阳离子催化剂、重均分子量为50000～900000的丙烯酸类树脂、导电性颗粒、以及脂环式环氧化合物或氢化环氧化合物，所述丙烯酸类树脂包含0.5～10wt％的丙烯酸和0.5～10wt％的具有羟基的丙烯酸酯，所述丙烯酸类树脂中的丙烯酸与所述环氧化合物反应，生成丙烯酸类树脂的岛与环氧化合物的海。
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