JP2003026763A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JP2003026763A JP2003026763A JP2001213365A JP2001213365A JP2003026763A JP 2003026763 A JP2003026763 A JP 2003026763A JP 2001213365 A JP2001213365 A JP 2001213365A JP 2001213365 A JP2001213365 A JP 2001213365A JP 2003026763 A JP2003026763 A JP 2003026763A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- cured product
- acid anhydride
- anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- Sealing Material Composition (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Led Device Packages (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術】本発明は、特に青色や白色発光ダ
イオード等の発光ダイオード（以下「ＬＥＤ」と略記す
る）で代表される光電変換素子の封止材料に好適なエポ
キシ樹脂組成物に関する。TECHNICAL FIELD The present invention relates to an epoxy resin composition suitable as a sealing material for a photoelectric conversion element represented by a light emitting diode (hereinafter abbreviated as “LED”) such as a blue or white light emitting diode.
【０００２】[0002]
【従来の技術】従来、ＬＥＤ等の光電変換素子の封止材
料には、無色透明性や電気特性に優れることから酸無水
物硬化系のエポキシ樹脂が使用されている。かかる光電
変換素子に用いられるエポキシ樹脂の硬化剤として、低
粘度で無色透明性の良好なメチルテトラヒドロ無水フタ
ル酸、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フ
タル酸等の脂環式酸無水物が一般的に使用され、また、
かかるエポキシ樹脂として、ビスフェノールＡ型エポキ
シ樹脂、ビスフェノールＦ型エポキシ樹脂等の芳香族エ
ポキシ樹脂、３，４−エポキシシクロヘキシルメチル−
３’，４’−エポキシシクロヘキサンカルボキシレート
等の脂環式エポキシ樹脂が一般的に使用されている。2. Description of the Related Art Conventionally, an acid anhydride curing type epoxy resin has been used as a sealing material for a photoelectric conversion element such as an LED because it is excellent in colorless transparency and electric characteristics. As a curing agent for the epoxy resin used in such a photoelectric conversion element, an alicyclic acid anhydride such as methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, etc., which has a low viscosity and is colorless and transparent, is generally used. Used and also
Examples of such epoxy resin include aromatic epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, 3,4-epoxycyclohexylmethyl-
Alicyclic epoxy resins such as 3 ', 4'-epoxycyclohexanecarboxylate are commonly used.
【０００３】近年、高輝度の青色ＬＥＤや白色ＬＥＤが
開発され、掲示板、フルカラーディスプレーや携帯電話
のバックライト等にその用途を広げている。青色ＬＥＤ
や白色ＬＥＤは近紫外線領域の光を発光するため、通電
寿命を長くするためにかかる用途に使用する封止材とし
て耐紫外線性が良好なことが求められている。更に、こ
れらＬＥＤの発光エネルギーが強く、そのため発熱が高
いため、かかる用途の封止材料には耐熱性が要求され
る。より具体的には、ガラス転移温度（以下「Ｔｇ」と
略記する）が高く、かつ長時間の加熱条件下でも変色が
少ないことが要求される。In recent years, high-intensity blue LEDs and white LEDs have been developed, and their applications are expanding to bulletin boards, full-color displays, backlights of mobile phones, and the like. Blue LED
Since white LEDs emit light in the near-ultraviolet region, they are required to have good ultraviolet resistance as a sealing material used in such applications in order to prolong the energization life. Further, since the light emission energy of these LEDs is strong and therefore the heat generation is high, heat resistance is required for the sealing material for such applications. More specifically, it is required that the glass transition temperature (hereinafter abbreviated as “Tg”) is high and that discoloration is small even under a long-time heating condition.
【０００４】ビスフェノールＡ型エポキシ樹脂、ビスフ
ェノールＦ型エポキシ樹脂は、Ｔｇが高く、吸湿率が低
く、透明な硬化物が得られるが、芳香環を含むため耐紫
外線性が悪いという問題を抱えている。そのため、青色
ＬＥＤや白色ＬＥＤの封止材に使用するエポキシ樹脂と
しては、３，４−エポキシシクロヘキシルメチル−
３’，４’−エポキシシクロヘキサンカルボキシレート
等の脂環式エポキシ樹脂が検討されている。しかし、こ
れら脂環式エポキシ樹脂は、Ｔｇは高いものの硬化物が
脆くクラックが発生しやすく、吸湿率が高く加湿試験で
電気特性が低下するという問題を抱えている。The bisphenol A type epoxy resin and the bisphenol F type epoxy resin have a high Tg, a low moisture absorption rate, and a transparent cured product can be obtained, but they have a problem of poor ultraviolet resistance because they contain an aromatic ring. . Therefore, as an epoxy resin used as a sealing material for blue LEDs and white LEDs, 3,4-epoxycyclohexylmethyl-
Alicyclic epoxy resins such as 3 ', 4'-epoxycyclohexanecarboxylate have been investigated. However, although these alicyclic epoxy resins have a high Tg, they have a problem that the cured product is brittle and cracks easily occur, the hygroscopicity is high, and the electrical characteristics are deteriorated in the humidification test.
【０００５】耐紫外線性の良好なエポキシ樹脂として、
水素化ビスフェノールＡとエピクロルヒドリンを酸触媒
存在下、付加反応を行いクロルヒドリンエーテル体を得
て、次いで水酸化ナトリウム等のアルカリで閉環して得
られる水素化ビスフェノールＡジグリシジルエーテルが
提案され、このものは耐候性に優れることが知られてい
る（特開平６−１３６０９２号）。しかしながら、該方
法で得られる水素化ビスフェノールＡジグリシジルエー
テルは塩素含有不純物を多量に含み、しかも純度が５０
％程度と低いため、硬化物のＴｇが低く耐熱性に劣り、
長時間の加熱下で変色が大きく、吸湿率が高く、さらに
加湿試験で電気特性が低下するという問題がある。As an epoxy resin having good ultraviolet resistance,
A hydrogenated bisphenol A diglycidyl ether obtained by subjecting hydrogenated bisphenol A and epichlorohydrin to an addition reaction in the presence of an acid catalyst to obtain a chlorohydrin ether body and then ring-closing with an alkali such as sodium hydroxide is proposed. It is known that the product has excellent weather resistance (Japanese Patent Laid-Open No. 6-136092). However, the hydrogenated bisphenol A diglycidyl ether obtained by this method contains a large amount of chlorine-containing impurities and has a purity of 50%.
%, The cured product has a low Tg and poor heat resistance.
There is a problem that discoloration is large under heating for a long time, the moisture absorption rate is high, and the electrical characteristics are deteriorated in a humidification test.
【０００６】従って、青色ＬＥＤや白色ＬＥＤの封止樹
脂として信頼性の高い製品を得るためには、硬化物が無
色透明で、Ｔｇが高く、耐紫外線性が良好で、吸湿率が
低く、長時間加熱下での変色が少なく、耐クラック性の
良好なエポキシ樹脂組成物が求められている。Therefore, in order to obtain a highly reliable product as a sealing resin for blue LEDs and white LEDs, the cured product is colorless and transparent, has a high Tg, has good ultraviolet resistance, has a low moisture absorption rate, and has a long life. There is a demand for an epoxy resin composition which has little discoloration under heating for a long time and has good crack resistance.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、硬化
物が無色透明で、Ｔｇが高く、耐紫外線性が良好で、吸
湿率が低く、長時間加熱下での変色が少なく、耐クラッ
ク性が良好な青ＬＥＤ、白色ＬＥＤ等の光電変換素子の
封止材料として有用なエポキシ樹脂組成物を提供するこ
とにある。The object of the present invention is to provide a cured product which is colorless and transparent, has a high Tg, has good resistance to ultraviolet rays, has a low moisture absorption rate, has little discoloration under heating for a long time, and is resistant to cracking. An object of the present invention is to provide an epoxy resin composition which is useful as a sealing material for photoelectric conversion elements such as blue LEDs and white LEDs having good properties.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意検討を行った結果、エポキシ樹脂とし
て使用するビスフェノールＡジグリシジルエーテル（以
下「ＤＧＥＢＡ」と略記する。）の核水素化物中の特定
の不純物の量が、得られる硬化物の諸特性に影響を与え
ることを見いだした。より詳細には、エポキシ樹脂とし
て特定の不純物の量を一定量以下にしたＤＧＥＢＡの核
水素化物及び硬化剤として酸無水物硬化剤を配合するこ
とにより、得られる硬化物は無色透明で、Ｔｇが高く、
耐紫外線性が良好で、吸湿率が低く、長時間加熱下での
変色が少なく、耐クラック性が良好なエポキシ樹脂組成
物が得られることを見出し、かかる知見に基づいて本発
明を完成するに至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have made a core of bisphenol A diglycidyl ether (hereinafter abbreviated as "DGEBA") used as an epoxy resin. It has been found that the amount of specific impurities in the hydride affects the properties of the resulting cured product. More specifically, by blending a nuclear hydride of DGEBA in which the amount of specific impurities is equal to or less than a certain amount as an epoxy resin and an acid anhydride curing agent as a curing agent, the resulting cured product is colorless and transparent and has a Tg of high,
UV resistance is good, low moisture absorption rate, little discoloration under heating for a long time, it was found that an epoxy resin composition having good crack resistance can be obtained, and based on such findings, the present invention was completed. I arrived.
【０００９】即ち、本発明は、次に示すエポキシ樹脂を
提供するものである。That is, the present invention provides the following epoxy resins.
【００１０】項１ エポキシ樹脂（Ａ）、酸無水物硬化
剤（Ｂ）、及び硬化促進剤（Ｃ）を必須成分とするエポ
キシ樹脂組成物に於いて、（Ａ）成分がビスフェノール
Ａジグリシジルエーテルの核水素化物であり、ＧＰＣ分
析において式（１）で表される化合物の含有量が５％以
下、及び核水素化率９５％以上で、かつエポキシ当量２
１０以下であることを特徴とするエポキシ樹脂組成物。
Item 1 In an epoxy resin composition containing an epoxy resin (A), an acid anhydride curing agent (B), and a curing accelerator (C) as essential components, the component (A) is bisphenol A diglycidyl ether. Which is 5% or less in the content of the compound represented by the formula (1) in the GPC analysis, and has a nuclear hydrogenation rate of 95% or more, and an epoxy equivalent of 2
An epoxy resin composition which is 10 or less.
【００１１】項２ Ｂ成分が二重結合を含まない脂環式
酸無水物である上記項１に記載のエポキシ樹脂組成物。Item 2 The epoxy resin composition according to Item 1, wherein the component B is an alicyclic acid anhydride containing no double bond.
【００１２】項３ （Ｂ）成分がメチルノルボルナン−
２，３−ジカルボン酸無物とノルボルナン−２，３−ジ
カルボン酸無水物の液状混合物である上記項１又は２に
記載のエポキシ樹脂組成物。Item 3 (B) component is methylnorbornane-
Item 3. The epoxy resin composition according to Item 1 or 2, which is a liquid mixture of 2,3-dicarboxylic acid-free and norbornane-2,3-dicarboxylic anhydride.
【００１３】項４ 請求項１〜３記載のエポキシ樹脂
組成物からなる光電変換素子封止材料。Item 4 A photoelectric conversion element encapsulating material comprising the epoxy resin composition according to any one of items 1 to 3.
【００１４】[0014]
【発明の実施の形態】（Ａ）成分：エポキシ樹脂
ＤＧＥＢＡの核水素化の際、通常不純物として式（１）
で表される化合物（以下「当該化合物」と略記する。）
が副成するが、例えば、下記の特願平２０００−２８７
２３８号記載の製造方法によりその含有量が５％以下の
（Ａ）成分のエポキシ樹脂を容易に得ることができる。
かくして得られた本発明に係る（Ａ）成分のエポキシ樹
脂は当該化合物の含有量が５％以下、及び核水素化率９
５％以上で、かつエポキシ当量２１０以下のＤＧＥＢＡ
の核水素化物（以下「当該エポキシ樹脂」と略記する）
である。当該エポキシ樹脂中に含まれる当該化合物の含
有量は５％以下で、好ましくは２％以下である。５％を
越えると、Ｔｇが低下するため好ましくない。ここで、
当該化合物の含有量は、ゲルパーミィエーションクロマ
トグラフ分析（以下「ＧＰＣ分析」と略記する。）にお
ける式（１）で表される化合物のピーク面積％を表す。BEST MODE FOR CARRYING OUT THE INVENTION (A) Component: In the nuclear hydrogenation of epoxy resin DGEBA, the compound represented by the formula (1)
A compound represented by (hereinafter abbreviated as “the compound”)
The following Japanese Patent Application No. 2000-287
By the manufacturing method described in No. 238, the epoxy resin of the component (A) having a content of 5% or less can be easily obtained.
The epoxy resin of the component (A) according to the present invention thus obtained has a content of the compound of 5% or less and a nuclear hydrogenation rate of 9
DGEBA with 5% or more and an epoxy equivalent of 210 or less
Nuclear hydride (hereinafter abbreviated as “the epoxy resin”)
Is. The content of the compound contained in the epoxy resin is 5% or less, preferably 2% or less. If it exceeds 5%, Tg is lowered, which is not preferable. here,
The content of the compound represents the peak area% of the compound represented by the formula (1) in gel permeation chromatography analysis (hereinafter abbreviated as “GPC analysis”).
【００１５】さらに、核水素化率は９５％以上である。
核水素化率が９５％未満では耐紫外線性が低下し好まし
くない。更に、エポキシ当量は２１０以下である。エポ
キシ当量が２１０を越えるとＴｇが低下し、長時間加熱
時の変色が大きくなり好ましくない。更に、一般式
（２）
［式中、ｎは０又は１を表す。］で表される当該エポキ
シ樹脂の純度は、ｎ＝０とｎ＝１の合計値で８０％以上
であることが好ましい。８０％未満の場合はＴｇが低下
し好ましくない。かかるエポキシ樹脂の純度は、ＧＰＣ
分析で得られるｎ＝０及びｎ＝１に由来するピークの面
積％の合計値を示す。Further, the nuclear hydrogenation rate is 95% or more.
If the nuclear hydrogenation rate is less than 95%, the ultraviolet resistance is lowered, which is not preferable. Furthermore, the epoxy equivalent is 210 or less. When the epoxy equivalent exceeds 210, Tg is lowered and discoloration becomes large when heated for a long time, which is not preferable. Furthermore, the general formula (2) [In the formula, n represents 0 or 1. ] The purity of the epoxy resin represented by the above is preferably 80% or more in the total value of n = 0 and n = 1. If it is less than 80%, Tg is lowered, which is not preferable. The purity of such epoxy resin is GPC
The total value of the area% of the peak derived from n = 0 and n = 1 obtained by the analysis is shown.
【００１６】当該エポキシ樹脂は、ＤＧＥＢＡの核水素
化物であり、核水素化の方法は特に制限されるものでは
なく、例えば本発明者らが提案したロジウム及び／又は
ルテニウム触媒を使用し、特定のエーテル基含有アルコ
ールの存在下、１〜２０ＭＰａの水素圧下、３０〜１０
０℃で核水素化することにより製造することができる。
（特願２０００−２８７２３８号）。The epoxy resin is a nuclear hydride of DGEBA, and the nuclear hydrogenation method is not particularly limited. For example, a rhodium and / or ruthenium catalyst proposed by the present inventors is used, and 30 to 10 under hydrogen pressure of 1 to 20 MPa in the presence of ether group-containing alcohol
It can be produced by nuclear hydrogenation at 0 ° C.
(Japanese Patent Application No. 2000-287238).
【００１７】本発明に係る（Ａ）成分のエポキシ樹脂に
は、本発明の効果を損なわない範囲で他のエポキシ樹脂
を混合して使用できる。混合して使用できるエポキシ樹
脂としては、例えば、ビスフェノールＡ型エポキシ樹
脂、ビスフェノールＦ型エポキシ樹脂、クレゾールノボ
ラック型エポキシ樹脂、フェノールノボラック型エポキ
シ樹脂、ビフェニル型エポキシ樹脂、スチルベン型エポ
キシ樹脂、ハイドロキノン型エポキシ樹脂、ナフタレン
骨格型エポキシ樹脂、テトラフェニロールエタン型エポ
キシ樹脂、ＤＰＰ型エポキシ樹脂、トリスヒドロキシフ
ェニルメタン型エポキシ樹脂、ジシクロペンタジェンフ
ェノール型エポキシ樹脂、３，４−エポキシシクロヘキ
シルメチル−３’，４’−エポキシシクロヘキサンカル
ボキシレートやビニルシクロヘキセンジエポキサイド等
の脂環式エポキシ樹脂、ビスフェノールＡエチレンオキ
サイド付加物のジグリシジルエーテル、ビスフェノール
Ａプロピレンオキサイド付加物のジグリシジルエーテ
ル、シクロヘキサンジメタノールジグリシジルエーテ
ル、脂肪族多価アルコールのポリグリシジルエーテル、
ヘキサヒドロ無水フタル酸のジグリシジルエステル等の
多塩基酸のポリグリシジルエステル、ブチルグリシジル
エーテル、ラウリルグリシジルエーテル等のアルキルグ
リシジルエーテル、フェニルグリシジルエーテル、クレ
ジルグリシジルエーテル等のエポキシ基を１個もったグ
リシジルエーテル等が挙げられる。これらの化合物は単
独で又は２種以上を適宜混合して使用することができ
る。The epoxy resin of the component (A) according to the present invention may be mixed with other epoxy resins within a range not impairing the effects of the present invention. Examples of the epoxy resin that can be mixed and used include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin. , Naphthalene skeleton type epoxy resin, tetraphenylolethane type epoxy resin, DPP type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, 3,4-epoxycyclohexylmethyl-3 ′, 4 ′ -Alicyclic epoxy resins such as epoxycyclohexanecarboxylate and vinylcyclohexene diepoxide, diglycidyl ether of bisphenol A ethylene oxide adduct, bisphenol Diglycidyl ethers of Nord A propylene oxide adduct, cyclohexane dimethanol diglycidyl ether, aliphatic polyhydric alcohol polyglycidyl ether,
Hexahydrophthalic anhydride polyglycidyl ester such as diglycidyl ester, alkyl glycidyl ether such as butyl glycidyl ether, lauryl glycidyl ether, glycidyl ether having phenyl glycidyl ether, cresyl glycidyl ether, etc. Etc. These compounds may be used alone or in admixture of two or more.
【００１８】これらの中でも、３，４−エポキシシクロ
ヘキシルメチル−３’，４’−シクロヘキサンカルボキ
シレート等の脂環式エポキシ樹脂、シクロヘキサンジメ
タノールジグリシジルエーテル、ヘキサヒドロ無水フタ
ル酸ジグリシジルエステル等の飽和多塩基酸のポリグリ
シジルエステル、脂肪族多価アルコールのポリグリシジ
ルエーテル、アルキルグリシジルエーテル等の二重結合
を有しないエポキシ樹脂が耐紫外線性を損なうことがな
い為より好ましい。Of these, alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3 ', 4'-cyclohexanecarboxylate, cyclohexanedimethanol diglycidyl ether, and saturated polyhydric acid such as hexahydrophthalic anhydride diglycidyl ester. Epoxy resins having no double bond, such as polyglycidyl esters of basic acids, polyglycidyl ethers of aliphatic polyhydric alcohols, and alkyl glycidyl ethers, are more preferable because they do not impair UV resistance.
【００１９】（Ｂ）成分：酸無水物硬化剤
本発明に係る（Ｂ）成分の酸無水物硬化剤として具体的
には、ヘキサヒドロ無水フタル酸、３−メチルヘキサヒ
ドロ無水フタル酸、４−メチルヘキサヒドロ無水フタル
酸、メチルノルボルナン−２，３−ジカルボン酸無水
物、ノルボルナン−２，３−ジカルボン酸無水物、無水
フタル酸、テトラヒドロ無水フタル酸、３−メチルテト
ラヒドロ無水フタル酸、４−メチルテトラヒドロ無水フ
タル酸、無水メチルナジック酸、ドデセニル無水コハク
酸、α−テルピネンやアロオシメン等のデカトリエンと
無水マレイン酸とのディールス・アルダー反応物及びそ
れらの水素添加物、構造異性体若しくは幾何異性体をは
じめ、それらの混合物や変性物が例示される。中でもこ
れら酸無水物の構造異性化、幾何異性化、２種以上の混
合等の方法により常温で液状とした酸無水物硬化剤が好
ましい。また、必要に応じてピロメリット酸二無水物、
ベンゾフェノンテトラカルボン酸二無水物、エチレング
リコールビスアンヒドロトリメリテート、トリアセチン
と無水トリメリット酸の脱酢酸縮合物やこれら化合物の
水素添加物等の常温で固体の多官能酸無水物を本発明の
効果を損なわない範囲の量で混合使用することができ
る。 Component (B): Acid Anhydride Curing Agent Specific examples of the acid anhydride curing agent of the component (B) according to the present invention include hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride and 4-methyl. Hexahydrophthalic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydro Phthalic anhydride, methyl nadic acid anhydride, dodecenyl succinic anhydride, Diels-Alder reaction product of decatrienes such as α-terpinene and alloocimene and maleic anhydride and hydrogenated products thereof, including structural isomers or geometric isomers, Examples thereof include mixtures and modified products. Among these, acid anhydride curing agents that are liquid at room temperature by a method such as structural isomerization, geometric isomerization of these acid anhydrides, or a mixture of two or more thereof are preferable. If necessary, pyromellitic dianhydride,
Benzophenone tetracarboxylic acid dianhydride, ethylene glycol bisanhydrotrimellitate, deacetic acid condensate of triacetin and trimellitic anhydride, hydrogenated products of these compounds, etc. It can be mixed and used in an amount that does not impair the effect.
【００２０】上記の脂環式化合物の中でも、Ｔｇが高
く、且つ耐紫外線性を損なわないためには、二重結合を
有しない脂環式酸無水物がより好ましい。かかる二重結
合を有しない脂環式酸無水物としては、具体的には、ヘ
キサヒドロ無水フタル酸、３−メチルヘキサヒドロ無水
フタル酸、４−メチルヘキサヒドロ無水フタル酸、メチ
ルノルボルナン−２，３−ジカルボン酸無水物、ノルボ
ルナン−２，３−ジカルボン酸無水物、α−テルピネン
やアロオシメン等のデカトリエンと無水マレイン酸との
ディールス・アルダー反応物の水素添加物や、これら酸
無水物の構造異性体若しくは幾何異性体をはじめ、それ
らの混合物や変性物が例示される。特に、メチルノルボ
ルナン−２，３−ジカルボン酸無水物とノルボルナン−
２，３−ジカルボン酸無水物の液状混合物が、Ｔｇが高
く、硬化物吸湿率が低い点で好ましい。Among the above-mentioned alicyclic compounds, alicyclic acid anhydrides having no double bond are more preferable because they have a high Tg and do not impair UV resistance. Specific examples of the alicyclic acid anhydride having no double bond include hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and methylnorbornane-2,3. -Dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, hydrogenated product of Diels-Alder reaction of maleic anhydride with decatriene such as α-terpinene and alloocimene, and structural isomers of these acid anhydrides Alternatively, examples thereof include geometric isomers and mixtures and modified products thereof. In particular, methylnorbornane-2,3-dicarboxylic anhydride and norbornane-
A liquid mixture of 2,3-dicarboxylic acid anhydride is preferable because it has a high Tg and a low moisture absorption rate of the cured product.
【００２１】かかる（Ｂ）成分の配合量は、所定の効果
が得られる限り特に限定されるものではないが、通常、
エポキシ基１モルに対する酸無水物基の当量比が０．７
〜１．５、好ましくは０．８〜１．３程度である。当量
比が０．７未満又は１．５を越える場合は、硬化物のＴ
ｇが低下し、耐湿性が低下し、無色透明性や長期間加熱
下での変色が大きくなるため好ましくない。特に、無色
透明性を重視し、長時間加熱下での変色を少なくする為
には、ヘキサヒドロ無水フタル酸、３−メチルヘキサヒ
ドロ無水フタル酸、４−メチルヘキサヒドロ無水フタル
酸やこの混合物の場合は当量比１．０〜１．３が更に好
ましく、メチルノルボルナン−２，３−ジカルボン酸無
水物、ノルボルナン−２，３−ジカルボン酸無水物及び
これらの混合物の場合は０．７〜１．０が更に好まし
い。The blending amount of the component (B) is not particularly limited as long as a predetermined effect is obtained, but it is usually
The equivalent ratio of acid anhydride groups to 1 mol of epoxy groups is 0.7
Is about 1.5, preferably about 0.8 to 1.3. When the equivalent ratio is less than 0.7 or exceeds 1.5, T of the cured product
It is not preferable because the g is lowered, the moisture resistance is lowered, and the transparency and the discoloration under heating for a long time become large. In particular, in the case of hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, or a mixture of these, in order to reduce discoloration under heating for a long time, with emphasis on colorless transparency. Is more preferably 1.0 to 1.3, and 0.7 to 1.0 in the case of methylnorbornane-2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride and a mixture thereof. Is more preferable.
【００２２】（Ｃ）成分：硬化促進剤
（Ｃ）成分の硬化促進剤としては特に限定されるもので
はないが、例えば、ベンジルジメチルアミン、トリス
（ジメチルアミノメチル）フェノール、ジメチルシクロ
ヘキシルアミン等の３級アミン類、１−シアノエチル−
２−エチル−４−メチルイミダゾール、２−エチル−４
−メチルイミダゾール、１−ベンジル−２−メチルイミ
ダゾール等のイミダゾール類、トリフェニルホスフィ
ン、亜リン酸トリフェニル等の有機リン系化合物、テト
ラフェニルホスホニウムブロマイド、テトラ−ｎ−ブチ
ルホスホニウムブロマイド等の４級ホスホニウム塩類、
１，８−ジアザビシクロ［５．４．０］ウンデセン−７
等やその有機酸塩等のジアザビシクロアルケン類、オク
チル酸亜鉛、オクチル酸錫やアルミニウムアセチルアセ
トン錯体等の有機金属化合物類、テトラエチルアンモニ
ウムブロマイド、テトラブチルアンモニウムブロマイド
等の４級アンモニウム塩類、三ふっ化ホウ素、トリフェ
ニルボレート等のホウ素化合物、塩化亜鉛、塩化第二錫
等の金属ハロゲン化物が挙げられる。更には、高融点イ
ミダゾール化合物、ジシアンジアミド、アミンをエポキ
シ樹脂等に付加したアミン付加型促進剤等の高融点分散
型潜在性促進剤、イミダゾール系、リン系、ホスフィン
系促進剤の表面をポリマーで被覆したマイクロカプセル
型潜在性促進剤、アミン塩型潜在性硬化促進剤、ルイス
酸塩、ブレンステッド酸塩等の高温解離型の熱カチオン
重合型の潜在性硬化促進剤等に代表される潜在性硬化促
進剤も使用することができる。これらの硬化促進剤は単
独又は２種以上を混合して使用することができる。 Component (C): Curing Accelerator The curing accelerator for the component (C) is not particularly limited, but examples thereof include 3 such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, and dimethylcyclohexylamine. Primary amines, 1-cyanoethyl-
2-Ethyl-4-methylimidazole, 2-ethyl-4
-Imidazoles such as methyl imidazole and 1-benzyl-2-methyl imidazole, organic phosphorus compounds such as triphenylphosphine and triphenyl phosphite, quaternary phosphonium such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide salts,
1,8-diazabicyclo [5.4.0] undecene-7
Etc. and their organic acid salts and other diazabicycloalkenes, zinc octylate, organometallic compounds such as tin octylate and aluminum acetylacetone complex, quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide, trifluoride Examples thereof include boron compounds such as boron and triphenylborate, and metal halides such as zinc chloride and stannic chloride. Furthermore, high melting point imidazole compounds, dicyandiamide, high melting point dispersion type latent accelerators such as amine addition type accelerators in which amines are added to epoxy resins, imidazole type, phosphorus type and phosphine type accelerators are coated with a polymer surface. Curing represented by microcapsule type latent accelerators, amine salt type latent curing accelerators, high temperature dissociative thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts Accelerators can also be used. These curing accelerators can be used alone or in combination of two or more.
【００２３】これらの硬化促進剤の中でも、４級ホスホ
ニウム塩類、ジアザビシクロアルケン類、有機金属化合
物類、４級アンモニウム塩類が、無色透明性で長時間加
熱での変色が少ない硬化物が得られる点で好ましい。Among these curing accelerators, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds and quaternary ammonium salts are colorless and transparent, and a cured product with little discoloration upon heating for a long time can be obtained. It is preferable in terms.
【００２４】かかる（Ｃ）成分の配合量は、Ａ成分のエ
ポキシ樹脂１００重量部に対して、０．１〜６重量部用
いるのが好ましく、より好ましくは０．３〜４重量部で
ある。配合量が０．１重量部未満であると硬化速度が低
下し、６重量％を越えると色相が悪化し、さらにＴｇや
機械的強度が低下するため好ましくない。The content of the component (C) is preferably 0.1 to 6 parts by weight, more preferably 0.3 to 4 parts by weight, based on 100 parts by weight of the epoxy resin of the component A. If the blending amount is less than 0.1 part by weight, the curing rate will be lowered, and if it exceeds 6% by weight, the hue will be deteriorated and Tg and mechanical strength will be lowered, which is not preferable.
【００２５】本発明では、酸無水物硬化剤以外の硬化剤
として、この分野で知られているものはいずれも使用で
きるが、一般的には、フェノール系硬化剤、ジシアンジ
アミド類、アジピン酸有機ヒドラジッド及びフタル酸ヒ
ドラジッド等の有機酸ヒドラジッド類等を得られる硬化
剤の特性を損なわない範囲で使用することもできる。In the present invention, as the curing agent other than the acid anhydride curing agent, any one known in this field can be used, but generally, a phenol type curing agent, dicyandiamides, adipic acid organic hydrazide are generally used. It is also possible to use organic acid hydrazides such as phthalic acid hydrazide and the like within a range that does not impair the properties of the curing agent that can be obtained.
【００２６】エポキシ樹脂組成物
本発明に係る液状エポキシ樹脂組成物には、必要に応じ
て、エチレングリコール、プロピレングリコール等脂肪
族ポリオール、脂肪族又は芳香族カルボン酸化合物、フ
ェノール化合物等の炭酸ガス発生防止剤、ポリアルキレ
ングリコール等の可撓性付与剤、酸化防止剤、可塑剤、
滑剤、シラン系等のカップリング剤、無機充填剤の表面
処理剤、難燃剤、帯電防止剤、着色剤、帯電防止剤、レ
ベリング剤、イオントラップ剤、摺動性改良剤、各種ゴ
ム、有機ポリマービーズ等の耐衝撃性改良剤、揺変性付
与剤、界面活性剤、表面張力低下剤、消泡剤、沈降防止
剤、光拡散剤、紫外線吸収剤、抗酸化剤、離型剤、蛍光
剤、導電性充填剤等の添加剤を得られる硬化剤の特性を
損なわない範囲で配合することができる。 Epoxy Resin Composition In the liquid epoxy resin composition of the present invention, if necessary, carbon dioxide gas such as aliphatic polyols such as ethylene glycol and propylene glycol, aliphatic or aromatic carboxylic acid compounds, and phenol compounds are generated. Antioxidant, flexibility-imparting agent such as polyalkylene glycol, antioxidant, plasticizer,
Lubricants, coupling agents such as silanes, surface treatment agents for inorganic fillers, flame retardants, antistatic agents, colorants, antistatic agents, leveling agents, ion trap agents, slidability improvers, various rubbers, organic polymers Impact resistance improver such as beads, thixotropic agent, surfactant, surface tension lowering agent, antifoaming agent, anti-settling agent, light diffusing agent, ultraviolet absorber, antioxidant, release agent, fluorescent agent, Additives such as electrically conductive fillers can be added within a range that does not impair the properties of the curing agent.
【００２７】本発明に係る液状エポキシ樹脂組成物を製
造する方法に特に制限はなく、従来公知の方法、例え
ば、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び必要に
応じて上記記載の添加剤を配合し、従来公知の方法で混
合することにより製造することができる。また、（Ａ）
成分のエポキシ樹脂を主成分とするエポキシ樹脂液と、
（Ｂ）成分及び（Ｃ）成分を主成分とする硬化剤液の２
液を調製しておき、使用前にエポキシ樹脂液と硬化剤液
を混合して液状エポキシ樹脂組成物を製造することもで
きる。さらに、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、
及び必要に応じて上記記載の添加剤を全て混合して、１
液の形態として液状エポキシ樹脂組成物を製造すること
もできる。The method for producing the liquid epoxy resin composition according to the present invention is not particularly limited, and it is a conventionally known method, for example, the component (A), the component (B), the component (C) and, if necessary, the above. It can be produced by mixing the additives described above and mixing them by a conventionally known method. Also, (A)
Epoxy resin liquid whose main component is epoxy resin,
2 of the curing agent liquid containing the component (B) and the component (C) as main components
It is also possible to prepare a liquid and mix the epoxy resin liquid and the curing agent liquid before use to produce a liquid epoxy resin composition. Furthermore, (A) component, (B) component, (C) component,
And, if necessary, mixing all the above-mentioned additives,
It is also possible to produce a liquid epoxy resin composition in the form of a liquid.
【００２８】液状エポキシ樹脂組成物の塗布、ポッティ
ング又は含浸の方法としては、特に制限はなく、ディス
ペンサーによる塗布又はポッティング、真空又は常圧ス
クリーン印刷による塗布、リアクションインジェクショ
ンモールディング等、従来公知の方法を採用することが
できる。The method of coating, potting or impregnating the liquid epoxy resin composition is not particularly limited, and conventionally known methods such as coating by a dispenser or potting, coating by vacuum or atmospheric pressure screen printing, reaction injection molding and the like are adopted. can do.
【００２９】液状エポキシ樹脂組成物の硬化方法には、
特に制限はなく、密閉式硬化炉や連続硬化が可能なトン
ネル炉等の従来公知の硬化装置を採用することができ
る。加熱源は特に制約されることなく、熱風循環、赤外
線加熱、高周波加熱等、従来公知の方法で行うことがで
きる。硬化温度及び硬化時間は、８０℃〜２５０℃で３
０秒〜１５時間の範囲が好ましい。硬化物の内部応力を
低減したい場合は、８０〜１２０℃、０．５時間〜５時
間の条件で前硬化した後、１２０〜１８０℃、０．１時
間〜１５時間の条件で後硬化することが好ましく、短時
間硬化を目的とする場合は１５０〜２５０℃、３０秒〜
３０分の条件で硬化することが好ましい。The method for curing the liquid epoxy resin composition includes
There is no particular limitation, and a conventionally known curing device such as a closed curing furnace or a tunnel furnace capable of continuous curing can be adopted. The heating source is not particularly limited, and it can be performed by a conventionally known method such as hot air circulation, infrared heating, and high frequency heating. The curing temperature and the curing time are 3 at 80 ° C to 250 ° C.
The range of 0 seconds to 15 hours is preferable. When it is desired to reduce the internal stress of the cured product, pre-cure under the conditions of 80 to 120 ° C. for 0.5 hours to 5 hours, and then post cure under the conditions of 120 to 180 ° C. for 0.1 hours to 15 hours. Is preferred, and for the purpose of short-time curing, 150 to 250 ° C., 30 seconds to
It is preferable to cure under the condition of 30 minutes.
【００３０】かくして得られた本発明のエポキシ樹脂組
成物は、その硬化物が無色透明で、Ｔｇが高く、耐紫外
線性が良好で、吸湿率が低く、長時間加熱下での変色が
少なく、耐クラック性が良好であるため、青色ＬＥＤ、
白色ＬＥＤの封止材等のエポキシ樹脂組成物として用い
ることができる。The thus obtained epoxy resin composition of the present invention has a cured product which is colorless and transparent, has a high Tg, has a good resistance to ultraviolet rays, has a low moisture absorption rate, and has little discoloration under heating for a long time. Due to good crack resistance, blue LED,
It can be used as an epoxy resin composition such as a white LED sealing material.
【００３１】本発明のエポキシ樹脂組成物は前記用途に
限定されるものではなく、その他のＬＥＤ、半導体レー
ザー等の発光素子、光導電素子、ホトダイオード、太陽
電池、ホトトランジスタ、ホトサイリスタ等の受光素
子、ホトカプラー、ホトインタラプター等の光結合素子
で代表される光電変換素子の絶縁封止材料、液晶等の接
着剤、光造形用の樹脂、更にプラスティック、ガラス、
金属等の表面コーティング剤、装飾材料等の透明性を要
求される用途にも用いることができる。The epoxy resin composition of the present invention is not limited to the above-mentioned applications, but other light emitting devices such as LEDs and semiconductor lasers, photoconductive devices, photodiodes, solar cells, phototransistors, photothyristors and the like. , Photo-coupler, photo-interrupter, etc. Photoelectric conversion device typified by insulating sealing material, liquid crystal and other adhesives, stereolithography resin, further plastic, glass,
It can also be used for applications requiring transparency such as surface coating agents such as metals and decorative materials.
【００３２】[0032]
【実施例】以下に、実施例及び比較例を挙げて本発明を
詳細に説明する。尚、エポキシ樹脂のＧＰＣ分析及び各
例で得られるエポキシ樹脂硬化物の物性は、次の方法に
より測定し評価した。EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. The GPC analysis of the epoxy resin and the physical properties of the cured epoxy resin obtained in each example were measured and evaluated by the following methods.
【００３３】エポキシ樹脂のＧＰＣ分析
ＧＰＣ分析は、島津製作所製ＬＣ−６Ａ（商品名）装置
を用いて、下記の条件で測定した。下記の製造例におい
て、式（１）で表される含有量及び一般式（２）（ｎ＝
０又はｎ＝１）で表さる化合物の純度は、それぞれＧＰ
Ｃ分析の結果得られるピークの面積％を表す（ただし、
上記の純度はｎ＝０及びｎ＝１の合計値）。
カラム：Ｓｈｉｍａｚｕ Ｓｈｉｍ−Ｐａｃｋ８０Ｍ
（内径８ｍｍ×長さ３０ｃｍ）＋ＴＯＳＯＨ ＴＳＫｇ
ｅｌ Ｇ２０００ＨＸＬ （内径７．８ｍｍ×長さ３０
ｃｍ）＋ＴＯＳＯＨ ＴＳＫｇｅｌ Ｇ１０００ＨＸＬ
（内径７．８ｍｍ×長さ３０ｃｍ）×３
流速：１．０ｍｌ／ｍｉｎ
温度：４０℃
検出器：ＲＩ GPC Analysis of Epoxy Resin GPC analysis was carried out by using an LC-6A (trade name) device manufactured by Shimadzu Corporation under the following conditions. In the following production examples, the content represented by the formula (1) and the general formula (2) (n =
The purity of the compound represented by 0 or n = 1) is GP
Represents the area% of the peak obtained as a result of C analysis (however,
The above-mentioned purity is the sum of n = 0 and n = 1). Column: Shimazu Shim-Pack80M
(Inner diameter 8 mm x length 30 cm) + TOSOH TSKg
el G2000H XL (inner diameter 7.8mm x length 30
cm) + TOSOH TSKgel G1000H XL
(Inner diameter 7.8 mm x length 30 cm) x 3 Flow rate: 1.0 ml / min Temperature: 40 ° C Detector: RI
【００３４】硬化物Ｔｇ
試料となるエポキシ樹脂組成物を内径６ｍｍのプラステ
ィック試験管に厚みが７ｍｍになるように流し込み、所
定条件で硬化して得た硬化物のガラス転移温度（Ｔｇ）
を、ＡＳＴＭ Ｄ３４１８−８２に記載の方法に従いＤ
ＳＣ法により測定した。硬化物Ｔｇが高い程、耐熱性が
優れることを示す。 Cured product Tg A glass transition temperature (Tg) of a cured product obtained by pouring an epoxy resin composition as a sample into a plastic test tube having an inner diameter of 6 mm so as to have a thickness of 7 mm and curing the composition under predetermined conditions.
According to the method described in ASTM D3418-82.
It was measured by the SC method. The higher the cured product Tg, the better the heat resistance.
【００３５】硬化物外観
試料となる液状エポキシ樹脂組成物を、ハードクロムメ
ッキした鋼板２枚で５ｍｍのスペーサーを挟み込んだ中
に流し込み、所定条件で硬化し、得られた２ｃｍ×４ｃ
ｍ×厚さ５ｍｍの硬化物の外観を目視にて観察した。 Appearance of cured product The liquid epoxy resin composition used as a sample was poured into two hard chrome-plated steel plates with a 5 mm spacer sandwiched therebetween and cured under predetermined conditions to obtain 2 cm × 4 c.
The appearance of the cured product of m × 5 mm in thickness was visually observed.
【００３６】加熱時変色性
硬化物外観の測定で使用した硬化物試料を１５０℃空気
オーブン中で１日間保持した後、紫外分光光度計で波長
４００ｎｍの光線透過率（％）を厚さ方向で測定した。
光線透過率が高いほど変色が少ないことを示す。The cured product sample used for the measurement of the appearance of the color-changed product upon heating was kept in an air oven at 150 ° C. for 1 day, and then the light transmittance (%) at a wavelength of 400 nm was measured with an ultraviolet spectrophotometer in the thickness direction. It was measured.
Higher light transmittance indicates less discoloration.
【００３７】耐紫外線性
硬化物外観の測定で使用した硬化物試料を、ウエザオメ
ーターＣｉ３５（ＡＴＲＡＳ社製）を用いキセノンバー
ナー（０．３９ｗ／ｍ２（ａｔ ３４０ｎｍ））を使用
して、ブラックパネル温度６３℃で３００時間暴露した
ものの黄変度を目視で観察した。変色のないものを○で
示し、黄変するものを×で示した。 UV resistance The cured product sample used for the measurement of the appearance of the cured product was blackened using a weather oximeter Ci35 (manufactured by ATRAS) using a xenon burner (0.39 w / m 2 (at 340 nm)). The degree of yellowing was visually observed after exposure for 300 hours at a panel temperature of 63 ° C. Those with no discoloration are shown with a circle, and those with yellowing are shown with a cross.
【００３８】硬化物吸湿率
試料となるエポキシ樹脂組成物を内径７０ｍｍの金属性
の皿に３ｍｍの厚みになるように入れ、所定条件で硬化
し、硬化物を得た。得られた硬化物をプレッシャー試験
機に入れ、１００℃、相対湿度１００％、２４時間の条
件で加湿試験を行ったあと、吸湿率として重量増加率
（重量％、（吸湿後の重量−吸湿前の重量）／吸湿前の
重量×１００）を測定した。吸湿率が低いほど硬化物の
耐湿性が良好であることを示す。Moisture Absorption of Cured Product The epoxy resin composition as a sample was placed in a metal dish having an inner diameter of 70 mm so as to have a thickness of 3 mm and cured under predetermined conditions to obtain a cured product. The obtained cured product was put into a pressure tester and subjected to a humidification test under the conditions of 100 ° C., relative humidity of 100% and 24 hours, and then, as a moisture absorption rate, a weight increase rate (weight%, (weight after moisture absorption−before moisture absorption Weight) / weight before moisture absorption × 100) was measured. The lower the moisture absorption rate, the better the moisture resistance of the cured product.
【００３９】耐クラック性
内径１８ｍｍφのポリプロピレン製試験管の中央にメー
トルネジ（内径６ｍｍ、７０ｍｍ長、２００ＰＣＳ）を
入れ、この中に試料となるエポキシ樹脂組成物１０ｇを
流し込み、所定条件で硬化して、メートルネジを埋め込
んだ硬化物試料を作成する。この硬化物試料を−５５℃
のドライアイスメタノール溶液中に入れて、クラックの
有無を観察する。７本の試験を実施し、３本以上でクラ
ックの発生した場合に×で示し、そうでない場合を○で
示した。 Crack resistance A metric screw (inner diameter 6 mm, 70 mm length, 200 PCS) is placed in the center of a polypropylene test tube having an inner diameter of 18 mmφ, 10 g of an epoxy resin composition as a sample is poured into this, and cured under predetermined conditions. Create a cured product sample with embedded metric screws. This cured product sample is -55 ° C.
Put it in the dry ice methanol solution of and observe for cracks. Seven tests were conducted, and when three or more cracks were generated, it was indicated by x, and when not, it was indicated by o.
【００４０】製造例１
電磁攪拌機を備えた５００ｍｌのステンレス製オ−トク
レ−ブにビスフェノ−ルＡジグリシジルエ−テル（「エ
ポトートＹＤ−８１２５」（商品名）、エポキシ当量１
７２、東都化成社製）４０ｇ、プロピレングリコールモ
ノメチルエーテル１２０ｇ及び市販の５％Ｒｕ−Ｃ触媒
（エヌ・イーケムキャット社製）０．４ｇを仕込み、系
内を水素で置換した後、攪拌しながら５０℃、水素圧２
０ＭＰａの条件下で５時間水素化を行った。反応後、触
媒を濾別し、１５０℃で２６６Ｐａにて溶媒を留去して
水素化ビスフェノールＡジグリシジルエーテルを得た
（「エポキシ樹脂Ａ」と略記する）。エポキシ樹脂Ａ
は、核水素化率９９．８％、エポキシ当量１８６であっ
た。ＧＰＣ分析の結果、式（１）で表される化合物の含
有量はは３．１％、式（２）で表される化合物の純度
は、ｎ＝０が９０％、またｎ＝１が０％で、９０％（合
計値）である。式（１）で表される化合物の構造はＧＣ
−ＭＳ測定の結果から確認された。Production Example 1 Bisphenol A diglycidyl ether ("Epototo YD-8125" (trade name), epoxy equivalent 1) was added to 500 ml of stainless steel autoclave equipped with a magnetic stirrer.
72, manufactured by Tohto Kasei Co., Ltd.), 40 g of propylene glycol monomethyl ether, and 0.4 g of a commercially available 5% Ru-C catalyst (manufactured by NE Chemcat Co., Ltd.) were charged, and after the system was replaced with hydrogen, 50 with stirring. ℃, hydrogen pressure 2
Hydrogenation was performed for 5 hours under the condition of 0 MPa. After the reaction, the catalyst was filtered off, and the solvent was distilled off at 150 ° C. at 266 Pa to obtain hydrogenated bisphenol A diglycidyl ether (abbreviated as “epoxy resin A”). Epoxy resin A
Had a nuclear hydrogenation rate of 99.8% and an epoxy equivalent of 186. As a result of GPC analysis, the content of the compound represented by the formula (1) was 3.1%, and the purity of the compound represented by the formula (2) was 90% when n = 0 and 0 when n = 1. %, 90% (total value). The structure of the compound represented by formula (1) is GC
-Confirmed from the result of MS measurement.
【００４１】製造例２
ビスフェノールＡジグリシジルエーテル（「Ｒ−１４０
Ｓ」（商品名）、エポキシ当量１８５、三井石油化学工
業社製、「ＤＧＥＢＡ」と略記する）４０ｇを用いた他
は製造例１と同様の条件で反応を行い水素化ビスフェノ
ールＡジグリシジルエーテルを得た（「エポキシ樹脂
Ｂ」と略記する）。エポキシ樹脂Ｂは、核水素化率９
９．８％、エポキシ当量２０２であった。ＧＰＣ分析の
結果、式（１）で表される化合物の含有量は１．５％、
式（２）で表される化合物の純度は、ｎ＝０が７５．４
％、またｎ＝１が１３．４％で、８８．８％（合計値）
である。Production Example 2 Bisphenol A diglycidyl ether ("R-140
S "(trade name), epoxy equivalent 185, manufactured by Mitsui Petrochemical Co., Ltd., abbreviated as" DGEBA ") 40 g was used to carry out the reaction under the same conditions as in Production Example 1 to obtain hydrogenated bisphenol A diglycidyl ether. Obtained (abbreviated as "epoxy resin B"). Epoxy resin B has a nuclear hydrogenation rate of 9
It was 9.8% and the epoxy equivalent was 202. As a result of GPC analysis, the content of the compound represented by the formula (1) was 1.5%,
The purity of the compound represented by the formula (2) is such that n = 0 is 75.4.
%, And n = 1 is 13.4%, 88.8% (total value)
Is.
【００４２】製造例３
５％Ｒｕ−Ｃ触媒量を１．４ｇ、水素圧力を３ＭＰａと
した他は製造例１と同様の条件で反応を行い水素化ビス
フェノールＡジグリシジルエーテルを得た（「エポキシ
樹脂Ｃ」と略記する）。エポキシ樹脂Ｃは、核水素化率
９９．８％、エポキシ当量１９９であった。式（１）で
表される化合物の含有量は７．３％、式（２）で表され
る化合物の純度は、ｎ＝０が７８．５％、またｎ＝１が
０％で、７８．５％（合計値）であった。Production Example 3 Hydrogenated bisphenol A diglycidyl ether was obtained by carrying out the reaction under the same conditions as in Production Example 1 except that the amount of 5% Ru-C catalyst was 1.4 g and the hydrogen pressure was 3 MPa. Resin C "is abbreviated). Epoxy resin C had a nuclear hydrogenation rate of 99.8% and an epoxy equivalent of 199. The content of the compound represented by the formula (1) is 7.3%, and the purity of the compound represented by the formula (2) is 78.5% when n = 0 and 0% when n = 1. It was 0.5% (total value).
【００４３】製造例４
水素圧力を１ＭＰａとした他は製造例１と同様の条件で
反応を行い水素化ビスフェノールＡジグリシジルエーテ
ルを得た（「エポキシ樹脂Ｄ」と略記する）。エポキシ
樹脂Ｄは、核水素化率８５．０％、エポキシ当量１９９
であった。式（１）で表される化合物の含有量は８．３
％、式（２）で表される化合物の純度は、ｎ＝０が６
５．９％、またｎ＝１が０％で、６５．９％（合算値）
あった。Production Example 4 Hydrogenated bisphenol A diglycidyl ether was obtained by performing the reaction under the same conditions as in Production Example 1 except that the hydrogen pressure was 1 MPa (abbreviated as "epoxy resin D"). Epoxy resin D has a nuclear hydrogenation rate of 85.0% and an epoxy equivalent of 199.
Met. The content of the compound represented by the formula (1) is 8.3.
%, The purity of the compound represented by the formula (2) is 6 when n = 0.
5.9%, and when n = 1 is 0%, 65.9% (total value)
there were.
【００４４】実施例１
４−メチルヘキサヒドロ無水フタル酸（「リカシッドＭ
Ｈ−７００」（商品名）、酸無水物当量１６４．８、新
日本理化社製、「Ｍｅ−ＨＨＰＡ」と略記する）９７．
５重量部、テトラフェニルホスフォニウムブロマイド
（「ＴＰＰ−ＰＢ」（商品名）、北興化学工業社製、Ｔ
ＰＰ−ＰＢと略記する）１重量部を７０℃×３０分混合
した後室温まで冷却し硬化剤液を得た。この硬化剤液に
エポキシ樹脂Ａ１００重量部を室温混合したあと真空脱
泡してエポキシ樹脂組成物を得た。エポキシ基１モルに
対する酸無水物基の当量比は１．１とした。得られたエ
ポキシ樹脂組成物を１００℃で２時間、さらに１３０℃
で５時間の条件で硬化し、硬化物Ｔｇ、硬化物外観、加
熱時変色性、耐紫外線性、硬化物吸湿率、及び耐クラッ
ク性を測定した。その測定結果を表１に示す。Example 1 4-Methylhexahydrophthalic anhydride ("Ricacid M
H-700 "(trade name), acid anhydride equivalent 164.8, manufactured by Shin Nippon Rika Co., Ltd., abbreviated as" Me-HHPA ") 97.
5 parts by weight, tetraphenylphosphonium bromide (“TPP-PB” (trade name), manufactured by Kitako Chemical Co., Ltd., T
1 part by weight (abbreviated as PP-PB) was mixed at 70 ° C. for 30 minutes and then cooled to room temperature to obtain a curing agent liquid. 100 parts by weight of epoxy resin A was mixed at room temperature with this curing agent liquid, and then degassed in vacuum to obtain an epoxy resin composition. The equivalent ratio of acid anhydride groups to 1 mol of epoxy groups was 1.1. The obtained epoxy resin composition is heated at 100 ° C. for 2 hours, then at 130 ° C.
After being cured for 5 hours, the cured product Tg, cured product appearance, discoloration upon heating, ultraviolet resistance, cured product moisture absorption rate, and crack resistance were measured. The measurement results are shown in Table 1.
【００４５】実施例２
エポキシ樹脂Ａに代えてエポキシ樹脂Ｂとした他は実施
例１と同様にエポキシ樹脂組成物を調製し、硬化物試料
を得た。Ｍｅ−ＨＨＰＡの配合量は、エポキシ基１モル
に対する酸無水物基の当量比が１．１となる様に配合し
た。配合比並びに、硬化物Ｔｇ、硬化物外観、加熱時変
色性、耐紫外線性、硬化物吸湿率、及び耐クラック性を
測定した。その測定結果を表１に示す。Example 2 An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin A was replaced with the epoxy resin B to obtain a cured product sample. The compounding amount of Me-HHPA was such that the equivalent ratio of the acid anhydride group to 1 mol of the epoxy group was 1.1. The compounding ratio, cured product Tg, cured product appearance, discoloration upon heating, ultraviolet resistance, cured product moisture absorption rate, and crack resistance were measured. The measurement results are shown in Table 1.
【００４６】実施例３
酸無水物硬化剤をＭｅ−ＨＨＰＡからメチルノルボルナ
ン−２，３−ジカルボン酸無水物８０重量％とノルボル
ナン−２，３−ジカルボン酸無水物２０重量％の液状混
合酸無水物（「リカシッドＨＮＡ−１００」（商品
名）、酸無水物当量１８２．５、新日本理化社製、「Ｈ
ＭｅＮＡ」と略記する）とした他は実施例１と同様にエ
ポキシ樹脂組成物を調製し、硬化物試料を得た。ＨＭｅ
ＮＡの配合量は、エポキシ基１モルに対する酸無水物基
の当量比が０．９となる様に配合した。配合比並びに、
硬化物Ｔｇ、硬化物外観、加熱時変色性、耐紫外線性、
硬化物吸湿率、及び耐クラック性を測定した。その測定
結果を表１に示す。Example 3 A liquid mixed acid anhydride of 80% by weight of methylnorbornane-2,3-dicarboxylic acid anhydride and 20% by weight of norbornane-2,3-dicarboxylic acid anhydride was used as an acid anhydride curing agent from Me-HHPA. ("Ricacid HNA-100" (trade name), acid anhydride equivalent 182.5, manufactured by Shin Nippon Rika Co., Ltd., "H
(Abbreviated as “MeNA”), an epoxy resin composition was prepared in the same manner as in Example 1 to obtain a cured product sample. HMe
The amount of NA blended was such that the equivalent ratio of acid anhydride groups to 1 mol of epoxy groups was 0.9. Mixing ratio and
Cured product Tg, cured product appearance, discoloration upon heating, UV resistance,
The moisture absorption of the cured product and the crack resistance were measured. The measurement results are shown in Table 1.
【００４７】比較例１〜５
エポキシ樹脂Ａをエポキシ樹脂Ｃ、エポキシ樹脂Ｄ、水
素化ビスフェノールＡとエピクロルヒドリンの反応によ
り製造された水素化ビスフェノールＡジグリシジルエー
テル（「リカレジンＨＢＥ−１００」（商品名）、新日
本理化社製、エポキシ当量２１４、全塩素含量４．５
％、式（２）で表される化合物の純度は、ｎ＝０が４
９．８％、またｎ＝１が０％で、４９．８％（合計
値）、「ＨＢＥ−１００」と略記する）、ＤＧＥＢＡ又
は３，４−エポキシシクロヘキシルメチル−３’，４’
−エポキシシクロヘキサンカルボキシレート（エポキシ
当量１３０、「脂環式エポキシ樹脂」と略記する）とし
た他は実施例１と同様にエポキシ樹脂組成物を調製し、
硬化物試料を得た。Ｍｅ−ＨＨＰＡの配合量は、エポキ
シ基１モルに対する酸無水物基の当量比が１．１となる
様に配合した。配合比並びに、硬化物Ｔｇ、硬化物外
観、加熱時変色性、耐紫外線性、硬化物吸湿率、及び耐
クラック性を測定した。その測定結果を表１に示す。Comparative Examples 1 to 5 Epoxy resin A was prepared by reacting epoxy resin C, epoxy resin D, hydrogenated bisphenol A with epichlorohydrin, and hydrogenated bisphenol A diglycidyl ether ("Licalesin HBE-100" (trade name). Manufactured by Shin Nippon Rika Co., Ltd., epoxy equivalent 214, total chlorine content 4.5
%, The purity of the compound represented by the formula (2) is such that n = 0 is 4
9.8%, n = 1 is 0%, 49.8% (total value, abbreviated as "HBE-100"), DGEBA or 3,4-epoxycyclohexylmethyl-3 ', 4'.
An epoxy resin composition was prepared in the same manner as in Example 1 except that epoxycyclohexanecarboxylate (epoxy equivalent 130, abbreviated as “alicyclic epoxy resin”) was used,
A cured product sample was obtained. The compounding amount of Me-HHPA was such that the equivalent ratio of the acid anhydride group to 1 mol of the epoxy group was 1.1. The compounding ratio, cured product Tg, cured product appearance, discoloration upon heating, ultraviolet resistance, cured product moisture absorption rate, and crack resistance were measured. The measurement results are shown in Table 1.
【００４８】 [0048]
【００４９】比較例４はエポキシ樹脂にＤＧＥＢＡを使
用したため、耐紫外線性、耐クラック性が不十分であ
る。比較例５は脂環式エポキシ樹脂を用いたため、硬化
物吸湿率が高く耐湿性が悪く、耐クラック性が不十分で
ある。比較例４は塩素含量が高く、純度の低いＨＢＥ−
１００を用いたためＴｇが低く、耐紫外線性、硬化物吸
湿率、加熱後の耐変色性が不十分である。比較例２は核
水素化率８５％のエポキシ樹脂Ｄを用いた為、耐紫外線
性が不十分である。比較例１は式（１）で表される化合
物の含有量が７．３％と高いエポキシ樹脂Ｃを用いた
為、Ｔｇが低く、硬化物耐湿性が不十分である。これら
と比較し、実施例１〜３は全ての性能が良好でバランス
が取れている。特に、酸無水物硬化剤にＨＭｅＮＡを用
いた実施例３は硬化物Ｔｇが高く、硬化物吸湿率が低い
点でＭｅ−ＨＨＰＡより優れる。In Comparative Example 4, since DGEBA was used as the epoxy resin, ultraviolet resistance and crack resistance were insufficient. In Comparative Example 5, since the alicyclic epoxy resin was used, the moisture absorption rate of the cured product was high, the moisture resistance was poor, and the crack resistance was insufficient. Comparative Example 4 has a high chlorine content and low purity HBE-
Since 100 was used, the Tg was low, and the ultraviolet resistance, the moisture absorption of the cured product, and the discoloration resistance after heating were insufficient. In Comparative Example 2, since the epoxy resin D having a nuclear hydrogenation rate of 85% was used, the ultraviolet resistance was insufficient. In Comparative Example 1, since the epoxy resin C having a high content of the compound represented by the formula (1) of 7.3% was used, Tg was low, and the moisture resistance of the cured product was insufficient. In comparison with these, Examples 1 to 3 have good performance and are well balanced. In particular, Example 3 using HMeNA as the acid anhydride curing agent is superior to Me-HHPA in that the cured product Tg is high and the moisture absorption of the cured product is low.
【００５０】[0050]
【本発明の効果】本発明のエポキシ樹脂組成物を用いて
得られる硬化物は無色透明で、Ｔｇが高く、耐紫外線性
が良好で、吸湿率が低く、長時間加熱下での変色が少な
く、耐クラック性が良好であるため光半導体素子の封止
材料、液晶接着剤、透明コーティング材料等の工業的用
途に広く使用することができる。なかでも特に、近紫外
線領域のＬＥＤ発光素子の封止材料に用いたときに通電
寿命が良好で信頼性のある絶縁封止が可能となるため、
青色ＬＥＤ、白色ＬＥＤ等の光半導体素子の封止材料と
して好適である。EFFECTS OF THE INVENTION The cured product obtained by using the epoxy resin composition of the present invention is colorless and transparent, has a high Tg, has good resistance to ultraviolet rays, has a low moisture absorption rate, and has little discoloration under heating for a long time. Since it has good crack resistance, it can be widely used for industrial applications such as encapsulating materials for optical semiconductor elements, liquid crystal adhesives, and transparent coating materials. In particular, when used as a sealing material for LED light-emitting elements in the near-ultraviolet region, it has a good energization life and enables reliable insulating sealing.
It is suitable as a sealing material for optical semiconductor elements such as blue LEDs and white LEDs.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｌ 33/00 (72)発明者 藤谷 貫剛 京都府京都市伏見区葭島矢倉町13番地 新 日本理化株式会社内 Ｆターム(参考） 4H017 AA04 AB08 AC16 AD06 AE05 4J036 AA01 AC02 AD07 AD08 AF06 AF08 AJ05 AJ08 AJ11 CD12 DA04 DB15 DB17 DB21 DB22 DC01 DC02 DC13 DC19 DC23 DC31 DC34 DC35 DC40 DC41 DC46 DD07 DD09 GA02 GA04 GA06 GA07 JA15 4M109 AA01 EA02 EB04 GA01 5F041 AA43 DA44 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI theme code (reference) H01L 33/00 (72) Inventor Kantan Fujitani 13 Yasaka-cho, Fukumi-ku, Kyoto-shi, Kyoto Shin-Nihon Rika Co., Ltd. Inner F-term (reference) 4H017 AA04 AB08 AC16 AD06 AE05 4J036 AA01 AC02 AD07 AD08 AF06 AF08 AJ05 AJ08 AJ11 CD12 DA04 DB15 DB17 DB21 DB22 DC01 DC02 DC13 DC19 DC23 DC31 DC34 DC35 DC40 DC41 DC46 DD07 DD09 GA02 GA04 GA02 AA15 JA04 GA02 GA04 GA07 GA07 GA07 GA07 GA07 GA15 GA01 5F041 AA43 DA44
Claims (4)
（Ｂ）、及び硬化促進剤（Ｃ）を必須成分とするエポキ
シ樹脂組成物に於いて、（Ａ）成分がビスフェノールＡ
ジグリシジルエーテルの核水素化物であり、ＧＰＣ分析
において式（１） で表される化合物の含有量が５％以下、及び核水素化率
９５％以上で、かつエポキシ当量２１０以下であること
を特徴とするエポキシ樹脂組成物。1. An epoxy resin composition containing an epoxy resin (A), an acid anhydride curing agent (B), and a curing accelerator (C) as essential components, wherein the component (A) is bisphenol A.
It is a nuclear hydride of diglycidyl ether and has the formula (1) in GPC analysis. An epoxy resin composition characterized in that the content of the compound represented by 5% or less, the nuclear hydrogenation rate is 95% or more, and the epoxy equivalent is 210 or less.
酸無水物である請求項１に記載のエポキシ樹脂組成物。2. The epoxy resin composition according to claim 1, wherein the component (B) is an alicyclic acid anhydride containing no double bond.
３−ジカルボン酸無物とノルボルナン−２，３−ジカル
ボン酸無水物の液状混合物である請求項１又は２に記載
のエポキシ樹脂組成物。3. The component (B) is methylnorbornane-2,
The epoxy resin composition according to claim 1 or 2, which is a liquid mixture of 3-dicarboxylic acid-free and norbornane-2,3-dicarboxylic anhydride.
物からなる光電変換素子封止材料。4. A photoelectric conversion element encapsulating material comprising the epoxy resin composition according to claim 1.
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