JP2003277473A - Epoxy resin composition for sealant of led, and led device - Google Patents
Epoxy resin composition for sealant of led, and led deviceInfo
- Publication number
- JP2003277473A JP2003277473A JP2002084801A JP2002084801A JP2003277473A JP 2003277473 A JP2003277473 A JP 2003277473A JP 2002084801 A JP2002084801 A JP 2002084801A JP 2002084801 A JP2002084801 A JP 2002084801A JP 2003277473 A JP2003277473 A JP 2003277473A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- equivalent
- component
- led
- resin composition
- 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.)
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Links
Landscapes
- Led Device Packages (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、透明で耐クラック
性及び耐熱性に優れたＬＥＤ(Ｌｉｇｈｔ ｅｍｉｔｔ
ｉｎｇ ｄｉｏｄｅ）封止材用エポキシ組成物及び、そ
の組成物で封止されたＬＥＤ装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an LED (Light emittance) which is transparent and has excellent crack resistance and heat resistance.
The present invention relates to an epoxy composition for an encapsulating material and an LED device encapsulated with the composition.
【０００２】[0002]
【従来の技術】エポキシ樹脂は、耐熱性、接着性、耐水
性、機械的強度及び電気特性等に優れていることから、
接着剤、塗料、土木建築用材料、電気・電子部品の絶縁
材料等、様々の分野で使用されている。常温又は加熱硬
化型のエポキシ樹脂としては、ビスフェノ−ルＡのジグ
リシジルエ−テル、ビスフェノ−ルＦのジグリシジルエ
−テル、フェノ−ル又はクレゾールノボラック型エポキ
シ樹脂等の芳香族エポキシ樹脂が一般的である。2. Description of the Related Art Epoxy resins are excellent in heat resistance, adhesiveness, water resistance, mechanical strength, electrical characteristics, etc.
It is used in various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electrical and electronic parts. As the room temperature or heat curing type epoxy resin, an aromatic epoxy resin such as a bisphenol A diglycidyl ether, a bisphenol F diglycidyl ether, a phenol or a cresol novolac type epoxy resin is generally used.
【０００３】近年、種々の表示板、画像読み取り用光
源、交通信号、大型ディスプレイ用ユニット等に実用化
されている光半導体（ＬＥＤ）等の発光装置は、大部分
が樹脂封止によって製造されている。ここに使用されて
いる封止用の樹脂は、上記の芳香族エポキシ樹脂と、硬
化剤として脂環式酸無水物が一般的である。しかし、こ
のＬＥＤチップを封止した樹脂硬化物は、冷熱サイクル
によりクラックを生じやすく、厳しい条件で使用するに
は問題がある。In recent years, most of light-emitting devices such as optical semiconductors (LEDs) which have been put to practical use in various display boards, light sources for image reading, traffic signals, units for large displays, etc. are manufactured by resin sealing. There is. The encapsulating resin used here is generally the above-mentioned aromatic epoxy resin and an alicyclic acid anhydride as a curing agent. However, the resin cured product encapsulating the LED chip is apt to cause cracks due to the heat cycle, and there is a problem in using it under severe conditions.
【０００４】また、今日のＬＥＤの飛躍的な進歩によ
り、ＬＥＤチップの高出力化及び短波長化が急速に現実
のものとなり始めていて、特に窒化物半導体を用いたＬ
ＥＤは、短波長でかつ高出力な発光が可能となる。しか
しながら、窒化物半導体を用いたＬＥＤチップを、上述
の芳香族エポキシ樹脂で封止すると、芳香環が短波長の
光を吸収するため経時的に封止した樹脂の劣化が起こ
り、黄変により発光輝度が顕著に低下するという問題が
発生する。Also, due to the dramatic progress of LEDs today, the high output and short wavelength of LED chips are rapidly becoming a reality, and particularly L using a nitride semiconductor is used.
The ED can emit light with a short wavelength and high output. However, when an LED chip using a nitride semiconductor is encapsulated with the above-mentioned aromatic epoxy resin, the aromatic ring absorbs light of a short wavelength, so that the encapsulated resin deteriorates over time, causing yellowing to emit light. There is a problem that the brightness is significantly reduced.
【０００５】そこで、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
シレートで代表される環状オレフィンを酸化して得られ
る脂環式エポキシ樹脂を用いて封止したＬＥＤが提案さ
れている（特開平９−２１３９９７号公報及び特開２０
００−１９６１５１号公報）。このような脂環式エポキ
シ樹脂で封止した硬化樹脂は非常に脆く、冷熱サイクル
によって亀裂破壊を生じ易く、耐湿性も悪いため、長時
間の信頼特性が要求される用途には不向きであった。Therefore, an LED sealed using an alicyclic epoxy resin obtained by oxidizing a cyclic olefin represented by 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate has been proposed. (JP-A-9-213997 and JP-A-20-213997)
No. 00-196151). A cured resin encapsulated with such an alicyclic epoxy resin is extremely brittle, easily cracks and breaks due to thermal cycling, and has poor moisture resistance, so it was unsuitable for applications requiring long-term reliability characteristics. .
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記問題点
を解決した、冷熱サイクルによるクラックの発生が改良
され、耐光性に優れた樹脂を与えることができるＬＥＤ
封止材用エポキシ樹脂組成物、及びその組成物で封止さ
れたＬＥＤ装置を提供しようとするものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and improves the generation of cracks due to cooling / heating cycles and can provide a resin having excellent light resistance.
It is intended to provide an epoxy resin composition for an encapsulant and an LED device encapsulated with the composition.
【０００７】[0007]
【課題を解決するための手段】本発明は、エポキシ当量
が２３０〜１０００ｇ／当量の範囲にある特定のエポキ
シ樹脂と、環状オレフィンをエポキシ化して得られる脂
環式エポキシ樹脂、及び酸無水物硬化剤又はカチオン重
合開始剤を含有するＬＥＤ封止材用エポキシ樹脂組成物
及び、そのエポキシ組成物でＬＥＤが封止されて成るＬ
ＥＤ装置に関する。The present invention is directed to a specific epoxy resin having an epoxy equivalent of 230 to 1000 g / equivalent, an alicyclic epoxy resin obtained by epoxidizing a cyclic olefin, and an acid anhydride cured. Epoxy resin composition for LED encapsulant containing a dye or a cationic polymerization initiator, and L formed by encapsulating an LED with the epoxy composition
Regarding an ED device.
【０００８】[0008]
【発明実施の形態】本発明のＬＥＤ封止材用エポキシ樹
脂組成物は、
（Ａ）成分；芳香族エポキシ樹脂を水素化して得られる
下記一般式（１）BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin composition for an LED encapsulant of the present invention comprises a component (A); the following general formula (1) obtained by hydrogenating an aromatic epoxy resin.
【化２】
（式中、Ｒ1及びＲ2は、互いに同一であっても異なって
もよく、水素原子、メチル基又はシクロヘキシル基を示
し、ｎは０〜２０の整数である）で示されるエポキシ当
量が２３０〜１０００ｇ／当量のエポキシ樹脂、及び芳
香族エポキシ樹脂を水素化して得られるエポキシ樹脂と
多価カルボン酸化合物とを反応させて得られるエポキシ
当量が２３０〜１０００ｇ／当量のエポキシ樹脂から選
ばれる少なくとも１種、
（Ｂ）成分；環状オレフィンをエポキシ化して得られる
脂環式エポキシ樹脂、及び
（Ｃ）成分：酸無水物硬化剤又はカチオン重合開始剤、
の各成分を含有して成るエポキシ樹脂組成物である。[Chemical 2] (Wherein R 1 and R 2 may be the same or different from each other and represent a hydrogen atom, a methyl group or a cyclohexyl group, and n is an integer of 0 to 20), and the epoxy equivalent thereof is 230. To 1000 g / equivalent epoxy resin, and at least one epoxy resin obtained by reacting an epoxy resin obtained by hydrogenating an aromatic epoxy resin with a polyvalent carboxylic acid compound is 230 to 1000 g / equivalent epoxy resin. Seed, (B) component; alicyclic epoxy resin obtained by epoxidizing cyclic olefin, and (C) component: acid anhydride curing agent or cationic polymerization initiator,
An epoxy resin composition containing each of the above components.
【０００９】また、本発明のＬＥＤ装置は、上記エポキ
シ組成物でＬＥＤが封止されて成るＬＥＤ装置である。The LED device of the present invention is an LED device in which an LED is encapsulated with the above epoxy composition.
【００１０】（Ａ成分）本発明のエポキシ樹脂組成物に
おける（Ａ）成分として用いられるエポキシ当量が２３
０〜１０００ｇ／当量の範囲内のエポキシ樹脂は、前記
一般式（１）の水素化エポキシ樹脂及び／又は各種の芳
香族エポキシ樹脂を水素化して得られる水素化エポキシ
樹脂と多価カルボン酸化合物を反応させて得られるエポ
キシ樹脂である。(Component A) The epoxy equivalent used as the component (A) in the epoxy resin composition of the present invention is 23.
The epoxy resin in the range of 0 to 1000 g / equivalent is a hydrogenated epoxy resin obtained by hydrogenating the hydrogenated epoxy resin of the general formula (1) and / or various aromatic epoxy resins and a polyvalent carboxylic acid compound. It is an epoxy resin obtained by reaction.
【００１１】一般式（１）で示されるエポキシ樹脂は、
対応する芳香族エポキシ樹脂を公知の方法で水素化する
ことにより製造することができる。当該水素化エポキシ
樹脂を製造する方法の例としては、一般式（１）のエポ
キシ樹脂における脂環式が芳香環である芳香族エポキシ
樹脂を無溶剤又は適当な有機溶剤に溶解して、ロジウム
又はルテニウムを活性炭又はグラファイトに担持した触
媒の存在下で水素添加して、芳香環を実質的に選択的に
水素化反応する方法が挙げられる。芳香環の水素化率は
芳香環が脂環構造に変化した割合であり、核磁気共鳴分
析により求められ、その水素化率は９０％以上であるこ
とが好ましい。芳香環の水素化率が９０％未満である
と、エポキシ樹脂硬化物の耐光性が低下するため好まし
くない。The epoxy resin represented by the general formula (1) is
It can be produced by hydrogenating the corresponding aromatic epoxy resin by a known method. As an example of the method for producing the hydrogenated epoxy resin, an aromatic epoxy resin in which the alicyclic ring in the epoxy resin of the general formula (1) is an aromatic ring is dissolved in a solvent-free or a suitable organic solvent to obtain rhodium or Examples include a method in which ruthenium is hydrogenated in the presence of a catalyst supported on activated carbon or graphite to substantially selectively hydrogenate an aromatic ring. The hydrogenation rate of the aromatic ring is the rate at which the aromatic ring is changed to an alicyclic structure, is determined by nuclear magnetic resonance analysis, and the hydrogenation rate is preferably 90% or more. When the hydrogenation rate of the aromatic ring is less than 90%, the light resistance of the cured epoxy resin is lowered, which is not preferable.
【００１２】また、本発明のエポキシ樹脂組成物の
（Ａ）成分として使用される、芳香族エポキシ樹脂を水
素化して得られるエポキシ樹脂と多価カルボン酸化合物
を反応させて得られるエポキシ当量が２３０〜１０００
ｇ／当量のエポキシ樹脂は、芳香族エポキシ樹脂を水素
化して得られるエポキシ樹脂と多価カルボン酸化合物を
無触媒又は触媒の存在下に加熱反応させて得ることがで
きる。使用できる水素化エポキシ樹脂は、前記一般式
（１）で示される水素化エポキシ樹脂を水素化して得れ
るエポキシ樹脂が好ましく、また、エポキシ当量が１５
０〜２５０ｇ／当量の水素化エポキシ樹脂が、ポリカル
ボン酸と反応させる時の取り扱い性が優れるため特に好
ましい。The epoxy equivalent obtained by reacting an epoxy resin obtained by hydrogenating an aromatic epoxy resin used as the component (A) of the epoxy resin composition of the present invention with a polycarboxylic acid compound is 230. ~ 1000
The g / equivalent epoxy resin can be obtained by heating the epoxy resin obtained by hydrogenating an aromatic epoxy resin and a polyvalent carboxylic acid compound in the absence of a catalyst or in the presence of a catalyst. The hydrogenated epoxy resin that can be used is preferably an epoxy resin obtained by hydrogenating the hydrogenated epoxy resin represented by the general formula (1), and has an epoxy equivalent of 15
A hydrogenated epoxy resin of 0 to 250 g / equivalent is particularly preferable because it has excellent handleability when reacted with a polycarboxylic acid.
【００１３】また、使用できる多価カルボン酸化合物
は、１分子中に２個のカルボキシル基を有するジカルボ
ン酸化合物が好ましく、光に対する安定性を向上させる
ため、分子中に芳香環及び２重結合の無い飽和脂環構造
を有するジカルボン酸化合物が特に好ましい。具体例と
しては、シクロヘキサンジカルボン酸、メチルシクロヘ
キサンジカルボン酸、主成分が下記一般式（２）で示さ
れる炭素数２１のジカルボン酸The polycarboxylic acid compound that can be used is preferably a dicarboxylic acid compound having two carboxyl groups in one molecule. In order to improve stability to light, an aromatic ring and a double bond are included in the molecule. Particularly preferred are dicarboxylic acid compounds having no saturated alicyclic structure. Specific examples thereof include cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, and dicarboxylic acid having a carbon number of 21 as the main component represented by the following general formula (2).
【化３】
及びオレイン酸、リノール酸、リノレン酸、リジン酸、
リシノール酸等の不飽和脂肪酸の２量体又は３量化体を
水素添加して得られるダイマー酸又はトリマー酸等であ
る。[Chemical 3] And oleic acid, linoleic acid, linolenic acid, lysine acid,
It is a dimer acid or trimer acid obtained by hydrogenating a dimer or trimer of an unsaturated fatty acid such as ricinoleic acid.
【００１４】水素化エポキシ樹脂と多価カルボン酸とを
反応させる条件としては、水素化エポキシ樹脂１００質
量部に対して、多価カルボン酸が１〜５０質量部、好ま
しくは３〜４０質量部である割合で、温度５０〜２００
℃の範囲、０.５〜２０時間の範囲で、無触媒又は触媒
の存在下に、エポキシ基とカルボキシル基を反応させる
ものであることが好ましい。The conditions for reacting the hydrogenated epoxy resin and the polyvalent carboxylic acid are 1 to 50 parts by mass, preferably 3 to 40 parts by mass of the polyvalent carboxylic acid with respect to 100 parts by mass of the hydrogenated epoxy resin. At a certain rate, temperature 50-200
It is preferable that the epoxy group and the carboxyl group are reacted with each other in the absence of a catalyst or in the presence of a catalyst within the range of 0 ° C for 0.5 to 20 hours.
【００１５】この水素化反応に使用できる触媒として
は、例えば、トリエチルアミン、トリブチルアミン、ベ
ンジルジメチルアミン等の３級アミン類、テトラエチル
アンモニウムクロライド、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ア
ンモニウム塩類、トリブチルホスフィン、トリフェニル
ホスフィン、トリス（ジメトキシフェニル）ホスフィン
等のホスフィン類、、テトラエチルホスホニウムブロマ
イド、テトラブチルホスホニウムブロマイド、テトラブ
チルホスホニウムアイオダイド等のホスホニウム塩類が
挙げられ、その使用割合は、水素化エポキシ樹脂１００
質量部に対し、０.００１〜０.５質量部の範囲内であ
る。Examples of the catalyst that can be used in this hydrogenation reaction include tertiary amines such as triethylamine, tributylamine and benzyldimethylamine, ammonium salts such as tetraethylammonium chloride, tetraethylammonium bromide and tetrabutylammonium bromide, and tributylphosphine. , Phosphines such as triphenylphosphine and tris (dimethoxyphenyl) phosphine, and phosphonium salts such as tetraethylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, etc., and the usage ratio thereof is hydrogenated epoxy resin 100.
It is in the range of 0.001 to 0.5 parts by mass with respect to parts by mass.
【００１６】本発明のエポキシ樹脂組成物における
（Ａ）成分としては、芳香族エポキシ樹脂を水素化して
得られる前記一般式（１）のエポキシ樹脂、及び芳香族
エポキシ樹脂を水素化して得られるエポキシ樹脂と多価
カルボン酸化合物を反応させて得られるエポキシ樹脂を
混合して使用することができるが、それぞれを単独で用
いても構わない。As the component (A) in the epoxy resin composition of the present invention, the epoxy resin of the general formula (1) obtained by hydrogenating an aromatic epoxy resin and the epoxy obtained by hydrogenating an aromatic epoxy resin are used. An epoxy resin obtained by reacting a resin with a polyvalent carboxylic acid compound can be mixed and used, but each may be used alone.
【００１７】また、本発明のエポキシ樹脂組成物におけ
る（Ａ）成分のエポキシ樹脂は、エポキシ当量が２３０
〜１０００ｇ／当量、好ましくは２５０〜８００ｇ／当
量の液体又は固体のエポキシ樹脂である。エポキシ当量
が２３０ｇ／当量未満であると、ＬＥＤを封止した時の
熱衝撃に対する抵抗力が減少する。また、１０００ｇ／
当量を越えると、加熱溶融させた時の粘度が非常に高
く、取り扱い性が悪くなるため好ましくない。The epoxy resin of the component (A) in the epoxy resin composition of the present invention has an epoxy equivalent of 230.
˜1000 g / equivalent, preferably 250-800 g / equivalent liquid or solid epoxy resin. When the epoxy equivalent is less than 230 g / equivalent, the resistance to thermal shock when the LED is sealed is reduced. In addition, 1000 g /
If the amount exceeds the equivalent, the viscosity when heated and melted is very high and the handleability becomes poor, which is not preferable.
【００１８】（Ｂ成分）本発明の（Ｂ）成分として用い
られる、環状オレフィンをエポキシ化して得られる脂環
式エポキシ樹脂は、本発明のエポキシ樹脂組成物を硬化
させた時、硬化物のガラス転移温度を向上させるのに有
効である。(Component B) The alicyclic epoxy resin obtained by epoxidizing a cyclic olefin used as the component (B) of the present invention is a glass of a cured product obtained by curing the epoxy resin composition of the present invention. It is effective in improving the transition temperature.
【００１９】脂環式エポキシ樹脂の具体例としては、一
般式（３）で表される化合物（例えば、ジャパンエポキ
シレジン社製、エピコート１７１、ダイセル化学社製、
セロキサイド２０２１など）、Specific examples of the alicyclic epoxy resin include compounds represented by the general formula (3) (for example, Japan Epoxy Resin Co., Epicoat 171, Daicel Chemical Co., Ltd.,
Celoxide 2021, etc.),
【化４】 [Chemical 4]
【００２０】一般式（４）で表される化合物、A compound represented by the general formula (4),
【化５】 [Chemical 5]
【００２１】一般式（５）で表される化合物、A compound represented by the general formula (5),
【化６】 [Chemical 6]
【００２２】一般式（６）で表される化合物（例えば、
ダイセル化学社製、セロキサイド３０００など）A compound represented by the general formula (6) (for example,
Daicel Chemical Co., Ltd., Celoxide 3000 etc.)
【化７】 [Chemical 7]
【００２３】一般式（７）で表される化合物、A compound represented by the general formula (7),
【化８】 [Chemical 8]
【００２４】一般式（８）で表される化合物（例えば、
ダイセル化学社製、セロキサイド２０８０など）A compound represented by the general formula (8) (for example,
(Ceroxide 2080 manufactured by Daicel Chemical Co., Ltd.)
【化９】 [Chemical 9]
【００２５】一般式（９）で表される化合物（例えば、
ダイセル化学社製、ＥＨＰＥ３１５０など）A compound represented by the general formula (9) (for example,
(Daicel Chemical Co., EHPE3150 etc.)
【化１０】
（式中、Ｒは炭素数２〜１０の炭化水素基である。ｎは
３〜５０の整数である。）[Chemical 10] (In the formula, R is a hydrocarbon group having 2 to 10 carbon atoms. N is an integer of 3 to 50.)
【００２６】一般式（１０）で表される化合物、A compound represented by the general formula (10),
【化１１】 [Chemical 11]
【００２７】一般式（１１）で表される化合物、A compound represented by the general formula (11),
【化１２】 [Chemical 12]
【００２８】一般式（１２）で表される化合物、A compound represented by the general formula (12),
【化１３】 [Chemical 13]
【００２９】一般式（１３）で表される化合物Compound represented by general formula (13)
【化１４】 [Chemical 14]
【００３０】一般式（１４）で表される化合物Compound represented by formula (14)
【化１５】 などが例示される。[Chemical 15] Are exemplified.
【００３１】これらの中で、一般式（３）で示される、
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及び一般式
（９）で示される脂環式固形エポキシ樹脂が、原料入手
の容易さ、及び本発明組成物のガラス転移温度向上の改
良効果に優れるという点でより好ましい。また、脂環式
エポキシ樹脂の使用割合は、（Ａ）成分のエポキシ樹脂
１００質量部に対し、（Ｂ）成分の脂環式エポキシ樹脂
が１０〜２００質量部の範囲である。脂環式エポキシ樹
脂が１０質量部未満であると、ガラス点転移温度の改良
効果が不十分となり、２００質量部を越えると硬化物が
脆くなり、封止材中にクラックが入りやすくなるため好
ましくない。Among these, represented by the general formula (3),
3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate and the alicyclic solid epoxy resin represented by the general formula (9) make it easy to obtain raw materials and improve the glass transition temperature of the composition of the present invention. It is more preferable in that it is excellent in the effect of improving. Further, the ratio of the alicyclic epoxy resin used is in the range of 10 to 200 parts by mass of the alicyclic epoxy resin of the component (B) with respect to 100 parts by mass of the epoxy resin of the component (A). When the amount of the alicyclic epoxy resin is less than 10 parts by mass, the effect of improving the glass point transition temperature becomes insufficient, and when it exceeds 200 parts by mass, the cured product becomes brittle and cracks easily occur in the sealing material, which is preferable. Absent.
【００３２】本発明の（Ｃ）成分として用いられる酸無
水物硬化剤としては、例えば、無水フタル酸、無水トリ
メリット酸、無水ピロメリット酸等の芳香族酸無水物
類、無水テトラヒドロフタル酸、無水メチルテトラヒド
ロフタル酸、無水ヘキサヒドロフタル酸、無水メチルヘ
キサヒドロフタル酸、無水メチルエンドエチレンテトラ
ヒドロフタル酸、無水トリアルキルテトラヒドロフタル
酸等の環状脂肪族酸無水物が挙げられる。これらの中
で、無水ヘキサヒドロフタル酸、無水メチルヘキサヒド
ロフタル酸等の飽和脂環式酸無水物を使用するのが、本
発明のエポキシ樹脂組成物の耐光性が向上する点で好ま
しい。酸無水物類の使用割合は、（Ａ）成分のエポキシ
樹脂と（Ｂ）成分の脂環式エポキシ樹脂の総和１００質
量部に対し、１０〜２００質量部の範囲内である。Examples of the acid anhydride curing agent used as the component (C) of the present invention include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride, tetrahydrophthalic anhydride, Examples thereof include cyclic aliphatic acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendoethylenetetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride. Among these, it is preferable to use saturated alicyclic acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride from the viewpoint of improving the light resistance of the epoxy resin composition of the present invention. The proportion of the acid anhydrides used is in the range of 10 to 200 parts by mass with respect to 100 parts by mass as the total of the epoxy resin as the component (A) and the alicyclic epoxy resin as the component (B).
【００３３】また、本発明の組成物に硬化を促進する目
的で、硬化促進剤を配合することができる。硬化促進剤
の例としては、３級アミン類、イミダゾール類、有機ホ
スフィン化合物類又はこれらの塩類、オクチル酸亜鉛、
オクチル酸スズ等の金属石鹸類が挙げられる。A curing accelerator may be added to the composition of the present invention for the purpose of promoting curing. Examples of the curing accelerator include tertiary amines, imidazoles, organic phosphine compounds or salts thereof, zinc octylate,
Examples thereof include metal soaps such as tin octylate.
【００３４】（Ｃ成分）本発明エポキシ樹脂組成物にお
ける（Ｃ）成分のカチオン重合開始剤としては、活性エ
ネルギー線によりカチオン種又はルイス酸を発生する活
性エネルギー線カチオン重合開始剤、又は熱によりカチ
オン種又はルイス酸を発生する熱カチオン重合開始剤を
用いることができる。(C component) The cationic polymerization initiator of the (C) component in the epoxy resin composition of the present invention is an active energy ray cationic polymerization initiator which generates a cationic species or a Lewis acid by an active energy ray, or a cation by heat. A thermal cationic polymerization initiator that generates a species or Lewis acid can be used.
【００３５】活性エネルギー線カチオン重合開始剤とし
ては、米国特許第３３７９６５３号明細書に記載された
ような金属フルオロ硼素錯塩及び三弗化硼素錯化合物；
米国特許第３５８６６１６号明細書に記載されたような
ビス（ペルフルオルアルキルスルホニル）メタン金属
塩；米国特許第３７０８２９６号明細書に記載されたよ
うなアリールジアゾニウム化合物；米国特許第４０５８
４００号明細書に記載されたようなＶＩａ族元素の芳香
族オニウム塩；米国特許第４０６９０５５号明細書に記
載されたようなＶａ族元素の芳香族オニウム塩；米国特
許第４０６８０９１号明細書に記載されたようなＩＩＩ
ａ〜Ｖａ族元素のジカルボニルキレート；米国特許第４
１３９６５５号明細書に記載されたようなチオピリリウ
ム塩；米国特許第４１６１４７８号明細書に記載された
ようなＭＦ6 -陰イオン（ここでＭは燐、アンチモン及び
砒素から選択される）の形のＶＩｂ元素；米国特許第４
２３１９５１号明細書に記載されたようなアリールスル
ホニウム錯塩；米国特許第４２５６８２８号明細書に記
載されたような芳香族ヨードニウム錯塩及び芳香族スル
ホニウム錯塩；Ｗ．Ｒ．Ｗａｔｔらによって「ジャーナ
ル・オブ・ポリマー・サイエンス（Ｊｏｕｒｎａｌ ｏ
ｆ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ）、ポリマー・ケ
ミストリー（Ｐｏｌｙｍｅｒ Ｃｈｅｍｉｓｔｒｙ）
版」、第２２巻、１７８９頁（１９８４年）に記載され
たようなビス[４−（ジフェニルスルホニオ）フェニル]
スルフィド−ビス−ヘキサフルオロ金属塩（例えばリン
酸塩、砒酸塩、アンチモン酸塩等）の一種以上が包含さ
れる。その他、鉄化合物の混合配位子金属塩及びシラノ
ール−アルミニウム錯体も使用することが可能である。As the active energy ray cationic polymerization initiator, metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat. No. 3,379,653;
Bis (perfluoroalkylsulfonyl) methane metal salts as described in U.S. Pat. No. 3,586,616; aryl diazonium compounds as described in U.S. Pat. No. 3,708,296; U.S. Pat.
Aromatic onium salts of Group VIa elements as described in US 400; Aromatic onium salts of Group Va elements as described in US Pat. No. 4069055; US Pat. No. 4068091. As was done III
Dicarbonyl chelates of elements a-Va; US Pat. No. 4,
Thiopyrylium salts as described in 139655 Pat; U.S. Pat. No. as described in 4,161,478 Pat MF 6 - in the form of anions (wherein M is selected from phosphorus, antimony and arsenic) VIb Element; US Patent No. 4
Arylsulfonium complex salts as described in U.S. Pat. No. 2,319,51; aromatic iodonium complex salts and aromatic sulfonium complex salts as described in U.S. Pat. No. 4,256,828; R. Watt et al., "Journal of Polymer Science"
f Polymer Science), Polymer Chemistry
Ed. ", Vol. 22, p. 1789 (1984), bis [4- (diphenylsulfonio) phenyl].
One or more of sulfide-bis-hexafluorometal salts (eg, phosphates, arsenates, antimonates, etc.) are included. In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
【００３６】好ましい陽イオン系活性エネルギー線カチ
オン重合開始剤には、アリールスルホニウム錯塩、ハロ
ゲン含有錯イオンの芳香族スルホニウム又はヨードニウ
ム塩並びにＩＩ族、Ｖ族及びＶＩ族元素の芳香族オニウ
ム塩が包含される。これらの塩のいくつかは、ＦＸ−５
１２（３Ｍ社）、ＵＶＲ−６９９０及びＵＶＲ−６９７
４[ユニオン・カーバイド（Ｕｎｉｏｎ Ｃａｒｂｉｄ
ｅ）社]、ＵＶＥ−１０１４及びＵＶＥ−１０１６[ジェ
ネラル・エレクトリック（Ｇｅｎｅｒａｌ Ｅｌｅｃｔ
ｒｉｃ）社]、ＫＩ−８５[デグッサ（Ｄｅｇｕｓｓａ）
社]、ＳＰ−１５０及びＳＰ−１７０（旭電化社）並び
にサンエイドＳＩ−６０Ｌ、ＳＩ−８０Ｌ及びＳＩ−１
００Ｌ（三新化学工業社）として商品として入手でき
る。Preferred cationic active energy ray cationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, and aromatic onium salts of Group II, V and VI elements. It Some of these salts are FX-5
12 (3M Company), UVR-6990 and UVR-697.
4 [Union Carbide
e) company, UVE-1014 and UVE-1016 [General Electric (General Electric)
ric) company, KI-85 [Degussa]
, SP-150 and SP-170 (Asahi Denka Co., Ltd.) and San-Aid SI-60L, SI-80L and SI-1.
It is available as a product as 00L (Sanshin Chemical Industry Co., Ltd.).
【００３７】熱カチオン重合開始剤としては、トリフル
酸（Ｔｒｉｆｌｉｃ ａｃｉｄ）塩、三弗化硼素エーテ
ル錯化合物、三弗化硼素等のようなカチオン系又はプロ
トン酸触媒が用いることができる。好ましい熱カチオン
重合開始剤としては、トリフル酸塩であり、例として
は、３Ｍ社からＦＣ−５２０として入手できるトリフル
酸ジエチルアンモニウム、トリフル酸トリエチルアンモ
ニウム、トリフル酸ジイソプロピルアンモニウム、トリ
フル酸エチルジイソプロピルアンモニウム等[これらの
多くはＲ．Ｒ．Ａｌｍによって１９８０年１０月発行の
モダン・コーティングス（Ｍｏｄｅｒｎ Ｃｏａｔｉｎ
ｇｓ）に記載されている]がある。また一方、活性エネ
ルギー線カチオン重合開始剤としても用いられる芳香族
オニウム塩のうち、熱によりカチオン種を発生するもの
があり、これらも熱カチオン重合開始剤として用いるこ
とができる。例としては、サンエイドＳＩ−６０Ｌ、Ｓ
Ｉ−８０Ｌ及びＳＩ−１００Ｌ（三新化学工業社）があ
る。As the thermal cationic polymerization initiator, cationic or protic acid catalysts such as triflic acid salt, boron trifluoride ether complex compound, boron trifluoride and the like can be used. A preferred thermal cationic polymerization initiator is a triflate salt, and examples thereof include diethylammonium triflate, triethylammonium triflate, diisopropylammonium triflate, and ethyldiisopropylammonium triflate, which are available as FC-520 from 3M Company. Many of these are R. R. Modern Coatings, published by Alm in October 1980.
gs)]]. On the other hand, among the aromatic onium salts that are also used as the active energy ray cationic polymerization initiator, there are those that generate a cationic species by heat, and these can also be used as the thermal cationic polymerization initiator. As an example, San-Aid SI-60L, S
There are I-80L and SI-100L (Sanshin Chemical Industry Co., Ltd.).
【００３８】これらの光及び熱カチオン重合開始剤の中
で、オニウム塩が、取り扱い性及び潜在性と硬化性のバ
ランスに優れるという点で好ましく、その中で、ジアゾ
ニウム塩、ヨードニウム塩、スルホニウム塩及びホスホ
ニウム塩が取り扱い性及び潜在性のバランスに優れると
いう点で特に好ましい。カチオン重合開始剤の使用量
は、（Ａ）成分のエポキシ樹脂と（Ｂ）成分の脂環式エ
ポキシ樹脂の総和１００質量部に対し、０．０１〜１５
質量部、より好ましくは０．０５〜５質量部の量で添加
する。上記範囲を外れると、エポキシ樹脂硬化物の耐熱
性及び耐湿性のバランスが悪くなるため好ましくない。Of these photo- and thermal-cationic polymerization initiators, onium salts are preferable in terms of excellent handling and latent balance between curability and diazonium salts, iodonium salts, sulfonium salts and The phosphonium salt is particularly preferable because it has an excellent balance of handleability and potential. The amount of the cationic polymerization initiator used is 0.01 to 15 with respect to 100 parts by mass of the total of the epoxy resin as the component (A) and the alicyclic epoxy resin as the component (B).
It is added in an amount of parts by mass, more preferably 0.05 to 5 parts by mass. If the amount is out of the above range, the heat resistance and moisture resistance of the cured epoxy resin will be unbalanced, which is not preferable.
【００３９】（エポキシ硬化物のガラス転移温度）本発
明エポキシ樹脂組成物を硬化させた時のガラス転移温度
は６０〜１６０℃が好ましく、特に好ましいのは８０〜
１５０℃の範囲である。ガラス転移温度が６０℃未満で
あると、温度が上昇した雰囲気下でＬＥＤを使用すると
封止材が劣化、着色し、発光輝度が低下するため好まし
くない。また、１６０℃を越えると硬化物は非常に脆く
なり、冷熱サイクルでクラックを生じるため好ましくな
い。本発明のガラス転移温度の測定方法は、熱機械分析
装置（ＴＭＡ）を用い、５℃／分で昇温した時に測定さ
れる線膨張率の変化から求めることができる。(Glass Transition Temperature of Epoxy Cured Product) The glass transition temperature when the epoxy resin composition of the present invention is cured is preferably 60 to 160 ° C., particularly preferably 80 to 160 ° C.
It is in the range of 150 ° C. When the glass transition temperature is lower than 60 ° C., when the LED is used in an atmosphere where the temperature rises, the sealing material is deteriorated and colored, and the emission brightness is reduced, which is not preferable. On the other hand, if the temperature exceeds 160 ° C., the cured product becomes very brittle and cracks are generated during the cooling / heating cycle, which is not preferable. The glass transition temperature measuring method of the present invention can be determined from the change in linear expansion coefficient measured when the temperature is raised at 5 ° C./min using a thermomechanical analyzer (TMA).
【００４０】（ＬＥＤチップの封止方法）ＬＥＤチップ
を本発明エポキシ樹脂組成物で封止する方法は、組成物
が液状である場合、型の中に組成物を流し込みＬＥＤチ
ップを封止する注型法が選択され、硬化は７０〜１７０
℃の温度、０.５〜１０時間の範囲の条件である。ま
た、組成物が固体である場合はトランスファー成形機を
用いてＬＥＤチップを封止する方法が好ましく、成形は
１００〜２００℃の温度、０．１〜２０分間の条件でＬ
ＥＤチップを封止する。更に成形後、より封止材性能の
向上を図るため、７０〜１７０℃の温度、０．１〜１０
時間の範囲で後硬化を行うことが好ましい。(Method for sealing LED chip) The method for sealing an LED chip with the epoxy resin composition of the present invention is such that when the composition is liquid, the composition is poured into a mold to seal the LED chip. Mold method selected, cure 70-170
The conditions are a temperature of 0 ° C. and a range of 0.5 to 10 hours. Further, when the composition is solid, a method of sealing the LED chip using a transfer molding machine is preferable, and molding is performed at a temperature of 100 to 200 ° C. for 0.1 to 20 minutes.
Seal the ED chip. Further, after molding, in order to further improve the performance of the sealing material, a temperature of 70 to 170 ° C., 0.1 to 10
It is preferable to carry out post-curing within the range of time.
【００４１】（任意成分）本発明のエポキシ樹脂組成物
には、必要に応じて次の成分を添加配合することができ
る。
（１）粉末状の補強剤や充填剤、例えば酸化アルミニウ
ム、酸化マグネシウムなどの金属酸化物、微粉末シリ
カ、溶融シリカ、結晶シリカなどのケイ素化合物、ガラ
スビーズ等の透明フィラー、水酸化アルミニウムなどの
金属水酸化物、その他、カオリン、マイカ、石英粉末、
グラファイト、二硫化モリブデン等。これらの補強剤や
充填剤は本発明の組成物１００質量部に対して、１０〜
２００質量部配合される。(Optional Components) The epoxy resin composition of the present invention may optionally contain the following components. (1) Reinforcing agents and fillers in powder form, for example, metal oxides such as aluminum oxide and magnesium oxide, fine powder silica, fused silica, silicon compounds such as crystalline silica, transparent fillers such as glass beads, and aluminum hydroxide. Metal hydroxide, others, kaolin, mica, quartz powder,
Graphite, molybdenum disulfide, etc. These reinforcing agents and fillers are 10 to 10 parts by mass of the composition of the present invention.
200 parts by mass are compounded.
【００４２】（２）着色剤又は顔料、例えば二酸化チタ
ン、モリブデン赤、紺青、群青、カドミウム 黄、カ
ドミウム赤等
（３）難燃剤、例えば、三酸化アンチモン、臭素化合物
及びリン化合物等。
（４）イオン吸着体
（５）カップリング剤
（６）酸化防止剤、紫外線吸収剤
これらは本発明のエポキシ樹脂組成物１００質量部に対
して、００.１〜３０質量部配合される。(2) Colorants or pigments such as titanium dioxide, molybdenum red, navy blue, ultramarine blue, cadmium yellow, cadmium red, etc. (3) Flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds. (4) Ion adsorbent (5) Coupling agent (6) Antioxidant, ultraviolet absorber These are blended in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin composition of the present invention.
【００４３】（７）さらに、エポキシ硬化物の性質を改
善する目的で種々の硬化性モノマ−、オリゴマ−及び合
成樹脂を配合することができる。例えば、脂肪族エポキ
シ化合物等のエポキシ樹脂用希釈剤、ジオール又はトリ
オール類、ビニルエーテル類、オキセタン化合物、フッ
素樹脂、アクリル樹脂、シリコ−ン樹脂等の１種又は２
種以上の組み合わせを挙げることができる。これらの化
合物及び樹脂類の配合割合は、本発明の樹脂組成物の本
来の性質を損なわない範囲の量、すなわち本発明の組成
物１００質量部に対して、５０質量部以下が好ましい。(7) Further, various curable monomers, oligomers and synthetic resins may be blended for the purpose of improving the properties of the epoxy cured product. For example, one or two kinds of diluents for epoxy resins such as aliphatic epoxy compounds, diols or triols, vinyl ethers, oxetane compounds, fluororesins, acrylic resins, silicone resins and the like.
Combinations of more than one species can be mentioned. The compounding ratio of these compounds and resins is preferably 50 parts by mass or less with respect to 100 parts by mass of the composition of the present invention, that is, an amount in a range that does not impair the original properties of the resin composition of the present invention.
【００４４】[0044]
【実施例】以下に、実施例及び比較例を挙げて本発明を
さらに詳しく説明する。なお、例中の部は質量部を意味
する。EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. In addition, the part in an example means a mass part.
【００４５】製造例１
撹拌機、冷却器及び温度計を備えた１０００ミリリット
ルのオートクレーブ内に、前記一般式（１）中、Ｒ1と
Ｒ2が共にメチル基で、ｎが平均値で２．１であるビス
フェノールＡ型エポキシ樹脂（ジャパンエポキシレジン
社商品名「エピコート１００１」；エポキシ当量；４６
５ｇ／当量）を１００ｇ、テトラヒドロフランを３００
ｇ及び、５％ロジウム／９５％グラファイト（グラファ
イトの表面積:１３０ｍ2／ｇ）触媒５.０ｇを仕込み、
水素圧力７ＭＰａ、温度７０〜１００℃、撹拌数５００
〜８００ｒｐｍの条件を保持しながら、５時間還元反応
を行った。反応終了後、冷却し、触媒を濾別した後、テ
トラヒドロフランをロータリーエバポレーターにて減圧
下、温度８０〜１２０℃で留去させて、無色透明半固体
の水素化エポキシ樹脂を得た。得られた水素化エポキシ
樹脂は、ＮＭＲより求めた水素化率は９９.５％で、エ
ポキシ当量は、５３４（g／当量）であった。Production Example 1 In a 1000 ml autoclave equipped with a stirrer, a cooler and a thermometer, in the general formula (1), R 1 and R 2 are both methyl groups and n is 2. 1 bisphenol A type epoxy resin (trade name "Epicoat 1001" of Japan Epoxy Resins; epoxy equivalent; 46)
5 g / equivalent) 100 g and tetrahydrofuran 300
g and 5.0% of 5% rhodium / 95% graphite (graphite surface area: 130 m 2 / g) catalyst,
Hydrogen pressure 7 MPa, temperature 70 to 100 ° C., stirring number 500
The reduction reaction was carried out for 5 hours while maintaining the condition of ~ 800 rpm. After completion of the reaction, the reaction mixture was cooled and the catalyst was filtered off. Then, tetrahydrofuran was distilled off under reduced pressure at a temperature of 80 to 120 ° C by a rotary evaporator to obtain a colorless transparent semi-solid hydrogenated epoxy resin. The hydrogenated epoxy resin obtained had a hydrogenation rate determined by NMR of 99.5% and an epoxy equivalent of 534 (g / equivalent).
【００４６】製造例２
前記一般式（１）におけるＲ1，Ｒ2が共にメチル基であ
り、ｎが平均値で０．１５である水素化ビスフェノール
Ａのジグリシジルエーテル（ジャパンエポキシレジン社
商品名「エピコートＹＸ８０００」；、エポキシ当量；
２０５ｇ／当量、水素化率；ほぼ１００％）２００ｇ、
不飽和脂肪酸の２量体及び３量体を水添して得られた水
添ダイマー酸（ユニケマジャパン社商品名「ＰＲＩＰＯ
Ｌ １００９」；酸価；１９６ｍｇＫＯＨ／ｇ）５０
ｇ、反応触媒として、テトラ−ｎ−ブチルホスホウホニ
ウムｏ，ｏ−ジエチルホスホロジチオネート（日本化学
工業社商品名「ヒシコーリン ＰＸ−４ＥＴ」）０.０
４ｇを添加し撹拌しながら窒素気流下、１２０℃で５時
間付加反応を行い、エポキシ当量２９３（g／当量）、
粘度８.４Ｐａ．Ｓ（２５℃）の無色透明なエポキシ樹
脂を得た。Production Example 2 Diglycidyl ether of hydrogenated bisphenol A (R trade name of Japan Epoxy Resin Co., Ltd.) in which R 1 and R 2 in the general formula (1) are both methyl groups and n has an average value of 0.15. "Epicoat YX8000";, epoxy equivalent;
205 g / equivalent, hydrogenation rate; almost 100%) 200 g,
Hydrogenated dimer acid obtained by hydrogenating dimers and trimers of unsaturated fatty acids (trade name "PRIPO, Unichema Japan Ltd.
L 1009 "; acid value; 196 mg KOH / g) 50
g, as a reaction catalyst, tetra-n-butylphosphorphonium o, o-diethylphosphorodithionate (Nippon Kagaku Kogyo Co., Ltd., trade name "Hishicolin PX-4ET") 0.0
4g was added and the addition reaction was carried out at 120 ° C. for 5 hours under a nitrogen stream with stirring to obtain an epoxy equivalent of 293 (g / equivalent),
Viscosity 8.4 Pa. A colorless and transparent epoxy resin of S (25 ° C.) was obtained.
【００４７】製造例３
前記一般式（１）におけるＲ1，Ｒ2が共に水素であり、
ｎが平均値で０．１５であるビスフェノールＦのジグリ
シジルエーテル（ジャパンエポキシレジン社商品名「エ
ピコート８０６」；エポキシ当量；１６５ｇ／当量）を
水素化した液状の水素化エポキシ樹脂（エポキシ当量；
１８１g／当量、水素化率；ほぼ１００％）２００ｇ、
ＰＲＩＰＯＬ １００９ ５７ｇに変える以外は、製造
例２と同様の操作を行い、エポキシ当量２８２（g／当
量）、粘度７.１Ｐａ．Ｓ（２５℃）の無色透明なエポ
キシ樹脂を得た。Production Example 3 R 1 and R 2 in the general formula (1) are both hydrogen,
Liquid hydrogenated epoxy resin obtained by hydrogenating diglycidyl ether of bisphenol F (trade name "Epicoat 806" of Japan Epoxy Resin Co .; epoxy equivalent; 165 g / equivalent) in which n is 0.15 in average value (epoxy equivalent;
181 g / equivalent, hydrogenation rate; almost 100%) 200 g,
The same operation as in Production Example 2 was carried out except that the amount of PRIPOL 1009 was changed to 57 g, and the epoxy equivalent was 282 (g / equivalent) and the viscosity was 7.1 Pa.s. A colorless and transparent epoxy resin of S (25 ° C.) was obtained.
【００４８】実施例１
製造例１より得られたエポキシ樹脂５０ｇ、脂環式エポ
キシ樹脂として前記式（９）で示される脂環式固形エポ
キシ樹脂（ダイセル化学社商品名「ＥＨＰＥ３１５
０」）５０ｇ、硬化剤としてスルホニウム塩型カチオン
重合開始剤（日本曹達社商品名「ＣＩ−２６２４」）１
部、透明フィラーとしてガラスビーズ（日本フリット社
製）３３ｇ、安定剤としてフェノール系酸化防止剤（Ｂ
ＨＴ）０.３ｇ及びリン系安定剤（三光化学社商品名
「エポクリーン」）０.３ｇを配合するために、ミキシ
ングロールを用い、５０〜８０℃の温度で５分間溶融混
合した。得られた溶融混合物はシート状に取り出し、粉
砕して成形材料を得た。上記により得られた成形材料
を、低圧トランスファー成形機を用い、金型温度１７５
℃、成形時間１８０秒で成形して、各試験片を得、更に
１４０℃で３時間ポストキュアーを行い無色透明な硬化
物を得た。この硬化物の物性値を表１に示す。Example 1 50 g of the epoxy resin obtained from Production Example 1 and an alicyclic solid epoxy resin represented by the above formula (9) as an alicyclic epoxy resin (trade name "EHPE315" manufactured by Daicel Chemical Co., Ltd.).
0 ") 50 g, sulfonium salt type cationic polymerization initiator as a curing agent (Nippon Soda Co., Ltd., trade name" CI-2624 ") 1
Part, 33 g of glass beads (manufactured by Nippon Frit Co., Ltd.) as a transparent filler, a phenolic antioxidant (B as a stabilizer)
HT) 0.3 g and a phosphorus-based stabilizer (Sanko Chemical Co., Ltd. trade name “Epoclean”) 0.3 g were mixed and mixed for 5 minutes at a temperature of 50 to 80 ° C. using a mixing roll. The obtained molten mixture was taken out as a sheet and pulverized to obtain a molding material. The molding material obtained as described above was subjected to a mold temperature 175 using a low-pressure transfer molding machine.
Each test piece was obtained by molding at 180 ° C. for 180 seconds, and post-cured at 140 ° C. for 3 hours to obtain a colorless and transparent cured product. The physical properties of this cured product are shown in Table 1.
【００４９】実施例２
製造例２より得られたエポキシ樹脂７０ｇ、脂環式エポ
キシ樹脂として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
（ジャパンエポキシレジン社商品名「エピコート１７１
Ｄ」；エポキシ当量；１３０g/当量）３０ｇ、硬化剤と
して無水メチルヘキサヒドロフタル酸（新日本理化社商
品名「ＭＨ−７００」）８０ｇ、硬化促進剤として、テ
トラ−ｎ−ブチルホスホウホニウムｏ，ｏ−ジエチルホ
スホロジチオネートヒシコーリン（日本化学工業社商品
名「ＰＸ−４ＥＴ」）１ｇ、安定剤としてフェノール系
酸化防止剤（ＢＨＴ）０.１ｇ及びリン系安定剤（三光
化学社商品名「エポクリーン」）０.１ｇを加え、加熱
混合し、脱泡後、均一な溶液としエポキシ樹脂組成物を
得た。次いで、上記組成物を型の中に流し込み、１００
℃で３時間、さらに１４０℃で３時間オーブン中にて硬
化を行い無色透明な硬化物を得た。この硬化物の物性値
を表１に示す。Example 2 70 g of the epoxy resin obtained in Production Example 2 and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate as an alicyclic epoxy resin (trade name “Epicoat 171 manufactured by Japan Epoxy Resin Co., Ltd.)
D "; epoxy equivalent; 130 g / equivalent) 30 g, methylhexahydrophthalic anhydride (Shin Nippon Rika Co., Ltd. trade name" MH-700 ") 80 g as a curing agent, tetra-n-butylphosphorphonium o as a curing accelerator , O-diethyl phosphorodithionate hishikorin (Nippon Kagaku Kogyo Co., Ltd., trade name "PX-4ET") 1 g, phenolic antioxidant (BHT) 0.1 g as a stabilizer and phosphorus stabilizer (Sanko Chemical Co., Ltd. trade name 0.1 g of "Epoclean") was added, and the mixture was heated and mixed, and after defoaming, a uniform solution was obtained to obtain an epoxy resin composition. The above composition is then poured into a mold and 100
Curing was performed in an oven at 3 ° C. for 3 hours and then at 140 ° C. for 3 hours to obtain a colorless and transparent cured product. The physical properties of this cured product are shown in Table 1.
【００５０】実施例３〜６、比較例１〜２
エポキシ樹脂、脂環式エポキシ樹脂及び硬化剤を表１の
ように変える以外は、実施例２と同様の操作を行ってエ
ポキシ樹脂組成物を得、更に硬化物を得た。物性値を表
１に示す。Examples 3 to 6 and Comparative Examples 1 to 2 An epoxy resin composition was prepared in the same manner as in Example 2 except that the epoxy resin, alicyclic epoxy resin and curing agent were changed as shown in Table 1. Then, a cured product was obtained. The physical property values are shown in Table 1.
【００５１】[0051]
【表１】 [Table 1]
【００５２】なお、上記表１における「耐熱衝撃試験」
の数値は、表２に示す「オリファントワッシャー法の変
法」に従った熱衝撃試験による「クラック抵抗」の平均
値を示している。The "thermal shock test" in Table 1 above
Shows the average value of "crack resistance" by a thermal shock test according to "a modification of the oliphant washer method" shown in Table 2.
【００５３】[0053]
【表２】 [Table 2]
【００５４】実施例７〜８及び比較例３
実施例２、実施例３及び比較例１と同様の配合組成及び
硬化条件を用い、ＧａＡｓＰ材質のＬＥＤチップを封止
し、直径５ｍｍのＬＥＤランプを得た。このＬＥＤラン
プの冷熱サイクル試験行い、クラック発生の有無を観察
した。結果を表３に示す。Examples 7 to 8 and Comparative Example 3 Using the same composition and curing conditions as those in Examples 2, 3 and Comparative Example 1, an LED chip made of GaAsP material was encapsulated to obtain an LED lamp having a diameter of 5 mm. Obtained. The LED lamp was subjected to a thermal cycle test and observed for cracks. The results are shown in Table 3.
【００５５】[0055]
【表３】 [Table 3]
【００５６】[0056]
【発明の効果】本発明により、特定の水素化エポキシ樹
脂と脂環式エポキシ樹脂を複合化させたエポキシ樹脂
を、酸無水物又はカチオン重合開始剤で硬化させること
により、無色透明で冷熱サイクルでのクラック発生が少
なく、耐熱性、耐光性に優れたエポキシ樹脂硬化物が得
られる。このエポキシ樹脂硬化物で封止したＬＥＤは耐
久性に優れるため、屋外の用途において有利に使用でき
る。Industrial Applicability According to the present invention, an epoxy resin obtained by complexing a specific hydrogenated epoxy resin and an alicyclic epoxy resin is cured with an acid anhydride or a cationic polymerization initiator to give a colorless, transparent and cold cycle. It is possible to obtain an epoxy resin cured product which has few cracks and is excellent in heat resistance and light resistance. The LED sealed with this cured epoxy resin has excellent durability, and thus can be advantageously used in outdoor applications.
───────────────────────────────────────────────────── 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） Ｃ０８Ｌ 63/00 Ｃ０８Ｌ 63/00 Ｃ ５Ｆ０４１ Ｃ０９Ｊ 175/04 Ｃ０９Ｊ 175/04 Ｃ０９Ｋ 3/10 Ｃ０９Ｋ 3/10 Ｌ Ｈ０１Ｌ 23/29 Ｈ０１Ｌ 33/00 Ｎ 23/31 23/30 Ｒ 33/00 Ｆターム(参考） 4H017 AA04 AA31 AB08 AC01 AC18 AD06 AE05 4J002 CD021 CD101 CD171 CD201 DD087 EF126 EJ018 EL136 EQ017 EV297 EW008 EW177 FD010 FD078 FD090 FD130 FD146 FD157 GQ05 4J036 AA05 AB01 AB07 AB09 AB10 AB11 AE07 AJ01 AJ02 AJ03 AJ08 AJ09 AK19 BA02 DD07 FA01 GA02 GA03 GA04 GA22 GA23 GA24 GA25 HA12 JA07 KA01 4J040 EF051 EF061 EF111 EF121 EF131 EF291 EF301 GA07 GA25 HA126 JA02 JA03 4M109 AA01 BA01 CA21 EA03 EA06 EB02 EB18 EC03 EC11 EC15 GA01 5F041 AA43 AA44 DA44 DA58 FF01─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C08L 63/00 C08L 63/00 C 5F041 C09J 175/04 C09J 175/04 C09K 3/10 C09K 3/10 L H01L 23/29 H01L 33/00 N 23/31 23/30 R 33/00 F term (reference) 4H017 AA04 AA31 AB08 AC01 AC18 AD06 AE05 4J002 CD021 CD101 CD171 CD201 DD087 EF126 EJ018 EL136 EQ017 EV297 EW008 EW177 FD010 FD078 FD090FD130FD FD157 GQ05 4J036 AA05 AB01 AB07 AB09 AB10 AB11 AE07 AJ01 AJ02 AJ03 AJ08 AJ09 AK19 BA02 DD07 FA01 GA02 GA03 GA04 GA22 GA23 GA24 GA25 HA12 JA07 KA01 4J040 CAEF JA07 JA01 A02 A01 A02 A01 A01 A02 A01 A25 AA02 AJ05 AJ05 AJA05 AA02 AB02 AB02 EC03 EC11 EC15 GA01 5F041 AA43 AA44 DA44 DA58 FF01
Claims (9)
有する、ＬＥＤ封止材用エポキシ樹脂組成物。 （Ａ）成分；芳香族エポキシ樹脂を水素化して得られる
エポキシ当量が２３０〜１０００ｇ／当量のエポキシ樹
脂、及び／又は芳香族エポキシ樹脂を水素化して得られ
るエポキシ樹脂と多価カルボン酸化合物とを反応させて
得られるエポキシ当量が２３０〜１０００ｇ／当量のエ
ポキシ樹脂。 （Ｂ）成分；環状オレフィンをエポキシ化して得られる
脂環式エポキシ樹脂、 （Ｃ）成分：酸無水物硬化剤又はカチオン重合開始剤。1. An epoxy resin composition for an LED encapsulant, which contains the following components (A), (B) and (C). Component (A): an epoxy resin obtained by hydrogenating an aromatic epoxy resin having an epoxy equivalent of 230 to 1000 g / equivalent, and / or an epoxy resin obtained by hydrogenating an aromatic epoxy resin and a polyvalent carboxylic acid compound. Epoxy resin having an epoxy equivalent of 230 to 1000 g / equivalent obtained by the reaction. Component (B); alicyclic epoxy resin obtained by epoxidizing cyclic olefin, Component (C): acid anhydride curing agent or cationic polymerization initiator.
を水素化して得られる下記一般式（１） 【化１】 （式中、Ｒ1及びＲ2は各々同一であっても異なってもよ
く、水素原子、メチル基又はシクロヘキシル基を示し、
ｎは０〜２０の整数である）で示されるエポキシ当量が
２３０〜１０００ｇ／当量のエポキシ樹脂、及び／又は
該一般式（１）のエポキシ樹脂と多価カルボン酸化合物
とを反応させて得られるエポキシ当量が２３０〜１００
０ｇ／当量のエポキシ樹脂であることを特徴とする、請
求項１記載のＬＥＤ封止材用エポキシ樹脂組成物。2. The component (A) is obtained by hydrogenating an aromatic epoxy resin and has the following general formula (1): (In the formula, R 1 and R 2 may be the same or different and each represents a hydrogen atom, a methyl group or a cyclohexyl group,
n is an integer of 0 to 20) and is obtained by reacting an epoxy resin having an epoxy equivalent of 230 to 1000 g / equivalent, and / or the epoxy resin of the general formula (1) with a polycarboxylic acid compound. Epoxy equivalent is 230-100
The epoxy resin composition for LED encapsulant according to claim 1, wherein the epoxy resin is 0 g / equivalent.
に対し、（Ｂ）成分の脂環式エポキシ樹脂が１０〜２０
０質量部、（Ａ）成分と（Ｂ）成分の総和１００質量部
に対し、（Ｃ）成分の酸無水物硬化剤又はカチオン重合
開始剤が０.０１〜２００質量部の割合で配合されてい
ることを特徴とする、請求項１又は２に記載のＬＥＤ封
止材用エポキシ樹脂組成物。3. 10 to 20 parts by weight of the alicyclic epoxy resin as the component (B) with respect to 100 parts by weight of the epoxy resin as the component (A).
0 parts by mass, the acid anhydride curing agent or the cationic polymerization initiator of the component (C) is blended in a proportion of 0.01 to 200 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). The epoxy resin composition for LED encapsulant according to claim 1 or 2, characterized in that
ポキシ樹脂１００質量部に対し脂環構造を有するジカル
ボン酸化合物を１〜５０質量部の割合で反応させて得ら
れたエポキシ樹脂であることを特徴とする、請求項１〜
３のいずれか１項に記載のＬＥＤ封止材用エポキシ樹脂
組成物。4. The epoxy resin as the component (A) is an epoxy resin obtained by reacting 100 parts by mass of a hydrogenated epoxy resin with a dicarboxylic acid compound having an alicyclic structure at a ratio of 1 to 50 parts by mass. It is characterized by the above-mentioned.
The epoxy resin composition for LED encapsulant according to any one of 3 above.
である、請求項１〜４のいずれか１項に記載のＬＥＤ封
止材用エポキシ樹脂組成物。5. The epoxy resin composition for an LED encapsulant according to claim 1, wherein the acid anhydride curing agent is a saturated alicyclic acid anhydride.
塩、ヨードニウム塩、ジアゾニウム塩、ホスホニム塩か
ら選ばれる少なくとも１種のオニウム塩である、請求項
１〜５のいずれか１項に記載のＬＥＤ封止材用エポキシ
樹脂組成物。6. The LED encapsulation according to claim 1, wherein the cationic polymerization initiator is at least one onium salt selected from a sulfonium salt, an iodonium salt, a diazonium salt, and a phosphonium salt. Epoxy resin composition for wood.
Ａ）で測定した熱膨張率の変化点で示されるガラス転移
温度が６０℃〜１６０℃であることを特徴とする、請求
項１〜６のいずれか１項に記載のＬＥＤ封止材用エポキ
シ樹脂組成物。7. The cured product is transparent and is subjected to thermomechanical analysis (TM).
Epoxy for LED encapsulants according to any one of claims 1 to 6, characterized in that the glass transition temperature indicated by the change point of the coefficient of thermal expansion measured in A) is from 60 ° C to 160 ° C. Resin composition.
防止剤を配合していることを特徴とする、請求項１〜７
のいずれか１項に記載のＬＥＤ封止材用エポキシ樹脂組
成物。8. A compound containing a phenolic antioxidant and a phosphorus antioxidant, characterized in that:
The epoxy resin composition for LED encapsulant according to any one of 1.
ポキシ樹脂組成物で封止されたＬＥＤ装置。9. An LED device encapsulated with the epoxy resin composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002084801A JP2003277473A (en) | 2002-03-26 | 2002-03-26 | Epoxy resin composition for sealant of led, and led device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002084801A JP2003277473A (en) | 2002-03-26 | 2002-03-26 | Epoxy resin composition for sealant of led, and led device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003277473A true JP2003277473A (en) | 2003-10-02 |
Family
ID=29231992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002084801A Pending JP2003277473A (en) | 2002-03-26 | 2002-03-26 | Epoxy resin composition for sealant of led, and led device |
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| Country | Link |
|---|---|
| JP (1) | JP2003277473A (en) |
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| JP2006188605A (en) * | 2005-01-06 | 2006-07-20 | Japan Epoxy Resin Kk | Hydrogenated epoxy resin, method for producing the same and epoxy resin composition |
| WO2006118323A1 (en) * | 2005-04-28 | 2006-11-09 | Nippon Shokubai Co., Ltd. | Composition containing fluorine-containing aromatic polymer and laminated body containing fluorine-containing aromatic polymer |
| WO2007029503A1 (en) * | 2005-09-02 | 2007-03-15 | Nippon Steel Chemical Co., Ltd. | Epoxy resin composition |
| WO2007125956A1 (en) | 2006-04-26 | 2007-11-08 | Sekisui Chemical Co., Ltd. | Thermosetting composition for optical semiconductor, die bond material for optical semiconductor device, underfill material for optical semiconductor device, sealing agent for optical semiconductor device, and optical semiconductor device |
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| JP2009001768A (en) * | 2007-06-22 | 2009-01-08 | Meian Kokusai Gigyo Kofun Yugenkoshi | Prepreg |
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