JP2011052102A - Epoxy resin curing agent, method for producing the same and epoxy resin composition - Google Patents
Epoxy resin curing agent, method for producing the same and epoxy resin composition Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
- C08G59/48—Amides together with other curing agents with polycarboxylic acids, or with anhydrides, halides or low-molecular-weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
Description
本発明は、エポキシ樹脂硬化剤、エポキシ樹脂組成物および前記硬化剤の製造方法に関する。 The present invention relates to an epoxy resin curing agent, an epoxy resin composition, and a method for producing the curing agent.
一般に、酸無水物とエポキシ樹脂から得られるエポキシ樹脂硬化物は、安価で、透明性、電気絶縁性、耐薬品性、耐湿性、接着性等に優れており、電気絶縁材料、半導体材料、接着材料、塗料材料等、様々な用途で用いられている。代表的な使用例の一つとして、発光ダイオード（Ｌｉｇｈｔ−ｅｍｉｔｔｉｎｇ ｄｉｏｄｅ：以下ＬＥＤと略す）の発光素子を保護するための封止材を挙げることができるが、近年になって短波長の光を発する光源と蛍光体とを組み合わせた白色ＬＥＤが普及するにつれ、封止材の劣化が問題視されるようになってきた。 Generally, epoxy resin cured products obtained from acid anhydrides and epoxy resins are inexpensive and have excellent transparency, electrical insulation, chemical resistance, moisture resistance, adhesiveness, etc., electrical insulation materials, semiconductor materials, adhesives It is used in various applications such as materials and paint materials. As a typical use example, a sealing material for protecting a light-emitting element of a light-emitting diode (hereinafter abbreviated as an LED) can be given. As white LEDs that combine a light source that emits light and a phosphor have become widespread, degradation of sealing materials has become a problem.
すなわち、白色ＬＥＤの場合、より高エネルギーの光源を用いるため、従来の赤色や緑色のＬＥＤに比べて封止材が劣化して着色しやすく、ＬＥＤの寿命が短くなってしまうという問題が発生する。また、発光素子の改良によって小型化及び大電流化が進むにつれ、ＬＥＤを長時間点灯させた場合に発生する熱も大きくなり、これによっても同様に封止材の劣化が引き起こされる。 That is, in the case of a white LED, since a higher energy light source is used, there is a problem that the sealing material is deteriorated and easily colored as compared with a conventional red or green LED, and the life of the LED is shortened. . In addition, as the size of the light emitting element is improved and the current is increased, the heat generated when the LED is lit for a long time is increased, which also causes deterioration of the sealing material.
このような光や熱による劣化を抑制することは、エポキシ樹脂のさらなる普及において重要な課題となっている。これを解決する方法として、光や熱により劣化しやすい芳香族エポキシ樹脂に代わって脂環式エポキシ樹脂を用いたエポキシ樹脂組成物の提案がなされている。 Suppressing such deterioration due to light and heat is an important issue in the further spread of epoxy resins. As a method for solving this problem, there has been proposed an epoxy resin composition using an alicyclic epoxy resin in place of an aromatic epoxy resin that is easily deteriorated by light or heat.
また、エポキシ樹脂硬化剤としては、炭素・炭素二重結合を水添した飽和脂環式ジカルボン酸無水物が用いられている。 As the epoxy resin curing agent, a saturated alicyclic dicarboxylic acid anhydride in which a carbon / carbon double bond is hydrogenated is used.
このような飽和脂環式ジカルボン酸無水物としては、３−および／または４−メチルヘキサヒドロフタル酸無水物からなるエポキシ樹脂硬化剤、ノルボルナンジカルボン酸無水物またはメチルノルボルナンジカルボン酸無水物からなるエポキシ樹脂硬化剤などが挙げられる。 Such saturated alicyclic dicarboxylic acid anhydrides include epoxy resin curing agents comprising 3- and / or 4-methylhexahydrophthalic anhydride, norbornane dicarboxylic acid anhydride or epoxy comprising methyl norbornane dicarboxylic acid anhydride. Resin curing agents and the like can be mentioned.
しかし、３−および／または４−メチルヘキサヒドロフタル酸無水物からなるエポキシ樹脂硬化剤は、室温にて液状であるものの、その硬化物の耐熱性および耐湿性が劣るという問題点を有する。 However, although the epoxy resin curing agent made of 3- and / or 4-methylhexahydrophthalic anhydride is liquid at room temperature, it has a problem that the cured product has poor heat resistance and moisture resistance.
また、ノルボルナンジカルボン酸無水物またはメチルノルボルナンジカルボン酸無水物からなるエポキシ樹脂硬化剤は、通常、室温にて固体であり、取扱いが不便であるという問題点を有している。 In addition, an epoxy resin curing agent made of norbornane dicarboxylic acid anhydride or methyl norbornane dicarboxylic acid anhydride is usually a solid at room temperature and has a problem that it is inconvenient to handle.
そこで、メチルノルボルナンジカルボン酸無水物の液状化方法として、メチルノルボルネンジカルボン酸無水物を酸触媒の存在下にて、メチレンノルボルナンジカルボン酸無水物へ異性化し、次いで水素化を行う方法が提案されている（特許文献１参照）。 Therefore, as a method for liquefying methylnorbornane dicarboxylic acid anhydride, a method in which methyl norbornene dicarboxylic acid anhydride is isomerized to methylene norbornane dicarboxylic acid anhydride in the presence of an acid catalyst and then hydrogenated is proposed. (See Patent Document 1).
しかし、この方法では、低凝固点のメチルノルボルナンジカルボン酸無水物を得るため、異性化時に１７０℃以上の温度と酸触媒を用いるため、汎用の製造設備では腐食等の問題がある。また、精製を行う場合も同様の問題がある。 However, in this method, a methylnorbornane dicarboxylic acid anhydride having a low freezing point is obtained, and a temperature of 170 ° C. or higher and an acid catalyst are used during isomerization. In addition, the same problem occurs when purification is performed.
また、ヘキサヒドロフタル酸無水物などを多量混ぜて硬化剤を液状にする方法（特許文献２参照）が提案されているが、上述したような近年の技術の発展に伴い、耐熱性が充分とは言えない。 Further, a method of mixing a large amount of hexahydrophthalic anhydride or the like to make the curing agent liquid (see Patent Document 2) has been proposed, but with the recent development of technology as described above, heat resistance is sufficient. I can't say that.
本発明は、上記の問題から、メチルノルボルナンジカルボン酸と多価カルボン酸を含むエポキシ樹脂の硬化剤を使用して、低粘度で、着色が少なく、耐熱性、曲げ強度、曲げ弾性率及び透明性に優れる硬化物を与えるエポキシ樹脂硬化剤、及びそれを使用したエポキシ樹脂組成物を提供するものである。 In view of the above problems, the present invention uses an epoxy resin curing agent containing methylnorbornane dicarboxylic acid and polyvalent carboxylic acid, has low viscosity, little coloration, heat resistance, bending strength, bending elastic modulus and transparency. The present invention provides an epoxy resin curing agent that provides a cured product having excellent resistance, and an epoxy resin composition using the same.
本発明者らは、上記の課題を解決するため鋭意検討した結果、メチルノルボルナンジカルボン酸と、多価カルボン酸を含むエポキシ樹脂硬化剤により、液状で取扱いが容易な、着色が少ない、耐熱性、曲げ強度、曲げ弾性率及び透明性に優れる硬化物を与えるエポキシ樹脂硬化剤が安価に得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a liquid, easy handling, low coloration, heat resistance, and an epoxy resin curing agent containing a polymethylcarboxylic acid and a methylnorbornane dicarboxylic acid. The present inventors have found that an epoxy resin curing agent that gives a cured product having excellent bending strength, flexural modulus, and transparency can be obtained at a low cost, and completed the present invention.
本発明は、以下に関する。
［１］メチルノルボルナンジカルボン酸と、多価カルボン酸とを含むエポキシ樹脂硬化剤であって、硬化剤中におけるメチルノルボルナンジカルボン酸の含有質量が、多価カルボン酸の含有質量より大きいことを特徴とするエポキシ樹脂硬化剤。
［２］硬化剤１００質量部に対して、メチルノルボルナンジカルボンを酸５１〜９９質量部と、多価カルボン酸無水物を１〜４９質量部とを含む前記［１］記載のエポキシ樹脂硬化剤。
［３］多価カルボン酸が、下記一般式（１）で表される無水物である前記［１］または［２］に記載のエポキシ樹脂硬化剤。
The present invention relates to the following.
[1] An epoxy resin curing agent containing methyl norbornane dicarboxylic acid and a polyvalent carboxylic acid, wherein the content of methyl norbornane dicarboxylic acid in the curing agent is larger than the content of polyvalent carboxylic acid. Epoxy resin curing agent.
[2] The epoxy resin curing agent according to [1], including 51 to 99 parts by mass of methylnorbornane dicarboxylic acid and 1 to 49 parts by mass of polyvalent carboxylic acid anhydride with respect to 100 parts by mass of the curing agent.
[3] The epoxy resin curing agent according to [1] or [2], wherein the polyvalent carboxylic acid is an anhydride represented by the following general formula (1).
［４］エポキシ樹脂と、前記［１］乃至［３］のいずれかに記載のエポキシ樹脂硬化剤とを含むエポキシ樹脂組成物。 [4] An epoxy resin composition comprising an epoxy resin and the epoxy resin curing agent according to any one of [1] to [3].
［５］前記［１］乃至［３］のいずれかに記載のエポキシ樹脂硬化剤を製造する方法であって、予めメチルノルボルネンジカルボン酸と多価カルボン酸を混合してから、当該混合物の水素化を行うことを特徴とするエポキシ樹脂硬化剤の製造方法。 [5] A method for producing the epoxy resin curing agent according to any one of [1] to [3], wherein methylnorbornene dicarboxylic acid and polyvalent carboxylic acid are mixed in advance, and hydrogenation of the mixture is performed. The manufacturing method of the epoxy resin hardening | curing agent characterized by performing.
［６］前記［１］乃至［３］のいずれかに記載のエポキシ樹脂硬化剤を製造する方法であって、メチルノルボルネンジカルボン酸を水素化し、得られたメチルノルボルナンジカルボン酸に多価カルボン酸を混合することを特徴とするエポキシ樹脂硬化剤の製造方法。 [6] A method for producing an epoxy resin curing agent according to any one of [1] to [3], wherein methylnorbornene dicarboxylic acid is hydrogenated, and polymethylcarboxylic acid is added to the obtained methylnorbornane dicarboxylic acid. The manufacturing method of the epoxy resin hardening | curing agent characterized by mixing.
本発明によれば、低粘度で取扱いが容易な、着色が少なく、耐熱性、曲げ強度、曲げ弾性率及び透明性に優れる硬化物を与えるエポキシ樹脂硬化剤、エポキシ樹脂組成物を得ることができる。 According to the present invention, it is possible to obtain an epoxy resin curing agent and an epoxy resin composition that give a cured product having low viscosity, easy handling, little coloration, and excellent heat resistance, bending strength, flexural modulus, and transparency. .
以下、本発明を詳細に説明する。
本発明に用いる多価カルボン酸は、メチルノルボルナンジカルボン酸以外であれば特に制限は無く、例えばヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸、メチルテトラヒドロフタル酸等が挙げられ、これらは二種類以上併用してもよい。
Hereinafter, the present invention will be described in detail.
The polyvalent carboxylic acid used in the present invention is not particularly limited as long as it is other than methylnorbornane dicarboxylic acid, and examples thereof include hexahydrophthalic acid, methylhexahydrophthalic acid, and methyltetrahydrophthalic acid. May be.
また、多価カルボン酸は無水物であってもよい。このため、本発明において「多価カルボン酸」とは無水物を含むものとし、また「多価カルボン酸（無水物）」とも示す。一般に、多価カルボン酸は無水物であるのが好ましい。
後述するメチルノルボルナンジカルボン酸の無水物についても同様である。
The polyvalent carboxylic acid may be an anhydride. For this reason, in the present invention, the “polycarboxylic acid” includes an anhydride and is also referred to as “polycarboxylic acid (anhydride)”. In general, the polycarboxylic acid is preferably an anhydride.
The same applies to the anhydride of methylnorbornane dicarboxylic acid described later.
本発明により得られる硬化物が、着色が少なく、耐熱性、曲げ強度、曲げ弾性率及び透明性に優れるという効果をより顕著に発揮させるためには、多価カルボン酸が下記一般式（１）で表される無水物であることが好ましい。
このような化合物としては、例えばヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。これらは二種類以上併用してもよい。 Examples of such compounds include hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. Two or more of these may be used in combination.
エポキシ樹脂組成物における硬化剤としての本発明のエポキシ樹脂硬化剤の使用量は、エポキシ樹脂中のエポキシ基１．０当量に対してカルボキシル基が１．０〜２．４当量（無水物の場合は、酸無水物基が０．５〜１．２当量）になるよう配合することが好ましく、カルボキシル基１．４〜２．０（無水物基０．７〜１．０当量）になるよう配合することがより好ましい。
カルボキシル基が１．０当量（酸無水物基が０．５当量）未満であると、硬化が不十分となり、硬化物の機械的特性が著しく低下するおそれがある。また、カルボキシル基が２．４当量（酸無水物基が１．２当量）を超える場合にも、同様に硬化物の機械的特性が低下するおそれがある。
The use amount of the epoxy resin curing agent of the present invention as a curing agent in the epoxy resin composition is 1.0 to 2.4 equivalents of carboxyl groups (1.0% equivalents to anhydrides) based on 1.0 equivalents of epoxy groups in the epoxy resin. Is preferably blended so that the acid anhydride group is 0.5 to 1.2 equivalent), so that the carboxyl group is 1.4 to 2.0 (anhydride group 0.7 to 1.0 equivalent). It is more preferable to mix.
If the carboxyl group is less than 1.0 equivalent (acid anhydride group is 0.5 equivalent), curing may be insufficient, and the mechanical properties of the cured product may be significantly reduced. Also, when the carboxyl group exceeds 2.4 equivalents (acid anhydride group is 1.2 equivalents), the mechanical properties of the cured product may be similarly reduced.
本発明に用いるメチルノルボルナンジカルボン酸は、メチルノルボルネンジカルボン酸を水素化して得られる。また、メチルノルボルナン−２，３−ジカルボン酸を無水物化した、メチルノルボルナンジカルボン酸無水物を使用することもできる。メチルノルボルナンジカルボン酸無水物には、エキソ体とエンド体の立体異性体が存在するが、エキソ体の比率が増加すると液状となりやすいため、取り扱いやすい。 The methyl norbornane dicarboxylic acid used in the present invention is obtained by hydrogenating methyl norbornene dicarboxylic acid. Moreover, methylnorbornane dicarboxylic acid anhydride obtained by anhydride-forming methyl norbornane-2,3-dicarboxylic acid can also be used. Methylnorbornane dicarboxylic acid anhydride has a stereoisomer of an exo form and an endo form, but is easy to handle because it tends to become liquid when the ratio of the exo form increases.
本発明の硬化剤において、メチルノルボルナンジカルボン酸（無水物）の含有質量は、多価カルボン酸の含有質量より大きいことが必要であり、エポキシ樹脂硬化剤１００質量部に対して、メチルノルボルナンジカルボン酸（無水物）は、５１〜９９質量部、多価カルボン酸（無水物）を１〜４９質量部含まれることが好ましく、メチルノルボルナンジカルボン酸（無水物）は、５５〜９０質量部であることがより好ましく、６０〜８０質量部であることが更に好ましい。また、多価カルボン酸（無水物）は、１０〜４５質量部であることがより好ましく、２０〜４０質量部含まれることが更に好ましい。多価カルボン酸が１質量部以上であれば、硬化剤が室温で固形になりにくく、４９質量部以下であると硬化物の耐光性が低下するおそれが少なくなるので、実用上好ましい。また、メチルノルボルナンジカルボン酸（無水物）の含有質量が多価カルボン酸の含有質量より大きいことにより、相対的にノルボルネン構造が多くなり、曲げ強度、曲げ弾性率が向上する傾向にある。 In the curing agent of the present invention, the content of methyl norbornane dicarboxylic acid (anhydride) needs to be larger than the content of polyvalent carboxylic acid, and methyl norbornane dicarboxylic acid with respect to 100 parts by mass of the epoxy resin curing agent. (Anhydride) is preferably contained in an amount of 51 to 99 parts by mass and polyvalent carboxylic acid (anhydride) in an amount of 1 to 49 parts by mass, and methylnorbornane dicarboxylic acid (anhydride) in an amount of 55 to 90 parts by mass. Is more preferable, and it is still more preferable that it is 60-80 mass parts. Moreover, as for polyvalent carboxylic acid (anhydride), it is more preferable that it is 10-45 mass parts, and it is still more preferable that 20-40 mass parts is contained. If the polyvalent carboxylic acid is 1 part by mass or more, the curing agent is less likely to be solid at room temperature, and if it is 49 parts by mass or less, the light resistance of the cured product is reduced, which is practically preferable. Moreover, when the content mass of methylnorbornane dicarboxylic acid (anhydride) is larger than the content mass of polyvalent carboxylic acid, the norbornene structure is relatively increased, and the bending strength and the flexural modulus tend to be improved.
本発明のエポキシ樹脂組成物に用いるエポキシ樹脂は特に制限は無いが、耐光性及び耐熱性の面から脂環式エポキシ樹脂が好ましい。脂環式エポキシ樹脂は、１分子中に脂環式骨格及び２個以上のエポキシ基を有するものであり、例えば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、ビス（３，４−エポキシシクロヘキシルメチル）アジペート、ビニルシクロヘキセンジオキサイド、水素添加ビスフェノールＡジグリシジルエーテル等が挙げられる。これらは二種類以上併用してもよい。 Although there is no restriction | limiting in particular in the epoxy resin used for the epoxy resin composition of this invention, An alicyclic epoxy resin is preferable from the surface of light resistance and heat resistance. The alicyclic epoxy resin has an alicyclic skeleton and two or more epoxy groups in one molecule. For example, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis ( 3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, hydrogenated bisphenol A diglycidyl ether, and the like. Two or more of these may be used in combination.
また、目的に応じて脂環式エポキシ樹脂以外のエポキシ樹脂も用いることができる。このようなエポキシ樹脂としては、例えばビスフェノールＡ、ビスフェノールＳ等のビスフェノール類とエピクロロヒドリンとの反応により得られるビスフェノール型エポキシ樹脂、フェノールノボラックとエピクロロヒドリンとの反応により得られるフェノールノボラック型エポキシ樹脂、多価カルボン酸とエピクロロヒドリンとの反応により得られるグリシジルエステル型エポキシ樹脂などが挙げられる。これらは二種類以上併用してもよい。 Further, an epoxy resin other than the alicyclic epoxy resin can also be used depending on the purpose. Examples of such epoxy resins include bisphenol type epoxy resins obtained by reaction of bisphenols such as bisphenol A and bisphenol S with epichlorohydrin, and phenol novolak types obtained by reaction of phenol novolac and epichlorohydrin. Examples thereof include an epoxy resin, a glycidyl ester type epoxy resin obtained by a reaction between a polyvalent carboxylic acid and epichlorohydrin. Two or more of these may be used in combination.
これらの脂環式エポキシ樹脂以外のエポキシ樹脂の使用量は、脂環式エポキシ樹脂１００質量部に対して０〜８０質量部とするのが好ましく、０〜２０質量部とするのがより好ましい。脂環式エポキシ樹脂以外のエポキシ樹脂の使用量が８０質量部を超えると硬化物の耐光性及び耐熱性が低下するおそれがある。 The amount of the epoxy resin other than these alicyclic epoxy resins used is preferably 0 to 80 parts by mass, more preferably 0 to 20 parts by mass with respect to 100 parts by mass of the alicyclic epoxy resin. When the usage-amount of epoxy resins other than an alicyclic epoxy resin exceeds 80 mass parts, there exists a possibility that the light resistance and heat resistance of hardened | cured material may fall.
本発明においては、メチルノルボルナンジカルボン酸（無水物）と多価カルボン酸（無水物）を混合することにより目的とするエポキシ樹脂硬化剤を得ることができるが、その製造方法としては、(A)予めメチルノルボルネンジカルボン酸と多価カルボン酸を混合してから、当該混合物の水素化を行うこともできるし、(B)メチルノルボルネンジカルボン酸無水物を水素化し、得られたメチルノルボルナンジカルボン酸に多価カルボン酸を混合することもできる。 In the present invention, a target epoxy resin curing agent can be obtained by mixing methylnorbornane dicarboxylic acid (anhydride) and polyvalent carboxylic acid (anhydride). After mixing methylnorbornene dicarboxylic acid and polyvalent carboxylic acid in advance, the mixture can be hydrogenated, or (B) methylnorbornene dicarboxylic acid anhydride is hydrogenated and the resulting methylnorbornane dicarboxylic acid Divalent carboxylic acids can also be mixed.
水素化する方法に特に制限はなく、種々の方法を用いることができる。例えば接触水素添加法、ヨウ化水素と赤リンまたはナトリウムとアルコールの組み合わせを用いる方法等が挙げられるが、これらに限定されない。好ましい方法は接触水素添加による水素化であり、これは回分反応、流通連続反応のいずれによっても良い。接触水素化は通常、水素添加触媒の存在下、かつ加熱下で、水素と接触させることによって行う。好ましい触媒としては、ルテニウム、白金、コバルト、パラジウム、ニッケル等が挙げられるが、これらに限定されない。担持触媒を使用しても良く、例えば５質量％の金属パラジウムをアルミナ粉末に担持したものを触媒として使用することができる。触媒の使用量に特に制限はないが、好ましくは原料酸無水物の質量に対し 0.1〜5質量％程度とする。 There is no restriction | limiting in particular in the method to hydrogenate, A various method can be used. Examples thereof include, but are not limited to, a catalytic hydrogenation method, a method using a combination of hydrogen iodide and red phosphorus or sodium and alcohol. A preferred method is hydrogenation by catalytic hydrogenation, which may be either batch reaction or continuous flow reaction. Catalytic hydrogenation is usually carried out by contacting with hydrogen in the presence of a hydrogenation catalyst and under heating. Preferred catalysts include, but are not limited to, ruthenium, platinum, cobalt, palladium, nickel and the like. A supported catalyst may be used. For example, a catalyst in which 5% by mass of metallic palladium is supported on alumina powder can be used. Although there is no restriction | limiting in particular in the usage-amount of a catalyst, Preferably it is set as about 0.1-5 mass% with respect to the mass of raw material acid anhydride.
水素添加反応時の水素圧は、1〜15 MPaとされ、2〜10 MPa程度とするのが好ましい。温度は、40〜100 ℃とされ、は40〜90 ℃が好ましく、１段もしくは２段で反応を行っても良い。反応時間は1〜15時間とされ、2〜10時間程度が好ましい。水素添加反応の際に溶媒は必要ではないが、溶媒、例えばテトラヒドロフラン、1,4-ジオキサン等を使用しても良い。上記のようにして水素化した後、好ましくは触媒及び使用した溶媒等を分離し、メチルノルボルナンジカルボン酸を含むエポキシ樹脂硬化剤を精製する。精製法に特に制限はなく、濾過、蒸留等の種々の方法を使用することができる。本発明の方法により得られるメチルノルボルナンジカルボン酸を含むエポキシ樹脂硬化剤は室温で液状かつ低粘度であり、作業性に優れる。 The hydrogen pressure during the hydrogenation reaction is 1 to 15 MPa, preferably about 2 to 10 MPa. The temperature is 40 to 100 ° C, preferably 40 to 90 ° C, and the reaction may be performed in one or two stages. The reaction time is 1 to 15 hours, preferably about 2 to 10 hours. A solvent is not necessary for the hydrogenation reaction, but a solvent such as tetrahydrofuran or 1,4-dioxane may be used. After hydrogenation as described above, preferably, the catalyst and the solvent used are separated, and the epoxy resin curing agent containing methylnorbornane dicarboxylic acid is purified. The purification method is not particularly limited, and various methods such as filtration and distillation can be used. The epoxy resin curing agent containing methyl norbornane dicarboxylic acid obtained by the method of the present invention is liquid and low viscosity at room temperature, and is excellent in workability.
本発明におけるエポキシ樹脂組成物は、目的に応じて硬化促進剤を適宜添加することができる。硬化促進剤としては、例えば２−エチル−４−メチルイミダゾール、１−メチルイミダゾール等のイミダゾール類、ベンジルジメチルアミン、Ｎ，Ｎ−ジメチルアニリン等の三級アミン、テトラメチルアンモニウムクロライド、ベンジルトリエチルアンモニウムクロライド等の四級アンモニウム塩、テトラ−ｎ−ブチルホスホニウム ｏ，ｏ−ジエチルホスホロジチオネート、テトラブチルホスホニウム ベンゾトリアゾラート等のホスホニウム塩、オクチル酸亜鉛、ステアリン酸亜鉛等の金属塩、アセチルアセトン亜鉛、ベンゾイルアセトン亜鉛等の金属錯体などが挙げられる。 In the epoxy resin composition of the present invention, a curing accelerator can be appropriately added depending on the purpose. Examples of the curing accelerator include imidazoles such as 2-ethyl-4-methylimidazole and 1-methylimidazole, tertiary amines such as benzyldimethylamine and N, N-dimethylaniline, tetramethylammonium chloride, and benzyltriethylammonium chloride. Quaternary ammonium salts such as tetra-n-butylphosphonium o, o-diethyl phosphorodithioate, phosphonium salts such as tetrabutylphosphonium benzotriazolate, metal salts such as zinc octylate and zinc stearate, zinc acetylacetone, Examples thereof include metal complexes such as benzoylacetone zinc.
硬化促進剤のエポキシ樹脂組成物中の配合量は、０．０１〜８質量％とするのが好ましく、０．１〜５質量％とするのがより好ましい。硬化促進剤の配合量が０．０１質量％以上であると、十分な効果が得られやすい。また、硬化促進剤の配合量が８質量％以下であれば、得られる硬化物が着色したり耐熱性が低下したりするおそれが少なくなる。 The blending amount of the curing accelerator in the epoxy resin composition is preferably 0.01 to 8% by mass, and more preferably 0.1 to 5% by mass. If the blending amount of the curing accelerator is 0.01% by mass or more, a sufficient effect can be easily obtained. Moreover, if the compounding quantity of a hardening accelerator is 8 mass% or less, there exists little possibility that the hardened | cured material obtained may be colored or heat resistance may fall.
本発明におけるエポキシ樹脂組成物には、得られる硬化物の特性を損ねない範囲で各種添加剤を目的に応じてさらに添加することができる。添加剤としては、可撓化剤、熱安定剤、紫外線吸収剤、難燃剤、帯電防止剤、消泡剤、チキソトロピー性付与剤、離型剤等が挙げられる。更に、例えば、硬化物の耐光性及び耐熱性をさらに向上させるための酸化防止剤、硬化における重合反応を制御するための連鎖移動剤、硬化物の機械的物性、接着性、取扱い性を改良するための充填剤、可塑剤、低応力化剤、カップリング剤、染料、光散乱剤などが挙げられる。 Various additives can be further added to the epoxy resin composition according to the present invention depending on the purpose within a range that does not impair the properties of the resulting cured product. Examples of the additive include a flexibilizer, a heat stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent, an antifoaming agent, a thixotropic agent, and a release agent. Furthermore, for example, an antioxidant for further improving the light resistance and heat resistance of the cured product, a chain transfer agent for controlling the polymerization reaction during curing, and improving the mechanical properties, adhesiveness, and handleability of the cured product. Fillers, plasticizers, stress reducing agents, coupling agents, dyes, light scattering agents and the like.
本発明におけるエポキシ樹脂組成物を加熱硬化させることにより、着色が少なく、耐熱性、曲げ強度、曲げ弾性率及び透明性に優れる硬化物を得ることができる。硬化物の製造方法には特に制限は無く、公知の方法を適用することができる。加熱硬化の温度及び時間は特に限定されないが、５０〜２３０℃、１〜１２時間で硬化することができるが、９０〜１８０℃で１〜１２時間が好ましい。エポキシ樹脂組成物を塗布、ポッティング、含浸等の方法により、ＬＥＤ発光素子等の表面上に設け、加熱硬化することにより、ＬＥＤ発光素子等を封止することができる。 By curing the epoxy resin composition of the present invention with heat, a cured product having little coloration and excellent in heat resistance, bending strength, bending elastic modulus and transparency can be obtained. There is no restriction | limiting in particular in the manufacturing method of hardened | cured material, A well-known method is applicable. The temperature and time for heat curing are not particularly limited, but can be cured at 50 to 230 ° C. for 1 to 12 hours, preferably 1 to 12 hours at 90 to 180 ° C. The LED light-emitting element or the like can be sealed by providing the epoxy resin composition on the surface of the LED light-emitting element or the like by a method such as coating, potting, or impregnation, followed by heat curing.
本発明の光半導体装置は、ＬＥＤ発光素子、フォトダイオード素子等の光半導体素子が上記硬化物で封止されたものであり、着色が少なく、耐熱性、曲げ強度、曲げ弾性率及び透明性に優れ、さらに耐光性にも優れるものである。 The optical semiconductor device of the present invention is an optical semiconductor element such as an LED light-emitting element or a photodiode element sealed with the above cured product, has little coloring, and has excellent heat resistance, bending strength, bending elastic modulus and transparency. It is excellent in light resistance.
以下、実施例により本発明をさらに具体的に説明する。本発明はこれらの実施例により制限されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by these examples.
（実施例１）
５００ｍｌのオートクレーブ中に、メチルノルボルネン-2,3-ジカルボン酸無水物（ＭＨＡＣ−Ｐ：日立化成工業株式会社製／酸無水物当量１７７（ｇ／ｅｑ））８０質量部とメチルテトラヒドロ無水フタル酸（ＨＮ−２２００：日立化成工業株式会社製／酸無水物当量１６６（ｇ／ｅｑ））２０質量部とパラジウム触媒（５質量％の金属パラジウムをカーボン粉末に担持したもの）１質量部を導入し、オートクレーブ内を水素で置換した後、水素圧６ＭＰａにて９０℃に加熱し、撹拌下で９時間水素添加反応を行った。反応終了後、減圧濾過にて触媒を除去し、精製操作を経て８６ｇの無色透明なエポキシ樹脂硬化剤（I）（酸無水物当量１８２（ｇ／ｅｑ））を得た。このエポキシ樹脂硬化剤（I）は室温にて液体であった。
Example 1
In a 500 ml autoclave, 80 parts by mass of methylnorbornene-2,3-dicarboxylic anhydride (MHAC-P: manufactured by Hitachi Chemical Co., Ltd./acid anhydride equivalent 177 (g / eq)) and methyltetrahydrophthalic anhydride ( HN-2200: Hitachi Chemical Co., Ltd./acid anhydride equivalent 166 (g / eq)) 20 parts by mass and palladium catalyst (5 mass% metal palladium supported on carbon powder) 1 part by mass were introduced, After replacing the inside of the autoclave with hydrogen, it was heated to 90 ° C. at a hydrogen pressure of 6 MPa, and a hydrogenation reaction was carried out for 9 hours with stirring. After completion of the reaction, the catalyst was removed by filtration under reduced pressure, and 86 g of a colorless and transparent epoxy resin curing agent (I) (acid anhydride equivalent 182 (g / eq)) was obtained through purification operation. This epoxy resin curing agent (I) was liquid at room temperature.
（硬化物作製例１）
エポキシ樹脂硬化剤（I）１２０質量部に対して、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（セロキサイド２０２１Ｐ：ダイセル化学工業株式会社製／エポキシ当量１３８（ｇ／ｅｑ））１００質量部、硬化促進剤としてテトラ−ｎ−ブチルホスホニウム ｏ，ｏ−ジエチルホスホロジチオネート（ヒシコーリンＰＸ−４ＥＴ：日本化学工業株式会社製）１質量部、安定剤として９，１０−ジヒドロ−９−ホスファ−１０−オキサフェナンスレン−９−オキシド（ＨＣＡ：三光化学株式会社製）１質量部を加え、８０℃に加熱して攪拌し、均一になるまで溶解させてエポキシ樹脂組成物（I）を得た。
(Hardened material preparation example 1)
3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P: manufactured by Daicel Chemical Industries, Ltd./epoxy equivalent 138 (120 parts by mass of epoxy resin curing agent (I)) g / eq)) 100 parts by mass, tetra-n-butylphosphonium o, o-diethyl phosphorodithionate (Hishicolin PX-4ET: manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator, 9, as a stabilizer Add 1 part by mass of 10-dihydro-9-phospha-10-oxaphenanthrene-9-oxide (HCA: manufactured by Sanko Chemical Co., Ltd.), heat to 80 ° C., stir, dissolve until uniform, epoxy Resin composition (I) was obtained.
次に、エポキシ樹脂組成物（I）を減圧下で十分に脱泡させてから、板状の金型に注入して、それぞれ１２０℃で１時間加熱した後にさらに１５０℃で４時間加熱して硬化物（I）を得た。 Next, the epoxy resin composition (I) is sufficiently degassed under reduced pressure, poured into a plate-shaped mold, heated at 120 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours. A cured product (I) was obtained.
（実施例２）
５００ｍｌのオートクレーブ中に、メチルノルボルネン-2,3-ジカルボン酸無水物（ＭＨＡＣ−Ｐ：日立化成工業株式会社製／酸無水物当量１７７（ｇ／ｅｑ））３００質量部とパラジウム触媒（５質量％の金属パラジウムをカーボン粉末に担持したもの）１．５質量部を導入し、オートクレーブ内を水素で置換した後、水素圧６ＭＰａにて９０℃に加熱し、撹拌下で５時間水素添加反応を行った。反応終了後、減圧濾過にて触媒を除去し、精製操作を経て２９４ｇの無色透明なメチルノルボルナン-2,3-ジカルボン酸無水物（II）（酸無水物当量１８７（ｇ／ｅｑ））を得た。このメチルノルボルナン-2,3-ジカルボン酸無水物（II）（以下、Ｈ−ＭＨＡＣともいう。）は室温にて固体であった。
(Example 2)
In a 500 ml autoclave, 300 parts by mass of methylnorbornene-2,3-dicarboxylic acid anhydride (MHAC-P: manufactured by Hitachi Chemical Co., Ltd./acid anhydride equivalent 177 (g / eq)) and a palladium catalyst (5% by mass) 1.5 parts by mass of metal palladium supported on carbon powder), the autoclave was replaced with hydrogen, heated to 90 ° C. at a hydrogen pressure of 6 MPa, and subjected to a hydrogenation reaction with stirring for 5 hours. It was. After completion of the reaction, the catalyst was removed by filtration under reduced pressure, and 294 g of colorless and transparent methylnorbornane-2,3-dicarboxylic acid anhydride (II) (acid anhydride equivalent 187 (g / eq)) was obtained through purification operation. It was. This methylnorbornane-2,3-dicarboxylic anhydride (II) (hereinafter also referred to as H-MHAC) was a solid at room temperature.
得られたメチルノルボルナン-2,3-ジカルボン酸無水物（II）８０質量部に対して、多価カルボン酸無水物としてメチルヘキサヒドロ無水フタル酸（ＨＮ−５５００Ｅ：日立化成工業株式会社製／酸無水物当量１６８（ｇ／ｅｑ））２０質量部を加え、７０℃に加熱して攪拌し、均一になるまで溶解させてエポキシ樹脂硬化剤（II）（酸無水物当量１８２（ｇ／ｅｑ））を得た。 With respect to 80 parts by mass of the obtained methylnorbornane-2,3-dicarboxylic acid anhydride (II), methylhexahydrophthalic anhydride (HN-5500E: manufactured by Hitachi Chemical Co., Ltd./acid) as a polyvalent carboxylic acid anhydride Add 20 parts by weight of anhydride equivalent 168 (g / eq), heat to 70 ° C., stir, dissolve until homogeneous and cure epoxy resin hardener (II) (acid anhydride equivalent 182 (g / eq) )
エポキシ樹脂硬化剤（II）１２０質量部を用いた以外は実施例１の硬化物作製例１と同様にして、硬化物（II）を得た。 Hardened | cured material (II) was obtained like the hardened | cured material preparation example 1 of Example 1 except having used 120 mass parts of epoxy resin hardening | curing agents (II).
（実施例３）
実施例２で得られたメチルノルボルナン-2,3-ジカルボン酸無水物（II）６０質量部に対して、多価カルボン酸無水物としてメチルヘキサヒドロ無水フタル酸（ＨＮ−５５００Ｅ：日立化成工業株式会社製／酸無水物当量１６８（ｇ／ｅｑ））４０質量部を加えた以外は実施例２と同様にしてエポキシ樹脂硬化剤（III）（酸無水物当量１７８（ｇ／ｅｑ））を得た。
(Example 3)
With respect to 60 parts by mass of methylnorbornane-2,3-dicarboxylic anhydride (II) obtained in Example 2, methylhexahydrophthalic anhydride (HN-5500E: Hitachi Chemical Co., Ltd.) as a polyvalent carboxylic anhydride Epoxy resin curing agent (III) (acid anhydride equivalent 178 (g / eq)) was obtained in the same manner as in Example 2 except that 40 parts by mass of company-made / acid anhydride equivalent 168 (g / eq) was added. It was.
得られたエポキシ樹脂硬化剤（III）を１１６質量部使用した以外は、実施例１の硬化物作製例１と同様にして硬化物を得た。 A cured product was obtained in the same manner as in the cured product preparation example 1 of Example 1 except that 116 parts by mass of the obtained epoxy resin curing agent (III) was used.
（比較例１）
多価カルボン酸を使用しない以外は、実施例２と同様にしてエポキシ樹脂硬化剤（メチルノルボルナン-2,3-ジカルボン酸無水物（II））を製造し、それを１２２質量部使用した以外は、実施例１の硬化物作製例１と同様にして硬化物を得た。
(Comparative Example 1)
Except not using a polyvalent carboxylic acid, an epoxy resin curing agent (methylnorbornane-2,3-dicarboxylic acid anhydride (II)) was produced in the same manner as in Example 2, except that 122 parts by mass of it was used. A cured product was obtained in the same manner as in the cured product preparation example 1 of Example 1.
（比較例２）
エポキシ樹脂硬化剤として、水素添加処理を行わず、多価カルボン酸も使用せず、メチルノルボルネン-2,3-ジカルボン酸（ＭＨＡＣ−Ｐ：日立化成工業株式会社製／酸無水物当量１７８（ｇ／ｅｑ））を１１６質量部使用した以外は、実施例１の硬化物作製例１と同様にして硬化物を得た。
(Comparative Example 2)
As an epoxy resin curing agent, no hydrogenation treatment was performed, no polycarboxylic acid was used, and methylnorbornene-2,3-dicarboxylic acid (MHAC-P: manufactured by Hitachi Chemical Co., Ltd./acid anhydride equivalent 178 (g A cured product was obtained in the same manner as in the cured product preparation example 1 of Example 1 except that 116 parts by mass of / eq)) was used.
（比較例３）
メチルノルボルナン-2,3-ジカルボン酸無水物（II）を５０質量部、メチルヘキサヒドロ無水フタル酸（ＨＮ−５５００Ｅ：日立化成工業株式会社製／酸無水物当量１６８（ｇ／ｅｑ））を５０質量部とした以外は実施例２と同様にしてエポキシ樹脂硬化剤を得た。このエポキシ樹脂硬化剤を１１７質量部用いた以外は、実施例１の硬化物作製例１と同様にして硬化物を得た。
(Comparative Example 3)
50 parts by mass of methylnorbornane-2,3-dicarboxylic anhydride (II) and 50 of methylhexahydrophthalic anhydride (HN-5500E: manufactured by Hitachi Chemical Co., Ltd./acid anhydride equivalent 168 (g / eq)) An epoxy resin curing agent was obtained in the same manner as in Example 2 except for changing to parts by mass. A cured product was obtained in the same manner as in the cured product preparation example 1 of Example 1 except that 117 parts by mass of this epoxy resin curing agent was used.
（比較例４）
メチルノルボルナン-2,3-ジカルボン酸無水物（II）を３０質量部、メチルヘキサヒドロ無水フタル酸（ＨＮ−５５００Ｅ：日立化成工業株式会社製／酸無水物当量１６８（ｇ／ｅｑ））を７０質量部とした以外は実施例２と同様にしてエポキシ樹脂硬化剤を得た。このエポキシ樹脂硬化剤を１１３質量部用いた以外は、実施例１の硬化物作製例１と同様にして硬化物を得た。
(Comparative Example 4)
30 parts by mass of methylnorbornane-2,3-dicarboxylic anhydride (II), 70 of methylhexahydrophthalic anhydride (HN-5500E: manufactured by Hitachi Chemical Co., Ltd./acid anhydride equivalent 168 (g / eq)) An epoxy resin curing agent was obtained in the same manner as in Example 2 except for changing to parts by mass. A cured product was obtained in the same manner as in the cured product production example 1 of Example 1 except that 113 parts by mass of this epoxy resin curing agent was used.
実施例１〜３及び比較例１〜４で得たエポキシ樹脂硬化剤の外観及び色相と粘度、硬化物の外観、ガラス転移温度、曲げ強度及び曲げ弾性率を評価し、その結果を表１に示した。表１における特性評価の方法は以下の通りである。
・外観：目視により判定した。
・色相：ＡＰＨＡ標準液と目視にて比較した。（比較例１は８０℃で加温し液状で測定）
・粘度：２５℃にて、Ｅ型粘度計にて測定した。
・ガラス転移温度：硬化物から２ｍｍ×５ｍｍ×５ｍｍの試料を切り出し、
機械的熱分析（ＴＭＡ）により測定した。
測定装置 ＳＳＣ−５２００（セイコー電子工業株式会社製）
測定条件 荷重２０ｇ／毎分１０℃加熱
・曲げ強度：ＪＩＳ Ｋ７１７１に従って測定した。
・曲げ弾性率：ＪＩＳ Ｋ７１７１に従って測定した。
The appearance and hue and viscosity of the epoxy resin curing agents obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated, the appearance of the cured product, the glass transition temperature, the bending strength, and the bending elastic modulus. Indicated. The characteristic evaluation method in Table 1 is as follows.
Appearance: Judged by visual inspection.
-Hue: Visually compared with APHA standard solution. (Comparative example 1 is heated at 80 ° C. and measured in liquid form)
Viscosity: Measured with an E-type viscometer at 25 ° C.
-Glass transition temperature: A 2 mm x 5 mm x 5 mm sample was cut out from the cured product,
Measured by mechanical thermal analysis (TMA).
Measuring device SSC-5200 (Seiko Electronics Co., Ltd.)
Measurement conditions Load 20 g / min 10 ° C. Heating / bending strength: Measured according to JIS K7171
-Flexural modulus: measured according to JIS K7171.
表１に示したように、実施例１〜３で得られたエポキシ樹脂硬化剤は比較例１に対し、粘度が低く液体で取扱いが容易であり、硬化物は、無色透明と同様であることが判った。それに対し比較例２の硬化物は、黄色に着色した。また、比較例３と４では、Ｔｇが若干低く、耐熱性もやや劣ることが判った。さらに、実施例１〜３で得られた硬化物は、特に比較例３、４に比べて曲げ強度、曲げ弾性率が優れることが判った。 As shown in Table 1, the epoxy resin curing agents obtained in Examples 1 to 3 have a low viscosity and are easy to handle with respect to Comparative Example 1, and the cured product is the same as colorless and transparent. I understood. In contrast, the cured product of Comparative Example 2 was colored yellow. In Comparative Examples 3 and 4, it was found that Tg was slightly low and heat resistance was slightly inferior. Furthermore, it turned out that the cured | curing material obtained in Examples 1-3 is excellent in bending strength and a bending elastic modulus especially compared with the comparative examples 3 and 4. FIG.
本発明により、液状で取扱いが容易なエポキシ樹脂硬化剤、着色が少ない、耐熱性、曲げ強度、曲げ弾性率及び透明性に優れる硬化物を与えるエポキシ樹脂組成物及びその硬化物を得ることができた。また、本発明を用いることによりエポキシ樹脂硬化剤を容易に製造することが推測される。 According to the present invention, an epoxy resin curing agent that is liquid and easy to handle, an epoxy resin composition that gives a cured product excellent in heat resistance, bending strength, flexural modulus, and transparency, and a cured product that is less colored, can be obtained. It was. Moreover, it is estimated that an epoxy resin hardening | curing agent is easily manufactured by using this invention.
Claims (6)
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| JP2009201755A JP2011052102A (en) | 2009-09-01 | 2009-09-01 | Epoxy resin curing agent, method for producing the same and epoxy resin composition |
| KR1020100064276A KR20110025062A (en) | 2009-09-01 | 2010-07-05 | Hardening agent for epoxy resin, method for producing thereof and epoxy-resin compound |
| CN2010102247481A CN102002144A (en) | 2009-09-01 | 2010-07-07 | Epoxy resin curing agent, its manufacture method and epoxy resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH03252418A (en) * | 1990-03-02 | 1991-11-11 | Tonen Corp | Epoxy resin hardener |
| JPH0632788A (en) * | 1992-07-14 | 1994-02-08 | Tonen Corp | Production of saturated alicyclic dicarboxylic anhydride |
| JP2001114868A (en) * | 1999-10-14 | 2001-04-24 | Tonen Chem Corp | Epoxy resin composition and insulating and sealing material using the same |
| JP2002080562A (en) * | 2000-06-21 | 2002-03-19 | Matsushita Electric Works Ltd | Liquid epoxy resin composition and semiconductor device |
| JP2003026763A (en) * | 2001-07-13 | 2003-01-29 | New Japan Chem Co Ltd | Epoxy resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03252418A (en) * | 1990-03-02 | 1991-11-11 | Tonen Corp | Epoxy resin hardener |
| JPH0632788A (en) * | 1992-07-14 | 1994-02-08 | Tonen Corp | Production of saturated alicyclic dicarboxylic anhydride |
| JP2001114868A (en) * | 1999-10-14 | 2001-04-24 | Tonen Chem Corp | Epoxy resin composition and insulating and sealing material using the same |
| JP2002080562A (en) * | 2000-06-21 | 2002-03-19 | Matsushita Electric Works Ltd | Liquid epoxy resin composition and semiconductor device |
| JP2003026763A (en) * | 2001-07-13 | 2003-01-29 | New Japan Chem Co Ltd | Epoxy resin composition |
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