JP2000143939A - Curing epoxy resin composition - Google Patents
Curing epoxy resin compositionInfo
- Publication number
- JP2000143939A JP2000143939A JP10327788A JP32778898A JP2000143939A JP 2000143939 A JP2000143939 A JP 2000143939A JP 10327788 A JP10327788 A JP 10327788A JP 32778898 A JP32778898 A JP 32778898A JP 2000143939 A JP2000143939 A JP 2000143939A
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- Prior art keywords
- epoxy resin
- hydrogenated
- weight
- resin composition
- aromatic
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塗料、印刷イン
キ、封止材、レジストインキ、接着剤、成形材料、注型
材料及びその他の電気絶縁材料として有用な、熱硬化又
は活性エネルギー線硬化により、耐熱性、電気特性及び
耐候性に優れた硬化物を与える硬化性エポキシ樹脂組成
物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting or active energy ray curing useful as a paint, printing ink, sealing material, resist ink, adhesive, molding material, casting material and other electric insulating materials. The present invention relates to a curable epoxy resin composition which gives a cured product having excellent heat resistance, electrical properties and weather resistance.
【０００２】[0002]
【従来の技術】従来、エポキシ化合物の熱硬化あるいは
活性エネルギー線硬化によるカチオン硬化技術は公知で
あり、各種エポキシ化合物、各種硬化剤及びカチオン硬
化開始剤の材料が広く市販されている。エポキシ化合物
としては、ビスフェノールＡのジグリシジルエーテル、
ビスフェノールＦのジグリシジルエーテル、フェノール
ノボラック型エポキシ樹脂などの芳香族エポキシ樹脂、
シクロオレフィンの過酢酸酸化により得られる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等の環状脂肪族エポキシ樹脂
あるいは水添ビスフエノールＡ等のアルコール類をエポ
キシ化して得られるアルコール型エポキシ樹脂などがあ
る。2. Description of the Related Art Conventionally, a cationic curing technique by thermal curing or active energy ray curing of an epoxy compound is known, and various epoxy compounds, various curing agents, and materials for a cationic curing initiator are widely commercially available. As the epoxy compound, diglycidyl ether of bisphenol A,
Aromatic epoxy resins such as diglycidyl ether of bisphenol F and phenol novolak type epoxy resin;
It is obtained by epoxidizing a cyclic aliphatic epoxy resin such as 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate obtained by peracetic acid oxidation of cycloolefin or an alcohol such as hydrogenated bisphenol A. There is an alcohol type epoxy resin.
【０００３】電気用途においては、近年、電気機器の小
型化により電気回路の多層化、高密化が進んでいる。こ
れに伴いそれに使用されるエポキシ樹脂に対しては、低
誘電率化、耐アーク性、耐トラッキング性が要求されて
いる。これらの電気特性向上のためには、芳香族エポキ
シ樹脂よりも、芳香環を持たない環状脂肪族エポキシ樹
脂あるいはアルコール型エポキシ樹脂が有利であること
は公知である。しかしながら、環状脂肪族エポキシ樹脂
の硬化物は脆く、衝撃強度や金属等への接着強度が大き
く不足している。また、水添ビスフェノールＡ等のアル
コールをエポキシ化させたアルコール型エポキシ樹脂
は、その製造上、製品中に多量の塩素が残存しやすく、
電気絶縁性の低下、誘電率、誘電正接値の上昇等、電気
特性の著しい劣化を招く。さらに、耐熱性も上記芳香族
エポキシ樹脂と比べてかなり低下する。[0003] In electrical applications, in recent years, the miniaturization of electric equipment has led to an increase in the number and density of electric circuits. Along with this, the epoxy resin used therefor is required to have a low dielectric constant, arc resistance and tracking resistance. It is known that a cycloaliphatic epoxy resin having no aromatic ring or an alcoholic epoxy resin is more advantageous than an aromatic epoxy resin for improving these electrical properties. However, the cured product of the cycloaliphatic epoxy resin is brittle, and the impact strength and the adhesive strength to metal or the like are largely insufficient. In addition, alcohol-type epoxy resins obtained by epoxidizing alcohols such as hydrogenated bisphenol A tend to cause a large amount of chlorine to remain in products due to their production.
Remarkable deterioration of electric characteristics such as a decrease in electric insulation, an increase in dielectric constant and a dielectric loss tangent value is caused. Further, the heat resistance is considerably reduced as compared with the aromatic epoxy resin.
【０００４】また、塗料用途においては、上記芳香族エ
ポキシ樹脂は耐候性に劣るため、耐候性を要求される用
途には上記環状脂肪族エポキシ樹脂又はアルコール型エ
ポキシ樹脂が用いられる。しかし、環状脂肪族エポキシ
樹脂の塗膜は脆く、耐衝撃性や基材への密着性に著しく
劣る。また一方、水添ビスフェノールＡ等のアルコール
類をエポキシ化して得られるアルコール型エポキシ樹脂
は、前述したように多量の塩素を含有するため、高信頼
性を要求される用途には不向きである。[0004] Further, the above-mentioned aromatic epoxy resin is inferior in weather resistance in coating applications, and the above-mentioned cycloaliphatic epoxy resin or alcohol-type epoxy resin is used in applications requiring weather resistance. However, the coating film of the cycloaliphatic epoxy resin is brittle and remarkably poor in impact resistance and adhesion to a substrate. On the other hand, an alcohol-type epoxy resin obtained by epoxidizing alcohols such as hydrogenated bisphenol A contains a large amount of chlorine as described above, and is not suitable for applications requiring high reliability.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、前記の問題
を解決し、塗料、印刷インキ、封止剤、レジスト、接着
剤、成形材料、注型材料及び電気絶縁材料として有用
な、熱硬化又は活性エネルギー線硬化により耐熱性、電
気特性及び耐候性に優れた硬化物を与える硬化性エポキ
シ樹脂組成物を提供することを目的とするものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and is useful as a paint, a printing ink, a sealant, a resist, an adhesive, a molding material, a casting material, and a thermosetting material. Another object of the present invention is to provide a curable epoxy resin composition that gives a cured product having excellent heat resistance, electrical properties, and weather resistance by active energy ray curing.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意研究を重ねた結果、これらの目的を達
成できる硬化性エポキシ樹脂組成物を見出し本発明に到
達した。すなわち、本発明は、 (1) (a) 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１０〜９０重量部、(b) シクロオレフィ
ンをエポキシ化して得られる環状脂肪族エポキシ樹脂１
０〜９０重量部、(c) 酸無水物類及び熱又は活性エネル
ギー線によりカチオン種又はルイス酸を発生するカチオ
ン重合開始剤からなる群から選ばれるエポキシ樹脂用硬
化剤０．０１〜２００重量部を含有する硬化性エポキシ
樹脂組成物に関するものである。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a curable epoxy resin composition which can achieve these objects, and have reached the present invention. That is, the present invention relates to (1) (a) 10 to 90 parts by weight of a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin, and (b) cycloaliphatic epoxy resin 1 obtained by epoxidizing a cycloolefin.
0 to 90 parts by weight, (c) 0.01 to 200 parts by weight of a curing agent for an epoxy resin selected from the group consisting of acid anhydrides and a cationic polymerization initiator which generates a cationic species or a Lewis acid by heat or active energy rays. The present invention relates to a curable epoxy resin composition containing
【０００７】(2) 本発明の前記水素化エポキシ樹脂は、
芳香環の水素化率が８５％以上で、エポキシ基の損失率
が２０％以下であり、かつ全塩素の含有量が０．３重量
％以下である、硬化性エポキシ樹脂組成物に関するもの
である。 (3) 本発明の前記水素化エポキシ樹脂は、芳香族エポキ
シ樹脂をエーテル系溶剤に溶解し、ロジウム又はルテニ
ウムをグラファイトに担持した触媒の存在下、加圧下に
水素化して得られた水素化エポキシ樹脂である、硬化性
エポキシ樹脂組成物に関するものである。(2) The hydrogenated epoxy resin of the present invention comprises:
The present invention relates to a curable epoxy resin composition having a hydrogenation rate of an aromatic ring of 85% or more, a loss rate of an epoxy group of 20% or less, and a total chlorine content of 0.3% by weight or less. . (3) The hydrogenated epoxy resin of the present invention is a hydrogenated epoxy resin obtained by dissolving an aromatic epoxy resin in an ether solvent and hydrogenating under pressure in the presence of a catalyst in which rhodium or ruthenium is supported on graphite. The present invention relates to a curable epoxy resin composition which is a resin.
【０００８】(4) 前記水素化エポキシ樹脂は、エポキシ
当量が１５０〜３００ｇ／ｅｑ．の範囲内のビスフェノ
ールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ
樹脂を水素化して得られる液状エポキシ樹脂である、硬
化性エポキシ樹脂組成物に関するものである。 (5) 前記環状脂肪族エポキシ樹脂は、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である、硬化性エポキシ樹脂組
成物に関するものである。 (6) 本発明の前記エポキシ樹脂用硬化剤が無水ヘキサヒ
ドロフタル酸、無水メチルヘキサヒドロフタル酸又は芳
香族オニウム塩から選ばれるものである、硬化性エポキ
シ樹脂組成物に関するものである。(4) The hydrogenated epoxy resin has an epoxy equivalent of 150 to 300 g / eq. The present invention relates to a curable epoxy resin composition which is a liquid epoxy resin obtained by hydrogenating a bisphenol A-type epoxy resin or a bisphenol F-type epoxy resin in the range described above. (5) The curable epoxy resin composition, wherein the cycloaliphatic epoxy resin is 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate. (6) The present invention relates to a curable epoxy resin composition, wherein the curing agent for an epoxy resin of the present invention is selected from hexahydrophthalic anhydride, methylhexahydrophthalic anhydride or an aromatic onium salt.
【０００９】[0009]
【発明の実施の形態】以下、本発明について詳細に説明
する。 (a) 成分：水素化エポキシ樹脂 本発明における(a) 成分の水素化エポキシ樹脂は、芳香
族エポキシ樹脂を水素化反応して得られる脂環式エポキ
シ樹脂である。この水素化エポキシ樹脂は、芳香環の水
素化率が８５％以上で、エポキシ基の損失率が２０％以
下であり、かつ全塩素の含有量が０．３重量％以下のエ
ポキシ樹脂が好ましい。エポキシ樹脂中の芳香環の水素
化率は、芳香環が脂肪族環に変化した割合であり、核磁
気共鳴分析により求められる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Component (a): Hydrogenated epoxy resin The hydrogenated epoxy resin of the component (a) in the present invention is an alicyclic epoxy resin obtained by hydrogenating an aromatic epoxy resin. The hydrogenated epoxy resin is preferably an epoxy resin having a hydrogenation rate of an aromatic ring of 85% or more, a loss rate of an epoxy group of 20% or less, and a total chlorine content of 0.3% by weight or less. The hydrogenation rate of the aromatic ring in the epoxy resin is a rate at which the aromatic ring is changed to an aliphatic ring, and is determined by nuclear magnetic resonance analysis.
【００１０】エポキシ基の損失率は、エポキシ樹脂が水
素化分解された割合であり、過塩素酸により滴定するこ
とにより、エポキシ基の損失率を求めることができる。
また、全塩素とは、エポキシ樹脂中に含有する有機塩素
及び無機塩素の総量のことであり、ビフェニルナトリウ
ムでエポキシ樹脂中の塩素を反応させた後、硝酸銀で滴
定することにより求められる。The epoxy group loss rate is the rate at which the epoxy resin is hydrogenolyzed, and the epoxy group loss rate can be determined by titration with perchloric acid.
The total chlorine refers to the total amount of organic chlorine and inorganic chlorine contained in the epoxy resin, and is determined by reacting chlorine in the epoxy resin with biphenyl sodium and then titrating with silver nitrate.
【００１１】芳香環の水素化率が８５％未満であると、
エポキシ樹脂硬化物の電気特性及び耐候性が大きく低下
するため好ましくない。また、エポキシ基の損失率が２
０％を越えると、そのエポキシ樹脂硬化物の耐熱性や機
械的物性が極端に低下するため好ましくない。更に、全
塩素含有量が０．３重量％を超えると、電気特性及び耐
湿性が低下するため、電気・電子材料用エポキシ樹脂と
して使用するには好ましくない。When the hydrogenation rate of the aromatic ring is less than 85%,
This is not preferable because the electrical properties and weather resistance of the cured epoxy resin are significantly reduced. In addition, the epoxy group loss rate is 2
Exceeding 0% is not preferred because the heat resistance and mechanical properties of the cured epoxy resin are extremely reduced. Further, when the total chlorine content exceeds 0.3% by weight, the electrical properties and the moisture resistance are reduced, which is not preferable for use as an epoxy resin for electric / electronic materials.
【００１２】（水素化エポキシ樹脂の製造方法）本発明
の(a) 成分の水素化エポキシ樹脂は、芳香族エポキシ樹
脂を触媒の存在下、加圧下で選択的に水素化反応を行う
ことにより得られる。芳香族エポキシ樹脂しては、例え
ばビスフェノールＡのジグリシジルエーテル、ビスフェ
ールＦのジグリシジルエーテル及びビスフェノールＳの
ジグリシジルエーテル等のビスフェノール型エポキシ樹
脂、フェノールノボラックエポキシ樹脂、クレゾールノ
ボラックエポキシ樹脂及びヒドロキシベンズアルデヒド
フェノールノボラックエポキシ樹脂等のノボラック型の
エポキシ樹脂、テトラヒドロキシフェニルメタンのグリ
シジルエーテル、テトラヒドロキシベンゾフェノンのグ
リシジルエーテル及びエポキシ化ポリビニルフェノール
等の多官能型のエポキシ等が挙げられる。(Production Method of Hydrogenated Epoxy Resin) The hydrogenated epoxy resin of the component (a) of the present invention is obtained by selectively performing a hydrogenation reaction of an aromatic epoxy resin under pressure in the presence of a catalyst. Can be Examples of the aromatic epoxy resin include bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F and diglycidyl ether of bisphenol S, phenol novolak epoxy resin, cresol novolak epoxy resin, and hydroxybenzaldehyde phenol. Novolak-type epoxy resins such as novolak epoxy resin, glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and polyfunctional epoxy such as epoxidized polyvinylphenol are exemplified.
【００１３】これらの中で、エポキシ当量が１５０〜３
００ｇ／ｅｑ．の範囲内のビスフェノールＡ型エポキシ
樹脂及びビスフェノールＦ型エポキシ樹脂が低粘度及び
水素化の容易さという点で好ましい。Among them, the epoxy equivalent is 150-3.
00g / eq. The bisphenol A type epoxy resin and the bisphenol F type epoxy resin in the range of are preferred from the viewpoints of low viscosity and ease of hydrogenation.
【００１４】本発明における(a) 成分の水素化エポキシ
樹脂の製造方法は、テトラヒドロフラン、ジオキサン等
のエーテル系の有機溶剤を用いて、ロジウム又はルテニ
ウムをグラファイト( 六方晶結晶の黒鉛) に担持した触
媒の存在下、芳香環を選択的に水素化する。グラファイ
トとしては表面積が１０ｍ2 ／ｇ以上、４００ｍ2 ／ｇ
以下の範囲の担体を用いる。反応は、圧力１〜３０ＭＰ
ａ、温度３０〜１５０℃、時間１〜２０時間の範囲内で
行う。反応終了後、触媒を濾過により除去し、減圧でエ
ーテル系有機溶剤が実質的になくなるまで留去し、水素
化エポキシ樹脂を得る。The process for producing the hydrogenated epoxy resin as the component (a) in the present invention is carried out by a catalyst comprising rhodium or ruthenium supported on graphite (hexagonal graphite) using an ether-based organic solvent such as tetrahydrofuran or dioxane. The aromatic ring is selectively hydrogenated in the presence of Graphite has a surface area of 10 m 2 / g or more, 400 m 2 / g
The following ranges of carriers are used. The reaction is performed at a pressure of 1 to 30MPa.
a, temperature: 30 to 150 ° C., time: 1 to 20 hours. After completion of the reaction, the catalyst is removed by filtration, and the catalyst is distilled off under reduced pressure until the ether organic solvent is substantially eliminated, to obtain a hydrogenated epoxy resin.
【００１５】本発明における(b) 成分は、シクロオレフ
ィンをエポキシ化して得られる環状脂肪族エポキシ樹脂
である。The component (b) in the present invention is a cycloaliphatic epoxy resin obtained by epoxidizing a cycloolefin.
【００１６】本発明の硬化性エポキシ樹脂組成物は、
(a) 成分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１０〜９０重量％に対して、(b) 成分
の環状脂肪族エポキシ樹脂を９０〜１０重量％の割合
で、硬化物の耐熱性を向上させるために用いる。この
(b) 成分の環状脂肪族エポキシ樹脂が１０重量％未満で
あると硬化物の耐熱性改良効果が減少し、また、９０重
量％を越えると硬化物が脆くなるため好ましくない。The curable epoxy resin composition of the present invention comprises:
A cured product of the cyclic aliphatic epoxy resin (b) in a proportion of 90 to 10% by weight based on 10 to 90% by weight of a hydrogenated epoxy resin obtained by hydrogenating the aromatic epoxy resin as the component (a). It is used to improve the heat resistance. this
If the content of the component (b) cycloaliphatic epoxy resin is less than 10% by weight, the effect of improving the heat resistance of the cured product decreases, and if it exceeds 90% by weight, the cured product becomes brittle, which is not preferable.
【００１７】(b) 成分の環状脂肪族エポキシ樹脂は、分
子量が１００以上、好ましくは１２０以上、２０００以
下、好ましくは１０００以下であり、脂肪族環にエポキ
シ基が結合している化合物である。分子量が小さすぎる
と環状脂肪族エポキシ化合物の揮発性が高く、作業環境
や塗工時の加工特性を著しく悪化させる。分子量が大き
すぎると組成物の粘度が高くなるため、所定形状に注
型、成形あるいは均一に塗工することが困難となるThe cycloaliphatic epoxy resin as the component (b) is a compound having a molecular weight of 100 or more, preferably 120 or more, and 2,000 or less, preferably 1,000 or less, and having an epoxy group bonded to an aliphatic ring. When the molecular weight is too small, the volatility of the cycloaliphatic epoxy compound is high, and the working environment and processing characteristics during coating are significantly deteriorated. If the molecular weight is too large, the viscosity of the composition becomes high, so that it is difficult to cast, mold, or uniformly apply a predetermined shape.
【００１８】環状脂肪族エポキシ樹脂の具体例として
は、表１に示した式(1) で表される化合物（例えば、油
化シェルエポキシ社製、エピコート１７１など）、式
(2) で表される化合物（例えば、旭チバ社製、アラルダ
イトＣＹ１７８）、式(3) で表される化合物（例えば、
チッソ社製、チッソノックス２０６など）、式(4) で表
される化合物（例えば、チッソ社製、チッソノックス２
０５など）、式(5) で表される化合物、式(6) で表され
る化合物、式(7) で表される化合物、式(8) で表される
化合物、式(9) で表される化合物、式(10)で表される化
合物などが例示され、これらの中で式１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が、本発明組成物の低
粘度化及び耐熱性の向上効果という点で好ましい。Specific examples of the cycloaliphatic epoxy resin include compounds represented by the formula (1) shown in Table 1 (for example, Epicoat 171 manufactured by Yuka Shell Epoxy Co., Ltd.),
A compound represented by the formula (2) (for example, Araldite CY178, manufactured by Asahi Ciba), a compound represented by the formula (3) (for example,
A compound represented by the formula (4) (for example, Chissonox 2 manufactured by Chisso Corporation);
05, etc.), a compound represented by the formula (5), a compound represented by the formula (6), a compound represented by the formula (7), a compound represented by the formula (8), and a compound represented by the formula (9). And a compound represented by the formula (10), and among these, 3,3 represented by the formula 1
4-Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate is preferred from the viewpoints of lowering the viscosity and improving heat resistance of the composition of the present invention.
【００１９】[0019]
【表１】 [Table 1]
【００２０】(c) 成分：エポキシ樹脂用硬化剤 本発明の(c) 成分のエポキシ樹脂用硬化剤は、公知の酸
無水物類又はカチオン重合開始剤から選ばれる硬化剤を
用いることができる。例えば、酸無水物類としては、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を使用するのが、本発明組
成物の耐候性が向上する点で好ましい。Component (c): curing agent for epoxy resin As the curing agent for epoxy resin of component (c) of the present invention, a curing agent selected from known acid anhydrides or cationic polymerization initiators can be used. For example, as the acid anhydrides, phthalic anhydride, trimellitic anhydride, aromatic acid anhydrides such as pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl anhydride Examples thereof include cyclic aliphatic acid anhydrides such as hexahydrophthalic acid, methylendoethylenetetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride. Among these, it is preferable to use hexahydrophthalic anhydride and methylhexahydrophthalic anhydride from the viewpoint of improving the weather resistance of the composition of the present invention.
【００２１】また、本発明組成物の酸無水物に硬化を促
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、イミダゾ一ル
類、有機ホスフィン化合物類又はこれらの塩類である。
酸無水物類の使用割合は、(a)成分と(b) 成分のエポキ
シ樹脂の総和に対して、２０〜２００重量部の範囲内で
ある。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。A curing accelerator can be added to the acid anhydride of the composition of the present invention for the purpose of accelerating the curing. Examples of curing accelerators are tertiary amines, imidazoles, organic phosphine compounds or salts thereof.
The proportion of the acid anhydrides used is in the range of 20 to 200 parts by weight based on the total amount of the epoxy resins of the components (a) and (b). As the cationic polymerization initiator, an active energy ray cationic polymerization initiator that generates a cationic species or Lewis acid by an active energy ray, or a thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heat can be used.
【００２２】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35
86616 号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4058400 号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406809
1 号に記載されたようなＩＩＩａ〜Ｖａ族元素のジカル
ボニルキレート；米国特許第4139655 号に記載されたよ
うなチオピリリウム塩；米国特許第4161478 号に記載さ
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族元素；米国
特許第4231951 号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 of Polymer Science)、ポリ
マー・ケミストリー(Po1ymer 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
−ベキサフルオロ金属塩（例えば燐酸塩、砒酸塩、アン
チモン酸塩等）の一種以上が包含される。Examples of the active energy ray cationic polymerization initiator include metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat.
Bis (perfluoroalkylsulfonyl) methane metal salts as described in 86616; aryldiazonium compounds as described in U.S. Pat. No. 3,708,296; Group VIa elements as described in U.S. Pat. Aromatic onium salts; aromatic onium salts of Group Va elements as described in US Pat. No. 4,065,055; US Pat.
Dicarbonyl chelates of IIIa~Va group element such as described in No. 1; US thiopyrylium salts as described in Patent No. 4,139,655; U.S. as described in Patent No. 4161478 MF 6 - anion (wherein Wherein M is selected from phosphorus, antimony and arsenic); an arylsulfonium complex as described in U.S. Pat. No. 4,231,951; an aromatic iodonium complex as described in U.S. Pat. No. 4,256,828 And aromatic sulfonium complex salts;
W. R. Watt et al., Journal of Polymer Science, Poymer Chemistry Edition, 22nd Edition.
Vol. 1, p. 1789 (1984).
(Diphenylsulfonio) phenyl] sulfide-bis-bexafluorometal salt (for example, phosphate, arsenate, antimonate and the like).
【００２３】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-512(3
M 社) 、UVR 一6990及びUVR-6974〔ユニオン・カーバイ
ド(UnionCarbide)社〕、UVE-1014及びUVE-1016〔ジェネ
ラル・エレクトリック(Genera1 E1ectric)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S1-100L(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. You. Some of these salts are FX-512 (3
M), UVR-6990 and UVR-6974 (Union Carbide), UVE-1014 and UVE-1016 (Genera1 E1ectric), KI-85
It is commercially available as Degussa, SP-150 and SP-170 (Asahi Denka), and Sun Aid SI-60L, SI-80L and S1-100L (Sanshin Chemical Industries).
【００２４】熱カチオン重合開始剤としては、トリフル
酸(Trif1ic 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-5
20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、トリフル酸エチルシイソプロピ
ルアンモニウム等〔これらの多くはR.R.A1m によって19
80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。As the thermal cationic polymerization initiator, a cationic or protonic acid catalyst such as triflic acid, boron trifluoride etherate, boron trifluoride or the like can be used. Preferred thermal cationic polymerization initiators are triflic acid salts, for example, FC-5 from 3M.
Diethylammonium trifurate available as 20,
Triethylammonium triflate / diisopropylammonium triflate, ethyl isopropylammonium triflate, etc. (many of these are
Modern Coatin published in October 1980
gs)).
【００２５】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上る。例として
は、サンエイドSI-60L、SI-80L及びSI-100L(三新化学工
業社) がある。これらのカチオン重合開始剤の中で、芳
香族オニウム塩が、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い。カチオン重合開始
剤の使用量は、(a) 成分の水素化エポキシ樹脂と(b) 成
分の環状脂肪族エポキシ樹脂の混合物１００重量部に対
して、０．０１〜１５重量％、より好ましくは０．１〜
１０重量％の量で添加するのが好ましい。On the other hand, among aromatic onium salts which are also used as active energy ray cationic polymerization initiators, there are those which generate cationic species by heat, and these can also be used as thermal cationic polymerization initiators. Examples include San-Aid SI-60L, SI-80L and SI-100L (Sanshin Chemical Industries). Among these cationic polymerization initiators, aromatic onium salts are preferred because they are excellent in balance between handleability and latency and curability. The amount of the cationic polymerization initiator used is preferably 0.01 to 15% by weight, more preferably 0 to 15% by weight, based on 100 parts by weight of the mixture of the hydrogenated epoxy resin (a) and the cycloaliphatic epoxy resin (b). .1 to
Preferably it is added in an amount of 10% by weight.
【００２６】（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、炭酸カルシウ
ム、炭酸マグネシウムなどの金属炭酸塩、ケイソウ土
粉、塩基性ケイ酸マグネシウム、焼成クレイ、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、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、さらに繊維質の補強剤や充填剤、たとえばガラス
繊維、セラミック繊維、カーボンファイバー、アルミナ
繊維、炭化ケイ素繊維、ボロン繊維、ポリエステル繊維
及びポリアミド繊維等である。これらは本発明の組成物
１００重量部に対して、１０〜９００重量部配合され
る。(Optional Components) The following components can be added to the epoxy resin composition of the present invention, if necessary. (1) Powdery reinforcing agents and fillers, for example, metal oxides such as aluminum oxide and magnesium oxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, basic magnesium silicate, calcined clay, and fine powder Silica, fused silica, silicon compounds such as crystalline silica, metal hydroxides such as aluminum hydroxide, etc., kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc., and fibrous reinforcing agents and fillers such as glass Fiber, ceramic fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, polyester fiber, polyamide fiber and the like. These are blended in an amount of 10 to 900 parts by weight based on 100 parts by weight of the composition of the present invention.
【００２７】(2) 着色剤、顔料、難燃剤、例えば二酸化
チタン、鉄黒、モリブデン赤、紺青、群青、カドミウム
黄、カドミウム赤、三酸化アンチモン、赤燐、ブロム化
合物及びトリフェニルホスフェイト等である。これらは
本発明の組成物１００重量部に対して、０．１〜２０重
量部配合される。(2) Colorants, pigments, flame retardants such as titanium dioxide, iron black, molybdenum red, navy blue, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, bromide compounds and triphenyl phosphate. is there. These are added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the composition of the present invention.
【００２８】(3) さらに、最終的な塗膜、接着層、成形
品などにおける樹脂の性質を改善する目的で種々の硬化
性モノマー、オリゴマー及び合成樹脂を配合することが
できる。例えば、モノエポキシ等のエポキシ樹脂用希釈
剤、フェノール樹脂、アルキド樹脂、メラミン樹脂、フ
ッ素樹脂、塩化ビニル樹脂、アクリル樹脂、シリコーン
樹脂、ポリエステル樹脂等の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重量部に対して、
５０重量部以下が好ましい。(3) Further, various curable monomers, oligomers and synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, molded product and the like. For example, mention may be made of diluents for epoxy resins such as monoepoxy, phenolic resins, alkyd resins, melamine resins, fluororesins, vinyl chloride resins, acrylic resins, silicone resins, polyester resins and the like, or combinations of two or more thereof. it can. The mixing ratio of these resins is an amount in a range that does not impair the original properties of the resin composition of the present invention, that is, 100 parts by weight of the composition of the present invention.
It is preferably at most 50 parts by weight.
【００２９】本発明の組成物及び任意成分の配合手段と
しては、加熱溶融混合、ロール、ニーダーによる溶融混
練、適当な有機溶剤を用いての湿式混合及び乾式混合等
が挙げられる。Examples of the means for compounding the composition of the present invention and optional components include heat-melt mixing, melt-kneading using a roll or a kneader, wet mixing using an appropriate organic solvent, and dry mixing.
【００３０】本発明の組成物は、酸無水物類又は熱カチ
オン重合開始剤を用いた場合は、熱により、また、活性
エネルギー線カチオン重合開始剤を用いた場合は、活性
エネルギー線で硬化される。酸無水物硬化の場合は、エ
ポキシ基と酸無水物が反応する温度以上で、熱カチオン
重合の場合は、通常、その熱カチオン重合開始剤がカチ
オン種やルイス酸の発生を開始する温度以上で行われ
る。両方とも通常５０〜２００℃にて実施される。活性
エネルギー線硬化の場合は、適当な活性エネルギー線と
して、高、低圧水銀ランプ、キセノンランプ、殺菌灯、
レーザー光などから得られる２０００〜７０００オング
ストロームの波長を有する電磁波エネルギーや電子線、
Ｘ線、放射線等の高エネルギー線を使用する。The composition of the present invention is cured by heat when an acid anhydride or a thermal cationic polymerization initiator is used, or by an active energy ray when an active energy ray cationic polymerization initiator is used. You. In the case of acid anhydride curing, the temperature is higher than the temperature at which the epoxy group reacts with the acid anhydride.In the case of thermal cationic polymerization, the temperature is usually higher than the temperature at which the thermal cationic polymerization initiator starts generating cationic species or Lewis acid. Done. Both are usually carried out at 50-200 ° C. In the case of active energy ray curing, high or low pressure mercury lamp, xenon lamp, germicidal lamp,
Electromagnetic wave energy or an electron beam having a wavelength of 2000 to 7000 angstroms obtained from a laser beam or the like;
Use high energy rays such as X-rays and radiation.
【００３１】活性エネルギー線への暴露は、活性エネル
ギー線の強度によるが、通常は０．１〜数十秒程度で十
分である。しかし、比較的厚い塗装物や注型物について
はそれ以上の時間をかけるのが好ましい。活性エネルギ
ー線照射後０．１〜数分後には、ほとんどの組成物はカ
チオン重合により指触乾燥するが、カチオン重合反応を
促進するために加熱を併用することも場合によっては好
ましい。Exposure to an active energy ray depends on the intensity of the active energy ray, but usually about 0.1 to several tens of seconds is sufficient. However, it is preferred to spend more time on relatively thick painted or cast objects. Almost 0.1 to several minutes after the irradiation with the active energy ray, most compositions dry to the touch by cationic polymerization, but it is sometimes preferable to use heating in combination to promote the cationic polymerization reaction.
【００３２】[0032]
【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、各例中の部は重量部を意
味する。The present invention will be described below in more detail with reference to examples and comparative examples. In addition, the part in each example means a weight part.
【００３３】（水素化エポキシ樹脂の製造例） 製造例１ 攪拌機及び温度計を備えた５００ミリリットルのオート
クレーブ内にエピコート８２８ＥＬ（商品名、油化シェ
ルエポキシ社製：ビスフェノールＡのジグリシジルエー
テル、全塩素含有量：０．１６１重量％、エポキシ当
量：１８６ｇ／ｅｑ．）を１００ｇ、テトラヒドロフラ
ンを１００ｇ及び、５重量％ロジウム／９５重量％グラ
ファイト（グラファイトの表面積：１３０ｍ2 ／ｇ）触
媒５ｇを仕込み、水素圧力７Ｍｐａ、温度５０℃、攪拌
数５００〜８００ｒｐｍの条件を保持しながら、３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エバポレーターにて減圧
下、温度５０℃で留去させて、無色透明液体の水素化エ
ポキシ樹脂９６．５ｇを得た。この水素化エポキシ樹脂
の全塩素含有量は０．１６８重量％、Ｅ型粘度計より求
めた２５℃での粘度が１．６Ｐａ・ｓ、過塩素酸滴定法
により求めたエポキシ基の損失率は８．０％、核磁気共
鳴分析により求めた芳香環の水素化率は、ほぼ１００％
であった。(Production Example of Hydrogenated Epoxy Resin) Production Example 1 Epicoat 828EL (trade name, manufactured by Yuka Shell Epoxy: diglycidyl ether of bisphenol A, total chlorine) in a 500 ml autoclave equipped with a stirrer and a thermometer. Content: 0.161 wt%, epoxy equivalent: 186 g / eq.), 100 g of tetrahydrofuran, and 5 g of a 5 wt% rhodium / 95 wt% graphite (graphite surface area: 130 m 2 / g) catalyst (5 g) were charged. The reduction reaction was performed for 3 hours while maintaining the conditions of a pressure of 7 Mpa, a temperature of 50 ° C., and a stirring number of 500 to 800 rpm. After completion of the reaction, the reaction mixture was cooled, and the catalyst was separated by filtration. Then, tetrahydrofuran was distilled off at a temperature of 50 ° C. under reduced pressure by an evaporator to obtain 96.5 g of a colorless transparent liquid hydrogenated epoxy resin. The hydrogenated epoxy resin had a total chlorine content of 0.168% by weight, a viscosity at 25 ° C. of 1.6 Pa · s determined by an E-type viscometer, and a loss rate of epoxy groups determined by a perchloric acid titration method. 8.0%, hydrogenation rate of aromatic ring determined by nuclear magnetic resonance analysis is almost 100%
Met.
【００３４】製造例２ 攪拌機及び温度計を備えた５００ミリリットルのオート
クレーブ内にエピコート８０７（商品名、油化シェルエ
ポキシ社製：ビスフェノールＦのジグリシジルエーテ
ル、全塩素含有量：０．１８６重量％、エポキシ当量：
１７１ｇ／ｅｑ．）を１００ｇ、テトラヒドロフランを
１００ｇ及び、５重量％ロジウム／９５重量％グラファ
イト（グラファイトの表面積：１３０ｍ2 ／ｇ）触媒５
ｇを仕込み、水素圧力７Ｍｐａ、温度５０℃、攪拌数５
００〜８００ｒｐｍの条件を保持しながら、３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エバポレーターにて減圧下、
温度５０℃で留去させて、無色透明液体の水素化エポキ
シ樹脂９７．２ｇを得た。この水素化エポキシ樹脂の全
塩素含有量は０．１８７重量％、Ｅ型粘度計より求めた
２５℃での粘度が０．４５Ｐａ・ｓ、過塩素酸滴定法に
より求めたエポキシ基の損失率は５．３％、核磁気共鳴
分析により求めた芳香環の水素化率は、９９％であっ
た。Production Example 2 Epicoat 807 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd .: diglycidyl ether of bisphenol F, total chlorine content: 0.186% by weight) was placed in a 500 ml autoclave equipped with a stirrer and a thermometer. Epoxy equivalent:
171 g / eq. ), 100 g of tetrahydrofuran and 5 wt% rhodium / 95 wt% graphite (surface area of graphite: 130 m 2 / g) Catalyst 5
g, hydrogen pressure 7 Mpa, temperature 50 ° C., stirring number 5
The reduction reaction was performed for 3 hours while maintaining the condition of 00 to 800 rpm. After completion of the reaction, the mixture was cooled, and the catalyst was separated by filtration.Tetrahydrofuran was evaporated under reduced pressure using an evaporator.
Distillation was performed at a temperature of 50 ° C. to obtain 97.2 g of a colorless transparent liquid hydrogenated epoxy resin. The total chlorine content of this hydrogenated epoxy resin was 0.187% by weight, the viscosity at 25 ° C. determined by an E-type viscometer was 0.45 Pa · s, and the epoxy group loss rate determined by perchloric acid titration was: The aromatic ring hydrogenation rate determined by 5.3% and nuclear magnetic resonance analysis was 99%.
【００３５】実施例１ 製造例１により得られた水素化エポキシ樹脂５０部、エ
ピコート１７１（商品名、油化シェルエポキシ社製：
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）５０部、リ
カシッドＭＨ−７００（商品名、新日本理化社製：無水
メチルテトラヒドロフタル酸）１００部及びＳＡ−１０
２〔商品名、サンアプロ社製：１，８−ジアザビシクロ
（５，４，０）ウンデセン−７とオクチル酸との塩）１
部を均一になるよう、５０℃の温度で充分攪拌混合した
後、減圧脱泡して、硬化性エポキシ樹脂組成物を得た。
次いで、上記組成物を型内に流し込み、１００℃で４時
間、さらに１５０℃で６時間オーブン中で硬化すること
により試験片を得、各種の物性測定を行った。結果を表
２に示す。Example 1 50 parts of a hydrogenated epoxy resin obtained in Production Example 1, Epicoat 171 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.):
3,4-epoxycyclohexylmethyl-3 ', 4'-
50 parts of epoxycyclohexanecarboxylate), 100 parts of RIKACID MH-700 (trade name, manufactured by Shin Nihon Rika Co., Ltd .: methyl tetrahydrophthalic anhydride) and SA-10
2 [trade name, manufactured by San Apro: salt of 1,8-diazabicyclo (5,4,0) undecene-7 and octylic acid]
After sufficiently stirring and mixing at a temperature of 50 ° C. so that the parts became uniform, the mixture was defoamed under reduced pressure to obtain a curable epoxy resin composition.
Next, the above composition was poured into a mold and cured in an oven at 100 ° C. for 4 hours and further at 150 ° C. for 6 hours to obtain a test piece, and various physical properties were measured. Table 2 shows the results.
【００３６】尚、これらの試験方法を以下に記載する。
熱変形温度は、ＡＳＴＭ Ｄ−６４８に示されている方
法にて試験を行った。耐衝撃性は、ＡＳＴＭ Ｄ−２５
６に示されているアイゾット衝撃試験（ノッチ付) にて
試験した。電気特性は、誘電率、誘電正接及び体積抵抗
率につき、ＪＩＳ Ｋ６９１１に示されている試験方法
により測定した。The test methods are described below.
The heat distortion temperature was tested by the method described in ASTM D-648. Impact resistance is ASTM D-25
The test was conducted by the Izod impact test (notched) shown in FIG. The electrical characteristics were measured for the dielectric constant, the dielectric loss tangent, and the volume resistivity by the test method shown in JIS K6911.
【００３７】実施例２ 水素化エポキシ樹脂を製造例２により得られた水素化エ
ポキシ樹脂５０部に変える以外は、実施例１と同様の操
作を行った。結果を表２に示す。Example 2 The same operation as in Example 1 was performed, except that the hydrogenated epoxy resin was changed to 50 parts of the hydrogenated epoxy resin obtained in Production Example 2. Table 2 shows the results.
【００３８】実施例３ 製造例１により得られた水素化エポキシ樹脂５０部、エ
ピコート１７１ ５０部を５０℃に加温し、これにカチ
オン重合開始剤としてサンエイドＳＩ−１００Ｌ（商品
名、三新化学工業社製：芳香族スルホニウム塩系カチオ
ン重合開始剤）１部を添加し、均一になるよう充分攪拌
混合し、減圧脱泡して、硬化性エポキシ樹脂組成物を得
た。次いで、組成物を型内に流し込み、９０℃で２時
間、さらに１８０℃で１時間オーブン中で硬化すること
により試験片を得、各種の物性測定を行った。結果を表
２に示す。Example 3 50 parts of the hydrogenated epoxy resin and 50 parts of Epicoat 171 obtained in Production Example 1 were heated to 50 ° C., and this was added to the mixture with San Aid SI-100L (trade name, Sanshin Chemical Co., Ltd.) as a cationic polymerization initiator. 1 part of an aromatic sulfonium salt-based cationic polymerization initiator (manufactured by Kogyo Co., Ltd.) was added, and the mixture was sufficiently stirred and mixed so as to be uniform, followed by defoaming under reduced pressure to obtain a curable epoxy resin composition. Next, the composition was poured into a mold and cured in an oven at 90 ° C. for 2 hours and further at 180 ° C. for 1 hour to obtain a test piece, and various physical properties were measured. Table 2 shows the results.
【００３９】また、塗膜物性試験として、デュポン衝撃
試験、エリクセン試験及び耐候性試験を行った。各試験
片の作成は、上記組成物１００部に、さらに酸化チタン
３０部を加え、３本ロールミルで混練したものをリン酸
亜鉛処理した軟鋼鈑に、アプリケータにより膜厚が約５
０ミクロンとなるように塗布し、９０℃で２時間、さら
に１８０℃で１時間オーブン中で硬化することにより行
った。デュポン衝撃試験は、デュポン衝撃試験機によ
り、撃芯１／２インチ、加重１ｋｇを用い、塗膜に亀裂
等の異常が出る高さを測定した。エリクセン試験は、エ
リクセン試験機を用い、塗膜にひび、亀裂や塗膜の基材
からのはがれ等の、異常が発生した押し出し距離を測定
した。耐候性試験は、キセノンテスター( 島津製作所)
による５００及び１０００時間処理後の光沢保持率を測
定した。当然、光沢保持率（％）の高いものほど耐候性
に優れる。As a coating film physical property test, a DuPont impact test, an Erichsen test and a weather resistance test were performed. Each test piece was prepared by adding an additional 30 parts of titanium oxide to 100 parts of the above composition, kneading with a three-roll mill, and applying a zinc phosphate-treated mild steel sheet to a thickness of about 5 μm with an applicator.
The coating was performed so as to have a thickness of 0 micron and cured in an oven at 90 ° C. for 2 hours and further at 180 ° C. for 1 hour. The DuPont impact test was performed using a DuPont impact tester with a 1/2 inch hammer and a load of 1 kg to measure the height at which abnormalities such as cracks appeared in the coating film. The Erichsen test was performed by using an Erichsen tester to measure the extrusion distance at which abnormalities such as cracks, cracks, and peeling of the coating film from the substrate occurred. Xenon tester (Shimadzu) for weather resistance test
The gloss retention after the treatment for 500 and 1000 hours was measured. Naturally, the higher the gloss retention (%), the better the weather resistance.
【００４０】実施例４ 水素化エポキシ樹脂を製造例２により得られた水素化エ
ポキシ樹脂５０部に変える以外は、実施例３と同様の操
作を行った。結果を表２に示す。Example 4 The same operation as in Example 3 was carried out except that the hydrogenated epoxy resin was changed to 50 parts of the hydrogenated epoxy resin obtained in Production Example 2. Table 2 shows the results.
【００４１】実施例５、６ 水素化エポキシ樹脂と環状脂肪族エポキシ樹脂の割合を
表２のように変える以外は、実施例３と同様の操作を行
った。結果を表２に示す。Examples 5 and 6 The same operation as in Example 3 was carried out except that the proportions of the hydrogenated epoxy resin and the cycloaliphatic epoxy resin were changed as shown in Table 2. Table 2 shows the results.
【００４２】比較例１〜３ エポキシ樹脂として、比較例１ではＨＢＥ−１００（商
品名、新日本理化社製：水添ビスフェノールＡから得ら
れたジグリシジルエーテル、全塩素含有量；４．９８重
量％、エポキシ当量：２１６ｇ／ｅｑ．）１００部を用
い、比較例２ではエピコートＥ−１７１を１００部用
い、また比較例３ではエピコートＥ−８２８ＥＬを１０
０部を、それぞれ用いる以外は、実施例３と同様の操作
を行った。結果を表２に示す。Comparative Examples 1 to 3 As an epoxy resin, in Comparative Example 1, HBE-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd .: diglycidyl ether obtained from hydrogenated bisphenol A, total chlorine content: 4.98 weight) %, Epoxy equivalent: 216 g / eq.) 100 parts, Comparative Example 2 used 100 parts of Epicoat E-171, and Comparative Example 3 used 10 parts of Epicoat E-828EL.
The same operation as in Example 3 was performed, except that 0 part was used, respectively. Table 2 shows the results.
【００４３】[0043]
【表２】 [Table 2]
【００４４】[0044]
【発明の効果】本発明の、水素化エポキシ樹脂、シクロ
オレフィンをエポキシ化して得られる環状脂肪族エポキ
シ樹脂及びエポキシ樹脂用硬化剤からなる組成物は、そ
の硬化物が、耐熱性、電気特性及び耐候性に非常に優
れ、さらに耐衝撃性、可撓性及び接着強度等の特性をバ
ランス長く備えた硬化物であるので、広範な用途に応用
展開が可能である。特に、電気絶縁材、注型電子・電気
部品、電子・電気部品用接着剤及び半導体封止剤等の電
気・電子分野、及び耐候性塗料、コーティング剤等の用
途において有利に使用できる。According to the composition of the present invention comprising a hydrogenated epoxy resin, a cycloaliphatic epoxy resin obtained by epoxidizing a cycloolefin, and a curing agent for an epoxy resin, the cured product exhibits heat resistance, electrical properties and Since it is a cured product having excellent weather resistance and a long balance of properties such as impact resistance, flexibility and adhesive strength, it can be applied to a wide range of applications. In particular, it can be advantageously used in electric and electronic fields such as electric insulating materials, cast electronic and electric parts, adhesives for electronic and electric parts and semiconductor encapsulants, and in applications such as weatherable paints and coatings.
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Claims (6)
られる水素化エポキシ樹脂９０重量部、(b) シクロオレ
フィンをエポキシ化して得られる環状脂肪族エポキシ樹
脂１０〜９０重量部、(c) 酸無水物類及び、熱又は活性
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
カチオン重合開始剤からなる群から選ばれるエポキシ樹
脂用硬化剤０．０１〜２００重量部を含有する硬化性エ
ポキシ樹脂組成物。(A) 90 parts by weight of a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin, (b) 10 to 90 parts by weight of a cycloaliphatic epoxy resin obtained by epoxidizing a cycloolefin, (c) A curable epoxy resin containing 0.01 to 200 parts by weight of an epoxy resin curing agent selected from the group consisting of acid anhydrides and a cationic polymerization initiator that generates a cationic species or a Lewis acid by heat or active energy rays. Composition.
素化率が８５％以上でエポキシ基の損失率が２０％以下
であり、かつ全塩素の含有量が０．３重量％以下であ
る、請求項１に記載の硬化性エポキシ樹脂組成物。2. The hydrogenated epoxy resin has a hydrogenation rate of an aromatic ring of 85% or more, a loss rate of an epoxy group of 20% or less, and a total chlorine content of 0.3% by weight or less. The curable epoxy resin composition according to claim 1.
キシ樹脂をエーテル系溶剤に溶解し、ロジウム又はルテ
ニウムをグラファイトに担持した触媒の存在下、加圧下
に水素化して得られた水素化エポキシ樹脂である、請求
項１又は請求項２に記載の硬化性エポキシ樹脂組成物。3. The hydrogenated epoxy resin obtained by dissolving an aromatic epoxy resin in an ether-based solvent and hydrogenating under pressure in the presence of a catalyst in which rhodium or ruthenium is supported on graphite. The curable epoxy resin composition according to claim 1 or 2, wherein
量が１５０〜３００ｇ／ｅｑ．の範囲内のビスフェノー
ルＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹
脂を水素化して得られる液状エポキシ樹脂である、請求
項１〜請求項３のいずれか１項に記載の硬化性エポキシ
樹脂組成物。4. The hydrogenated epoxy resin has an epoxy equivalent of 150 to 300 g / eq. The curable epoxy resin composition according to any one of claims 1 to 3, wherein the curable epoxy resin composition is a liquid epoxy resin obtained by hydrogenating a bisphenol A type epoxy resin or a bisphenol F type epoxy resin in the range described above.
−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ある、請求項１〜
４のいずれか１項に記載の硬化性エポキシ樹脂組成物。5. The cycloaliphatic epoxy resin according to claim 3, wherein
-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate.
5. The curable epoxy resin composition according to any one of 4.
ヒドロフタル酸、無水メチルヘキサヒドロフタル酸又は
芳香族オニウム塩から選ばれる硬化剤である、請求項１
〜請求項５のいずれか１項に記載の硬化性エポキシ樹脂
組成物。6. The curing agent for an epoxy resin according to claim 1, wherein the curing agent is selected from hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and an aromatic onium salt.
The curable epoxy resin composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32778898A JP3415047B2 (en) | 1998-11-18 | 1998-11-18 | Curable epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32778898A JP3415047B2 (en) | 1998-11-18 | 1998-11-18 | Curable epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000143939A true JP2000143939A (en) | 2000-05-26 |
| JP3415047B2 JP3415047B2 (en) | 2003-06-09 |
Family
ID=18203000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32778898A Expired - Lifetime JP3415047B2 (en) | 1998-11-18 | 1998-11-18 | Curable epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3415047B2 (en) |
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| JP2002302537A (en) * | 2001-04-03 | 2002-10-18 | Ricoh Co Ltd | Epoxy resin composition for producing inkjet head and method for producing inkjet head |
| WO2003002661A1 (en) * | 2001-06-28 | 2003-01-09 | Toray Industries, Inc. | Epoxy resin composition excellent in weather resistance and fiber-reinforced composite materials |
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| JP2002097251A (en) * | 2000-09-21 | 2002-04-02 | New Japan Chem Co Ltd | Alicyclic compound containing glycidyl group, its production method and epoxy resin composition using the same |
| JP2002302537A (en) * | 2001-04-03 | 2002-10-18 | Ricoh Co Ltd | Epoxy resin composition for producing inkjet head and method for producing inkjet head |
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| WO2007029598A1 (en) | 2005-09-05 | 2007-03-15 | Idemitsu Kosan Co., Ltd. | Adamantane derivative, epoxy resin, and optical electronic member using resin composition comprising them |
| JP2007131772A (en) * | 2005-11-11 | 2007-05-31 | Japan Epoxy Resin Kk | Hydrogenated epoxy resin, its production method, epoxy resin composition and epoxy resin composition for light-emitting element sealant |
| JP2007146021A (en) * | 2005-11-29 | 2007-06-14 | Daicel Chem Ind Ltd | Curable resin composition and interlaminar insulating film |
| JP2007169348A (en) * | 2005-12-20 | 2007-07-05 | Daicel Chem Ind Ltd | Curable resin composition and interlayer insulation film |
| JP4744286B2 (en) * | 2005-12-20 | 2011-08-10 | ダイセル化学工業株式会社 | Curable resin composition and interlayer insulating film |
| JP2007317945A (en) * | 2006-05-26 | 2007-12-06 | Taiyo Ink Mfg Ltd | Flexible substrate, solder resist composition therefor, and manufacturing method thereof |
| JP2011105949A (en) * | 2011-02-01 | 2011-06-02 | Mitsubishi Chemicals Corp | Hydrogenated epoxy resin, method for producing the same and epoxy resin composition |
| JP2015532336A (en) * | 2012-10-10 | 2015-11-09 | ハンツマン・アドバンスド・マテリアルズ・アメリカズ・エルエルシー | UV resistant epoxy structural adhesive |
| CN113816929A (en) * | 2021-09-29 | 2021-12-21 | 西安瑞联新材料股份有限公司 | Aliphatic epoxy compound and pouring sealant prepared from same |
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| JP3415047B2 (en) | 2003-06-09 |
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