JP2000351829A - Novel episulfide resin, its preparation, and curable resin composition - Google Patents
Novel episulfide resin, its preparation, and curable resin compositionInfo
- Publication number
- JP2000351829A JP2000351829A JP11165680A JP16568099A JP2000351829A JP 2000351829 A JP2000351829 A JP 2000351829A JP 11165680 A JP11165680 A JP 11165680A JP 16568099 A JP16568099 A JP 16568099A JP 2000351829 A JP2000351829 A JP 2000351829A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- epoxy resin
- episulfide
- general formula
- epoxy
- 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.)
- Granted
Links
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規なエピサルフ
ァイド樹脂、その製造方法及び該樹脂を含む硬化性樹脂
組成物に関するものである。特に本発明は、粘度が低
く、電気特性、耐候性に優れた硬化物を与えるので、半
導体封止用樹脂、積層板用樹脂、電気絶縁材料、耐候性
塗料及び光学用材料等として有用であるエピサルファイ
ド樹脂に関するものである。TECHNICAL FIELD The present invention relates to a novel episulfide resin, a method for producing the same, and a curable resin composition containing the resin. In particular, the present invention provides a cured product having a low viscosity and excellent electrical properties and weather resistance, and thus is useful as a resin for semiconductor encapsulation, a resin for a laminate, an electrical insulating material, a weather-resistant paint, an optical material, and the like. It relates to an episulfide resin.
【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、
塗料、接着剤及び電気・電子用途等の様々の分野で使用
されている。一方、エピサルファイド樹脂は、英国特許
968,424号公報に記載されているように、エポキシ樹脂
と硫化剤を反応させることにより得られ、硬化性に優
れ、耐熱性、耐水性等に優れた硬化物になることが知ら
れているが、未だ実用化されていない。この理由とし
て、保存安定性に優れる、取り扱いの容易な液状のエピ
サルファイド樹脂が得られていないことが挙げられる。2. Description of the Related Art Epoxy resins are excellent in heat resistance, adhesiveness, water resistance, mechanical strength and electrical properties.
It is used in various fields such as paints, adhesives and electric / electronic applications. On the other hand, episulfide resin is
As described in 968,424, it is known that it is obtained by reacting an epoxy resin with a sulfurizing agent, and has excellent curability, heat resistance, and a cured product excellent in water resistance, It has not been put to practical use yet. The reason for this is that a liquid episulfide resin having excellent storage stability and easy handling has not been obtained.
【０００３】代表的なビスフェノールＡのエポキシ樹脂
から得られるエピサルファイド樹脂は、製造後は液状だ
が、保存中に結晶化し、融点が約８０℃の固体となるた
め取り扱い性に劣る。更に、エピサルファイド樹脂は製
造中に反応器内でゲル化を起こしたり、増粘するため工
業的に製造するのが非常に難しい。。ところが、近年、
塗料、土木分野及び電気・電子分野などで使用される材
料も、低温硬化性、耐湿性及び耐熱性が非常に要求され
るようになってきたため、これらの特性に優れる、エピ
サルファイド樹脂が再び注目され始めている。[0003] A typical episulfide resin obtained from a bisphenol A epoxy resin is liquid after production, but crystallizes during storage and becomes a solid having a melting point of about 80 ° C, so that it is inferior in handleability. In addition, episulfide resins are very difficult to produce industrially due to gelling and thickening in the reactor during production. . However, in recent years,
Materials used in paints, civil engineering, and electrical and electronic fields are also required to have low-temperature curability, moisture resistance, and heat resistance, and episulfide resins, which excel in these properties, are attracting attention again. Is starting to be.
【０００４】そこで、J.P.Bell等は、”Synthesis and
Properties of Epoxy-Episulfide Resin" Makromolekul
are Chemie 240 (1996) 67-81 (4229)の文献に記載され
ているように、エポキシ樹脂とエピサルファイド樹脂を
混合して使用し、エポキシ樹脂の改質を試みている。し
かし、この方法は混合初期には均一であるが、保存時
に、エピサルファイド樹脂が結晶化し析出してしまうと
いう根本的な問題は解決されていない。Thus, JP Bell and others described "Synthesis and
Properties of Epoxy-Episulfide Resin "Makromolekul
As described in the literature of are Chemie 240 (1996) 67-81 (4229), an epoxy resin and an episulfide resin are mixed and used to modify the epoxy resin. However, although this method is uniform at the beginning of mixing, the fundamental problem that the episulfide resin crystallizes and precipitates during storage has not been solved.
【０００５】[0005]
【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、従来品に無い低粘度のエピサルファイド樹
脂であり、電気特性、耐湿性、耐候性のバランスに優れ
た硬化物を与えることができるエピサルファイド樹脂、
その製造方法及び硬化性樹脂組成物を提供しようとする
ものである。DISCLOSURE OF THE INVENTION The present invention is an episulfide resin having a low viscosity, which has not been found in the conventional products, which solves the above-mentioned problems, and provides a cured product having an excellent balance of electric properties, moisture resistance and weather resistance. Episulfide resin, which can
An object of the present invention is to provide a production method and a curable resin composition.
【０００６】[0006]
【課題を解決するための手段】本発明は、エピサルファ
イド樹脂、その製造及び該化合物を含む硬化性樹脂組成
物を提供するものである。本発明は、以下の各発明を包
含する。SUMMARY OF THE INVENTION The present invention provides an episulfide resin, its production, and a curable resin composition containing the compound. The present invention includes the following inventions.
【０００７】一般式（１）General formula (1)
【化５】 （１） 〔式中、Ｒ1 〜Ｒ6 は水素原子又は炭素数１〜６のアル
キル基を示し、ｎは０〜２０の数を示し、Ｚ1 及びＺ2
は硫黄原子又は酸素原子を示し、少なくともいずれか一
方が硫黄原子である。〕で示されるエピサルファイド樹
脂。Embedded image (1) [wherein, R 1 to R 6 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents a number of 0 to 20, Z 1 and Z 2
Represents a sulfur atom or an oxygen atom, at least one of which is a sulfur atom. ] The episulfide resin shown by these.
【０００８】一般式（２）General formula (2)
【化６】 （２） 〔式中、Ｒ1 〜Ｒ6 は水素原子又は炭素数１〜６のアル
キル基を示し、ｎは０〜２０の数である。〕で示される
エポキシ樹脂と、硫化剤を反応させることを特徴とす
る、一般式（１）Embedded image (2) [wherein, R 1 to R 6 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is a number of 0 to 20. Wherein the epoxy resin represented by the general formula (1) is reacted with a sulfurizing agent.
【化７】 （１） 〔式中、Ｒ1 〜Ｒ6 は水素原子又は炭素数１〜６のアル
キル基を示し、ｎは０〜２０の数を示し、Ｚ1 及びＺ2
は硫黄原子又は酸素原子を示し、少なくともいずれか一
方が硫黄原子である。〕のエピサルファイド樹脂の製造
方法。Embedded image (1) [wherein, R 1 to R 6 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents a number of 0 to 20, Z 1 and Z 2
Represents a sulfur atom or an oxygen atom, at least one of which is a sulfur atom. ] The method for producing an episulfide resin described above.
【０００９】一般式（１）General formula (1)
【化８】 （１） 〔式中、Ｒ1 〜Ｒ6 は水素原子又は炭素数１〜６のアル
キル基を示し、ｎは０〜２０の数を示し、Ｚ1 及びＺ2
は硫黄原子又は酸素原子を示し、少なくともいずれか一
方が硫黄原子である。〕のエピサルファイド樹脂に硬化
剤が配合されて成る、硬化性樹脂組成物。Embedded image (1) [wherein, R 1 to R 6 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents a number of 0 to 20, Z 1 and Z 2
Represents a sulfur atom or an oxygen atom, at least one of which is a sulfur atom. ] The curable resin composition which mix | blends a hardening | curing agent with the episulfide resin of 1).
【００１０】[0010]
【発明実施の形態】（エピサルファイド化合物）本発明
のエピサルファイド化合物は、下記一般式（３）で示さ
れるジエピサルファイド化合物及び一般式（４）で示さ
れるモノエピサルファイド化合物である。BEST MODE FOR CARRYING OUT THE INVENTION (Episulfide Compound) The episulfide compound of the present invention is a diepisulfide compound represented by the following general formula (3) and a monoepisulfide compound represented by the following general formula (4).
【００１１】[0011]
【化９】 （３） 〔式中、Ｒ1 〜Ｒ6 及びｎは前記に同じ〕Embedded image (3) [wherein, R 1 to R 6 and n are the same as described above]
【００１２】[0012]
【化１０】 （４） 〔式中、Ｒ1 〜Ｒ6 及びｎは前記に同じ〕Embedded image (4) [wherein, R 1 to R 6 and n are the same as above]
【００１３】本発明のエピサルファイド樹脂は、前記一
般式（１）中のＺ1 及びＺ2 における硫黄原子の割合
が、Ｚ1 及びＺ2 における硫黄原子と酸素原子の和に対
して、５〜９５％の範囲内であることが、得られるエピ
サルファイド樹脂を低粘度、速硬化性にすることがで
き、かつ硬化物の電気特性を発現できる点で好ましい。In the episulfide resin of the present invention, the ratio of the sulfur atom in Z 1 and Z 2 in the general formula (1) is 5 to 5 with respect to the sum of the sulfur atom and the oxygen atom in Z 1 and Z 2 . The content within the range of 95% is preferable in that the obtained episulfide resin can have low viscosity and quick curability, and can exhibit the electrical characteristics of the cured product.
【００１４】（エピサルファイド樹脂の製造方法）本発
明のエピサルファイド樹脂の製造は、一般式（２）で示
されるエポキシ樹脂と硫化剤を反応させることにより得
られるが、エポキシ樹脂のエポキシ基１当量に対して、
硫化剤が０．０５〜５モルの範囲内で反応させるのが好
ましい。即ち、本発明のエピサルファイド樹脂を製造す
る時、硫化剤の使用量が水素化エポキシ樹脂１当量に対
して、０．０５モル未満であると、得られるエピサルフ
ァイド樹脂中の硫黄原子の割合が、硫黄原子と酸素原子
の和に対し、５％未満となってしまうため好ましくな
い。また、５モルを越えると、不必要な硫化剤を多量に
使用することになり不経済である。(Method for producing episulfide resin) The episulfide resin of the present invention can be produced by reacting an epoxy resin represented by the general formula (2) with a sulfurizing agent. Against
It is preferred that the sulfurizing agent be reacted within the range of 0.05 to 5 mol. That is, when producing the episulfide resin of the present invention, if the amount of the sulfurizing agent used is less than 0.05 mol based on 1 equivalent of the hydrogenated epoxy resin, the ratio of sulfur atoms in the obtained episulfide resin is reduced. Is less than 5% of the sum of sulfur atoms and oxygen atoms, which is not preferable. On the other hand, if it exceeds 5 moles, an unnecessary sulfurizing agent is used in a large amount, which is uneconomical.
【００１５】上記のような仕込み割合で、適当な溶媒の
存在下、反応温度−１５〜１００℃、好ましくは０〜５
０℃、反応時間０．５〜３０時間の範囲内で反応を行
う。用いられる硫化剤は、チオシアン酸ナトリウム、チ
オシアン酸カリウム、チオシアン酸アンモニウム等のチ
オシアン酸塩類、チオ尿素、Ｎ−メチルチオ尿素、１，
３−ジエチルチオ尿素等のチオ尿素類、ホスフィンサル
ファイド、ジメチルチオホルムアミド、Ｎ−メチルベン
ゾチアゾール−２−チオン等が挙げられる。これらの中
でチオシアン酸塩類、チオ尿素類が原料入手の容易さの
点で好ましい。At the charging ratio as described above, a reaction temperature of -15 to 100 ° C., preferably 0 to 5 in the presence of a suitable solvent.
The reaction is carried out at 0 ° C. for a reaction time in the range of 0.5 to 30 hours. Sulfurizing agents used include thiocyanates such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, thiourea, N-methylthiourea,
Thiourea such as 3-diethylthiourea; phosphine sulfide; dimethylthioformamide; N-methylbenzothiazole-2-thione; Of these, thiocyanates and thioureas are preferable in terms of availability of raw materials.
【００１６】用いられる溶媒としては、例えば、水、メ
タノール、エタノール及びプロパノール等のアルコール
類、ジエチルエーテル、テトラヒドロフラン及びジオキ
サン等のエーテル類、ベンゼン、トルエン、キシレン及
びエチルベンゼン等の芳香族炭化水素類、アセトン、メ
チルエチルケトン及びメチルイソブチルケトン等のケト
ン類、塩化メチレン、クロロホルム、ジクロルエタン及
びクロルベンゼン等のハロゲン化炭化水素類、メチルセ
ロソルブ、エチルセロソルブ及びブチルセロソルブ等の
セロソルブ類、ジメチルホルムアミド、ジメチルアセト
アミド及びジメチルスルホキシド等の非プロトン性極性
溶媒等が挙げられる。これらは単独あるいは２種以上を
混合して用いることができる。Examples of the solvent used include water, alcohols such as methanol, ethanol and propanol, ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, acetone. Ketones such as methyl ethyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane and chlorobenzene; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; dimethylformamide, dimethylacetamide and dimethyl sulfoxide Aprotic polar solvents and the like. These can be used alone or in combination of two or more.
【００１７】反応終了後、反応生成物を抽出、水洗、濃
縮等の方法により、分離精製することにより、目的とす
るエピサルファイド樹脂を得ることができる。また、本
発明のエピサルファイド樹脂の原料である、前記一般式
（２）で示されるエポキシ樹脂は、芳香族エポキシ樹脂
を水添反応した水素化エポキシ樹脂が、得られるエピサ
ルファイド樹脂の純度が向上するため好ましい。更に、
用いられる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、全塩素の含有量が０．３重量％以下である樹脂が、
耐候性、耐熱性及び電気特性に優れるエピサルファイド
樹脂の硬化物が得られるという点で特に好ましい。After completion of the reaction, the desired episulfide resin can be obtained by separating and purifying the reaction product by a method such as extraction, washing with water, and concentration. The epoxy resin represented by the general formula (2), which is a raw material of the episulfide resin of the present invention, is a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin, and the purity of the obtained episulfide resin is improved. Is preferred. Furthermore,
The hydrogenated epoxy resin used has a hydrogenation rate of the aromatic ring of 85% or more, a loss rate of the epoxy group of 20% or less, and a resin having a total chlorine content of 0.3% by weight or less.
It is particularly preferable in that a cured product of an episulfide resin having excellent weather resistance, heat resistance, and electrical properties can be obtained.
【００１８】また、前記一般式（２）で示されるエポキ
シ樹脂のＲ1 〜Ｒ2 が水素原子又はメチル基であり、Ｒ
3 〜Ｒ6 が水素原子であり、ｎが０〜５であるエポキシ
樹脂が、得られるエピサルファイド樹脂の純度が向上す
るという点で好ましい。更に、本発明のエピサルファイ
ド樹脂を製造する際、耐熱性向上の目的で、一般式
（２）で示されるエポキシ樹脂中に、多官能の脂環式エ
ポキシ樹脂を添加しても構わない。用いることのできる
多官能エポキシ樹脂としては、フェノールノボラックか
ら得られる水素化エポキシ樹脂、クレゾールノボラック
から得られる水素化エポキシ樹脂、水素化ビスフェノー
ルＡのノボラックエポキシ樹脂及びフェノール類とヒド
ロキシベンズアルデヒド類から得られる水素化ノボラッ
クエポキシ樹脂等である。In the epoxy resin represented by the general formula (2), R 1 to R 2 are a hydrogen atom or a methyl group;
Epoxy resins in which 3 to R 6 are hydrogen atoms and n is 0 to 5 are preferred in that the purity of the obtained episulfide resin is improved. Further, when producing the episulfide resin of the present invention, a polyfunctional alicyclic epoxy resin may be added to the epoxy resin represented by the general formula (2) for the purpose of improving heat resistance. Examples of the polyfunctional epoxy resin that can be used include hydrogenated epoxy resin obtained from phenol novolak, hydrogenated epoxy resin obtained from cresol novolak, novolak epoxy resin of hydrogenated bisphenol A, and hydrogen obtained from phenols and hydroxybenzaldehydes. Novolak epoxy resin.
【００１９】また、水素化エポキシ樹脂の製造例として
は、芳香族エポキシ樹脂を無溶剤又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、触
媒の存在下、芳香環を選択的に水素化することにより好
適に行うことができる。特に好ましい触媒としては、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）に担持した触媒である。また、グラファイトは、表
面積が１０ｍ2 ／ｇ以上、４００ｍ2 ／ｇ以下の範囲の
担体を用いることが好ましい。反応は、圧力、１〜３０
ＭＰａ、温度３０〜１５０℃、時間１〜２０時間の範囲
内で行うことが好ましい。反応終了後、触媒を濾過によ
り除去し、エーテル系有機溶剤を使用した時は減圧で有
機溶剤が、実質的に無くなるまで留去し、水素化エポキ
シ樹脂が得られる。As an example of producing a hydrogenated epoxy resin, an aromatic epoxy resin is selectively hydrogenated in the presence of a catalyst by using an aromatic epoxy resin without a solvent or an ether organic solvent such as tetrahydrofuran or dioxane. This can be suitably performed. A particularly preferred catalyst is a catalyst in which rhodium or ruthenium is supported on graphite (hexagonal crystal graphite). Further, it is preferable to use a carrier having a surface area of 10 m 2 / g or more and 400 m 2 / g or less for graphite. The reaction is performed under pressure, 1 to 30
It is preferable to carry out the reaction at a pressure of 30 to 150 ° C. for 1 to 20 hours. After the completion of the reaction, the catalyst is removed by filtration, and when an ether organic solvent is used, the organic solvent is distilled off under reduced pressure until the organic solvent substantially disappears to obtain a hydrogenated epoxy resin.
【００２０】（硬化樹脂組成物）本発明のエピサルファ
イド樹脂は硬化剤を用い、硬化させることができる。用
いられる硬化剤としては、一般のエポキシ樹脂用硬化剤
が用いられる。たとえば次のものが挙げられる。(Curing Resin Composition) The episulfide resin of the present invention can be cured using a curing agent. As a curing agent to be used, a general curing agent for epoxy resin is used. For example:
【００２１】アミン類；ジエチレントリアミン、トリエ
チレンテトラミン、テトラエチレンペンタミン、Ｎ−ア
ミノエチルピペラジン、イソホロンジアミン、ビス（４
−アミノシクロヘキシル）メタン、ビス（アミノメチ
ル）シクロヘキサン、ｍ−キシリレンジアミン、３，９
−ビス（３−アミノプロピル）−２，４，８，１０−テ
トラスピロ［５，５］ウンデカン等の脂肪族及び脂環族
アミン類、ポリアミド類、メタフェニレンジアミン、ジ
アミノジフェニルメタン、ジアミノジフェニルスルホン
等の芳香族アミン類、ベンジルジメチルアミン、２，
４，６−トリス（ジメチルアミノメチル）フェノール、
１，８−ジアザビシクロ（５，４，０）ウンデセン−
７、１，５−ジアザビシクロ（４，３，０）ノネン−７
等の３級アミン類及びその塩類。Amines: diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-aminoethylpiperazine, isophoronediamine, bis (4
-Aminocyclohexyl) methane, bis (aminomethyl) cyclohexane, m-xylylenediamine, 3,9
Aliphatic and alicyclic amines such as -bis (3-aminopropyl) -2,4,8,10-tetraspiro [5,5] undecane, polyamides, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc. Aromatic amines, benzyldimethylamine, 2,
4,6-tris (dimethylaminomethyl) phenol,
1,8-diazabicyclo (5,4,0) undecene-
7,1,5-diazabicyclo (4,3,0) nonene-7
Tertiary amines and salts thereof.
【００２２】酸無水物類；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、無水メチルエンドメチレンテトラヒドロ
フタル酸、無水ドデセニルコハク酸、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類。Acid anhydrides; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydride Cyclic aliphatic acid anhydrides such as hydrophthalic acid, methylendomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride;
【００２３】多価フェノール類；カテコール、レゾルシ
ン、ハイドロキノン、ビスフェノールＦ、ビスフェノー
ルＡ、ビスフェノールＳ、ビフェノール、フェノールノ
ボラック類、クレゾールノボラック類、ビスフェノール
Ａ等の２価フェノールのノボラック化物類、トリスヒド
ロキシフェニルメタン類、アラルキルポリフェノール
類、ジシクロペンタジエンポリフェノール類等。Polyhydric phenols: catechol, resorcinol, hydroquinone, bisphenol F, bisphenol A, bisphenol S, biphenol, phenol novolaks, cresol novolaks, novolaks of dihydric phenols such as bisphenol A, trishydroxyphenylmethanes , Aralkyl polyphenols, dicyclopentadiene polyphenols and the like.
【００２４】その他；２−メチルイミダゾール、２−エ
チル−４−イミダゾール及び２−フェニルイミダゾール
等のイミダゾール系化合物及びその塩類、アミンのＢＦ
3 錯体化合物、脂肪族スルホニウム塩及び芳香族スルホ
ニウム塩等のブレンステッド酸塩類、ジシアンジアミド
類、アジピン酸ジヒドラジッド及びフタル酸ジヒドラジ
ッド等の有機酸ヒドラジッド類、ポリメルカプタン類、
トリフェニルホスフィン等の有機ホスフィン化合物類
等。Others: imidazole compounds such as 2-methylimidazole, 2-ethyl-4-imidazole and 2-phenylimidazole and salts thereof, amine BF
3 complex compounds, Bronsted acid salts such as aliphatic sulfonium salts and aromatic sulfonium salts, dicyandiamides, organic acid hydrazides such as adipic dihydrazide and phthalic dihydrazide, polymercaptans,
Organic phosphine compounds such as triphenylphosphine and the like.
【００２５】これらのエポキシ樹脂用硬化剤は、単独で
使用してもよいが、２種以上を併用して使用することも
可能である。上記した硬化剤の使用割合は、本発明のエ
ピサルファイド樹脂１００重量部に対して、硬化剤が
０．０１〜２００重量部となるように配合されている。
この範囲を外れると、硬化物の耐熱性が低下し、耐湿性
が悪くなるため好ましくない。These curing agents for epoxy resins may be used alone or in combination of two or more. The curing agent is used in an amount of 0.01 to 200 parts by weight with respect to 100 parts by weight of the episulfide resin of the present invention.
Outside of this range, the heat resistance of the cured product decreases, and the moisture resistance deteriorates.
【００２６】（任意成分）本発明の硬化性樹脂組成物に
は、必要に応じて次の成分を添加配合することができ
る。粉末状の補強剤や充填剤、たと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。これらは本発明の硬化性
樹脂組成物の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 curable resin composition of the present invention, if necessary. Powdered 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, fine powdered silica, molten 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 fibers and ceramics 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 curable resin composition of the present invention.
【００２７】着色剤、顔料、難燃剤、たとえば二酸化チ
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、ブロム合
物及びトリフェニルホスフェイト等である。これらは硬
化性樹脂組成物の１００重量部に対して、０．１〜３０
重量部配合される。Colorants, pigments, flame retardants such as titanium dioxide, iron black, molybdenum red, navy blue, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, bromide and triphenyl phosphate. These are 0.1 to 30 parts by weight based on 100 parts by weight of the curable resin composition.
It is blended by weight.
【００２８】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。たとえば、モノエポキシ等のエポキシ樹脂用希釈
剤、一般の芳香族及び脂環式エポキシ樹脂、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−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、すなわち硬
化性樹脂組成物の１００重量部に対して、５０重量部以
下が好ましい。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, diluents for epoxy resins such as monoepoxy, general aromatic and alicyclic epoxy resins, phenol resins, alkyd resins, melamine resins, fluororesins, vinyl chloride resins, acrylic resins, silicone resins, polyester resins, etc. Or a combination of two or more. The mixing ratio of these resins is preferably in an amount that does not impair the original properties of the resin composition of the present invention, that is, 50 parts by weight or less based on 100 parts by weight of the curable resin composition.
【００２９】本発明のエピサルファイド樹脂、硬化剤及
び任意成分の配合手段としては、加熱溶融混合、ロ−
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。As means for compounding the episulfide resin, the curing agent and the optional components of the present invention, heat-melt mixing, low-temperature mixing,
And kneading with a kneader or a kneader, wet mixing and dry mixing using an appropriate organic solvent, and the like.
【００３０】[0030]
【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。 実施例１ 攪拌機、冷却器及び温度計を備えた１リットルのガラス
フラスコ内に、エピコート８０７（油化シェルエポキシ
社商品名；ビスフェノールＦのジグリシジルエーテル）
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／ｅｑ．、水素化率；ほぼ１００％、エポ
キシ基の損失率；２．８％、全塩素量；０．２３重量
％、「水素化Ｅ８０７」ともいう）１００ｇ（０．５５
２当量）及びテトラヒドロフランを１００ｇ仕込み、室
温にて攪拌してエポキシ化合物を溶解した。溶解後、チ
オ尿素を６３ｇ（０．８２９モル）及びメタノールを１
５０ｇ添加し、温度３０〜３５℃で、撹拌しながら５時
間反応を行った。反応終了後、メチルイソブチルケトン
を３００ｇ添加した後、純水５００ｇで５回水洗した。
水洗後、メチルイソブチルケトンをロータリーエバポレ
ーターにて減圧下、温度１００℃で留去させて、無色透
明液体のエピサルファイド樹脂１０５．５ｇを得た。得
られたエピサルファイド樹脂の性状を表１に示す。The present invention will be described below in more detail with reference to examples and comparative examples. Example 1 Epicoat 807 (trade name of Yuka Shell Epoxy; diglycidyl ether of bisphenol F) was placed in a 1-liter glass flask equipped with a stirrer, a cooler, and a thermometer.
Of hydrogenated epoxy resin (epoxy equivalent; 181 g / eq., Hydrogenation rate; almost 100%, loss rate of epoxy group; 2.8%, total chlorine amount: 0.23% by weight, hydrogen 100 g (0.55)
2 equivalents) and 100 g of tetrahydrofuran, and stirred at room temperature to dissolve the epoxy compound. After dissolution, 63 g (0.829 mol) of thiourea and 1 part of methanol were added.
50 g was added, and the reaction was performed at a temperature of 30 to 35 ° C. for 5 hours while stirring. After completion of the reaction, 300 g of methyl isobutyl ketone was added, and the mixture was washed five times with 500 g of pure water.
After washing with water, methyl isobutyl ketone was distilled off at a temperature of 100 ° C. under reduced pressure using a rotary evaporator to obtain 105.5 g of a colorless and transparent liquid episulfide resin. Table 1 shows the properties of the obtained episulfide resin.
【００３１】得られた化合物が目的物であるかどうか
は、赤外吸収スペクトル（図１）及びＧＣ−マススペク
トルにより確認した。 赤外吸収スペクトル；９１０ｃｍ-1のエポキシ基がほぼ
消滅し、６１０ｃｍ-1のエピサルファイド基の吸収が新
たに出現した。（図１参照） ＧＣ−マススペクトル；各ピークの帰属を決定した後、
トータルイオンクロマトグラフの重量百分率より、ジエ
ピサルファイド、モノエピサルファイド及び未反応エポ
キシの割合を求めた。Whether the obtained compound was the target compound was confirmed by infrared absorption spectrum (FIG. 1) and GC-mass spectrum. Infrared absorption spectrum; the epoxy group at 910 cm -1 almost disappeared, and the absorption of an episulfide group at 610 cm -1 appeared newly. (See FIG. 1) GC-mass spectrum; After determining the assignment of each peak,
From the weight percentage of the total ion chromatograph, the ratios of diepisulfide, monoepisulfide and unreacted epoxy were determined.
【００３２】実施例２ チオ尿素の仕込み量を、４２ｇ（０．５５２モル）に変
える以外は、上記実施例１と同様の操作を行い、無色透
明液体のエピサルファイド樹脂１０３．５ｇを得た。得
られたエピサルファイド樹脂の性状を表１に示す。Example 2 The same operation as in Example 1 was carried out except that the charged amount of thiourea was changed to 42 g (0.552 mol), to obtain 103.5 g of a colorless transparent liquid episulfide resin. Table 1 shows the properties of the obtained episulfide resin.
【００３３】実施例３ 原料水素化エポキシ樹脂をエピコート８２８ＥＬ（油化
シェルエポキシ社商品名；ビスフェノールＡのジグリシ
ジルエーテル）を水素化した液状の水素化エポキシ樹脂
（エポキシ当量；２００ｇ／ｅｑ．、水素化率；ほぼ１
００％、エポキシ基の損失率；４．０％、全塩素量；
０．１１重量％、「水素化Ｅ８２８」ともいう）１００
ｇ（０．５００当量）へ、チオ尿素を３８．０ｇ（０．
５００モル）に変える以外は、上記実施例１と同様の操
作を行い、無色透明液体のエピサルファイド樹脂１０
３．１ｇを得た。得られたエピサルファイド樹脂の性状
を表１に示す。Example 3 A liquid hydrogenated epoxy resin (epoxy equivalent: 200 g / eq., Hydrogen) obtained by hydrogenating a raw material hydrogenated epoxy resin from Epicoat 828EL (trade name of Yuka Shell Epoxy Co., Ltd .; diglycidyl ether of bisphenol A) Conversion rate: Almost 1
00%, loss rate of epoxy group; 4.0%, total chlorine amount;
0.11% by weight, also referred to as "hydrogenated E828") 100
g (0.500 equivalents) to 38.0 g (0.
500 mol), and the same operation as in Example 1 described above was carried out.
3.1 g were obtained. Table 1 shows the properties of the obtained episulfide resin.
【００３４】実施例４ 実施例１により得られたエピサルファイド樹脂１００
部、ＭＨ−７００（新日本理化社商品名；無水メチルヘ
キサヒドロフタル酸）４０部、及び２−エチル−４−メ
チルイミダゾール１部を温度６０℃で攪拌混合し、脱泡
後、均一な溶液とした後、硬化性樹脂組成物を得た。次
いで、上記組成物を型内に流し込み、１００℃で４時
間、更に１５０℃で６時間オーブン中で硬化を行い硬化
物を得た。この硬化物の物性値を表２に示す。Example 4 Episulfide resin 100 obtained according to Example 1
Part, MH-700 (Shin Nippon Rika Co., Ltd. trade name; methylhexahydrophthalic anhydride) 40 parts and 2-ethyl-4-methylimidazole 1 part are stirred and mixed at a temperature of 60 ° C., and after defoaming, a homogeneous solution After that, a curable resin composition was obtained. 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 cured product. Table 2 shows the physical properties of the cured product.
【００３５】実施例５〜６ エピサルファイド樹脂を実施例２、又は実施例３で得ら
れた樹脂に変える以外は、実施例４と同様の操作を行い
組成物を得、硬化物を得た。この硬化物の物性値を表２
に示す。Examples 5 to 6 The procedure of Example 4 was repeated, except that the episulfide resin was changed to the resin obtained in Example 2 or 3, to obtain a composition and a cured product. Table 2 shows the physical properties of the cured product.
Shown in
【００３６】比較例１ エピサルファイド樹脂を、実施例１と同じエピコート８
０７を水素化した液状の水素化エポキシ樹脂「水素化Ｅ
８０７」に変える以外は、実施例４と同様の操作を行い
組成物を得、硬化物を得た。この硬化物の物性値を表２
に示す。COMPARATIVE EXAMPLE 1 The same epicoat 8 as in Example 1 was used instead of the episulfide resin.
07 hydrogenated epoxy resin "Hydrogenated E"
807 ", except that the composition was obtained and a cured product was obtained. Table 2 shows the physical properties of the cured product.
Shown in
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【表２】 [Table 2]
【００３９】[0039]
【発明の効果】本発明の実施により、脂環式構造を有す
る従来にない低塩素のエピサルファイド樹脂が容易に得
られる。また、硬化剤で硬化させた樹脂硬化物は、耐熱
性が高く 耐湿性も良好であり、屈折率も高いことが予
想されるので広範な用途に応用展開が可能である。特
に、半導体封止材及び電気絶縁材等の電気・電子分野、
レンズ用樹脂等の光学材料等の用途において有利に使用
できる。According to the present invention, an unprecedented low chlorine episulfide resin having an alicyclic structure can be easily obtained. The cured resin cured with a curing agent has high heat resistance, good moisture resistance, and is expected to have a high refractive index, so that it can be applied to a wide range of applications. In particular, electric and electronic fields such as semiconductor encapsulants and electric insulating materials,
It can be advantageously used in applications such as optical materials such as resin for lenses.
【図１】図１は、実施例１で合成したエピサルファイド
樹脂の赤外吸収スペクトル図である。FIG. 1 is an infrared absorption spectrum of an episulfide resin synthesized in Example 1.
フロントページの続き Ｆターム(参考） 4J036 AJ01 AJ13 CC01 DB06 DB21 DB22 DC03 DC05 DC06 DC09 DC10 DC19 DC31 DC35 DC39 DC41 DD07 FB06 FB08 FB13 FB15 GA22 JA01 JA05 JA07 JA08 JA15 4J038 DB161 DB401 GA13 JA42 JA64 JB01 JB12 JB17 JB32 JC02 JC26 KA03 NA03 NA17 NA21 PB08 PB09 PC02 PC03 PC08 4J040 EJ011 HA046 HB36 HB47 HC01 HC15 HC18 HC24 HD03 HD06 HD08 HD22 KA16 LA01 LA07 LA09 Continued on the front page F term (reference) 4J036 AJ01 AJ13 CC01 DB06 DB21 DB22 DC03 DC05 DC06 DC09 DC10 DC19 DC31 DC35 DC39 DC41 DD07 FB06 FB08 FB13 FB15 GA22 JA01 JA05 JA07 JA08 JA15 4J038 DB161 DB401 GA13 JA42 JA64 JB01 JB12 J03 NA03 NA17 NA21 PB08 PB09 PC02 PC03 PC08 4J040 EJ011 HA046 HB36 HB47 HC01 HC15 HC18 HC24 HD03 HD06 HD08 HD22 KA16 LA01 LA07 LA09
Claims (10)
キル基を示し、ｎは０〜２０の数を示し、Ｚ1 及びＺ2
は硫黄原子又は酸素原子を示し、少なくともいずれか一
方が硫黄原子である。〕で示されるエピサルファイド樹
脂。1. A compound of the general formula (1) (1) [wherein, R 1 to R 6 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents a number of 0 to 20, Z 1 and Z 2
Represents a sulfur atom or an oxygen atom, at least one of which is a sulfur atom. ] The episulfide resin shown by these.
ける硫黄原子の割合が、Ｚ1 及びＺ2 における硫黄原子
と酸素原子の和に対して、５〜９５％の範囲内であるこ
とを特徴とする、請求項１記載のエピサルファイド樹
脂。 2. The proportion of sulfur atoms in Z 1 and Z 2 in the general formula (1) is within a range of 5 to 95% with respect to the sum of sulfur atoms and oxygen atoms in Z 1 and Z 2 . The episulfide resin according to claim 1, wherein:
キル基を示し、ｎは０〜２０の数である。〕で示される
エポキシ樹脂と、硫化剤を反応させることをを特徴とす
る、一般式（１） 【化３】 （１） 〔式中、Ｒ1 〜Ｒ6 は水素原子又は炭素数１〜６のアル
キル基を示し、ｎは０〜２０の数を示し、Ｚ1 及びＺ2
は硫黄原子又は酸素原子を示し、少なくともいずれか一
方が硫黄原子である。〕で示されるエピサルファイド樹
脂の製造方法。3. A compound of the general formula (2) (2) [wherein, R 1 to R 6 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is a number of 0 to 20. Wherein the epoxy resin represented by the general formula (1) is reacted with a sulfurizing agent. (1) [wherein, R 1 to R 6 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents a number of 0 to 20, Z 1 and Z 2
Represents a sulfur atom or an oxygen atom, at least one of which is a sulfur atom. ] The manufacturing method of the episulfide resin shown by these.
香族エポキシ樹脂を水素化して得られる、水素化エポキ
シ樹脂であることを特徴とする、請求項３記載のエピサ
ルファイド樹脂の製造方法。4. The method for producing an episulfide resin according to claim 3, wherein the epoxy resin of the general formula (2) is a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin. .
香族エポキシ樹脂を水素化して得られる、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、全塩素の含有量が０．３重量％以下であるエポ
キシ樹脂であることを特徴とする、請求項３又は４記載
のエピサルファイド樹脂の製造方法。5. The epoxy resin of the general formula (2), obtained by hydrogenating an aromatic epoxy resin, has a hydrogenation rate of an aromatic ring of 85% or more and an epoxy group loss rate of 20% or less. 5. The method for producing an episulfide resin according to claim 3, wherein the epoxy resin has a total chlorine content of 0.3% by weight or less. 6.
るＲ1 〜Ｒ2 が水素原子又はメチル基であり、Ｒ3 〜Ｒ
6 が水素原子であり、ｎが０〜５であることを特徴とす
る、請求項３〜５のいずれか１項記載のエピサルファイ
ド樹脂の製造方法。6. a R 1 to R 2 is a hydrogen atom or a methyl group in the epoxy resin of the general formula (2), R 3 ~R
The method for producing an episulfide resin according to any one of claims 3 to 5, wherein 6 is a hydrogen atom, and n is 0 to 5.
キシ基１当量に対して、硫化剤を０. ０５〜５モルの範
囲内を添加し反応させることを特徴とする、請求項３〜
６のいずれか１項記載のエピサルファイド樹脂の製造方
法。7. The method according to claim 3, wherein a sulfurizing agent is added in an amount of 0.05 to 5 mol per 1 equivalent of the epoxy group of the epoxy resin of the general formula (2) and reacted.
7. The method for producing an episulfide resin according to any one of 6.
類である、請求項３〜７のいずれか１項記載のエピサル
ファイド樹脂の製造方法。8. The method for producing an episulfide resin according to claim 3, wherein the sulfurizing agent is a thiocyanate or a thiourea.
０．０１〜２００重量部の割合で配合されてなる、硬化
性樹脂組成物。9. The general formula (1) (1) A curable resin composition comprising a curing agent in an amount of 0.01 to 200 parts by weight based on 100 parts by weight of the episulfide resin.
価フェノール類、イミダゾール類、ブレンステッド酸塩
類、ジシアンジアミド類、有機酸ヒドラジッド類、ポリ
メルカプタン類及び有機ホスフィン類から選ばれる少な
くとも１種の化合物である、請求項９記載の硬化性樹脂
組成物。10. The curing agent is at least one selected from amines, acid anhydrides, polyphenols, imidazoles, Bronsted acid salts, dicyandiamides, organic acid hydrazides, polymercaptans, and organic phosphines. The curable resin composition according to claim 9, which is a kind of compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16568099A JP3983935B2 (en) | 1999-06-11 | 1999-06-11 | Method for producing episulfide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16568099A JP3983935B2 (en) | 1999-06-11 | 1999-06-11 | Method for producing episulfide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000351829A true JP2000351829A (en) | 2000-12-19 |
| JP3983935B2 JP3983935B2 (en) | 2007-09-26 |
Family
ID=15817010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16568099A Expired - Lifetime JP3983935B2 (en) | 1999-06-11 | 1999-06-11 | Method for producing episulfide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3983935B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002212267A (en) * | 2001-01-18 | 2002-07-31 | Hitachi Chem Co Ltd | Resin paste composition and semiconductor device using the same |
| JP2007238952A (en) * | 2002-05-10 | 2007-09-20 | Mitsui Chemicals Inc | Method for producing lens |
| JP2012046634A (en) * | 2010-08-26 | 2012-03-08 | Panasonic Electric Works Co Ltd | Epoxy resin composition for sealing semiconductor, and semiconductor device using the same |
| EP2698393A1 (en) | 2007-07-26 | 2014-02-19 | Ajinomoto Co., Inc. | Resin composition |
-
1999
- 1999-06-11 JP JP16568099A patent/JP3983935B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002212267A (en) * | 2001-01-18 | 2002-07-31 | Hitachi Chem Co Ltd | Resin paste composition and semiconductor device using the same |
| JP2007238952A (en) * | 2002-05-10 | 2007-09-20 | Mitsui Chemicals Inc | Method for producing lens |
| EP2698393A1 (en) | 2007-07-26 | 2014-02-19 | Ajinomoto Co., Inc. | Resin composition |
| JP2012046634A (en) * | 2010-08-26 | 2012-03-08 | Panasonic Electric Works Co Ltd | Epoxy resin composition for sealing semiconductor, and semiconductor device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3983935B2 (en) | 2007-09-26 |
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