JP2887213B2 - New compounds, resins, resin compositions and cured products - Google Patents
New compounds, resins, resin compositions and cured productsInfo
- Publication number
- JP2887213B2 JP2887213B2 JP10967491A JP10967491A JP2887213B2 JP 2887213 B2 JP2887213 B2 JP 2887213B2 JP 10967491 A JP10967491 A JP 10967491A JP 10967491 A JP10967491 A JP 10967491A JP 2887213 B2 JP2887213 B2 JP 2887213B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- weight
- epoxy resin
- resin
- formula
- 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.)
- Expired - Fee Related
Links
Landscapes
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は高信頼性半導体封止用の
材料として有用な化合物、樹脂、樹脂組成物及びその硬
化物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound, a resin, a resin composition and a cured product thereof useful as a material for encapsulating a highly reliable semiconductor.
【0002】[0002]
【従来の技術】熱硬化樹脂はその硬化物の優れた電気特
性、耐熱性、接着性等により電気電子部品等の分野で幅
広く用いられている。2. Description of the Related Art Thermosetting resins are widely used in the field of electric and electronic parts due to their excellent electrical properties, heat resistance, adhesiveness and the like.
【0003】しかし、近年特に電気・電子分野の発展に
伴い、耐熱性をはじめ耐湿性、密着性等の諸特性のより
一層の向上が求められており、これら諸特性の向上を図
るためエポキシ樹脂やエポキシ硬化剤及びその組成物に
ついて多くの提案がなされてはいるが、吸水、吸湿後の
熱衝撃によりクラックが発生しやすいなど、未だ充分と
はいえない。However, in recent years, particularly with the development of the electric and electronic fields, further improvements in various properties such as heat resistance, moisture resistance and adhesion have been demanded. In order to improve these properties, epoxy resins have been used. Although many proposals have been made for epoxy resins and epoxy curing agents and their compositions, they are still insufficient, for example, cracks are easily generated by thermal shock after water absorption and moisture absorption.
【0004】[0004]
【発明が解決しようとする課題】本発明は溶融粘度が低
く、しかもその硬化物において優れた耐熱性、耐湿性を
与える高信頼性半導体封止用に適した樹脂及びその硬化
物を提供するものである。SUMMARY OF THE INVENTION The present invention is to provide a resin which has a low melt viscosity and which gives a cured product having excellent heat resistance and moisture resistance and is suitable for highly reliable semiconductor encapsulation, and a cured product thereof. It is.
【0005】[0005]
【課題を解決するための手段】本発明者らは前記のよう
な特性を付与向上する方法について鋭意研究の結果、本
発明を完成させた。Means for Solving the Problems The present inventors have made intensive studies on methods for imparting and improving the above-mentioned properties, and as a result, completed the present invention.
【0006】即ち、本発明は、(1)式(1)That is, the present invention provides the following equation (1).
【0007】[0007]
【化7】 Embedded image
【0008】(式中、R1 、R2 、R3 、R4 、R
´1 、R´2 、R´3 、R´4 はそれぞれ独立して水素
原子、ハロゲン原子、炭素数1〜4のアルキル基、また
はアリール基を示す。)で表される化合物、(2)式
(2)Wherein R 1 , R 2 , R 3 , R 4 , R
'1, R'2, R'3 , showing each R'4 independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, having 1 to 4 carbon atoms. A compound represented by the formula (2):
【0009】[0009]
【化8】 Embedded image
【0010】で表される1−ナフトールジメチロール化
物と式(P)1-naphthol dimethylol compound represented by the formula (P):
【0011】[0011]
【化9】 Embedded image
【0012】(式中、R1 、R2 、R3 及びR4 はそれ
ぞれ独立して水素原子、ハロゲン原子、炭素数1−4の
アルキル基またはアリール基を示す。)で表されるフェ
ノール類の一種又は二種以上を酸触媒の存在下に反応さ
せて得られ、式(1)の化合物を30重量%以上含む樹
脂、(3)式(3)Wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group. A resin obtained by reacting one or more of the above in the presence of an acid catalyst and containing 30% by weight or more of the compound of the formula (1);
【0013】[0013]
【化10】 Embedded image
【0014】(式中、R1 、R2 、R3 、R4 はそれぞ
れ独立して水素原子、ハロゲン原子、炭素数1〜4のア
ルキル基、またはアリール基を示す。)で表されるフェ
ノール類モノメチロール化物の一種又は二種以上と1−
ナフトールを酸触媒の存在下に反応させて得られ、式
(1)の化合物を30重量%以上含む樹脂、(4)式
(4)(Wherein R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group). One or more monomethylol compounds and 1-
A resin obtained by reacting naphthol in the presence of an acid catalyst and containing at least 30% by weight of the compound of the formula (1);
【0015】[0015]
【化11】 Embedded image
【0016】(式中、R1 、R2 、R3 、R4 、R
´1 、R´2 、R´3 、R´4 はそれぞれ独立して水素
原子、ハロゲン原子、炭素数1〜4のアルキル基、また
はアリール基を示す。)で表されるエポキシ化合物、
(5)式(1)の化合物又は上記(2)又は(3)の樹
脂を、式(E)(Wherein R 1 , R 2 , R 3 , R 4 , R
'1, R'2, R'3 , showing each R'4 independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, having 1 to 4 carbon atoms. An epoxy compound represented by
(5) The compound of the formula (1) or the resin of the above (2) or (3) is converted to a compound of the formula (E)
【0017】[0017]
【化12】 Embedded image
【0018】(式中、Yはハロゲン原子を示す)で表さ
れるエピハロヒドリンと反応させて得られ、式(4)の
エポキシ化合物を30重量%以上含むエポキシ樹脂、An epoxy resin obtained by reacting with an epihalohydrin represented by the formula (wherein Y represents a halogen atom) and containing at least 30% by weight of an epoxy compound of the formula (4):
【0019】(6)エポキシ樹脂、硬化剤及び硬化促進
剤を含むエポキシ樹脂組成物において、(A)エポキシ
樹脂として、式(4)の化合物又は上記(5)のエポキ
シ樹脂を用い、及び/又は(B)硬化剤として式(1)
の化合物又は上記(2)又は(3)の樹脂を用いる、エ
ポキシ樹脂組成物、(6) In the epoxy resin composition containing an epoxy resin, a curing agent and a curing accelerator, a compound of the formula (4) or the epoxy resin of the above (5) is used as the epoxy resin (A), and / or (B) Formula (1) as a curing agent
An epoxy resin composition using the compound of the above or the resin of the above (2) or (3),
【0020】(7)上記(6)のエポキシ樹脂組成物の
硬化物、に関する。(7) A cured product of the epoxy resin composition of (6).
【0021】以下、本発明を詳細に説明する。上記式
(1)で表される化合物、又は、該化合物を30重量%
以上含む樹脂は上記式(2)で表される1−ナフトール
ジメチロール化物と式(P)で表されるフェノール類と
を、又は、上記式(3)で表されるフェノール類モノメ
チロール化物と1−ナフトールとを、いずれも酸触媒の
存在下、脱水縮合反応を行わせることにより合成され
る。Hereinafter, the present invention will be described in detail. The compound represented by the above formula (1) or 30% by weight of the compound
The above-mentioned resin contains a 1-naphthol dimethylol compound represented by the above formula (2) and a phenol represented by the formula (P), or a phenol monomethylol compound represented by the above formula (3). All are synthesized by performing a dehydration condensation reaction with 1-naphthol in the presence of an acid catalyst.
【0022】更に上記式(2)で表される1−ナフトー
ルジメチロール化物は1−ナフトールとホルムアルデヒ
ドをアルカリ金属水酸化物の存在下、反応を行うことに
より得られる。又、上記式(3)で表されるフェノール
類モノメチロール化物はフェノール類とホルムアルデヒ
ドをアルカリ金属水酸化物の存在下、反応を行うことに
より得られる。式(2)及び(3)の化合物は、いずれ
も公知化合物である。Further, the 1-naphthol dimethylol compound represented by the above formula (2) can be obtained by reacting 1-naphthol with formaldehyde in the presence of an alkali metal hydroxide. The phenol monomethylol compound represented by the above formula (3) can be obtained by reacting a phenol with formaldehyde in the presence of an alkali metal hydroxide. The compounds of the formulas (2) and (3) are all known compounds.
【0023】式(2)の1−ナフトールジメチロール化
物としては、2,4−ジメチロール−1−ナフトール等
が挙げられる。Examples of the 1-naphthol dimethylol compound of the formula (2) include 2,4-dimethylol-1-naphthol.
【0024】式(P)のフェノール類としては、フェノ
ール、2,4−キシレノール、2,6−キシレノール、
2,3,6−トリメチルフェノール、2−t−ブチル−
4−メチルフェノール、2,4−ジクロロフェノール、
2,4−ジブロモフェノール、2,4,5−トリクロロ
フェノール、6−フェニル−2−クロロフェノール、o
−クレゾール、m−クレゾ−ル、p−クレゾール、o−
エチルフェノール、p−エチルフェノール、o−フェニ
ルフェノール、p−フェニルフェノール、2,3,5−
トリメチルフェノール、p−t−ブチルフェノール、o
−クロロフェノール、o−ブロモフェノール、4−クロ
ル−3,5−キシレノール等が挙げられるがこれらに限
定されるものではない。The phenols of the formula (P) include phenol, 2,4-xylenol, 2,6-xylenol,
2,3,6-trimethylphenol, 2-t-butyl-
4-methylphenol, 2,4-dichlorophenol,
2,4-dibromophenol, 2,4,5-trichlorophenol, 6-phenyl-2-chlorophenol, o
-Cresol, m-cresol, p-cresol, o-
Ethylphenol, p-ethylphenol, o-phenylphenol, p-phenylphenol, 2,3,5-
Trimethylphenol, pt-butylphenol, o
-Chlorophenol, o-bromophenol, 4-chloro-3,5-xylenol and the like, but are not limited thereto.
【0025】式(3)のフェノール類モノメチロール化
物としては、式(P)のフェノール類として例示した上
記化合物の2−位、4−位、又は6−位の水素原子の代
りにメチロール基が付いた化合物が挙げられる。The phenol monomethylol compound of the formula (3) includes a methylol group in place of the hydrogen atom at the 2-, 4- or 6-position of the compound exemplified as the phenol of the formula (P). Attached compounds.
【0026】脱水縮合反応を行なう場合,式(2)の1
−ナフトールジメチロール化物と式(P)のフェノール
類との反応においては、1−ナフトール−ジメチロール
化物に対して好ましくは1〜20モル倍、特に好ましく
は2〜10モル倍の範囲でフェノール類を使用すること
が出来る。又、式(3)のフェノール類モノメチロール
化物と1−ナフトールとの反応の場合は、フェノール類
モノメチロール化物に対して好ましくは0.3〜1モル
倍、特に好ましくは0.4〜0.6モル倍の範囲で1−
ナフトールを使用することが出来る。又、この反応にお
いてフェノール類、または、フェノール類モノメチロー
ル化物は2種以上を混合し使用することもできる。When the dehydration condensation reaction is performed, one of the formula (2)
In the reaction between the naphthol dimethylol compound and the phenol of the formula (P), the phenol is preferably used in an amount of 1 to 20 moles, more preferably 2 to 10 moles, based on 1-naphthol dimethylol. Can be used. In the case of the reaction between the phenol monomethylol compound of the formula (3) and 1-naphthol, it is preferably 0.3 to 1 mol times, particularly preferably 0.4 to 0.1 mol times the phenol monomethylol compound. 1- in the range of 6 mole times
Naphthol can be used. In this reaction, two or more phenols or phenol monomethylolates may be used in combination.
【0027】更に脱水縮合反応時の酸触媒としては塩
酸、硝酸、硫酸、リン酸、パラトルエンスルホン酸など
のプロトン酸、三弗化ホウ素、三弗化ホウ素エーテル錯
体、塩化亜鉛、塩化アルミニウムなどのルイス酸、酢
酸、シュウ酸等を用いることができる。これらのうち塩
酸、パラトルエンスルホン酸、シュウ酸などが好ましく
用いられ、酸触媒使用量は1−ナフトール−ジメチロー
ル化物またはフェノール類モノメチロール化物に対し好
ましくは0.001〜0.1モル倍の間で選定される。
この酸触媒存在下における脱水縮合反応は通常0〜12
0℃の間で行われ、好ましくは80℃以下である。ま
た、反応時間は好ましくは1〜10時間の範囲である。
また、この反応は水を始めメタノール、トルエン、メチ
ルイソブチルケトン等の適当な溶媒の存在下で行うこと
ができる。Further, acid catalysts for the dehydration condensation reaction include protonic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, boron trifluoride, boron trifluoride ether complex, zinc chloride and aluminum chloride. Lewis acid, acetic acid, oxalic acid and the like can be used. Of these, hydrochloric acid, paratoluenesulfonic acid, oxalic acid and the like are preferably used, and the amount of the acid catalyst used is preferably 0.001 to 0.1 mol times with respect to 1-naphthol-dimethylolated product or phenolic monomethylolated product. Is selected.
The dehydration / condensation reaction in the presence of the acid catalyst is usually performed in the range of 0 to 12
The reaction is carried out at 0 ° C., preferably 80 ° C. or less. The reaction time is preferably in the range of 1 to 10 hours.
This reaction can be carried out in the presence of a suitable solvent such as water, methanol, toluene, methyl isobutyl ketone and the like.
【0028】上記脱水縮合反応により得られた反応液は
過剰のトルエン、メチルイソブチルケトン等の溶媒存在
下その系内が中性になるまで水洗を繰り返し、水を分離
後、加熱減圧下、未反応物及び溶媒を除去することによ
り式(1)で表される化合物、又は、該化合物を30重
量%以上好ましくは35重量%以上含む樹脂が得られ
る。The reaction solution obtained by the dehydration condensation reaction is repeatedly washed with water in the presence of an excess solvent such as toluene or methyl isobutyl ketone until the inside of the system becomes neutral. By removing the substance and the solvent, a compound represented by the formula (1) or a resin containing the compound in an amount of 30% by weight or more, preferably 35% by weight or more is obtained.
【0029】つぎに本発明のエポキシ化合物、又は、該
エポキシ化合物を30重量%以上好ましくは35重量%
以上含むエポキシ樹脂は、式(1)の化合物、又は、該
化合物を30重量%以上含む樹脂にエピハロヒドリンを
反応させることによって得ることが出来る。エピハロヒ
ドリンとしてはエピクロルヒドリン、エピブロムヒドリ
ン等が使用されるが工業的にはエピクロルヒドリンが容
易に入手でき好ましい。この反応は従来公知のノボラッ
ク型フェノール樹脂とエピハロヒドリンとからポリグリ
シジルエーテルを得る方法に準じて行うことが出来る。Next, the epoxy compound of the present invention or the epoxy compound is added in an amount of 30% by weight or more, preferably 35% by weight.
The epoxy resin containing the above can be obtained by reacting the compound of the formula (1) or a resin containing the compound in an amount of 30% by weight or more with epihalohydrin. As epihalohydrin, epichlorohydrin, epibromohydrin and the like are used, but epichlorohydrin is industrially preferable because it is easily available. This reaction can be carried out according to a conventionally known method for obtaining a polyglycidyl ether from a novolak-type phenol resin and epihalohydrin.
【0030】例えば、式(1)の化合物又は該化合物を
30重量%以上含む樹脂と過剰のエピハロヒドリンの混
合物に、水酸化ナトリウム、水酸化カリウム等のアルカ
リ金属水酸化物の固体を添加し、又は、添加しながら2
0℃〜120℃の間の温度で反応させる。この際アルカ
リ金属水酸化物はその水溶液を使用してもよく、その場
合は該アルカリ金属水酸化物水溶液を連続的に添加する
と共に反応系内から減圧下、または常圧下、連続的に水
及びエピクロルヒドリンを留出せしめ更に分液し水は除
去しエピクロルヒドリンは反応系内に連続的に戻す方法
でもよい。For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a mixture of a compound of the formula (1) or a resin containing 30% by weight or more of the compound and an excess of epihalohydrin, or , While adding 2
The reaction is carried out at a temperature between 0 ° C and 120 ° C. At this time, the alkali metal hydroxide may be used in the form of an aqueous solution.In this case, the aqueous solution of the alkali metal hydroxide is continuously added and the water and the water are continuously reduced under reduced pressure or normal pressure from the reaction system. A method may be employed in which epichlorohydrin is distilled off, liquid is further separated, water is removed, and epichlorohydrin is continuously returned into the reaction system.
【0031】上記の方法においてエピクロルヒドリンの
使用量は該化合物又は樹脂の水酸基1当量に対して通常
1〜20モル、好ましくは2〜10モルである。アルカ
リ金属水酸化物の使用量は該化合物の水酸基1当量に対
し通常0.8〜1.5モル、好ましくは0.9〜1.1
モルの範囲である。更に、反応を円滑に進行させるため
にメタノール、エタノール、などのアルコール類の他ジ
メチルスルホン、ジメチルスルホオキシド(以下DMS
O)などの非プロトン性極性溶媒を添加することが好ま
しく、この反応は通常1〜20時間の範囲で行われる。In the above method, the amount of epichlorohydrin used is usually 1 to 20 mol, preferably 2 to 10 mol, per 1 equivalent of the hydroxyl group of the compound or resin. The amount of the alkali metal hydroxide to be used is generally 0.8 to 1.5 mol, preferably 0.9 to 1.1 mol, per equivalent of the hydroxyl group of the compound.
Range of moles. Further, in order to make the reaction proceed smoothly, in addition to alcohols such as methanol and ethanol, dimethyl sulfone and dimethyl sulfoxide (hereinafter referred to as DMS)
It is preferable to add an aprotic polar solvent such as O), and this reaction is usually carried out for 1 to 20 hours.
【0032】又、該化合物又は該樹脂と過剰のエピハロ
ヒドリンとの混合物にテトラメチルアンモニウムクロラ
イド、テトラメチルアンモニウムブロマイド、トリメチ
ルベンジルアンモニウムクロライドなどの第四級アンモ
ニウム塩を触媒として加え好ましくは50℃〜150℃
で反応させ得られるハロヒドリンエーテルに水酸化ナト
リウム、水酸化カリウム等のアルカリ金属水酸化物の固
体または水溶液を加え、再び好ましくは20℃〜120
℃の間の温度で反応させてハロヒドリンエーテルを閉環
させてエポキシ化合物又はエポキシ樹脂を得ることもで
きる。この場合第四級アンモニュウム塩の使用量は式
(1)の化合物又はこれを30重量%以上含む樹脂の水
酸基1当量に対して好ましくは0.001〜0.2モ
ル、特に好ましくは0.005〜0.1モルの範囲であ
る。A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to the compound or a mixture of the resin and an excess of epihalohydrin.
A solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the halohydrin ether obtained by the reaction in
The reaction can be carried out at a temperature between ° C and the ring closure of the halohydrin ether to give an epoxy compound or epoxy resin. In this case, the amount of the quaternary ammonium salt used is preferably 0.001 to 0.2 mol, particularly preferably 0.005 mol per equivalent of the hydroxyl group of the compound of the formula (1) or a resin containing 30% by weight or more. 〜0.1 mol.
【0033】通常これらの1段目の反応物は水洗後、又
は、水洗無しに加熱減圧下、過剰のエピハロヒドリンを
除去した後、再びトルエン、メチルイソブチルケトン等
の溶媒に溶解し、水酸化ナトリウム、水酸化カリウム等
のアルカリ金属水酸化物の水溶液を加えて2段目の反応
を行い閉環を確実なものとする。この場合アルカリ金属
水酸化物の使用量は水酸基1当量に対して好ましくは
0.01〜0.2モル、特に好ましくは0.05〜0.
1モルである。反応温度は好ましくは50〜120℃で
あり、反応時間は通常0.5〜2時間である。Usually, the first-stage reaction product is washed with water or without heating, without heating, under reduced pressure with heating to remove excess epihalohydrin, and then dissolved again in a solvent such as toluene, methyl isobutyl ketone, and sodium hydroxide. An aqueous solution of an alkali metal hydroxide such as potassium hydroxide is added to carry out a second-stage reaction to ensure ring closure. In this case, the amount of the alkali metal hydroxide to be used is preferably 0.01 to 0.2 mol, particularly preferably 0.05 to 0.1 mol, per equivalent of the hydroxyl group.
1 mole. The reaction temperature is preferably from 50 to 120 ° C, and the reaction time is usually from 0.5 to 2 hours.
【0034】2段目反応終了後、生成した塩を濾過、水
洗等により除去し、更に、加熱減圧下トルエン、メチル
イソブチルケトン等の溶媒を留去することにより加水分
解性ハロゲンの少ない本発明のエポキシ化合物又はエポ
キシ樹脂を得ることが出来る。After the completion of the second-stage reaction, the formed salt is removed by filtration, washing with water, etc., and further, the solvent such as toluene, methyl isobutyl ketone or the like is distilled off under reduced pressure under heating, whereby the hydrolyzed halogen of the present invention is reduced. An epoxy compound or an epoxy resin can be obtained.
【0035】以下、本発明のエポキシ樹脂組成物につい
て説明する。前記(6)のエポキシ樹脂組成物におい
て、式(4)の化合物又は前記(5)のエポキシ樹脂
(以下、本発明のエポキシ樹脂等という)は単独で又
は、他のエポキシ樹脂と併用して使用することができ
る。併用する場合、本発明のエポキシ樹脂等の全エポキ
シ樹脂中に占める割合は30重量%以上が好ましく、特
に40重量%以上が好ましい。Hereinafter, the epoxy resin composition of the present invention will be described. In the epoxy resin composition of the above (6), the compound of the formula (4) or the epoxy resin of the above (5) (hereinafter referred to as the epoxy resin of the present invention) is used alone or in combination with another epoxy resin. can do. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.
【0036】本発明のエポキシ樹脂等と併用される他の
エポキシ樹脂としては、ノボラック型エポキシ樹脂、ビ
スフェノールA型エポキシ樹脂、ビスフェノールF型エ
ポキシ樹脂、ビスフェノールS型エポキシ樹脂、脂環式
エポキシ樹脂、ビフェノール型エポキシ樹脂等が挙げら
れるが、ノボラック型エポキシ樹脂が耐熱性の点で特に
有利である。具体的には、クレゾールノボラック型エポ
キシ樹脂、フェノールノボラック型エポキシ樹脂、臭素
化フェノールノボラック型エポキシ樹脂などが挙げられ
るがこれらに限定されるものではない。これらは単独で
用いてもよく、2種以上併用してもよい。Other epoxy resins used in combination with the epoxy resin of the present invention include novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, biphenol A novolak type epoxy resin is particularly advantageous in terms of heat resistance. Specific examples include, but are not limited to, cresol novolak epoxy resins, phenol novolak epoxy resins, brominated phenol novolak epoxy resins, and the like. These may be used alone or in combination of two or more.
【0037】前記(6)のエポキシ樹脂組成物におい
て、式(1)の化合物又は前記(2)又は(3)の樹脂
(以下、本発明のノボラック型樹脂等という)は単独で
又は、他の硬化剤と併用して使用することができる。併
用する場合、本発明のノボラック型樹脂等の全硬化剤中
に占める割合は、30重量%以上が好ましく、特に40
重量%以上が好ましい。In the epoxy resin composition of the above (6), the compound of the formula (1) or the resin of the above (2) or (3) (hereinafter referred to as the novolak type resin of the present invention) may be used alone or in another form. It can be used in combination with a curing agent. When used in combination, the proportion of the total curing agent such as the novolak resin of the present invention is preferably 30% by weight or more, and particularly preferably 40% by weight or more.
% By weight or more is preferred.
【0038】本発明のノボラック型樹脂等と併用される
他の硬化剤としては、例えば、脂肪族ポリアミン、芳香
族ポリアミン、ポリアミドポリアミン等のポリアミン系
硬化剤、無水ヘキサヒドロフタル酸、無水メチルテトラ
ヒドロフタル酸等の酸無水物系硬化剤、フェノールノボ
ラック、クレゾールノボラック等のフェノール系硬化
剤、三フッ化ホウ素等のルイス酸又はそれらの塩類、ジ
シアンジアミド類等の硬化剤等が挙げられるが、これら
に限定されるものではない。これらは単独で用いてもよ
く、2種以上併用してもよい。Other curing agents used in combination with the novolak resin of the present invention include, for example, polyamine curing agents such as aliphatic polyamines, aromatic polyamines and polyamide polyamines, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride. Acid anhydride-based hardeners such as acids, phenol novolaks, phenol-based hardeners such as cresol novolak, Lewis acids such as boron trifluoride or salts thereof, hardeners such as dicyandiamide, and the like, but are not limited thereto. It is not something to be done. These may be used alone or in combination of two or more.
【0039】前記(6)のエポキシ樹脂組成物におい
て、エポキシ樹脂として本発明のエポキシ樹脂等を用い
る場合、硬化剤としては、前記の他の硬化剤や本発明の
ノボラック型樹脂等を用いることができる。In the epoxy resin composition of the above (6), when the epoxy resin of the present invention is used as the epoxy resin, the other curing agent or the novolak resin of the present invention may be used as the curing agent. it can.
【0040】又、前記のエポキシ樹脂組成物において、
硬化剤として本発明のノボラック型樹脂等を用いる場
合、エポキシ樹脂としては、前記の他のエポキシ樹脂や
本発明のエポキシ樹脂等を用いることができる。Further, in the epoxy resin composition,
When the novolak resin of the present invention or the like is used as a curing agent, the other epoxy resin described above, the epoxy resin of the present invention, or the like can be used as the epoxy resin.
【0041】本発明のエポキシ樹脂組成物において、硬
化剤の使用量は、エポキシ樹脂のエポキシ基1当量に対
して0.5〜1.5当量が好ましく特に0.6〜1.2
当量が好ましい。In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, more preferably 0.6 to 1.2 equivalents, per equivalent of the epoxy group of the epoxy resin.
Equivalents are preferred.
【0042】硬化促進剤としては、2−メチルイミダゾ
ール、2−エチルイミダゾール等の、イミダゾール系化
合物、2−(ジメチルアミノメチル)フェノール等の第
3アミン系化合物、トリフェニルホスフィン化合物等が
挙げられ、公知の種々の硬化剤促進剤が使用でき、特に
限定されるものではない。硬化促進剤の使用量はエポキ
シ樹脂100重量部に対して0.01〜15重量部の範
囲が好ましく、特に、0.1〜10重量部の範囲が好ま
しい。Examples of the curing accelerator include imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, tertiary amine compounds such as 2- (dimethylaminomethyl) phenol, and triphenylphosphine compounds. Various known hardener accelerators can be used and are not particularly limited. The amount of the curing accelerator used is preferably in the range of 0.01 to 15 parts by weight, particularly preferably in the range of 0.1 to 10 parts by weight, based on 100 parts by weight of the epoxy resin.
【0043】本発明のエポキシ樹脂組成物には、さらに
必要に応じて公知の添加剤を配合することができ、添加
剤としては、例えば、シリカ、アルミナ、タルク、ガラ
ス繊維等の無機充填剤、シランカップリング剤のような
充填剤の表面処理剤、離型剤、顔料等が挙げられる。The epoxy resin composition of the present invention may further contain known additives as necessary. Examples of the additives include inorganic fillers such as silica, alumina, talc and glass fiber. Examples include filler surface treatment agents such as silane coupling agents, release agents, and pigments.
【0044】本発明のエポキシ樹脂組成物は、各成分を
均一に混合することにより得られ、通常130〜170
℃の温度で30〜300秒の範囲で予備硬化し、さらに
150〜200℃の温度で2〜8時間、後硬化すること
により充分な硬化反応が進行し、本発明の硬化物が得ら
れる。又、エポキシ樹脂組成物の成分を溶剤等に均一に
分散又は溶解させ、溶媒を除去し硬化させることもでき
る。The epoxy resin composition of the present invention can be obtained by uniformly mixing the components, and is usually from 130 to 170.
Precuring at a temperature of 30 ° C. for 30 to 300 seconds and post-curing at a temperature of 150 to 200 ° C. for 2 to 8 hours allow a sufficient curing reaction to proceed to obtain the cured product of the present invention. Alternatively, the components of the epoxy resin composition can be uniformly dispersed or dissolved in a solvent or the like, and the solvent can be removed and cured.
【0045】こうして得られる硬化物は、耐熱性を保持
しながら、低吸水性を有するという二つの特性を兼ね備
えた優れた性能を有する。従って、本発明の上記化合物
又は樹脂は、耐熱性、低吸水性の要求される広範な分野
で、エポキシ樹脂として、あるいは、硬化剤として用い
ることかできる。具体的には、絶縁材料、積層板、封止
材料等あらゆる電気・電子材料の配合成分として有用で
ある。又、成形材料、塗料材料、複合材料等の分野に用
いることもできる。The cured product thus obtained has excellent performance having both of the characteristics of low water absorption while maintaining heat resistance. Therefore, the compound or resin of the present invention can be used as an epoxy resin or as a curing agent in a wide range of fields requiring heat resistance and low water absorption. Specifically, it is useful as a compounding component of all electric and electronic materials such as an insulating material, a laminate, and a sealing material. Further, it can be used in the fields of molding materials, coating materials, composite materials and the like.
【0046】エポキシ樹脂成分、硬化剤成分の両方に本
発明エポキシ樹脂と本発明のノボラック型樹脂を用いる
ことによりその効果は倍増する。さらに、本発明の樹脂
は、ナフトール環を有するにも拘わらず軟化点が低く抑
えられているためトランスファ−成型等、従来通りの手
法を用いることができ作業性も良好である。The effect is doubled by using the epoxy resin of the present invention and the novolak resin of the present invention for both the epoxy resin component and the curing agent component. Furthermore, since the resin of the present invention has a low softening point despite having a naphthol ring, conventional techniques such as transfer molding can be used, and workability is good.
【0047】[0047]
【実施例】以下本発明を実施例により更に具体的に説明
するが、本発明はこれらに限定されるものではない。
尚、実施例中の軟化点とはJIS K2425(環球
法)による値、加水分解性塩素とはジオキサン中、1N
−KOH〜エタノールで30分間、還流下分解した時の
塩素量ppm、水酸基当量及びエポキシ当量はg/eq
を示す。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
The softening point in the examples is a value according to JIS K2425 (ring and ball method), and the hydrolyzable chlorine is 1N in dioxane.
-Ppm of chlorine, hydroxyl equivalent and epoxy equivalent when decomposed under reflux with KOH to ethanol for 30 minutes are g / eq
Is shown.
【0048】実施例1 (1)メチロール化物の合成 温度計、滴下ロート、冷却管、撹拌器を取り付けたフラ
スコに1−ナフトール144重量部(1モル)、20wt
%-水酸化ナトリウム水溶液210重量部(1.05モ
ル)を仕込み50℃で30分間反応させた。次いで、系
内を10℃に冷却後、粒状パラホルムアルデヒド(純分
92重量%)68重量部(2.1モル)を一気に添加し
10℃で2時間反応した。反応終了後、38wt%-塩酸水
溶液100重量部を発熱に注意しながら添加し中和し
た。この反応液を次の液体クロマトグラフィーで分析し
たところ1−ナフトールジメチロール化物は93%(面
積%)であった。Example 1 (1) Synthesis of Methylol Compound In a flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, 144 parts by weight (1 mol) of 1-naphthol, 20 wt.
210 parts by weight (1.05 mol) of a% -aqueous sodium hydroxide solution were charged and reacted at 50 ° C. for 30 minutes. Next, after cooling the system to 10 ° C., 68 parts by weight (2.1 mol) of granular paraformaldehyde (92% by weight pure) was added at a stretch, and the mixture was reacted at 10 ° C. for 2 hours. After the completion of the reaction, 100 parts by weight of a 38 wt% -hydrochloric acid aqueous solution was added while paying attention to heat generation, and neutralized. The reaction solution was analyzed by the following liquid chromatography to find that 1-naphthol dimethylol was 93% (area%).
【0049】 液体クロマト装置 :日立製作所 L−6000 カラム :ガスクロ工業 イナートシル ODS−2 4.6id * 250mm、 カラム温度 50℃ 溶媒 :水 − アセトニトリル(1:1)0.8ml/min 検出器 :RILiquid chromatograph: Hitachi L-6000 Column: Gaschrom Industry Inertsil ODS-2 4.6 id * 250 mm, column temperature 50 ° C. Solvent: water-acetonitrile (1: 1) 0.8 ml / min Detector: RI
【0050】(2)脱水縮合物の合成 この反応液にo−クレゾールを432重量部(4モ
ル)、メタノールを150重量部仕込み、系内を40℃
に調節した。更に、38wt%-塩酸水溶液5重量部を添加
し2時間反応させ、次いで70℃で2時間反応させた。
反応終了後、反応混合物を分液ロートに移し、メチルイ
ソブチルケトン600重量部を添加し、次いで、水洗を
繰り返し、中性に戻した。その後油層よりロータリーエ
バポレーターを使って加熱減圧下メチルイソブチルケト
ン及び未反応o−クレゾールを除去し、室温で淡黄色、
固体の本発明の樹脂(No.1)376重量部を得た。(2) Synthesis of Dehydration Condensate 432 parts by weight (4 mol) of o-cresol and 150 parts by weight of methanol were charged into the reaction solution, and the temperature of the system was increased to 40 ° C.
Was adjusted to Further, 5 parts by weight of a 38 wt% hydrochloric acid aqueous solution was added and reacted for 2 hours, and then reacted at 70 ° C. for 2 hours.
After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and 600 parts by weight of methyl isobutyl ketone was added. Thereafter, methyl isobutyl ketone and unreacted o-cresol were removed from the oil layer using a rotary evaporator under heating and reduced pressure, and the mixture was pale yellow at room temperature.
376 parts by weight of the solid resin of the present invention (No. 1) was obtained.
【0051】得られた樹脂の軟化点は86℃、150℃
におけるICI粘度は1.5psであり、水酸基当量
(g/eq)は129であった。又、この樹脂(No.
1)を溶媒にテトラヒドロフラン(THF)を用いて、
次のGPC分析装置により分析したところ図1に示され
る分子量分布曲線を得た。The obtained resin has a softening point of 86 ° C. and 150 ° C.
Was 1.5 ps, and the hydroxyl equivalent (g / eq) was 129. In addition, this resin (No.
1) Using tetrahydrofuran (THF) as a solvent,
When analyzed by the following GPC analyzer, the molecular weight distribution curve shown in FIG. 1 was obtained.
【0052】 GPC装置:島津製作所 カラム :GPC KF−803(1本)+GPC KF−802.5(2本) +GPC KF−802(1本) 溶媒 :テトラヒドロフラン 1ml/min 検出器 :RIGPC apparatus: Shimadzu Corporation Column: GPC KF-803 (1) + GPC KF-802.5 (2) + GPC KF-802 (1) Solvent: Tetrahydrofuran 1 ml / min Detector: RI
【0053】この分析条件で標準ポリスチレンを使用し
た検量線よりメインピークの化合物の分子量はナフトー
ル環1個、ベンゼン環2個を有する3核体のリテンショ
ンタイムに相当し、この3核体と思われるピーク成分を
分取し、マススペクトル(FAB−MS)によって分析
したところM+ 384が得られたことにより、この化合
物は次式(5)で表される3核体であることを確認し
た。Under these analytical conditions, the molecular weight of the compound at the main peak from the calibration curve using standard polystyrene corresponds to the retention time of a trinuclear compound having one naphthol ring and two benzene rings, and is considered to be the trinuclear compound. The peak component was separated and analyzed by mass spectrum (FAB-MS). As a result, M + 384 was obtained, and thus it was confirmed that this compound was a trinuclear compound represented by the following formula (5).
【0054】[0054]
【化13】 Embedded image
【0055】分子量分布曲線より、式(5)の化合物の
樹脂(No.1)中の含有量は56重量%であることが
わかった。From the molecular weight distribution curve, it was found that the content of the compound of the formula (5) in the resin (No. 1) was 56% by weight.
【0056】実施例2 (1)メチロール化物の合成 温度計、滴下ロート、冷却管、撹拌器を取り付けたフラ
スコに1−ナフトール144重量部(1モル)、20wt
%-水酸化ナトリウム水溶液210重量部(1.05モ
ル)を仕込み40℃で30分間反応させた。次いで、系
内を10℃に冷却後、粒状パラホルムアルデヒド(純分
92重量%)68重量部(2.1モル)を一気に添加し
10℃で2時間反応した。反応終了後、38wt%-塩酸水
溶液100重量部を発熱に注意しながら添加し中和し
た。Example 2 (1) Synthesis of Methylolated Compound A flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer was charged with 144 parts by weight of 1-naphthol (1 mol), 20 wt.
210 parts by weight (1.05 mol) of a% -aqueous sodium hydroxide solution were charged and reacted at 40 ° C. for 30 minutes. Next, after cooling the system to 10 ° C., 68 parts by weight (2.1 mol) of granular paraformaldehyde (92% by weight pure) was added at a stretch, and the mixture was reacted at 10 ° C. for 2 hours. After the completion of the reaction, 100 parts by weight of a 38 wt% -hydrochloric acid aqueous solution was added while paying attention to heat generation, and neutralized.
【0057】(2)脱水縮合物の合成 この反応液に2,6−キシレノール488重量部(4モ
ル)、メタノール200重量部を仕込み、系内を40℃
に調節した。更に、38wt%-塩酸水溶液5重量部を添加
し2時間反応させ、次いで、70℃で2時間反応させ
た。反応終了後、反応混合物を分液ロートに移し、メチ
ルイソブチルケトン600重量部を添加した。次いで、
水洗を繰り返し中性に戻した。その後、油層よりロータ
リーエバポレーターを使って加熱減圧下メチルイソブチ
ルケトン及び未反応2,6−キシレノールを除去し、室
温で淡黄色、固体の本発明の樹脂(No.2)400重
量部を得た。(2) Synthesis of Dehydration Condensate 488 parts by weight (4 mol) of 2,6-xylenol and 200 parts by weight of methanol were charged into the reaction solution, and the temperature of the system was reduced to 40 ° C.
Was adjusted to Further, 5 parts by weight of a 38 wt% -hydrochloric acid aqueous solution was added and reacted for 2 hours, and then reacted at 70 ° C. for 2 hours. After completion of the reaction, the reaction mixture was transferred to a separating funnel, and 600 parts by weight of methyl isobutyl ketone was added. Then
The washing was repeatedly returned to neutral. Thereafter, methyl isobutyl ketone and unreacted 2,6-xylenol were removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 400 parts by weight of a pale yellow solid resin of the present invention (No. 2) at room temperature.
【0058】得られた樹脂の軟化点は89℃、150℃
におけるICI粘度は1.8psであり、水酸基当量
(g/eq)は138であった。この樹脂(No.2)
を液体クロマトグラフィー(GPC、分析条件は実施例
1と同じ)で分析し、図2に示される分子量分布曲線を
得た。又、3核体と思われるピーク成分を分取しマスス
ペクトル(FAB−MS)により分析したところM+ 4
12が得られたことにより、この化合物は次式(6)で
表される3核体であることを確認した。The obtained resin has a softening point of 89 ° C. and 150 ° C.
Was 1.8 ps, and the hydroxyl equivalent (g / eq) was 138. This resin (No. 2)
Was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1) to obtain a molecular weight distribution curve shown in FIG. Also, M + 4 was analyzed by 3 Shi preparative peak component appears nucleus min Mass spectrum (FAB-MS)
By obtaining 12, it was confirmed that this compound was a trinuclear body represented by the following formula (6).
【0059】[0059]
【化14】 Embedded image
【0060】分子量分布曲線より、式(6)の化合物の
樹脂(No.2)中の含有量は51重量%であることが
わかった。From the molecular weight distribution curve, it was found that the content of the compound of the formula (6) in the resin (No. 2) was 51% by weight.
【0061】実施例3 (1)メチロール化物の合成 温度計、滴下ロート、冷却管、撹拌器を取り付けたフラ
スコに1−ナフトール144重量部(1.0モル)、2
0wt%-水酸化ナトリウム水溶液210重量部(1.05
モル)を仕込み40℃で30分間反応させた。次いで、
系内を10℃に冷却後、粒状パラホルムアルデヒド(純
分92重量%)68重量部(2.1モル)を一気に添加
し10℃で2時間反応した。反応終了後、38wt%-塩酸
水溶液100重量部を発熱に注意しながら添加し中和し
た。Example 3 (1) Synthesis of Methylol Compound 144 parts by weight (1.0 mol) of 1-naphthol was added to a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer.
0 wt% -210 parts by weight of aqueous sodium hydroxide solution (1.05%
Mol) was reacted at 40 ° C. for 30 minutes. Then
After cooling the system to 10 ° C., 68 parts by weight (2.1 mol) of granular paraformaldehyde (92% by weight pure) were added at once, and the reaction was carried out at 10 ° C. for 2 hours. After the completion of the reaction, 100 parts by weight of a 38 wt% -hydrochloric acid aqueous solution was added while paying attention to heat generation, and neutralized.
【0062】(2)脱水縮合物の合成 この反応液に2,3,6−トリメチルフェノールを54
4重量部(4モル)、メチルイソブチルケトン300重
量部を仕込み、系内を40℃に調節した。38wt%-塩酸
水溶液3重量部を添加し2時間反応させ、次いで、60
℃で2時間反応させた。反応終了後、反応混合物を分液
ロートに移し、メチルイソブチルケトン500重量部を
添加した。次いで、水洗を数回繰り返し中性に戻した。
その後、油層よりロータリーエバポレーターを使って加
熱減圧下メチルイソブチルケトン及び未反応2,3,6
−トリメチルフェノールを除去し、室温で淡黄色、固体
の本発明の樹脂(No.3)420重量部を得た。(2) Synthesis of Dehydration Condensate 2,3,6-Trimethylphenol was added to this reaction
4 parts by weight (4 mol) and 300 parts by weight of methyl isobutyl ketone were charged, and the temperature in the system was adjusted to 40 ° C. 38 wt% -hydrochloric acid aqueous solution (3 parts by weight) was added and reacted for 2 hours.
The reaction was carried out at 2 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and 500 parts by weight of methyl isobutyl ketone was added. Then, washing was repeated several times to return to neutral.
Then, methyl isobutyl ketone and unreacted 2,3,6 were removed from the oil layer under heating and reduced pressure using a rotary evaporator.
-The trimethylphenol was removed to obtain 420 parts by weight of a resin (No. 3) of the present invention as a pale yellow solid at room temperature.
【0063】得られた樹脂の軟化点は107℃、150
℃におけるICI粘度は6.4psであり、水酸基当量
(g/eq)は147であった。この樹脂(No.3)
を液体クロマトグラフィー(GPC、分析条件は実施例
1と同じ)で分析し、図3に示される分子量分布曲線を
得た。又、3核体と思われるピーク成分を分取しマスス
ペクトル(FAB−MS)により分析したところM+ 4
40が得られたことにより、この化合物は次式(7)で
表される3核体であることを確認した。The softening point of the obtained resin was 107 ° C. and 150 ° C.
The ICI viscosity at ℃ was 6.4 ps, and the hydroxyl equivalent (g / eq) was 147. This resin (No. 3)
Was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1) to obtain a molecular weight distribution curve shown in FIG. Also, M + 4 was analyzed by 3 Shi preparative peak component appears nucleus min Mass spectrum (FAB-MS)
By obtaining 40, it was confirmed that this compound was a trinuclear body represented by the following formula (7).
【0064】[0064]
【化15】 Embedded image
【0065】分子量分布曲線より、式(7)の化合物の
樹脂(No.3)中の含有量は53重量%であることが
わかった。From the molecular weight distribution curve, it was found that the content of the compound of the formula (7) in the resin (No. 3) was 53% by weight.
【0066】実施例4 (1)メチロール化物の合成 温度計、滴下ロート、冷却管、撹拌器を取り付けたフラ
スコに2,4−キシレノール244重量部(2モル)、
40wt%-水酸化ナトリウム水溶液100重量部(1モ
ル)を仕込み系内を40℃に加熱し30分間反応させ
た。次いで粒状パラホルムアルデヒド(純分92%)6
8重量部を添加し50℃で1時間、次いで60℃で3時
間反応させた。反応終了後、系内を10℃に冷却し、3
8wt%-塩酸水溶液96重量部を発熱に注意しながら滴下
し中和した。Example 4 (1) Synthesis of Methylolated Compound A flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer was charged with 244 parts by weight of 2,4-xylenol (2 mol),
A 40 wt% aqueous solution of sodium hydroxide (100 parts by weight (1 mol)) was charged and the system was heated to 40 ° C. and reacted for 30 minutes. Next, granular paraformaldehyde (92% pure) 6
8 parts by weight were added and reacted at 50 ° C. for 1 hour and then at 60 ° C. for 3 hours. After the completion of the reaction, the system was cooled to 10 ° C.
96 parts by weight of an 8 wt% -hydrochloric acid aqueous solution was neutralized by dropping while paying attention to heat generation.
【0067】(2)脱水縮合化物の合成 次いで、この反応液にメチルイソブチルケトン400重
量部、1−ナフトール144重量部(1モル)を仕込
み、系内を60℃に調節した後、パラトルエンスルホン
酸2重量部を溶解したメチルイソブチルケトン10重量
部を添加し2時間反応させ、更に75℃で1時間反応さ
せた。反応終了後、反応混合物を分液ロートに移し、メ
チルイソブチルケトン200重量部を添加した。次い
で、水洗を数回繰り返し、中性に戻した。その後、油層
よりロータリーエバポレーターを使って加熱減圧下メチ
ルイソブチルケトン及び未反応物を除去し、室温で淡黄
色、固体の本発明の樹脂(No.4)386重量部を得
た。(2) Synthesis of Dehydration Condensate Next, 400 parts by weight of methyl isobutyl ketone and 144 parts by weight (1 mol) of 1-naphthol were charged into this reaction solution, and the system was adjusted to 60 ° C. 10 parts by weight of methyl isobutyl ketone in which 2 parts by weight of an acid was dissolved was added, and reacted for 2 hours, and further reacted at 75 ° C. for 1 hour. After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and 200 parts by weight of methyl isobutyl ketone was added. Next, washing with water was repeated several times to return to neutral. Thereafter, methyl isobutyl ketone and unreacted substances were removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 386 parts by weight of a pale yellow, solid resin (No. 4) of the present invention at room temperature.
【0068】得られた樹脂の軟化点は84.5℃、15
0℃におけるICI粘度は0.8psであり、水酸基当
量(g/eq)は138であった。この樹脂(No.
4)を液体クロマトグラフィー(GPC、分析条件は実
施例1と同じ)で分析し、図4に示される分子量分布曲
線を得た。又、3核体と思われるピーク成分を分取しマ
ススペクトル(FAB−MS)により分析したところM
+ 412が得られたことにより、この化合物は次式
(8)で表される3核体であることを確認した。The softening point of the obtained resin was 84.5 ° C., 15
The ICI viscosity at 0 ° C. was 0.8 ps, and the hydroxyl equivalent (g / eq) was 138. This resin (No.
4) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and the molecular weight distribution curve shown in FIG. 4 was obtained. Further, peak components considered to be trinuclear were fractionated and analyzed by mass spectrum (FAB-MS).
By + 412 is obtained, this compound was confirmed to be 3 nuclei expressed in the following equation (8).
【0069】[0069]
【化16】 Embedded image
【0070】分子量分布曲線より、式(8)の化合物の
樹脂(No.4)中の含有量は58重量%であることが
わかった。From the molecular weight distribution curve, it was found that the content of the compound of the formula (8) in the resin (No. 4) was 58% by weight.
【0071】実施例5 実施例1で得られた樹脂(No.1)129重量部にエ
ピクロルヒドリン555重量部(6モル)、DMSOを
280重量部加え溶解後、50℃に加熱しフレーク状水
酸化ナトリウム(純分99%)42重量部(1.04モ
ル)を100分間かけて添加し、その後さらに60℃で
2時間、70℃で1時間反応させた。反応終了後、水洗
を繰り返し、水層は分離除去し、油層より加熱減圧下過
剰のエピクロルヒドリンを留去し、残留物に500重量
部のメチルイソブチルケトンを加え残留物を溶解した。Example 5 To 129 parts by weight of the resin (No. 1) obtained in Example 1, 555 parts by weight (6 moles) of epichlorohydrin and 280 parts by weight of DMSO were added and dissolved. Then, 42 parts by weight (1.04 mol) of sodium (99% pure) was added over 100 minutes, and the mixture was further reacted at 60 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, washing with water was repeated, the aqueous layer was separated and removed, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 500 parts by weight of methyl isobutyl ketone was added to the residue to dissolve the residue.
【0072】更に、このメチルイソブチルケトンの溶液
を70℃に加熱下し30重量%の水酸化ナトリウム水溶
液10重量部を添加し、1時間反応させた後、水洗を繰
り返しpHを中性とした。更に水層は分離除去し、油層
から加熱減圧下メチルイソブチルケトンを留去し、本発
明のエポキシ樹脂(No.5)176重量部を得た。Further, the solution of methyl isobutyl ketone was heated to 70 ° C., and 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added. The mixture was reacted for 1 hour, and then washed repeatedly with water to make the pH neutral. Further, the aqueous layer was separated and removed, and methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 176 parts by weight of the epoxy resin (No. 5) of the present invention.
【0073】得られたエポキシ樹脂の軟化点は57.5
℃、150℃におけるICI粘度は1.0psであり、
エポキシ当量は190、加水分解性塩素は310ppm
であった。このエポキシ樹脂(No.5)を液体クロマ
トグラフィー(GPC、分析条件は実施例1と同じ)で
分析し、図5に示される分子量分布曲線を得た。又、3
核体と思われるピーク成分を分取しマススペクトル(F
AB−MS)により分析したところM+ 552が得られ
たことにより、この化合物は次式(9)で表される3核
体であることを確認した。The obtained epoxy resin has a softening point of 57.5.
° C, the ICI viscosity at 150 ° C is 1.0 ps,
Epoxy equivalent is 190, hydrolyzable chlorine is 310 ppm
Met. This epoxy resin (No. 5) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and a molecular weight distribution curve shown in FIG. 5 was obtained. 3
A peak component considered to be a nucleus is collected and mass spectrum (F
(AB-MS), M + 552 was obtained. Thus, it was confirmed that this compound was a trinuclear compound represented by the following formula (9).
【0074】[0074]
【化17】 Embedded image
【0075】分子量分布曲線より、式(9)の化合物の
エポキシ樹脂(No.5)中の含有量は50重量%であ
ることがわかった。From the molecular weight distribution curve, it was found that the content of the compound of the formula (9) in the epoxy resin (No. 5) was 50% by weight.
【0076】実施例6 実施例2で得た樹脂(No.2)を138重量部使用し
た以外は実施例5と同様にエポキシ化反応を行い、本発
明のエポキシ樹脂(No.6)176重量部を得た。
得られたエポキシ樹脂の軟化点は60.5℃、ICI粘
度は1.4psであり、エポキシ当量は199、加水分
解性塩素は285ppmであった。このエポキシ樹脂
(No.6)を液体クロマトグラフィー(GPC、分析
条件は実施例1と同じ)で分析し、図6に示される分子
量分布曲線を得た。又、3核体と思われるピーク成分を
分取しマススペクトル(FAB−MS)により分析した
ところM+ 580が得られたことにより、この化合物は
次式(10)で表される3核体であることを確認した。Example 6 An epoxidation reaction was carried out in the same manner as in Example 5 except that 138 parts by weight of the resin (No. 2) obtained in Example 2 was used, and 176 parts by weight of the epoxy resin (No. 6) of the present invention was obtained. Got a part.
The obtained epoxy resin had a softening point of 60.5 ° C., an ICI viscosity of 1.4 ps, an epoxy equivalent of 199, and a hydrolyzable chlorine of 285 ppm. This epoxy resin (No. 6) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and the molecular weight distribution curve shown in FIG. 6 was obtained. Further, a peak component considered to be a trinuclear compound was collected and analyzed by mass spectrum (FAB-MS) to obtain M + 580. Therefore, this compound was a trinuclear compound represented by the following formula (10). Was confirmed.
【0077】[0077]
【化18】 Embedded image
【0078】分子量分布曲線より、式(10)の化合物
のエポキシ樹脂(No.6)中の分有量は42重量%で
あることがわかった。From the molecular weight distribution curve, it was found that the content of the compound of the formula (10) in the epoxy resin (No. 6) was 42% by weight.
【0079】実施例7 実施例3で得た樹脂(No.3)を147重量部使用し
た以外は実施例5と同様にエポキシ化反応を行い、本発
明のエポキシ樹脂(No.7)183重量部を得た。得
られたエポキシ樹脂の軟化点は78℃、ICI粘度は
4.1psであり、エポキシ当量は207、加水分解性
塩素は340ppmであった。このエポキシ樹脂(N
o.7)を液体クロマトグラフィー(GPC、分析条件
は実施例1と同じ)で分析し、図7に示される分子量分
布曲線を得た。又、3核体と思われるピーク成分を分取
しマススペクトル(FAB−MS)により分析したとこ
ろM+ 608が得られたことにより、この化合物は次式
(11)で表される3核体であることを確認した。Example 7 An epoxidation reaction was carried out in the same manner as in Example 5 except that 147 parts by weight of the resin (No. 3) obtained in Example 3 was used, and 183 parts by weight of the epoxy resin (No. 7) of the present invention was obtained. Got a part. The obtained epoxy resin had a softening point of 78 ° C., an ICI viscosity of 4.1 ps, an epoxy equivalent of 207, and hydrolysable chlorine of 340 ppm. This epoxy resin (N
o. 7) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and the molecular weight distribution curve shown in FIG. 7 was obtained. Further, a peak component thought to be a trinuclear compound was collected and analyzed by mass spectrum (FAB-MS) to obtain M + 608. Thus, the compound was a trinuclear compound represented by the following formula (11). Was confirmed.
【0080】[0080]
【化19】 Embedded image
【0081】分子量分布曲線より、式(11)の化合物
のエポキシ樹脂(No.7)中の含有量は46重量%で
あることがわかった。From the molecular weight distribution curve, it was found that the content of the compound of the formula (11) in the epoxy resin (No. 7) was 46% by weight.
【0082】実施例8 実施例4で得られた樹脂(No.4)を138重量部使
用した以外は実施例5と同様にエポキシ化反応を行い、
本発明のエポキシ樹脂(No.8)176重量部を得
た。得られたエポキシ樹脂の軟化点は57℃、ICI粘
度は0.9psであり、エポキシ当量は204、加水分
解性塩素は315ppmであった。このエポキシ樹脂
(No.8)を液体クロマトグラフィー(GPC、分析
条件は実施例1と同じ)で分析し、図8に示される分子
量分布曲線を得た。又、3核体と思われるピーク成分を
分取しマススペクトル(FAB−MS)により分析した
ところM+ 580が得られたことにより、この化合物は
次式(12)で表される3核体であることを確認した。Example 8 An epoxidation reaction was carried out in the same manner as in Example 5, except that 138 parts by weight of the resin (No. 4) obtained in Example 4 was used.
176 parts by weight of the epoxy resin of the present invention (No. 8) was obtained. The obtained epoxy resin had a softening point of 57 ° C., an ICI viscosity of 0.9 ps, an epoxy equivalent of 204, and hydrolyzable chlorine of 315 ppm. This epoxy resin (No. 8) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and a molecular weight distribution curve shown in FIG. 8 was obtained. Further, a peak component thought to be a trinuclear compound was collected and analyzed by mass spectrum (FAB-MS) to obtain M + 580. Thus, the compound was a trinuclear compound represented by the following formula (12). Was confirmed.
【0083】[0083]
【化20】 Embedded image
【0084】分子量分布曲線より、式(12)の化合物
のエポキシ樹脂(No.8)中の含有量は48重量%で
あることがわかった。From the molecular weight distribution curve, it was found that the content of the compound of the formula (12) in the epoxy resin (No. 8) was 48% by weight.
【0085】試験例1〜8、比較例1〜2 上記実施例1から4で得られた樹脂を使用し、又、比較
例1としてビスフェノールA型樹脂(水酸基当量11
6、150℃におけるICI粘度0.1ps)を使用
し、これら硬化剤100重量部に対してエポキシ樹脂
(o−クレゾールノボラック型エポキシ樹脂、EOCN
−1020(日本化薬(株)製)、エポキシ当量20
0、150℃におけるICI粘度3.2ps)及び硬化
促進剤(トリフェニルホスフィン)を表2に示す使用量
で配合し、トランスファー成形により樹脂成形体を調製
し表2に示す硬化条件により硬化させた。Test Examples 1 to 8 and Comparative Examples 1 and 2 The resins obtained in Examples 1 to 4 were used. As Comparative Example 1, a bisphenol A resin (having a hydroxyl equivalent of 11
6, an ICI viscosity at 150 ° C. of 0.1 ps) and an epoxy resin (o-cresol novolac type epoxy resin, EOCN)
-1020 (manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent 20
0, an ICI viscosity at 150 ° C. of 3.2 ps) and a curing accelerator (triphenylphosphine) were blended in the amounts shown in Table 2, and a resin molded article was prepared by transfer molding and cured under the curing conditions shown in Table 2. .
【0086】更に、上記実施例5から8で得られたエポ
キシ樹脂を使用し、又、比較例2としてビスフェノール
A型エポキシ樹脂(エポキシ当量189、150℃にお
けるICI粘度0.1ps以下)を使用し、これらエポ
キシ樹脂150重量部に対して硬化剤(フェノールノボ
ラック型樹脂、PN−80(日本化薬(株)製)、水酸
基当量106g/eq、150℃におけるICI粘度
1.5ps)及び硬化促進剤(トリフェニルホスフィ
ン)を表3に示す使用量で配合し、トランスファー成形
により樹脂成形体を調製し表3に示す硬化条件により硬
化させた。Further, the epoxy resin obtained in the above Examples 5 to 8 was used, and a bisphenol A type epoxy resin (epoxy equivalent: 189, ICI viscosity at 150 ° C. 0.1 ps or less) was used as Comparative Example 2. A curing agent (phenol novolak type resin, PN-80 (manufactured by Nippon Kayaku Co., Ltd.), hydroxyl equivalent 106 g / eq, ICI viscosity at 150 ° C. 1.5 ps) with 150 parts by weight of these epoxy resins, and a curing accelerator (Triphenylphosphine) was blended in the amounts shown in Table 3, and a resin molded product was prepared by transfer molding and cured under the curing conditions shown in Table 3.
【0087】この様にして得られた硬化物の熱変形温
度、吸水率を測定した結果を表2、表3にそれぞれ示
す。なお、熱変形温度及び吸水率の測定条件は次のとお
り。Tables 2 and 3 show the results of measuring the heat distortion temperature and the water absorption of the cured product thus obtained. The measurement conditions of the heat distortion temperature and the water absorption are as follows.
【0088】 熱変形温度 JIS K7207に規定された条件 吸水率 試験片 直径 50mm (硬化物) 厚サ 3mm 円板 条件 100℃の水中で24時間煮沸した後の重量増加量(重量 %)Heat deformation temperature Condition specified in JIS K7207 Water absorption Test piece Diameter 50 mm (cured product) Thickness 3 mm Disk Condition Weight increase after boiling in water at 100 ° C. for 24 hours (% by weight)
【0089】 表 2 試験例 1 2 3 4 比較例1 樹脂 No.1 No.2 No.3 No.4 水酸基当量 g/eq 129 138 147 138 116 エポキシ樹脂 wt部 155 145 136 145 173 硬化促進剤 wt部 1.6 1.5 1.4 1.5 1.7 硬化条件 160℃*2時間 + 180 ℃*8時間 熱変形温度 ℃ 150 168 170 140 120 吸水率 wt% 1.1 1.3 1.2 1.0 1.5 Table 2 Test Example 1 2 3 4 Comparative Example 1 Resin No. 1 No. 2 No. 3 No. 4 Hydroxyl equivalent g / eq 129 138 147 138 138 116 Epoxy resin wt part 155 145 136 145 173 Curing accelerator wt Part 1.6 1.5 1.4 1.5 1.7 Curing conditions 160 ° C * 2 hours + 180 ° C * 8 hours Heat deformation temperature ℃ 150 168 170 140 120 Water absorption wt% 1.1 1.3 1.2 1.0 1.5
【0090】 表 3 試験例 5 6 7 8 比較例2 エポキシ樹脂 No.5 No.6 No.7 No.8 エポキシ当量 g/eq 190 199 207 204 189 硬化剤 wt部 84 80 77 78 84 硬化促進剤 wt部 1.5 1.5 1.5 1.5 1.5 硬化条件 160℃*2時間 + 180 ℃*8時間 熱変形温度 ℃ 161 171 175 149 125 吸水率 wt% 1.2 1.3 1.1 1.1 1.4 Table 3 Test Example 5 6 7 8 Comparative Example 2 Epoxy resin No. 5 No. 6 No. 7 No. 8 Epoxy equivalent g / eq 190 199 207 207 204 189 Curing agent wt part 84 80 77 78 84 Curing accelerator wt part 1.5 1.5 1.5 1.5 1.5 Curing conditions 160 ° C * 2 hours + 180 ° C * 8 hours Heat deformation temperature ° C 161 171 175 149 125 Water absorption wt% 1.2 1.3 1.1 1.1 1.4
【0091】[0091]
【発明の効果】本発明の化合物、樹脂又はエポキシ樹脂
をエポキシ樹脂硬化物の原料として使用した場合、その
硬化物において、優れた耐熱性、及び耐湿性を得ること
ができるほか、加水分解性塩素量が極めて少ないことか
ら高信頼性半導体封止用樹脂として提供することが出来
る。When the compound, resin or epoxy resin of the present invention is used as a raw material for a cured epoxy resin, the cured product can have excellent heat resistance and moisture resistance, and can be hydrolyzed with chlorine. Since the amount is extremely small, it can be provided as a highly reliable semiconductor sealing resin.
【図1】実施例1で得られた樹脂(No.1)の分子量
分布曲線FIG. 1 is a molecular weight distribution curve of a resin (No. 1) obtained in Example 1.
【図2】実施例2で得られた樹脂(No.2)の分子量
分布曲線FIG. 2 is a molecular weight distribution curve of a resin (No. 2) obtained in Example 2.
【図3】実施例3で得られた樹脂(No.3)の分子量
分布曲線FIG. 3 is a molecular weight distribution curve of a resin (No. 3) obtained in Example 3.
【図4】実施例4で得られた樹脂(No.4)の分子量
分布曲線FIG. 4 is a molecular weight distribution curve of a resin (No. 4) obtained in Example 4.
【図5】実施例5で得られたエポキシ樹脂(No.5)
の分子量分布曲線FIG. 5 is an epoxy resin obtained in Example 5 (No. 5).
Molecular weight distribution curve of
【図6】実施例6で得られたエポキシ樹脂(No.6)
の分子量分布曲線FIG. 6 is an epoxy resin obtained in Example 6 (No. 6).
Molecular weight distribution curve of
【図7】実施例7で得られたエポキシ樹脂(No.7)
の分子量分布曲線FIG. 7: Epoxy resin obtained in Example 7 (No. 7)
Molecular weight distribution curve of
【図8】実施例8で得られたエポキシ樹脂(No.8)
の分子量分布曲線FIG. 8: Epoxy resin obtained in Example 8 (No. 8)
Molecular weight distribution curve of
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C08G 59/06 C08G 59/06 59/32 59/32 59/62 59/62 61/12 61/12 H01L 23/29 H01L 23/30 R 23/31 (56)参考文献 特開 平3−50223(JP,A) 特開 平4−279627(JP,A) (58)調査した分野(Int.Cl.6,DB名) C07C 39/12 C07D 303/28 C08G 8/00 C08G 59/00 C08G 61/12 CA(STN) REGISTRY(STN)────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification code FI C08G 59/06 C08G 59/06 59/32 59/32 59/62 59/62 61/12 61/12 H01L 23/29 H01L 23 / 30 R 23/31 (56) References JP-A-3-50223 (JP, A) JP-A-4-279627 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C07C 39/12 C07D 303/28 C08G 8/00 C08G 59/00 C08G 61/12 CA (STN) REGISTRY (STN)
Claims (7)
´3 、R´4 はそれぞれ独立して水素原子、ハロゲン原
子、炭素数1〜4のアルキル基、またはアリール基を示
す。)で表される化合物。(1) Formula (1) (Wherein R 1 , R 2 , R 3 , R 4 , R ′ 1 , R ′ 2 , R
'3, respectively is R'4 independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, having 1 to 4 carbon atoms. ).
水素原子、ハロゲン原子、炭素数1〜4のアルキル基ま
たはアリール基を示す。)で表されるフェノール類の一
種又は二種以上を酸触媒の存在下に反応させて得られ、
請求項1の化合物を30重量%以上含む樹脂。(2) Formula (2) 1-naphthol dimethylol compound represented by the formula and a compound represented by the formula (P): (In the formula, R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group having 1 to 4 carbon atoms.) Obtained by reacting two or more kinds in the presence of an acid catalyst,
A resin comprising the compound of claim 1 in an amount of 30% by weight or more.
素原子、ハロゲン原子、炭素数1〜4のアルキル基、ま
たはアリール基を示す。)で表されるフェノール類モノ
メチロール化物の一種又は二種以上と1−ナフトールを
酸触媒の存在下に反応させて得られ、請求項1の化合物
を30重量%以上含む樹脂。(3) Formula (3) (Wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group). A resin obtained by reacting one or two or more kinds of compounds with 1-naphthol in the presence of an acid catalyst and containing at least 30% by weight of the compound of claim 1.
´3 、R´4 はそれぞれ独立して水素原子、ハロゲン原
子、炭素数1〜4のアルキル基、またはアリール基を示
す。)で表されるエポキシ化合物。(4) Formula (4) (Wherein R 1 , R 2 , R 3 , R 4 , R ′ 1 , R ′ 2 , R
'3, respectively is R'4 independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, having 1 to 4 carbon atoms. An epoxy compound represented by).
脂を、式(E) 【化6】 (式中、Yはハロゲン原子を示す)で表されるエピハロ
ヒドリンと反応させて得られ、請求項4の化合物を30
重量%以上含むエポキシ樹脂。5. The compound of claim 1 or the resin of claim 2 or 3 is a compound of formula (E) (Wherein Y represents a halogen atom), and obtained by reacting the compound of claim 4 with an epihalohydrin represented by the following formula:
Epoxy resin containing more than weight%.
むエポキシ樹脂組成物において、(A)エポキシ樹脂と
して、請求項4の化合物又は請求項5の樹脂を用い、及
び/又は(B)硬化剤として請求項1の化合物又は請求
項2又は3の樹脂を用いる、エポキシ樹脂組成物。6. An epoxy resin composition containing an epoxy resin, a curing agent and a curing accelerator, wherein (A) the compound of claim 4 or the resin of claim 5 is used as the epoxy resin, and / or (B) curing. An epoxy resin composition using the compound according to claim 1 or the resin according to claim 2 or 3 as an agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10967491A JP2887213B2 (en) | 1991-04-16 | 1991-04-16 | New compounds, resins, resin compositions and cured products |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10967491A JP2887213B2 (en) | 1991-04-16 | 1991-04-16 | New compounds, resins, resin compositions and cured products |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04316528A JPH04316528A (en) | 1992-11-06 |
JP2887213B2 true JP2887213B2 (en) | 1999-04-26 |
Family
ID=14516305
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10967491A Expired - Fee Related JP2887213B2 (en) | 1991-04-16 | 1991-04-16 | New compounds, resins, resin compositions and cured products |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2887213B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180006001A (en) * | 2016-07-07 | 2018-01-17 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5648847B2 (en) * | 2011-02-04 | 2015-01-07 | Dic株式会社 | Method for producing naphthol-type calix (4) arene compound |
JP6618115B2 (en) * | 2016-01-26 | 2019-12-11 | 日本化薬株式会社 | Epoxy resin and composition thereof |
JP6834175B2 (en) * | 2016-05-18 | 2021-02-24 | 昭和電工マテリアルズ株式会社 | Resin for paint and coating film using it |
-
1991
- 1991-04-16 JP JP10967491A patent/JP2887213B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180006001A (en) * | 2016-07-07 | 2018-01-17 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same |
KR101955762B1 (en) | 2016-07-07 | 2019-03-07 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same |
Also Published As
Publication number | Publication date |
---|---|
JPH04316528A (en) | 1992-11-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0429667B1 (en) | Phenolic novolac resin, product of curing thereof, and method of production thereof | |
JP4100791B2 (en) | Production method of naphthol resin | |
JP3132610B2 (en) | Naphthalene ring-containing resin, resin composition and cured product thereof | |
JP2887213B2 (en) | New compounds, resins, resin compositions and cured products | |
JP2631560B2 (en) | Novolak epoxy resins with phenols and their production | |
JP3074013B2 (en) | Epoxy resin composition and cured product thereof | |
JP3982661B2 (en) | Naphthol resin, epoxy resin, epoxy resin composition and cured product thereof | |
JPH04323214A (en) | Novolak resin, its production, epoxy resin, resin composition and its cured product | |
JP2887214B2 (en) | Naphthol compound, its production method, epoxy compound, composition and cured product | |
EP0458417B1 (en) | Adducts of phenolic compounds and cyclic terpenes and derivatives of said adducts | |
JP3636409B2 (en) | Phenolic resins, epoxy resins, epoxy resin compositions and cured products thereof | |
JP2856565B2 (en) | Resin manufacturing method | |
JP2870709B2 (en) | New compounds, resins, resin compositions and cured products | |
JP3075496B2 (en) | Polyphenol resin, polyphenol epoxy resin and production method thereof | |
JP3141960B2 (en) | New epoxy resin, resin composition and cured product | |
JPH06329741A (en) | Resin, epoxy resin, its production, resin composition and cured product of said composition | |
JP3852789B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
JP3939000B2 (en) | Novolac resin, epoxy resin, epoxy resin composition and cured product thereof | |
JP2823056B2 (en) | Epoxy resin composition and cured product thereof | |
JP2981759B2 (en) | Epoxy compound and epoxy resin composition | |
JPH07330645A (en) | Compound of polyphenols, epoxy resin, epoxy resin composition and cured material thereof | |
JP3192471B2 (en) | Epoxy resin, resin composition and cured product | |
JP2870710B2 (en) | New compounds, resins, resin compositions and cured products | |
JPH0920819A (en) | Modified phenol novlak resin, epoxy resin, epoxy resin composition and its cured product | |
JPH04366117A (en) | New resin, production thereof, resin composition, and cured article |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |