JP2694188B2 - Epoxy resin composition for casting - Google Patents
Epoxy resin composition for castingInfo
- Publication number
- JP2694188B2 JP2694188B2 JP63028443A JP2844388A JP2694188B2 JP 2694188 B2 JP2694188 B2 JP 2694188B2 JP 63028443 A JP63028443 A JP 63028443A JP 2844388 A JP2844388 A JP 2844388A JP 2694188 B2 JP2694188 B2 JP 2694188B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- bisphenol
- general formula
- casting
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は注型用エポキシ樹脂、特に耐熱衝撃性に優れ
たエポキシ樹脂組成付に関する。DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to an epoxy resin for casting, particularly an epoxy resin composition having excellent thermal shock resistance.
「従来の技術」 エポキシ樹脂は接着性、電気特性、耐熱性等に優れて
いることから電子部品、電気機器、自動車部品など広範
囲に、しかも多量に使用されている。エポキシ樹脂とし
てはビスフェノールＡジグリシジルエーテル型のもの、
例えば東都化成（株）製YD−128（エポキシ当量188g/e
q）が汎用品として用いられている。しかしこの型の樹
脂は硬い硬化物が得られるが、硬化時の発熱による歪み
のため冷熱サイクルによつてクラックを生じ易く、耐熱
衝撃性が劣るという欠点を有していた。そこで耐熱衝撃
性を向上させるためにエポキシ樹脂中のエポキシ基の一
部を一官応性変性剤例えばモノアルキルフェノールで変
性して架橋点を少なくする手法等が用いられていた。か
かるものとして例えば東都化成（株）製YC−195（エポ
キシ当量390g/eq）があげられる。これらの方法により
硬化物の架橋密度が下がる為耐熱衝撃性の向上がみら
れ、同時に硬化時の発熱が抑えられる為、大型注型にも
使用出来るようになつたのである。しかしモノアルキル
フェノールは一般に昇華性を有しており、モノアルキル
フェノール変性樹脂の製造時に目的通りの変性率を達成
させる事、ロット間でバラツキ無く製造する事などに困
難であつた。特に高圧用変圧器、高圧用変流器などの絶
縁材料としての使用の際には他の用途に比べ高度の特
性、特に長期間の信頼性が要求されるものであり、その
為充分に管理された一定品質の製造が必要である。しか
し上述のようにモノアルキルフェノールによるエポキシ
樹脂の変性は安定生産が困難であつた。一方ビスフェノ
ールとしてビスフェノールＦ（R2＝水素）を構成成分と
した液状エポキシ樹脂例えば東都化成（株）製YDF−170
（R1＝水素）等が知られているがYD−128と同様に大型
注型品とした場合耐熱衝撃性に劣るものである。"Prior Art" Epoxy resin is widely used in a wide range of electronic parts, electric devices, automobile parts and the like because of its excellent adhesiveness, electrical characteristics, heat resistance and the like. Bisphenol A diglycidyl ether type epoxy resin,
For example, YD-128 manufactured by Tohto Kasei Co., Ltd. (epoxy equivalent: 188 g / e
q) is used as a general-purpose product. However, although this type of resin gives a hard cured product, it has a drawback that cracks are likely to occur due to the heat cycle during curing due to distortion due to heat generated during curing and the thermal shock resistance is poor. Therefore, in order to improve the thermal shock resistance, a method has been used in which a part of the epoxy groups in the epoxy resin is modified with a monofunctional modifier such as monoalkylphenol to reduce the cross-linking points. An example thereof is YC-195 (epoxy equivalent 390 g / eq) manufactured by Tohto Kasei Co., Ltd. By these methods, the crosslink density of the cured product is lowered, so that the thermal shock resistance is improved, and at the same time, the heat generation during curing is suppressed, so that it can be used for large-scale casting. However, monoalkylphenols generally have sublimation properties, and it has been difficult to achieve a desired modification rate during the production of monoalkylphenol-modified resins, and to produce them without variation among lots. Especially when used as an insulating material for high voltage transformers, high voltage current transformers, etc., it is required to have a higher level of characteristics than other applications, especially long-term reliability. It is necessary to have a certain quality of production. However, as described above, it is difficult to stably produce the epoxy resin modified with a monoalkylphenol. On the other hand, a liquid epoxy resin containing bisphenol F (R 2 = hydrogen) as a bisphenol component, such as YDF-170 manufactured by Tohto Kasei Co., Ltd.
(R 1 = hydrogen) is known, but it is inferior in thermal shock resistance when made into a large-sized cast product like YD-128.
「発明が解決しようとする課題」 本発明は上述のように安定生産が困難であつたモノア
ルキルフェノールによるエポキシ樹脂の変性の代わりに
安定生産が出来しかも硬化時、従来品以上の耐熱衝撃性
をはじめ、諸特性に優れた新規な注型用エポキシ樹脂組
成物を提供しようとするものである。[Problems to be Solved by the Invention] The present invention enables stable production instead of modification of an epoxy resin with a monoalkylphenol, which has been difficult to achieve stable production as described above. The present invention aims to provide a novel epoxy resin composition for casting which is excellent in various properties.
「課題を解決するための手段」 本発明は上記課題を解決したもので、下記一般式
（１）で示される液状エポキシ樹脂１モルと、下記一般
式（２）で示されるビスフェノール化合物0.2〜0.6モル
との反応によつて得られたエポキシ樹脂と硬化剤よりな
る注型用エポキシ樹脂組成物である。"Means for Solving the Problems" The present invention has solved the above problems and comprises 1 mol of a liquid epoxy resin represented by the following general formula (1) and 0.2 to 0.6 of a bisphenol compound represented by the following general formula (2). A casting epoxy resin composition comprising an epoxy resin obtained by reaction with a mole and a curing agent.
一般式（１） 一般式（２） 但しｎは０〜３の数を示し、R1、R2は水素原子および
／又はメチル基を示すがR1、R2の全てが同時に水素原子
またはメチル基となる事はない。General formula (1) General formula (2) However, n represents a number of 0 to 3, and R 1 and R 2 represent a hydrogen atom and / or a methyl group, but not all of R 1 and R 2 simultaneously become a hydrogen atom or a methyl group.
即ち一般式（１）および（２）のそれぞれはR1とR2が
水素原子およびメチル基で示される化合物の混合物であ
ってもよいが、全てが同時に水素原子またはメチル基と
なることはない。That is, each of the general formulas (1) and (2) may be a mixture of compounds in which R 1 and R 2 are a hydrogen atom or a methyl group, but not all of them are a hydrogen atom or a methyl group at the same time. .
上記のように本発明組成物に使用する変性エポキシ樹
脂にはビスフェノールＦ（R2＝水素）を構成の必須成分
としているものである。即ち一般式（１）で示されるエ
ポキシ樹脂が通常のビスフェノールＡ型エポキシ樹脂
（R1＝メチル基）の場合は一般式（２）で示されるビス
フェノールの少なくとも一部はビスフェノールＦである
ことが必要であり、一般式（１）で示されるエポキシ樹
脂がビスフェノールＦ型エポキシ樹脂（R1＝水素原子）
の場合は既にビスフェノールＦを構成成分としているの
で、一般式（２）で示されるビスフェノールの少なくと
も一部はビスフェノールＡである必要がある。As described above, the modified epoxy resin used in the composition of the present invention contains bisphenol F (R 2 = hydrogen) as an essential component of its constitution. That is, when the epoxy resin represented by the general formula (1) is a normal bisphenol A type epoxy resin (R 1 = methyl group), at least a part of the bisphenol represented by the general formula (2) needs to be bisphenol F. And the epoxy resin represented by the general formula (1) is a bisphenol F type epoxy resin (R 1 = hydrogen atom)
In this case, since bisphenol F has already been a constituent component, at least a part of the bisphenol represented by the general formula (2) needs to be bisphenol A.
一般式（１）で示されるエポキシ樹脂と一般式（２）
で示されるビスフェノールとの反応はモノ比で1:0.2〜
0.6であり、ビスフェノールが0.2モルより少ないと耐熱
衝撃性が充分改良されず、又0.6モル以上では耐熱衝撃
性の向上は期待出来るものの粘度が高すぎエポキシ樹
脂、硬化剤、充填材の混合、分散が行いがたく好ましく
ない。エポキシ樹脂（１）とビスフェノール（２）との
反応は公知の方法によればよく例えば金属酸化物、無機
塩基、有機塩基及びその塩類やいわゆるオニウム化合物
などを触媒とする方法等がある。The epoxy resin represented by the general formula (1) and the general formula (2)
The reaction with bisphenol shown in is in a mono ratio of 1: 0.2 ~
It is 0.6, and if the amount of bisphenol is less than 0.2 mol, the thermal shock resistance is not sufficiently improved, and if it is 0.6 mol or more, the thermal shock resistance can be expected to be improved, but the viscosity is too high, and the epoxy resin, curing agent, and filler are mixed and dispersed. Is difficult to perform and is not preferable. The reaction between the epoxy resin (1) and the bisphenol (2) may be carried out by a known method, for example, a method using a metal oxide, an inorganic base, an organic base and salts thereof or a so-called onium compound as a catalyst.
本発明組成物の硬化剤としては、酸無水物、ポリアミ
ン系化合物、その他慣用されている硬化剤のいずれでも
よく、その配合量は変性エポキシ樹脂１当量に対して0.
5〜1.2好ましくは0.9〜1.0当量である。又本発明組成物
には石英粉、酸化チタン、アルミナ等の慣用されている
充填材、及び顔料が必要に応じて配合されるものであ
る。The curing agent of the composition of the present invention may be an acid anhydride, a polyamine compound, or any other commonly used curing agent, and the compounding amount thereof is 0 relative to 1 equivalent of the modified epoxy resin.
5 to 1.2, preferably 0.9 to 1.0 equivalent. Further, the composition of the present invention may contain a commonly used filler such as quartz powder, titanium oxide and alumina, and a pigment, if necessary.
「作用」 本発明において特定しているビスフェノールは高融点
であり、エポキシ樹脂との反応温度である100〜200℃に
おいても昇華することなく規定量でエポキシ樹脂を変性
することができ、ロット間のバラツキが殆どなく安定し
た品質の物が得られ、変性エポキシ樹脂の安定生産が可
能である。さらに本発明組成物は耐熱衝撃性において従
来のモノアルキルフェノールによる変性の場合と同等あ
るいはそれ以上である。従つて厳密な規格を要求される
高圧用変圧器、高圧用交流器等の絶縁材料としての大型
注型品の製造が容易になつたのである。"Function" The bisphenol specified in the present invention has a high melting point and can modify the epoxy resin in a specified amount without sublimation even at 100 to 200 ° C, which is the reaction temperature with the epoxy resin, and between lots. A stable quality product with almost no variation can be obtained, and a stable production of a modified epoxy resin is possible. Furthermore, the composition of the present invention has a thermal shock resistance equal to or higher than that in the case of modification with a conventional monoalkylphenol. Therefore, it became easy to manufacture large-scale cast products as insulating materials for high-voltage transformers, high-voltage ACs, etc., which require strict standards.
「実施例及び比較例」 次に実施例及び比較例をあげて本発明を具体的に説明
する。"Examples and Comparative Examples" Next, the present invention will be specifically described with reference to Examples and Comparative Examples.
実施例１ YDF−170（東都化成KK製ビスフェノールＦジグリシジ
ルエーテル、EEW170g/eq）1700gとビスフェノールＡ
（以下BPA）456g（２モル）、反応触媒として水酸化ナ
トリウム1gを水溶液として用い、180℃で５時間反応さ
せEEW387g/eq、軟化点54℃の樹脂Ａを得た。Example 1 1700 g of YDF-170 (bisphenol F diglycidyl ether manufactured by Tohto Kasei KK, EEW 170 g / eq) and bisphenol A
(The following BPA) 456 g (2 mol) and sodium hydroxide 1 g as a reaction catalyst were used as an aqueous solution and reacted at 180 ° C. for 5 hours to obtain a resin A having EEW of 387 g / eq and a softening point of 54 ° C.
実施例２ YD−128 1880g（５モル）とBPF400g、反応触媒として
テトラフェニルホスホニウムクロライド2gをメタノール
溶液として用い、実施例１と同条件でEEW391g/eq、軟化
点57℃の樹脂Ｂを得た。Example 2 Using 1880 g (5 mol) of YD-128 and 400 g of BPF and 2 g of tetraphenylphosphonium chloride as a reaction catalyst in a methanol solution, a resin B having an EEW of 391 g / eq and a softening point of 57 ° C. was obtained under the same conditions as in Example 1.
実施例３ YD−128 940gとYDF−170 850g、BPF400g、反応触媒と
して酸化カルシウム5gを用いて実施例１と同条件でEEW3
93g/eq、軟化点55℃の樹脂Ｃを得た。Example 3 EEW3 under the same conditions as in Example 1 using 940 g of YD-128, 850 g of YDF-170, 400 g of BPF and 5 g of calcium oxide as a reaction catalyst.
Resin C having 93 g / eq and a softening point of 55 ° C. was obtained.
実施例４ YDF−170 1700gとBPA228g、BPF200g、反応触媒として
トリフェニルホスフィン3gを用いて、実施例１と同条件
でEEW391g/eq、軟化点54℃の樹脂Ｄを得た。Example 4 Using 1700 g of YDF-170, 228 g of BPA and 200 g of BPF, and 3 g of triphenylphosphine as a reaction catalyst, EEW391 g / eq and a resin D having a softening point of 54 ° C. were obtained under the same conditions as in Example 1.
以下に実施例で得た樹脂の硬化後の特性を比較例と共
に示し本発明の効果を説明する。The effects of the present invention will be described below by showing the characteristics of the resins obtained in Examples after curing together with Comparative Examples.
硬化物作成条件 硬化剤はYC−195H（東都化成KK製酸無水物系硬化剤中
和価740、融点80℃）を用いて、上記配合比で140℃×18
hrの硬化をおこなつた。 Cured product preparation conditions The curing agent used was YC-195H (Toto Kasei KK acid anhydride curing agent, neutralization number 740, melting point 80 ° C), and the above mixing ratio was 140 ° C x 18
Hardened hr.
クラック抵抗はオリファントワッシャー変法にてｎ＝
10で下表に従い平均の数値で標記した。Crack resistance is n =
The value of 10 is indicated by the average value according to the table below.
以上のクラック抵抗から明らかなように、本発明のエ
ポキシ樹脂であれば、モノアルキルフェノールの様な変
性剤を用いる事無しに現行品（例えばYC−195）と同等
以上の耐熱衝撃性を有する注型用エポキシ樹脂が安定に
製造出来る事が確認出来る。一方製造ロットの異なる変
性樹脂Ａ〜Ｄのそれぞれについて前記と同様に注型品を
作りクラック抵抗を測定した。その結果はいずれも前記
と略同じ数値を示しロット間のバラツキは全くなかつ
た。 As is apparent from the above crack resistance, the epoxy resin of the present invention has a thermal shock resistance equal to or higher than that of the current product (for example, YC-195) without using a modifier such as monoalkylphenol. It can be confirmed that the epoxy resin for use can be manufactured stably. On the other hand, with respect to each of the modified resins A to D of different production lots, a cast product was prepared in the same manner as described above, and the crack resistance was measured. All the results showed the same numerical values as above, and there was no variation between lots.
実施例５〜６及び比較例４ 主剤として樹脂Ａ、Ｂ及びYC−195を用い、硬化剤と
してカヤハードＡ−Ａ（日本化薬KK製、芳香族アミン）
を用い、下記配合比で140℃×18hrの硬化を行つた。そ
の結果を下表に示す。Examples 5 to 6 and Comparative Example 4 Resins A, B and YC-195 were used as the main components, and Kayahard A-A (manufactured by Nippon Kayaku KK, aromatic amine) as the curing agent.
Was used to cure at 140 ° C. for 18 hours at the following compounding ratio. The results are shown in the table below.
実施例７〜８及び比較例５ 主剤として樹脂Ａ、Ｄ及びYC−195を用い、硬化剤と
して軟化点90℃のフェノールノボラック樹脂、硬化促進
剤として２エチル４メチルイミダゾール（四国化成工業
KK製）を用い、下記配合比で140℃×18hrの硬化を行つ
た。その結果を下表に示す。 Examples 7 to 8 and Comparative Example 5 Resins A, D and YC-195 were used as the main components, a phenol novolac resin having a softening point of 90 ° C. was used as the curing agent, and 2 ethyl 4-methyl imidazole (Shikoku Chemicals Co., Ltd. as the curing accelerator.
KK) was used to cure at 140 ° C. for 18 hours at the following compounding ratio. The results are shown in the table below.
「発明の効果」 本発明に使用する変性エポキシ樹脂は一般式（２）で
示されるビスフェノールで変性されているので、製造時
の昇華に起因する製造ロット間のバラツキが殆どないと
いう効果を有し、安定生産ができるという特徴を有する
ものである。又ビスフェノールＦを必須反応成分とした
変性エポキシ樹脂を主剤とする本発明組成物は、従来の
モノアルキルフェノール変性エポキシ樹脂を主剤とする
組成物以上の耐熱衝撃性を有するという優れた効果を示
すものである。 "Effect of the invention" Since the modified epoxy resin used in the present invention is modified with the bisphenol represented by the general formula (2), it has an effect that there is almost no variation between production lots due to sublimation during production. The feature is that stable production is possible. Further, the composition of the present invention containing a modified epoxy resin containing bisphenol F as an essential reaction component as a main component exhibits an excellent effect of having a thermal shock resistance higher than that of a composition containing a conventional monoalkylphenol modified epoxy resin as a main component. is there.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−144323（ＪＰ，Ａ) 特開 昭57−25321（ＪＰ，Ａ) 特開 昭54−74898（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-60-144323 (JP, A) JP-A-57-25321 (JP, A) JP-A-54-74898 (JP, A)
Claims (1)
樹脂１モルと、下記一般式（２）で示されるビスフェノ
ール化合物0.2〜0.6モルとの反応によって得られたエポ
キシ樹脂と硬化剤よりなる注型用エポキシ樹脂組成物。 一般式（１） 一般式（２） 但しｎは０〜３の数を示し、R1、R2は水素原子および／
又はメチル基を示すがR1、R2の全てが同時に水素原子ま
たはメチル基となる事はない。1. An epoxy resin obtained by reacting 1 mol of a liquid epoxy resin represented by the following general formula (1) with 0.2 to 0.6 mol of a bisphenol compound represented by the following general formula (2), and a curing agent. Epoxy resin composition for casting. General formula (1) General formula (2) However, n represents a number of 0 to 3, R 1 and R 2 are hydrogen atoms and /
Alternatively, it represents a methyl group, but not all of R 1 and R 2 simultaneously become a hydrogen atom or a methyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63028443A JP2694188B2 (en) | 1988-02-09 | 1988-02-09 | Epoxy resin composition for casting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63028443A JP2694188B2 (en) | 1988-02-09 | 1988-02-09 | Epoxy resin composition for casting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01203422A JPH01203422A (en) | 1989-08-16 |
| JP2694188B2 true JP2694188B2 (en) | 1997-12-24 |
Family
ID=12248823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63028443A Expired - Lifetime JP2694188B2 (en) | 1988-02-09 | 1988-02-09 | Epoxy resin composition for casting |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2694188B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213846A (en) * | 1989-09-27 | 1993-05-25 | Dai Nippon Toryo Co., Ltd. | Corrison resistant coating composition |
| CN101824137B (en) * | 2010-04-14 | 2011-08-31 | 宜兴市宏博乳化剂有限公司 | Modified bisphenol A epoxy acrylate and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5474898A (en) * | 1977-11-29 | 1979-06-15 | Asahi Glass Co Ltd | Preparation of epoxy resin |
| JPS5725321A (en) * | 1980-07-21 | 1982-02-10 | Hitachi Chem Co Ltd | Production of epoxy resin |
| JPS60144323A (en) * | 1984-01-04 | 1985-07-30 | Asahi Chem Ind Co Ltd | Production of high-mw poly(hydroxy ether) |
-
1988
- 1988-02-09 JP JP63028443A patent/JP2694188B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01203422A (en) | 1989-08-16 |
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