JPH07145300A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH07145300A JPH07145300A JP31898093A JP31898093A JPH07145300A JP H07145300 A JPH07145300 A JP H07145300A JP 31898093 A JP31898093 A JP 31898093A JP 31898093 A JP31898093 A JP 31898093A JP H07145300 A JPH07145300 A JP H07145300A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- allyl
- resin composition
- phenol novolac
- resin
- 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.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はエポキシ樹脂組成物に関
する。詳しくは、耐熱性および低吸水性に優れたエポキ
シ樹脂組成物に関する。FIELD OF THE INVENTION The present invention relates to an epoxy resin composition. Specifically, it relates to an epoxy resin composition having excellent heat resistance and low water absorption.
【０００２】[0002]
【従来の技術】従来より、エポキシ樹脂は塗料、積層
板、電気・電子材料等のさまざまな用途に使用されてい
る。また、エポキシ樹脂は一般に硬化剤と組み合わせて
使用されており、特に、電気・電子材料関係の分野にお
いては、耐熱性に優れることから硬化剤としてフェノー
ルノボラック樹脂が好適に用いられている。2. Description of the Related Art Epoxy resins have hitherto been used in various applications such as paints, laminated plates and electric / electronic materials. Further, the epoxy resin is generally used in combination with a curing agent, and particularly in the field of electric / electronic materials, a phenol novolac resin is preferably used as the curing agent because of its excellent heat resistance.
【０００３】しかし、フェノールノボラック樹脂は、エ
ポキシ樹脂と反応して網目構造物となり、その際に反応
に関与しないフェノール性水酸基が未反応のまま残存す
るため、水との親和性が強く、一般的に吸湿性が高いと
いった欠点があった。そのため、フェノールノボラック
樹脂を硬化剤としてなるエポキシ樹脂組成物が封止材等
に用いられた場合には、実装時に気化する水分の蒸気圧
により材料にクラックが生じるといった問題があった。
こうした問題を解決するために低吸水性のアリルフェノ
ール系化合物のノボラック樹脂が提案されているが、軟
化点が低く実用的でなかった。However, the phenol novolac resin reacts with the epoxy resin to form a network structure, and at that time, the phenolic hydroxyl groups that do not participate in the reaction remain unreacted, so that they have a strong affinity with water and are generally used. It had a drawback that it had a high hygroscopicity. Therefore, when an epoxy resin composition using a phenol novolac resin as a curing agent is used as a sealing material or the like, there is a problem that the material is cracked due to the vapor pressure of water vaporized during mounting.
To solve these problems, a novolac resin of an allylphenol compound having low water absorption has been proposed, but it has a low softening point and is not practical.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、硬化剤とし
てフェノールノボラック樹脂を使用してなり、しかも耐
熱性および低吸水性に優れたエポキシ樹脂組成物を提供
することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide an epoxy resin composition which uses a phenol novolac resin as a curing agent and is excellent in heat resistance and low water absorption.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意検討を重ねた結果、エポキシ樹脂組成
物の硬化剤として、エポキシ樹脂との反応性を満足し、
かつ硬化後の残存水酸基により吸水性が問題とならない
程度にフェノール性水酸基の一部をアリルエーテル化し
てなる部分アリルエーテル化フェノールノボラック樹脂
を使用すれば、耐熱性および低吸水性に優れたエポキシ
樹脂組成物が得られることを見出し、本発明を完成する
に至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a curing agent for an epoxy resin composition satisfies the reactivity with an epoxy resin,
Also, if a partially allyl etherified phenol novolac resin is used which is obtained by allyl etherifying a part of the phenolic hydroxyl groups to the extent that water absorption does not become a problem due to residual hydroxyl groups after curing, an epoxy resin with excellent heat resistance and low water absorption The inventors have found that a composition can be obtained, and completed the present invention.
【０００６】すなわち、本発明は、（１）数平均分子量
４５０〜１０００のフェノールノボラック樹脂中の水酸
基の５〜６０％をアリルエーテル化してなり、かつ軟化
点が５０〜１３０℃である部分アリルエーテル化フェノ
ールノボラック樹脂、（２)多官能性エポキシ樹脂およ
び（３）硬化促進剤を含有してなるエポキシ樹脂組成物
に関する。That is, according to the present invention, (1) a partial allyl ether obtained by allyl etherifying 5 to 60% of hydroxyl groups in a phenol novolac resin having a number average molecular weight of 450 to 1,000 and having a softening point of 50 to 130 ° C. The present invention relates to an epoxy resin composition containing a modified phenol novolac resin, (2) a polyfunctional epoxy resin, and (3) a curing accelerator.
【０００７】本発明では、（１）硬化剤として、数平均
分子量４５０〜１０００のフェノールノボラック樹脂中
の水酸基の５〜６０％をアリルエーテル化してなり、軟
化点が５０〜１３０℃である部分アリルエーテル化フェ
ノールノボラック樹脂を使用する。好ましくは水酸基の
アリルエーテル化率が２０〜４０％であり、軟化点は７
０〜１００℃である。In the present invention, (1) as a curing agent, partial allyl having a softening point of 50 to 130 ° C., which is obtained by allyl etherifying 5 to 60% of hydroxyl groups in a phenol novolac resin having a number average molecular weight of 450 to 1,000. Uses etherified phenol novolac resin. The allyl etherification rate of the hydroxyl group is preferably 20 to 40%, and the softening point is 7
It is 0 to 100 ° C.
【０００８】数平均分子量４５０〜１０００のフェノー
ルノボラック樹脂としては、酸性条件下でフェノール類
とホルムアルデヒド類とを付加縮合して得られる公知の
ものを使用できる。たとえば、フェノール類としては、
フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−ク
レゾール、２，３−キシレノール、２，４−キシレノー
ル、２，５−キシレノール、２，６−キシレノール、
３，４−キシレノール、３，５−キシレノール、ｐ−エ
チルフェノール、ｐ−イソプロピルフェノール、ｐ−タ
ーシャリーブチルフェノール、ｐ−オクチルフェノー
ル、ノニルフェノール、ｐ−フェニルフェノール、ｐ−
クロロフェノール、ｐ−ブロモフェノールなどが挙げら
れ、これらは単独でも２種以上混合して用いてもよい。
フェノールノボラック樹脂の数平均分子量が４５０に満
たない場合にはエポキシ樹脂組成物の耐熱性を満足しえ
ず、１０００を越える場合には溶融粘度が高くなり作業
性が悪くなる。また、フェノールノボラック樹脂の軟化
点は９０℃程度以上であるのが好ましい。９０℃に満た
ない場合は部分アリルエーテル化フェノールノボラック
樹脂の軟化点が低くなり、エポキシ樹脂組成物の耐熱性
を満足しえなくなる。As the phenol novolac resin having a number average molecular weight of 450 to 1,000, known resins obtained by addition-condensing phenols and formaldehyde under acidic conditions can be used. For example, as phenols,
Phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol,
3,4-xylenol, 3,5-xylenol, p-ethylphenol, p-isopropylphenol, p-tert-butylphenol, p-octylphenol, nonylphenol, p-phenylphenol, p-
Examples thereof include chlorophenol and p-bromophenol, and these may be used alone or in combination of two or more kinds.
When the number average molecular weight of the phenol novolac resin is less than 450, the heat resistance of the epoxy resin composition cannot be satisfied, and when it exceeds 1000, the melt viscosity becomes high and the workability deteriorates. The softening point of the phenol novolac resin is preferably about 90 ° C or higher. If the temperature is lower than 90 ° C., the softening point of the partially allyl etherified phenol novolac resin becomes low, and the heat resistance of the epoxy resin composition cannot be satisfied.
【０００９】また部分アリルエーテル化フェノールノボ
ラック樹脂中の水酸基のアリルエーテル化率が５％に満
たない場合には、エポキシ樹脂の硬化に関与しない残存
水酸基が多く、エポキシ樹脂組成物を低吸水性にするこ
とはできない。一方、アリルエーテル化率が６０％を越
える場合には、部分アリルエーテル化フェノールノボラ
ック樹脂の軟化点が低くなり、またエポキシ樹脂との反
応点が少なくなるため硬化したエポキシ樹脂の架橋密度
が低くなり、耐熱性を満足しえなくなる。また、部分ア
リルエーテル化フェノールノボラック樹脂の軟化点が５
０℃に満たない場合には、硬化物のガラス転移点が低く
なり耐熱性を満足しえなくなる。If the allyl etherification ratio of the hydroxyl groups in the partially allyl etherified phenol novolac resin is less than 5%, there are many residual hydroxyl groups that are not involved in the curing of the epoxy resin and the epoxy resin composition has low water absorption. You cannot do it. On the other hand, if the allyl etherification rate exceeds 60%, the softening point of the partially allyl etherified phenol novolac resin will be low, and the reaction points with the epoxy resin will be low, so the crosslink density of the cured epoxy resin will be low. , Heat resistance will not be satisfied. In addition, the softening point of the partially allyl etherified phenol novolac resin is 5
If the temperature is lower than 0 ° C, the glass transition point of the cured product will be low and the heat resistance will not be satisfied.
【００１０】かかる部分アリルエーテル化フェノールノ
ボラック樹脂は、前記公知のフェノールノボラック樹脂
の水酸基に対し、前記アリルエーテル化率となるような
ハロゲン化アリルを、水酸化ナトリウム等のアルカリ存
在下に反応させることにより製造できる。なお、ハロゲ
ン化アリルの使用量は、所望のアリルエーテル化率の
１．５倍程度の過剰量とするのが好ましい。反応は、通
常、メチルイソブチルケトン等の溶剤中で、反応温度４
０〜７０℃程度、反応時間２〜５時間の条件で行い、得
られた部分アリルエーテル化フェノールノボラック樹脂
は、溶剤抽出し水洗した後、これを濃縮して使用する。The partially allyl etherified phenol novolac resin is obtained by reacting an allyl halide having the above allyl etherification ratio with the hydroxyl group of the above known phenol novolac resin in the presence of an alkali such as sodium hydroxide. Can be manufactured by The amount of allyl halide used is preferably about 1.5 times the desired allyl etherification rate. The reaction is usually carried out in a solvent such as methyl isobutyl ketone at a reaction temperature of 4
The partially allyl etherified phenol novolac resin thus obtained is subjected to solvent extraction and washing with water, and then concentrated to be used.
【００１１】本発明において前記の部分アリルエーテル
化フェノールノボラック樹脂により硬化する（２）多官
能性エポキシ樹脂は各種公知ものを使用できる。たとえ
ば、オルソ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等のノボラック樹脂型
エポキシ樹脂；ビスフェノールＡ、ビスフェノールＦな
どのジグリシジルエーテル類、フタル酸、ダイマー酸な
どの多塩基酸類およびエピクロロヒドリンを反応させて
得られるグリシジルエステル型エポキシ樹脂；ジアミノ
ジフェニルメタン、イソシアヌル酸などのポリアミン類
とエピクロロヒドリンを反応させて得られるグリシジル
アミン型エポキシ樹脂；オレフィン結合を過酢酸などの
過酸で酸化して得られる線状脂肪族エポキシ樹脂および
脂環式エポキシ樹脂などをあげることができ、これらの
１種を単独でまたは２種以上を適宜に組み合わせて使用
できる。In the present invention, as the polyfunctional epoxy resin (2) which is cured with the partially allyl etherified phenol novolac resin, various known ones can be used. For example, novolac resin type epoxy resins such as orthocresol novolac type epoxy resin and phenol novolac type epoxy resin; diglycidyl ethers such as bisphenol A and bisphenol F; polybasic acids such as phthalic acid and dimer acid; and epichlorohydrin. Glycidyl ester type epoxy resin obtained by reaction; polyamines such as diaminodiphenylmethane and isocyanuric acid, and glycidyl amine type epoxy resin obtained by reacting epichlorohydrin; Olefin bond is oxidized with peracid such as peracetic acid The linear aliphatic epoxy resin and alicyclic epoxy resin obtained can be mentioned, and these 1 type can be used individually or in combination of 2 or more types.
【００１２】また、本発明では、多官能性エポキシ樹脂
と部分アリルエーテル化フェノールノボラック樹脂の硬
化反応を促進するため（３）硬化促進剤を使用する。硬
化促進剤としては、例えば、１，８−ジアザ−ビシクロ
（５，４，０）ウンデセン−７、トリエチレンジアミ
ン、ベンジルジメチルアミン、トリエタノールアミン、
ジメチルアミノエタノール、トリス（ジメチルアミノメ
チル）フェノールなどの三級アミン類；２−メチルイミ
ダゾール、２−フェニルイミダゾール、２−フェニル−
４−メチルイミダゾール、２−ヘプタデシルイミダゾー
ルなどのイミダゾール類；トリブチルホスフィン、メチ
ルジフェニルホスフィン、トリフェニルホスフィン、ジ
フェニルホスフィン、フェニルホスフィンなどの有機ホ
スフィン類；テトラフェニルホスホニウム・テトラフェ
ニルボーレート、２−エチル−４−メチルイミダゾール
・テトラフェニルボーレート、Ｎ−メチルモルホリン・
テトラフェニルボーレートなどのテトラフェニルボロン
塩などをあげることができる。Further, in the present invention, (3) a curing accelerator is used to accelerate the curing reaction of the polyfunctional epoxy resin and the partially allyl etherified phenol novolac resin. Examples of the curing accelerator include 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine,
Tertiary amines such as dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-
Imidazoles such as 4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4 -Methylimidazole tetraphenylborate, N-methylmorpholine
Examples thereof include tetraphenylboron salts such as tetraphenylborate.
【００１３】本発明では、前記（１）部分アリルエーテ
ル化フェノールノボラック樹脂、（２）多官能性エポキ
シ樹脂および（３）硬化促進剤を、以下の使用割合で配
合してエポキシ樹脂組成物を調製する。通常は、（２）
多官能性エポキシ樹脂のエポキシ当量１当量に対し、
（１）部分アリルエーテル化フェノールノボラック樹脂
の水酸基当量が０．５〜１．５当量となるように使用す
る。０．５当量未満の場合には硬化速度が遅くなり、
１．５当量を越える場合にはゲル化反応を起こすことが
あり好ましくない。また（３）硬化促進剤は（２）多官
能性エポキシ樹脂の１００重量部に対し、０．１〜５重
量部の割合で使用する。０．１重量部未満では硬化促進
の効果が殆どなく、５重量部を越える場合には硬化物の
耐熱性、機械特性等の特性を損なう傾向があり好ましく
ない。In the present invention, the above-mentioned (1) partially allyl etherified phenol novolac resin, (2) polyfunctional epoxy resin and (3) curing accelerator are blended in the following use ratios to prepare an epoxy resin composition. To do. Usually (2)
To 1 equivalent of epoxy equivalent of polyfunctional epoxy resin,
(1) Partially allyl etherified phenol novolac resin is used such that the hydroxyl group equivalent is 0.5 to 1.5 equivalent. If it is less than 0.5 equivalent, the curing speed will be slower,
If it exceeds 1.5 equivalents, gelation reaction may occur, which is not preferable. The curing accelerator (3) is used in a proportion of 0.1 to 5 parts by weight based on 100 parts by weight of the polyfunctional epoxy resin (2). If the amount is less than 0.1 parts by weight, the effect of promoting curing is scarce, and if the amount exceeds 5 parts by weight, the cured product tends to impair properties such as heat resistance and mechanical properties, which is not preferable.
【００１４】その他、エポキシ樹脂組成物には、必要に
応じて、溶剤、充填剤、離型剤、表面処理剤、難燃剤等
を配合してもよい。なお、エポキシ樹脂組成物は、通
常、ロール、ニーダー等を用いて加熱混合される。In addition, a solvent, a filler, a release agent, a surface treatment agent, a flame retardant and the like may be added to the epoxy resin composition, if necessary. The epoxy resin composition is usually heated and mixed using a roll, a kneader or the like.
【００１５】[0015]
【発明の効果】本発明によれば、フェノールノボラック
樹脂の有する耐熱性を維持し、かつ低吸水性に優れたエ
ポキシ樹脂組成物を提供できる。EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an epoxy resin composition which maintains the heat resistance of a phenol novolac resin and is excellent in low water absorption.
【００１６】[0016]
【実施例】以下に実施例及び比較例をあげて本発明をさ
らに詳細に説明するが、本発明はこれら実施例に限定さ
れるものではない。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
【００１７】製造例１ 撹拌機、温度計及び冷却器を備えた１０００ｍｌ容フラ
スコ内を窒素ガスで置換した後、フリーフェノールを除
去した軟化点１１５℃、数平均分子量６５０のフェノー
ルノボラック樹脂（水酸基当量１０６）１０６ｇおよび
メチルイソブチルケトン２００ｇを加えて溶解した。次
いで臭化アリル６０．５ｇを添加し、続いて２４％水酸
化ナトリウム水溶液８３．４ｇを１時間かけて滴下した
後、６０℃で３時間保温した。その後、４００ｇの水で
５回水洗し、有機溶媒層を濃縮して１２７ｇの樹脂を得
た。これを化合物Ａという。化合物Ａの軟化点は７９．
５℃、アリルエーテル化率は３１％、水酸基当量は１７
１であった。Production Example 1 A phenol novolac resin having a softening point of 115 ° C. and a number average molecular weight of 650 after removing free phenol after replacing the inside of a 1000 ml flask equipped with a stirrer, a thermometer and a condenser (hydroxyl equivalent) 106) 106 g and 200 g of methyl isobutyl ketone were added and dissolved. Next, 60.5 g of allyl bromide was added, and subsequently 83.4 g of a 24% aqueous sodium hydroxide solution was added dropwise over 1 hour, and then the mixture was kept at 60 ° C. for 3 hours. Then, it was washed 5 times with 400 g of water and the organic solvent layer was concentrated to obtain 127 g of resin. This is called compound A. The softening point of compound A is 79.
5 ° C, allyl etherification rate is 31%, hydroxyl equivalent is 17
It was 1.
【００１８】製造例２ 実施例１において、軟化点１１５℃、数平均分子量６５
０のフェノールノボラック樹脂１０６ｇを、軟化点１１
０℃、数平均分子量７００のオルソクレゾールノボラッ
ク樹脂（水酸基当量１２０）１２０ｇに代えた他は、実
施例１と同様に反応を行い１４７ｇの樹脂を得た。これ
を化合物Ｂという。化合物Ｂの軟化点は７６℃、アリル
エーテル化率は３０％、水酸基当量は１８９であった。Production Example 2 In Example 1, the softening point was 115 ° C. and the number average molecular weight was 65.
106g of phenol novolac resin of 0, softening point 11
147 g of a resin was obtained by performing the same reaction as in Example 1 except that 120 g of an orthocresol novolac resin (hydroxyl group equivalent 120) having a number average molecular weight of 700 at 0 ° C. was used. This is called compound B. Compound B had a softening point of 76 ° C., an allyl etherification rate of 30% and a hydroxyl group equivalent of 189.
【００１９】製造例３ 実施例１において、臭化アリルの使用量を４８．４ｇに
代えた他は、実施例１と同様に反応を行い１２５ｇの樹
脂を得た。これを化合物Ｃという。化合物Ｃの軟化点は
８７℃、アリルエーテル化率は２３．０％、水酸基当量
は１５０であった。Production Example 3 125 g of a resin was obtained in the same manner as in Example 1 except that the amount of allyl bromide used was changed to 48.4 g. This is called compound C. Compound C had a softening point of 87 ° C., an allyl etherification rate of 23.0%, and a hydroxyl group equivalent of 150.
【００２０】製造例４ 軟化点８３℃、数平均分子量４２０、水酸基当量１０６
のフェノールノボラック樹脂を用いた。これを化合物Ｄ
という。Production Example 4 Softening point 83 ° C., number average molecular weight 420, hydroxyl group equivalent 106
Of phenol novolac resin was used. This is compound D
Say.
【００２１】実施例１〜３および比較例１ エポキシ樹脂（ＥＳＣＭ１９５ＸＬ、住友化学工業
（株）製、エポキシ当量１９８）１９６ｇに、上記製造
例１〜４で得られた化合物Ａ〜Ｄおよび硬化促進剤ＤＢ
Ｕ（１，８−ジアザ−ビシクロ（５，４，０）ウンデセ
ン−７）をそれぞれ表１に示す割合で配合し、１７５℃
で１０時間硬化させ厚さ２ｍｍの板状の試験片を得た。
得られた硬化物のガラス転移温度、吸水率を測定した結
果を表１に示す。Examples 1 to 3 and Comparative Example 1 196 g of an epoxy resin (ESCM195XL, manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 198) was added to 196 g of the compounds A to D obtained in the above Production Examples 1 to 4 and a curing accelerator. DB
U (1,8-diaza-bicyclo (5,4,0) undecene-7) was blended in the proportions shown in Table 1, respectively, and added at 175 ° C.
After curing for 10 hours, a plate-shaped test piece having a thickness of 2 mm was obtained.
The results of measuring the glass transition temperature and water absorption of the obtained cured product are shown in Table 1.
【００２２】なお、ガラス転移温度（Ｔｇ）はセイコー
電子工業( 株) ＴＭＡ１２０を用いて測定した。また、
吸水率は厚さ２ｍｍ×直径５０ｍｍの円盤状試験片を恒
温恒湿器（タバイ製、ＨＵＭＩＤＩＴＹ ＣＡＢＩＮＥ
Ｔ、ＬＨＬ−１１１）を用いて、８５℃、８５％湿度の
条件で９６時間放置した後における重量の増加率であ
る。The glass transition temperature (Tg) was measured using TMA120 manufactured by Seiko Instruments Inc. Also,
The water absorption rate is 2 mm in thickness and 50 mm in diameter, and a disk-shaped test piece is made into a thermo-hygrostat (manufactured by Tabai, HUMIDITY CABINE
T, LHL-111) and the rate of increase in weight after being left for 96 hours under the conditions of 85 ° C. and 85% humidity.
【００２３】[0023]
【表１】 [Table 1]
【００２４】表１の結果から、本発明のエポキシ樹脂組
成物の硬化物は、殆ど同じガラス転移温度（耐熱性）を
有する、従来のエポキシ樹脂組成物の硬化物に比べて、
吸水性が低いことが認められる。From the results shown in Table 1, the cured product of the epoxy resin composition of the present invention has almost the same glass transition temperature (heat resistance) as compared with the cured product of the conventional epoxy resin composition.
It is recognized that the water absorption is low.
Claims (1)
フェノールノボラック樹脂中の水酸基の５〜６０％をア
リルエーテル化してなり、かつ軟化点が５０〜１３０℃
である部分アリルエーテル化フェノールノボラック樹
脂、（２) 多官能性エポキシ樹脂および（３）硬化促進
剤を含有してなるエポキシ樹脂組成物。(1) Allyl etherification of 5 to 60% of hydroxyl groups in a phenol novolac resin having a number average molecular weight of 450 to 1000 and a softening point of 50 to 130 ° C.
An epoxy resin composition comprising the partially allyl etherified phenol novolac resin which is, (2) a polyfunctional epoxy resin, and (3) a curing accelerator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31898093A JPH07145300A (en) | 1993-11-24 | 1993-11-24 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31898093A JPH07145300A (en) | 1993-11-24 | 1993-11-24 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07145300A true JPH07145300A (en) | 1995-06-06 |
Family
ID=18105149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31898093A Pending JPH07145300A (en) | 1993-11-24 | 1993-11-24 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07145300A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000319360A (en) * | 1999-05-06 | 2000-11-21 | Toshiba Chem Corp | Resin composition for sealing and semiconductor sealing apparatus |
| EP2404946A1 (en) | 2010-07-08 | 2012-01-11 | Nitto Denko Corporation | Method for manufacturing cured product of thermosetting resin composition and cured product obtained thereby |
-
1993
- 1993-11-24 JP JP31898093A patent/JPH07145300A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000319360A (en) * | 1999-05-06 | 2000-11-21 | Toshiba Chem Corp | Resin composition for sealing and semiconductor sealing apparatus |
| EP2404946A1 (en) | 2010-07-08 | 2012-01-11 | Nitto Denko Corporation | Method for manufacturing cured product of thermosetting resin composition and cured product obtained thereby |
| US20120010373A1 (en) * | 2010-07-08 | 2012-01-12 | Nitto Denko Corporation | Method for manufacturing cured product of thermosetting resin composition and cured product obtained thereby |
| JP2012017423A (en) * | 2010-07-08 | 2012-01-26 | Nitto Denko Corp | Method for producing cured product of thermosetting resin composition and cured product obtained by the same |
| CN102372835A (en) * | 2010-07-08 | 2012-03-14 | 日东电工株式会社 | Method for manufacturing cured product of thermosetting resin composition and cured product obtained thereby |
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