JP4609692B2 - エポキシ樹脂、エポキシ樹脂の製造方法、エポキシ樹脂組成物およびその硬化物 - Google Patents
エポキシ樹脂、エポキシ樹脂の製造方法、エポキシ樹脂組成物およびその硬化物 Download PDFInfo
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- JP4609692B2 JP4609692B2 JP2003321195A JP2003321195A JP4609692B2 JP 4609692 B2 JP4609692 B2 JP 4609692B2 JP 2003321195 A JP2003321195 A JP 2003321195A JP 2003321195 A JP2003321195 A JP 2003321195A JP 4609692 B2 JP4609692 B2 JP 4609692B2
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- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
(1)前記エポキシ樹脂組成物から得られるプリプレグは、フェノールノボラック樹脂とエピハロヒドリンとから誘導されるフェノールノボラック型エポキシ樹脂とオルソクレゾールノボラック樹脂とエピハロヒドリンとから誘導されるオルソクレゾールノボラック型エポキシ樹脂とをそれぞれ単独に用いた樹脂組成物から得られるプリプレグと比べ、ドレープ性やタック性に優れる。
[3]軟化点:JIS K−7234に準じた方法で測定した。
[4]エポキシ樹脂組成物の調整:エポキシ樹脂、硬化剤、硬化促進剤、および熱可塑性樹脂を、ニーダーを用いて混練し、エポキシ樹脂組成物を調製した。
[9]樹脂硬化物の引張伸度:[8]と同様にして作製した樹脂硬化板より、JIS K7113に従い、小型1(1/2)号形試験片を切り出し、引張伸度を求めた。
加熱装置と攪拌装置とコンデンサと温度計および下部に分液コックが装着された反応装置に、表1〜3に示す量のノボラック樹脂とエピクロルヒドリンおよびエピクロルヒドリン100重量部に対し30重量部のイソプロピルアルコールを添加した。尚、エピクロルヒドリン添加量は全てフェノール性水酸基1モルに対して4.0モルである。次いで表1〜3に示す量の35重量%水酸化カリウム水溶液を2段階に分けて添加した。まず40℃で全量の10重量%を添加して、40℃を保ちながら4時間攪拌した。次いで50℃に昇温して残りの90重量%を50℃を保持しながら3時間要して滴下した。さらに50℃で30分間攪拌した後に、生成塩が飽和濃度になるような量の水を添加して塩を溶解して、攪拌を止めて水層を棄却した。未反応のエピクロルヒドリンを1時間かけて150℃まで加熱し蒸留回収した。次いで150℃を保持したまま気相の圧力が最終的に1.3kPaとなるまで減圧を行いながら、未反応のエピクロルヒドリンを蒸留回収し、粗樹脂を得た。得られた粗樹脂に対し、重量基準1.5倍量のメチルイソブチルケトンを添加して溶解した後、n−ブタノール50重量部と10%水酸化ナトリウム水溶液12重量部を加えて、80℃で2時間攪拌して分液した。それに第一燐酸ソーダで中和した後に、共沸によって脱水し、精密濾過を経た後にメチルイソブチルケトンを蒸溜によって溜去して表1〜3記載のエポキシ当量のエポキシ樹脂を得た。
加熱装置と攪拌装置とコンデンサと温度計および下部に分液コックが装着された反応装置に、表4に示す量のノボラック樹脂とエピクロルヒドリンおよびエピクロルヒドリン100重量部に対し30重量部のイソプロピルアルコールを添加した。尚、エピクロルヒドリン添加量は全てフェノール性水酸基1モルに対して4.0モルである。次いで表4に示す量の35重量%水酸化カリウム水溶液を2段階に分けて添加した。まず40℃で全量の10重量%を添加して、40℃を保ちながら4時間攪拌した。次いで50℃に昇温して残りの90重量%を50℃を保持しながら3時間要して滴下した。さらに50℃で30分間攪拌した後に、生成塩が飽和濃度になるような量の水を添加して塩を溶解して、攪拌を止めて水層を棄却した。未反応のエピクロルヒドリンを1時間かけて150℃まで加熱し蒸留回収した。次いで150℃を保持したまま気相の圧力が最終的に1.3kPaとなるまで減圧を行いながら、未反応のエピクロルヒドリンを蒸留回収し、粗樹脂を得た。得られた粗樹脂に対し、重量基準1.5倍量のメチルイソブチルケトンを添加して溶解した後、n−ブタノール50重量部と10%水酸化ナトリウム水溶液12重量部を加えて、80℃で2時間攪拌して分液した。それに第一燐酸ソーダで中和した後に、共沸によって脱水し、精密濾過を経た後にメチルイソブチルケトンを蒸溜によって溜去して表4記載のエポキシ当量のエポキシ樹脂を得た。
前記した方法に従い,プリプレグの特性および樹脂硬化物特性を評価した結果を表5に示した。
EPICLON 850:大日本インキ化学工業(株)製BPA型液状エポキシ樹脂
EPICLON 1055:大日本インキ化学工業(株)製BPA型固形エポキシ樹脂
3−(3,4−ジクロロフェニル)−1,1−ジメチル尿素:保土ヶ谷化学工業(株)製DCMU99(型番))
ポリビニルホルマール:(重量平均分子量5.3〜6.2万;ガラス転移温度105℃)
Claims (6)
- フェノールノボラック樹脂(A)とオルソクレゾールノボラック樹脂(B)とを混合比(重量比)[(A)/(B)]が80/20〜20/80となる割合で含有する混合物とエピハロヒドリンとを反応させて得られるエポキシ樹脂と硬化剤とを含有することを特徴とするエポキシ樹脂組成物。
- 前記エポキシ樹脂が、エピハロヒドリンをフェノールノボラック樹脂(A)とオルソクレゾールノボラック樹脂(B)の混合物中のフェノール性水酸基1モルに対して3.0〜10.0モル使用して得られるものである請求項1記載のエポキシ樹脂組成物。
- 前記エポキシ樹脂のエポキシ当量が180〜210g/eqである請求項1記載のエポキシ樹脂組成物。
- 請求項1〜3の何れか1つに記載のエポキシ樹脂組成物を強化繊維に含浸されてなるプリプレグ。
- 請求項1〜3の何れか1つに記載のエポキシ樹脂組成物を硬化してなる硬化物。
- 請求項4のプリプレグを硬化してなる硬化物。
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