JPWO2017038880A1 - エポキシ樹脂組成物、プリプレグおよび炭素繊維強化複合材料 - Google Patents
エポキシ樹脂組成物、プリプレグおよび炭素繊維強化複合材料 Download PDFInfo
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- JPWO2017038880A1 JPWO2017038880A1 JP2016555794A JP2016555794A JPWO2017038880A1 JP WO2017038880 A1 JPWO2017038880 A1 JP WO2017038880A1 JP 2016555794 A JP2016555794 A JP 2016555794A JP 2016555794 A JP2016555794 A JP 2016555794A JP WO2017038880 A1 JPWO2017038880 A1 JP WO2017038880A1
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- epoxy resin
- resin composition
- carbon fiber
- mass
- general formula
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
[A]:特定構造の繰り返しユニット内に1つ以上の縮合多環芳香族炭化水素骨格と主として2つのエポキシ基を有するエポキシ樹脂
[B]:分子内に3個以上のグリシジル基を有するグリシジルアミン型エポキシ樹脂
[C]:スルホン系またはイミド系の熱可塑性樹脂
[D]:エポキシ樹脂硬化剤
Description
[A]:一般式[1]または[4]で示される繰り返しユニット内に1つ以上の縮合多環芳香族炭化水素骨格と主として2つのエポキシ基を有するエポキシ樹脂
[B]:分子内に3個以上のグリシジル基を有するグリシジルアミン型エポキシ樹脂
[C]:スルホン系またはイミド系の熱可塑性樹脂
[D]:エポキシ樹脂硬化剤
また、本発明のプリプレグは、前記エポキシ樹脂組成物を強化繊維に含浸させてなるプリプレグであり、強化繊維は織物の形態である基材でもよい。さらに、本発明の繊維強化複合材料は、前記プリプレグを硬化させてなる繊維強化複合材料である。
・3フッ化ホウ素モノエチルアミン(例えば、ステラケミファ株式会社製):3質量部
・アセトン(例えば、和光純薬工業株式会社製):4質量部。
一般式[1]または[4]におけるXがメチレン基、Yがナフタレン骨格、Zがナフタレン骨格であるエポキシ樹脂。
・“エピクロン(登録商標)”HP−4770(ビスナフタレン型エポキシ、DIC(株)製、エポキシ当量:205)。なお“エピクロン”HP−4770は特開2011−213784公報記載によると、ビスナフタレン型エポキシ樹脂の3官能、4官能体も含まれている。
一般式[1]または[4]におけるXがメチレン基、Yがトルエン骨格、Zがナフタレン骨格であるエポキシ樹脂。
・NC−7300L(ナフトール型エポキシ、ナガセケムテックス(株)製、エポキシ当量:220)。
・“ARALDITE(登録商標)”MY721(テトラグリシジルジアミノジフェニルメタン、ハンツマンアドバンスドマテリアル社製、エポキシ当量:112)
・TGDDS(テトラグリシジルジアミノジフェニルスルホン、小西化学(株)製、エポキシ当量:112)
・“ARALDITE(登録商標)”(登録商標)MY0510(トリグリシジル−p−アミノフェノール、ハンツマンアドバンスドマテリアル社製、エポキシ当量:100)
・“ARALDITE(登録商標)”登録商標)MY0600(トリグリシジル−m−アミノフェノール、ハンツマンアドバンスドマテリアル社製、エポキシ当量:105)。
・“スミカエクセル(登録商標)”PES5003P(水酸基末端ポリエーテルスルホン、住友化学(株)製、Tg=225℃)
・“Virantage(登録商標)”VW−10700RP(水酸基末端ポリエーテルスルホン、Solvay Advanced Polymers(株)製、Tg=220℃)
・“スミカエクセル(登録商標)”PES7600P(塩素末端ポリエーテルスルホン、住友化学(株)製、Tg=225℃)
・“Virantage(登録商標)”VW−30500RP(ポリスルホン、Solvay Advanced Polymers(株)製、Tg=205℃)
・“ULTEM(登録商標)”1010(ポリエーテルイミド、Sabic Innovative Plastics(株)製、Tg=215℃)。
・3,3’−DAS(3,3’−ジアミノジフェニルスルホン、三井化学ファイン(株)製、活性水素当量:62、23℃で固形)
・セイカキュアS(4,4’−ジアミノジフェニルスルホン、和歌山精化工業(株)製、活性水素当量:62、23℃で固形)
・“Lonzacure(登録商標)”MIPA(4,4’−メチレンビス(2−メチル−6−イソプロピル)ベンゼンアミン、Lonza(株)製、活性水素当量:78、23℃で固体)。
・イソフタル酸ジヒドラジド、大塚化学(株)製。
・“jER(登録商標)”807(ビスフェノールF型エポキシ、三菱化学(株)製、エポキシ当量:170)
・“jER(登録商標)”825(ビスフェノールA型エポキシ、三菱化学(株)製、エポキシ当量:175)。
“グリルアミド(登録商標)”TR55(エムスケミ社製)を衝撃式粉砕機により粉砕分級することにより数平均粒径20μmの粒径の微粒子とした。
ニーダー中に、構成要素[A]のエポキシ樹脂、構成要素[B]のエポキシ樹脂、構成要素[C]の熱可塑樹脂、構成要素[E]のエポキシ樹脂を加熱しつつ混練し、構成要素[C]を溶解させ透明な粘稠液を得た。この液に、構成要素[D]の硬化剤を添加混練し、エポキシ樹脂組成物を得た。各実施例、比較例の成分配合比は表1〜5に示すとおりであった。
エポキシ樹脂組成物の粘度は、動的粘弾性装置ARES−G2(ティー・エイ・インスツルメント社製)を用いて測定した。上下部測定冶具に直径40mmの平板のパラレルプレートを用い、上部と下部の冶具間距離が1mmとなるように該エポキシ樹脂組成物をセット後、角周波数:3.14rad/sで測定した。40℃から120℃まで速度1.5℃/分で昇温し、80℃の粘度η80を読み取った。
直径25mmの平板のパラレルプレートを用いた以外は同様にして、40℃から120℃まで速度1.5℃/分で昇温し、120℃で1時間ホールドした後の120℃1時間ホールド後の粘度(η120h)を求めた。
未硬化の樹脂組成物を真空中で脱泡した後、2mm厚の“テフロン(登録商標)”製のスペーサーを用い、厚み2mmになるよう設定したモールド中で、180℃の温度で2時間硬化させた。得られた厚み2mmの樹脂硬化物を幅10±0.1mm、長さ60±1mmでカットし、試験片を得た。インストロン万能試験機(インストロン社製)を用いJIS−K7171(1994)に従い、スパン間32mmの3点曲げを実施し、弾性率を測定した。測定数はN=6とし、その平均値を求めた。
(3)に示す寸法に作成した試験片を98℃の恒温槽に20時間浸漬後、(3)に示すインストロン万能試験機(インストロン社製)に設置した恒温槽を121℃に設定し、3分間槽内の環境に保持した後、(3)と同様の測定条件で弾性率を測定した。
上記(3)で得られた樹脂硬化物のガラス転移温度について、示差走査熱量計(DSC)を用いて、JIS−K7121(1987)に基づいてもとめ、中間点温度をTgとした。
上記(1)で調製したエポキシ樹脂組成物を離型紙上にコーティングし、所定の樹脂目付の樹脂フィルムを作製した。この樹脂フィルムをプリプレグ作製機にセットし、強化繊維織物の両面から重ね、加熱加圧して熱硬化性樹脂組成物を含浸させ、繊維目付193g/m2、樹脂含有率が38質量%の織物プリプレグを作製した。なお、強化繊維織物は“トレカ(登録商標)”T400H−3K(繊維数3000本、引張強度4410MPa、引張弾性率250MPa、引張伸度1.8%)からなる平織織物を用いた。
織物プリプレグの経糸方向を揃え9枚積層してオートクレーブ中で温度180℃、圧力6.10kgf/cm2Paで2時間加熱加圧して硬化し、複合材料を作製した。得た複合材料から、幅25±0.5mm、長さ250±1.0mm、タブ間スパン130±1.0mmの試験片を作製し、EN2597Bに従い、経糸引張強度を測定した。
織物プリプレグの経糸方向を揃え9枚積層して、上記(7)の成形条件で成形した複合材料から、幅12.5±0.2mm、長さ75〜80mm、タブ間スパン5.25±0.25mmの試験片を作製し、EN2850Bに従い、経糸圧縮強度を測定した。
織物プリプレグ24枚を経糸方向を0°として[45°/0°/−45°/90°]3s(記号sは、鏡面対称を示す)で疑似等方的に積層し、上記(7)の成形条件で成形した複合材料から、幅100±0.2mm、長さ150±0.2mmの試験片を作製した。この中央に落下高さ468mmで5.4kgの落錘衝撃を与えた後SACMA SRM 2R−94が示す圧縮治具用治具を用い、クロスヘッドスピード0.5mm/minで圧縮し、圧縮強度を求めた。測定数はN=6とし、その平均値を求めた。
表1〜2に示すとおり、実施例1〜12では構成要素[A]、[B]、[C]、[D]を配合し、得られた樹脂硬化物および繊維強化複合材料の試験を行い、各物性とも優れた弾性率、Tg、経糸引張強度および経糸圧縮強度が得られた。
表2に示すとおり、構成要素[B]を2成分とした以外は実施例1〜12と同様にして得られた樹脂硬化物および繊維強化複合材料の試験を行い、優れた物性が得られた。
表2に示すとおり、構成要素[A]、[B]、[C]、[D]に、さらに構成要素[E]を加えた以外は実施例1〜12と同様にして得られた樹脂硬化物および繊維強化複合材料の試験を行い、優れた物性が得られた。
表3に示すとおり、比較例1のように構成要素[A]を含まない場合、樹脂硬化物の弾性率および経糸圧縮強度が低下した。比較例2のように構成要素[B]を含まない場合、樹脂硬化物の弾性率および経糸圧縮強度が低下した。比較例3のように構成要素[B]を含む量が少ないとき、樹脂硬化物の弾性率および経糸圧縮強度が低下した。比較例4のように構成要素[C]を含まない場合、樹脂硬化物の弾性率、吸湿高温下での樹脂硬化物の弾性率、経糸引張強度、経糸圧縮強度ともに低下した。比較例5のように構成要素[A]と構成要素[C]を両方とも含まない場合、樹脂硬化物の弾性率が低く経糸圧縮強度も低下した。比較例6のように構成要素[A]が過多である場合、樹脂硬化物の弾性率、吸湿高温下での樹脂硬化物の弾性率、経糸圧縮強度ともに低下した。比較例7のように、構成要素[E]が過多であるとき、樹脂降下物の弾性率、吸湿高温下での樹脂硬化物の弾性率、経糸圧縮強度が低下した。
表4に示すとおり、エポキシ樹脂組成物の調製時に熱可塑性樹脂粒子を入れた以外は、実施例1と同様に織物プリプレグを作製し、繊維強化複合材料の層間樹脂層を形成し、繊維強化複合材料の耐衝撃性を実施例1の場合と比較した。熱可塑性樹脂粒子を付与した実施例20では、実施例1に比べ耐衝撃性が向上していることが確認できた。
表5に示すとおり、エポキシ樹脂組成物の調製時に有機酸ヒドラジド化合物として実施例21ではイソフタル酸ジヒドラジドを入れた以外は、実施例18と同様に構成要素[A][B][C][D]を配合し、エポキシ樹脂組成物の粘度測定、得られた樹脂硬化物および繊維強化複合材料の試験を行った。120℃1時間ホールド後の粘度(η120h)は実施例18に対し、有機酸ヒドラジド化合物を入れた実施例21では25Pa・s、まで上昇し、ハニカム成形性が良好な粘度範囲となった。有機酸ヒドラジド化合物を入れることで、吸湿高温下での樹脂硬化物弾性率はわずかに低下したが、合格範囲内であった。
Claims (18)
- 少なくとも次の構成要素[A]〜[D]を含むエポキシ樹脂組成物であって、エポキシ樹脂総量100質量部に対して、構成要素[A]を5〜40質量部と構成要素[B]を20〜95質量部含み、さらに構成要素[C]を1〜25質量部含むエポキシ樹脂組成物。
[A]:一般式[1]または[4]で示される繰り返しユニット内に1つ以上の縮合多環芳香族炭化水素骨格と主として2つのエポキシ基を有するエポキシ樹脂
[B]:分子内に3個以上のグリシジル基を有するグリシジルアミン型エポキシ樹脂
[C]:スルホン系またはイミド系の熱可塑性樹脂
[D]:エポキシ樹脂硬化剤 - 構成要素[D]に、有機酸ヒドラジド化合物を0.01〜10質量%含む請求項1に記載のエポキシ樹脂組成物。
- 構成要素[A]の一般式[1]において、Xの炭素数が1であり、YとZがともにナフタレン骨格である、請求項1または2に記載のエポキシ樹脂組成物。
- 構成要素[A]の一般式[1]において、Xの炭素数が1であり、Yがトルエン骨格、Zがナフタレン骨格である、請求項1または2に記載のエポキシ樹脂組成物。
- 構成要素[C]のガラス転移温度が180℃以上である請求項1〜4のいずれかに記載のエポキシ樹脂組成物。
- 構成要素[D]が、23℃で固形である請求項1〜5のいずれかに記載のエポキシ樹脂組成物。
- 構成要素[D]が、芳香族アミンである請求項1〜6のいずれかに記載のエポキシ樹脂組成物。
- 構成要素[D]が、分子内に1〜4個のフェニル基を有し、そのうち少なくとも1個のフェニル基がオルト位またはメタ位にアミノ基を有する芳香族ポリアミンである請求項1〜7のいずれかに記載のエポキシ樹脂組成物。
- さらに構成要素[E]:2官能エポキシ樹脂を含む請求項1〜8のいずれかに記載のエポキシ樹脂組成物。
- 構成要素[E]がビスフェノールA型エポキシ樹脂またはビスフェノールF型エポキシ樹脂である請求項9に記載のエポキシ樹脂組成物。
- エポキシ樹脂総量100質量部中に、構成要素[E]を5質量部以上40質量部以下含む請求項9または10に記載のエポキシ樹脂組成物。
- 120℃1時間ホールド後の粘度η120hが10〜50Pa・sである請求項1〜11のいずれかに記載のエポキシ樹脂組成物。
- 請求項1〜12のいずれかに記載のエポキシ樹脂組成物を炭素繊維に含浸させてなるプリプレグ。
- 炭素繊維表面上または樹脂中に数平均粒径が5〜50μmの熱可塑性粒子を配置した請求項13に記載のプリプレグ。
- 炭素繊維が織物の形態である請求項13または14に記載のプリプレグ。
- 請求項1〜12のいずれかに記載のエポキシ樹脂組成物および炭素繊維を含む炭素繊維強化複合材料。
- 炭素繊維が織物の形態である請求項16に記載の炭素繊維強化複合材料。
- 請求項13〜15のいずれかに記載のプリプレグを硬化させてなる炭素繊維強化複合材料。
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EP3563927A1 (en) * | 2018-04-30 | 2019-11-06 | Hexion Research Belgium SA | Purification of high performance epoxy resins via membrane filtration technology |
EP3797991A4 (en) * | 2018-06-26 | 2022-03-16 | Toray Industries, Inc. | PREPREG AND METHOD OF MANUFACTURE THEREOF, SLIT-TAPE-PREPREG, CARBON FIBER REINFORCED COMPOSITE |
WO2020058766A1 (en) * | 2018-09-21 | 2020-03-26 | Toray Industries, Inc. | Epoxy resin composition, prepreg, and fiber reinforced composite material |
KR20210062034A (ko) | 2018-09-21 | 2021-05-28 | 도레이 카부시키가이샤 | 에폭시 수지 조성물, 프리프레그 및 섬유 강화 복합재료 |
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