JP6291221B2 - プリプレグ、繊維強化複合材料及び粒子含有樹脂組成物 - Google Patents
プリプレグ、繊維強化複合材料及び粒子含有樹脂組成物 Download PDFInfo
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- JP6291221B2 JP6291221B2 JP2013238888A JP2013238888A JP6291221B2 JP 6291221 B2 JP6291221 B2 JP 6291221B2 JP 2013238888 A JP2013238888 A JP 2013238888A JP 2013238888 A JP2013238888 A JP 2013238888A JP 6291221 B2 JP6291221 B2 JP 6291221B2
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 150000003513 tertiary aromatic amines Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Description
[式(A−1)中、R5は、炭素数1〜12の鎖状アルキル基、炭素数3〜8の環状アルキル基、炭素数6〜14のアリール基、又は炭素数1〜12の鎖状アルキル基若しくはハロゲンで置換されたアリール基を示す。結合手には水素原子が結合されていてもよい。]
[式(C−1)中、R1、R2、R3及びR4は水素原子又は炭化水素基を示し、R1、R2、R3又はR4が炭化水素基である場合、それらは炭素数1〜4の直鎖若しくは分岐のアルキル基である、又は、隣り合うR1及びR2若しくは隣り合うR3及びR4が結合して炭素数6〜10の置換若しくは無置換の芳香環又は炭素数6〜10の置換若しくは無置換の脂環構造を形成しており、xは、0又は1を示す。]
各実施例、比較例について、表1に示す割合で原料を加熱混合し、粒子を含有しない第1の樹脂組成物(表中の「第1」の組成)と、粒子を含有する第2の樹脂組成物(表中の「第2」の組成)を得た。なお、ここで用いた原料は以下に示す通りである。
F−a:ビスフェノールF−アニリン型(F−a型ベンゾオキサジン、四国化成(株)製)
P−a:フェノール−アニリン型(P−a型ベンゾオキサジン、四国化成(株)製)
(B)成分:エポキシ樹脂
2021P:「セロキサイド」(登録商標)2021P(ダイセル化学工業(株)製)
(C)成分:硬化剤
TDP:ビス(4−ヒドロキシフェニル)スルフィド(東京化成(株)製)
BPF:9,9−ビス(4−ヒドロキシフェニル)フルオレン(大阪ガスケミカル製)
(D)成分:ポリアミド樹脂粒子
(D1)成分
PA12(1):ポリアミド12樹脂粒子(ベストジント2158、平均粒子径20μm、ダイセル・エボニック株式会社製)
PA12(2):ポリアミド12樹脂粒子(ベストジント2159、平均粒子径10μm、ダイセル・エボニック株式会社製)
(D2)成分
PA1010:ポリアミド1010樹脂粒子(ベストジント9158、平均粒子径20μm、ダイセル・エボニック株式会社製)
(E)成分:靭性向上剤
YP70:フェノキシ樹脂(YP−70、新日鐵住金化学株式会社製)
得られた第1及び第2の樹脂組成物をそれぞれ離型紙上に70〜100℃で塗布し、18g/m2の第1の樹脂フィルム及び25g/m2の第2の樹脂フィルムを得た。得られた第1の樹脂フィルムを、一方向に引き揃えた炭素繊維の上下から供給して繊維間に含浸し、炭素繊維層を形成した。続いて、第2の樹脂フィルムを炭素繊維層の上下からラミネートして表面層を形成し、プリプレグを作製した。このプリプレグの単位面積当たりの炭素繊維量は150g/m2であり、炭素繊維層及び表面層中の合計の樹脂組成物量(マトリックス樹脂量)は86g/m2であった。
上記(D)成分であるポリアミド12樹脂粒子及びポリアミド1010樹脂粒子を、示差熱量計(DSC)を用いて、25℃から10℃/分の速度で昇温し、得られた吸熱ピークのトップをポリアミド樹脂粒子の融点とした。ポリアミド12樹脂粒子の融点は184℃であり、ポリアミド1010樹脂粒子の融点は205℃であった。
得られた第2の樹脂組成物を、示差熱量計(DSC)を用いて、25℃から10℃/分の速度で昇温し、得られた吸熱ピークのトップを第2の樹脂組成物中でのポリアミド樹脂粒子の融解温度とした。結果を表1に示す。表1中の融解温度欄において、二つの融解温度が記載されている例において、上段は(D1)成分の融解温度、下段は(D2)成分の融解温度を示す。また、一例として、実施例1の第2の樹脂組成物のDSCチャートを図5に示す。
得られた第2の樹脂組成物を、オーブン中、室温から2.0℃/分の昇温速度で185℃まで昇温し、同温度で2時間硬化して樹脂硬化物を得た。得られた硬化物を、示差熱量計(DSC)を用いて、JIS K7121(1987)に基づいて求めた中間点温度をガラス転移温度として測定した。結果を表1に示す。
得られた第2の樹脂組成物を、オーブン中、室温から2.0℃/分の昇温速度で185℃まで昇温し、同温度で2時間硬化させ、厚さ2mmの樹脂硬化物を得た。この樹脂硬化物についてJIS J 7171に従い曲げ弾性率測定を行った。結果を表1に示す。
得られたプリプレグを、[+45°/0°/−45°/90°]4s構成で、擬似等方的に32プライ(層)積層し、オートクレーブにて、圧力0.6MPa、室温から2.0℃/分の昇温速度で185℃まで昇温した後、同温度で2時間加熱硬化し、繊維強化複合材料を得た。この繊維強化複合材料について、ASTM D7136及びD7137に従い、縦150mm×横100mmのサンプルを切り出し、サンプルの中心部に6.7J/mmの落錘衝撃を与え、負荷速度1.0mm/minで衝撃後圧縮強度(CAI)を求めた。結果を表1に示す。
得られたプリプレグを炭素繊維の方向が同じ方向になるように揃えて26プライ積層し、中央層間(13層目と14層目の間)の一部の領域に、炭素繊維の方向と垂直な積層体側面に予亀裂が導入されるように、カプトンフィルム(1mil)(東レ・デュポン社製)をはさんだ。なお、1milは、1/1000インチで、25.3995μmを示す。これをオートクレーブにて、圧力0.6MPa、室温から2.0℃/分の昇温速度で185℃まで昇温した後、同温度で2時間加熱硬化し、繊維強化複合材料を得た。この繊維強化複合材料について、縦(繊維方向)264.0mm×横25.4mmのサンプルを切り出し、端部にヒンジを接着した試験片を得た。この試験片に対して、ASTM D5528に従い、負荷速度1.0mm/minで、ダブルカンチレバービーム試験を実施し、モードI層間破壊靭性値(G1c)を求めた。結果を表1に示す。
得られたプリプレグを炭素繊維の方向が同じ方向になるように揃えて26プライ積層し、中央層間(13層目と14層目の間)の一部の領域に、炭素繊維の方向と垂直な積層体側面に予亀裂が導入されるように、カプトンフィルム(1mil)(東レ・デュポン社製)をはさんだ。なお、1milは、1/1000インチで、25.3995μmを示す。これをオートクレーブにて、圧力0.6MPa、室温から2.0℃/分の昇温速度で185℃まで昇温した後、同温度で2時間加熱硬化し、繊維強化複合材料を得た。この繊維強化複合材料について、縦(繊維方向)264.0mm×横25.4mmのサンプルを切り出し、試験片を得た。この試験片に対して、Composite Materials Handbook 17−1に従い、負荷速度1.0mm/minで端面切欠き曲げ試験を実施し、モードII層間破壊靭性値(G2c)を求めた。結果を表1に示す。結果を表1に示す。
CAIの測定をする際に得られた繊維強化複合材料中の任意の炭素繊維が伸びる方向に直交する面で繊維強化複合材料を切断したときの切断面を顕微鏡観察(500倍)により分析し、500μm×100μmの範囲について画像解析を行うことでポリアミド粒子の分布を観察することにより、炭素繊維層間の1つの樹脂硬化物に含まれるポリアミド樹脂の含有量C1と、1つの炭素繊維層内に含まれるポリアミド樹脂の含有量C2とを算出した。この測定を、異なる炭素繊維層及び樹脂硬化物の組み合わせとなる任意の5箇所について行い、C1及びC2の5箇所の平均値を用いて、1プリプレグ当たりのC1の容量割合{C1/(C1+C2)}×100を求めた。結果を表1に示す。
更に、CAI、G1c及びG2cについて、昇温速度を0.3℃/分に変更した以外は上記と同様の評価を行った。結果を、2.0℃/分での評価結果と合わせて表2に示す。
Claims (5)
- 強化繊維と、前記強化繊維の繊維間に含浸された、(A)ベンゾオキサジン樹脂、(B)エポキシ樹脂、及び、(C)分子中に2個以上のフェノール性水酸基を有する硬化剤を含有する樹脂組成物と、を含む強化繊維層と、
前記強化繊維層の少なくとも一方の表面上に設けられた、(A)ベンゾオキサジン樹脂、(B)エポキシ樹脂、(C)分子中に2個以上のフェノール性水酸基を有する硬化剤、及び、(D)平均粒子径が5〜50μmのポリアミド樹脂粒子を含有する表面層と、
を備え、
前記ポリアミド樹脂粒子は、ポリアミド12樹脂粒子及びポリアミド1010樹脂粒子を含む、プリプレグ。 - 前記表面層は、前記(A)成分と前記(B)成分との合計を100質量部としたときに、前記(A)成分を65〜78質量部、前記(B)成分を22〜35質量部、前記(C)成分を5〜20質量部、及び前記(D)成分を15〜45質量部含有する、請求項1に記載のプリプレグ。
- 請求項1又は2に記載のプリプレグを複数積層し、加圧下で加熱して得られる繊維強化複合材料。
- 前記強化繊維層間の樹脂硬化物に含まれるポリアミド樹脂の含有量C1と、前記強化繊維層内に含まれるポリアミド樹脂の含有量C2との合計量に占めるC1の容量割合{C1/(C1+C2)}×100が、80容量%以上である、請求項3に記載の繊維強化複合材料。
- (A)ベンゾオキサジン樹脂と、
(B)エポキシ樹脂と、
(C)分子中に2個以上のフェノール性水酸基を有する硬化剤と、
(D)平均粒子径が5〜50μmのポリアミド樹脂粒子と、
を含有し、
前記ポリアミド樹脂粒子は、ポリアミド12樹脂粒子及びポリアミド1010樹脂粒子を含む、粒子含有樹脂組成物。
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JP2013238888A JP6291221B2 (ja) | 2013-11-19 | 2013-11-19 | プリプレグ、繊維強化複合材料及び粒子含有樹脂組成物 |
CN201480063143.5A CN105764964B (zh) | 2013-11-19 | 2014-10-28 | 预浸料、纤维强化复合材料及含有颗粒的树脂组合物 |
PCT/JP2014/078592 WO2015076069A1 (ja) | 2013-11-19 | 2014-10-28 | プリプレグ、繊維強化複合材料及び粒子含有樹脂組成物 |
KR1020167016038A KR20160097218A (ko) | 2013-11-19 | 2014-10-28 | 프리프레그, 섬유 강화 복합 재료 및 입자 함유 수지 조성물 |
US15/037,517 US20160289405A1 (en) | 2013-11-19 | 2014-10-28 | Prepreg, fibre-reinforced composite material, and particle-containing resin composition |
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WO2018016138A1 (ja) | 2016-07-19 | 2018-01-25 | ダイセル・エボニック株式会社 | ポリアミド粒子及びその製造方法、樹脂組成物並びに成形品 |
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JP7166995B2 (ja) * | 2019-08-02 | 2022-11-08 | Eneos株式会社 | プリプレグの製造方法及びプリプレグ |
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