JP6708312B2 - 繊維強化成形材料及びそれを用いた成形品 - Google Patents
繊維強化成形材料及びそれを用いた成形品 Download PDFInfo
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- JP6708312B2 JP6708312B2 JP2019553791A JP2019553791A JP6708312B2 JP 6708312 B2 JP6708312 B2 JP 6708312B2 JP 2019553791 A JP2019553791 A JP 2019553791A JP 2019553791 A JP2019553791 A JP 2019553791A JP 6708312 B2 JP6708312 B2 JP 6708312B2
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- fiber
- molding material
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- reinforced molding
- unsaturated monomer
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
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- 125000003118 aryl group Chemical group 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- -1 aromatic isocyanate Chemical class 0.000 description 39
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
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- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
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- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 2
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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Description
炭素繊維への樹脂含浸性がより向上することから、200〜8000mPa・s(25℃)の範囲が好ましい。
温度計、窒素導入管、撹拌機を設けた2Lフラスコに、エポキシ樹脂(DIC株式会社製「エピクロン850」、ビスフェノールA型エポキシ樹脂、エポキシ当量188)667質量部、ビスフェノールA 96.9質量部、及び2−メチルイミダゾール0.38質量部を仕込み、120℃に昇温して3時間反応させ、エポキシ当量を測定した。エポキシ当量が設定通り283になったことを確認後、60℃付近まで冷却した後、メタクリル酸228質量部、及びt−ブチルハイドロキノン0.29質量部を仕込み、窒素と空気とを1対1で混合したガス流通下で、90℃まで昇温した。ここに2−メチルイミダゾール0.23質量部を入れ、110℃に昇温して10時間反応させると、酸価が6以下になったので、反応を終了した。60℃付近まで冷却した後、反応容器より取り出し、水酸基価204mgKOH/gのビニルエステル(A−1)を得た。
合成例1で得たビニルエステル(A−1)55質量部をフェノキシエチルメタクリレート45質量部に溶解させた樹脂溶液100質量部に、ポリエチレン微粉末(住友精化株式会社製「フローセンUF−20S」、23℃におけるフェノキシエチルメタクリレートに対する溶解度:0.1g/100g以下)20質量部を分散させた後、ポリイソシアネート(三井化学株式会社製「コスモネートLL」、以下、「ポリイソシアネート(D−1)」と略記する。)21質量部、及び重合開始剤(化薬アクゾ株式会社製「カヤカルボンAIC−75」、有機過酸化物、以下、「重合開始剤(E−1)」と略記する。)1質量部を混合し、樹脂組成物(X−1)を得た。この樹脂組成物(X−1)におけるモル比(NCO/OH)は0.74であった。
実施例1で使用したポリエチレン微粉末20質量部を、スチレン−ジビニルベンゼン共重合体(綜研化学株式会社製「SGP−70C」、23℃におけるフェノキシエチルメタクリレートに対する溶解度:0.1g/100g以下)20質量部に変更した以外は、実施例1と同様にして、樹脂組成物(X−2)及び繊維強化成形材料(2)を得た。樹脂組成物(X−2)におけるモル比(NCO/OH)は0.74であり、繊維強化成形材料(2)の目付け量は、2kg/m2であった。
実施例1で使用したポリエチレン微粉末を使用しなかった以外は、実施例1と同様にして、樹脂組成物(RX−1)及び繊維強化成形材料(R1)を得た。樹脂組成物(RX−1)におけるモル比(NCO/OH)は0.74であり、繊維強化成形材料(R1)の目付け量は、2kg/m2であった。
実施例1で使用したフェノキシエチルメタクリレート45質量部をスチレン45質量部に変更し、ポリエチレン微粉末を使用しなかった以外は、実施例1と同様にして、樹脂組成物(RX−2)及び繊維強化成形材料(R2)を得た。樹脂組成物(RX−2)におけるモル比(NCO/OH)は0.37であり、繊維強化成形材料(R1)の目付け量は、2kg/m2であった。
上記で得られたシート状の繊維強化成形材料を、金型温度140℃、加圧時間3分、加圧力10MPaの成形条件にて30cm角金型の投影面積に対し50%チャージ率にて加圧成形し、板厚2mmの平板成形品を得た。
上記で得られた成形品を矯正する事なく24時間放置し、成形品端部一点を固定し、反り上がった他の端部の最大高さを測定し、下記評価基準により、寸法精度(反り変形量)を評価した。
○:反り変形量が2mm未満
×:反り変形量が2mm以上
Claims (5)
- エポキシ当量が180〜500の範囲であるエポキシ樹脂(a1)と(メタ)アクリル酸(a2)との反応物であるビニルエステル(A)、引火点が100℃以上の不飽和単量体(B)、熱可塑性樹脂(C)、ポリイソシアネート(D)、重合開始剤(E)、及び繊維長2.5〜50mmの炭素繊維(F)を必須原料とする繊維強化成形材料であって、前記熱可塑性樹脂(C)の23℃における前記不飽和単量体(B)に対する溶解度が1g/100g以下であり、前記ビニルエステル(A)と前記不飽和単量体(B)との質量比((A)/(B))が40/60〜85/15の範囲であり、前記ポリイソシアネート(D)のイソシアネート基(NCO)と前記ビニルエステル(A)の水酸基(OH)とのモル比(NCO/OH)が0.25〜0.85の範囲であり、前記熱可塑性樹脂(C)の含有量が、前記ビニルエステル(A)と前記不飽和単量体(B)との総量に対して、5〜50質量%の範囲であることを特徴とする繊維強化成形材料。
- 前記不飽和単量体(B)が、フェノキシエチルメタクリレート及び/又はベンジルメタクリレートである請求項1記載の繊維強化成形材料。
- 前記エポキシ樹脂(a1)のエポキシ基(EP)と前記(メタ)アクリル酸(a2)のカルボキシル基(COOH)とのモル比(COOH/EP)が0.6〜1.1の範囲である請求項1又は2記載の繊維強化成形材料。
- 前記ポリイソシアネート(D)が、芳香族系ポリイソシアネートである請求項1〜3のいずれか1項記載の繊維強化成形材料。
- 請求項1〜4のいずれか1項記載の繊維強化成形材料を用いた成形品。
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WO2011034042A1 (ja) * | 2009-09-18 | 2011-03-24 | Dic株式会社 | 繊維強化複合材料用樹脂組成物、その硬化物、繊維強化複合材料、繊維強化樹脂成形品、及びその製造方法 |
WO2015133289A1 (ja) * | 2014-03-07 | 2015-09-11 | Dic株式会社 | 加熱圧縮成形用成形材料、それを用いた成形品及びその製造方法 |
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ES2935840T3 (es) | 2023-03-10 |
EP3715405A4 (en) | 2021-08-11 |
CN111372980A (zh) | 2020-07-03 |
US11390716B2 (en) | 2022-07-19 |
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US20200277454A1 (en) | 2020-09-03 |
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