JP2018044023A - ガラス繊維強化樹脂組成物 - Google Patents
ガラス繊維強化樹脂組成物 Download PDFInfo
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- JP2018044023A JP2018044023A JP2016177237A JP2016177237A JP2018044023A JP 2018044023 A JP2018044023 A JP 2018044023A JP 2016177237 A JP2016177237 A JP 2016177237A JP 2016177237 A JP2016177237 A JP 2016177237A JP 2018044023 A JP2018044023 A JP 2018044023A
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- Prior art keywords
- unsaturated dicarboxylic
- copolymer
- styrene
- monomer
- glass fiber
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 239000011521 glass Substances 0.000 title abstract description 11
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- -1 polypropylene Polymers 0.000 claims abstract description 30
- 229920001155 polypropylene Polymers 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000003365 glass fiber Substances 0.000 claims abstract description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 21
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims 2
- 238000000465 moulding Methods 0.000 abstract description 3
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- 238000000034 method Methods 0.000 description 30
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
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- 150000003141 primary amines Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
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- 230000014759 maintenance of location Effects 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
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- 239000003063 flame retardant Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
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- 229920005606 polypropylene copolymer Polymers 0.000 description 2
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
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Abstract
Description
(2)ポリプロピレン系樹脂(A)と不飽和ジカルボン酸無水物系共重合体(B)の相容化剤(D)を含有する(1)に記載の樹脂組成物。
(3)(1)または(2)に記載の樹脂組成物からなる成形体。
本願明細書において、例えば、「A〜B」なる記載は、A以上でありB以下であることを意味する。
ポリプロピレン系樹脂(A)として、ポリプロピレンを使用した。ポリプロピレンは、日本ポリプロ株式会社製のノバテックPP MA3Hを用いた。
不飽和ジカルボン酸無水物系共重合体(B)として、以下に示す製造方法にて作製したスチレン−メチルメタクリレート−無水マレイン酸共重合体を使用した。t−ブチルパーオキシ−2−エチルヘキサノエートが2質量%となるようにメチルイソブチルケトンに希釈した2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液とを事前に調製し、重合に使用した。攪拌機を備えた120リットルのオートクレーブ中に、25%マレイン酸無水物溶液3.52kg、スチレン23kg、メチルメタクリレート8.2kg、t−ドデシルメルカプタン30gを仕込み、気相部を窒素ガスで置換した後、攪拌しながら40分かけて92℃まで昇温した。昇温後92℃を保持しながら、25%マレイン酸無水溶液と、2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液とを各々連続的に分添開始した。25%マレイン酸無水物溶液は、分添開始4時間目までが3.96kg/時、4時間目から7時間目までが3.17kg/時、7時間目から10時間目までが1.58kg/時、10時間目から13時間目までが0.54kg/時の分添速度となるように段階的に分添速度を変え、合計で31.71kg添加した。2%t−ブチルパーオキシ−2−エチルヘキサノエート溶液は、分添開始から7時間目までが0.24kg/時、7時間目から13時間目までが0.39kg/時の分添速度となるように段階的に分添速度を変え、合計で4.02kg添加した。重合温度は、分添開始から7時間目までは92℃を保持し、その後4℃/時の昇温速度で6時間かけて116℃まで昇温し、さらに116℃を1時間保持して重合を終了させた。重合液は、ギヤーポンプを用いて二軸脱揮押出機に連続的にフィードし、メチルイソブチルケトンおよび微量の未反応モノマー等を脱揮処理して、ストランド状に押出し切断することによりペレット形状のスチレン−メチルメタクリレート−無水マレイン酸共重合体を得た。13C−NMR法により構成単位を分析した結果、スチレン単位含有量が57質量%、メチルメタクリレート単位含有量が21質量%、無水マレイン酸単位含有量が22質量%であった。また、重量平均分子量は、12.5万であり、数平均分子量(Mn)との比であるMw/Mnは2.2であった
ガラス繊維(C)として、エポキシシランで変性された日本電気硝子社製ECS 03 T−120を用いた。なお、ガラス繊維の繊維径は13μm、繊維長は3mmであった。
ポリプロピレン系樹脂と不飽和ジカルボン酸無水物系共重合体の相容化剤として、水添スチレン系熱可塑性エラストマー(SEBS)を用いた。SEBSは、S/EBの質量比が67/33である旭化成株式会社製のタフテックH1043を用いた。
無水マレイン酸の含有量が5質量%である三洋化成株式会社製のユーメックス1010を使用した。
ポリプロピレン、不飽和ジカルボン酸無水物系共重合体、ガラス繊維、SEBS、無水マレイン酸変性PPを表1に示す配合で、押出機を用いて溶融混錬し、樹脂組成物を得た。押出機は株式会社井元製作所製二軸溶融混練押出機(L/D=26)を使用した。混練温度は230℃、スクリュー回転数は90rpmとした。
試験片は、株式会社新興セルビック製電動射出成形機C.Mobile0813を使用して、長さ50mm、幅5mm、厚さ2mmの短冊状試験片を作製した。
曲げ強度は、株式会社イマダ製電動スタンドMX−500NにデジタルフォースゲージZTA−500Nを設置した力学試験機にて測定した。
アイゾット衝撃強さは、株式会社マイズ試験機製アイゾッド衝撃試験機にて測定した。ノッチは株式会社井元製作所製ノッチ入れマシンを用いて、幅方向に約1mm導入した。
密閉容器に水道水を約500ml、試験片を15本投入した後、エスペック株式会社製恒温槽ST−100に入れ、水温が90℃となるように恒温槽を設定して、1、2、3週間浸漬させた。指定期間浸漬させた試験片を取り出し、常温大気下で2日間放置した後、曲げ強度、曲げ弾性率およびアイゾッド衝撃強さ測定を実施した。
Claims (3)
- ポリプロピレン系樹脂(A)と、不飽和ジカルボン酸無水物系共重合体(B)と、ガラス繊維(C)を含有し、前記共重合体(B)は不飽和ジカルボン酸無水物系単量体単位とスチレン系単量体単位を有する共重合体であるガラス繊維強化樹脂組成物。
- ポリプロピレン系樹脂(A)と不飽和ジカルボン酸無水物系共重合体(B)の相容化剤(D)を含有する請求項1に記載の樹脂組成物。
- 請求項1または2に記載の樹脂組成物からなる成形体。
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JPS62243633A (ja) * | 1986-04-16 | 1987-10-24 | Idemitsu Petrochem Co Ltd | ポリオレフイン樹脂組成物 |
US5225483A (en) * | 1991-07-22 | 1993-07-06 | Exxon Chemical Patents Inc. | Thermoplastic composition of polypropylene and styrene copolymer resins |
CN105623097A (zh) * | 2016-03-02 | 2016-06-01 | 北京航天试验技术研究所 | 一种纳米材料复合长玻纤增强聚丙烯材料及其制备方法 |
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JPS62243633A (ja) * | 1986-04-16 | 1987-10-24 | Idemitsu Petrochem Co Ltd | ポリオレフイン樹脂組成物 |
US5225483A (en) * | 1991-07-22 | 1993-07-06 | Exxon Chemical Patents Inc. | Thermoplastic composition of polypropylene and styrene copolymer resins |
CN105623097A (zh) * | 2016-03-02 | 2016-06-01 | 北京航天试验技术研究所 | 一种纳米材料复合长玻纤增强聚丙烯材料及其制备方法 |
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WO2021192900A1 (ja) * | 2020-03-27 | 2021-09-30 | 国立大学法人京都大学 | 撥水材料および積層体 |
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