JP6361555B2 - Resin coated carbon fiber and its carbon fiber reinforced composite material - Google Patents
Resin coated carbon fiber and its carbon fiber reinforced composite material Download PDFInfo
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- JP6361555B2 JP6361555B2 JP2015075158A JP2015075158A JP6361555B2 JP 6361555 B2 JP6361555 B2 JP 6361555B2 JP 2015075158 A JP2015075158 A JP 2015075158A JP 2015075158 A JP2015075158 A JP 2015075158A JP 6361555 B2 JP6361555 B2 JP 6361555B2
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- copolymerized polyamide
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- nylon
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 172
- 239000004917 carbon fiber Substances 0.000 title claims description 172
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 166
- 229920005989 resin Polymers 0.000 title claims description 65
- 239000011347 resin Substances 0.000 title claims description 65
- 239000011208 reinforced composite material Substances 0.000 title claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 74
- 229920002647 polyamide Polymers 0.000 claims description 74
- 238000004513 sizing Methods 0.000 claims description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 61
- 238000000465 moulding Methods 0.000 claims description 54
- 239000000835 fiber Substances 0.000 claims description 30
- 239000003822 epoxy resin Substances 0.000 claims description 26
- 229920000647 polyepoxide Polymers 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 22
- 229920006122 polyamide resin Polymers 0.000 claims description 16
- 239000004745 nonwoven fabric Substances 0.000 claims description 14
- 229920002292 Nylon 6 Polymers 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 239000004925 Acrylic resin Substances 0.000 claims description 9
- 229920000178 Acrylic resin Polymers 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 7
- 229920000299 Nylon 12 Polymers 0.000 claims description 7
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
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- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
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- 238000007493 shaping process Methods 0.000 claims 2
- 238000000034 method Methods 0.000 description 21
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- -1 3,4-epoxycyclohexyl alcohol Chemical compound 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
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- 239000004677 Nylon Substances 0.000 description 6
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- 238000001035 drying Methods 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
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- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 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 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 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
- 239000007921 spray Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
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- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
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Description
本発明は、ＲＩＭ成形に好適な成形用炭素繊維と、それにより強化された炭素繊維強化複合材に関する。 The present invention relates to a molding carbon fiber suitable for RIM molding and a carbon fiber reinforced composite material reinforced thereby.
近年、繊維強化プラスチックを製造する方法として、炭素繊維束の樹脂含浸性を改良する目的で、反応射出成形（以下ＲＩＭ成形とする）が注目されている。これは、金型内に繊維強化材を配置した状態でポリアミド（ナイロン）、エポキシ樹脂、ポリウレタン等からなるマトリックス樹脂の低粘度の未反応原料液を注入し、金型内で繊維強化材に上記原料液を含浸させながら反応を起こさせて固化させる成形法であるため、炭素繊維束の含浸性の悪さをカバーできるからである。 In recent years, reaction injection molding (hereinafter referred to as RIM molding) has attracted attention as a method for producing fiber-reinforced plastics for the purpose of improving the resin impregnation property of carbon fiber bundles. This is done by injecting a low-viscosity raw material liquid of a matrix resin made of polyamide (nylon), epoxy resin, polyurethane, etc. in a state where the fiber reinforcement is placed in the mold, This is because it is a molding method in which a reaction is caused to solidify while impregnating the raw material liquid, so that the poor impregnation property of the carbon fiber bundle can be covered.
ＲＩＭ成形においてマトリックス樹脂として用いられるのはポリウレタン、ポリウレア、ポリアミド、エポキシ樹脂、不飽和ポリエステル、ジシクロペンタジエン等があるが、その中でもリサイクル性等を考慮して注目されているポリアミドＲＩＭ（ナイロンＲＩＭ）は、ε−カプロラクタムのアニオン重合法によって成形物が生成され、触媒としてアルカリ金属、アルカリ土類金属、グリニア試薬等との反応生成物であるアニオン触媒が用いられている。 Polyurethane, polyurea, polyamide, epoxy resin, unsaturated polyester, dicyclopentadiene, etc. are used as matrix resins in RIM molding. Among them, polyamide RIM (nylon RIM) has been attracting attention in consideration of recyclability. Is produced by an anionic polymerization method of ε-caprolactam, and an anion catalyst which is a reaction product with an alkali metal, an alkaline earth metal, a grinder reagent, or the like is used as a catalyst.
従来から使用されている炭素繊維束の多くは、エポキシ基等の反応性基を有するサイジング剤が塗布されている。これは、反応性基は炭素繊維の活性基と反応して、炭素繊維によく接着するためである。ところが、エポキシ基等の反応性基はポリアミドＲＩＭの原料中の触媒と反応するため、ポリアミド重合に必要な触媒が不足し、結果として失活させることになる。そのため樹脂の硬化が阻害され、成形性不良や物性の低下を引き起こす。 Many carbon fiber bundles conventionally used are coated with a sizing agent having a reactive group such as an epoxy group. This is because the reactive group reacts with the active group of the carbon fiber and adheres well to the carbon fiber. However, reactive groups such as epoxy groups react with the catalyst in the raw material of polyamide RIM, so that a catalyst necessary for polyamide polymerization is insufficient, resulting in deactivation. For this reason, the curing of the resin is hindered, resulting in poor moldability and physical properties.
この成形性不良や物性の低下を防ぐため、特許文献１には、ＲＩＭ成形時に硬化剤が影響を受ける水分、反応性基を有さないサイジング剤として特定の共重合ポリアミド樹脂が、提案されている。このサイジング剤は、マトリックス樹脂となるナイロンとの相溶性が良好であり、かつ、成形物の物性も良好であった。しかし、このサイジング剤は、反応性基を有さないため、炭素繊維との密着性が悪かった。 In order to prevent this poor moldability and deterioration of physical properties, Patent Document 1 proposes a specific copolymerized polyamide resin as a sizing agent that does not have moisture and reactive groups that are affected by the curing agent during RIM molding. Yes. This sizing agent had good compatibility with nylon as a matrix resin, and the physical properties of the molded product were also good. However, since this sizing agent does not have a reactive group, the adhesion with the carbon fiber was poor.
本発明は、かかる従来技術の背景に鑑み、ＲＩＭ成形に適した成形用炭素繊維を提供し、自動車部品等に用いることができる、炭素繊維で強化された熱可塑樹脂の成形物を提供せんとするものである。 In view of the background of the prior art, the present invention provides a molding carbon fiber suitable for RIM molding, and provides a molded product of a thermoplastic resin reinforced with carbon fiber, which can be used for automobile parts and the like. To do.
本発明は、上記課題、ＲＩＭ成形時に硬化不良を発生させない炭素繊維について鋭意検討し、ＲＩＭ成形時に硬化剤が影響を受ける水分、反応性基を有さない特定の共重合ポリアミド樹脂を開発し、さらに、反応性基を有するサイジング剤で処理された炭素繊維束のサイジング剤表面に、該共重合ポリアミドを上塗りした樹脂コーティング炭素繊維が、マトリックス樹脂との接着性も向上させ得ることを見出したものである。 The present invention has been intensively studied on the above-mentioned problem, carbon fibers that do not cause poor curing during RIM molding, and developed a specific copolyamide resin that does not have moisture and reactive groups that affect the curing agent during RIM molding. Furthermore, it has been found that the resin-coated carbon fiber coated with the copolymer polyamide on the surface of the sizing agent of the carbon fiber bundle treated with the sizing agent having a reactive group can improve the adhesion to the matrix resin. It is.
本発明は以下の発明を包含する。
（１）反応性基を有するサイジング剤が表面に付与された炭素繊維を、共重合ポリアミドを含む水性分散体で処理し、炭素繊維のサイジング剤表面上に共重合ポリアミドがコーティングされたＲＩＭ成形用樹脂コーティング炭素繊維であって、共重合ポリアミドが、ナイロン６、ナイロン６６およびナイロン１２から選択される２種以上のモノマー単位で構成される２元以上の共重合ポリアミドであり、反応性基を有するサイジング剤の付着量が、炭素繊維に対して０．０５〜１．０重量％であり、共重合ポリアミドの付着量が、炭素繊維に対して０．２〜２０重量％である、ＲＩＭ成形用樹脂コーティング炭素繊維。
（２）反応性基を有するサイジング剤が、エポキシ樹脂、カルボン酸変性ポリオレフィン樹脂、無水カルボン酸変性ポリオレフィン樹脂、エポキシ・ビニルエステル樹脂、エポキシ・ポリエステル樹脂、エポキシ基を有するアクリル樹脂およびカルボン酸基を有するアクリル樹脂から選択される少なくとも１種である、（１）に記載のＲＩＭ成形用樹脂コーティング炭素繊維。
（３）反応性基を有するサイジング剤が、エポキシ樹脂またはエポキシ基を有するアクリル樹脂である、（１）または（２）に記載のＲＩＭ成形用樹脂コーティング炭素繊維。
（４）共重合ポリアミドが、ナイロン６、ナイロン６６およびナイロン１２のモノマー単位で構成される３元共重合ポリアミドである、（１）〜（３）のいずれかに記載のＲＩＭ成形用樹脂コーティング炭素繊維。
（５）共重合ポリアミドの水性分散体が、共重合ポリアミド１００重量部を水性媒体１００〜１００００重量部に分散させたものであり、水性分散体中の共重合ポリアミドの平均粒子径が、０．１〜２０μｍである、（１）〜（４）のいずれかに記載のＲＩＭ成形用樹脂コーティング炭素繊維。
（６）反応性基を有するサイジング剤が付与された炭素繊維束を開繊しながら共重合ポリアミドの水性分散体をコーティングすることにより、炭素繊維のサイジング剤表面上に均一に共重合ポリアミド皮膜が形成されたことを特徴とする、（１）〜（５）のいずれかに記載のＲＩＭ成形用樹脂コーティング炭素繊維。
（７）炭素繊維束、カットファイバー、熱可塑性捲縮繊維との不織布または開繊された織物の形状である、（１）〜（６）のいずれかに記載のＲＩＭ成形用樹脂コーティング炭素繊維。
（８）（１）〜（７）のいずれかに記載のＲＩＭ成形用樹脂コーティング炭素繊維およびポリアミド樹脂をＲＩＭ成形して得られる炭素繊維強化複合材。
The present invention includes the following inventions.
(1) For RIM molding in which a carbon fiber provided with a reactive group-containing sizing agent is treated with an aqueous dispersion containing a copolymerized polyamide, and the surface of the carbon fiber sizing agent is coated with the copolymerized polyamide. Resin-coated carbon fiber, wherein the copolymerized polyamide is a binary or more copolymerized polyamide composed of two or more monomer units selected from nylon 6, nylon 66 and nylon 12, and has a reactive group For RIM molding, the adhesion amount of the sizing agent is 0.05 to 1.0% by weight with respect to the carbon fiber, and the adhesion amount of the copolymerized polyamide is 0.2 to 20% by weight with respect to the carbon fiber. Resin coated carbon fiber.
(2) A sizing agent having a reactive group includes an epoxy resin, a carboxylic acid-modified polyolefin resin, a carboxylic acid anhydride-modified polyolefin resin, an epoxy / vinyl ester resin, an epoxy / polyester resin, an acrylic resin having an epoxy group, and a carboxylic acid group. The resin-coated carbon fiber for RIM molding according to (1), which is at least one selected from acrylic resins having.
(3) The resin-coated carbon fiber for RIM molding according to (1) or (2), wherein the sizing agent having a reactive group is an epoxy resin or an acrylic resin having an epoxy group.
(4) The resin-coated carbon for RIM molding according to any one of (1) to (3), wherein the copolymerized polyamide is a ternary copolymerized polyamide composed of nylon 6, nylon 66 and nylon 12 monomer units. fiber.
(5) The aqueous dispersion of the copolymerized polyamide is obtained by dispersing 100 parts by weight of the copolymerized polyamide in 100 to 10,000 parts by weight of the aqueous medium, and the average particle size of the copolymerized polyamide in the aqueous dispersion is 0.00. The resin-coated carbon fiber for RIM molding according to any one of (1) to (4), which is 1 to 20 μm.
(6) By coating the aqueous dispersion of the copolymerized polyamide while opening the carbon fiber bundle provided with the sizing agent having a reactive group, the copolymerized polyamide film is uniformly formed on the surface of the carbon fiber sizing agent. The resin-coated carbon fiber for RIM molding according to any one of (1) to (5), which is formed.
(7) The resin-coated carbon fiber for RIM molding according to any one of (1) to (6), which is in the form of a nonwoven fabric with carbon fiber bundles, cut fibers, and thermoplastic crimped fibers, or an opened woven fabric.
(8) A carbon fiber reinforced composite material obtained by RIM molding the resin-coated carbon fiber for RIM molding and the polyamide resin according to any one of (1) to (7).
本発明によれば、ＲＩＭ成形に適した成形用樹脂コーティング炭素繊維を安定して提供することができ、自動車部品等に用いることができる、炭素繊維で強化された熱可塑樹脂の成形物を提供することができる。 According to the present invention, a molding resin-coated carbon fiber suitable for RIM molding can be stably provided, and a molded product of a thermoplastic resin reinforced with carbon fiber, which can be used for automobile parts and the like, is provided. can do.
本発明のＲＩＭ成形用樹脂コーティング炭素繊維は、エポキシ樹脂等の反応性基を有するサイジング剤によって処理された炭素繊維のサイジング剤表面上に、共重合ポリアミド（共重合ポリアミド樹脂）が上塗りコーティングされたものである。共重合ポリアミドは、反応性基を有するサイジング剤が表面に付与された炭素繊維を、該共重合ポリアミドの水性分散体で処理することで、炭素繊維のサイジング剤表面に上塗りコーティングされる。すなわち、本発明の炭素繊維は、反応性基を有するサイジング剤層を炭素繊維表面に有し、該サイジング剤層の表面に共重合ポリアミド樹脂コーティングを有するものである。本発明の炭素繊維は、かかる構造であることにより、サイジング剤の炭素繊維との密着性が良好であり、かつ、ＲＩＭ成形時に樹脂の硬化が阻害されない。
本発明に用いられる炭素繊維は、特に限定されず、公知の炭素繊維を用いることができる。例えば、ポリアクリロニトリル系炭素繊維、レイヨン系炭素繊維、リグニン系炭素繊維、ピッチ系炭素繊維、気相成長炭素繊維、カーボンナノチューブ等、繊維状であれば種類は特に限らない。安価なコストを実現できる点と炭素繊維から得られる炭素繊維強化複合材が良好な機械的特性を持つという点で、ポリアクリロニトリル系炭素繊維が好適に用いられる。
The resin-coated carbon fiber for RIM molding of the present invention is obtained by overcoating a copolymerized polyamide (copolymerized polyamide resin) on the surface of a sizing agent treated with a sizing agent having a reactive group such as an epoxy resin. Is. The copolyamide is overcoated on the surface of the sizing agent of the carbon fiber by treating the carbon fiber provided with a sizing agent having a reactive group on the surface with an aqueous dispersion of the copolyamide. That is, the carbon fiber of the present invention has a sizing agent layer having a reactive group on the surface of the carbon fiber, and a copolymerized polyamide resin coating on the surface of the sizing agent layer. Since the carbon fiber of the present invention has such a structure, the adhesion of the sizing agent to the carbon fiber is good, and the curing of the resin is not inhibited during RIM molding.
The carbon fiber used for this invention is not specifically limited, A well-known carbon fiber can be used. For example, the type is not particularly limited as long as it is fibrous, such as polyacrylonitrile-based carbon fiber, rayon-based carbon fiber, lignin-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, and carbon nanotube. Polyacrylonitrile-based carbon fiber is preferably used in that it can realize an inexpensive cost and a carbon fiber reinforced composite material obtained from carbon fiber has good mechanical properties.
本発明に用いられる反応性基を有するサイジング剤は、特に限定されずに、例えば、エポキシ樹脂、カルボン酸変性ポリオレフィン樹脂、無水カルボン酸変性ポリオレフィン樹脂、エポキシ・ビニルエステル樹脂、エポキシ・ポリエステル樹脂、エポキシ基を有するビニルエステル樹脂、エポキシ基を有するアクリル樹脂およびカルボン酸基を有するアクリル樹脂等であり、好ましくはエポキシ樹脂およびエポキシ基を有するアクリル樹脂であり、特に好ましいものはエポキシ樹脂である。本発明において、反応性基を有するサイジング剤は、２種以上を用いてもよい。 The sizing agent having a reactive group used in the present invention is not particularly limited, and examples thereof include an epoxy resin, a carboxylic acid-modified polyolefin resin, a carboxylic anhydride-modified polyolefin resin, an epoxy / vinyl ester resin, an epoxy / polyester resin, and an epoxy. A vinyl ester resin having a group, an acrylic resin having an epoxy group, an acrylic resin having a carboxylic acid group, etc., preferably an epoxy resin and an acrylic resin having an epoxy group, particularly preferably an epoxy resin. In the present invention, two or more sizing agents having a reactive group may be used.
本発明において、「エポキシ・ビニルエステル樹脂」とは、アクリル酸又はメチルメタアクリル酸が、グリシジルアルコール、３，４−エポキシシクロヘキシルアルコール等のエポキシ基を有するアルコールでエステル化されたモノマーが共重合されたビニルエステル樹脂である。 In the present invention, “epoxy vinyl ester resin” is a copolymer of a monomer obtained by esterifying acrylic acid or methyl methacrylic acid with an alcohol having an epoxy group such as glycidyl alcohol or 3,4-epoxycyclohexyl alcohol. Vinyl ester resin.
本発明において、「エポキシ・ポリエステル樹脂」とは、エポキシ樹脂とポリエステル樹脂とをエポキシ当量／酸当量比が所定の値になるように配合し、硬化触媒（例えば、テトラブチルアンモニウムブロマイド）を添加した混合溶液を加熱することにより得られる樹脂である。 In the present invention, the term “epoxy / polyester resin” means that an epoxy resin and a polyester resin are blended so that an epoxy equivalent / acid equivalent ratio becomes a predetermined value, and a curing catalyst (for example, tetrabutylammonium bromide) is added. It is a resin obtained by heating a mixed solution.
本発明の炭素繊維は、反応性基を有するサイジング剤が、炭素繊維に対して０．０５〜１．０重量％付着した炭素繊維であり、好ましくは炭素繊維に対して０．０７〜０．７重量％付着した炭素繊維である。 The carbon fiber of the present invention is a carbon fiber in which a sizing agent having a reactive group is adhered to 0.05 to 1.0% by weight with respect to the carbon fiber, and preferably 0.07 to 0.00. 7% by weight of attached carbon fiber.
反応性基を有するサイジング剤の付着量が、炭素繊維に対して０．０５重量％以上であると、炭素繊維とサイジング剤との密着性がよく、かつ、樹脂コーティング炭素繊維束の製造工程において毛羽等が発生せず、加工性に優れる。また、反応性基を有するサイジング剤の付着量が、炭素繊維に対して１．０重量％以下であると、下塗りのサイジング剤の反応性基がナイロンの重合反応を阻害する虞がない。 When the amount of the sizing agent having a reactive group is 0.05% by weight or more with respect to the carbon fiber, the adhesion between the carbon fiber and the sizing agent is good, and in the production process of the resin-coated carbon fiber bundle There is no fluffing and excellent workability. Further, when the adhesion amount of the sizing agent having a reactive group is 1.0% by weight or less with respect to the carbon fiber, there is no possibility that the reactive group of the sizing agent of the undercoat inhibits the polymerization reaction of nylon.
反応性基を有するサイジング剤による炭素繊維の処理は、例えば、炭素繊維または炭素繊維束を、反応性基を有するサイジング剤の水溶液中に浸漬させることで行うことができる。反応性基を有するサイジング剤の水溶液は、該サイジング剤以外の成分として、界面活性剤や分散剤等の他の成分を含んでいてもよい。 The treatment of the carbon fiber with the sizing agent having a reactive group can be performed, for example, by immersing the carbon fiber or the carbon fiber bundle in an aqueous solution of the sizing agent having a reactive group. The aqueous solution of the sizing agent having a reactive group may contain other components such as a surfactant and a dispersant as components other than the sizing agent.
本発明に用いられる共重合ポリアミドは、ナイロン６、ナイロン６６およびナイロン１２から選択される２種以上のモノマー単位で構成される２元以上の共重合ポリアミドである。つまり、２種類の上記モノマーを用いて共重合した２元共重合ポリアミド、３種類の上記モノマーを用いて共重合した３元共重合ポリアミド等である。 The copolymerized polyamide used in the present invention is a binary or higher copolymerized polyamide composed of two or more monomer units selected from nylon 6, nylon 66 and nylon 12. That is, a binary copolymerized polyamide copolymerized using two types of the above monomers, a ternary copolymerized polyamide copolymerized using the above three types of the monomers, and the like.
本発明に用いられる共重合ポリアミドの中でも好ましい共重合ポリアミドは、ナイロン６、ナイロン６６およびナイロン１２のモノマー単位からなる３元共重合ポリアミドである。 Among the copolyamides used in the present invention, a preferred copolyamide is a ternary copolyamide composed of nylon 6, nylon 66 and nylon 12 monomer units.
そして、共重合ポリアミドは、好ましくは、融点が７０〜１６０℃であり、より好ましくは１００〜１５５℃、特に好ましくは１２０〜１５０℃である。該共重合ポリアミドは、共重合成分の組成比を変更することにより、目的とする融点となるように調整を行うことができる。 The copolymerized polyamide preferably has a melting point of 70 to 160 ° C, more preferably 100 to 155 ° C, and particularly preferably 120 to 150 ° C. The copolymerized polyamide can be adjusted to have a target melting point by changing the composition ratio of the copolymerization components.
通常、接着強度を高くするためには、接着加工する場合の処理温度を高くすることが望ましいが、接着加工時の熱処理により、被接着素材は少なからず熱履歴を経て、変質や性能低下を起こす。このため、接着成分となるポリマーの融点は低い方が望ましい。 Usually, in order to increase the bonding strength, it is desirable to increase the processing temperature when bonding, but due to the heat treatment during bonding processing, the material to be bonded undergoes a thermal history, causing deterioration and performance degradation. . For this reason, it is desirable that the melting point of the polymer serving as the adhesive component is low.
そこで、本発明に関わる炭素繊維用サイジングとしての共重合ポリアミドの融点は１６０℃以下とする。これにより、接着加工時の熱処理温度を低くすることができ、被接着素材の変質や性能低下を最小限に軽減することができる。また、エネルギー消費の観点、コストの点から見ても、接着加工時の熱処理温度は低い方が好ましい。 Therefore, the melting point of the copolymerized polyamide as the carbon fiber sizing according to the present invention is 160 ° C. or less. Thereby, the heat processing temperature at the time of an adhesive process can be made low, and the quality change and performance fall of a to-be-adhered material can be reduced to the minimum. Further, from the viewpoint of energy consumption and cost, it is preferable that the heat treatment temperature during the bonding process is low.
一方、共重合ポリアミドの融点が７０℃以上であると、保管中や輸送中の高温多湿の環境により、炭素繊維糸の糸条同士が融着を起こし、解舒不良や糸質低下が発生する虞がない。また、接着加工を施した被接着素材に熱処理を施した際に、剥離するなど耐久性が乏しくなることもない。 On the other hand, when the melting point of the copolymerized polyamide is 70 ° C. or higher, the yarns of the carbon fiber yarns are fused with each other due to the hot and humid environment during storage or transportation, and unwinding failure and deterioration of the yarn quality occur. There is no fear. In addition, when heat treatment is performed on the material to be bonded that has been subjected to the bonding process, durability such as peeling does not occur.
なお、本発明に関わる炭素繊維の上塗り剤としての共重合ポリアミドの融点は、ＪＩＳ−Ｋ７１２１に記載の方法に準じて、理学電機株式会社製の示差走査熱量計Ｔｈｅｒｍｏ ｐｌｕｓ ＤＳＣ８２３０Ｌ型を使用し、昇温速度１０℃／分で測定する。 The melting point of the copolymerized polyamide as the carbon fiber topcoat relating to the present invention is increased by using a differential scanning calorimeter Thermo plus DSC8230L type manufactured by Rigaku Corporation in accordance with the method described in JIS-K7121. Measure at a temperature rate of 10 ° C / min.
炭素繊維のサイジング剤表面への共重合ポリアミドのコーティングは、例えば、エポキシ樹脂等の反応性基を有するサイジング剤によって処理された炭素繊維束を予熱加熱し、炭素繊維束を開繊しながら、共重合ポリアミドの水性分散体中に浸漬させることで行うことができる。反応性基を有するサイジング剤が付与された炭素繊維束を開繊しながら共重合ポリアミドの水性分散体をコーティングすると、炭素繊維のサイジング剤表面上に均一に共重合ポリアミド皮膜が形成される。 The coating of the copolymerized polyamide on the surface of the sizing agent of the carbon fiber is performed, for example, by preheating and heating the carbon fiber bundle treated with a sizing agent having a reactive group such as an epoxy resin and opening the carbon fiber bundle. It can be performed by immersing in an aqueous dispersion of polymerized polyamide. When an aqueous dispersion of copolymerized polyamide is coated while opening a carbon fiber bundle to which a sizing agent having a reactive group is applied, a copolymerized polyamide film is uniformly formed on the surface of the carbon fiber sizing agent.
炭素繊維束の開繊方法としては、限定されるものではないが、例えば気流による開繊、梨地面等の粗い表面を持つロールやバー等による衝打や振動による開繊等が良好であり、炭素繊維の開繊度をあげるには、気流による開繊がより良好である。 The opening method of the carbon fiber bundle is not limited, but for example, opening by airflow, hitting by a roll or bar having a rough surface such as pear ground, opening by vibration, etc. are good. In order to increase the degree of opening of the carbon fiber, the opening by airflow is better.
さらに、これら炭素繊維束の開繊を行う前に、炭素繊維束を予備的に加熱することによって、開繊することがより有効である。その結果、サイジング剤で処理した炭素繊維束が、毛羽等の問題がなく、開繊工程をよりスムーズに実施することができる。 Furthermore, it is more effective to open the carbon fiber bundle by preliminarily heating the carbon fiber bundle before opening the carbon fiber bundle. As a result, the carbon fiber bundle treated with the sizing agent is free from problems such as fluff and the opening process can be carried out more smoothly.
開繊された炭素繊維束を共重合ポリアミドの水性分散体に浸漬させて、共重合ポリアミドをこの炭素繊維束に均一に付着せしめ、次いで熱ローラー等に接触させて、水分の含有量が５重量％以下、好ましくは１重量％以下になるまで加熱・乾燥することにより炭素繊維束のサイジング剤表面上に共重合ポリアミドがコーティングされた樹脂コーティング炭素繊維束が得られる。 The opened carbon fiber bundle is immersed in an aqueous dispersion of copolymerized polyamide, and the copolymerized polyamide is uniformly attached to the carbon fiber bundle, and then brought into contact with a heat roller or the like, so that the water content is 5 wt. The resin-coated carbon fiber bundle in which the copolyamide is coated on the surface of the sizing agent of the carbon fiber bundle is obtained by heating and drying until it becomes less than or equal to 1%, preferably less than 1% by weight.
共重合ポリアミドの水性分散体中の共重合ポリアミドの平均粒子径は、０．１〜２０μｍ、好ましくは０．１〜１０μｍに調整される。共重合ポリアミドの水性分散体中の共重合ポリアミドの平均粒子径が０．１μｍ以上であると、粒子が凝集しゲル化し難いため、高い共重合ポリアミド濃度にすることができる。共重合ポリアミドの水性分散体中の共重合ポリアミドの平均粒子径が２０μｍ以下であると、共重合ポリアミドの付着均一性が良好であり、樹脂コーティング炭素繊維束の表面に凹凸が生じず、樹脂コーティング炭素繊維束の表面平滑性に影響を与えない。 The average particle diameter of the copolymerized polyamide in the aqueous dispersion of the copolymerized polyamide is adjusted to 0.1 to 20 μm, preferably 0.1 to 10 μm. When the average particle size of the copolymerized polyamide in the aqueous dispersion of copolymerized polyamide is 0.1 μm or more, the particles are aggregated and hardly gelled, so that a high copolymerized polyamide concentration can be obtained. When the average particle size of the copolymerized polyamide in the aqueous dispersion of the copolymerized polyamide is 20 μm or less, the adhesion uniformity of the copolymerized polyamide is good, the surface of the resin-coated carbon fiber bundle is not uneven, and the resin coating Does not affect the surface smoothness of the carbon fiber bundle.
共重合ポリアミドの水性分散体は、共重合ポリアミドの他に、界面活性剤や分散剤等の通常用いられる他の成分を含んでいてもよい。 The aqueous dispersion of the copolymerized polyamide may contain other commonly used components such as a surfactant and a dispersant in addition to the copolymerized polyamide.
かかる共重合ポリアミドを開繊された炭素繊維束にコーティングする方法は特に限定されない。例えば、ディップ法、スプレー法あるいはローラー法等の通常の方法により、開繊状態を維持しながら、炭素繊維束または炭素繊維束中の炭素繊維にコーティングする。共重合ポリアミドの付着量は、共重合ポリアミドの水性分散体中の共重合ポリアミドの有効濃度とマングル等のニップローラーの圧力調整（絞り）とで炭素繊維束に対する付着量を容易に調整することができる。 The method for coating the copolymerized polyamide on the opened carbon fiber bundle is not particularly limited. For example, the carbon fiber bundle or the carbon fiber in the carbon fiber bundle is coated by a normal method such as a dip method, a spray method, or a roller method while maintaining the opened state. The adhesion amount of the copolymerized polyamide can be easily adjusted by adjusting the effective concentration of the copolymerized polyamide in the aqueous dispersion of the copolymerized polyamide and adjusting the pressure (squeezing) of the nip roller such as mangle. it can.
本発明に関する炭素繊維における共重合ポリアミドの付着量は、炭素繊維に対して０．２〜２０重量％であり、好ましくは０．３〜１０重量％である。共重合ポリアミドの付着量が２０重量％以下であると、共重合ポリアミド自体の物性が成形物の物性に影響を与えない。共重合ポリアミドの付着量が０．２重量％以上であると、下塗りされたサイジング剤の反応性基により、樹脂の硬化不良を起こす虞がない。更に、充分な集束性を炭素繊維に付与することができる。 The adhesion amount of the copolymerized polyamide in the carbon fiber according to the present invention is 0.2 to 20% by weight, preferably 0.3 to 10% by weight, based on the carbon fiber. When the adhesion amount of the copolymerized polyamide is 20% by weight or less, the physical properties of the copolymerized polyamide itself do not affect the physical properties of the molded product. When the adhesion amount of the copolymerized polyamide is 0.2% by weight or more, there is no possibility of causing poor curing of the resin due to the reactive group of the undercoat sizing agent. Furthermore, sufficient bundling property can be imparted to the carbon fiber.
本発明の炭素繊維は、炭素繊維束またはカットファイバーの形状で用いることができ、あるいは、本発明の炭素繊維と、ナイロン６等の捲縮繊維とから得られた不織布として用いてもよく、よく開繊された織物として用いてもよい。 The carbon fiber of the present invention can be used in the form of a carbon fiber bundle or cut fiber, or may be used as a nonwoven fabric obtained from the carbon fiber of the present invention and crimped fibers such as nylon 6, It may be used as a spread fabric.
共重合ポリアミドを成形用炭素繊維束に付着させる場合は、ＲＩＭ成形により得られる成形体の特性を高めるために、フィラメント数を多くした炭素繊維束であるのが好ましく、具体的には好ましくは０．６万本以上、より好ましくは１．２万本以上のフィラメント数を持つものであるのが良い。なお、かかるフィラメント本数の上限は、好ましくは多くとも１０万本、さらに好ましくは７万本以下であるのが、拡がり性の上から選択される。 When the copolyamide is adhered to the carbon fiber bundle for molding, it is preferably a carbon fiber bundle having a larger number of filaments in order to improve the properties of the molded product obtained by RIM molding. It is preferable that the number of filaments is 60,000 or more, more preferably 12,000 or more. The upper limit of the number of filaments is preferably at most 100,000, more preferably not more than 70,000, from the viewpoint of spreadability.
本発明の成形用炭素繊維束は、かかるＲＩＭ成形に拘ることなく、たとえば該成形用炭素繊維束をカットファイバー化して、これを成形用樹脂に混合させて、金型に投入して成形することもできる。このような場合には、３〜２０ｍｍのカットファイバーが好ましく用いられる。 The molding carbon fiber bundle of the present invention can be molded by, for example, converting the molding carbon fiber bundle into a cut fiber, mixing it with a molding resin, and putting it into a mold, regardless of the RIM molding. You can also. In such a case, a cut fiber of 3 to 20 mm is preferably used.
また、本発明の炭素繊維束には、発明の目的を損なわない範囲で少量の他の繊維種が含まれていても良い。他の繊維種としては、例えば、ガラス繊維、アラミド繊維、アルミナ繊維、炭化珪素繊維、ボロン繊維、金属繊維等の高強度高弾性率繊維が挙げられ、これらを１種以上含有してもよい。 In addition, the carbon fiber bundle of the present invention may contain a small amount of other fiber types as long as the object of the invention is not impaired. Examples of other fiber types include high-strength and high-modulus fibers such as glass fiber, aramid fiber, alumina fiber, silicon carbide fiber, boron fiber, and metal fiber, and one or more of these may be contained.
本発明は、上記の本発明の炭素繊維およびマトリックス樹脂をＲＩＭ成形して得られる炭素繊維強化複合材にも関する。本発明は、特に、上記の炭素繊維およびポリアミド樹脂をＲＩＭ成形して得られる炭素繊維強化複合材に関する。本発明の炭素繊維およびマトリックス樹脂としてのポリアミド樹脂をＲＩＭ成形すると、樹脂の硬化阻害を引き起こすことなく、炭素繊維強化複合材を製造することができる。 The present invention also relates to a carbon fiber reinforced composite material obtained by RIM molding of the above-described carbon fiber and matrix resin of the present invention. The present invention particularly relates to a carbon fiber reinforced composite material obtained by RIM molding of the above carbon fiber and polyamide resin. When the carbon fiber of the present invention and the polyamide resin as the matrix resin are RIM-molded, a carbon fiber reinforced composite material can be produced without causing inhibition of resin curing.
本発明において、マトリックス樹脂としては、熱硬化性樹脂および熱可塑性樹脂を選択することができるが、得られる炭素繊維強化複合材の機械的特性が良好であり、かつ成形効率の高いプレス成形またはＲＩＭ成形が可能である熱可塑性樹脂が好ましい。 In the present invention, a thermosetting resin and a thermoplastic resin can be selected as the matrix resin, but the obtained carbon fiber reinforced composite material has good mechanical properties and high molding efficiency, such as press molding or RIM. A thermoplastic resin that can be molded is preferred.
熱可塑性樹脂としては、ポリエステル（例えばポリエチレンテレフタレート、ポリブチレンテレフタレート等）、ポリオレフィン（例えばポリエチレン、ポリプロピレン、ポリブチレン等）の他、スチレン系樹脂、ポリオキシメチレン、ポリアミド、ポリカーボネート、ポリメチレンメタクリレート、ポリ塩化ビニル、ポリフェニレンスルフィド、ポリフェニレンエーテル、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリスルホン、ポリエーテルスルホン、ポリケトン、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリアリレート、ポリエーテルニトリル、フェノールフェノキシ樹脂、フッ素樹脂等が挙げられ、さらに、ポリスチレン系、ポリオレフィン系、ポリウレタン系、飽和ポリエステル系、ポリアミド系、ポリブタジエン系、ポリイソプレン系、フッ素系等の熱可塑性エラストマー等も挙げられるが、好ましくは、機械的特性が良好な炭素繊維強化複合化材を得ることができるポリアミド樹脂が用いられる。また、これらの共重合体、変性体、およびこれらを２種類以上ブレンドしたものを熱可塑性樹脂として用いることもできる。なお、ここでの変性体とは、分子構造内のカルボキシル基等の反応性のある官能基を置換して得られた誘導体や、分子構造内にオキシエチレン基等のジオールを付加させた誘導体をいう。 Thermoplastic resins include polyester (eg, polyethylene terephthalate, polybutylene terephthalate, etc.), polyolefin (eg, polyethylene, polypropylene, polybutylene, etc.), styrenic resin, polyoxymethylene, polyamide, polycarbonate, polymethylene methacrylate, polyvinyl chloride. , Polyphenylene sulfide, polyphenylene ether, polyimide, polyamideimide, polyetherimide, polysulfone, polyethersulfone, polyketone, polyetherketone, polyetheretherketone, polyarylate, polyethernitrile, phenolphenoxy resin, fluorine resin, etc. Furthermore, polystyrene, polyolefin, polyurethane, saturated polyester, polyamide, poly Tajien system, polyisoprene, thermoplastic elastomers and fluorine-containing resins and the like are also mentioned, but preferably, a polyamide resin which can be mechanical properties obtain good carbon fiber reinforced composite material is used. In addition, these copolymers, modified products, and blends of two or more of these may be used as the thermoplastic resin. Here, the modified body means a derivative obtained by substituting a reactive functional group such as a carboxyl group in the molecular structure, or a derivative obtained by adding a diol such as an oxyethylene group in the molecular structure. Say.
本発明の炭素繊維強化複合材は、例えば、本発明の炭素繊維およびマトリックス樹脂を混合し、混合物を金型内でＲＩＭ成形することにより得ることができる。混合割合は特に制限されないが、例えばマトリックス樹脂１００重量部に対して本発明の炭素繊維が好ましくは２．５〜１０００重量部、より好ましくは５〜３００重量部の量である。本発明の炭素繊維とマトリックス樹脂の混合には、これらを均一に混合できる公知の方法を用いることができ、例えば一軸押出し機、二軸押出し機、プレス機、高速ミキサー、射出成形機、引抜成形機等の公知の装置を用いて、常法に従って行うことができる。混合物は、その組成、配合方法等により、マトリックス樹脂と炭素繊維との粉末状混合物、この混合物からなる造粒物等の各種の形態で得られる。当該混合物には必要に応じて他の公知の添加剤を併用することも可能である。添加剤の具体例としては、酸化防止剤や耐熱安定剤、耐候剤、離型剤および滑剤、顔料、染料、可塑剤、帯電防止剤、難燃剤、強化材等が挙げられる。 The carbon fiber reinforced composite material of the present invention can be obtained, for example, by mixing the carbon fiber of the present invention and a matrix resin, and RIM molding the mixture in a mold. The mixing ratio is not particularly limited, but for example, the carbon fiber of the present invention is preferably 2.5 to 1000 parts by weight, more preferably 5 to 300 parts by weight with respect to 100 parts by weight of the matrix resin. For mixing the carbon fiber and the matrix resin of the present invention, a known method capable of uniformly mixing them can be used, for example, a single screw extruder, a twin screw extruder, a press machine, a high speed mixer, an injection molding machine, a pultrusion molding. It can carry out in accordance with a conventional method using well-known apparatuses, such as a machine. The mixture can be obtained in various forms such as a powdery mixture of matrix resin and carbon fiber, and a granulated product made of this mixture, depending on its composition, blending method, and the like. Other known additives may be used in combination with the mixture as necessary. Specific examples of the additive include an antioxidant, a heat stabilizer, a weathering agent, a release agent and a lubricant, a pigment, a dye, a plasticizer, an antistatic agent, a flame retardant, and a reinforcing material.
本発明の炭素繊維は、マトリックス樹脂としてポリアミド樹脂を用いたＲＩＭ成形において、樹脂の硬化阻害を引き起こすことなく、曲げ強度や曲げ弾性率等の機械的特性が良好な炭素繊維強化複合化材を提供することができる。 The carbon fiber of the present invention provides a carbon fiber reinforced composite material having good mechanical properties such as bending strength and bending elastic modulus without causing inhibition of resin curing in RIM molding using a polyamide resin as a matrix resin. can do.
以下に本発明について実施例を挙げてさらに詳細に説明するが、本発明は実施例に特に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not particularly limited to the examples.
［共重合ポリアミドの水分散体］
例１
直径３５０ｍｍのタービン型撹拌羽根を備えた内径７００ｍｍ、高さ１５００ｍｍ、内容積４５０Ｌのジャケット付きの耐圧オートクレーブ中に、ナイロン６、ナイロン６６およびナイロン１２のモノマー単位で構成される３元共重合ポリアミド樹脂（アルケマ社製、商品名Ｈ００５ＦＡ、融点約１２０℃）１５０ｋｇ、水１４９．６ｋｇおよび水酸化ナトリウム０．４ｋｇを仕込み密閉した。次に、撹拌機を始動し毎分１５０回転で攪拌しながら、オートクレーブ内部を１５０℃付近までに昇温した。内温を１４０〜１５０℃に保ちながら、さらに３０分間撹拌した後、内容物を５０℃まで冷却し、樹脂濃度５０重量％の共重合ポリアミド樹脂の水性分散液を得た。
[Aqueous dispersion of copolymerized polyamide]
Example 1
A terpolymer polyamide resin composed of monomer units of nylon 6, nylon 66 and nylon 12 in a pressure-resistant autoclave with a jacket having a diameter of 700 mm, a height of 1500 mm and an internal volume of 450 L equipped with a turbine type stirring blade having a diameter of 350 mm 150 kg (manufactured by Arkema, trade name: H005FA, melting point: about 120 ° C.) 150 kg, water 149.6 kg and sodium hydroxide 0.4 kg were charged and sealed. Next, the inside of the autoclave was heated up to around 150 ° C. while starting the stirrer and stirring at 150 rpm. The mixture was further stirred for 30 minutes while maintaining the internal temperature at 140 to 150 ° C., and then the contents were cooled to 50 ° C. to obtain an aqueous dispersion of a copolymerized polyamide resin having a resin concentration of 50% by weight.
得られた共重合ポリアミド樹脂の水性分散液のメジアン径をレーザー回折式粒度分布測定装置（堀場製作所製ＬＡ−９１０）で測定したところ、メジアン径は０．３５μｍであった。 The median diameter of the aqueous dispersion of the obtained copolymerized polyamide resin was measured with a laser diffraction particle size distribution analyzer (LA-910, manufactured by Horiba, Ltd.), and the median diameter was 0.35 μm.
［サイジング剤の除去および付着量の測定］
約２ｇの炭素繊維束を１０５℃で３０分乾燥させた後、デシケーター内において３０分室温に冷却し秤量（Ｗ１）した。その後、炭素繊維束をアセトン中に浸漬し、サイジング剤を洗浄除去した。洗浄したサンプルを１０５℃にて１時間乾燥し、デシケーター内で３０分室温に冷却して秤量（Ｗ２）した。そして、次式よりサイジング剤付着量を求めた。
サイジング剤付着量（重量％）＝［Ｗ１（ｇ）−Ｗ２（ｇ）］／［Ｗ２（ｇ）］×１００
[Removal of sizing agent and measurement of adhesion amount]
About 2 g of carbon fiber bundles were dried at 105 ° C. for 30 minutes, then cooled to room temperature in a desiccator for 30 minutes and weighed (W1). Thereafter, the carbon fiber bundle was immersed in acetone to wash away the sizing agent. The washed sample was dried at 105 ° C. for 1 hour, cooled to room temperature in a desiccator for 30 minutes, and weighed (W2). And the sizing agent adhesion amount was calculated | required from following Formula.
Sizing agent adhesion amount (% by weight) = [W1 (g) −W2 (g)] / [W2 (g)] × 100
［ＲＩＭ重合評価］
試験管Ａ
窒素雰囲気下においてε−カプロラクタム（１５ｇ）とジシクロヘキシルカルボジイミド（０．５５ｇ）を試験管に入れ、さらに後述する実施例または比較例で得た炭素繊維束３ｇを加えた。
試験管Ｂ
窒素雰囲気下において別の試験管にε−カプロラクタム（１５ｇ）と水素化ナトリウム（０．０７ｇ）を加えた。
[RIM polymerization evaluation]
Test tube A
Under a nitrogen atmosphere, ε-caprolactam (15 g) and dicyclohexylcarbodiimide (0.55 g) were placed in a test tube, and 3 g of carbon fiber bundles obtained in Examples or Comparative Examples described later were further added.
Test tube B
Under a nitrogen atmosphere, ε-caprolactam (15 g) and sodium hydride (0.07 g) were added to another test tube.
試験管Ａと試験管Ｂを２００℃のオイルバスで２０分間加熱し、ε−カプロラクタムを溶融させ、試験管Ａと試験管Ｂの内容物を混合し、１５０℃で重合反応を行った。重合反応阻害の判定は何も被覆していない炭素繊維束を加えた系での硬化時間に対してどの程度硬化時間が長くなったかを評価した。 Test tube A and test tube B were heated in an oil bath at 200 ° C. for 20 minutes to melt ε-caprolactam, the contents of test tube A and test tube B were mixed, and a polymerization reaction was performed at 150 ° C. Determination of polymerization reaction inhibition evaluated how much hardening time became long with respect to the hardening time in the system which added the carbon fiber bundle which has not coat | covered anything.
［ＲＩＭ重合評価基準］
何も付与しない炭素繊維束使用時の硬化時間に対して、
○：１．１倍未満の硬化時間で硬化
△：１．１〜１．５倍の硬化時間で硬化
×：１．５倍超の硬化時間で硬化
と判定した。
[RIM polymerization evaluation criteria]
For the curing time when using a carbon fiber bundle that does not give anything,
○: Cured with a curing time of less than 1.1 times Δ: Cured with a curing time of 1.1 to 1.5 times ×: Cured with a curing time of more than 1.5 times.
［繊維強化成形物の曲げ強度、曲げ弾性力の測定］
ＪＩＳ−７１７１に準じて測定を行った。
[Measurement of bending strength and bending elastic force of fiber reinforced moldings]
Measurement was performed according to JIS-7171.
［炭素繊維束の製造］
実施例１
繊維径が７μｍ、構成繊維本数２４０００本のＰＡＮ系炭素繊維糸条（三菱レイヨン社製ＧＲＡＦＩＬ ３４−７００ＷＤ２４Ｋ）を、連続的に脱サイジングし、引続いてエポキシ樹脂Ａ（三菱化学株式会社製、製品名：ｊＥＲ８２８）４０重量部、エポキシ樹脂Ｂ（三菱化学株式会社製、製品名：ｊＥＲ１００１）４０重量部、ノニオン系界面活性剤２０重量部の混合物（サイジング剤−Ａ）のサイジング水溶液中に浸漬させて、炭素繊維上にエポキシ樹脂系サイジング剤が０．３重量％付与された炭素繊維を得た。
[Manufacture of carbon fiber bundles]
Example 1
A PAN-based carbon fiber yarn (GRAFIL 34-700WD24K manufactured by Mitsubishi Rayon Co., Ltd.) having a fiber diameter of 7 μm and constituting fibers of 24,000 is continuously desized, and subsequently epoxy resin A (manufactured by Mitsubishi Chemical Corporation, product) Name: jER828) 40 parts by weight, epoxy resin B (manufactured by Mitsubishi Chemical Co., Ltd., product name: jER1001) 40 parts by weight, nonionic surfactant 20 parts by weight A mixture (sizing agent-A) in a sizing aqueous solution Thus, carbon fiber provided with 0.3% by weight of an epoxy resin sizing agent on the carbon fiber was obtained.
得られた炭素繊維束に共重合ポリアミドの上塗りを、連続的に糸条を走行させ第一工程の予熱工程を含む開繊工程、第二工程のサイジング工程、および第三工程の乾燥工程によって行った。 Copolymerized polyamide topcoat is applied to the obtained carbon fiber bundle by a yarn opening process including a preheating process in the first process, a sizing process in the second process, and a drying process in the third process. It was.
具体的には、先ず、エポキシ樹脂でサイジングされた炭素繊維を、約１００℃の熱ローラーを使用して予備加熱し、気流開繊により、約２倍の幅（糸条幅：約１６ｍｍ）に開繊しながら、例１により得られた共重合ポリアミド樹脂にイオン交換水を加えて得られた、有効濃度６重量％の共重合ポリアミド水分散浴にロール浸漬させてコーティング処理を行い、ニップローラーにて炭素繊維上の共重合ポリアミド付着量が所定量になるように調整した。引き続いて、１２０℃に加熱された乾燥ローラーに１５０秒間押圧接触させて乾燥させ、更に１００秒間１８０℃に加熱された空気を送風することにより、二次乾燥を行った。得られた炭素繊維束の共重合ポリアミド付着量は３重量％であった。 Specifically, first, carbon fiber sized with an epoxy resin is preheated using a hot roller at about 100 ° C., and opened to about twice the width (yarn width: about 16 mm) by airflow opening. While fibering, coating treatment was performed by immersing the roll in a copolymerized polyamide resin dispersion obtained by adding ion-exchanged water to the copolymerized polyamide resin obtained in Example 1 and having an effective concentration of 6% by weight. Thus, the amount of the copolyamide deposited on the carbon fiber was adjusted to a predetermined amount. Subsequently, secondary drying was performed by pressing and contacting a drying roller heated to 120 ° C. for 150 seconds and then blowing air heated to 180 ° C. for 100 seconds. The amount of the copolyamide adhered to the obtained carbon fiber bundle was 3% by weight.
実施例２および３は、上塗りする共重合ポリアミド樹脂の水性分散体の有効濃度を変えて炭素繊維上のサイジング剤の付着量を変えた以外は、実施例１と同様にして行った。これらの結果は、表１に纏めた。 Examples 2 and 3 were carried out in the same manner as in Example 1 except that the effective concentration of the aqueous dispersion of copolymer polyamide resin to be overcoated was changed to change the amount of sizing agent deposited on the carbon fiber. These results are summarized in Table 1.
実施例４および５は、エポキシ樹脂のサイジング量を変えた炭素繊維を使用する以外は、実施例１と同様にして共重合ポリアミド樹脂を上塗りした。これらの結果は、表１に纏めた。 In Examples 4 and 5, a copolymerized polyamide resin was overcoated in the same manner as in Example 1 except that carbon fibers having different sizing amounts of the epoxy resin were used. These results are summarized in Table 1.
実施例６は、上塗りコーティング層を形成する共重合ポリアミドの付着量を変えた以外、実施例４と同様にして行った。 Example 6 was carried out in the same manner as in Example 4 except that the amount of the copolyamide forming the top coat layer was changed.
比較例１は、ＰＡＮ系炭素繊維糸条（三菱レイヨン社製ＧＲＡＦＩＬ ３４−７００ＷＤ２４Ｋ、エポキシ樹脂系サイジング剤１．４重量％）を何の処理も行わず、ＲＩＭ重合評価を行った。 In Comparative Example 1, RIM polymerization evaluation was performed without performing any treatment on PAN-based carbon fiber yarn (GRAFIL 34-700WD24K manufactured by Mitsubishi Rayon Co., Ltd., 1.4% by weight of epoxy resin-based sizing agent).
比較例２および３は、それぞれ、上塗り共重合ポリアミドの付着量（比較例２）及びエポキシ樹脂のサイジング量（比較例３）を変更した以外は、実施例２と同様にして行った。 Comparative Examples 2 and 3 were carried out in the same manner as in Example 2, except that the amount of the topcoat copolymerized polyamide (Comparative Example 2) and the amount of sizing of the epoxy resin (Comparative Example 3) were changed.
表１から明らかなように、エポキシ樹脂系サイジング剤をサイジングされた炭素繊維のサイジング剤表面上に、共重合ポリアミドを適量コーティングした炭素繊維（以下、樹脂コーティング炭素繊維とする）は、ε―カプロラクタムを使用したＲＩＭ成形において硬化阻害を起こさないことが明らかになった。 As is apparent from Table 1, carbon fiber (hereinafter referred to as resin-coated carbon fiber) obtained by coating a suitable amount of copolymerized polyamide on the surface of a carbon fiber sizing agent sized with an epoxy resin sizing agent is ε-caprolactam. It was revealed that no curing inhibition was caused in the RIM molding using A.
［炭素繊維不織布の製造］
実施例７
実施例５によって得られた樹脂コーティング炭素繊維束の５０ｍｍのチョップド繊維７０重量％とナイロン６の短繊維（東レ社製、ナイロン６繊維）３０重量％との混綿を、オプナー、ローラーカード、クロスレイアー、ローラーカードおよびニードルパンチングの各工程に通して得られたタテ・ヨコ強度のバランスに優れた不織布を使用して、評価を行った。
[Manufacture of carbon fiber nonwoven fabric]
Example 7
A blend of 70% by weight of 50 mm chopped fibers of the resin-coated carbon fiber bundle obtained in Example 5 and 30% by weight of nylon 6 short fibers (manufactured by Toray Industries, Ltd., nylon 6 fibers) was mixed with an OPNER, a roller card, and a cross layer. Evaluation was carried out using a nonwoven fabric having an excellent balance of vertical and horizontal strength obtained through each step of roller carding and needle punching.
実施例８
実施例５によって得られた樹脂コーティング炭素繊維束の替わりに実施例２によって得られた樹脂コーティング炭素繊維束を使用すること以外、実施例７と同様にして得られた不織布を使用して、評価を行った。
Example 8
Evaluation was performed using the nonwoven fabric obtained in the same manner as in Example 7, except that the resin-coated carbon fiber bundle obtained in Example 2 was used instead of the resin-coated carbon fiber bundle obtained in Example 5. Went.
［ナイロンＲＩＭによる炭素繊維強化複合材の製造］
金型を所定の温度に加熱した後、金型内部を真空ポンプにより大気圧から−９０ｋＰａ減圧にした。次に、乾燥機で原料Ａ（ε―カプロラクタム＋ジシクロヘキシルカルボジイミド）と原料Ｂ（ε―カプロラクタム＋水素化ナトリウム）を１１０℃に加熱し、溶融を行った。溶融後、原料Ａと原料Ｂを素早く混合してモノマー溶融液とし、実施例７で得られた１６０×１６０ｍｍ２の炭素繊維不織布を８層重ね合わせて金型内に配置した後、１６０℃に加熱された金型内部へと注入し、成形を行った。これらの成形物の物性は表２に纏められている。
[Manufacture of carbon fiber reinforced composites using nylon RIM]
After the mold was heated to a predetermined temperature, the inside of the mold was reduced from atmospheric pressure to -90 kPa by a vacuum pump. Next, the raw material A (ε-caprolactam + dicyclohexylcarbodiimide) and the raw material B (ε-caprolactam + sodium hydride) were heated to 110 ° C. and melted with a dryer. After melting, raw material A and raw material B were quickly mixed to form a monomer melt, and eight layers of 160 × 160 mm 2 carbon fiber nonwoven fabric obtained in Example 7 were placed in the mold, and then heated to 160 ° C. Poured into the heated mold and molded. The physical properties of these molded products are summarized in Table 2.
比較例４は、炭素繊維（三菱レイヨン社製ＧＲＡＦＩＬ ３４−７００ＷＤ２４Ｋ、エポキシ樹脂系サイジング剤１．４重量％）を脱サイジング処理した炭素繊維の５０ｍｍのチョップド繊維の７０重量％とナイロン６の短繊維の３０重量％との混綿を用いて実施例７と同様にして不織布を得た。この不織布を使用して、評価を行った。 In Comparative Example 4, carbon fiber (GRAFIL 34-700WD24K manufactured by Mitsubishi Rayon Co., Ltd., 1.4% by weight of an epoxy resin-based sizing agent) was desized, and 70% by weight of 50 mm chopped fiber and nylon 6 short fiber. A nonwoven fabric was obtained in the same manner as in Example 7 using 30% by weight of mixed cotton. Evaluation was performed using this nonwoven fabric.
比較例５は、炭素繊維（三菱レイヨン社製ＧＲＡＦＩＬ ３４−７００ＷＤ２４Ｋ、エポキシ樹脂系サイジング剤１．４重量％）を脱サイジング処理した後、例１によって得られた共重合ポリアミドを１重量％リサイジングされた炭素繊維の５０ｍｍのチョップド繊維７０重量％と、ナイロン６の短繊維３０重量％との混綿を用いて実施例７と同様にして不織布を得た。この不織布を使用して、評価を行った。 In Comparative Example 5, carbon fiber (GRAFIL 34-700WD24K manufactured by Mitsubishi Rayon Co., Ltd., 1.4% by weight of epoxy resin sizing agent) was desized, and then 1% by weight of the copolymerized polyamide obtained in Example 1 was resized. A non-woven fabric was obtained in the same manner as in Example 7 by using a mixed cotton of 70% by weight of 50 mm chopped fiber of carbon fiber and 30% by weight of short fiber of nylon 6. Evaluation was performed using this nonwoven fabric.
比較例６は、エポキシ樹脂系サイジング剤で処理された炭素繊維（三菱レイヨン社製ＧＲＡＦＩＬ ３４−７００ＷＤ２４Ｋ）のチョップド繊維とナイロン６短繊維とから得られた不織布を使用して、同様なＲＩＭ成形を行ったが、硬化阻害により良好な成形物を得ることができなかった。 Comparative Example 6 uses a non-woven fabric obtained from chopped fiber of carbon fiber (GRAFIL 34-700WD24K manufactured by Mitsubishi Rayon Co., Ltd.) and nylon 6 short fiber treated with an epoxy resin sizing agent, and performs the same RIM molding. However, a good molded product could not be obtained due to inhibition of curing.
表２は、樹脂コーティング炭素繊維から得られた不織布は、サイジング処理がされていない炭素繊維、および、共重合ポリアミドによってのみサイジングされた炭素繊維から得られた不織布に比べて良好な物性を有する成形物を提供できることを示している。 Table 2 shows that the non-woven fabric obtained from the resin-coated carbon fiber has better physical properties than the non-sized carbon fiber and the non-woven fabric obtained from the carbon fiber sized only by the copolymerized polyamide. It shows that you can provide things.
［ナイロンＲＩＭによる炭素繊維強化複合材の製造］
実施例９
金型を所定の温度に加熱した後、金型内部を真空ポンプにより大気圧から−９０ｋＰａ減圧にした。次に、乾燥機で原料Ａ（ε―カプロラクタム＋ジシクロヘキシルカルボジイミド）と原料Ｂ（ε―カプロラクタム＋水素化ナトリウム）を１１０℃に加熱し、溶融を行った。溶融後、原料Ａと原料Ｂを素早く混合してモノマー溶融液とし、実施例１によって得られた樹脂コーティング炭素繊維束を使用して製織された炭素繊維の平織物を裁断して１６０×１６０ｍｍ２の炭素繊維クロスを８層重ね合わせて金型内に配置した後、１６０℃に加熱された金型内部へと注入し、成形を行った。これらの成形物の物性は表３に纏められている。
[Manufacture of carbon fiber reinforced composites using nylon RIM]
Example 9
After the mold was heated to a predetermined temperature, the inside of the mold was reduced from atmospheric pressure to -90 kPa by a vacuum pump. Next, the raw material A (ε-caprolactam + dicyclohexylcarbodiimide) and the raw material B (ε-caprolactam + sodium hydride) were heated to 110 ° C. and melted with a dryer. After melting, raw material A and raw material B are quickly mixed to form a monomer melt, and a plain weave of carbon fiber woven using the resin-coated carbon fiber bundle obtained in Example 1 is cut to 160 × 160 mm 2. 8 layers of carbon fiber cloth were stacked and placed in the mold, and then injected into the mold heated to 160 ° C. to perform molding. The physical properties of these molded products are summarized in Table 3.
実施例１０
実施例１の替わりに実施例２によって得られた樹脂コーティング炭素繊維を使用して製織された炭素繊維の平織物を使用して実施例９と同様にして成形物を得た。これらの物性は、表３に纏めた。
Example 10
A molded product was obtained in the same manner as in Example 9, using a plain fabric of carbon fibers woven using the resin-coated carbon fibers obtained in Example 2 instead of Example 1. These physical properties are summarized in Table 3.
実施例１１
実施例１の替わりに実施例３によって得られた樹脂コーティング炭素繊維を使用して製織された炭素繊維の平織物を使用して実施例９と同様にして成形物を得た。これらの物性は、表３に纏めた。
Example 11
A molded product was obtained in the same manner as in Example 9 using a plain fabric of carbon fibers woven using the resin-coated carbon fibers obtained in Example 3 instead of Example 1. These physical properties are summarized in Table 3.
比較例７は、炭素繊維束（三菱レイヨン社製ＧＲＡＦＩＬ ３４−７００ＷＤ２４Ｋ）を脱サインジングした後、例１によって得られた共重合ポリアミドを１重量％リサイジングされた炭素繊維を使用して製織された平織物を１６０×１６０ｍｍ２に裁断して、評価を行った。これらの物性は表３に纏められている。 In Comparative Example 7, carbon fiber bundles (GRAFIL 34-700WD24K manufactured by Mitsubishi Rayon Co., Ltd.) were designed and then woven using 1% by weight of the resized carbon fiber of the copolymerized polyamide obtained in Example 1. The flat woven fabric was cut into 160 × 160 mm 2 and evaluated. These physical properties are summarized in Table 3.
比較例８は、脱サイジングされた炭素繊維束（三菱レイヨン社製ＧＲＡＦＩＬ ３４−７００ＷＤ２４Ｋ）を使用して製織しようとしたが、毛羽が多く良好な平織物を得ることはできなかった。 Although the comparative example 8 tried to weave using the carbon fiber bundle (GRAFIL 34-700WD24K by Mitsubishi Rayon Co., Ltd.) which was desized, it had many fuzz and was not able to obtain a good plain fabric.
比較例９は、炭素繊維の平織物（三菱レイヨン社製：パイロフィル ＴＲ１１２０Ｍ、縦糸：ＴＲ４０ １Ｌ、横糸：ＴＲ４０ １Ｌ）を１６０×１６０ｍｍ２に裁断して、何の処理も施すことなく使用して、同様にＲＩＭ成形を行ったが、硬化阻害により良好な成形物を得ることができなかった。 In Comparative Example 9, carbon fiber plain fabric (manufactured by Mitsubishi Rayon Co., Ltd .: Pyrofil TR1120M, warp yarn: TR40 1L, weft yarn: TR40 1L) was cut into 160 × 160 mm 2 and used without any treatment. Similarly, RIM molding was performed, but a good molded product could not be obtained due to inhibition of curing.
表３は、樹脂コーティング炭素繊維束を使用して製織された平織物は、共重合ポリアミドによってのみサイジングされた炭素繊維から得られた平織物に比べても、ＲＩＭ成形時の硬化不良を起こすことなく良好な物性を有する成形物を提供できることを示している。 Table 3 shows that plain fabrics woven using resin-coated carbon fiber bundles cause poor curing during RIM molding compared to plain fabrics obtained from carbon fibers sized only with copolymerized polyamide. This indicates that a molded article having good physical properties can be provided.
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