JP2021059661A - Molding material and method for producing molding - Google Patents
Molding material and method for producing molding Download PDFInfo
- Publication number
- JP2021059661A JP2021059661A JP2019184506A JP2019184506A JP2021059661A JP 2021059661 A JP2021059661 A JP 2021059661A JP 2019184506 A JP2019184506 A JP 2019184506A JP 2019184506 A JP2019184506 A JP 2019184506A JP 2021059661 A JP2021059661 A JP 2021059661A
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- Prior art keywords
- resin
- molding material
- molding
- producing
- meth
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000465 moulding Methods 0.000 title abstract description 21
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- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
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- 238000000427 thin-film deposition Methods 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- 125000002947 alkylene group Chemical group 0.000 description 1
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- 230000001588 bifunctional effect Effects 0.000 description 1
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
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- HHZAIOOQYMFSFC-UHFFFAOYSA-L cobalt(2+);3-oxobutanoate Chemical compound [Co+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O HHZAIOOQYMFSFC-UHFFFAOYSA-L 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 239000000806 elastomer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HNPDNOZNULJJDL-UHFFFAOYSA-N ethyl n-ethenylcarbamate Chemical compound CCOC(=O)NC=C HNPDNOZNULJJDL-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- GUYMMHOQXYZMJQ-UHFFFAOYSA-N n-ethyl-3-methylaniline Chemical compound CCNC1=CC=CC(C)=C1 GUYMMHOQXYZMJQ-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000006187 phenyl benzyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
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- 238000013001 point bending Methods 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、成形材料及び成形品の製造方法に関する。 The present invention relates to a molding material and a method for producing a molded product.
炭素繊維を強化繊維としてエポキシ樹脂や不飽和ポリエステル樹脂等の熱硬化性樹脂を強化した繊維強化樹脂複合材料は、軽量でありながら耐熱性や機械強度に優れる特徴が注目され、自動車や航空機の筐体或いは各種部材をはじめ、様々な構造体用途での利用が拡大している。この繊維強化樹脂複合材料で、エポキシ樹脂を使用した材料の成形方法としては、プリプレグと呼ばれる材料を加圧可能なオートクレーブで加熱し硬化させるオートクレーブ法が知られており、不飽和ポリエステル樹脂を使用した材料の成形方法としては、シートモールディングコンパウンド（ＳＭＣ）、バルクモールディングコンパウンド（ＢＭＣ）と呼ばれる中間材料を用いて、プレス成形、射出成形等の手法により、硬化、成形させる方法が知られている。特に近年では、生産性に優れる材料開発が活発に行われている。 A fiber-reinforced resin composite material reinforced with a thermosetting resin such as an epoxy resin or an unsaturated polyester resin using carbon fiber as a reinforced fiber is attracting attention for its light weight and excellent heat resistance and mechanical strength. Its use in various structural applications such as bodies and various members is expanding. As a method for molding a material using an epoxy resin in this fiber-reinforced resin composite material, an autoclave method in which a material called prepreg is heated and cured by a pressurable autoclave is known, and an unsaturated polyester resin is used. As a method for molding a material, a method of curing and molding by a method such as press molding or injection molding using an intermediate material called a sheet molding compound (SMC) or a bulk molding compound (BMC) is known. Especially in recent years, the development of highly productive materials has been actively carried out.
このような成形材料としては、例えば、ビニルエステル樹脂、不飽和単量体、ポリイソシアネート、重合開始剤、及び炭素繊維を必須原料とする繊維強化成形材料が提案されている（特許文献１参照。）。しかしながら、この成形材料は、増粘工程における環境（湿度等）の相違により、タック性等の取り扱い性にばらつきが生じる問題があった。 As such a molding material, for example, a fiber-reinforced molding material containing a vinyl ester resin, an unsaturated monomer, a polyisocyanate, a polymerization initiator, and carbon fiber as essential raw materials has been proposed (see Patent Document 1). ). However, this molding material has a problem that the handleability such as tackiness varies due to the difference in the environment (humidity and the like) in the thickening process.
本発明が解決しようとする課題は、成形材料のフィルム剥ぎ性やタック性等の取り扱い性に優れ、曲げ強さ等の各種物性に優れる成形品が得られる成形材料及びその成形品の製造方法を提供することである。 The problem to be solved by the present invention is to obtain a molding material which is excellent in handleability such as film peeling property and tackiness of the molding material and which is excellent in various physical properties such as bending strength, and a method for manufacturing the molded product. To provide.
本発明者等は、ビニルエステル樹脂、不飽和単量体、ポリイソシアネート、及び重合開始剤を必須原料とする樹脂コンパウンドを、特定の方法により増粘させる工程を有する成形材料の製造方法により、取り扱い性に優れ、曲げ強さ等の各種物性に優れる成形品を得られることを見出し、本発明を完成した。 The present inventors handle a resin compound containing a vinyl ester resin, an unsaturated monomer, a polyisocyanate, and a polymerization initiator as essential raw materials by a method for producing a molding material having a step of thickening by a specific method. The present invention has been completed by finding that a molded product having excellent properties and various physical properties such as bending strength can be obtained.
すなわち、ビニルエステル樹脂（Ａ）、不飽和単量体（Ｂ）、ポリイソシアネート（Ｃ）、及び重合開始剤（Ｄ）を必須原料とする樹脂コンパウンドを、蒸着フィルムで梱包し、該蒸着フィルム内で増粘させる工程を有する成形材料及び成形品の製造方法に関する。 That is, a resin compound containing a vinyl ester resin (A), an unsaturated monomer (B), a polyisocyanate (C), and a polymerization initiator (D) as essential raw materials is packed in a vapor-deposited film, and the inside of the vapor-deposited film is packed. The present invention relates to a molding material having a step of thickening with and a method for producing a molded product.
本発明の繊維強化成形材料から得られる成形品は、取り扱い性、外観、曲げ強さ、曲げ弾性率等に優れることから、自動車部材、鉄道車両部材、航空宇宙機部材、船舶部材、住宅設備部材、スポーツ部材、軽車両部材、建築土木部材、ＯＡ機器等の筐体等に好適に用いることができる。 Since the molded product obtained from the fiber-reinforced molding material of the present invention is excellent in handleability, appearance, bending strength, flexural modulus, etc., it is therefore an automobile member, a railroad vehicle member, an aerospace machine member, a ship member, a housing equipment member, and the like. , Sports members, light vehicle members, building civil engineering members, housings for OA equipment, etc.
本発明の成形材料の製造方法は、ビニルエステル樹脂（Ａ）、不飽和単量体（Ｂ）、ポリイソシアネート（Ｃ）、及び重合開始剤（Ｄ）を必須原料とする樹脂コンパウンドを、蒸着フィルムで梱包し、該蒸着フィルム内で増粘させる工程を有するものである。 In the method for producing a molding material of the present invention, a resin compound containing a vinyl ester resin (A), an unsaturated monomer (B), a polyisocyanate (C), and a polymerization initiator (D) as essential raw materials is used as a vapor-deposited film. It has a step of packing with and thickening in the vaporized film.
前記ビニルエステル樹脂（Ａ）は、エポキシ樹脂（ａ１）と（メタ）アクリル酸（ａ２）とを反応させることにより得られるが、成形時のフィルム剥離性やタック性等の取扱性と流動性とのバランスにより優れることから、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）を０．６〜１．１の範囲で反応させることが好ましい。また、この観点から、前記エポキシ樹脂（ａ１）のエポキシ当量は１８０〜５００の範囲が好ましく、１８０〜３７０の範囲がより好ましく、１８０〜２５０の範囲がさらに好ましい。 The vinyl ester resin (A) is obtained by reacting the epoxy resin (a1) with the (meth) acrylic acid (a2), and has the handleability and fluidity such as film peelability and tackiness during molding. The molar ratio (COOH / EP) of the epoxy group (EP) of the epoxy resin (a1) to the carboxyl group (COOH) of the (meth) acrylic acid (a2) is 0.6 to 1 because the balance is superior. It is preferable to react in the range of 1. From this viewpoint, the epoxy equivalent of the epoxy resin (a1) is preferably in the range of 180 to 500, more preferably in the range of 180 to 370, and even more preferably in the range of 180 to 250.
なお、本発明において、「（メタ）アクリル酸」とは、アクリル酸とメタクリル酸の一方又は両方をいい、「（メタ）アクリレート」とは、アクリレートとメタクリレートの一方又は両方をいう。 In the present invention, "(meth) acrylic acid" means one or both of acrylic acid and methacrylic acid, and "(meth) acrylate" means one or both of acrylate and methacrylate.
前記エポキシ樹脂（ａ１）としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールフルオレン型エポキシ樹脂、ビスクレゾールフルオレン型等のビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂、オキゾドリドン変性エポキシ樹脂、これらの樹脂の臭素化エポキシ樹脂等のフェノールのグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ビスフェノールＡのアルキレンオキサイド付加物のジグリシジルエーテル、水素化ビスフェノールＡのジグリシジルエーテル等の多価アルコールのグリシジルエーテル、３，４−エポキシ−６−メチルシクロヘキシルメチル−３，４−エポキシ−６−メチルシクロヘキサンカルボキシレート、１−エポシエチル−３，４−エポキシシクロヘキサン等の脂環式エポキシ樹脂、フタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ジグリシジル−ｐ−オキシ安息香酸、ダイマー酸グリシジルエステルなどのグリシジルエステル、テトラグリシジルジアミノジフェニルメタン、テトラグリシジル−ｍ−キシレンジアミン、トリグリシジル−ｐ一アミノフェノール、Ｎ，Ｎ−ジグリシジルアニリンなどのグリシジルアミン、１，３−ジグリシジル−５，５−ジメチルヒダントイン、トリグリシジルイソシアヌレートなどの複素環式エポキシ樹脂などが挙げられる。これらの中でも、成形品強度と成形材料の取り扱い性、成形材料の成形時の流動性により優れることから２官能性芳香族系エポキシ樹脂が好ましく、ビスフェノールＡ型エポキシ樹脂およびビスフェノールＦ型エポキシ樹脂がより好ましい。なお、これらのエポキシ樹脂は、単独で用いることも２種以上併用することもできる。 Examples of the epoxy resin (a1) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol fluorene type epoxy resin, biscresol fluorene type and other bisphenol type epoxy resins, phenol novolac type epoxy resin, and cresol novolac type epoxy. Novolak type epoxy resin such as resin, oxodoridone modified epoxy resin, phenolic glycidyl ether such as brominated epoxy resin of these resins, dipropylene glycol diglycidyl ether, trimethylpropan triglycidyl ether, alkylene oxide adduct of bisphenol A Diglycidyl ether, glycidyl ether of polyhydric alcohols such as diglycidyl ether of bisphenol A hydride, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-epociethyl- Alicyclic epoxy resin such as 3,4-epoxycyclohexane, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, glycidyl ester such as dimer acid glycidyl ester, tetraglycidyldiaminodiphenylmethane, tetra Glycidyl amines such as glycidyl-m-xylene diamine, triglycidyl-p monoaminophenol, N, N-diglycidyl aniline, heterocyclic epoxies such as 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate. Examples include resin. Among these, a bifunctional aromatic epoxy resin is preferable because it is superior in the strength of the molded product, the handleability of the molding material, and the fluidity during molding of the molding material, and the bisphenol A type epoxy resin and the bisphenol F type epoxy resin are more preferable. preferable. These epoxy resins can be used alone or in combination of two or more.
また、前記エポキシ樹脂（ａ１）としては、エポキシ当量を調整するために、ビスフェノールＡ等の二塩基酸により高分子量化し使用してもよい。 Further, the epoxy resin (a1) may be used by increasing the molecular weight with a dibasic acid such as bisphenol A in order to adjust the epoxy equivalent.
前記したエポキシ樹脂と（メタ）アクリル酸との反応は、エステル化触媒を用い、６０〜１４０℃において行われることが好ましい。また、重合禁止剤等を使用することもできる。 The reaction between the epoxy resin and (meth) acrylic acid is preferably carried out at 60 to 140 ° C. using an esterification catalyst. Further, a polymerization inhibitor or the like can also be used.
前記不飽和単量体（Ｂ）としては、例えば、スチレン、ｐ−メチルスチレン、ｐ−エチルスチレン、ｐ−プロピルスチレン、ｐ−イソプロピルスチレン、ｐ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｏ−メチルスチレン、ｏ−エチルスチレン、ｏ−プロピルスチレン、ｏ−イソプロピルスチレン、ｍ−メチルスチレン、ｍ−エチルスチレン、ｍ−プロピルスチレン、ｍ−イソプロピルスチレン、ｍ−ブチルスチレン、メシチルスチレン、２，４−ジメチルスチレン、２，５−ジメチルスチレン、３，５−ジメチルスチレン、４−ブテニルスチレン等のアルキルスチレン、ｐ−クロロスチレン、ｍ−クロロスチレン、ｏ−クロロスチレン、ｐ−ブロモスチレン、ｍ−ブロモスチレン、ｏ−ブロモスチレン、ｐ−フルオロスチレン、ｍ−フルオロスチレン、ｏ−フルオロスチレン、ｏ−メチル−ｐ−フルオロスチレン等のハロゲン化スチレン、ｐ−メトキシスチレン、ｏ−メトキシスチレン、ｍ−メトキシスチレン等のアルコキシスチレン、ヒドロキシスチレン、シアノスチレン、ビニル安息香酸エステル等のスチレン系化合物；１，３−ジビニルベンゼン、１，４−ジビニルベンゼン、１，３−ジイソプロペニルベンゼン、１，４−ジイソプロペニルベンゼン等のジビニルベンゼン系化合物；メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレート、シクロへキシル（メタ）アクリレート、イソボロニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソトリデシル（メタ）アクリレート、ｎ−ステアリル（メタ）アクリレート、テトラヒドロフルフリルメタクリレート、ベンジル（メタ）アクリレート、メチルベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、メチルフェノキシエチル（メタ）アクリレート、モルホリン（メタ）アクリレート、フェニルフェノキシエチルアクリレート、フェニルベンジル（メタ）アクリレート、フェニルメタクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニルメタクリレート、ポリエチレングリコール（メタ）アクリレートアルキルエーテル、ポリプロピレングリコール（メタ）アクリレートアルキルエーテル等の単官能（メタ）アクリレート化合物；ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート等の水酸基含有（メタ）アクリレート化合物；エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，３−ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ビスフェノールジ（メタ）アクリレート、１，４−シクロヘキサンジメタノールジ（メタ）アクリレート等のジ（メタ）アクリレート化合物等が挙げられる。これらは単独で用いることも、２種以上併用することもできる。 Examples of the unsaturated monomer (B) include styrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, o-. Methyl styrene, o-ethyl styrene, o-propyl styrene, o-isopropyl styrene, m-methyl styrene, m-ethyl styrene, m-propyl styrene, m-isopropyl styrene, m-butyl styrene, mesityl styrene, 2,4 -Alkylstyrene such as dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, 4-butenylstyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m- Halogenized styrene such as bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, p-methoxystyrene, o-methoxystyrene, m-methoxy Alkoxystyrene such as styrene, styrene compounds such as hydroxystyrene, cyanostyrene, vinyl benzoic acid ester; 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-di Divinylbenzene compounds such as isopropenylbenzene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) Acrylate, Isobolonyl (meth) acrylate, Isodecyl (meth) acrylate, Lauryl (meth) acrylate, Isotridecyl (meth) acrylate, n-stearyl (meth) acrylate, tetrahydrofurfuryl methacrylate, benzyl (meth) acrylate, methylbenzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methylphenoxyethyl (meth) acrylate, morpholin (meth) acrylate, phenylphenoxyethyl acrylate, phenylbenzyl (meth) acrylate, phenylmethacrylate, dicyclopentenyl ( Meta) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl methacrylate, polyethylene glycol (meth) acrylate alkyl ether, poly Monofunctional (meth) acrylate compounds such as propylene glycol (meth) acrylate alkyl ethers; hydroxyl group-containing (meth) acrylate compounds such as hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, and hydroxybutyl (meth) acrylates; ethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 Examples thereof include di (meth) acrylate compounds such as −hexanediol di (meth) acrylate, bisphenol di (meth) acrylate, and 1,4-cyclohexanedimethanol di (meth) acrylate. These can be used alone or in combination of two or more.
前記不飽和単量体（Ｂ）は、成形作業時の臭気を抑制できるとともに、高温単時間成形が可能となることから、引火点が１００℃以上であることが好ましく、それらの中でも、より高強度の成形材料が得られることから、芳香族を有する不飽和単量体がより好ましく、ベンジルメタクリレート、フェノキシエチルメタクリレートがさらに好ましい。 The unsaturated monomer (B) preferably has a flash point of 100 ° C. or higher, and is higher among them, because it can suppress an odor during molding work and can be molded at a high temperature for a single time. An unsaturated monomer having an aromatic substance is more preferable, and benzyl methacrylate and phenoxyethyl methacrylate are further preferable, because a strong molding material can be obtained.
なお、本発明における引火点は、ＪＩＳＫ２２６５−４：２００７に規定されたクリーブランド開放法により測定した引火点とする。 The flash point in the present invention is the flash point measured by the Cleveland opening method specified in JIS K2265-4: 2007.
前記ビニルエステル樹脂（Ａ）と前記不飽和単量体（Ｂ）との質量比（（Ａ）／（Ｂ））は、４０／６０〜８５／１５の範囲であるが、強化繊維への樹脂含浸性、取り扱い性（フィルム剥離性及びタック性）と硬化性のバランスがより向上することから、５０／５０〜７０／３０の範囲が好ましい。 The mass ratio ((A) / (B)) of the vinyl ester resin (A) to the unsaturated monomer (B) is in the range of 40/60 to 85/15, but is a resin for reinforcing fibers. The range of 50/50 to 70/30 is preferable because the balance between impregnation property, handleability (film peeling property and tack property) and curability is further improved.
また、前記ビニルエステル樹脂（Ａ）と前記不飽和単量体（Ｂ）との混合物の粘度は、
強化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。
The viscosity of the mixture of the vinyl ester resin (A) and the unsaturated monomer (B) is
The range of 200 to 8000 mPa · s (25 ° C.) is preferable because the resin impregnation property of the reinforcing fibers is further improved.
前記ポリイソシアネート（Ｃ）は、例えば、ジフェニルメタンジイソシアネート（４，４’−体、２，４’−体、又は２，２’−体、若しくはそれらの混合物）、ジフェニルメタンジイソシアネートのカルボジイミド変性体、ヌレート変性体、ビュレット変性体、ウレタンイミン変性体、ジエチレングリコールやジプロピレングリコール等の数平均分子量１，０００以下のポリオールで変性したポリオール変性体等のジフェニルメタンジイソシアネート変性体、トリレンジイソシアネート、トリジンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート、キシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、テトラメチルキシレンジイソシアネート等の芳香族ポリイソシアネート；イソホロンジイソシアネート、水添ジフェニルメタンジイソシアネート、水添キシリレンジイソシアネート、ノルボルネンジイソシアネート等の脂環式ポリイソシアネート；ヘキサメチレンジイソシアネート、ヘキサメチレンジイソシアネートのヌレート変性体、ビュレット変性体、アダクト体、ダイマー酸ジイソシアネート等の脂肪族ポリイソシアネートなどを用いることができる。これらの中でも、取り扱い性（フィルム剥離性及びタック性）に優れる成形材料が得られることから、芳香族ポリイソシアネートが好ましい。なお、これらのポリイソシアネート（Ｃ）は、単独で用いることも２種以上併用することもできる。 The polyisocyanate (C) is, for example, a diphenylmethane diisocyanate (4,4'-form, 2,4'-form, or 2,2'-form, or a mixture thereof), a carbodiimide-modified product of diphenylmethane diisocyanate, or a nurate-modified product. Diphenylmethane diisocyanate modified product such as body, bullet modified product, urethane imine modified product, polyol modified product modified with polyol having a number average molecular weight of 1,000 or less such as diethylene glycol and dipropylene glycol, tolylene diisocyanate, trizine diisocyanate, polymethylene poly Aromatic polyisocyanates such as phenyl polyisocyanate, xylylene diisocyanate, 1,5-naphthalenediocyanate, tetramethylxylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate; Hexamethylene diisocyanate, a nurate-modified product of hexamethylene diisocyanate, a bullet-modified product, an adduct-isocyanate, an aliphatic polyisocyanate such as diisocyanate dimerate, or the like can be used. Among these, aromatic polyisocyanates are preferable because a molding material having excellent handleability (film peelability and tackiness) can be obtained. These polyisocyanates (C) can be used alone or in combination of two or more.
前記ポリイソシアネート（Ｃ）のイソシアネート基（ＮＣＯ）と前記ビニルエステル樹脂（Ａ）の水酸基（ＯＨ）とのモル比（ＮＣＯ／ＯＨ）は、取り扱い性（フィルム剥ぎ性及びタック性）と柔軟性とのバランスがより優れることから０．５〜０．９５の範囲が好ましく、０．５５〜０．８５の範囲がより好ましい。 The molar ratio (NCO / OH) of the isocyanate group (NCO) of the polyisocyanate (C) to the hydroxyl group (OH) of the vinyl ester resin (A) is determined by the handleability (film peeling property and tack property) and flexibility. The range of 0.5 to 0.95 is preferable, and the range of 0.55 to 0.85 is more preferable.
前記重合開始剤（Ｄ）としては、特に限定されないが、有機過酸化物が好ましく、例えば、ジアシルパーオキサイド化合物、パーオキシエステル化合物、ハイドロパーオキサイド化合物、ケトンパーオキサイド化合物、アルキルパーエステル化合物、パーカーボネート化合物、パーオキシケタール等が挙げられ、成形条件に応じて適宜選択できる。なお、これらの重合開始剤（Ｄ）は、単独で用いることも２種以上併用することもできる。 The polymerization initiator (D) is not particularly limited, but an organic peroxide is preferable, and for example, a diacyl peroxide compound, a peroxy ester compound, a hydroperoxide compound, a ketone peroxide compound, an alkyl per ester compound, and a per. Examples thereof include carbonate compounds and peroxyketal, which can be appropriately selected depending on the molding conditions. These polymerization initiators (D) may be used alone or in combination of two or more.
また、これらの中でも、成形時間を短縮する目的で１０時間半減期を得るための温度が７０℃以上１１０℃以下の重合開始剤を使用するのが好ましい。７０℃以上１１０℃以下であれば繊維強化成形材料の常温でのライフが長く、また加熱により短時間で硬化ができるため好ましく、硬化性と成形性のバランスがより優れる。このような重合開始剤としては、例えば、１，６−ビス（ｔ−ブチルパーオキシカルボニロキシ）ヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−アミルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ヘキシルパーオキシ）シクロヘキサン、ｔ−ブチルパーオキシジエチルアセテート、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−アミルパーオキシイソプロピルカーボネート、ｔ−ヘキシルパーオキシイソプロピルカーボネート、ジーｔｅｒｔ−ブチルパーオキシヘキサハイドロテレフタレート、ｔ−アミルパーオキシトリメチルヘキサノエート等が挙げられる。 Further, among these, it is preferable to use a polymerization initiator having a temperature of 70 ° C. or higher and 110 ° C. or lower for obtaining a 10-hour half-life for the purpose of shortening the molding time. When the temperature is 70 ° C. or higher and 110 ° C. or lower, the life of the fiber-reinforced molding material at room temperature is long, and it can be cured in a short time by heating, which is preferable, and the balance between curability and moldability is more excellent. Examples of such a polymerization initiator include 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis (t-butylperoxy) cyclohexane, and 1,1-bis (t-). Amylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, t-butylperoxydiethylacetate, t-butylperoxyisopropyl carbonate, t-amylperoxyisopropylcarbonate, t-hexylperoxyisopropyl Examples thereof include carbonate, di-tert-butylperoxyhexahydroterephthalate, t-amylperoxytrimethylhexanoate and the like.
前記重合開始剤（Ｄ）の含有量としては、硬化特性と保存安定性が共に優れることから、前記ビニルエステル樹脂（Ａ）と前記不飽和単量体（Ｂ）との総量に対して、０．３〜３質量％の範囲が好ましい。 The content of the polymerization initiator (D) is 0 with respect to the total amount of the vinyl ester resin (A) and the unsaturated monomer (B) because both the curing characteristics and the storage stability are excellent. The range of 3 to 3% by mass is preferable.
前記樹脂コンパウンドは、より高強度の成形品が得られることから、強化繊維（Ｅ）を含有することが好ましい。 The resin compound preferably contains reinforcing fibers (E) because a molded product having higher strength can be obtained.
前記強化繊維（Ｅ）としては、炭素繊維、ガラス繊維、炭化ケイ素繊維、アルミナ繊維、ボロン繊維、金属繊維、アラミド繊維、ビニロン繊維、テトロン繊維等の有機繊維などが挙げられるが、より高強度、高弾性の成形品が得られることから、炭素繊維又はガラス繊維が好ましく、炭素繊維がより好ましい。これらの強化繊維（Ｅ）は単独で用いることも、２種以上併用することもできる。 Examples of the reinforcing fiber (E) include organic fibers such as carbon fiber, glass fiber, silicon carbide fiber, alumina fiber, boron fiber, metal fiber, aramid fiber, vinylon fiber, and tetron fiber. Since a highly elastic molded product can be obtained, carbon fiber or glass fiber is preferable, and carbon fiber is more preferable. These reinforcing fibers (E) can be used alone or in combination of two or more.
前記ガラス繊維としては、例えば、含アルカリガラス、低アルカリガラス、無アルカリガラス等を原料にして得られたものを使用することができるが、経時劣化も少なく機械的特性が安定している無アルカリガラス（Ｅガラス）を使用することが好ましい。 As the glass fiber, for example, those obtained by using alkali-containing glass, low-alkali glass, non-alkali glass or the like as raw materials can be used, but the non-alkali fiber has little deterioration with time and has stable mechanical properties. It is preferable to use glass (E glass).
前記炭素繊維としては、ポリアクリロニトリル系、ピッチ系、レーヨン系などの各種のものが使用できるが、これらの中でも、容易に高強度の炭素繊維が得られることから、ポリアクリロニトリル系のものが好ましい。 As the carbon fibers, various types such as polyacrylonitrile-based, pitch-based, and rayon-based ones can be used, but among these, polyacrylonitrile-based ones are preferable because high-strength carbon fibers can be easily obtained.
前記強化繊維（Ｅ）としては、例えば、撚糸、紡糸、紡績加工、不織加工したものを使用することができる。また、前記強化繊維（Ｅ）の形状としては、フィラメント、ヤーン、ロービング、ストランド、チョップドストランド、フェルト、ニードルパンチ、クロス、ロービングクロス、ミルドファイバー、ナノファイバー等のものを使用することができる。 As the reinforcing fiber (E), for example, twisted yarn, spun, spun processed, and non-woven processed fibers can be used. Further, as the shape of the reinforcing fiber (E), filaments, yarns, rovings, strands, chopped strands, felts, needle punches, cloths, roving cloths, milled fibers, nanofibers and the like can be used.
また、前記強化繊維（Ｅ）として使用される繊維束のフィラメント数は、樹脂含浸性及び成形品の機械的物性がより向上することから、１，０００〜６０，０００の範囲が好ましい。 The number of filaments in the fiber bundle used as the reinforcing fiber (E) is preferably in the range of 1,000 to 60,000 because the resin impregnation property and the mechanical physical characteristics of the molded product are further improved.
前記強化繊維（Ｅ）としては、成形時の金型内流動性、成形品の外観及び機械的物性がより向上することから、２．５〜５０ｍｍの長さにカットした強化繊維が好ましく、５〜４０ｍｍにカットした強化繊維がより好ましい。 As the reinforcing fiber (E), a reinforcing fiber cut to a length of 2.5 to 50 mm is preferable because the fluidity in the mold at the time of molding, the appearance of the molded product and the mechanical characteristics are further improved. Reinforcing fibers cut to ~ 40 mm are more preferable.
本発明の繊維強化成形材料の成分中の、前記強化繊維（Ｅ）の含有率は、得られる成形品の機械的物性がより向上することから、２５〜８０質量％の範囲が好ましく、４０〜７０質量％の範囲がより好ましい。 The content of the reinforcing fiber (E) in the components of the fiber-reinforced molding material of the present invention is preferably in the range of 25 to 80% by mass, preferably 40 to 80% by mass, because the mechanical properties of the obtained molded product are further improved. The range of 70% by mass is more preferable.
また、本発明の繊維強化成形材料中の前記炭素繊維（Ｅ）は、繊維方向がランダムな状態で樹脂に含浸している。 Further, the carbon fibers (E) in the fiber-reinforced molding material of the present invention are impregnated with the resin in a state where the fiber directions are random.
前記樹脂コンパウンドの成分としては、前記ビニルエステル樹脂（Ａ）、前記不飽和単量体（Ｂ）、前記ポリイソシアネート（Ｃ）、前記重合開始剤（Ｄ）、前記強化繊維（Ｅ）以外のものを使用してもよく、例えば、前記ビニルエステル樹脂（Ａ）以外の熱硬化性樹脂、熱可塑性樹脂、重合禁止剤、硬化促進剤、充填剤、低収縮剤、離型剤、増粘剤、減粘剤、顔料、酸化防止剤、可塑剤、難燃剤、抗菌剤、紫外線安定剤、補強材、光硬化剤等を含有することができる。 The components of the resin compound include those other than the vinyl ester resin (A), the unsaturated monomer (B), the polyisocyanate (C), the polymerization initiator (D), and the reinforcing fibers (E). May be used, for example, a thermosetting resin other than the vinyl ester resin (A), a thermoplastic resin, a polymerization inhibitor, a curing accelerator, a filler, a low shrinkage agent, a mold release agent, a thickener, and the like. It can contain a thickener, a pigment, an antioxidant, a plastic agent, a flame retardant, an antibacterial agent, an ultraviolet stabilizer, a reinforcing material, a photocuring agent and the like.
前記熱硬化性樹脂としては、例えば、ビニルウレタン樹脂、不飽和ポリエステル樹脂、アクリル樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、フラン樹脂等が挙げられる。また、これらの熱硬化性樹脂は、単独で用いることも２種以上併用することもできる。 Examples of the thermosetting resin include vinyl urethane resin, unsaturated polyester resin, acrylic resin, epoxy resin, phenol resin, melamine resin, furan resin and the like. In addition, these thermosetting resins can be used alone or in combination of two or more.
前記熱可塑性樹脂としては、例えば、ポリアミド樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリカーボネート樹脂、ウレタン樹脂、ポリプロピレン樹脂、ポリエチレン樹脂、ポリスチレン樹脂、アクリル樹脂、ポリブタジエン樹脂、ポリイソプレン樹脂およびこれらを共重合等により変性させたものが挙げられる。また、これらの熱可塑性樹脂は、単独で用いることも２種以上併用することもできる。 Examples of the thermoplastic resin include polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, urethane resin, polypropylene resin, polyethylene resin, polystyrene resin, acrylic resin, polybutadiene resin, polyisoprene resin, and copolymerization thereof. Examples thereof include those modified by the above. In addition, these thermoplastic resins can be used alone or in combination of two or more.
前記重合禁止剤としては、例えば、ハイドロキノン、トリメチルハイドロキノン、ｐ−ｔ−ブチルカテコール、ｔ−ブチルハイドロキノン、トルハイドロキノン、ｐ−ベンゾキノン、ナフトキノン、ハイドロキノンモノメチルエーテル、フェノチアジン、ナフテン酸銅、塩化銅、ニトロキシラジカル等が挙げられる。これらの重合禁止剤は、単独で用いることも、２種以上を併用することもできる。 Examples of the polymerization inhibitor include hydroquinone, trimethylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, copper chloride, and nitroxy. Examples include radicals. These polymerization inhibitors may be used alone or in combination of two or more.
前記硬化促進剤としては、例えば、ナフテン酸コバルト、オクテン酸コバルト、オクテン酸バナジル、ナフテン酸銅、ナフテン酸バリウム等の金属石鹸類、バナジルアセチルアセテート、コバルトアセチルアセテート、鉄アセチルアセトネート等の金属キレート化合物が挙げられる。またアミン類として、Ｎ，Ｎ−ジメチルアミノ−ｐ−ベンズアルデヒド、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、Ｎ−エチル−ｍ−トルイジン、トリエタノールアミン、ｍ−トルイジン、ジエチレントリアミン、ピリジン、フェニルモルホリン、ピペリジン、ジエタノールアニリン等が挙げられる。これらの硬化促進剤は、単独で用いることも、２種以上を併用することもできる。 Examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octate, vanazyl octate, copper naphthenate, and barium naphthenate, and metal chelates such as vanadylacetyl acetate, cobalt acetylacetate, and iron acetylacetonate. Examples include compounds. As amines, N, N-dimethylamino-p-benzaldehyde, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N-ethyl-m-toluidine, triethanol Examples thereof include amines, m-toluidine, diethylenetriamine, pyridine, phenylmorpholin, piperidine, diethanolaniline and the like. These curing accelerators can be used alone or in combination of two or more.
前記充填剤としては、無機化合物、有機化合物があり、成形品の強度、弾性率、衝撃強度、疲労耐久性等の物性を調整するために使用できる。 Examples of the filler include inorganic compounds and organic compounds, which can be used to adjust physical properties such as strength, elastic modulus, impact strength, and fatigue durability of molded products.
前記無機化合物としては、例えば、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、マイカ、タルク、カオリン、クレー、セライト、アスベスト、バーライト、バライタ、シリカ、ケイ砂、ドロマイト石灰石、石こう、アルミニウム微粉、中空バルーン、アルミナ、ガラス粉、水酸化アルミニウム、寒水石、酸化ジルコニウム、三酸化アンチモン、酸化チタン、二酸化モリブデン、鉄粉等が挙げられる。 Examples of the inorganic compound include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, burlite, baryta, silica, silica sand, dolomite limestone, gypsum, aluminum fine powder, hollow balloon, and the like. Alumina, glass powder, aluminum hydroxide, cold water stone, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder and the like can be mentioned.
前記有機化合物としては、セルロース、キチン等の天然多糖類粉末や、合成樹脂粉末等があり、合成樹脂粉末としては、硬質樹脂、軟質ゴム、エラストマーまたは重合体（共重合体）などから構成される有機物の粉体やコアシェル型などの多層構造を有する粒子を使用できる。具体的には、ブタジエンゴムおよび／またはアクリルゴム、ウレタンゴム、シリコンゴム等からなる粒子、ポリイミド樹脂粉末、フッ素樹脂粉末、フェノール樹脂粉末などが挙げられる。これらの充填剤は、単独で用いることも、２種以上を併用することもできる。 Examples of the organic compound include natural polysaccharide powders such as cellulose and chitin, synthetic resin powders, and the like, and synthetic resin powders are composed of hard resins, soft rubbers, elastomers, polymers (copolymers), and the like. Particles having a multi-layer structure such as organic powder or core-shell type can be used. Specific examples thereof include particles made of butadiene rubber and / or acrylic rubber, urethane rubber, silicon rubber and the like, polyimide resin powder, fluororesin powder, phenol resin powder and the like. These fillers can be used alone or in combination of two or more.
前記離型剤としては、例えば、ステアリン酸亜鉛、ステアリン酸カルシウム、パラフィンワックス、ポリエチレンワックス、カルナバワックスなどが挙げられる。好ましくは、パラフィンワックス、ポリエチレンワックス、カルナバワックス等が挙げられる。これらの離型剤は、単独で用いることも、２種以上を併用することもできる。 Examples of the release agent include zinc stearate, calcium stearate, paraffin wax, polyethylene wax, carnauba wax and the like. Preferably, paraffin wax, polyethylene wax, carnauba wax and the like can be mentioned. These release agents can be used alone or in combination of two or more.
前記増粘剤としては、例えば、酸化マグネシウム、水酸化マグネシウム、酸化カルシウム、水酸化カルシウム等の金属酸化物や金属水酸化物など、アクリル樹脂系微粒子などが挙げられ、本発明の繊維強化成形材料の取り扱い性によって適宜選択できる。これらの増粘剤は、単独で用いることも、２種以上を併用することもできる。 Examples of the thickener include metal oxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, acrylic resin-based fine particles such as metal hydroxides, and the fiber-reinforced molding material of the present invention. It can be appropriately selected depending on the handleability of. These thickeners can be used alone or in combination of two or more.
本発明の製造方法から得られる成形材料としては、生産性に優れる観点及びデザイン多様性を有する成形性の観点から、シートモールディングコンパウンド（以下、「ＳＭＣ」と略記する。）又はバルクモールディングコンパウンド（以下、「ＢＭＣ」と略記する。）であることが好ましい。 The molding material obtained from the production method of the present invention includes a sheet molding compound (hereinafter abbreviated as “SMC”) or a bulk molding compound (hereinafter, abbreviated as “SMC”) or a bulk molding compound (hereinafter, abbreviated as “SMC”) from the viewpoint of excellent productivity and moldability having design diversity. , "BMC" is abbreviated.).
前記ＳＭＣの製造方法としては、通常のミキサー、インターミキサー、プラネタリーミキサー、ロール、ニーダー、押し出し機などの混合機を用いて、前記ビニルエステル樹脂（Ａ）、前記不飽和単量体（Ｂ）、前記ポリイソシアネート（Ｃ）、前記重合開始剤（Ｄ）等の各成分を混合・分散し、得られた樹脂組成物を上下に設置されたキャリアフィルムに均一な厚さになるように塗布し、前記強化繊維（Ｅ）を前記上下に設置されたキャリアフィルム上の樹脂組成物で挟み込み、次いで、全体を含浸ロールの間に通して、圧力を加えて前記強化繊維（Ｅ）に樹脂組成物を含浸させた後、ロール状に巻き取る又はつづら折りに畳む方法等が挙げられる。さらに、この後に、増粘工程として、１０〜６０℃の温度で、２〜４８時間熟成させることにより、ＳＭＣが得られる。 As a method for producing the SMC, the vinyl ester resin (A) and the unsaturated monomer (B) are produced by using a mixer such as an ordinary mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder. , The polyisocyanate (C), the polymerization initiator (D) and the like are mixed and dispersed, and the obtained resin composition is applied to the carrier films placed on the upper and lower sides so as to have a uniform thickness. , The reinforcing fiber (E) is sandwiched between the resin compositions on the carrier films installed above and below, and then the whole is passed between the impregnated rolls, and pressure is applied to the reinforcing fiber (E). After impregnating with the resin, a method of winding it into a roll or folding it into a zigzag fold can be mentioned. Further, after this, as a thickening step, SMC is obtained by aging at a temperature of 10 to 60 ° C. for 2 to 48 hours.
前記増粘工程は、成形材料の取り扱い性（フィルム剥離性及びタック性）が、湿度条件等によらず、安定的に優れたものとなるため、樹脂コンパウンドを蒸着フィルムで梱包し、該蒸着フィルム内で行うこと重要である。 In the thickening step, the handleability (film peelability and tackiness) of the molding material becomes stable and excellent regardless of the humidity conditions, etc. Therefore, the resin compound is packed with a thin-film deposition film, and the vapor-deposited film is packed. It is important to do it within.
前記蒸着フィルムは、取り扱い性（フィルム剥離性及びタック性）が、より安定的に優れたものとなることから、水蒸気透過度が２．０ｇ／ｍ２／ｄａｙ（温度４０℃、湿度９０％ＲＨ）以下であるものが好ましく、１．５ｇ／ｍ２／ｄａｙ（温度４０℃、湿度９０％ＲＨ）以下であるものがより好ましい。 Since the vapor-filmed film has excellent handleability (film peelability and tackiness) in a more stable manner, the water vapor permeability is 2.0 g / m 2 / day (temperature 40 ° C., humidity 90% RH). ) Or less, and more preferably 1.5 g / m 2 / day (temperature 40 ° C., humidity 90% RH) or less.
また、前記蒸着フィルムは、ガスバリア性と防湿性、遮光性、保香性などに優れ、ラミネート特性も良く、折り曲げなどによるピンホールが発生しづらいことから、アルミ蒸着フィルムであることが好ましい。 Further, the thin-film vapor-deposited film is preferably an aluminum-film-deposited film because it is excellent in gas barrier property, moisture-proof property, light-shielding property, aroma-retaining property, etc.
蒸着フィルムにより本態様のＳＭＣが梱包される梱包形態は、特に限定されないが、例えば、本態様のＳＭＣが枚葉であれば、蒸着フィルムの梱包内に枚葉のＳＭＣが真空封入された梱包形態、蒸着フィルムの梱包内に枚葉のＳＭＣが封入され、梱包内がドライエアや乾燥窒素で充填された梱包形態等とすることができる。また、本態様のＳＭＣがロール状に巻回されたＳＭＣであれば、蒸着フィルムで上記ＳＭＣロールが覆われており、内部が真空脱気された梱包形態や上記内部がドライエアや乾燥窒素で充填された梱包形態等とすることができる。梱包内には、公知の乾燥剤が入っていてもよい。 The packaging form in which the SMC of this embodiment is packed by the vapor-deposited film is not particularly limited. , The single-wafered SMC is enclosed in the package of the thin-film deposition film, and the inside of the package can be filled with dry air or dry nitrogen. Further, if the SMC of this embodiment is an SMC wound in a roll shape, the SMC roll is covered with a vapor-deposited film, and the inside is evacuated and the inside is filled with dry air or dry nitrogen. It can be in a packaged form or the like. A known desiccant may be contained in the package.
前記ＢＭＣの製造方法としては、前記ＳＭＣの製造方法と同様に、通常のミキサー、インターミキサー、プラネタリーミキサー、ロール、ニーダー、押し出し機などの混合機を用いて、前記ビニルエステル樹脂（Ａ）、前記不飽和単量体（Ｂ）、前記ポリイソシアネート（Ｃ）、前記重合開始剤（Ｄ）等の各成分を混合・分散し、得られた樹脂組成物に前記強化繊維（Ｅ）を混合・分散させる方法等が挙げられる。さらに、この後に、上記したＳＭＣと同様に、増粘工程として、蒸着フィルム梱包材内で１０〜６０℃の温度で、２〜４８時間熟成させることにより、ＢＭＣが得られる。 As the method for producing the BMC, the vinyl ester resin (A) can be produced by using a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder in the same manner as the method for producing the SMC. Each component such as the unsaturated monomer (B), the polyisocyanate (C), and the polymerization initiator (D) is mixed and dispersed, and the reinforcing fiber (E) is mixed with the obtained resin composition. Examples include a method of dispersing. Further, after this, as in the SMC described above, BMC is obtained by aging in the vapor-deposited film packing material at a temperature of 10 to 60 ° C. for 2 to 48 hours as a thickening step.
本発明の成形品は、前記成形材料より得られるが、生産性に優れる点とデザイン多様性に優れる観点からその成形方法としては、ＳＭＣ又はＢＭＣの加熱圧縮成形が好ましい。 The molded product of the present invention can be obtained from the above-mentioned molding material, but from the viewpoint of excellent productivity and excellent design diversity, heat compression molding of SMC or BMC is preferable as the molding method.
前記加熱圧縮成形としては、例えば、ＳＭＣ、ＢＭＣ等の成形材料を所定量計量し、予め１１０〜１８０℃に加熱した金型に投入し、圧縮成形機にて型締めを行い、成形材料を賦型させ、０．１〜３０ＭＰａの成形圧力を保持することによって、成形材料を硬化させ、その後成形品を取り出し成形品を得る製造方法が用いられる。具体的な成形条件としては、金型内で金型温度１２０〜１６０℃にて、成形品の厚さ１ｍｍ当たり１〜５分間、１〜１５ＭＰａの成形圧力を保持する成形条件が好ましく、生産性がより向上することから、金型温度１４０〜１６０℃にて、成形品の厚さ１ｍｍ当たり１〜３分間、１〜１５ＭＰａの成形圧力を保持する成形条件がより好ましい。 In the heat compression molding, for example, a predetermined amount of a molding material such as SMC or BMC is weighed, put into a mold preheated to 110 to 180 ° C., molded by a compression molding machine, and the molding material is applied. A manufacturing method is used in which a molding material is cured by molding and holding a molding pressure of 0.1 to 30 MPa, and then the molded product is taken out to obtain a molded product. As specific molding conditions, molding conditions in which the molding pressure of 1 to 15 MPa is maintained in the mold at a mold temperature of 120 to 160 ° C. for 1 to 5 minutes per 1 mm of thickness of the molded product is preferable, and productivity is preferable. More preferably, the molding conditions are such that the molding pressure of 1 to 15 MPa is maintained for 1 to 3 minutes per 1 mm of the thickness of the molded product at a mold temperature of 140 to 160 ° C.
本発明の製造方法により得られる成形材料を用いた成形品は、外観、曲げ強さ、曲げ弾性率等に優れることから、自動車部材、鉄道車両部材、航空宇宙機部材、船舶部材、住宅設備部材、スポーツ部材、軽車両部材、建築土木部材、ＯＡ機器等の筐体等に好適に用いることができる。 A molded product using a molding material obtained by the manufacturing method of the present invention is excellent in appearance, bending strength, flexural modulus, etc., and therefore, therefore, an automobile member, a railroad vehicle member, an aerospace machine member, a ship member, a housing equipment member, etc. , Sports members, light vehicle members, building civil engineering members, housings for OA equipment, etc.
以下に本発明を具体的な実施例を挙げてより詳細に説明する。なお、水酸基価は、樹脂試料１ｇをＪＩＳ Ｋ−００７０の規定の方法に基づきアセチル化剤を用いて、規定温度及び時間で反応させた時に生成した酢酸を中和するのに要する水酸化カリウムのミリグラム数（ｍｇＫＯＨ／ｇ）を測定した。 Hereinafter, the present invention will be described in more detail with reference to specific examples. The hydroxyl value of potassium hydroxide required to neutralize acetic acid produced when 1 g of a resin sample was reacted at a specified temperature and time using an acetylating agent based on the method specified in JIS K-0070. The number of milligrams (mgKOH / g) was measured.
（合成例１：ビニルエステル樹脂（Ａ−１）の合成）
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８６０」、ビスフェノールＡ型エポキシ樹脂、エポキシ当量 ２２０） ７２５質量部、メタクリル酸 ２８４質量部、及びｔ−ブチルハイドロキノン ０．２８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 ０．６０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 ２１５ｍｇＫＯＨ／ｇのビニルエステル樹脂（Ａ−１）を得た。
(Synthesis Example 1: Synthesis of Vinyl Ester Resin (A-1))
In a 2L flask equipped with a thermometer, a nitrogen introduction tube, and a stirrer, 725 parts by mass of epoxy resin (“Epiclon 860” manufactured by DIC Corporation, bisphenol A type epoxy resin, epoxy equivalent 220), 284 parts by mass of methacrylic acid, and t. -Butylhydroquinone 0.28 parts by mass was charged, and the temperature was raised to 90 ° C. under a gas flow in which nitrogen and air were mixed 1: 1. When 0.60 parts by mass of 2-methylimidazole was added thereto, the temperature was raised to 110 ° C. and the reaction was carried out for 10 hours, the acid value became 6 or less, and the reaction was terminated. After cooling to around 60 ° C., the mixture was taken out from the reaction vessel to obtain a vinyl ester resin (A-1) having a hydroxyl value of 215 mgKOH / g.
（実施例１：成形材料（１）の製造及び評価）
合成例１で得たビニルエステル樹脂（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、ポリイソシアネート（ＢＡＳＦ社製「ルプラネートＭＩ」、芳香族ポリイソシアネート；以下、「ポリイソシアネート（Ｃ−１）」と略記する。）２２．０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（Ｄ−１）」と略記する。）１．２質量部、及び重合禁止剤（パラベンゾキノン；以下、重合禁止剤（１）と略記する。）０．０３５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０．８３であった。
(Example 1: Production and evaluation of molding material (1))
Polyisocyanate (“Luplanate MI” manufactured by BASF, aromatic polyisocyanate) was added to 100 parts by mass of a resin solution prepared by dissolving 55 parts by mass of the vinyl ester resin (A-1) obtained in Synthesis Example 1 in 45 parts by mass of phenoxyethyl methacrylate. (Hereinafter abbreviated as "polyisocyanate (C-1)") 22.0 parts by mass, and a polymerization initiator ("Kayacarboxylic AIC-75" manufactured by Chemical Axo Co., Ltd., organic peroxide; hereinafter, "polymerization" Initiator (D-1) "is abbreviated.) 1.2 parts by mass and 0.035 parts by mass of a polymerization inhibitor (parabenzoquinone; hereinafter abbreviated as polymerization inhibitor (1)) are mixed to form a resin. The composition (X-1) was obtained. The molar ratio (NCO / OH) in this resin composition (X-1) was 0.83.
上記で得られた樹脂組成物（Ｘ−１）を、ポリエチレン及びポリプロピレンのラミネートフィルム上に塗布量が平均０．５ｋｇ／ｍ２となるよう塗布し、この上に、炭素繊維ロービング（東レ株式会社製「Ｔ７００ＳＣ−１２０００−５０Ｃ」）を２５ｍｍにカットした炭素繊維（以下、炭素繊維（Ｅ−１）と略記する。）を繊維方向性が無く厚みが均一で炭素繊維含有率が５０質量％になるよう空中から均一落下させ、上記と同様に樹脂組成物（Ｘ−１）を０．５ｋｇ／ｍ２となるよう塗布したフィルムで挟み込み炭素繊維に樹脂を含浸させ、シート状の樹脂コンパウンド（１）を得た。このシート状の樹脂コンパウンド（１）（１ｍ×１ｍ）を、アルミ蒸着フィルム（中井工業株式会社製「メタライトＭ−Ｎ−１」、水蒸気透過度：１．１ｇ／ｍ２／ｄａｙ（温度４０℃、湿度９０％ＲＨ））で梱包、密閉し、温度４０℃、相対湿度４０％の恒温機中に２０時間放置し、シート状の成形材料（１）を得た。このシート状の成形材料（１）の目付け量は、２ｋｇ／ｍ２であり、厚さは２ｍｍであった。 The resin composition (X-1) obtained above was applied onto a polyethylene and polypropylene laminated film so that the average coating amount was 0.5 kg / m 2, and carbon fiber roving (Toray Co., Ltd.) was applied thereto. A carbon fiber (hereinafter abbreviated as carbon fiber (E-1)) obtained by cutting a product "T700SC-12000-50C") to 25 mm has no fiber directionality, a uniform thickness, and a carbon fiber content of 50% by mass. The resin composition (X-1) is sandwiched between films coated at 0.5 kg / m 2 in the same manner as above, and the carbon fibers are impregnated with the resin so that the carbon fibers are uniformly dropped from the air so that the carbon fibers are impregnated with the resin. ) Was obtained. This sheet-shaped resin compound (1) (1 m × 1 m) is applied to an aluminum vapor-deposited film (“Metalite MN-1” manufactured by Nakai Industrial Co., Ltd., water vapor permeability: 1.1 g / m 2 / day (temperature 40 ° C.). , Humidity 90% RH)), sealed, and left in a thermostat at a temperature of 40 ° C. and a relative humidity of 40% for 20 hours to obtain a sheet-shaped molding material (1). The basis weight of the sheet-shaped molding material (1) was 2 kg / m 2 , and the thickness was 2 mm.
［取り扱い性（フィルム剥ぎ性）の評価］
上記で得られた成形材料（１）をポリエチレン及びポリプロピレンのラミネートフィルムフィルムから剥がす際の取り扱い性を下記の基準に従って評価した。
○：フィルムに樹脂の付着がなし
△：フィルムに樹脂の付着が少しあり
×：フィルムに樹脂の付着があり
[Evaluation of handleability (film peelability)]
The handleability of the molding material (1) obtained above when peeled from the polyethylene and polypropylene laminated film films was evaluated according to the following criteria.
◯: No resin adhered to the film Δ: Some resin adhered to the film ×: Resin adhered to the film
［取り扱い性（タック性）の評価］
上記で得られた成形材料（１）を室温でフィルムから剥がした後のタック性を下記の基準に従って評価した。
○：指に成形材料の付着がなし
△：指に成形材料の付着が少しあり
×：指に成形材料の付着があり
[Evaluation of handleability (tackiness)]
The tackiness after peeling the molding material (1) obtained above from the film at room temperature was evaluated according to the following criteria.
◯: No molding material adhered to the finger △: Molding material adhered slightly to the finger ×: Molding material adhered to the finger
［成形品の作製］
上記で得られたシート状の繊維強化成形材料（１）をフィルムから剥離し、２６．５ｃｍ×２６．５ｃｍにカットしたものを３枚重ね、３０×３０ｃｍ２の平板金型の中央部にセットし、プレス金型温度１５０℃、プレス時間５分間、プレス圧力１２ＭＰａで成形し、厚さ３ｍｍの平板状の成形品（１）を得た。
[Manufacturing of molded products]
The sheet-shaped fiber-reinforced molding material (1) obtained above was peeled off from the film, three pieces cut into 26.5 cm × 26.5 cm were stacked, and set in the center of a 30 × 30 cm 2 flat plate mold. Then, the product was molded at a press die temperature of 150 ° C., a press time of 5 minutes, and a press pressure of 12 MPa to obtain a flat plate-shaped molded product (1) having a thickness of 3 mm.
［曲げ強さ・曲げ弾性率の評価］
上記で得られた成形品（１）のうち、左半分（１５ｃｍ×３０ｃｍ）から水平方向及び垂直方向にサンプルを５本ずつ切り出し、ＪＩＳ Ｋ７０７４に準拠し、３点曲げ試験を行い、曲げ強さ、曲げ弾性率を測定した。
[Evaluation of flexural strength and flexural modulus]
Of the molded product (1) obtained above, five samples were cut out from the left half (15 cm x 30 cm) in the horizontal and vertical directions, and a three-point bending test was performed in accordance with JIS K7074 to perform a bending strength. , The flexural modulus was measured.
（比較例１：成形材料（Ｒ１）の作製及び評価）
シート状の樹脂コンパウンド（１）をアルミ蒸着フィルムで梱包しなかった以外は、実施例１と同様にして、シート状の成形材料（Ｒ１）を得た。このシート状の成形材料（Ｒ１）の目付け量は、２ｋｇ／ｍ２であり、厚さは２ｍｍであった。
さらに、シート状の成形材料（１）を、シート状の成形材料（Ｒ１）に変更した以外は、実施例１と同様に操作し、厚さ３ｍｍの平板上の成形品（Ｒ１）を作製し、各評価を行った。
(Comparative Example 1: Preparation and Evaluation of Molding Material (R1))
A sheet-shaped molding material (R1) was obtained in the same manner as in Example 1 except that the sheet-shaped resin compound (1) was not packed with an aluminum-deposited film. The basis weight of this sheet-shaped molding material (R1) was 2 kg / m 2 , and the thickness was 2 mm.
Further, the same operation as in Example 1 was performed except that the sheet-shaped molding material (1) was changed to the sheet-shaped molding material (R1) to prepare a molded product (R1) on a flat plate having a thickness of 3 mm. , Each evaluation was performed.
上記で得られた成形材料（１）及び（Ｒ１）の評価結果を表１に示す。 Table 1 shows the evaluation results of the molding materials (1) and (R1) obtained above.
実施例１の本発明の成形材料は、取り扱い性に優れ、得られる成形品は曲げ強さ及び曲げ弾性率に優れることが確認された。 It was confirmed that the molding material of the present invention of Example 1 was excellent in handleability, and the obtained molded product was excellent in bending strength and flexural modulus.
一方、比較例１は、増粘工程において、蒸着フィルム梱包材を使用しなかった例であるが、取り扱い性が劣ることが確認された。 On the other hand, Comparative Example 1 was an example in which the vapor-deposited film packing material was not used in the thickening step, but it was confirmed that the handleability was inferior.
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|---|---|---|---|---|
| JP2001240815A (en) * | 2000-02-25 | 2001-09-04 | Nippon Shokubai Co Ltd | Method of producing double-layered material |
| JP2019099609A (en) * | 2017-11-29 | 2019-06-24 | Dic株式会社 | Fiber-reinforced molding material and molded article using the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023089999A1 (en) * | 2021-11-18 | 2023-05-25 | Dic株式会社 | Radical curable resin composition, fiber-reinforced molding material, and molded article using same |
| JP7298800B1 (en) * | 2021-11-18 | 2023-06-27 | Dic株式会社 | Radical-curable resin composition, fiber-reinforced molding material, and molded article using the same |
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