JPH11147965A - Fiber-reinforced resin composite and prepreg - Google Patents
Fiber-reinforced resin composite and prepregInfo
- Publication number
- JPH11147965A JPH11147965A JP33358097A JP33358097A JPH11147965A JP H11147965 A JPH11147965 A JP H11147965A JP 33358097 A JP33358097 A JP 33358097A JP 33358097 A JP33358097 A JP 33358097A JP H11147965 A JPH11147965 A JP H11147965A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- resin
- composite material
- epoxy resin
- reinforced
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000805 composite resin Substances 0.000 title claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 52
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 230000009477 glass transition Effects 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 7
- 239000011229 interlayer Substances 0.000 claims abstract description 3
- 230000006835 compression Effects 0.000 claims abstract 2
- 238000007906 compression Methods 0.000 claims abstract 2
- 230000002787 reinforcement Effects 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 37
- 239000000835 fiber Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 239000004697 Polyetherimide Substances 0.000 claims description 8
- 229920001601 polyetherimide Polymers 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- -1 urethane modified bisphenol A Chemical class 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 229920002312 polyamide-imide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 239000012783 reinforcing fiber Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 13
- 238000010998 test method Methods 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- 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 9
- 239000003063 flame retardant Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 7
- 229920003319 Araldite® Polymers 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 4
- 239000003733 fiber-reinforced composite Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920004747 ULTEM® 1000 Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000007689 inspection Methods 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
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011208 reinforced composite material Substances 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐着火性、難燃性
に優れ、しかも耐衝撃性に優れた繊維強化樹脂複合材料
及び該繊維強化樹脂複合材料を得るためのプリプレグに
関する。更に詳しくは、鉄道車両等の交通機関に使用す
るのに好適な繊維強化エポキシ樹脂複合材料及びプリプ
レグに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced resin composite material having excellent ignition resistance, flame retardancy and impact resistance, and a prepreg for obtaining the fiber-reinforced resin composite material. More specifically, the present invention relates to a fiber-reinforced epoxy resin composite material and a prepreg suitable for use in transportation such as railway vehicles.
【０００２】[0002]
【従来の技術】炭素繊維を強化材とした樹脂との複合材
料は、その優れた機械的特性からスポーツ用品を初めと
して産業資材、交通機関等の分野に利用されてきてい
る。特に航空宇宙分野、車両分野等を対象とした分野で
は、各種エポキシ樹脂を主成分としたマトリックス樹脂
との複合材料が開発されてきているが、近年、特に難燃
性・耐衝撃性の向上が強く要望されるようになってきて
いる。2. Description of the Related Art Composite materials with carbon fiber-reinforced resins have been used in the fields of sports goods, industrial materials, transportation, etc. due to their excellent mechanical properties. Especially in the fields of aerospace and vehicles, composite materials with matrix resins containing various epoxy resins as main components have been developed. There is a strong demand.
【０００３】従来、エポキシ樹脂をマトリックスとした
繊維強化複合材料の難燃化方法としては、 ａ．ハロゲン化エポキシ樹脂をマトリックスに配合する
繊維強化複合材料の難燃化方法（例えば、特開昭５５−
９２７５７号公報）； ｂ．ハロゲン化合物、リン化合物等の添加物をマトリッ
クスに配合する繊維強化複合材料の難燃化方法； ｃ．水酸化アルミニウム等の無機質充填材をマトリック
スに配合する繊維強化複合材料の難燃化方法（例えば、
特開平１−１９７５５４号公報）；等が知られている。[0003] Conventionally, methods for flame retarding fiber-reinforced composite materials using an epoxy resin as a matrix include: a. Flame-retardant methods for fiber-reinforced composite materials in which a halogenated epoxy resin is blended in a matrix (see, for example,
No. 92775); b. A method for flame retarding a fiber reinforced composite material in which additives such as a halogen compound and a phosphorus compound are blended in a matrix; c. Flame-retardant methods for fiber-reinforced composite materials in which an inorganic filler such as aluminum hydroxide is blended in the matrix (for example,
JP-A-1-197554); and the like.
【０００４】上記ａ〜ｃの難燃化方法の対象物は強化繊
維とマトリックス樹脂との積層物からなる複合材料であ
り、燃焼時に対象物から発生するハロゲンガスや水蒸気
等によって、複合材料と空気とを遮断し、酸素の供給を
止め、複合材料の燃焼を制御しようとする方法である。
また、無機粉末成分添加によって、有機成分いわゆる可
燃成分を少なくし、燃焼を制御する方法である。The object of the flame-retarding methods a to c is a composite material composed of a laminate of a reinforcing fiber and a matrix resin. To stop the supply of oxygen and control the combustion of the composite material.
In addition, this is a method of controlling combustion by reducing an organic component, that is, a combustible component, by adding an inorganic powder component.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、複合材
料は、一般に薄い材料の積層物であるため、上記の積層
物と空気とを遮断する手法によると、対象物である複合
材料が熱に暴露した時に、複合材料の表層付近の層間に
気泡が生じ、積層前の各単位である薄い各積層材に剥離
し、その結果、薄い積層材に着火し、燃焼初期に表層が
燃焼し、ついで対象物から発生するハロゲンガスや水蒸
気等によって、空気を遮断する現象を生ずる。However, since the composite material is generally a laminate of a thin material, according to the above-described technique of shutting off the laminate and the air, the composite material as an object is exposed to heat. Occasionally, air bubbles are generated between layers near the surface layer of the composite material, and peeled off into thin laminated materials that are each unit before lamination, and as a result, the thin laminated material is ignited, and the surface layer is burned in the early stage of combustion, and then the target object is burned. Halogen gas or water vapor generated from the air causes a phenomenon of shutting off air.
【０００６】このように一端着火すると、燃焼によるガ
スバリアを生じ難燃化目的が達成されるが、この際に生
ずるハロゲンガスや燃焼ガスによって人体に悪影響を及
ぼす結果となる。[0006] When the ignition is performed once as described above, a gas barrier due to combustion is generated to achieve the purpose of flame retardation, but the halogen gas and the combustion gas generated at this time have a bad effect on the human body.
【０００７】交通機関用の材料では、まず着火しないこ
とが重要であり、運輸省鉄運８１号でも耐着火性の判定
基準を定め、材料の耐着火性を求めている。[0007] It is important that a material for transportation use is not ignited first, and the Ministry of Transport, Iron Transportation No. 81 also sets a criterion for determining the ignition resistance and seeks the ignition resistance of the material.
【０００８】また、上述のように、火災の初期段階での
熱暴露によって積層物内にガスを生じると、機械的特
性、特に衝撃後の強度が極端に低下し、難燃化の目的は
達成されても、内部構造材として機能し得ないという問
題を生ずる。Further, as described above, when gas is generated in the laminate by heat exposure at an early stage of a fire, mechanical properties, particularly strength after impact, are extremely reduced, and the object of flame retardancy is achieved. Even if it is performed, there arises a problem that it cannot function as an internal structural material.
【０００９】また、上記ａ．ｂ．の手法では、特開昭５
５−９２７５７号公報等で指摘されているように、臭素
含有エポキシ樹脂の配合割合が多くなると、熱暴露前で
も機械的特性、耐熱性に優れた樹脂組成物が得難くなる
という問題を有する。Further, in the above a. b. In the method of
As pointed out in, for example, Japanese Patent Application Laid-Open No. 5-92757, there is a problem that it becomes difficult to obtain a resin composition having excellent mechanical properties and heat resistance even before exposure to heat, when the proportion of the bromine-containing epoxy resin is increased.
【００１０】また、上記ｃ．の手法では、特開平１−１
９７５５４号公報等で指摘されているように、水酸化ア
ルミニウム等の無機質充填材の配合割合が多くなるとチ
クソトロピー性が増し、成形性が不良になる。且つ、機
械的特性も大きく低下してしまう。無機成分の投入によ
る方法では、やはり機械的特性が大きく低下してしま
う。The above c. According to the method described in
As pointed out in Japanese Patent No. 97554 and the like, when the blending ratio of the inorganic filler such as aluminum hydroxide increases, the thixotropy increases and the moldability deteriorates. In addition, the mechanical properties are greatly reduced. In the method based on the addition of the inorganic component, the mechanical properties are also greatly reduced.
【００１１】そこで本発明は、火災暴露によっても着火
せず、熱暴露時にもハロゲンガス、水蒸気等の分解ガス
を発生せず、しかも、熱暴露後の機械的性質が良好で、
成形性にも優れた炭素繊維強化複合材料及び該繊維強化
樹脂複合材料を得るためのプリプレグを提供することを
目的とする。Therefore, the present invention does not ignite even by fire exposure, does not generate decomposition gases such as halogen gas and water vapor upon heat exposure, and has good mechanical properties after heat exposure.
An object of the present invention is to provide a carbon fiber reinforced composite material excellent in moldability and a prepreg for obtaining the fiber reinforced resin composite material.
【００１２】[0012]
【課題を解決するための手段】前記した問題点を解決す
るために本発明は、繊維強化材とマトリックス樹脂から
なる繊維強化樹脂複合材料であって、後述する運輸省鉄
運８１号に準処した着火試験で実質的に着火せず、しか
も後述する熱暴露試験後において、衝撃後圧縮強度が１
５ｋｇｆ／ｍｍ2 以上、層間剪断強度が７ｋｇｆ／ｍｍ
2 以上であることを特徴とする繊維強化樹脂複合材料で
あり、さらにまた、この複合材料を製造するためのプリ
プレグである。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention relates to a fiber reinforced resin composite material comprising a fiber reinforced material and a matrix resin. Did not substantially ignite in the ignited test, and had a compressive strength after impact of 1 after the heat exposure test described later.
5 kgf / mm 2 or more, interlayer shear strength is 7 kgf / mm
It is a fiber-reinforced resin composite material characterized by being 2 or more, and further a prepreg for producing this composite material.
【００１３】本発明の繊維強化樹脂複合材料は、ガス自
体の発生を抑え、着火自体を阻止しようとするものであ
り、従来の難燃化手段の技術思想、即ち、燃焼時にハロ
ゲンガス、水蒸気等を発生させることによって燃焼物と
空気とを遮断し、これによって難燃化の目的を達成する
という技術思想とは、発想自体を異にする。The fiber-reinforced resin composite material of the present invention is intended to suppress the generation of gas itself and to prevent ignition itself. Therefore, the technical concept of the conventional flame-retardant means, that is, halogen gas, water vapor and the like during combustion. The idea itself is different from the technical idea of shutting off the combustion material and the air by generating the gas, thereby achieving the purpose of flame retardancy.
【００１４】本発明の繊維強化樹脂複合材料は上記の着
火しない性質に加え、耐衝撃性にも優れた効果を発揮す
る。このような繊維強化樹脂複合材料は、自動車用材料
や鉄道車両用材料の用途に好適である。The fiber-reinforced resin composite material of the present invention exerts excellent effects on impact resistance in addition to the above property of not igniting. Such a fiber-reinforced resin composite material is suitable for use as a material for automobiles and a material for railway vehicles.
【００１５】本発明において熱暴露試験、着火試験、耐
衝撃試験、層間剪断強度試験、ガラス転移温度測定等の
各種の試験は下記の方法に従う。In the present invention, various tests such as a heat exposure test, an ignition test, an impact resistance test, an interlaminar shear strength test, and a measurement of a glass transition temperature are performed according to the following methods.
【００１６】熱暴露試験 衝撃後圧縮試験及び層間剪断試験用の試験片を機械的特
性を測定する前に、２５０℃に加熱されたオーブンに１
０分間静置し、熱暴露後の剥離の有無を超音波探傷機で
測定する。各試験に用いられる試料の寸法は後述の各試
験における規格に準処する。 Heat exposure test Specimens for compression test after impact and interlaminar shear test were placed in an oven heated to 250 ° C. before measuring mechanical properties.
After leaving still for 0 minutes, the presence or absence of peeling after heat exposure is measured by an ultrasonic flaw detector. The dimensions of the sample used in each test conform to the standards in each test described later.
【００１７】着火試験 運輸省鉄運８１号に準処した着火試験を行う。試料の厚
みについては２ｍｍとする。[0017] performing the ignition test was Junsho to ignition test Ministry of Transport Tetsuun 81 issue. The thickness of the sample is 2 mm.
【００１８】鉄運８１号に規定の着火試験は次の内容か
らなる。Ｂ５判の試料を４５°に傾斜させて保持し、試
料下面の中心の垂直下２５．４ｍｍのところに容器の中
心がくるように燃料容器を受台に乗せ、エチルアルコー
ル０．５ｃｃを入れて着火し、燃料が燃え尽きるまで放
置する。燃焼性の判定はアルコールの燃焼中と燃焼後に
分け、燃焼中は着火、着炎、発煙状態、炎の状態を観察
し、燃焼後は、残炎、残じん、炭化、変形状態を調べ
る。[0018] The ignition test specified in Tetsu-No-81 consists of the following contents. A sample of B5 size is held at an inclination of 45 °, and the fuel container is placed on a pedestal so that the center of the container is located 25.4 mm below the center of the lower surface of the sample, and 0.5 cc of ethyl alcohol is put in the pedestal. Ignite and leave until fuel burns out. The determination of flammability is divided into during and after burning of alcohol. During burning, the ignition, ignition, smoke state, and flame state are observed, and after combustion, the after-flame, dust, carbonization, and deformation are examined.
【００１９】上記観察結果が、例えば、「着火」あり、
「着炎」あり、「煙」普通、「火勢」炎が試験片の上端
を越えない、「残炎」なし、「残じん」なし、「炭化」
試験片の上端に達する、「変形」縁に達する変形・局部
的貫通であれば、その判定結果は「難燃性」となる。ま
た、「着火」なし、「着炎」なし、「煙」僅少、「炭
化」１００ｍｍ以下の変色、「変形」１００ｍｍ以下の
表面的変形であれば、「不燃性」となる。If the above observation result is, for example, “ignition”,
There is "flaming", "smoke" is normal, "fire" flame does not exceed the upper end of the test piece, "no residual flame", "no residual dust", "carbonized"
If the deformation / local penetration reaches the “deformed” edge reaching the upper end of the test piece, the determination result is “flame retardant”. If there is no "ignition", no "flame", little "smoke", "carbonization" discoloration of 100 mm or less, and "deformation" surface deformation of 100 mm or less, it is "nonflammable".
【００２０】尚、鉄運８１号は、英著「プラスチックの
難燃化−低発煙化と有害燃焼ガス対策」日刊工業新聞
（１９７８）及び西沢著「増補新版ポリマーの難燃化−
その科学と実際技術」大成社（１９９２）に詳説されて
いる。Incidentally, Tetsu-kun No. 81 is described in the English-language book "Plastic Flame Retardation-Smoke Reduction and Countermeasures against Hazardous Combustion Gases", Nikkan Kogyo Shimbun (1978) and Nishizawa, "Flame-retardant New Polymers-
"Science and Practical Technology", Taiseisha (1992).
【００２１】次の垂直燃焼試験と水平燃焼試験は、燃焼
性を定量的に評価するためのＵＬ９４規格に準拠した燃
焼試験である。The following vertical combustion test and horizontal combustion test are combustion tests based on UL94 standard for quantitatively evaluating flammability.
【００２２】垂直燃焼試験 垂直燃焼試験は、難燃性を定量的に評価するためのもの
であり、ＵＬ９４規格に準処した燃焼試験である。その
試験方法は次のようにして行う。 Vertical Burning Test The vertical burning test is for quantitatively evaluating the flame retardancy, and is a combustion test conforming to the UL94 standard. The test method is performed as follows.
【００２３】試料寸法は１２７ｍｍ×１２．７ｍｍ×４
ｍｍとする。ブンゼンバーナーによる火炎を取り去った
後、消火までの平均時間が５秒以内なら９４Ｖ−０、２
５秒以内なら９４Ｖ−１となる。平均時間が２５秒以内
でも有炎滴下物がある場合は、９４Ｖ−２となる。垂直
燃焼試験に合格しない場合は、ＵＬ９４規格に準処する
水平燃焼試験を行う。The sample size is 127 mm × 12.7 mm × 4
mm. 94V-0, 2 if the average time to extinguishing after removing the flame by the Bunsen burner is within 5 seconds.
If within 5 seconds, it will be 94V-1. If there is a flaming drop even if the average time is within 25 seconds, it will be 94V-2. If the test does not pass the vertical combustion test, a horizontal combustion test according to the UL94 standard is performed.
【００２４】水平燃焼試験 試料寸法は１２７ｍｍ×１２．７ｍｍ×４ｍｍとする。
ブンゼンバーナーによる火炎を取り去った後の燃焼速度
が３８ｍｍ／分以下ならば、９４ＨＢとなる。The sample size for the horizontal combustion test is 127 mm × 12.7 mm × 4 mm.
If the burning speed after removing the flame by the Bunsen burner is 38 mm / min or less, it will be 94 HB.
【００２５】耐衝撃試験（衝撃後の強度試験） プリプレグを３２枚擬似等方的に積層し、成形した後、
成形板に１０００ｉｎ−ｌｂ／ｉｎの落錘衝撃エネルギ
ーを与え、衝撃後圧縮強度を測定する。 Impact resistance test (strength test after impact) After quasi-isotropically laminating 32 prepregs and molding them,
A falling weight impact energy of 1000 in-lb / in is applied to the formed plate, and the compressive strength after impact is measured.
【００２６】層間剪断強度試験 プリプレグ１４枚を一方向に積層し、成形後、層間剪断
強度（ＩＬＳＳ）をＡＳＴＭ Ｄ２３４４に従い測定す
る。Interlaminar shear strength test 14 prepregs are laminated in one direction, and after molding, the interlaminar shear strength (ILSS) is measured according to ASTM D2344.
【００２７】ガラス転移温度 ＴＭＡ針入モードを用いて、昇温速度２０℃／分で測定
する。The glass transition temperature is measured at a heating rate of 20 ° C./min using a TMA penetration mode.
【００２８】本発明の複合材料は、下記の〔Ａ〕、
〔Ｂ〕、〔Ｃ〕成分を構成要素として含むことが好まし
い。The composite material of the present invention comprises the following [A],
It is preferable to include the components [B] and [C] as constituent elements.
【００２９】〔Ａ〕：ハロゲンを含有しないエポキシ樹
脂 〔Ｂ〕：金属酸化物 〔Ｃ〕：ガラス転移温度が１２０℃以上の熱可塑性樹脂 本発明に使用することができる繊維強化材には、炭素繊
維、炭化ケイ素繊維、ガラス繊維、アルミナ繊維、セラ
ミック繊維等の無機繊維が挙げられる。[A]: Epoxy resin containing no halogen [B]: Metal oxide [C]: Thermoplastic resin having a glass transition temperature of 120 ° C. or more The fiber reinforcing material that can be used in the present invention includes carbon Inorganic fibers such as fiber, silicon carbide fiber, glass fiber, alumina fiber, ceramic fiber and the like can be mentioned.
【００３０】本発明に使用することができる炭素繊維に
は、アクリロニトリル系、ピッチ系炭素繊維が挙げられ
る。これらの炭素繊維は、長繊維、短繊維、チョップ
状、シート状、織物状、編物状、マット状、紙状のいず
れの形状でも使用することができる。The carbon fibers usable in the present invention include acrylonitrile-based and pitch-based carbon fibers. These carbon fibers can be used in any form of long fiber, short fiber, chop, sheet, woven, knit, mat, or paper.
【００３１】〔Ａ〕成分のエポキシ樹脂には、ハロゲン
フリーのものが使用される。具体的には、エポキシ樹脂
はグリシジルアミン型エポキシ樹脂、ノボラック型エポ
キシ樹脂、ビスフェノールＡ型エポキシ樹脂、ウレタン
変性ビスフェノールＡ型エポキシ樹脂、脂環式エポキシ
樹脂の単独又は混合物が挙げられる。A halogen-free epoxy resin is used as the component (A). Specifically, examples of the epoxy resin include a glycidylamine type epoxy resin, a novolak type epoxy resin, a bisphenol A type epoxy resin, a urethane modified bisphenol A type epoxy resin, and a single or a mixture of alicyclic epoxy resins.
【００３２】前記のグリシジルアミン型エポキシ樹脂と
しては、エポトートＹＨ４３４（商品名、東都化成社
製）、ＹＤＭ１２０（商品名、東都化成社製）等があ
る。前記のノボラック型エポキシ樹脂のうち、フェノー
ルノボラック型エポキシ樹脂としては例えば、シェル化
学社製のエピコート１５２（商品名）、エピコート１５
４（商品名）、ダウケミカル社製のダウエポキシＤＥＮ
４３１（商品名）、ダウエポキシＤＥＮ４３（商品
名）、ダウエポキシＤＥＮ４３９（商品名）、また、Ｅ
ＰＰＮ２０１（商品名、日本化薬社製）、エピクロンＮ
７４０（商品名、大日本インキ社製）等が挙げられ、更
にクレゾールノボラック型エポキシ樹脂としては、チバ
・ガイギー社製のアラルダイトＥＣＮ１２７３（商品
名）、アラルダイトＥＣＮ１２８０（商品名）等が挙げ
られる。Examples of the glycidylamine type epoxy resin include Epototo YH434 (trade name, manufactured by Toto Kasei Co., Ltd.) and YDM120 (trade name, manufactured by Toto Kasei Co., Ltd.). Among the novolak-type epoxy resins described above, examples of the phenol novolak-type epoxy resin include Epicoat 152 (trade name) and Epicoat 15 manufactured by Shell Chemical Company.
4 (trade name), Dow Epoxy DEN manufactured by Dow Chemical
431 (trade name), Dow Epoxy DEN43 (trade name), Dow Epoxy DEN 439 (trade name), and E
PPN201 (trade name, manufactured by Nippon Kayaku Co., Ltd.), Epicron N
740 (trade name, manufactured by Dainippon Ink) and cresol novolak type epoxy resins include Araldite ECN1273 (trade name) and Araldite ECN1280 (trade name) manufactured by Ciba Geigy Corporation.
【００３３】前記のビスフェノールＡ型エポキシ樹脂と
しては、例えば、シェル化学社製のエピコート８２７
（商品名）、エピコート８２８（商品名）、エピコート
１００１（商品名）、エピコート１００２（商品名）、
エピコート１００４（商品名）等が挙げられる。Examples of the bisphenol A type epoxy resin include, for example, Epicoat 827 manufactured by Shell Chemical Company.
(Trade name), Epicoat 828 (trade name), Epicoat 1001 (trade name), Epicoat 1002 (trade name),
Epicoat 1004 (trade name) and the like.
【００３４】前記のウレタン変性ビスフェノールＡ型エ
ポキシ樹脂としては、旭電化社製のアデカレジンＥＰＵ
−６（商品名）、アデカレジンＥＰＵ−１０（商品
名）、アデカレジンＥＰＵ−１５（商品名）等があり、
前記の脂環式エポキシ樹脂としては、チバ・ガイギー社
製のアラルダイトＣＹ−１７９（商品名）、アラルダイ
トＣＹ−１７８（商品名）、アラルダイトＣＹ−１８２
（商品名）、アラルダイトＣＹ−１８３（商品名）等が
挙げられる。As the urethane-modified bisphenol A type epoxy resin, Adeka Resin EPU manufactured by Asahi Denka Co., Ltd.
-6 (trade name), Adeka Resin EPU-10 (trade name), Adeka Resin EPU-15 (trade name), etc.
Examples of the alicyclic epoxy resin include Araldite CY-179 (trade name), Araldite CY-178 (trade name) and Araldite CY-182 manufactured by Ciba Geigy.
(Trade name), Araldite CY-183 (trade name) and the like.
【００３５】本発明における〔Ａ〕成分のエポキシ樹脂
は、単独で使用又は２種類以上を併用してもよい。The epoxy resin (A) in the present invention may be used alone or in combination of two or more.
【００３６】エポキシ樹脂用硬化剤は特に限定されるも
のではないが、芳香族アミン類、ジシアンジアミド、三
フッ化ほう素錯塩類、酸無水物、イミダゾール類の単独
又は混合系を挙げることができる。The curing agent for the epoxy resin is not particularly limited, and examples thereof include aromatic amines, dicyandiamide, boron trifluoride complex salts, acid anhydrides, and imidazoles alone or in a mixture.
【００３７】前記芳香族アミン類としては、メタフェニ
レンジアミン、ジアミノジフェニルメタン、ジアミノジ
フェニルスルフォン、メタキシレンジアミン等がある。
三フッ化ほう素錯塩類としては、ＢＦ３ モノエチルア
ミン、Ｂ３ ベンジルアミン等が使用できる。Examples of the aromatic amines include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and metaxylenediamine.
As the boron trifluoride complex salts, BF3 monoethylamine, B3 benzylamine and the like can be used.
【００３８】前記酸無水物としては、無水フタル酸、ト
リメリット酸無水物、無水ピロメリット酸、無水ベンゾ
フェノンテトラカルボキシル酸等がある。イミダゾール
類としては、２−エチル−４−イミダゾール、２−エチ
ルイミダゾール、２，４−ジメチルイミダゾール、２−
フェニルイミダゾール等が使用できる。Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and the like. Examples of imidazoles include 2-ethyl-4-imidazole, 2-ethylimidazole, 2,4-dimethylimidazole,
Phenylimidazole and the like can be used.
【００３９】前記エポキシ樹脂用硬化剤に加えて、例え
ば、３−（３，４−ジクロロフェニル）−１，１−ジメ
チルウレアを硬化促進剤として併用することができる。In addition to the epoxy resin curing agent, for example, 3- (3,4-dichlorophenyl) -1,1-dimethylurea can be used in combination as a curing accelerator.
【００４０】〔Ｂ〕成分の金属酸化物は、特に限定され
ないが、耐火性の観点から、酸化マグネシウム、酸化ア
ルミニウムが好ましい。特に熱伝導率が高い酸化マグネ
シウムが難燃性向上に有用であり好ましい。前記酸化マ
グネシウムには、５０％粒径が０．５〜２０μｍ範囲の
ものが特に好ましい。The metal oxide of the component (B) is not particularly limited, but from the viewpoint of fire resistance, magnesium oxide and aluminum oxide are preferred. Particularly, magnesium oxide having a high thermal conductivity is useful for improving the flame retardancy and is preferred. It is particularly preferable that the magnesium oxide has a 50% particle size in the range of 0.5 to 20 μm.
【００４１】〔Ｃ〕成分の熱可塑性樹脂としては、ガラ
ス転移温度Ｔｇで１２０℃以上の樹脂、例えば、ポリア
ミドイミド樹脂（Ｔｇ２６０℃）、ポリイミド樹脂（Ｔ
ｇ２５９℃）、ポリエーテルサルフォン樹脂（Ｔｇ２２
３℃）、ポリエーテルイミド樹脂（Ｔｇ２１６℃）等で
ある。特にポリエーテルイミド樹脂がエポキシ樹脂の耐
衝撃性向上に有用であるために望ましい。Examples of the thermoplastic resin (C) include resins having a glass transition temperature Tg of 120 ° C. or higher, for example, polyamideimide resin (Tg 260 ° C.), polyimide resin (Tg
g259 ° C), polyethersulfone resin (Tg22
3 ° C.), polyetherimide resin (Tg 216 ° C.) and the like. In particular, a polyetherimide resin is desirable because it is useful for improving the impact resistance of an epoxy resin.
【００４２】本発明における樹脂組成物中の含有比率は
以下の比が望ましい。すなわち、〔Ａ〕成分１００重量
部に対して〔Ｂ〕成分である金属酸化物は、１０〜３０
重量部が好ましい。１０重量部未満では難燃性が不十分
であり、３０重量部を越えると機械的特性の低下が大き
くなる。The content ratio in the resin composition of the present invention is desirably the following ratio. That is, the metal oxide as the component (B) is 10 to 30 parts by weight based on 100 parts by weight of the component (A).
Parts by weight are preferred. If the amount is less than 10 parts by weight, the flame retardancy is insufficient. If the amount exceeds 30 parts by weight, the mechanical properties are greatly reduced.
【００４３】〔Ｃ〕成分は、〔Ａ〕成分１００重量部に
対して３〜３０重量部とするのが好ましい。３重量部未
満では耐衝撃性が不十分であり、３０重量部を越える
と、溶融粘度が高くなるので、プリプレグ製造時の作業
性及びプリプレグの成形性が不良となり、積層板に欠陥
を生じ易くなる。The component (C) is preferably used in an amount of 3 to 30 parts by weight based on 100 parts by weight of the component (A). If the amount is less than 3 parts by weight, the impact resistance is insufficient, and if the amount exceeds 30 parts by weight, the melt viscosity becomes high, so that the workability during prepreg production and the moldability of the prepreg become poor, and the laminate tends to have defects. Become.
【００４４】エポキシ樹脂用硬化剤の配合量は、特に限
定されないが、例えば、硬化剤として４，４’−ジアミ
ノジフェニルスルホンを使用した場合は、エポキシ樹脂
１００重量部に対して化学量論的に求められる添加量、
すなわち、（アミン当量／エポキシ当量）×１００重量
部の７０〜９０％を配合する。また、ジシアンジアミド
を用いた場合は、エポキシ樹脂１００重量部に対して、
１〜１０重量部、好ましくは、３〜８重量部である。The amount of the epoxy resin curing agent is not particularly limited. For example, when 4,4'-diaminodiphenyl sulfone is used as the curing agent, the stoichiometric amount is based on 100 parts by weight of the epoxy resin. Required addition amount,
That is, 70 to 90% of (amine equivalent / epoxy equivalent) × 100 parts by weight is blended. When dicyandiamide is used, the epoxy resin is used in an amount of 100 parts by weight.
It is 1 to 10 parts by weight, preferably 3 to 8 parts by weight.
【００４５】〔Ａ〕、〔Ｂ〕、〔Ｃ〕成分及びエポキシ
樹脂用硬化剤の各成分はこの含有比率の範囲内において
適宜選択される。The components [A], [B] and [C] and the respective components of the epoxy resin curing agent are appropriately selected within the range of this content ratio.
【００４６】繊維強化材の使用量は用途によって異なる
が、積層材や成形材料としては、樹脂組成物１００重量
部に対して４００重量部まで使用できる。The amount of the fiber reinforcing material used varies depending on the application, but as a laminate or a molding material, it can be used up to 400 parts by weight based on 100 parts by weight of the resin composition.
【００４７】任意成分：本発明の複合材料成分には、本
発明の目的を害さない範囲で、必要に応じて次の（１）
〜（４）の成分を添加することができる。Optional components: The composite material component of the present invention may optionally include the following (1) as long as the object of the present invention is not impaired.
Components (4) to (4) can be added.
【００４８】（１）難燃助剤、例えば三酸化アンチモ
ン、五酸化アンチモン等である。これら難燃助剤の使用
量は、エポキシ樹脂１００重量部に対して１０重量部未
満、好ましくは５重量部未満が望ましい。(1) Flame retardant aids, for example, antimony trioxide, antimony pentoxide and the like. The amount of these flame retardant aids used is less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the epoxy resin.
【００４９】（２）粉末状の補強材、充填材及びチクソ
トロピー付与剤、例えばシリカ、酸性白土、ベントナイ
ト、ガラスビーズ、カーボンブラック、ゼオライト、ケ
イソウ土、マイカ、カオリン、タルク等である。これら
の補強材や充填材の使用量は、エポキシ樹脂１００重量
部に対して５重量部未満が望ましい。(2) Powdered reinforcing materials, fillers and thixotropic agents, for example, silica, acid clay, bentonite, glass beads, carbon black, zeolite, diatomaceous earth, mica, kaolin, talc and the like. The amount of these reinforcing materials and fillers used is preferably less than 5 parts by weight based on 100 parts by weight of the epoxy resin.
【００５０】（３）着色剤、顔料、例えば二酸化チタ
ン、黄鉛、カーボンブラック等である。これら着色剤、
顔料の使用量は、エポキシ樹脂１００重量部に対して５
重量部未満が望ましい。(3) Colorants and pigments such as titanium dioxide, graphite, carbon black and the like. These colorants,
The amount of the pigment used is 5 per 100 parts by weight of the epoxy resin.
Less than parts by weight is desirable.
【００５１】（４）硬化促進剤、例えば、３−（３，４
−ジクロロフェニル）−１，１−ジメチルウレアを前記
エポキシ樹脂用硬化剤と併用することができる。エポキ
シ樹脂に対する硬化促進剤の配合量は、エポキシ樹脂１
００重量部に対して１〜５重量部が望ましい。(4) A curing accelerator, for example, 3- (3,4)
-Dichlorophenyl) -1,1-dimethylurea can be used in combination with the curing agent for epoxy resin. The compounding amount of the curing accelerator to the epoxy resin is as follows.
1 to 5 parts by weight with respect to 00 parts by weight is desirable.
【００５２】樹脂の調製方法：本発明のプリプレグにお
ける樹脂組成物の調製は、例えば、以下の方法により行
うことができる。即ち、各成分を混練装置に供給し、加
熱混練する。この際の加熱温度はエポキシ樹脂の硬化開
始温度より低温とする。この際、エポキシ樹脂用硬化剤
は最後に加熱混練するのがよい。通常は、５０〜１００
℃の温度にて調製する。Method for Preparing Resin: The resin composition in the prepreg of the present invention can be prepared, for example, by the following method. That is, each component is supplied to a kneading device and heated and kneaded. The heating temperature at this time is lower than the curing start temperature of the epoxy resin. At this time, the epoxy resin curing agent is preferably kneaded with heat last. Usually 50-100
Prepare at a temperature of ° C.
【００５３】プリプレグの製造方法：本発明のプリプレ
グの製造方法は特に限定されないが、例えば、ホットメ
ルト法あるいは溶剤法を採用することが可能である。Production method of prepreg: The production method of the prepreg of the present invention is not particularly limited. For example, a hot melt method or a solvent method can be adopted.
【００５４】[0054]
【実施例】本発明について実施例を挙げて更に詳しく説
明する。特に指定しない限り「％」、「部」は重量基準
である。EXAMPLES The present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” are based on weight.
【００５５】〔実施例１〜８及び比較例１〜７〕〔Ａ〕
〜〔Ｃ〕成分を下記の表１に示す配合処方の組成比で混
合し、更に硬化剤１０重量部、硬化促進剤３重量部を加
え、本実施例１〜８及び比較例１〜７の各難燃性エポキ
シ樹脂組成物を得た。フィルムコーターを用いてこれら
の各樹脂組成物から各樹脂フィルムを作製した。これら
の各樹脂フィルムを、引き揃えた炭素繊維ベスファイト
ＩＭ−４００（登録商標、東邦レーヨン（株）製、引張
強度４５１０ＭＰａ、引張弾性率２９４ＧＰａ）の両面
から圧着させ、炭素繊維目付１５０ｇ／ｍ2 、樹脂含有
率３４％の本実施例１〜８及び比較例１〜７の各一方向
プリプレグを得た。[Examples 1 to 8 and Comparative Examples 1 to 7] [A]
The components [C] to [C] were mixed at the composition ratios shown in Table 1 below, and 10 parts by weight of a curing agent and 3 parts by weight of a curing accelerator were further added. Each flame-retardant epoxy resin composition was obtained. Each resin film was produced from each of these resin compositions using a film coater. Each of these resin films is pressed from both sides of aligned carbon fiber Vesfight IM-400 (registered trademark, manufactured by Toho Rayon Co., Ltd., tensile strength 4510 MPa, tensile modulus 294 GPa), and the carbon fiber weight is 150 g / m 2. The unidirectional prepregs of Examples 1 to 8 and Comparative Examples 1 to 7 having a resin content of 34% were obtained.
【００５６】これらの各プリプレグを、１２５℃、５ｋ
ｇ／ｃｍ2 、２時間の条件でオートクレーブ成形し、前
述の試験方法で以下の項目を評価した。Each of these prepregs was heated at 125 ° C. for 5 k
Autoclave molding was performed under the conditions of g / cm 2 and 2 hours, and the following items were evaluated by the test method described above.
【００５７】着火性：鉄運８１号 強制的に着火させた後の難燃性：ＵＬ９４規格 火災初期の熱暴露を想定した熱安定性：熱暴露後の膨れ
の有無 熱暴露後の機械的特性：衝撃後圧縮強度（ＣＡＩ）、層
間剪断強度（ＩＬＳＳ） これらの結果を下記の表１（実施例１〜８）、表２（比
較例１〜７）に示す。Flammability after forced ignition: UL94 standard Thermal stability assuming heat exposure in the early stage of fire: Presence or absence of blistering after heat exposure Mechanical properties after heat exposure : Compressive strength after impact (CAI), Interlaminar shear strength (ILSS) These results are shown in Table 1 (Examples 1 to 8) and Table 2 (Comparative Examples 1 to 7) below.
【００５８】[0058]
【表１】 [Table 1]
【００５９】[0059]
【表２】 [Table 2]
【００６０】＊１ エピコート８３４：ビスフェノール
Ａジグリシジルエーテル型エポキシ樹脂（油化シェルエ
ポキシ（株）製） ＊２ エピコート１００２：ビスフェノールＡジグリシ
ジルエーテル型エポキシ樹脂（油化シェルエポキシ
（株）製） ＊３ エピコート６０４：Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ
グリシジルジアミノジフェニルメタン（油化シェルエポ
キシ（株）製） ＊４ ＥＰＵ−６：ウレタン変性エポキシ樹脂（旭電化
工業（株）製） ＊５ ＰＥＩ Ｕｌｔｅｍ１０００：ポリエーテルイミ
ド樹脂（日本ジーイープラスチック（株）製） ＊６ ＰＥＳ ５００３Ｐ：ポリエーテルサルフォン樹
脂（住友化学工業（株）製） ＊７ ＤＤＳ：４，４’−ジアミノジフェニルスルホン ＊８ ＤＣＭＵ：３−（３，４−ジクロロフェニル）−
１，１−ジメチルウレア ＊９ ＰＰＳ Ｔ−４：ポリフェニレンスルフィド
（（株）トープレン製） ＊１０ 着火性試験片の繊維体積含有率 ＊１１ ２５０℃×１０分熱暴露後に超音波探傷機で検
査 ＊１２ ２５０℃×１０分熱暴露後に１０００ｉｎ−ｌ
ｂ／ｉｎの衝撃エネルギーを付与した後、圧縮強度を測
定 ＊１３ ２５０℃×１０分熱暴露後に測定 ＊１４ 熱暴露後に膨れを生じたので、測定不可* 1 Epicoat 834: Bisphenol A diglycidyl ether type epoxy resin (manufactured by Yuka Shell Epoxy) * 2 Epicoat 1002: Bisphenol A diglycidyl ether type epoxy resin (manufactured by Yuka Shell Epoxy) * 3 Epicoat 604: N, N, N ', N'-tetraglycidyldiaminodiphenylmethane (manufactured by Yuka Shell Epoxy) * 4 EPU-6: urethane-modified epoxy resin (manufactured by Asahi Denka Kogyo) * 5 PEI Ultem 1000: polyether imide resin (manufactured by Nippon GE Plastics) * 6 PES 5003P: polyether sulfone resin (manufactured by Sumitomo Chemical Co., Ltd.) * 7 DDS: 4,4'-diaminodiphenyl sulfone * 8 DCMU: 3- (3,4-dichlorophenyl)-
1,1-dimethylurea * 9 PPS T-4: polyphenylene sulfide (manufactured by Topren Co., Ltd.) * 10 Fiber volume content of ignitable test piece * 11 Inspection with ultrasonic flaw detector after exposure to heat at 250 ° C. for 10 minutes * 12 1000 in-l after exposure to heat at 250 ° C for 10 minutes
Compressive strength is measured after applying b / in impact energy. * 13 Measured after heat exposure at 250 ° C x 10 minutes. * 14 Measurement not possible due to swelling after heat exposure.
【００６１】前記表１及び表２によれば、本発明の実施
例は比較例に比べて以下の効果を有することが理解され
る。According to Tables 1 and 2, it is understood that the examples of the present invention have the following effects as compared with the comparative examples.
【００６２】実施例１及び比較例１を対比すると明らか
なように、〔Ｂ〕成分として酸化マグネシウム、〔Ｃ〕
成分としてポリエーテルイミドを配合することで、熱暴
露後の衝撃後圧縮強度（ＣＡＩ）、耐着火性及び難燃性
を向上させることが可能である。As is apparent from comparison between Example 1 and Comparative Example 1, magnesium oxide and [C] were used as the component [B].
By blending polyetherimide as a component, it is possible to improve the compressive strength after impact (CAI), ignition resistance and flame retardancy after heat exposure.
【００６３】実施例１、比較例２及び比較例３を対比す
ると明らかなように、〔Ｂ〕成分が無い場合は、耐着火
性が不十分であり、〔Ｃ〕成分がない場合は、熱暴露後
の衝撃後圧縮強度が大幅に低下する。As is clear from the comparison between Example 1, Comparative Example 2 and Comparative Example 3, when there is no component [B], the ignition resistance is insufficient. The compressive strength after impact after exposure is greatly reduced.
【００６４】実施例１、実施例２、比較例３を対比する
と明らかなように、〔Ｃ〕成分のポリエーテルイミド配
合量の増加に伴い、熱暴露後の衝撃後圧縮強度が増加す
る。As is clear from comparison between Example 1, Example 2, and Comparative Example 3, the compressive strength after impact after heat exposure increases with an increase in the amount of the polyetherimide of the component [C].
【００６５】実施例１、実施例３及び実施例４を対比す
ると明らかなように、〔Ｂ〕成分の酸化マグネシウムが
１２重量部の場合、若干難燃性が低く、２８重量部の場
合、熱暴露後の耐衝撃性及び機械的特性が若干低下す
る。As is apparent from comparison of Examples 1, 3 and 4, when the magnesium oxide component (B) is 12 parts by weight, the flame retardancy is slightly low. The impact resistance and mechanical properties after exposure are slightly reduced.
【００６６】実施例１及び比較例４を対比すると明らか
なように、ガラス転移温度が１２０℃以下のＰＰＳ樹脂
（Ｔｇ８５℃）を使用すると、難燃性が若干低下する。As is clear from comparison between Example 1 and Comparative Example 4, when a PPS resin having a glass transition temperature of 120 ° C. or lower (Tg of 85 ° C.) is used, the flame retardancy is slightly reduced.
【００６７】実施例５及び比較例１を対比すると明らか
なように、〔Ｂ〕成分として酸化アルミニウム、〔Ｃ〕
成分としてポリエーテルイミドを配合することで、熱暴
露後の衝撃後圧縮強度、耐着火性及び難燃性を向上させ
ることが可能である。As is clear from comparison between Example 5 and Comparative Example 1, aluminum oxide and [C] were used as the component [B].
By blending polyetherimide as a component, it is possible to improve the compressive strength after impact after heat exposure, ignition resistance, and flame retardancy.
【００６８】実施例１及び比較例５を対比すると明らか
なように、難燃剤として、水酸化アルミニウムを用いる
と、熱暴露試験時の積層板に膨れを生じ、強度測定不可
となるので、構造材として機能し得なくなる。As is clear from the comparison between Example 1 and Comparative Example 5, when aluminum hydroxide was used as the flame retardant, the laminate was swelled during the heat exposure test, and the strength could not be measured. Can no longer function as
【００６９】実施例１、実施例６及び実施例７を対比す
ると明らかなように、繊維体積含有率が５６％の場合、
若干難燃性が低く、６４％の場合、熱暴露後の機械的特
性が若干低下する。As is clear from comparison between Examples 1, 6 and 7, when the fiber volume content is 56%,
When the flame retardancy is slightly low, and when it is 64%, the mechanical properties after heat exposure are slightly reduced.
【００７０】実施例１、比較例６及び比較例７を対比す
ると明らかなように、繊維体積含有率が５０％の場合、
耐着火性、難燃性が低く、７２％の場合、熱暴露後の機
械的特性が低下する。As is clear from comparison of Example 1, Comparative Examples 6 and 7, when the fiber volume content is 50%,
When the ignition resistance and the flame retardancy are low, and when it is 72%, the mechanical properties after heat exposure are reduced.
【００７１】実施例８及び比較例１を対比すると明らか
なように、〔Ｂ〕成分として酸化マグネシウム、〔Ｃ〕
成分としてポリエーテルサルフォンを配合することで、
熱暴露後の衝撃後圧縮強度、耐着火性及び難燃性を向上
させることが可能である。As is clear from comparison between Example 8 and Comparative Example 1, magnesium oxide and [C] were used as the component [B].
By blending polyether sulfone as an ingredient,
It is possible to improve compressive strength after impact after heat exposure, ignition resistance and flame retardancy.
【００７２】以上の結果より、実施例１〜実施例８、特
に実施例１、２、５、８の場合、比較例１〜比較例７と
比べ耐着火性、難燃性、熱安定性、熱暴露後の機械的特
性においてバランスに優れた複合材料であることが分か
る。From the above results, it was found that Examples 1 to 8 and especially Examples 1, 2, 5, and 8 exhibited ignition resistance, flame retardancy, thermal stability, and the like as compared with Comparative Examples 1 to 7. It can be seen that the composite material has an excellent balance in mechanical properties after heat exposure.
【００７３】[0073]
【発明の効果】本発明のプリプレグを用いて製造された
繊維強化樹脂複合材料は、耐着火性を有し、しかも熱暴
露時にもハロゲンガス、水蒸気等の分解ガスを発生せ
ず、しかも、熱暴露後に機械的強度の低下がない。本発
明の繊維強化樹脂複合材料は運輸省鉄運８１号の試験に
合格し、鉄道車両の用途に用いることができる。The fiber reinforced resin composite material produced by using the prepreg of the present invention has ignition resistance, and does not generate decomposition gases such as halogen gas and water vapor even when exposed to heat. No decrease in mechanical strength after exposure. The fiber reinforced resin composite material of the present invention has passed the test of the Ministry of Transportation, Iron Transportation No. 81, and can be used for railway vehicles.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ０８Ｌ 63:00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI // C08L 63:00
Claims (11)
る繊維強化樹脂複合材料であって、運輸省鉄運８１号に
準処した着火試験で実質的に着火せず、しかも２５０℃
に加熱されたオーブンに１０分間静置してなる熱暴露試
験後において、衝撃後圧縮強度が１５ｋｇｆ／ｍｍ2 以
上、層間剪断強度が７ｋｇｆ／ｍｍ2以上であることを
特徴とする繊維強化樹脂複合材料。1. A fiber-reinforced resin composite material comprising a fiber-reinforced material and a matrix resin, which does not substantially ignite in an ignition test according to the Ministry of Transport, Iron Transport No. 81, and has a temperature of 250 ° C.
A fiber reinforced resin composite having a compressive strength after impact of 15 kgf / mm 2 or more and an interlayer shear strength of 7 kgf / mm 2 or more after a heat exposure test left standing in an oven heated for 10 minutes. material.
生のない請求項１記載の繊維強化樹脂複合材料。2. The fiber-reinforced resin composite material according to claim 1, wherein substantially no decomposition gas is generated in the heat exposure test.
2 以上、層間剪断強度が９ｋｇｆ／ｍｍ2 以上である請
求項１記載の繊維強化樹脂複合材料。3. The compression strength after impact is 18 kgf / mm.
2. The fiber-reinforced resin composite material according to claim 1, wherein the shear strength is 2 kg or more and the shear strength between layers is 9 kgf / mm 2 or more.
１記載の繊維強化樹脂複合材料。4. The fiber-reinforced resin composite material according to claim 1, wherein said fiber-reinforced material is carbon fiber.
％である請求項１記載の繊維強化樹脂複合材料。5. The volume fraction of the reinforcing fibers is 55 to 65.
%. The fiber reinforced resin composite material according to claim 1.
〔Ｂ〕、〔Ｃ〕成分及びエポキシ樹脂用硬化剤を必須と
して含有する請求項１記載の繊維強化樹脂複合材料： 〔Ａ〕：ハロゲンを含有しないエポキシ樹脂； 〔Ｂ〕：金属酸化物； 〔Ｃ〕：ガラス転移温度が１２０℃以上の熱可塑性樹
脂。6. The method according to claim 1, wherein the matrix resin comprises the following [A]:
2. The fiber-reinforced resin composite material according to claim 1, which contains [B] and [C] components and a curing agent for an epoxy resin as essential components: [A]: an epoxy resin containing no halogen; [B]: a metal oxide; C]: a thermoplastic resin having a glass transition temperature of 120 ° C. or higher.
がグリシジルアミン型エポキシ樹脂、ノボラック型エポ
キシ樹脂、ピスフェノールＡ型エポキシ樹脂、ウレタン
変性ビスフェノールＡ型エポキシ樹脂、脂環式エポキシ
樹脂から選ばれたハロゲンを含有しないエポキシ樹脂の
単独又は２種以上の混合物である請求項６記載の繊維強
化樹脂複合材料。7. The halogen-free epoxy resin is a halogen selected from glycidylamine type epoxy resin, novolak type epoxy resin, pisphenol A type epoxy resin, urethane modified bisphenol A type epoxy resin and alicyclic epoxy resin. 7. The fiber-reinforced resin composite material according to claim 6, which is a single epoxy resin or a mixture of two or more epoxy resins.
樹脂、ポリイミド樹脂、ポリエーテルサルフォン樹脂、
ポリエーテルイミド樹脂から選ばれた熱可塑性樹脂の単
独又は２種以上の混合物である請求項６記載の繊維強化
樹脂複合材料。8. The thermoplastic resin is a polyamide-imide resin, a polyimide resin, a polyether sulfone resin,
The fiber-reinforced resin composite material according to claim 6, which is a thermoplastic resin selected from a polyetherimide resin alone or a mixture of two or more.
酸化アルミニウムから選ばれた単独又は２種の混合物で
ある請求項６記載の繊維強化樹脂複合材料。9. The fiber-reinforced resin composite material according to claim 6, wherein the metal oxide is a single material or a mixture of two materials selected from magnesium oxide and aluminum oxide.
合重量比が、下記の割合である請求項６記載の繊維強化
樹脂複合材料： 〔Ａ〕：１００重量部； 〔Ｂ〕：１０〜３０重量部； 〔Ｃ〕： ３〜３０重量部。10. The fiber-reinforced resin composite material according to claim 6, wherein the component weight ratio of the components [A], [B] and [C] is as follows: [A]: 100 parts by weight; ]: 10 to 30 parts by weight; [C]: 3 to 30 parts by weight.
エポキシ樹脂用硬化剤を必須として含有するマトリック
ス樹脂が、繊維強化材に含浸されてなるプリプレグ： 〔Ａ〕：ハロゲンを含有しないエポキシ樹脂； 〔Ｂ〕：金属酸化物； 〔Ｃ〕：ガラス転移温度が１２０℃以上の熱可塑性樹
脂。11. A prepreg obtained by impregnating a fiber reinforcement with a matrix resin essentially containing the following components [A], [B], [C] and a curing agent for an epoxy resin: [A]: halogen [B]: metal oxide; [C]: a thermoplastic resin having a glass transition temperature of 120 ° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33358097A JPH11147965A (en) | 1997-11-18 | 1997-11-18 | Fiber-reinforced resin composite and prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33358097A JPH11147965A (en) | 1997-11-18 | 1997-11-18 | Fiber-reinforced resin composite and prepreg |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11147965A true JPH11147965A (en) | 1999-06-02 |
Family
ID=18267642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33358097A Pending JPH11147965A (en) | 1997-11-18 | 1997-11-18 | Fiber-reinforced resin composite and prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11147965A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1526152A1 (en) * | 2003-10-24 | 2005-04-27 | United Technologies Corporation | Composite material, its manufacturing method and its use |
| JP2006169481A (en) * | 2004-12-20 | 2006-06-29 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg, and laminate |
| JP2007084595A (en) * | 2005-09-20 | 2007-04-05 | Kanebo Ltd | Epoxy resin composition |
| EP2543693A1 (en) | 2004-02-27 | 2013-01-09 | Toray Industries, Inc. | Epoxy resin composition for carbon-fiber-reinforced composite material, prepreg, integrated molding, fiber-reinforced composite sheet, and casing for electrical/electronic equipment |
| JP2015081329A (en) * | 2013-10-24 | 2015-04-27 | Dic株式会社 | Urethane-modified epoxy resin, curable composition, cured product thereof, fiber- reinforced composite material and fiber- reinforced resin molded article |
-
1997
- 1997-11-18 JP JP33358097A patent/JPH11147965A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1526152A1 (en) * | 2003-10-24 | 2005-04-27 | United Technologies Corporation | Composite material, its manufacturing method and its use |
| EP2543693A1 (en) | 2004-02-27 | 2013-01-09 | Toray Industries, Inc. | Epoxy resin composition for carbon-fiber-reinforced composite material, prepreg, integrated molding, fiber-reinforced composite sheet, and casing for electrical/electronic equipment |
| JP2006169481A (en) * | 2004-12-20 | 2006-06-29 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg, and laminate |
| JP2007084595A (en) * | 2005-09-20 | 2007-04-05 | Kanebo Ltd | Epoxy resin composition |
| JP2015081329A (en) * | 2013-10-24 | 2015-04-27 | Dic株式会社 | Urethane-modified epoxy resin, curable composition, cured product thereof, fiber- reinforced composite material and fiber- reinforced resin molded article |
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