JPS6145663B2 - - Google Patents
Info
- Publication number
- JPS6145663B2 JPS6145663B2 JP9428777A JP9428777A JPS6145663B2 JP S6145663 B2 JPS6145663 B2 JP S6145663B2 JP 9428777 A JP9428777 A JP 9428777A JP 9428777 A JP9428777 A JP 9428777A JP S6145663 B2 JPS6145663 B2 JP S6145663B2
- Authority
- JP
- Japan
- Prior art keywords
- cured
- ionizing radiation
- resin composition
- resin
- cure
- 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.)
- Expired
Links
- 239000011342 resin composition Substances 0.000 claims description 45
- 230000005865 ionizing radiation Effects 0.000 claims description 34
- 229920000647 polyepoxide Polymers 0.000 claims description 22
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000001723 curing Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 229920001187 thermosetting polymer Polymers 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- -1 methacryloyl groups Chemical group 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 5
- 125000000466 oxiranyl group Chemical group 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 2
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 claims 1
- 125000004386 diacrylate group Chemical group 0.000 claims 1
- 238000013007 heat curing Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 9
- 238000010894 electron beam technology Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 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 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 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 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 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 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 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 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- ATMABMRDZYWJJU-UHFFFAOYSA-L chromium(2+);2-methylprop-2-enoate;chloride Chemical compound [Cl-].[Cr+2].CC(=C)C([O-])=O ATMABMRDZYWJJU-UHFFFAOYSA-L 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 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
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001021 polysulfide Chemical class 0.000 description 1
- 239000005077 polysulfide Chemical class 0.000 description 1
- 150000008117 polysulfides Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Description
【発明の詳細な説明】
本発明は、電離性放射線によつて容易に硬化し
うる樹脂組成物Ａと、加熱によつて硬化しうる
が、放射線によつては、硬化しない、あるいは、
しにくい樹脂組成物Ｂを混合し、シート状、フイ
ルム状に成型、あるいは他の基材へ塗布もしくは
含浸させ、電離性放射線を照射することにより前
記Ａのみを硬化させて作製される半硬化成型物に
関するものであり、熱硬化性プリプレグ、接着用
フイルム、加熱硬化テープ等に使用される加熱硬
化型先駆体である。DETAILED DESCRIPTION OF THE INVENTION The present invention comprises a resin composition A that is easily curable by ionizing radiation, and a resin composition that is curable by heating but not curable by radiation;
Semi-cured molding made by mixing resin composition B that is difficult to cure, molding it into a sheet or film, or coating or impregnating it on other base materials, and curing only the above A by irradiating with ionizing radiation. It is a thermosetting precursor used for thermosetting prepregs, adhesive films, thermosetting tapes, etc.
従来熱硬化性プリプレグを始めとする加熱硬化
型先駆体は、エポキシ樹脂、不飽和ポリエステル
樹脂等の熱硬化性樹脂とその硬化剤であるアミン
類、酸無水物類、ポリアミド類、アミン錯塩ある
いはパーオキサイド等のラジカル反応開始剤を混
合し、さらにこれらに溶剤や希釈剤を加えた後、
これを基体上に塗布、含浸し、熱の作用により上
記樹脂を半硬化状態にすることにより、作製され
ている。この場合、溶剤の残留が後の２次硬化や
接着の段階でボイドの原因になつたり、製品の特
性を低下させるため、溶剤を十分に除去しなけれ
ばならず、長い加熱炉を使う必要があり、発生す
る溶剤が公害のもとになり、作業環境上も好しく
ない。又、製品の特性を均質にかつ良好に保つた
めには、上記樹脂を半硬化状態にする時の加熱炉
の温度や、他の製造条件を厳しく制御する必要が
あつた。又、熱硬化性樹脂の硬化反応はいずれも
発熱反応であり、上記のプリプレグ製造工程にお
いて加熱炉の条件以外にもこの発熱反応により発
生する熱が、条件の設定を困難にし、製品のバラ
ツキを生じる原因であつた。 Conventionally, thermosetting precursors such as thermosetting prepregs are made of thermosetting resins such as epoxy resins and unsaturated polyester resins, and their curing agents such as amines, acid anhydrides, polyamides, amine complex salts, or permeable resins. After mixing radical reaction initiators such as oxides and adding solvents and diluents to them,
It is produced by coating and impregnating the resin onto a substrate and bringing the resin into a semi-cured state by the action of heat. In this case, residual solvent can cause voids during the subsequent secondary curing and adhesion stages, and reduce the properties of the product, so the solvent must be thoroughly removed and a long heating furnace must be used. The solvent generated is a source of pollution and is not good for the working environment. In addition, in order to maintain uniform and good product characteristics, it is necessary to strictly control the temperature of the heating furnace when bringing the resin into a semi-cured state and other manufacturing conditions. In addition, all curing reactions of thermosetting resins are exothermic reactions, and in addition to the conditions of the heating furnace in the prepreg manufacturing process described above, the heat generated by this exothermic reaction makes it difficult to set the conditions and reduces product variation. It was the cause of this.
本発明は上記のような欠点をもつ現用のプリプ
レグ等の加熱硬化型先駆体に対し、全く新しい製
造方法、特徴をもつた加熱硬化型先駆体を提供す
るものである。 The present invention provides a completely new manufacturing method and a heat-curable precursor having characteristics, compared to the currently used heat-curable precursors such as prepregs which have the above-mentioned drawbacks.
これは、電離性放射線によつて容易に硬化しう
る樹脂組成物Ａと加熱によつて硬化しうるが電離
性放射線によつては、硬化しないあるいは、しに
くい樹脂組成物Ｂを混合し、シート、フイルム状
に成型あるいは、他の基材、例えば金属、ガラス
クロス、マツト、ポリマー繊維のクロスマツト、
ロツクウール、木材チツプ紙フイルム等に塗布あ
るいは、含浸させ、電離性放射線を照射すること
により、前記Ａのみを硬化させて半硬化状態にす
ることによつてえられる。 This is made by mixing a resin composition A that can be easily cured by ionizing radiation and a resin composition B that can be cured by heating but not or difficult to cure by ionizing radiation. , molded into a film or other base materials such as metal, glass cloth, mat, polymer fiber cross mat,
It can be obtained by coating or impregnating rock wool, wood chip paper film, etc., and irradiating it with ionizing radiation to cure only the above A to a semi-cured state.
本発明の特徴は、数多くあるが、まず電離性放
射線を用いることにより、樹脂組成物Ａの硬化を
行う際には、この組成物の硬化触媒を添加してお
く必要はなく、Ａの配合量と電離性放射線の照射
量を制御することにより、該加熱硬化型先駆体の
硬さ、特性を自由に制御できることが挙げられ
る。又、電離性放射線による硬化は一般に加熱、
硬化に比べて迅速に硬化させることができるた
め、大巾に生産性を上げることができる。 There are many features of the present invention, but first, when curing resin composition A by using ionizing radiation, there is no need to add a curing catalyst for this composition, and the amount of compound A is By controlling the irradiation amount of ionizing radiation, the hardness and properties of the thermosetting precursor can be freely controlled. In addition, curing by ionizing radiation is generally done by heating,
Since it can be cured more quickly than curing, productivity can be greatly increased.
樹脂組成物Ａとして、液状で樹脂組成物Ｂと相
溶性のあるものを用いることによつて混合物の粘
度を下げることは可能であり、従来の溶剤型の製
造法と全く同様に基材への塗布、含浸等は行うこ
とができる。 By using a liquid resin composition A that is compatible with resin composition B, it is possible to lower the viscosity of the mixture, and it is possible to reduce the viscosity of the mixture to the base material in exactly the same way as the conventional solvent-based manufacturing method. Coating, impregnation, etc. can be performed.
又、樹脂組成物ＡとＢの組合わせは、両者の相
溶性、配合比の許すかぎり、自由に選ぶことがで
きるのもこの発明の特徴であり、このことによ
り、従来とは異つた特性をもつプリプレグ、フイ
ルムをえることも可能である。本発明の製造法
は、従来の溶剤型、加熱型のそれと比して加熱炉
等の熱源を必要とせず、又無溶剤型であるため、
本質的に無公害である。 Another feature of this invention is that the combination of resin compositions A and B can be freely selected as long as their compatibility and blending ratio allow. It is also possible to obtain prepregs and films containing the same. The manufacturing method of the present invention does not require a heat source such as a heating furnace, compared to conventional solvent-based and heating-based methods, and is solvent-free.
Essentially non-polluting.
本発明で用いられる電離性放射線で硬化しうる
樹脂組成物Ａの主成分となる樹脂としては、次の
ものがあげられる。 Examples of the resin that is the main component of the ionizing radiation-curable resin composition A used in the present invention include the following.
すなわち、分子中に２個以上のアクリロイル基
又はメタアクリロイル基をもつエステルアクリレ
ートあるいはエステルメタアクリレート、不飽和
ポリエステル樹脂、ジアリルフタレート、トリア
リルイソシアヌレート等のアリル化合物のプレポ
リマー、１分子中に２個以上のオキシラン環をも
つエポキサイドとαβ不飽和カルボン酸の反応よ
りえられるいわゆる不飽和エポキシ樹脂、ポリブ
タジエン、等ラジカル反応性炭素―炭素不飽和結
合を分子中に２個以上もつオリゴマーあるいはポ
リマーである。これらの樹脂に対していわゆるビ
ニル系モノマーを混合して、電離性放射線を照射
することにより、樹脂―モノマーの共重合によ
り、硬化することは可能であり、これらのビニル
系モノマーを配合したものも、ここでいう樹脂組
成物Ａに含まれるものである。ビニル系モノマー
として用いることができるものとしては、オレフ
イン類、ジエン類、ハロゲン化ビニル系モノマー
類、スチレンおよびスチレン誘導体、アクリル
酸、メタクリル酸、アクリロニトリル、アクリル
酸アミド、マレイン酸、無水マレイン酸などのア
クリル酸、ビニル酢酸および不飽和二塩基酸性誘
導体；アクリル酸メチル、アクリル酸エチル等の
アクリル酸エステルモノマー類；メタクリル酸メ
チル、メタクリル酸エチル等のメタクリル酸エス
テルモノマー類；酢酸ビニルなどのビニルエステ
ル類；アリルアルコールおよびアリルエステル
類；ビニルエーテル類；Ｎ―ビニル―２ピロリド
ン、Ｎビニルカルバゾール等のＮ―ビニル誘導
体；メチルビニルケトン等のビニル型カルボニル
化合物；メタクリル酸グリシジル、アクリル酸グ
リシジル等の不飽和エポキサイド類；ビニルトリ
エトキシシラン、ビニルトリメトキシシラン等の
ビニルアルコキシシラン類が挙げられる。 That is, prepolymers of allyl compounds such as ester acrylates or ester methacrylates, unsaturated polyester resins, diallyl phthalate, triallyl isocyanurate, etc. having two or more acryloyl or methacryloyl groups in the molecule, two or more in one molecule. These are oligomers or polymers having two or more radically reactive carbon-carbon unsaturated bonds in the molecule, such as so-called unsaturated epoxy resins, polybutadiene, and polybutadiene obtained by the reaction of epoxides having an oxirane ring with αβ-unsaturated carboxylic acids. By mixing so-called vinyl monomers with these resins and irradiating them with ionizing radiation, it is possible to cure them through resin-monomer copolymerization, and products containing these vinyl monomers can also be cured. , which is included in the resin composition A here. Examples of vinyl monomers that can be used include olefins, dienes, halogenated vinyl monomers, styrene and styrene derivatives, acrylic acid, methacrylic acid, acrylonitrile, acrylamide, maleic acid, and maleic anhydride. Acrylic acid, vinyl acetic acid and unsaturated dibasic acid derivatives; Acrylic acid ester monomers such as methyl acrylate and ethyl acrylate; Methacrylic acid ester monomers such as methyl methacrylate and ethyl methacrylate; Vinyl esters such as vinyl acetate ; Allyl alcohol and allyl esters; Vinyl ethers; N-vinyl derivatives such as N-vinyl-2-pyrrolidone and N-vinylcarbazole; Vinyl-type carbonyl compounds such as methyl vinyl ketone; Unsaturated epoxides such as glycidyl methacrylate and glycidyl acrylate. Examples include vinyl alkoxysilanes such as vinyltriethoxysilane and vinyltrimethoxysilane.
次に本発明で用いられる加熱によつて硬化しう
るが、電離性放射線によつては、硬化しない、あ
るいは、しにくい樹脂組成物Ｂは常温以上の温度
で加熱することにより、三次元網目構造を形成し
て硬化するいわゆる熱硬化性樹脂のうち、単独で
は、電離性放射線を照射しても硬化しない、ある
いはしにくいものであり、前記電離性放射線を照
射することにより硬化する樹脂組成物Ａと相溶性
あるものであれば、本発明に適用しうる。例え
ば、エポキシ樹脂、ウレタン樹脂、フエノール樹
脂、メラミン樹脂、ユリア樹脂、尿素樹脂、キシ
レン樹脂、シリコーン樹脂、アルキド樹脂等を主
成分とする樹脂組成物があげられる。これらの樹
脂組成物を加熱硬化させる方法はいずれも公知で
あり、例えばエポキシ樹脂ではアミン類、酸無水
物類、ポリアミド類、変成アミン類を適当量あら
かじめ混合しておけばよく、これらの硬化剤も上
記樹脂組成物Ｂ中に含まれるものである。 Next, resin composition B, which can be cured by heating as used in the present invention, but does not or is difficult to cure by ionizing radiation, can be heated to a temperature higher than room temperature to form a three-dimensional network structure. Among the so-called thermosetting resins that cure by forming a resin, those that do not cure or are difficult to cure even when irradiated with ionizing radiation when used alone, and the resin composition A that cures by irradiating with ionizing radiation. Any substance that is compatible with the above can be applied to the present invention. Examples include resin compositions containing epoxy resins, urethane resins, phenolic resins, melamine resins, urea resins, urea resins, xylene resins, silicone resins, alkyd resins, and the like as main components. All of the methods for heating and curing these resin compositions are well known; for example, in the case of epoxy resins, appropriate amounts of amines, acid anhydrides, polyamides, and modified amines may be mixed in advance; Also included in the resin composition B above.
又、樹脂組成物Ｂに対して、必要に応じて顔
料、染料、有機・無機フイラー等の充填材、シラ
ンカツプリング剤、アルキルチタネート、メタク
リレートクロムクロリド等の表面処理剤を添加す
ることも可能であり、これらを含むものも、本発
明の樹脂組成物Ｂに含まれるものである。 Furthermore, it is also possible to add fillers such as pigments, dyes, organic and inorganic fillers, and surface treatment agents such as silane coupling agents, alkyl titanates, and methacrylate chromium chloride to the resin composition B, if necessary. Those containing these are also included in the resin composition B of the present invention.
電離性放射線を照射することにより硬化する樹
脂組成物Ａと加熱によつて硬化するが、電離性放
射線によつては硬化しない、あるいは、しにくい
樹脂組成物Ｂの形態組合わせ、配合比は両者の相
溶性、混合物の粘度、加熱硬化型先駆体の特性お
よび本発明を適用する対象による。樹脂組成物
Ａ、Ｂはそれぞれ固体、液体いずれの態でもよい
が、作業性の面から両者共液状あるいは少くとも
一方が液状であり、混合物の粘度が低い方が望ま
しい。又、樹脂組成物Ａ、Ｂは、均一に分散しう
るものであればさしつかえないが、本発明の加熱
硬化型先駆体の均一性を保つためには両者が完全
に相溶あるいは固状樹脂組成物が、液状樹脂組成
物に完全に溶解することが望ましい。 The form combination and blending ratio of resin composition A, which hardens by irradiation with ionizing radiation, and resin composition B, which hardens by heating but does not or is difficult to harden by ionizing radiation, are both depending on the compatibility of the mixture, the viscosity of the mixture, the properties of the heat-curable precursor and the object to which the invention is applied. Resin compositions A and B may be either solid or liquid, but from the viewpoint of workability, it is desirable that both or at least one of them be liquid and that the viscosity of the mixture is low. Further, resin compositions A and B may be used as long as they can be uniformly dispersed, but in order to maintain the uniformity of the heat-curable precursor of the present invention, they must be completely compatible or have a solid resin composition. It is desirable that the material be completely dissolved in the liquid resin composition.
樹脂組成物Ａの樹脂組成物Ｂに対する配合比
は、加熱硬化型先駆体の特性より10〜50重量％で
あることが望ましい。すなわち、樹脂組成物Ａの
比率が10％以下になると、加熱硬化型先駆体の形
態保持が困難あるいは、表面が著しく、ベタつく
等のへい害が生じ、逆に50％以上になると加熱硬
化型先駆体が、硬すぎて可撓性に乏しく後に加熱
によつて樹脂組成物Ｂを硬化させる際にも樹脂の
流れが悪くなり、お互い同士あるいは、他の基材
に対する接着性が低くなつてしまう。 The blending ratio of resin composition A to resin composition B is preferably 10 to 50% by weight in view of the properties of the heat-curable precursor. In other words, when the proportion of resin composition A is less than 10%, it becomes difficult to maintain the shape of the heat-curable precursor, or the surface becomes extremely sticky, causing damage such as stickiness. The body is too hard and has poor flexibility, and when the resin composition B is later cured by heating, the flow of the resin is poor, resulting in poor adhesion to each other or to other substrates.
電離性放射線を照射することにより、硬化する
樹脂組成物Ａと加熱により硬化するが、電離性放
射線によつては硬化しない、あるいは、しにくい
樹脂組成物Ｂの組合わせで、最も良好な結果を与
えるのは、Ａとして１分子中に２個以上のアクリ
ロイル基又は、メタアクリロイル基をもつ、エス
テルアクリレートあるいはエステルメタアクリレ
ートをＢとして１分子中に２個以上のオキシラン
基をもつエポキシ樹脂を用いる系である。該アク
リレートあるいはメタアクリレートは電離性放射
線に対する活性が高く、数Mradの線量を照射す
るだけで、100％硬化不溶化しうるため、製造速
度をあげることが可能になるだけでなく、混合す
る樹脂組成物Ｂあるいは塗布、含浸等に使う基材
に対する放射線損傷を小さく押えることができ
る。又、該アクリレートあるいはメタアクリレー
トはエポキシ樹脂との相溶性が高く、両者の配合
比をほとんど自由に選択できるだけでなく、後述
の樹脂系において、分子量の範囲を限定すること
により、低粘度のものがえられるため、混合物の
粘度を下げ、作業性を高めることも可能である。
分子中に２個以上のアクリロイル基又は、メタア
クリロイル基をもつアクリレート又は、メタアク
リレートとしては、次に示すものが挙げられる。
（以下、（メタ）アクリレートとはアクリレート又
はメタアクリレートを示す。）
脂肪族、脂環族、芳香族の多価アルコールおよ
びポリアルキレングリコールのポリ（メタ）アク
リレート、例えばエチレングリコール（メタ）ア
クリレート、ポリエチレングリコールジ（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、トリメチロールプロパントリ
（メタ）アクリレート等；ポリエステルのポリ
（メタ）アクリレート、例えばマレイン酸とエチ
レングリコールのポリエステルジオールのジ（メ
タ）アクリレート、フタル酸とジエチレングリコ
ールとのポリエステルジオールのジ（メタ）アク
リレート、テトラヒドロフタル酸とペンタエリス
リトールのポリエステルポリオールのポリ（メ
タ）アクリレート等；ビスフエノールＡジグリシ
ジルエーテル型、ポリアルキレングリコールジグ
リシジルエーテル等のエポキシ樹脂と（メタ）ア
クリル酸との付加反応生成物であるエポキシ（メ
タ）アクリレート類；２―ヒドロキシエチル（メ
タ）アクリレートとジイソシアネートとの付加反
応生成物、２―ヒドロキシエチル（メタ）アクリ
レートとジイソシアネートと２価アルコールとの
付加反応生成物の如きポリウレタン（メタ）アク
リレート類；ポリアミド型多価アルコールに（メ
タ）アクリル酸を反応させるか、あるいはポリア
ミド型多価カルボン酸にヒドロキシ基含有（メ
タ）アクリレート又はエポキシ基含有（メタ）ア
クリレートを反応させてえられるポリアミド（メ
タ）アクリレート；側鎖及び／又は、末端に（メ
タ）アクリロイル基を有するビニル系又はジエン
系重合体、例えば（メタ）アクリル変成１，２―
ポリブタジエン；等があげられる。 The best results can be obtained by combining resin composition A, which is cured by irradiation with ionizing radiation, and resin composition B, which is cured by heating, but is not or is difficult to cure by ionizing radiation. What is given is a system in which A is an ester acrylate or ester methacrylate having two or more acryloyl or methacryloyl groups in one molecule, and B is an epoxy resin having two or more oxirane groups in one molecule. It is. The acrylate or methacrylate has high activity against ionizing radiation, and can be 100% cured and insolubilized by irradiation with a dose of several Mrad, which not only makes it possible to increase the production speed but also improves the resin composition to be mixed. B, radiation damage to base materials used for coating, impregnation, etc. can be kept to a minimum. In addition, the acrylate or methacrylate has high compatibility with epoxy resin, and not only can the blending ratio of the two be almost freely selected, but by limiting the molecular weight range in the resin system described below, it is possible to create a low-viscosity product. Therefore, it is possible to lower the viscosity of the mixture and improve workability.
Examples of acrylates or methacrylates having two or more acryloyl groups or methacryloyl groups in the molecule include those shown below.
(Hereinafter, (meth)acrylate refers to acrylate or methacrylate.) Poly(meth)acrylates of aliphatic, alicyclic, and aromatic polyhydric alcohols and polyalkylene glycols, such as ethylene glycol (meth)acrylate, polyethylene Glycoldi (Meta)
Acrylate, 1,4-butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.; poly(meth)acrylate of polyester, di(meth)acrylate of polyester diol of maleic acid and ethylene glycol, phthalic acid di(meth)acrylate of polyester diol with diethylene glycol, poly(meth)acrylate of polyester polyol of tetrahydrophthalic acid and pentaerythritol, etc.; epoxy resin such as bisphenol A diglycidyl ether type, polyalkylene glycol diglycidyl ether, etc. Epoxy (meth)acrylates which are addition reaction products with meth)acrylic acid; addition reaction products between 2-hydroxyethyl (meth)acrylate and diisocyanate, 2-hydroxyethyl (meth)acrylate, diisocyanate and dihydric alcohol Polyurethane (meth)acrylates such as addition reaction products with polyamide-type polyhydric alcohols and (meth)acrylic acid, or polyamide-type polyhydric carboxylic acids with (meth)acrylates containing hydroxy groups or epoxy groups. Polyamide (meth)acrylate obtained by reacting (meth)acrylate; vinyl or diene polymer having (meth)acryloyl groups in side chains and/or terminals, such as (meth)acrylic modified 1,2-
Examples include polybutadiene; etc.
又、ここでいうエポキシ樹脂とは、一分子中に
２個以上のオキシラン基をもつポリエポキサイド
であり、ビスフエノールＡのジグリシジルエーテ
ルの如き多価フエノールのポリグリシジルエーテ
ル；ノボラツクのポリグリシジルエーテル；ネオ
ペンチルグリコール、グリセロール、１，４―ブ
タンジオール、ポリエチレングリコールのような
多価アルコールのポリグリシジルエーテル；フタ
ル酸、アジピン酸、ヘキサヒドロフタル酸のよう
なジカルボン酸のポリグリシジルエステル等を指
すものである。これらのエポキシ樹脂に対する加
熱硬化用の硬化触媒としては、ジアミノジフエニ
ルメタン、ジアミノジフエニルスルホン等の芳香
族アミン；三フツ化ホウ素アミン錯化合物；無水
フタル酸、メチルナジツク酸無水物、メチルエン
ドメチレンテトラヒドロフタル酸無水物等の酸無
水物；ボリアミド化合物；ポリサルフアイド化合
物等が適当である。これら硬化剤に対しては、必
要に応じて、ベンジルメチルアミン、オクチル酸
亜鉛、トリフエニルフオスフエート、芳香族アミ
ンアダクト等の硬化触媒を併用すればよい。 In addition, the epoxy resin referred to herein is a polyepoxide having two or more oxirane groups in one molecule, and includes polyglycidyl ethers of polyhydric phenols such as diglycidyl ether of bisphenol A; polyglycidyl ethers of novolac; Polyglycidyl ethers of polyhydric alcohols such as neopentyl glycol, glycerol, 1,4-butanediol, and polyethylene glycol; polyglycidyl esters of dicarboxylic acids such as phthalic acid, adipic acid, and hexahydrophthalic acid, etc. be. Curing catalysts for heating and curing these epoxy resins include aromatic amines such as diaminodiphenylmethane and diaminodiphenyl sulfone; boron trifluoride amine complex compounds; phthalic anhydride, methylnadic anhydride, and methylendomethylenetetrahydro. Acid anhydrides such as phthalic anhydride; polyamide compounds; polysulfide compounds, etc. are suitable. For these curing agents, a curing catalyst such as benzylmethylamine, zinc octylate, triphenyl phosphate, aromatic amine adduct, etc. may be used in combination, if necessary.
本発明の実施態様を、実施例によつて述べる。
その１例は、電離性放射線を照射することにより
硬化しうる樹脂組成物Ａとして、ポリエチレング
リコールジメタアクリレートを、加熱することに
より硬化しうるが、電離性放射線によつては、硬
化しない、あるいは、しにくい樹脂組成物Ｂとし
てエポキシ樹脂およびその硬化剤を用い、Ａ，Ｂ
両者の混合物を、ガラス繊維、炭素繊維、ポリマ
ー繊維等を使つたクロス、マツト、テープ等に含
浸し、形を整えた後、電離性放射線を照射してえ
られるプリプレグである。このプリプレグは既に
述べた如く無溶剤型であり、一般の溶剤型のプリ
プレグ製造法における様な、大型の加熱乾燥炉を
使つた溶剤蒸発によるエネルギーのロス、作業環
境の悪化、大気汚染などの幣害をなくすことがで
きるだけでなく、時間的にも、溶剤型、加熱硬化
型のプリプレグ製造が、数分という長時間を要す
るのに対し、わずか数秒の電離性放射線の照射で
製造することができ、生産性を大巾に上げること
ができる。それのみならず、本発明によるプリプ
レグは、実施例１、２に示す如く、積層して成型
品を作製した場合にも、一般の積層成型品と、同
等の強度をえることができた。又、実施例３に示
す如く、銅はくに対する接着性も十分であつた。 Embodiments of the present invention will be described by way of examples.
One example is polyethylene glycol dimethacrylate, which can be cured by heating as a resin composition A that can be cured by irradiation with ionizing radiation, but does not cure by ionizing radiation, or , using an epoxy resin and its curing agent as resin composition B that is difficult to harden;
A prepreg is obtained by impregnating a mixture of the two into a cloth, mat, tape, etc. made of glass fiber, carbon fiber, polymer fiber, etc., shaping it, and then irradiating it with ionizing radiation. As mentioned above, this prepreg is solvent-free, and unlike general solvent-based prepreg manufacturing methods, it does not require energy loss due to solvent evaporation using a large heating drying oven, deterioration of the working environment, and air pollution. Not only can it eliminate harmful effects, but it can also be manufactured in just a few seconds by irradiation with ionizing radiation, whereas solvent-based and heat-curable prepreg manufacturing takes several minutes. , productivity can be greatly increased. In addition, as shown in Examples 1 and 2, the prepreg according to the present invention was able to obtain strength equivalent to that of a general laminate molded product even when a molded product was produced by laminating the prepregs. Furthermore, as shown in Example 3, the adhesion to copper foil was also sufficient.
本発明による加熱硬化型先駆体は、実施例６に
示す如くフイルム状にすることも可能であり、こ
れによつて、熱硬化型の接着性フイルムがえられ
る。 The thermosetting precursor according to the present invention can also be made into a film as shown in Example 6, thereby providing a thermosetting adhesive film.
本発明に用いられる電離性放射線としては、加
速電子線、γ線、Ｘ線の他、中性子線、α線、β
線等がある。 In addition to accelerated electron beams, gamma rays, and X-rays, ionizing radiation used in the present invention includes neutron beams, alpha rays, and beta rays.
There are lines etc.
以下の実施例において、部は重量部を表わす。 In the following examples, parts represent parts by weight.
実施例 １
ノボラツク型のエポキシ樹脂（DEN438（商品
名）、ダウケミカル社製）100部、ポリエチレング
リコールジメタアクリレート（NKエステル4G
（商品名）新中村化学社製）50部にエポキシ樹脂
硬化剤として、三フツ化ホウ素モノエチルアミン
錯塩、３部を添加し50℃１時間かくはんし、透明
均一な溶液をえた。この混合物を0.21mm厚Ｅガラ
スの朱子織クロス（ES―21（商品名）日本硝子
繊維社製）に含浸し、ポリエステルフイルムには
さんだ後、加速電子線によつて1.2秒で、6Mrad
の照射を行つたところ可撓性をもつたプリプレグ
がえられた。このプリプレグの樹脂部分につい
て、メチルエチルケトン中で室温24時間の抽出を
行つた前後の重量変化により不溶解分を測定した
ところ35％であつた。これは樹脂混合物中のポリ
エチレングリコールジメタアクリレートの重量に
ほぼ等しい。Example 1 100 parts of novolac type epoxy resin (DEN438 (trade name), manufactured by Dow Chemical Company), polyethylene glycol dimethacrylate (NK Ester 4G
(Product name: Shin Nakamura Chemical Co., Ltd.) 3 parts of boron trifluoride monoethylamine complex salt was added as an epoxy resin curing agent to 50 parts of the solution and stirred at 50°C for 1 hour to obtain a transparent and uniform solution. This mixture was impregnated into a 0.21 mm thick E-glass satin weave cloth (ES-21 (product name) manufactured by Nippon Glass Fiber Co., Ltd.), sandwiched between polyester films, and then heated to 6 Mrad in 1.2 seconds using an accelerated electron beam.
After irradiation, a flexible prepreg was obtained. The resin portion of this prepreg was extracted in methyl ethyl ketone at room temperature for 24 hours, and the insoluble content was measured by the weight change before and after, and it was found to be 35%. This is approximately equal to the weight of polyethylene glycol dimethacrylate in the resin mixture.
上記の如く、えられたプリプレグを11枚重ねて
150℃20Kg/cm2で90分のプレス加工を行い、３mm厚
の積層板をえた。 As shown above, stack the 11 prepregs obtained.
Pressing was performed for 90 minutes at 150°C and 20 kg/cm 2 to obtain a 3 mm thick laminate.
この積層板の曲げ強度を測定したところ35Kg/
mm2弾性率1700Kg/mm2という値がえられた。 The bending strength of this laminate was measured and was 35Kg/
A value of mm 2 elastic modulus of 1700 Kg/mm 2 was obtained.
実施例 ２
ビスフエノールＡジグリシジルエーテル型のエ
ポキシ樹脂（エピコート828（商品名）シエル化
学）100部；ポリエチレングリコールジメタアク
リレート（NKエステル4G）25部に三フツ化ホウ
素モノエチルアミン錯塩３部を添加し、40℃１時
間かくはんし、透明均一な溶液をえた。この溶液
を実施例１と同様にガラスクロスに含浸し、1.2
秒6Mradの電子線照射を行つたところ、可撓性に
優れたプリプレグがえられた。MEK抽出により
エポキシ樹脂は、３次元硬化していないことが確
められた。このプリプレグを12枚重ねて150℃20
Kg/cm2で、120分プレス硬化を行い、３mm厚の積層
板をえた。このものの曲げ強度は41.3Kg/mm2曲げ
弾性率は1910Kg/mm2であつた。Example 2 100 parts of bisphenol A diglycidyl ether type epoxy resin (Epicote 828 (trade name) Ciel Chemical); 3 parts of boron trifluoride monoethylamine complex salt was added to 25 parts of polyethylene glycol dimethacrylate (NK Ester 4G). The mixture was stirred at 40°C for 1 hour to obtain a transparent and homogeneous solution. A glass cloth was impregnated with this solution in the same manner as in Example 1, and 1.2
When irradiated with an electron beam at 6 Mrad per second, a prepreg with excellent flexibility was obtained. MEK extraction confirmed that the epoxy resin was not three-dimensionally cured. Layer 12 sheets of this prepreg at 150℃20
Press hardening was performed at Kg/cm 2 for 120 minutes to obtain a 3 mm thick laminate. The bending strength of this product was 41.3Kg/mm 2 and the bending modulus was 1910Kg/mm 2 .
実施例 ３
ビスフエノールＡジグリシジルエーテル型のエ
ポキシ樹脂（エピコート1001（商品名）シエル化
学）100部、ポリエチレングリコールジメタアク
リレート（NKエステル9G（商品名）新中村化
学）100部に三フツ化ホウ素モノエチルアミン錯
塩３部を添加し、50℃２時間かくはんし、透明均
一な溶液をえた。Example 3 Boron trifluoride was added to 100 parts of bisphenol A diglycidyl ether type epoxy resin (Epicote 1001 (trade name) Ciel Chemical), 100 parts of polyethylene glycol dimethacrylate (NK Ester 9G (trade name) Shin-Nakamura Chemical) 3 parts of monoethylamine complex salt was added and stirred at 50°C for 2 hours to obtain a transparent and homogeneous solution.
この混合物を0.13mm厚Ｅガラスの平織クロス
（EMH1302（商品名）日本硝子繊維社製）に含浸
し、ポリエステルフイルムにはさんで加速電子線
により12Mradの照射を行つたところ、可撓性に
優れたプリプレグがえられた。このプリプレグを
0.035mm厚の銅はくにはり付け、150℃40Kg/cm2で
90分プレスした。こうして作製した銅はり板の剥
離強度を10mm／Ｍの引張強度で測定したところ、
3.80Kg／25mm巾という値がえられた。 This mixture was impregnated into a 0.13 mm thick E glass plain weave cloth (EMH1302 (trade name) manufactured by Nippon Glass Fiber Co., Ltd.), sandwiched between polyester films, and irradiated with an accelerated electron beam at 12 Mrad. Prepreg was obtained. This prepreg
Glued to 0.035mm thick copper foil, 150℃ 40Kg/cm 2
Pressed for 90 minutes. The peel strength of the copper beam plate prepared in this way was measured at a tensile strength of 10 mm/M.
A value of 3.80Kg/25mm width was obtained.
実施例 ４
ビスフエノールＡジグリシジルエーテル型のエ
ポキシ樹脂（エピコート828）100部、三フツ化ホ
ウ素モノエチルアミン錯塩３部を60℃で混合溶解
した液に不飽和ポリエステル樹脂とスチレンモノ
マーの混合体（クラミナツク＃6443（商品名）ク
ラレ社製）50部を混合溶解して透明均一な溶液を
えた。Example 4 A mixture of unsaturated polyester resin and styrene monomer (Claminac) was mixed and dissolved in a solution of 100 parts of bisphenol A diglycidyl ether type epoxy resin (Epicoat 828) and 3 parts of boron trifluoride monoethylamine complex salt at 60°C. 50 parts of #6443 (trade name, manufactured by Kuraray Co., Ltd.) were mixed and dissolved to obtain a transparent and uniform solution.
この混合液をアルミ製のシヤーレに流し込み、
ポリエステルフイルムで表面をカバーして3.6秒
で18Mradの電子線照射を行つたところ、可撓性
に優れた半硬化物がえられた。さらにこの半硬化
物を150℃で60分加熱すると、溶剤不溶の硬質硬
化物がえられた。 Pour this mixture into an aluminum tray,
When the surface was covered with a polyester film and irradiated with an electron beam of 18 Mrad for 3.6 seconds, a semi-cured product with excellent flexibility was obtained. When this semi-cured product was further heated at 150°C for 60 minutes, a hard cured product that was insoluble in solvents was obtained.
実施例 ５
実施例４における不飽和ポリエステル樹脂のか
わりにエポキシアクリレート樹脂とスチレンモノ
マーの混合体（リポキシＲ―840DA（商品名）昭
和高分子製）を50部混合溶解した系に実施例４と
同様に電子線照射を行つたところ、可撓性半硬化
物がえられ、さらに150℃．60分の加熱により、
溶剤不溶の硬質硬化物がえられた。実施例４、５
において電子線照射によつて作製した半硬化物を
メチルエチルケトン中で室温24時間の抽出を行つ
たところ、不溶解分は34〜36％であり、不飽和ポ
リエステル樹脂あるいはエポキシアクリレートの
重量分率に相当するものであつた。Example 5 The same procedure as in Example 4 was made in a system in which 50 parts of a mixture of epoxy acrylate resin and styrene monomer (Lipoxy R-840DA (trade name) manufactured by Showa Kobunshi Co., Ltd.) was mixed and dissolved instead of the unsaturated polyester resin in Example 4. When irradiated with electron beam, a flexible semi-cured product was obtained, and further heated at 150℃. By heating for 60 minutes,
A hard cured product insoluble in solvents was obtained. Examples 4 and 5
When the semi-cured material prepared by electron beam irradiation was extracted in methyl ethyl ketone at room temperature for 24 hours, the insoluble content was 34-36%, which corresponds to the weight fraction of unsaturated polyester resin or epoxy acrylate. It was something to do.
実施例 ６
ビスフエノールＡジグリシジルエーテル型のエ
ポキシ樹脂（エピコート828）100部、グリシジル
メタアクリレートモノマー25部、三フツ化ホウ素
モノエチルアミン錯塩３部を混合溶解し、さらに
ポリエチレングリコールジメタアクリレート
（NKエステル4G）を25部加え、混合して透明均
一な溶液をえた。Example 6 100 parts of bisphenol A diglycidyl ether type epoxy resin (Epicote 828), 25 parts of glycidyl methacrylate monomer, and 3 parts of boron trifluoride monoethylamine complex salt were mixed and dissolved, and polyethylene glycol dimethacrylate (NK ester) was mixed and dissolved. 4G) was added and mixed to obtain a clear homogeneous solution.
この樹脂組成物をポリエステルフイルムの間に
はさみ、1.2秒で6Mradの電子線照射を行い、厚
さ約70μｍのやわらかいフイルムをえた。このフ
イルムを厚さ１mmのアルミ板の間にはさみ、150
℃で５Kg/cm2のプレスを90分行い、アルミ板を接
着した後、引張せん断強度を測定したところ100
Kg/cm2という値がえられた。 This resin composition was sandwiched between polyester films and irradiated with an electron beam of 6 Mrad for 1.2 seconds to obtain a soft film with a thickness of about 70 μm. Sandwich this film between 1 mm thick aluminum plates and
After pressing at 5Kg/ cm2 at ℃ for 90 minutes and adhering the aluminum plate, the tensile shear strength was measured and it was 100.
A value of Kg/cm 2 was obtained.
Claims (1)
しうる樹脂組成物Ａと加熱することによつて硬化
しうるが、電離性放射線によつては硬化しない
か、あるいはしにくい樹脂組成物Ｂを混合し、こ
の混合物をシート状、フイルム状に成形あるいは
他の基材へもしくは含浸させ、電離性放射線を照
射することにより、前記Ａのみを硬化させてなる
加熱硬化型先駆体であつて、前記Ａの前記Ｂに対
する配合比が10〜50重量％であることを特徴とす
る加熱硬化型先駆体。 ２ 電離性放射線を照射することにより硬化しう
る樹脂組成物Ａが、１分子中に２個以上のアクリ
ロイル基又はメタアクリロイル基をもつアクリレ
ート又は、メタアクリレートを主成分とし、加熱
することによつて硬化しうるが、電離性放射線に
よつては硬化しないか、あるいはしにくい樹脂組
成物Ｂが、１分子中に２個以上のオキシラン基を
もつエポキシ樹脂およびエポキシ樹脂の硬化剤を
主成分とすることを特徴とする特許請求範囲１項
記載の加熱硬化型先駆体。 ３ 電離性放射線を照射することにより、硬化し
うる樹脂組成物Ａが、不飽和ポリエステル樹脂を
主成分とし、加熱することにより硬化しうるが、
電離性放射線によつては硬化しないか、あるいは
しにくい樹脂組成物Ｂが、１分子中に２個以上の
オキシラン基をもつエポキシ樹脂およびエポキシ
樹脂の硬化剤を主成分とすることを特徴とする特
許請求範囲１項記載の加熱硬化型先駆体。 ４ 電離性放射線を照射することにより、硬化し
うる樹脂組成物Ａがポリエチレングリコールのジ
アクリレート又はジメタアクリレートを主成分と
することを特徴とする特許請求範囲２項記載の加
熱硬化型先駆体。 ５ 電離性放射線を照射することにより硬化しう
る樹脂組成物Ａがエポキシ樹脂とアクリル酸又は
メタアクリル酸の付加反応でえられるエポキシア
クリレートあるいはエポキシメタアクリレートを
主成分とすることを特徴とする特許請求範囲２項
記載の加熱硬化型先駆体。 ６ 電離性放射線を照射することによつて、硬化
しうる樹脂組成物Ａと、加熱することによつて硬
化しうるが電離性放射線によつては硬化しない
か、あるいはしにくい樹脂組成物Ｂを混合し、こ
の混合物をガラス繊維に含浸成型し、電離性放射
線を照射することにより樹脂組成物Ａのみを硬化
させたことを特徴とする特許請求範囲１項記載の
加熱硬化型先駆体。[Claims] 1. Resin composition A that can be cured by irradiation with ionizing radiation can be cured by heating, but does not cure or does not cure by ionizing radiation. A heat-curing type precursor, which is obtained by mixing a hard resin composition B, molding the mixture into a sheet or film shape, or impregnating or impregnating it onto another base material, and curing only the above A by irradiating the mixture with ionizing radiation. 1. A heat-curable precursor, characterized in that the blending ratio of A to B is 10 to 50% by weight. 2. Resin composition A that can be cured by irradiation with ionizing radiation has an acrylate or methacrylate as a main component having two or more acryloyl groups or methacryloyl groups in one molecule, and is cured by heating. Resin composition B that can be cured but does not or is difficult to cure by ionizing radiation mainly contains an epoxy resin having two or more oxirane groups in one molecule and a curing agent for the epoxy resin. The heat-curable precursor according to claim 1, characterized in that: 3. Resin composition A that can be cured by irradiation with ionizing radiation contains an unsaturated polyester resin as a main component and can be cured by heating,
Resin composition B, which does not cure or is difficult to cure by ionizing radiation, is characterized in that the main component is an epoxy resin having two or more oxirane groups in one molecule and a curing agent for the epoxy resin. A heat-curable precursor according to claim 1. 4. The thermosetting precursor according to claim 2, wherein the resin composition A, which can be cured by irradiation with ionizing radiation, contains polyethylene glycol diacrylate or dimethacrylate as a main component. 5. A patent claim characterized in that the resin composition A, which can be cured by irradiation with ionizing radiation, contains as a main component epoxy acrylate or epoxy methacrylate obtained by an addition reaction between an epoxy resin and acrylic acid or methacrylic acid. A heat-curable precursor according to Item 2. 6. Resin composition A that can be cured by irradiation with ionizing radiation, and resin composition B that can be cured by heating but does not or is difficult to cure by ionizing radiation. 2. The heat-curable precursor according to claim 1, wherein only the resin composition A is cured by mixing, impregnating and molding the mixture into glass fibers, and irradiating with ionizing radiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9428777A JPS5428356A (en) | 1977-08-05 | 1977-08-05 | Heat-curable precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9428777A JPS5428356A (en) | 1977-08-05 | 1977-08-05 | Heat-curable precursor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5428356A JPS5428356A (en) | 1979-03-02 |
| JPS6145663B2 true JPS6145663B2 (en) | 1986-10-09 |
Family
ID=14106034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9428777A Granted JPS5428356A (en) | 1977-08-05 | 1977-08-05 | Heat-curable precursor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5428356A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58132067A (en) * | 1982-01-30 | 1983-08-06 | Nitto Electric Ind Co Ltd | Reinforcing adhesive sheet |
| JPS58132065A (en) * | 1982-01-30 | 1983-08-06 | Nitto Electric Ind Co Ltd | Reinforcing adhesive sheet |
| JPS58132066A (en) * | 1982-01-30 | 1983-08-06 | Nitto Electric Ind Co Ltd | Reinforcing adhesive sheet |
| JPS60221478A (en) * | 1984-04-18 | 1985-11-06 | Hitachi Chem Co Ltd | Production of radiation curing adhesive tape |
| JPS60221479A (en) * | 1984-04-18 | 1985-11-06 | Hitachi Chem Co Ltd | Production of radiation curing adhesive tape |
| JPS6399283A (en) * | 1986-10-16 | 1988-04-30 | Ibiden Co Ltd | Thermosetting adhesive sheet |
| JPH0715087B2 (en) * | 1988-07-21 | 1995-02-22 | リンテック株式会社 | Adhesive tape and method of using the same |
-
1977
- 1977-08-05 JP JP9428777A patent/JPS5428356A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5428356A (en) | 1979-03-02 |
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