WO2022210246A1 - Epoxy resin composition, cured epoxy resin product, and coated fiber-reinforced resin molded article obtained using same - Google Patents
Epoxy resin composition, cured epoxy resin product, and coated fiber-reinforced resin molded article obtained using same Download PDFInfo
- Publication number
- WO2022210246A1 WO2022210246A1 PCT/JP2022/013895 JP2022013895W WO2022210246A1 WO 2022210246 A1 WO2022210246 A1 WO 2022210246A1 JP 2022013895 W JP2022013895 W JP 2022013895W WO 2022210246 A1 WO2022210246 A1 WO 2022210246A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- epoxy
- fiber
- resin composition
- reinforced
- Prior art date
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 178
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 177
- 229920005989 resin Polymers 0.000 title claims abstract description 140
- 239000011347 resin Substances 0.000 title claims abstract description 140
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 73
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 43
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 28
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 23
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 20
- 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 abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 59
- 238000000576 coating method Methods 0.000 claims description 59
- 239000011247 coating layer Substances 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000004918 carbon fiber reinforced polymer Substances 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 5
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 abstract description 35
- 239000007788 liquid Substances 0.000 description 41
- 239000000463 material Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 38
- 239000003733 fiber-reinforced composite Substances 0.000 description 27
- -1 thiol compound Chemical class 0.000 description 27
- 229920000049 Carbon (fiber) Polymers 0.000 description 22
- 239000004917 carbon fiber Substances 0.000 description 22
- 239000000835 fiber Substances 0.000 description 21
- 239000004593 Epoxy Substances 0.000 description 18
- 150000004714 phosphonium salts Chemical group 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 239000012783 reinforcing fiber Substances 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 238000002845 discoloration Methods 0.000 description 12
- 239000004744 fabric Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 150000003573 thiols Chemical class 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000011342 resin composition Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011295 pitch Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 4
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011151 fibre-reinforced plastic Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000011417 postcuring Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- LABQKWYHWCYABU-UHFFFAOYSA-N 4-(3-sulfanylbutanoyloxy)butyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCCCOC(=O)CC(C)S LABQKWYHWCYABU-UHFFFAOYSA-N 0.000 description 3
- 239000004412 Bulk moulding compound Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000003677 Sheet moulding compound Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- LYMYULOYDUWMOP-UHFFFAOYSA-M diethoxy-sulfanylidene-sulfido-$l^{5}-phosphane;tetrabutylphosphanium Chemical compound CCOP([S-])(=S)OCC.CCCC[P+](CCCC)(CCCC)CCCC LYMYULOYDUWMOP-UHFFFAOYSA-M 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- PAEWNKLGPBBWNM-UHFFFAOYSA-N 1,3,5-tris[2-(3-sulfanylbutoxy)ethyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(S)CCOCCN1C(=O)N(CCOCCC(C)S)C(=O)N(CCOCCC(C)S)C1=O PAEWNKLGPBBWNM-UHFFFAOYSA-N 0.000 description 2
- XETDBHNHTOJWPZ-UHFFFAOYSA-M 2-(1,3-dioxan-2-yl)ethyl-triphenylphosphanium;bromide Chemical compound [Br-].O1CCCOC1CC[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XETDBHNHTOJWPZ-UHFFFAOYSA-M 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 description 2
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 2
- YJPDLBMZLGTDRZ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;tributyl(methyl)phosphanium Chemical compound CCCC[P+](C)(CCCC)CCCC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YJPDLBMZLGTDRZ-UHFFFAOYSA-N 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
- 230000007547 defect Effects 0.000 description 2
- LSDYBCGXPCFFNM-UHFFFAOYSA-M dimethyl phosphate;tributyl(methyl)phosphanium Chemical compound COP([O-])(=O)OC.CCCC[P+](C)(CCCC)CCCC LSDYBCGXPCFFNM-UHFFFAOYSA-M 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 2
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- RLZMYANQLOCZOB-UHFFFAOYSA-M tributyl(methyl)phosphanium;iodide Chemical compound [I-].CCCC[P+](C)(CCCC)CCCC RLZMYANQLOCZOB-UHFFFAOYSA-M 0.000 description 2
- FWBSWSPGFNAXPP-UHFFFAOYSA-M (2,4-dichlorophenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].ClC1=CC(Cl)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 FWBSWSPGFNAXPP-UHFFFAOYSA-M 0.000 description 1
- VRAAQIWOSHYDHE-UHFFFAOYSA-M (2-chlorophenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].ClC1=CC=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 VRAAQIWOSHYDHE-UHFFFAOYSA-M 0.000 description 1
- VJVZPTPOYCJFNI-UHFFFAOYSA-M (2-ethoxy-2-oxoethyl)-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)OCC)C1=CC=CC=C1 VJVZPTPOYCJFNI-UHFFFAOYSA-M 0.000 description 1
- FKKZGQXMWVGPMH-UHFFFAOYSA-N (2-hydroxyphenyl)methyl-triphenylphosphanium;bromide Chemical compound [Br-].OC1=CC=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 FKKZGQXMWVGPMH-UHFFFAOYSA-N 0.000 description 1
- VCWBQLMDSMSVRL-UHFFFAOYSA-M (2-methoxy-2-oxoethyl)-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)OC)C1=CC=CC=C1 VCWBQLMDSMSVRL-UHFFFAOYSA-M 0.000 description 1
- BLALYSCMLUQKSG-UHFFFAOYSA-M (3,4-dimethoxyphenyl)methyl-triphenylphosphanium;bromide Chemical compound [Br-].C1=C(OC)C(OC)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BLALYSCMLUQKSG-UHFFFAOYSA-M 0.000 description 1
- NNJRPZZMNBNRFJ-UHFFFAOYSA-N (3-ethoxy-3-oxo-2-phenylpropyl)azanium;chloride Chemical compound Cl.CCOC(=O)C(CN)C1=CC=CC=C1 NNJRPZZMNBNRFJ-UHFFFAOYSA-N 0.000 description 1
- DPYDLIVUYPUXBV-UHFFFAOYSA-M (3-methoxyphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].COC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 DPYDLIVUYPUXBV-UHFFFAOYSA-M 0.000 description 1
- FQJYKXVQABPCRA-UHFFFAOYSA-M (4-bromophenyl)methyl-triphenylphosphanium;bromide Chemical compound [Br-].C1=CC(Br)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 FQJYKXVQABPCRA-UHFFFAOYSA-M 0.000 description 1
- RAHOAHBOOHXRDY-UHFFFAOYSA-M (4-chlorophenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].C1=CC(Cl)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 RAHOAHBOOHXRDY-UHFFFAOYSA-M 0.000 description 1
- MZBKKJRCQNVENM-UHFFFAOYSA-M (4-ethoxyphenyl)methyl-triphenylphosphanium;bromide Chemical compound [Br-].C1=CC(OCC)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MZBKKJRCQNVENM-UHFFFAOYSA-M 0.000 description 1
- IPJPTPFIJLFWLP-UHFFFAOYSA-M (4-nitrophenyl)methyl-triphenylphosphanium;bromide Chemical compound [Br-].C1=CC([N+](=O)[O-])=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 IPJPTPFIJLFWLP-UHFFFAOYSA-M 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N 1-butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- CEUQYYYUSUCFKP-UHFFFAOYSA-N 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol Chemical compound SCCSCC(CS)SCCS CEUQYYYUSUCFKP-UHFFFAOYSA-N 0.000 description 1
- YIIHEMGEQQWSMA-UHFFFAOYSA-M 2-(dimethylamino)ethyl-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCN(C)C)C1=CC=CC=C1 YIIHEMGEQQWSMA-UHFFFAOYSA-M 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- BXYWKXBAMJYTKP-UHFFFAOYSA-N 2-[2-[2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOCCOCCOC(=O)CCS BXYWKXBAMJYTKP-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 description 1
- TZLVUWBGUNVFES-UHFFFAOYSA-N 2-ethyl-5-methylpyrazol-3-amine Chemical compound CCN1N=C(C)C=C1N TZLVUWBGUNVFES-UHFFFAOYSA-N 0.000 description 1
- XAMZZEBAJZJERT-UHFFFAOYSA-M 2-oxopropyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)C)C1=CC=CC=C1 XAMZZEBAJZJERT-UHFFFAOYSA-M 0.000 description 1
- NKVJKVMGJABKHV-UHFFFAOYSA-N 3-carboxypropyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC(=O)O)C1=CC=CC=C1 NKVJKVMGJABKHV-UHFFFAOYSA-N 0.000 description 1
- AVMUCZNGCWTULU-UHFFFAOYSA-N 4-bromo-3-chlorobenzohydrazide Chemical compound NNC(=O)C1=CC=C(Br)C(Cl)=C1 AVMUCZNGCWTULU-UHFFFAOYSA-N 0.000 description 1
- MLOSJPZSZWUDSK-UHFFFAOYSA-N 4-carboxybutyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCC(=O)O)C1=CC=CC=C1 MLOSJPZSZWUDSK-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- OAAPJLMVZWDEJE-UHFFFAOYSA-N CCCCC[P+](CC)(CC)CC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F Chemical compound CCCCC[P+](CC)(CC)CC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F OAAPJLMVZWDEJE-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- GIGIQZILMFVZQM-UHFFFAOYSA-M [2-(1,3-dioxan-2-yl)phenyl]-methyl-diphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C(=CC=CC=1)C1OCCCO1)(C)C1=CC=CC=C1 GIGIQZILMFVZQM-UHFFFAOYSA-M 0.000 description 1
- ZGLFRTJDWWKIAK-UHFFFAOYSA-M [2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)OC(C)(C)C)C1=CC=CC=C1 ZGLFRTJDWWKIAK-UHFFFAOYSA-M 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UBGVHKXCHHMPRK-UHFFFAOYSA-N benzotriazol-2-ide;tetrabutylphosphanium Chemical compound C1=CC=CC2=N[N-]N=C21.CCCC[P+](CCCC)(CCCC)CCCC UBGVHKXCHHMPRK-UHFFFAOYSA-N 0.000 description 1
- WTEPWWCRWNCUNA-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 WTEPWWCRWNCUNA-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- VGANZAMOUWXNNY-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide triethyl(octyl)phosphanium Chemical compound CCCCCCCC[P+](CC)(CC)CC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F VGANZAMOUWXNNY-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YFTMLUSIDVFTKU-UHFFFAOYSA-M bromomethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CBr)C1=CC=CC=C1 YFTMLUSIDVFTKU-UHFFFAOYSA-M 0.000 description 1
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 description 1
- SXYFAZGVNNYGJQ-UHFFFAOYSA-M chloromethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCl)C1=CC=CC=C1 SXYFAZGVNNYGJQ-UHFFFAOYSA-M 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- DOMOOBQQQGXLGU-UHFFFAOYSA-N cyanoiminomethylideneazanide;trihexyl(tetradecyl)phosphanium Chemical compound [N-]=C=NC#N.CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC DOMOOBQQQGXLGU-UHFFFAOYSA-N 0.000 description 1
- ARPLQAMUUDIHIT-UHFFFAOYSA-M cyanomethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC#N)C1=CC=CC=C1 ARPLQAMUUDIHIT-UHFFFAOYSA-M 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- XMPWFKHMCNRJCL-UHFFFAOYSA-M cyclopropyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C1CC1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XMPWFKHMCNRJCL-UHFFFAOYSA-M 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- VRAYVWUMBAJVGH-UHFFFAOYSA-M ethenyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=C)C1=CC=CC=C1 VRAYVWUMBAJVGH-UHFFFAOYSA-M 0.000 description 1
- TUDUDQJRUPFUMA-UHFFFAOYSA-M ethyl(trioctyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCC[P+](CC)(CCCCCCCC)CCCCCCCC TUDUDQJRUPFUMA-UHFFFAOYSA-M 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- FATAVLOOLIRUNA-UHFFFAOYSA-N formylmethyl Chemical group [CH2]C=O FATAVLOOLIRUNA-UHFFFAOYSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- WCZSOHSGMBVYFW-UHFFFAOYSA-M heptyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCC)C1=CC=CC=C1 WCZSOHSGMBVYFW-UHFFFAOYSA-M 0.000 description 1
- PWDFZWZPWFYFTC-UHFFFAOYSA-M hexyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCC)C1=CC=CC=C1 PWDFZWZPWFYFTC-UHFFFAOYSA-M 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- SJFNDMHZXCUXSA-UHFFFAOYSA-M methoxymethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(COC)C1=CC=CC=C1 SJFNDMHZXCUXSA-UHFFFAOYSA-M 0.000 description 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 1
- QRPRIOOKPZSVFN-UHFFFAOYSA-M methyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 QRPRIOOKPZSVFN-UHFFFAOYSA-M 0.000 description 1
- JNMIXMFEVJHFNY-UHFFFAOYSA-M methyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 JNMIXMFEVJHFNY-UHFFFAOYSA-M 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- MOYSMPXSEXYEJV-UHFFFAOYSA-M naphthalen-1-ylmethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC2=CC=CC=C2C=1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MOYSMPXSEXYEJV-UHFFFAOYSA-M 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- VAUKWMSXUKODHR-UHFFFAOYSA-M pentyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCC)C1=CC=CC=C1 VAUKWMSXUKODHR-UHFFFAOYSA-M 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- AEHDSYHVTDJGDN-UHFFFAOYSA-M phenacyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1C(=O)C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AEHDSYHVTDJGDN-UHFFFAOYSA-M 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- ZOMVKCHODRHQEV-UHFFFAOYSA-M tetraethylphosphanium;hydroxide Chemical compound [OH-].CC[P+](CC)(CC)CC ZOMVKCHODRHQEV-UHFFFAOYSA-M 0.000 description 1
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- AEFPPQGZJFTXDR-UHFFFAOYSA-M tetraphenylphosphanium;iodide Chemical compound [I-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AEFPPQGZJFTXDR-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- JBKMIQBGAFQGNO-UHFFFAOYSA-M tributyl(1,3-dioxan-2-ylmethyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CC1OCCCO1 JBKMIQBGAFQGNO-UHFFFAOYSA-M 0.000 description 1
- JCHWNYYARSRCKZ-UHFFFAOYSA-M tributyl(cyanomethyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC#N JCHWNYYARSRCKZ-UHFFFAOYSA-M 0.000 description 1
- ABJGUZZWSKMTEI-UHFFFAOYSA-M tributyl(dodecyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC ABJGUZZWSKMTEI-UHFFFAOYSA-M 0.000 description 1
- RYVBINGWVJJDPU-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC RYVBINGWVJJDPU-UHFFFAOYSA-M 0.000 description 1
- NNENFOSYDBTCBO-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC NNENFOSYDBTCBO-UHFFFAOYSA-M 0.000 description 1
- UJMLRSWRUXXZEW-UHFFFAOYSA-M tributyl(octyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCC[P+](CCCC)(CCCC)CCCC UJMLRSWRUXXZEW-UHFFFAOYSA-M 0.000 description 1
- XUNCOSCFGRBTRX-UHFFFAOYSA-M triethyl(octyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCC[P+](CC)(CC)CC XUNCOSCFGRBTRX-UHFFFAOYSA-M 0.000 description 1
- HESQQIOZXPMZKL-UHFFFAOYSA-M triethyl(pentyl)phosphanium;bromide Chemical compound [Br-].CCCCC[P+](CC)(CC)CC HESQQIOZXPMZKL-UHFFFAOYSA-M 0.000 description 1
- JXLXUMBTJJLQGB-UHFFFAOYSA-M triphenyl(1-trimethylsilylpropan-2-yl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(C[Si](C)(C)C)C)C1=CC=CC=C1 JXLXUMBTJJLQGB-UHFFFAOYSA-M 0.000 description 1
- NEUMNYXEDIPGJD-UHFFFAOYSA-M triphenyl(2-trimethylsilylethoxymethyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(COCC[Si](C)(C)C)C1=CC=CC=C1 NEUMNYXEDIPGJD-UHFFFAOYSA-M 0.000 description 1
- NXZYPOSEOPBJMW-UHFFFAOYSA-M triphenyl(2-trimethylsilylethyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC[Si](C)(C)C)C1=CC=CC=C1 NXZYPOSEOPBJMW-UHFFFAOYSA-M 0.000 description 1
- FWYKRJUVEOBFGH-UHFFFAOYSA-M triphenyl(prop-2-enyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 FWYKRJUVEOBFGH-UHFFFAOYSA-M 0.000 description 1
- FKMJROWWQOJRJX-UHFFFAOYSA-M triphenyl(prop-2-enyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 FKMJROWWQOJRJX-UHFFFAOYSA-M 0.000 description 1
- AFZDAWIXETXKRE-UHFFFAOYSA-M triphenyl(prop-2-ynyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC#C)C1=CC=CC=C1 AFZDAWIXETXKRE-UHFFFAOYSA-M 0.000 description 1
- HHBXWXJLQYJJBW-UHFFFAOYSA-M triphenyl(propan-2-yl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(C)C)C1=CC=CC=C1 HHBXWXJLQYJJBW-UHFFFAOYSA-M 0.000 description 1
- XMQSELBBYSAURN-UHFFFAOYSA-M triphenyl(propyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 XMQSELBBYSAURN-UHFFFAOYSA-M 0.000 description 1
- FUMBGFNGBMYHGH-UHFFFAOYSA-M triphenyl(tetradecyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCCCCCCCCC)C1=CC=CC=C1 FUMBGFNGBMYHGH-UHFFFAOYSA-M 0.000 description 1
- PJQVALHFZIYJMT-UHFFFAOYSA-M triphenyl(thiophen-2-ylmethyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CS1 PJQVALHFZIYJMT-UHFFFAOYSA-M 0.000 description 1
- APIBROGXENTUGB-ZUQRMPMESA-M triphenyl-[(e)-3-phenylprop-2-enyl]phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C\C=C\C1=CC=CC=C1 APIBROGXENTUGB-ZUQRMPMESA-M 0.000 description 1
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
Definitions
- the present invention relates to an epoxy resin composition, a cured epoxy resin, and a coated fiber-reinforced resin molded product using the same.
- FRP fiber reinforced plastic
- Sheet molding compound (SMC) molding methods and bulk molding compound (BMC) molding methods are often used as manufacturing methods for fiber-reinforced resin molded products.
- the resin transfer molding (RTM) method has attracted attention and is being applied.
- the resin transfer molding (RTM) method can use reinforcing fibers in the form of continuous fibers, has very high mechanical properties, and is excellent in productivity because it can be molded in a short cycle time.
- fiber-reinforced resin molded products obtained by these molding methods have defects due to insufficient resin filling on the surface, and surface unevenness occurs due to the shape of the reinforcing fiber and the shrinkage of the resin.
- the surface smoothness is inferior to that of metal members that are often used from the ground up.
- the surface of the fiber-reinforced resin molded article needs to be repaired and polished before being painted, which sometimes requires a great deal of labor.
- the surface may not be sufficiently smooth in some cases.
- the fiber-reinforced resin molded product is transferred to a mold having a molding temperature lower than the curing temperature.
- a composition (a resin different from the matrix resin) for covering the fiber-reinforced resin molded product is injected and cured between the surface of the fiber-reinforced resin molded product and the surface of the mold, thereby reducing the fibers on the surface of the molded product.
- a coated fiber-reinforced resin molded article with hidden eyes and pinholes was obtained.
- the composition used for coating the fiber-reinforced resin molding used in this case includes, for example, a combination of an aliphatic epoxy resin having an alicyclic skeleton, a thiol compound, and phosphines, and low-temperature fast-curing properties, weather resistance, Tg
- a coating resin composition (Patent Document 2) that aims to improve the transparency, and an epoxy resin composition that combines a quaternary phosphonium salt, a secondary or tertiary thiol compound, and a polyepoxy compound and has excellent transparency
- Patent Document 3 a curable epoxy resin composition for optical semiconductor encapsulation, which is obtained by combining an epoxy resin having an epoxy group having an alicyclic structure, that is, an alicyclic epoxy resin, a monoallyl diglycidyl isocyanurate compound, and an acid anhydride-based curing agent.
- Patent Document 4 an epoxy resin composition for light-emitting diodes having excellent light transmittance and refractive index, which is obtained by combining an epoxy resin having no carbon-carbon double bond and a polythiol-based curing agent (Patent Document 5).
- JP 2017-109502 A Japanese Patent Application No. 2018-539446 JP 2013-221091 A JP 2015-034297 A JP 2007-109915 A
- composition for coating the fiber-reinforced resin molded article described in Patent Document 1 has excellent transparency as a coating, shortens the occupancy time in the mold, and improves productivity, so it has a low viscosity. Curing in a short time at low temperature, high weather resistance and Tg are required, respectively, thiol-based curing agent excellent in low-temperature fast curing, epoxy resin with an epoxy group having an alicyclic structure with excellent weather resistance and Tg, Thus, a combination of cycloaliphatic epoxies is preferred.
- the reaction between an alicyclic epoxy and a thiol-based curing agent has a slow reaction rate from the viewpoint of steric hindrance, and is not suitable for low-temperature rapid curing.
- the epoxy resin described in the epoxy resin composition described in Patent Document 2 has an alicyclic skeleton and has fast curing properties. In comparison, the Tg improving effect is not sufficient.
- Patent Document 3 if an epoxy resin containing an aromatic ring is used, both Tg and fast curability can be achieved, but the weather resistance is poor because it absorbs ultraviolet rays.
- Patent Document 4 is excellent in terms of Tg and weather resistance, but is insufficient in low-temperature rapid curability due to the use of an acid anhydride.
- Patent Document 5 there is no description of forming a film of a fiber-reinforced composite material, and the composition is based on the premise of high-temperature curing.
- the object of the present invention is to provide an epoxy resin that can reduce the surface unevenness caused by the temperature difference between the molding temperature (curing temperature) and normal temperature when molding a fiber reinforced resin, and has high surface quality and excellent weather resistance.
- An object of the present invention is to provide a composition, a cured epoxy resin product, and a coated fiber-reinforced resin molded product using the same.
- the epoxy resin composition of the present invention comprises an epoxy resin (A) comprising a single or multiple epoxy resins, a thiol group-containing curing agent (B), a catalyst
- the epoxy resin (A1) which accounts for 50% or more by weight of the epoxy resins constituting the epoxy resin (A), has a difunctional epoxy group having a glycidyl structure. above and one or more epoxy groups having an alicyclic structure.
- the ratio of the functional group number [AG] of the epoxy group having a glycidyl structure contained in the epoxy resin (A) to the functional group number [AF] of the epoxy group having an alicyclic structure is has a relationship of [AG]/[AF]>0.7.
- neither the epoxy resin (A) nor the thiol group-containing curing agent (B) contain carbon-carbon unsaturated bonds.
- the epoxy resin cured product of the present invention is an epoxy resin cured product obtained by curing the epoxy resin composition of the present invention, and has a glass transition temperature (Tg) of 40°C or higher.
- the coated fiber-reinforced resin molded article of the present invention is obtained by coating at least part of the surface of the fiber-reinforced resin molded article with the cured epoxy resin of the present invention as a coating layer.
- the fiber-reinforced resin molded article is carbon fiber-reinforced plastic.
- a coating film is further formed by clear coating on the surface of the coating layer.
- the present invention when a fiber-reinforced resin is molded, it is possible to greatly reduce the surface unevenness caused by the temperature difference between the molding temperature (curing temperature) and normal temperature, and the epoxy resin composition has excellent weather resistance. It becomes possible to provide epoxy resin cured products and coated fiber-reinforced resin molded products.
- the epoxy resin composition of the present invention is an epoxy resin composition containing at least an epoxy resin (A) consisting of a single or multiple epoxy resins, a thiol group-containing curing agent (B), and a catalyst (C), wherein the epoxy resin Among the epoxy resins constituting (A), the epoxy resin (A1), which accounts for 50% or more by weight, has two or more functional epoxy groups having a glycidyl structure and one or more functional epoxy groups having an alicyclic structure.
- the term “epoxy group having a glycidyl structure” refers to a glycidyl group ((C 2 H 3 O)—CH 2 ) in which methylene is bonded to oxirane.
- the term “epoxy group having an alicyclic structure” refers to a compound in which an epoxy group is partly contained in a compound in which carbon atoms are cyclically bonded (alicyclic compound).
- Epoxy groups with a glycidyl structure react quickly with thiols even at low temperatures. Therefore, since the epoxy group having a glycidyl structure has two or more functionalities, the epoxy resin can be incorporated into the network structure of the cured product even if it is cured at a low temperature in a short time, reducing the amount of epoxy resin that remains as a low molecular weight. and have sufficient adhesion to remove from the mold.
- neither the epoxy resin (A) nor the thiol group-containing curing agent (B) contain a carbon-carbon unsaturated bond.
- a carbon-carbon unsaturated bond By not containing a carbon-carbon unsaturated bond, discoloration of the resin due to ultraviolet rays can be prevented, and it can be used outdoors for a long period of time.
- the fiber-reinforced resin molded product is coated with the epoxy resin composition used in the present invention and then coated with a paint containing an ultraviolet absorber
- the shape of the fiber-reinforced resin molded product to be coated includes an upright surface, Dripping of the paint occurs during painting, and the coating film thickness becomes uneven due to work variations, and the effect of the ultraviolet absorber is reduced in areas where the film thickness is thin. It is important to keep it.
- the expression "including standing surfaces” means that adjacent surfaces in the fiber-reinforced resin molded article have surfaces in which the other surface is inclined by 30° or more with respect to the tangential direction of one surface.
- the coating film thickness is preferably 100 ⁇ m or less, more preferably 60 ⁇ m, and still more preferably 40 ⁇ m or less.
- the epoxy equivalent and active hydrogen equivalent of the epoxy resin (A) and thiol group-containing curing agent (B) used in the present invention are preferably 170 g/eq or less. By keeping the epoxy equivalent low, it is possible to have a dense three-dimensional structure, which increases the Tg of the cured product. It also has good adhesion to plastic products with small surface free energy such as fiber reinforced resin molded products containing
- the viscosity of each of the epoxy resin (A) and the thiol group-containing curing agent (B) is preferably 80 Pa ⁇ s or less at 25°C.
- the viscosity of each of the epoxy resin (A) and the thiol group-containing curing agent (B) is preferably 80 Pa ⁇ s or less at 25°C.
- the epoxy resin (A) and the thiol group-containing curing agent (B) can be mixed with a static mixer. , more preferred.
- the viscosity after mixing the epoxy resin (A) and the thiol group-containing curing agent (B) is 10 Pa s or less at 25 ° C., it can be sufficiently flowed into the mold even at a low temperature. preferable.
- the epoxy resin composition is composed only of non-volatile matter.
- the epoxy resin composition of the present invention preferably has a vapor pressure of 0.5 kPa or less in a mold temperature environment.
- the epoxy resin (A1) which accounts for 50% or more by weight, has an epoxy group having a glycidyl structure with at least two functionalities and an alicyclic It has one or more functional epoxy groups having a structure.
- the epoxy resin (A1) may be any epoxy resin having two or more functional epoxy groups having a glycidyl structure and one or more functional epoxy groups having an alicyclic structure. Diglycidyl 4,5-epoxyhexahydrophthalate is preferred because it has high weather resistance and low viscosity because it does not contain any.
- epoxy resin (A1) when two or more types of epoxy resins having two or more functional epoxy groups having a glycidyl structure and one or more functional epoxy groups having an alicyclic structure are included, the total content of these epoxy resins is 50 by weight. % or more, these epoxy resins are combined to be the epoxy resin (A1).
- the epoxy resin (A) may contain an epoxy resin (A2) as an epoxy resin other than the epoxy resin (A1).
- epoxy resins (A2) include 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 1-epoxyethyl-3,4- Those having an alicyclic structure such as epoxycyclohexane, limonene diepoxide, dicyclopentadiene diepoxide, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, sorbitol Liquid epoxy resins having an epoxy group having a glycidyl structure such as polyglycidyl ether, glycerol polyglycidyl ether, polyglyce
- the thiol group-containing curing agent (B) used in the present invention more specifically refers to a compound having two or more thiol groups in one molecule capable of reacting with the epoxy group of the epoxy resin (A). acts as a curing agent for
- a thiol compound as a curing agent, it is expected that even when forming a cured film at a temperature lower than the temperature at which the fiber-reinforced composite material is molded, it will be possible to cure at a sufficiently high speed and increase productivity. be done.
- thiol group-containing curing agents (B) include pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate ), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine- 2,4,6(1H,3H,5H)-trione, bisphenol A-type thiol,
- the thiol group-containing curing agent (B) preferably has a secondary thiol structure or a tertiary thiol structure, and more preferably has two or more thiol structures represented by the following chemical formula (1).
- R 7 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- R 8 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- n a natural number of 1 or more.
- the resin composition for coating is highly stable when prepared, does not easily thicken in a short period of time, and is easy to mold.
- n represents a natural number of 1 or more and 10 or less, and more preferably, n represents a natural number of 1 or more and 5 or less.
- Examples of thiol compounds having two or more thiol structures represented by Chemical Formula 1 include 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5 -tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.
- the contents of the epoxy resin (A) and the thiol group-containing curing agent (B) in the epoxy resin composition of the present invention are determined by the number of thiol groups (H) in the component thiol group-containing curing agent (B) and the epoxy resin (A) It is a preferred embodiment that the ratio of the total number of epoxy groups (E) in the compound, the H/E ratio, satisfies the range of 0.8 to 1.3. If the H/E ratio is less than 0.8, excessive polymerization of the epoxy resin may proceed, resulting in deterioration of the physical properties of the cured product. If the H/E ratio exceeds 1.3, the concentration of reaction sites in the system decreases due to excessive curing agent components, and the reaction rate decreases, resulting in a failure to exhibit sufficient high-speed curability.
- the catalyst (C) used in the present invention is preferably a quaternary phosphonium salt.
- the quaternary phosphonium salt acts as a curing accelerator for rapid curing.
- quaternary phosphonium salts used as the catalyst (C) in the present invention include tetraethylphosphonium bromide, tributylmethylphosphonium iodide, tetraethylphosphonium hexafluorophosphate, tetraethylphosphonium tetrafluoroborate, tributyl(cyanomethyl)phosphonium chloride, Tetrakis(hydroxymethyl)phosphonium chloride, tetrabutylphosphonium hydroxide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrakis(hydroxymethyl)phosphonium sulfate, tributyl-n-octylphosphonium bromide, tetra-n-octylphosphonium bromide, tetra Butylphosphonium tetrafluoroborate, tetrabutylphosphonium
- the compound represented by the chemical formula (2) is preferred.
- Specific examples of the compound represented by Chemical Formula 2 include methyltributylphosphonium dimethylphosphate and tetrabutylphosphonium o,o-diethylphosphorodithioate.
- R 1 to R 4 each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. .
- R 5 and R 6 each independently represent an alkyl group having 1 to 20 carbon atoms.
- M 1 and M 2 each independently represent an element selected from Group 16 of the periodic table, and oxygen and sulfur are particularly preferred.
- the content of the catalyst (C) used in the present invention is preferably 0.1 parts by mass or more and less than 15 parts by mass, more preferably 0.1 parts by mass or more and 12 parts by mass based on 100 parts by mass of the epoxy resin (A). or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less. If the amount of the catalyst (C) is less than 0.1 parts by mass, the time required for curing may become longer and sufficient high-speed curability may not be exhibited. On the other hand, when the amount of the catalyst (C) is 15 parts by mass or more, the time to maintain the low viscosity is shortened, and it may become difficult to pour the resin composition into the cavity in the mold.
- the epoxy resin composition of the present invention comprises, for example, a main component liquid containing an epoxy resin (A) and a thiol group-containing curing agent (B) as main components (the main component herein means the mass of the curing agent liquid). It means that it is the component with the maximum amount as a standard.) and the curing agent liquid contained in each of the above-mentioned amounts, and just before use, mix the main liquid and the curing agent so that the above-mentioned amounts are obtained. Obtained by mixing liquids.
- the catalyst (C) described above can be blended in either the main liquid or the curing agent liquid, it is more preferably contained in the curing agent liquid.
- compounding ingredients can be blended into either the main liquid or the hardener liquid, and can be used by mixing with either or both in advance.
- the main component liquid and the curing agent liquid are preferably heated separately before mixing, and are mixed using a mixer immediately before use such as injection into a mold to obtain a two-component epoxy resin composition. is preferable from the standpoint of the pot life of the resin.
- the epoxy resin cured product of the present invention is an epoxy resin cured product obtained by curing the epoxy resin composition of the present invention, and has a glass transition temperature (Tg) of 40°C or higher.
- Tg glass transition temperature
- This Tg means that a cured resin plate is prepared by the method described in ⁇ Preparation of cured resin plate> below, and DMA (dynamic viscoelasticity) is measured by the method described in ⁇ Measurement of glass transition temperature Tg of cured resin> below.
- DMA dynamic viscoelasticity
- the Tg of the cured epoxy resin is more preferably 50°C or higher.
- Epoxy resin cured products that have a low Tg and are in a rubbery state at room temperature are susceptible to side reactions, even if they are cured products of epoxy resins that do not have unsaturated bonds and thiol group-containing curing agents. and discoloration due to ultraviolet light is likely to occur.
- the epoxy resin cured product of the present invention since the epoxy resin cured product of the present invention has a Tg higher than room temperature, it has sufficient hardness, and the coated molded product is less likely to be damaged during handling.
- Machinability at normal temperature is also good, so when polishing the surface of the coated fiber reinforced resin molded article as a pretreatment for coating the fiber reinforced resin molded article coated with the epoxy resin cured product of the present invention, Because it does not soften even when heat is trapped, it can be polished in a short time even with fine-grained paper. It is more preferable that the hardness of the coating resin of the coated fiber-reinforced resin molded product is H or higher than the pencil hardness under standard conditions of temperature of 23° C. and humidity of 50%.
- Weather resistance of the epoxy resin cured product of the present invention is preferably such that discoloration is slight even when exposed to an ultraviolet dose (308 MJ/m 2 ) equivalent to one year exposure to Florida in a high temperature environment (47°C).
- the color difference ( ⁇ E) of a cured epoxy resin product having a thickness of 2 mm is preferably 30 or less, more preferably 20 or less. With this plate thickness and this color difference, if the film thickness of the paint containing the ultraviolet absorber applied to the fiber-reinforced resin molded product coated with the epoxy resin cured product is 10 ⁇ m or more, the discoloration will be slight. Further, if the color difference ( ⁇ E) of the epoxy resin cured product having a thickness of 2 mm is 4 or less, discoloration is slight even without a coating containing an ultraviolet absorber.
- the coated fiber-reinforced resin molded product of the present invention is obtained by coating at least part of the surface of the fiber-reinforced resin molded product with the cured epoxy resin of the present invention as a coating layer.
- the fiber-reinforced resin molded product to be coated is preferably carbon fiber-reinforced plastic.
- Carbon fiber reinforced plastics are lightweight, have high rigidity and strength, and can be used in automobiles, railways, aircraft, drones, etc. to reduce their weight, thereby increasing fuel efficiency and cruising range.
- carbon fiber reinforced resin molded articles using fabrics such as plain weave, twill weave, and satin weave for the surface layer are also required to be aesthetically pleasing, and are suitable as objects to be coated with the epoxy resin composition of the present invention.
- the fabric used has a carbon fiber basis weight of preferably 180 g/m 2 or more, more preferably 215 g/m 2 or more.
- the commercial value of the molded article is particularly high in the case of a product in which the fabric itself is visible from the outside by applying a clear coating without applying a colored coating in whole or in part.
- the carbon fiber used in the coated fiber-reinforced resin molded article of the present invention is not particularly limited, polyacrylonitrile-based carbon fiber, rayon-based carbon fiber, pitch-based carbon fiber, and the like are preferably used. Among them, polyacrylonitrile-based carbon fibers having high tensile strength are particularly preferably used. Twisted yarn, untwisted yarn, non-twisted yarn, and the like can be used as the form of the carbon fiber.
- Such carbon fibers preferably have a tensile modulus in the range of 180 to 600 GPa. If the tensile modulus is within this range, the obtained fiber-reinforced composite material can be given rigidity, so that the obtained molded article can be reduced in weight. In general, carbon fibers tend to have a lower strength as the modulus of elasticity increases, but within this range the strength of the carbon fibers themselves can be maintained.
- a more preferable elastic modulus is in the range of 200 to 440 GPa, more preferably in the range of 220 to 300 GPa. The range may be a combination of any of the above upper and lower limits.
- the tensile modulus of carbon fiber is a value measured according to JIS R7601-2006.
- Carbon fibers include "Torayca (registered trademark)" T300 (tensile strength: 3.5 GPa, tensile modulus: 230 GPa), “Torayca (registered trademark)” T300B (tensile strength: 3.5 GPa, tensile modulus : 230 GPa), “Torayca (registered trademark)” T400HB (tensile strength: 4.4 GPa, tensile modulus: 250 GPa), “Torayca (registered trademark)” T700SC (tensile strength: 4.9 GPa, tensile modulus: 230 GPa), “Torayca (registered trademark)” T800HB (tensile strength: 5.5 GPa, tensile modulus: 294 GPa), “Torayca (registered trademark)” T800SC (tensile strength: 5.9 GPa, tensile modulus: 294 GPa), “Torayca (registered trademark)” Trademark) “
- the number of filaments of the carbon fiber is not particularly limited, but when the woven fabric described later is used for the coated fiber-reinforced resin molded product of the present invention, the weaving productivity, the required tensile strength of the coated fiber-reinforced resin molded product, From the viewpoint of flexural modulus, strength, and plate design, the carbon fiber bundle preferably has a range of 1,000 to 70,000 filaments, more preferably 1,000 to 60,000 filaments. It is.
- the form of the reinforcing fibers used in the coated fiber-reinforced resin molded product of the present invention is not particularly limited, but the above reinforcing fibers are aligned in one direction and combined with the matrix resin described later. It is preferable to adopt a directional fiber reinforced plastic or a fabric reinforced plastic in which the above-mentioned reinforcing fibers are processed into a fabric and then combined with a matrix resin to be described later.
- the weave structure of the woven fabric is not particularly limited, but plain weave, twill weave, satin weave, ridge weave, satin weave, nest weave, huck weave, imitation weave, and pear weave are preferably used. .
- the ridge weave can be exemplified by warp ridge weave, weft ridge weave, and variable ridge weave, and can be selected according to the design properties required for the coated fiber-reinforced resin molded product.
- the nanako weave includes regular nanako weave, variable nanako weave, irregular nanako weave, variable nanako weave, and counter nanako weave. can do.
- the reinforcing fiber constituting the woven fabric a single glass fiber, a single carbon fiber, or a plurality of different types of glass fibers and carbon fibers may be used. Alternatively, at least one type of glass fiber and at least one type of carbon fiber may be combined and woven together because of their excellent performance, cost and design.
- the fiber-reinforced resin plastic to be coated may be molded by any method for molding fiber-reinforced plastic, but the reinforcing fiber bundle cut to an appropriate length is pre-impregnated with a thermosetting resin and formed into a sheet.
- the SMC molding method in which an intermediate base material is pressurized and heated in a molding die to mold it into a predetermined shape, and the intermediate material that is bulk-shaped by mixing reinforcing fiber bundles cut to an appropriate length, thermosetting resin, and filler.
- a BMC molding method in which a material is pressurized and heated in a molding die to mold it into a predetermined shape.
- An intermediate base material in which reinforcing fiber bundles that are arranged in parallel or woven into a sheet are impregnated with a matrix resin is impregnated with a matrix resin.
- a prepreg molding method in which a certain prepreg is laminated and arranged in a mold and heated and pressed with a press, laminated and arranged in a mold and vacuum bagged and heated, or molded by pressurizing and heating in an autoclave.
- Liquid compression method, RTM method (resin transfer molding method), etc. in which a liquid matrix resin is supplied onto a reinforcing fiber base material such as a fabric or NCF placed on one mold, and the double-sided mold is closed and pressurized and heated. is.
- the prepreg molding method using prepreg and the RTM molding method are suitable as molding methods for coated fiber-reinforced resin molded products that require less disturbance of the texture of the fabric and are required to be aesthetically pleasing.
- thermoplastic resin and a thermosetting resin can be appropriately applied as the matrix resin of the fiber-reinforced resin plastic to be coated.
- Thermosetting resins such as unsaturated polyester resins, epoxy resins, phenolic resins, and polyurethane resins are preferably used as the matrix resin because they provide coated fiber-reinforced resin moldings with excellent mechanical properties.
- epoxy resins of the same type as the epoxy resin composition of the present invention are more preferable because covalent bonds can be formed with each other and adhesion is further improved.
- the glass transition temperature of the matrix resin is preferably 100° C. or higher.
- the epoxy resin composition of the present invention can coat a fiber reinforced resin molded article at a low temperature in a short time with a large film thickness
- a coated fiber reinforced resin molded article obtained by coating a fiber reinforced resin molded article with the epoxy resin composition of the present invention can be obtained.
- the surface roughness of the fiber-reinforced resin molded product to be coated is more effective if the undulation curve (Wt) is 3 ⁇ m or more, because the unevenness does not disappear unless the coated surface is polished after coating by the conventional coating method. .
- a method of coating a fiber-reinforced resin molded product with the epoxy resin composition of the present invention there is a method described in Patent Document 1, or a single-sided mold is coated with the epoxy resin composition of the present invention, and a fiber-reinforced resin molded product is coated thereon. It is also possible to use a method of covering the design surface of , and curing while drawing a vacuum.
- the fiber-reinforced resin molded product may have a release material applied to the mold that is transferred to the surface so that it can be easily released from the mold, or an internal mold release material added to the matrix resin.
- the adhesion of the fiber-reinforced resin molded product may not be sufficiently exhibited, so the surface on which the coating layer is formed may be polished with an abrasive or the like to remove the matrix resin and mold release agent on the surface of the fiber-reinforced resin molded product.
- surface treatment may be applied to chemically improve adhesion.
- the surface of the fiber reinforced resin layer that has been pretreated to improve adhesion to the coating layer is polished with sandpaper or the like to remove the outermost layer or to form polishing marks. Therefore, the epoxy resin composition of the present invention may be coated. By performing these treatments, irregularities that may occur in the molded article can be made smaller than irregularities caused by fibers.
- the post-heating temperature may be higher than the temperature at which the epoxy resin composition of the present invention is coated.
- the coated epoxy resin cured product has a higher elastic modulus than the liquid epoxy resin composition, so it is difficult to follow the heat shrinkage of the surface irregularities of the fiber reinforced resin molded product caused by post-heating. This is because even if the resin composition is post-cured at a temperature higher than the temperature at which the resin composition is cured, deterioration in surface quality is slight.
- the post-heating temperature is preferably +70°C or lower, more preferably +60°C or lower with respect to the complete curing Tg of the epoxy resin composition of the present invention.
- the post-heating temperature is preferably +70°C or lower, more preferably +60°C or lower with respect to the complete curing Tg of the epoxy resin composition of the present invention.
- the thickness of the coating layer of the coated fiber-reinforced resin molded product of the present invention is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more.
- the thickness of the coating layer of the coated fiber-reinforced resin molded product of the present invention is preferably 600 ⁇ m or less, more preferably 500 ⁇ m or less.
- the effect of the present invention can be evaluated by quantifying surface unevenness.
- typical means for this are a method of measuring using a surface roughness meter, or a cross section of the coated fiber reinforced resin using a microscope or the like.
- it may be obtained from the waviness curve (Wt) using a contact-type surface roughness meter, or may be obtained from a cross section using a microscope. If it is difficult to see the interface between the coating agent and the fiber-reinforced resin molded product, X-ray fluorescence analysis, SEM, or the like may be used.
- the evaluation of the present invention uses WaveScan, which can quantify the clarity of the image and the phenomenon that waviness appears on the painted surface (also called orange peel) when a certain level of glossiness is obtained. can also be measured.
- the best surface condition is called "Class A”.
- SW short wave
- LW long wave
- SW is 20 or less
- LW is 4 or less.
- the waviness curve (Wt) is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less. If the thickness is 2 ⁇ m or less, class A can be achieved with only one coating.
- the molded product has a particularly high commercial value.
- the unique pattern expressed by the woven structure is excellent in design, plain weave, twill weave, satin weave, and the like are often preferred.
- the basis weight of the base material also affects the design. When used for a product whose woven structure is visible from the outside, it is preferable to use a base material of approximately 100 g/m 2 to 300 g/m 2 .
- Epoxy resin Syna Epoxy 186 (manufactured by SYNASIA): diglycidyl 4,5-epoxyhexahydrophthalate, epoxy equivalent 110 - "Celoxide” (registered trademark) 2021P (manufactured by Daicel Corporation): 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, epoxy equivalent 130 EHPE3150 (manufactured by Daicel Corporation): 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxy equivalent 180 ⁇ HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.): Hydrogenated bisphenol A type epoxy resin, epoxy equivalent 215 ⁇ RD 129 (manufactured by epotec): pentaerythritol polyglycidyl ether, epoxy equivalent 160 2.
- the component (B) (thiol compound), the component (C) (quaternary phosphonium salt) and other substances were blended at the blending ratio shown in Table 1 to prepare a curing agent liquid.
- An epoxy resin composition was prepared by using these base liquids and curing agent liquids and mixing them at the compounding ratios shown in Table 1.
- Tg of cured resin A test piece of 40 mm ⁇ 10 mm was cut out from the cured resin plate, and Tg was measured using a DMA (dynamic viscoelasticity measurement) device (ARES-G2 manufactured by TA Instruments). The measurement conditions are a temperature increase rate of 5° C./min. Measurement was performed in the temperature range of -50°C to 130°C, and the point at which the storage modulus changed (On set) was defined as the glass transition point.
- DMA dynamic viscoelasticity measurement
- ⁇ Coloring of cured product The presence or absence of coloration was determined for the resin-cured plate. Specifically, a test piece of 30 mm square and 2 mm in thickness cut out from a cured resin plate is used, and a spectrophotometer (CM-700d, manufactured by Konica Minolta Co., Ltd.) is used to set the color tone of the cured product to L. *a*b* color system.
- the L*a*b* color system is used to represent the color of a substance, where L* represents lightness and a* and b* represent chromaticity.
- a* indicates the red direction
- -a* indicates the green direction
- b* indicates the yellow direction
- -b* indicates the blue direction.
- Spectral transmittance was measured in a wavelength range of 380 to 780 nm, with a D65 light source and a 10° field of view, and without specular reflection. At this time, the case where
- the fiber-reinforced composite material used was produced by the following RTM molding method.
- Carbon fiber fabric CO6343B (carbon fiber: T300-3K, texture: plain weave, basis weight: 198 g / m 2 , manufactured by Toray Industries, Inc.) was placed in the cavity of a mold having a plate-shaped cavity of 350 mm ⁇ 700 mm ⁇ 1.6 mm as a reinforcing fiber. ) and a glass fiber fabric M340 (Unitika Ltd.) as an intermediate layer were placed, and the mold was clamped with a press. Next, the inside of the mold held at a temperature of 120° C.
- molding temperature is evacuated to atmospheric pressure ⁇ 0.1 MPa by a vacuum pump, and 100 parts by mass of an epoxy resin composition (TR-C38 manufactured by Toray Industries, Inc.)
- TR-C38 manufactured by Toray Industries, Inc.
- a mixed resin containing 1 part by mass of IC-35 was injected using a resin injection machine.
- the surface smoothness of the obtained fiber-reinforced composite material was measured by SURF COM 480A (manufactured by ACCRETECH) in the "wave undulation curve" mode, measuring length 10 mm, cutoff 0.25 mm, resin made at the intersection of the warp and weft of the fabric. Measurements were taken 10 times so as to pass through the chisel, and the maximum value was 7.5 ⁇ m.
- ⁇ Coating molding> The temperature of the cavity coating mold of a mold having a plate-shaped cavity of 350 mm ⁇ 350 mm ⁇ 1.9 mm is adjusted to 50 ° C., a fiber reinforced composite material cut into 350 mm ⁇ 350 mm is placed on the lower mold, and the fiber reinforced resin is produced. Two spacers of 350 mm ⁇ 10 mm ⁇ 0.3 mmt were placed on both ends of the upper surface, and after the upper mold was closed, the inside of the mold was evacuated. Then, according to the compounding ratio of Table 1, the epoxy resin composition was injected using a resin injection machine. The resin was poured into the mold, and after 10 minutes, the upper mold was opened and the fiber-reinforced resin molded product with the film formed on the surface was taken out.
- a fiber reinforced composite material cut to 350 mm ⁇ 350 mm is placed on a hot plate, and the temperature of the hot plate is adjusted so that the surface temperature of the fiber reinforced composite material is 50 ° C., and then the fiber reinforced composite material on the hot plate is coated with a thickness
- Two spacers of 50 mm x 20 mm x 0.2 mm wrapped in 0.05 mm paper were arranged with a 10 mm separation between them so that the longitudinal direction was horizontal.
- the surface smoothness of the coated coated fiber-reinforced resin molded product was evaluated by wave scan (WS) value of the surface of the molded product.
- the WS value is called “class A” when the surface is the best in automobile applications.
- SW short wave
- LW long wave
- the LW value of the surface of the coated fiber-reinforced resin molded product on which the coating layer was formed was measured five times using a wave scan device (Wave Scan Dual), and the average value is shown in Table 1.
- Weather resistance was evaluated by placing a 2 mm thick resin cured plate in a metering weather meter (M6T manufactured by Suga Test Instruments Co., Ltd.), temperature 47° C., humidity 50%, irradiation amount 1250 W/m 2 , cumulative irradiation amount 308 MJ/. Tests were performed on m2 . Before and after standing, the color difference ( ⁇ E) was measured with a spectrophotometer (CM-700d, manufactured by Konica Minolta, Inc.).
- Example 1 As shown in Table 1, a main agent liquid consisting of 100 parts by mass of "Syna Epoxy 186" having two functional epoxy groups having a glycidyl structure in one molecule and one functional epoxy group having an alicyclic structure was added to the main agent tank.
- An epoxy resin composition was prepared using a resin injection machine in which a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET” was dissolved in 124 parts by mass of a thiol compound "Karenzu MT PE1" was placed in a curing agent tank. was prepared by mixing.
- the temperature of the main agent tank and the curing agent tank was controlled to 25° C., respectively, and mixing was performed via a static mixer.
- This epoxy resin composition had a low viscosity even at a temperature of 25° C., and could be injected into the entire mold with sufficient margin in the method described in ⁇ Coating Molding> above.
- the mixing state of the main component liquid and the curing agent liquid was also good.
- Even after curing at 50°C for 10 minutes, the adhesiveness to the fiber-reinforced composite material was good, and the mold could be demolded without any problems.
- the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
- a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
- Example 2 To 100 parts by mass of "Syna Epoxy 186", 50 parts of "Celoxide 2021P” having a bifunctional epoxy group having an alicyclic structure was added to prepare a main liquid, and 117 parts by mass of the thiol compound "Karenz MT PE1" was added to the fourth.
- the procedure was carried out in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a grade phosphonium salt "Hishikorin PX-4ET” was dissolved was put into a curing agent tank. Compared with Example 1, it had a lower viscosity and could be quickly injected into the entire mold in the method described in ⁇ Coating Molding> above.
- Example 1 Although the adhesive strength at demolding was lower than that of Example 1, the mold could be demolded without any problems.
- the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
- a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
- Example 3 To 100 parts by mass of "Syna Epoxy 186", 12.5 parts of “Celoxide 2021P” having an epoxy group having an alicyclic structure and 12.5 parts of “EHPE3150” having an epoxy group having a glycidyl structure were added to prepare a main component liquid. was mixed. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector.
- Example 1 was carried out in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET” was dissolved in 117 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
- Example 1 As with Example 1, it had a low viscosity and could be quickly injected into the entire mold by the method described in ⁇ Coating molding> above.
- the adhesive strength at the time of demolding was the same, and the mold could be demolded without any problem.
- the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
- a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
- Example 4 25 parts of "EHPE3150” having an epoxy group having a glycidyl structure was added to 100 parts by mass of "Syna Epoxy 186" to prepare a main component liquid. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector. Performed in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt “Hishikorin PX-4ET” was dissolved in 113 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
- Example 1 As with Example 1, it had a low viscosity, and could be injected into the entire mold without any problems in the method described in ⁇ Coating molding> above.
- the adhesive strength at the time of demolding was high, and the mold could be demolded without any problem.
- the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
- a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
- Example 5 Example 5 was repeated except that the post-curing temperature was 80°C for Example 5 and 125°C for Example 6. Even when the post-curing temperature was changed, the cured product of the epoxy resin composition showed no coloration, slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film prepared using this epoxy resin composition exhibits better surface smoothness when the post-curing temperature is lower, but sufficiently good surface smoothness is exhibited even at a high temperature. had. The surface smoothness after coating was also very good. Table 1 shows the results.
- Example 7 To 100 parts by mass of “Syna Epoxy 186" was added 50 parts of "EHPE3150” having an epoxy group having a glycidyl structure to prepare a main component liquid. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector.
- Example 4 was carried out in the same manner as in Example 4, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET” was dissolved in 108 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
- Example 1 Although the viscosity was slightly higher than that of Example 1, it could be injected into the entire mold without any problems in the method described in ⁇ Coating Molding> above.
- the adhesive strength at the time of demolding was very high, and the mold could be demolded without any problem.
- the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
- a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
- the cured product of the epoxy resin composition was not colored, but had a Tg much lower than the temperature of the test environment, was greatly discolored due to being exposed to ultraviolet rays in a rubber state, and did not have sufficient weather resistance.
- the cured film prepared using this epoxy resin composition was soft, and when polishing was performed before painting, the cured film was missing and clogging occurred on the surface of the Scotchbride. Compared to 1, the time and number of scotch brides required increased.
- a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and although the surface smoothness after coating was inferior to that of Example 1, it was good. Table 2 shows the results.
- the coating was peeled off when the mold was demolded, and the adhesion was low when the mold was demolded.
- the cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance.
- a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 2 shows the results.
- the cured product of the epoxy resin composition was not colored, but had a Tg much lower than the temperature of the test environment, was greatly discolored due to being exposed to ultraviolet rays in a rubber state, and did not have sufficient weather resistance.
- the cured film prepared using this epoxy resin composition was soft, and when polishing was performed before painting, the cured film was missing and clogging occurred on the surface of the Scotchbride. Compared to 1, the time and number of scotch brides required increased.
- a fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibits good surface smoothness, and although the surface smoothness after coating is inferior to that of Example 1, it is durable for use. rice field. Table 2 shows the results.
- the epoxy resin composition of the present invention significantly reduces the surface unevenness that occurs on the surface due to the shape of the reinforcing fibers caused by the temperature difference between the molding temperature (curing temperature) and normal temperature when the fiber reinforced resin is molded. and excellent weather resistance, it is suitable for use as a fiber-reinforced composite material for automobile applications, which particularly require high appearance quality. As a result, it can be expected to contribute to the improvement of fuel efficiency by further reducing the weight of automobiles and the reduction of greenhouse gas emissions.
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Abstract
The purpose of the present invention is to provide: an epoxy resin composition which, when a fiber-reinforced resin is molded, can reduce surface unevenness caused by a difference in temperature between a molding temperature (a curing temperature) and normal temperature and exhibits high surface quality and excellent weathering resistance; a cured epoxy resin product; and a coated fiber-reinforced resin molded article obtained using same. To achieve the foregoing, this epoxy resin composition contains at least: an epoxy resin (A) comprising one or more epoxy resins; a thiol group-containing curing agent; and a catalyst (C). An epoxy resin (A1), which accounts for 50% or more in terms of weight ratio of the epoxy resins that constitute the epoxy resin (A), has 2 or more epoxy groups having a glycidyl structure and 1 or more epoxy groups having an alicyclic structure.
Description
本発明は、エポキシ樹脂組成物、エポキシ樹脂硬化物及びそれを用いた被覆繊維強化樹脂成形品に関する。
The present invention relates to an epoxy resin composition, a cured epoxy resin, and a coated fiber-reinforced resin molded product using the same.
近年、マトリクス樹脂と強化繊維から成る繊維強化樹脂（Ｆｉｂｅｒ Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃ：ＦＲＰ）部材、その中でも炭素繊維を用いたＣＦＲＰは、軽量で機械特性に優れることから、輸送用機器などへの適用が進んでいる。中でも自動車の外装部材用途などの機械特性に加えて高い美観性が要求される用途において、ＣＦＲＰは欠陥が無く平滑である表面が求められることが多い。
In recent years, fiber reinforced plastic (FRP) members consisting of matrix resin and reinforcing fibers, among which CFRP using carbon fiber, is lightweight and has excellent mechanical properties, so it is being applied to transportation equipment and the like. there is In particular, CFRP is often required to have a defect-free and smooth surface in applications that require high aesthetics in addition to mechanical properties, such as automobile exterior parts.
繊維強化樹脂成形品の製造方法としては、シートモールディングコンパウンド（ＳＭＣ）成形法やバルクモールディングコンパウンド（ＢＭＣ）成形法などが使われることが多い。近年は、レジントランスファーモールディング（ＲＴＭ）法が注目され、適用が進んでいる。レジントランスファーモールディング（ＲＴＭ）法は、強化繊維を連続繊維の形態で使用することができ、機械的特性が非常に高く、かつ短いサイクルタイムで成形できることにより生産性に優れる。
Sheet molding compound (SMC) molding methods and bulk molding compound (BMC) molding methods are often used as manufacturing methods for fiber-reinforced resin molded products. In recent years, the resin transfer molding (RTM) method has attracted attention and is being applied. The resin transfer molding (RTM) method can use reinforcing fibers in the form of continuous fibers, has very high mechanical properties, and is excellent in productivity because it can be molded in a short cycle time.
しかし、これらの成形法で得られた繊維強化樹脂成形品は、表面に樹脂の充填不良による欠陥が生じたり、強化繊維の形態と樹脂の収縮に伴って表面凹凸が発生したりして、従来からよく用いられている金属部材に比べて表面の平滑性が劣ることが多かった。この課題を解消するために繊維強化樹脂成形品の表面を補修・研磨してから塗装する必要があり、そのために大きな労力をかけなくてはならない場合があった。しかし、このような処理を行ったとしても、表面の平滑性が十分出ない場合もあった。特に、表面積の大きなものや、曲面や垂直に屈曲した面等の複雑な形状を有している繊維強化樹脂成形品は、補修・研磨に多くの時間がかかることが多かった。
However, fiber-reinforced resin molded products obtained by these molding methods have defects due to insufficient resin filling on the surface, and surface unevenness occurs due to the shape of the reinforcing fiber and the shrinkage of the resin. In many cases, the surface smoothness is inferior to that of metal members that are often used from the ground up. In order to solve this problem, the surface of the fiber-reinforced resin molded article needs to be repaired and polished before being painted, which sometimes requires a great deal of labor. However, even if such a treatment is performed, the surface may not be sufficiently smooth in some cases. In particular, it often takes a long time to repair and polish a fiber-reinforced resin molded article having a large surface area or a complicated shape such as a curved surface or a vertically bent surface.
このような課題に対し、以下の方法が提案されている。まず、特許文献１に係る方法では、強化繊維に含浸されたマトリクス樹脂を硬化させて繊維強化樹脂成形品を得た後に、その硬化温度より成形温度が低い金型に繊維強化樹脂成形品を移し替え、繊維強化樹脂成形品の表面と金型表面の間に繊維強化樹脂成形体を被覆するための組成物（マトリクス樹脂とは別の樹脂）を注入・硬化させることで、成形体表面の繊維目やピンホールを隠蔽した被覆繊維強化樹脂成形品を得ていた。
The following methods have been proposed to address these issues. First, in the method according to Patent Document 1, after curing the matrix resin impregnated with the reinforcing fibers to obtain a fiber-reinforced resin molded product, the fiber-reinforced resin molded product is transferred to a mold having a molding temperature lower than the curing temperature. Alternatively, a composition (a resin different from the matrix resin) for covering the fiber-reinforced resin molded product is injected and cured between the surface of the fiber-reinforced resin molded product and the surface of the mold, thereby reducing the fibers on the surface of the molded product. A coated fiber-reinforced resin molded article with hidden eyes and pinholes was obtained.
この際に用いられる、繊維強化樹脂成形体を被覆するための組成物には、例えば、脂環骨格を有する脂肪族エポキシ樹脂とチオール化合物とホスフィン類を組み合わせ低温速硬化性と、耐候性、Ｔｇの向上を図った被覆用樹脂組成物（特許文献２）、４級ホスホニウム塩と２級または３級チオール化合物と、多価エポキシ化合物を組み合わせた、透明性に優れるエポキシ樹脂組成物（特許文献３）、脂環構造を有するエポキシ基をもつエポキシ樹脂すなわち脂環式エポキシ樹脂と、モノアリルジグリシジルイソシアヌレート化合物と酸無水物系硬化剤を組み合わせた、光半導体封止用硬化性エポキシ樹脂組成物（特許文献４）、炭素－炭素二重結合を持たないエポキシ樹脂とポリチオール系硬化剤を組み合わせた光透過性や屈折率に優れた発光ダイオード用エポキシ樹脂組成物（特許文献５）が該当する。
The composition used for coating the fiber-reinforced resin molding used in this case includes, for example, a combination of an aliphatic epoxy resin having an alicyclic skeleton, a thiol compound, and phosphines, and low-temperature fast-curing properties, weather resistance, Tg A coating resin composition (Patent Document 2) that aims to improve the transparency, and an epoxy resin composition that combines a quaternary phosphonium salt, a secondary or tertiary thiol compound, and a polyepoxy compound and has excellent transparency (Patent Document 3 ), a curable epoxy resin composition for optical semiconductor encapsulation, which is obtained by combining an epoxy resin having an epoxy group having an alicyclic structure, that is, an alicyclic epoxy resin, a monoallyl diglycidyl isocyanurate compound, and an acid anhydride-based curing agent. (Patent Document 4), and an epoxy resin composition for light-emitting diodes having excellent light transmittance and refractive index, which is obtained by combining an epoxy resin having no carbon-carbon double bond and a polythiol-based curing agent (Patent Document 5).
特許文献１に記載の繊維強化樹脂成形体を被覆するための組成物には、被膜として透明性に優れることや、金型内の占有時間を短縮し、生産性を向上させるため、粘度が低く低温短時間で硬化すること、高い耐候性やＴｇが求められ、それぞれ、低温速硬化性に優れたチオール系硬化剤、耐候性とＴｇに優れた脂環構造を有するエポキシ基を持つエポキシ樹脂、すなわち脂環式エポキシの組合せが好適である。一方、脂環式エポキシとチオール系硬化剤の反応は、立体障害の観点から、反応速度が遅く、低温速硬化性に向いていない。特許文献２に記載のエポキシ樹脂組成物に記載のエポキシ樹脂は脂環骨格を有しており、速硬化性はあるが、脂肪族グリシジルエーテル構造を有するエポキシでは、脂環式エポキシを用いる場合と比較して、Ｔｇ向上効果は十分ではない。特許文献３は、芳香環を含むエポキシ樹脂を用いればＴｇと速硬化性を両立できるが、紫外線を吸収するため、耐候性が劣る。特許文献４はＴｇ、耐候性の面で優れているが、酸無水物を使用しているため、低温速硬化性が十分でない。特許文献５においては、繊維強化複合材料の被膜として形成することについて記載がなく、高温硬化を前提とした組成である。
The composition for coating the fiber-reinforced resin molded article described in Patent Document 1 has excellent transparency as a coating, shortens the occupancy time in the mold, and improves productivity, so it has a low viscosity. Curing in a short time at low temperature, high weather resistance and Tg are required, respectively, thiol-based curing agent excellent in low-temperature fast curing, epoxy resin with an epoxy group having an alicyclic structure with excellent weather resistance and Tg, Thus, a combination of cycloaliphatic epoxies is preferred. On the other hand, the reaction between an alicyclic epoxy and a thiol-based curing agent has a slow reaction rate from the viewpoint of steric hindrance, and is not suitable for low-temperature rapid curing. The epoxy resin described in the epoxy resin composition described in Patent Document 2 has an alicyclic skeleton and has fast curing properties. In comparison, the Tg improving effect is not sufficient. According to Patent Document 3, if an epoxy resin containing an aromatic ring is used, both Tg and fast curability can be achieved, but the weather resistance is poor because it absorbs ultraviolet rays. Patent Document 4 is excellent in terms of Tg and weather resistance, but is insufficient in low-temperature rapid curability due to the use of an acid anhydride. In Patent Document 5, there is no description of forming a film of a fiber-reinforced composite material, and the composition is based on the premise of high-temperature curing.
そこで本発明の課題は、繊維強化樹脂を成形した際、成形温度（硬化温度）と常温との温度差により生じる表面凹凸を低減することができ、かつ表面品位が高く耐候性にも優れるエポキシ樹脂組成物と、エポキシ樹脂硬化物及びそれを用いた被覆繊維強化樹脂成形品を提供することにある。
Therefore, the object of the present invention is to provide an epoxy resin that can reduce the surface unevenness caused by the temperature difference between the molding temperature (curing temperature) and normal temperature when molding a fiber reinforced resin, and has high surface quality and excellent weather resistance. An object of the present invention is to provide a composition, a cured epoxy resin product, and a coated fiber-reinforced resin molded product using the same.
本発明は、上記の課題を解決せんとするものであり、本発明のエポキシ樹脂組成物は、単一または複数のエポキシ樹脂からなるエポキシ樹脂（Ａ）、チオール基含有硬化剤（Ｂ）、触媒（Ｃ）を少なくとも含むエポキシ樹脂組成物であって、エポキシ樹脂（Ａ）を構成するエポキシ樹脂のうち、重量比で５０％以上を占めるエポキシ樹脂（Ａ１）がグリシジル構造を有するエポキシ基を２官能以上、及び脂環構造を有するエポキシ基を１官能以上有する。
The present invention is intended to solve the above problems, and the epoxy resin composition of the present invention comprises an epoxy resin (A) comprising a single or multiple epoxy resins, a thiol group-containing curing agent (B), a catalyst In an epoxy resin composition containing at least (C), the epoxy resin (A1), which accounts for 50% or more by weight of the epoxy resins constituting the epoxy resin (A), has a difunctional epoxy group having a glycidyl structure. above and one or more epoxy groups having an alicyclic structure.
本発明のエポキシ樹脂組成物の好ましい態様によれば、エポキシ樹脂（Ａ）に含まれるグリシジル構造を有するエポキシ基の官能基数［ＡＧ］と脂環構造を有するエポキシ基の官能基数［ＡＦ］の比が［ＡＧ］／［ＡＦ］＞０．７の関係を有する。
According to a preferred embodiment of the epoxy resin composition of the present invention, the ratio of the functional group number [AG] of the epoxy group having a glycidyl structure contained in the epoxy resin (A) to the functional group number [AF] of the epoxy group having an alicyclic structure is has a relationship of [AG]/[AF]>0.7.
本発明のエポキシ樹脂組成物の好ましい態様によれば、エポキシ樹脂（Ａ）およびチオール基含有硬化剤（Ｂ）のいずれにも炭素－炭素不飽和結合を含まない。
According to a preferred embodiment of the epoxy resin composition of the present invention, neither the epoxy resin (A) nor the thiol group-containing curing agent (B) contain carbon-carbon unsaturated bonds.
本発明のエポキシ樹脂硬化物は、本発明のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物であって、４０℃以上のガラス転移点温度（Ｔｇ）を有する。
The epoxy resin cured product of the present invention is an epoxy resin cured product obtained by curing the epoxy resin composition of the present invention, and has a glass transition temperature (Tg) of 40°C or higher.
本発明の被覆繊維強化樹脂成形品は、本発明のエポキシ樹脂硬化物を被覆層として繊維強化樹脂成形品の表面の少なくとも一部に被覆してなる。
The coated fiber-reinforced resin molded article of the present invention is obtained by coating at least part of the surface of the fiber-reinforced resin molded article with the cured epoxy resin of the present invention as a coating layer.
本発明の被覆繊維強化樹脂成形品の好ましい態様によれば、前記繊維強化樹脂成形品が炭素繊維強化プラスチックである。
According to a preferred aspect of the coated fiber-reinforced resin molded article of the present invention, the fiber-reinforced resin molded article is carbon fiber-reinforced plastic.
本発明の被覆繊維強化樹脂成形品の好ましい態様によれば、前記被覆層の表面にさらにクリアー塗装による塗膜を形成した構成である。
According to a preferred embodiment of the coated fiber-reinforced resin molded product of the present invention, a coating film is further formed by clear coating on the surface of the coating layer.
本発明によれば、繊維強化樹脂を成形した際、成形温度（硬化温度）と常温との温度差により生じる、表面凹凸を大幅に低減することができ、耐候性にも優れるエポキシ樹脂組成物、エポキシ樹脂硬化物及び被覆繊維強化樹脂成形品を提供することが可能となる。
According to the present invention, when a fiber-reinforced resin is molded, it is possible to greatly reduce the surface unevenness caused by the temperature difference between the molding temperature (curing temperature) and normal temperature, and the epoxy resin composition has excellent weather resistance. It becomes possible to provide epoxy resin cured products and coated fiber-reinforced resin molded products.
本発明の望ましい実施の形態について、詳細に説明する。
A preferred embodiment of the present invention will be described in detail.
本発明のエポキシ樹脂組成物は、単一または複数のエポキシ樹脂からなるエポキシ樹脂（Ａ）、チオール基含有硬化剤（Ｂ）、触媒（Ｃ）を少なくとも含むエポキシ樹脂組成物であって、エポキシ樹脂（Ａ）を構成するエポキシ樹脂のうち、重量比で５０％以上を占めるエポキシ樹脂（Ａ１）がグリシジル構造を有するエポキシ基を２官能以上、及び脂環構造を有するエポキシ基を１官能以上有する。なお、本発明において、「グリシジル構造を有するエポキシ基」とはオキシランにメチレンが結合したグリシジル基（（Ｃ２Ｈ３Ｏ）－ＣＨ２）のことをいう。また、「脂環構造を有するエポキシ基」とは、炭素が環状に結合した化合物（脂環式化合物）の一部にエポキシ基が含まれる化合物のことをいう。
The epoxy resin composition of the present invention is an epoxy resin composition containing at least an epoxy resin (A) consisting of a single or multiple epoxy resins, a thiol group-containing curing agent (B), and a catalyst (C), wherein the epoxy resin Among the epoxy resins constituting (A), the epoxy resin (A1), which accounts for 50% or more by weight, has two or more functional epoxy groups having a glycidyl structure and one or more functional epoxy groups having an alicyclic structure. In the present invention, the term “epoxy group having a glycidyl structure” refers to a glycidyl group ((C 2 H 3 O)—CH 2 ) in which methylene is bonded to oxirane. In addition, the term “epoxy group having an alicyclic structure” refers to a compound in which an epoxy group is partly contained in a compound in which carbon atoms are cyclically bonded (alicyclic compound).
グリシジル構造を有するエポキシ基はチオールと低温でも素早く反応する。そのため、グリシジル構造を有するエポキシ基が２官能以上有することで、低温短時間で硬化させても、硬化物のネットワーク構造内にエポキシ樹脂を取り込むことができるため、低分子のまま残るエポキシ樹脂を減らすことができ、金型から取り出すのに十分な密着性を有することができる。また、金型から取り出した後、常温で養生、ないしは、後加熱することで、チオールとの反応性は悪いが、高Ｔｇ成分である脂環構造を有するエポキシ基と、チオールを被覆に必要な、高価な金型やプレスを占有することなく、反応させることができ、高Ｔｇを有する硬化物を得ることができる。
Epoxy groups with a glycidyl structure react quickly with thiols even at low temperatures. Therefore, since the epoxy group having a glycidyl structure has two or more functionalities, the epoxy resin can be incorporated into the network structure of the cured product even if it is cured at a low temperature in a short time, reducing the amount of epoxy resin that remains as a low molecular weight. and have sufficient adhesion to remove from the mold. In addition, after being removed from the mold, it is cured at room temperature or post-heated, so that although the reactivity with thiol is poor, the epoxy group having an alicyclic structure, which is a high Tg component, and the thiol necessary for coating , the reaction can be performed without occupying an expensive mold or press, and a cured product having a high Tg can be obtained.
本発明のエポキシ樹脂組成物において、エポキシ樹脂（Ａ）に含まれるグリシジル構造を有するエポキシ基の官能基数［ＡＧ］と脂環構造を有するエポキシ基の官能基数［ＡＦ］の比が［ＡＧ］／［ＡＦ］＞０．７の関係を有することが好ましい。グリシジル構造を有するエポキシ基の官能基の数と脂環式構造を有するエポキシ基の官能基数の比が、この関係を満たすことで、低温速硬化特性と、高Ｔｇ特性を両立した樹脂特性を発現できる。
[AG]/ It is preferable to have a relationship of [AF]>0.7. When the ratio of the number of functional groups of the epoxy group having a glycidyl structure to the number of functional groups of the epoxy group having an alicyclic structure satisfies this relationship, resin properties that achieve both low-temperature rapid curing properties and high Tg properties are expressed. can.
本発明のエポキシ樹脂組成物において、エポキシ樹脂（Ａ）およびチオール基含有硬化剤（Ｂ）のいずれにも炭素－炭素不飽和結合を含まないことが好ましい。炭素－炭素不飽和結合を含まないことで、紫外線による樹脂の変色を防ぐことができ、野外で長期間用いることができる。特に本発明に用いるエポキシ樹脂組成物を繊維強化樹脂成形品にコーティングし、さらに紫外線吸収剤を含んだ塗料を塗装する場合、被覆する繊維強化樹脂成形品の形状に立ち面を含んでいると、塗装時に塗料の液だれが発生したり、作業ばらつきによって、塗装膜厚が不均一になり、膜厚の薄い箇所では紫外線吸収剤の効果が落ちるため、被覆するエポキシ樹脂組成物そのものに耐候性を持たせておくことが重要となる。立ち面を含むとは、繊維強化樹脂成形品内の隣り合う面が一方の面の接線方向に対して、もう一方の面が３０°以上傾いている面を有することをいう。また、被覆するエポキシ樹脂組成物そのものに耐候性を持たせておくと、紫外線吸収剤が含有している塗料の膜厚を薄くすることができ、塗料による製品重量の増加を減らすことが可能であり、厚く塗装することで発生する塗料の沸きといった、欠点の発生を抑制することができる。この場合、塗装膜厚は１００μｍ以下、より好ましくは６０μｍ、さらに好ましくは４０μｍ以下にすることが好ましい。
In the epoxy resin composition of the present invention, it is preferred that neither the epoxy resin (A) nor the thiol group-containing curing agent (B) contain a carbon-carbon unsaturated bond. By not containing a carbon-carbon unsaturated bond, discoloration of the resin due to ultraviolet rays can be prevented, and it can be used outdoors for a long period of time. Especially when the fiber-reinforced resin molded product is coated with the epoxy resin composition used in the present invention and then coated with a paint containing an ultraviolet absorber, if the shape of the fiber-reinforced resin molded product to be coated includes an upright surface, Dripping of the paint occurs during painting, and the coating film thickness becomes uneven due to work variations, and the effect of the ultraviolet absorber is reduced in areas where the film thickness is thin. It is important to keep it. The expression "including standing surfaces" means that adjacent surfaces in the fiber-reinforced resin molded article have surfaces in which the other surface is inclined by 30° or more with respect to the tangential direction of one surface. In addition, by imparting weather resistance to the epoxy resin composition itself, it is possible to reduce the film thickness of the paint containing the ultraviolet absorber, thereby reducing the increase in product weight due to the paint. It is possible to suppress the occurrence of defects such as boiling of the paint that occurs due to thick coating. In this case, the coating film thickness is preferably 100 μm or less, more preferably 60 μm, and still more preferably 40 μm or less.
本発明に用いるエポキシ樹脂（Ａ）とチオール基含有硬化剤（Ｂ）のエポキシ当量及び活性水素当量は、１７０ｇ／ｅｑ以下であることが好ましい。エポキシ当量を低く抑えることで、密な３次元構造を取ることができ、硬化物のＴｇが上がるとともに、エポキシ基とチオール基が反応して生成される、極性の高い水酸基によって、内部離型剤を含有している繊維強化樹脂成形品等の表面自由エネルギーが小さなプラスチック製品とも良好な密着性を有する。
The epoxy equivalent and active hydrogen equivalent of the epoxy resin (A) and thiol group-containing curing agent (B) used in the present invention are preferably 170 g/eq or less. By keeping the epoxy equivalent low, it is possible to have a dense three-dimensional structure, which increases the Tg of the cured product. It also has good adhesion to plastic products with small surface free energy such as fiber reinforced resin molded products containing
本発明のエポキシ樹脂組成物において、エポキシ樹脂（Ａ）とチオール基含有硬化剤（Ｂ）の粘度はそれぞれ２５℃で８０Ｐａ・ｓ以下であることが好ましい。樹脂を脱泡する際に、樹脂の温度を上げて粘度を下げることで、脱泡しやすくする方法が一般的であるが、８０Ｐａ・ｓ以下の粘度だと、エポキシ樹脂組成物を繊維強化樹脂成形品に被覆するための金型温度以上に樹脂を加温する必要がないため、エポキシ樹脂（Ａ）とチオール基含有硬化剤（Ｂ）を混ぜて、注入配管内に流しても、金型内よりも反応速度は遅くなり、金型内に樹脂が満たされるまで、樹脂の粘度を低いまま保つごとができる。また、エポキシ樹脂（Ａ）とチオール基含有硬化剤（Ｂ）の粘度差が１００倍以内であれば、スタティックミキサーでエポキシ樹脂（Ａ）とチオール基含有硬化剤（Ｂ）を混ぜることができるため、より好ましい。さらに、エポキシ樹脂（Ａ）とチオール基含有硬化剤（Ｂ）を混合した後の粘度が、２５℃で１０Ｐａ・ｓ以下であれば、低温でも十分に金型内に流すことができるため、さらに好ましい。また、金型内を減圧してエポキシ樹脂組成物を流すため、エポキシ樹脂組成物は、不揮発分のみで構成されていることが好ましい。具体的には、本発明のエポキシ樹脂組成物は、金型温度環境下での蒸気圧が０．５ｋＰａ以下であることが好ましい。
In the epoxy resin composition of the present invention, the viscosity of each of the epoxy resin (A) and the thiol group-containing curing agent (B) is preferably 80 Pa·s or less at 25°C. When defoaming the resin, it is common to raise the temperature of the resin to lower the viscosity to facilitate defoaming. Since it is not necessary to heat the resin above the mold temperature for coating the molded product, even if the epoxy resin (A) and the thiol group-containing curing agent (B) are mixed and poured into the injection pipe, the mold The reaction rate becomes slower than inside, and the viscosity of the resin can be kept low until the inside of the mold is filled with resin. Also, if the viscosity difference between the epoxy resin (A) and the thiol group-containing curing agent (B) is within 100 times, the epoxy resin (A) and the thiol group-containing curing agent (B) can be mixed with a static mixer. , more preferred. Furthermore, if the viscosity after mixing the epoxy resin (A) and the thiol group-containing curing agent (B) is 10 Pa s or less at 25 ° C., it can be sufficiently flowed into the mold even at a low temperature. preferable. Moreover, since the pressure inside the mold is reduced to flow the epoxy resin composition, it is preferable that the epoxy resin composition is composed only of non-volatile matter. Specifically, the epoxy resin composition of the present invention preferably has a vapor pressure of 0.5 kPa or less in a mold temperature environment.
本発明のエポキシ樹脂組成物において、エポキシ樹脂（Ａ）を構成するエポキシ樹脂のうち、重量比で５０％以上を占めるエポキシ樹脂（Ａ１）がグリシジル構造を有するエポキシ基を２官能以上、及び脂環構造を有するエポキシ基を１官能以上有する。エポキシ樹脂（Ａ１）は、グリシジル構造を有するエポキシ基を２官能以上、及び脂環構造を有するエポキシ基を１官能以上有するエポキシ樹脂であれば、いずれでも良いが、特に不飽和結合を有していないため耐候性が高く、粘度が低いことから、４，５－エポキシヘキサヒドロフタル酸ジグリシジルが好適である。また、グリシジル構造を有するエポキシ基を２官能以上、及び脂環構造を有するエポキシ基を１官能以上有するエポキシ樹脂が２種類以上含まれる場合は、それらのエポキシ樹脂の合計含有量が重量比で５０％以上であれば、それらのエポキシ樹脂を合わせてエポキシ樹脂（Ａ１）とする。
In the epoxy resin composition of the present invention, among the epoxy resins constituting the epoxy resin (A), the epoxy resin (A1), which accounts for 50% or more by weight, has an epoxy group having a glycidyl structure with at least two functionalities and an alicyclic It has one or more functional epoxy groups having a structure. The epoxy resin (A1) may be any epoxy resin having two or more functional epoxy groups having a glycidyl structure and one or more functional epoxy groups having an alicyclic structure. Diglycidyl 4,5-epoxyhexahydrophthalate is preferred because it has high weather resistance and low viscosity because it does not contain any. Further, when two or more types of epoxy resins having two or more functional epoxy groups having a glycidyl structure and one or more functional epoxy groups having an alicyclic structure are included, the total content of these epoxy resins is 50 by weight. % or more, these epoxy resins are combined to be the epoxy resin (A1).
本発明において、エポキシ樹脂（Ａ）は、エポキシ樹脂（Ａ１）以外のエポキシ樹脂として、エポキシ樹脂（Ａ２）を含有してもよい。エポキシ樹脂（Ａ２）の例としては、３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、１－エポキシエチル－３，４－エポキシシクロヘキサン、リモネンジエポキシド、ジシクロペンタジエンジエポキシド等の脂環構造を有するものや、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、水添ビスフェノールＡジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル等のグリシジル構造を有するエポキシ基を有する液状のエポキシ樹脂や、イソシアヌル酸トリグリシジル、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物といった固形エポキシ樹脂も他のエポキシ樹脂と混ぜることで使用することができる。
In the present invention, the epoxy resin (A) may contain an epoxy resin (A2) as an epoxy resin other than the epoxy resin (A1). Examples of epoxy resins (A2) include 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 1-epoxyethyl-3,4- Those having an alicyclic structure such as epoxycyclohexane, limonene diepoxide, dicyclopentadiene diepoxide, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, sorbitol Liquid epoxy resins having an epoxy group having a glycidyl structure such as polyglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, triglycidyl isocyanurate, 2,2-bis(hydroxymethyl Solid epoxy resins such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of )-1-butanol can also be used by blending with other epoxy resins.
本発明で用いられるチオール基含有硬化剤（Ｂ）は、より具体的には、エポキシ樹脂（Ａ）のエポキシ基と反応可能なチオール基を一分子中に２個以上有する化合物を指し、エポキシ樹脂の硬化剤として作用する。
The thiol group-containing curing agent (B) used in the present invention more specifically refers to a compound having two or more thiol groups in one molecule capable of reacting with the epoxy group of the epoxy resin (A). acts as a curing agent for
硬化剤としてチオール化合物を用いることで、繊維強化複合材料を成形した温度よりも低い温度で硬化被膜を形成する際にも、十分に高速硬化させ、生産性を高めることが可能となることが期待される。
By using a thiol compound as a curing agent, it is expected that even when forming a cured film at a temperature lower than the temperature at which the fiber-reinforced composite material is molded, it will be possible to cure at a sufficiently high speed and increase productivity. be done.
チオール基含有硬化剤（Ｂ）の例としては、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）、トリス－［（３－メルカプトプロピオニルオキシ）－エチル］－イソシアヌレート、テトラエチレングリコールビス（３－メルカプトプロピオネート）、１，２－ビス（２－メルカプトエチルチオ）－３－メルカプトプロパン、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、ビスフェノールＡ型チオール等が挙げられる。中でも、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンがより好ましい。
Examples of thiol group-containing curing agents (B) include pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate ), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine- 2,4,6(1H,3H,5H)-trione, bisphenol A-type thiol, and the like. Among them, 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5- More preferred is triazine-2,4,6(1H,3H,5H)-trione.
一方で、成形型内のキャビティへ樹脂組成物を流し込む間には、十分流し込める低粘度を維持する安定性が求められる。その観点からチオール基含有硬化剤（Ｂ）は２級チオール構造または３級チオール構造を有することが好ましく、以下の化学式（１）で示されるチオール構造を２個以上有することがより好ましい。
On the other hand, while the resin composition is being poured into the cavity in the mold, stability is required to maintain a sufficiently low viscosity for pouring. From that point of view, the thiol group-containing curing agent (B) preferably has a secondary thiol structure or a tertiary thiol structure, and more preferably has two or more thiol structures represented by the following chemical formula (1).
Ｒ７は、水素原子、炭素数１～２０のアルキル基、炭素数３～８のシクロアルキル基或いは炭素数７～２０のアラルキル基、又は炭素数６～２０のアリール基を示す。
R 7 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
Ｒ８は、炭素数１～２０のアルキル基、炭素数３～８のシクロアルキル基或いは炭素数７～２０のアラルキル基、又は炭素数６～２０のアリール基を示す。
R 8 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
ｎは、１以上の自然数を示す。
n represents a natural number of 1 or more.
Ｒ７、Ｒ８のいずれか、または両方が水素原子でない場合、被膜用樹脂組成物を調製した際に安定性が高く、短時間で増粘しにくく、成型が容易である。
When either or both of R 7 and R 8 are not hydrogen atoms, the resin composition for coating is highly stable when prepared, does not easily thicken in a short period of time, and is easy to mold.
好ましくは、ｎは１以上１０以下の自然数を示し、より好ましくは、ｎは１以上５以下の自然数を示す。
Preferably, n represents a natural number of 1 or more and 10 or less, and more preferably, n represents a natural number of 1 or more and 5 or less.
化学式１で示されるチオール構造を２個以上有するチオール化合物の例としては、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンなどが挙げられる。
Examples of thiol compounds having two or more thiol structures represented by Chemical Formula 1 include 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5 -tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.
本発明のエポキシ樹脂組成物におけるエポキシ樹脂（Ａ）とチオール基含有硬化剤（Ｂ）の含有量は、成分チオール基含有硬化剤（Ｂ）中のチオール基数（Ｈ）と、エポキシ樹脂（Ａ）中のエポキシ基総数（Ｅ）の比、Ｈ／Ｅ比が０．８～１．３の範囲を満たす含有量であることが好ましい態様である。Ｈ／Ｅ比が０．８を下回る場合、過剰に存在するエポキシ樹脂同士の重合が進み、硬化物の物性の低下を招く場合がある。また、Ｈ／Ｅ比が１．３を上回る場合、過剰に存在する硬化剤成分のために系の反応点の濃度が減少し、反応速度が低下し、十分な高速硬化性を発揮できなくなる場合がある。
The contents of the epoxy resin (A) and the thiol group-containing curing agent (B) in the epoxy resin composition of the present invention are determined by the number of thiol groups (H) in the component thiol group-containing curing agent (B) and the epoxy resin (A) It is a preferred embodiment that the ratio of the total number of epoxy groups (E) in the compound, the H/E ratio, satisfies the range of 0.8 to 1.3. If the H/E ratio is less than 0.8, excessive polymerization of the epoxy resin may proceed, resulting in deterioration of the physical properties of the cured product. If the H/E ratio exceeds 1.3, the concentration of reaction sites in the system decreases due to excessive curing agent components, and the reaction rate decreases, resulting in a failure to exhibit sufficient high-speed curability. There is
本発明で用いられる触媒（Ｃ）は、第四級ホスホニウム塩が好ましい。第四級ホスホニウム塩は速硬化性発現のための硬化促進剤として作用する。
The catalyst (C) used in the present invention is preferably a quaternary phosphonium salt. The quaternary phosphonium salt acts as a curing accelerator for rapid curing.
第四級ホスホニウム塩を本発明に適用すると、詳細な機構は定かではないが、主剤液と硬化剤液を混合した後の粘度上昇が少なく安定であり、成形型内のキャビティに樹脂組成物を流し込む際の低粘度安定性に優れる一方で、その後の硬化反応が十分に速く硬化時間を短縮できる。
When a quaternary phosphonium salt is applied to the present invention, although the detailed mechanism is not clear, it is stable with little increase in viscosity after mixing the main component liquid and the curing agent liquid, and the resin composition is injected into the cavity in the mold. While excellent in low viscosity stability when poured, the subsequent curing reaction is sufficiently fast and the curing time can be shortened.
本発明における触媒（Ｃ）として用いられる第四級ホスホニウム塩の具体例としては、テトラエチルホスホニウムブロミド、トリブチルメチルホスホニウムヨージド、テトラエチルホスホニウムヘキサフルオロホスフェート、テトラエチルホスホニウムテトラフルオロボレート、トリブチル（シアノメチル）ホスホニウムクロリド、テトラキス（ヒドロキシメチル）ホスホニウムクロリド、テトラブチルホスホニウムヒドロキシド、テトラブチルホスホニウムブロミド、テトラブチルホスホニウムクロリド、テトラキス（ヒドロキシメチル）ホスホニウムスルファート、トリブチル－ｎ－オクチルホスホニウムブロミド、テトラ－ｎ－オクチルホスホニウムブロミド、テトラブチルホスホニウムテトラフルオロボレート、テトラブチルホスホニウムヘキサフルオロホスフェート、トリブチルドデシルホスホニウムブロミド、トリブチルヘキサデシルホスホニウムブロミド、トリヘキシル（テトラデシル）ホスホニウムジシアナミド、メチルトリフェニルホスホニウムヨージド、メチルトリフェニルホスホニウムブロミド、メチルトリフェニルホスホニウムクロリド、トリブチルメチルホスホニウムビス（トリフルオロメタンスルホニル）イミド、テトラフェニルホスホニウムブロミド、テトラフェニルホスホニウムクロリド、テトラフェニルホスホニウムヨージド、（ブロモメチル）トリフェニルホスホニウムブロミド、（クロロメチル）トリフェニルホスホニウムクロリド、（シアノメチル）トリフェニルホスホニウムクロリド、エチルトリフェニルホスホニウムブロミド、エチルトリフェニルホスホニウムヨージド、イソプロピルトリフェニルホスホニウムヨージド、トリフェニルビニルホスホニウムブロミド、アリルトリフェニルホスホニウムブロミド、アリルトリフェニルホスホニウムクロリド、ブチルトリフェニルホスホニウムブロミド、（ホルミルメチル）トリフェニルクロリド、（メトキシメチル）トリフェニルホスホニウムクロリド、トリフェニルプロピルホスホニウムブロミド、トリフェニルプロパルギルホスホニウムブロミド、アミルトリフェニルホスホニウムブロミド、アセトニルトリフェニルホスホニウムクロリド、ベンジルトリフェニルホスホニウムクロリド、３－ブロモプロピルトリフェニルホスホニウムブロミド、ベンジルトリフェニルホスホニウムブロミド、シクロプロピルトリフェニルホスホニウムブロミド、２－ジメチルアミノエチルトリフェニルホスホニウムブロミド、ヘキシルトリフェニルホスホニウムブロミド、ヘプチルトリフェニルホスホニウムブロミド、テトラフェニルホスホニウムテトラフェニルボレート、（３－トリメチルシリル－２－プロピル）トリフェニルホスホニウムブロミド、トリフェニル（テトラデシル）ホスホニウムブロミド、（２－トリメチルシリルエチル）トリフェニルホスホニウムヨージド、テトラブチルホスホニウムテトラフェニルボレート、トリブチル（１，３－ジオキサン－２－イルメチル）ホスホニウムブロミド、ｔｒａｎｓ－２－ブタン－１，４－ビス（トリフェニルホスホニウムクロリド）、（ｔｅｒｔ－ブトキシカルボニルメチル）トリフェニルホスホニウムブロミド、（４－ブロモベンジル）トリフェニルホスホニウムブロミド、シンナミルトリフェニルホスホニウムブロミド、（４－クロロベンジル）トリフェニルホスホニウムクロリド、（３－カルボキシプロピル）トリフェニルホスホニウムブロミド、（２－クロロベンジル）トリフェニルホスホニウムクロリド、エトキシカルボニルメチル（トリフェニル）ホスホニウムブロミド、メトキシカルボニルメチル（トリフェニル）ホスホニウムブロミド、（１－ナフチルメチル）トリフェニルホスホニウムクロリド、フェナシルトリフェニルホスホニウムブロミド、２－（トリメチルシリル）エトキシメチルトリフェニルホスホニウムクロリド、テトラフェニルホスホニウムテトラ－ｐ－トリルボレート、４－（カルボキシブチル）トリフェニルホスホニウムブロミド、（１，３－ジオキサン－２－イル）メチルトリフェニルホスホニウムブロミド、（２，４－ジクロロベンジル）トリフェニルホスホニウムクロリド、（３，４－ジメトキシベンジル）トリフェニルホスホニウムブロミド、４－エトキシベンジルトリフェニルホスホニウムブロミド、（２－ヒドロキシベンジル）トリフェニルホスホニウムブロミド、（３－メトキシベンジル）トリフェニルホスホニウムクロリド、（４－ニトロベンジル）トリフェニルホスホニウムブロミド、２－（１，３－ジオキサン－２－イル）エチルトリフェニルホスホニウムブロミド、２－（１，３－ジオキサン－２－イル）エチルトリフェニルホスホニウムブロミド、トリフェニル（２－チエニルメチル）ホスホニウムブロミド、ドデシルトリブチルホスホニウムクロリド、エチルトリオクチルホスホニウムブロミド、ヘキサデシルトリブチルホスホニウムクロリド、メチルトリブチルホスホニウムジメチルホスフェート、メチルトリブチルホスホニウムヨージド、テトラエチルホスホニウムブロミド、テトラエチルホスホニウムヒドロキシド、テトラブチルホスホニウムブロミド、テトラブチルホスホニウムクロリド、テトラブチルホスホニウムｏ，ｏ－ジエチルホスホロジチオエート、テトラブチルホスホニウムベンゾトリアゾレート、テトラブチルホスホニウムテトラフェニルボレート、トリエチルペンチルホスホニウムブロミド、トリエチルオクチルホスホニウムブロミド、トリエチルペンチルホスホニウムビス（トリフルオロメチルスルホニル）イミド、トリエチルオクチルホスホニウムビス（トリフルオロメチルスルホニル）イミド、トリ－ｎ－ブチルメチルホスホニウムビス（トリフルオロメチルスルホニル）イミドなどが挙げられる。
Specific examples of the quaternary phosphonium salts used as the catalyst (C) in the present invention include tetraethylphosphonium bromide, tributylmethylphosphonium iodide, tetraethylphosphonium hexafluorophosphate, tetraethylphosphonium tetrafluoroborate, tributyl(cyanomethyl)phosphonium chloride, Tetrakis(hydroxymethyl)phosphonium chloride, tetrabutylphosphonium hydroxide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrakis(hydroxymethyl)phosphonium sulfate, tributyl-n-octylphosphonium bromide, tetra-n-octylphosphonium bromide, tetra Butylphosphonium tetrafluoroborate, tetrabutylphosphonium hexafluorophosphate, tributyldodecylphosphonium bromide, tributylhexadecylphosphonium bromide, trihexyl(tetradecyl)phosphonium dicyanamide, methyltriphenylphosphonium iodide, methyltriphenylphosphonium bromide, methyltriphenylphosphonium chloride , tributylmethylphosphonium bis(trifluoromethanesulfonyl)imide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium iodide, (bromomethyl)triphenylphosphonium bromide, (chloromethyl)triphenylphosphonium chloride, (cyanomethyl)triphenyl Phosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, isopropyltriphenylphosphonium iodide, triphenylvinylphosphonium bromide, allyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, (formylmethyl ) triphenyl chloride, (methoxymethyl) triphenylphosphonium chloride, triphenylpropylphosphonium bromide, triphenylpropargylphosphonium bromide, amyltriphenylphosphonium bromide, acetonyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, 3-bromopropyltri phenylphosphonium bromide, benzyltriphenylphosphonium bromide, cyclopropyltriphenyl phosphonium bromide, 2-dimethylaminoethyltriphenylphosphonium bromide, hexyltriphenylphosphonium bromide, heptyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, (3-trimethylsilyl-2-propyl)triphenylphosphonium bromide, triphenyl ( tetradecyl)phosphonium bromide, (2-trimethylsilylethyl)triphenylphosphonium iodide, tetrabutylphosphonium tetraphenylborate, tributyl(1,3-dioxan-2-ylmethyl)phosphonium bromide, trans-2-butane-1,4-bis (triphenylphosphonium chloride), (tert-butoxycarbonylmethyl)triphenylphosphonium bromide, (4-bromobenzyl)triphenylphosphonium bromide, cinnamyltriphenylphosphonium bromide, (4-chlorobenzyl)triphenylphosphonium chloride, (3 -carboxypropyl)triphenylphosphonium bromide, (2-chlorobenzyl)triphenylphosphonium chloride, ethoxycarbonylmethyl (triphenyl)phosphonium bromide, methoxycarbonylmethyl (triphenyl)phosphonium bromide, (1-naphthylmethyl)triphenylphosphonium chloride , phenacyltriphenylphosphonium bromide, 2-(trimethylsilyl)ethoxymethyltriphenylphosphonium chloride, tetraphenylphosphonium tetra-p-tolylborate, 4-(carboxybutyl)triphenylphosphonium bromide, (1,3-dioxane-2- yl) methyltriphenylphosphonium bromide, (2,4-dichlorobenzyl)triphenylphosphonium chloride, (3,4-dimethoxybenzyl)triphenylphosphonium bromide, 4-ethoxybenzyltriphenylphosphonium bromide, (2-hydroxybenzyl)tri Phenylphosphonium bromide, (3-methoxybenzyl)triphenylphosphonium chloride, (4-nitrobenzyl)triphenylphosphonium bromide, 2-(1,3-dioxan-2-yl)ethyltriphenylphosphonium bromide, 2-(1, 3-dioxan-2-yl)ethyltriphenylphosphonium bromide, triphenyl(2-thienylmethyl)phosphonium bromide, dodecyltributyl Sulfonium chloride, ethyltrioctylphosphonium bromide, hexadecyltributylphosphonium chloride, methyltributylphosphonium dimethylphosphate, methyltributylphosphonium iodide, tetraethylphosphonium bromide, tetraethylphosphonium hydroxide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium o,o-diethyl phosphorodithioate, tetrabutylphosphonium benzotriazolate, tetrabutylphosphonium tetraphenylborate, triethylpentylphosphonium bromide, triethyloctylphosphonium bromide, triethylpentylphosphonium bis(trifluoromethylsulfonyl)imide, triethyloctylphosphonium bis(trifluoromethylsulfonyl)imide, tri-n-butylmethylphosphonium bis(trifluoromethylsulfonyl)imide and the like.
本発明における触媒（Ｃ）として用いられる第四級ホスホニウム塩としては、エポキシ樹脂（Ａ）やチオール基含有硬化剤（Ｂ）への溶解性やコスト、さらに低粘度安定性と高速硬化性の両立の観点から化学式（２）で示される化合物が好ましい。化学式２で示される化合物の具体例としては、メチルトリブチルホスホニウムジメチルホスフェート、テトラブチルホスホニウムｏ，ｏ－ジエチルホスホロジチオエートなどが挙げられる。
As the quaternary phosphonium salt used as the catalyst (C) in the present invention, the solubility and cost in the epoxy resin (A) and the thiol group-containing curing agent (B), and compatibility between low viscosity stability and high-speed curing From the viewpoint of the above, the compound represented by the chemical formula (2) is preferred. Specific examples of the compound represented by Chemical Formula 2 include methyltributylphosphonium dimethylphosphate and tetrabutylphosphonium o,o-diethylphosphorodithioate.
Ｒ１～Ｒ４はそれぞれ独立して、炭素数１～２０のアルキル基、炭素数３～８のシクロアルキル基或いは炭素数７～２０のアラルキル基、又は炭素数６～２０のアリール基を示す。
R 1 to R 4 each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. .
Ｒ５及びＲ６はそれぞれ独立して、炭素数１～２０のアルキル基を示す。
R 5 and R 6 each independently represent an alkyl group having 1 to 20 carbon atoms.
Ｍ１及びＭ２はそれぞれ独立して、周期表における第１６族から選ばれる元素を示し、特に酸素、硫黄であることが好ましい。
M 1 and M 2 each independently represent an element selected from Group 16 of the periodic table, and oxygen and sulfur are particularly preferred.
本発明で用いられる触媒（Ｃ）の含有量は、エポキシ樹脂（Ａ）１００質量部に対して０．１質量部以上１５質量部未満が好ましく、より好ましくは０．１質量部以上１２質量部以下であり、さらに好ましくは０．１質量部以上１０質量部以下である。触媒（Ｃ）が０．１質量部よりも少ない場合、硬化に要する時間が長くなり十分な高速硬化性を発揮できない場合がある。一方、触媒（Ｃ）が１５質量部以上の場合、低粘度を維持する時間が短くなり、成形型内のキャビティに樹脂組成物を流し込むことが困難となる場合がある。
The content of the catalyst (C) used in the present invention is preferably 0.1 parts by mass or more and less than 15 parts by mass, more preferably 0.1 parts by mass or more and 12 parts by mass based on 100 parts by mass of the epoxy resin (A). or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less. If the amount of the catalyst (C) is less than 0.1 parts by mass, the time required for curing may become longer and sufficient high-speed curability may not be exhibited. On the other hand, when the amount of the catalyst (C) is 15 parts by mass or more, the time to maintain the low viscosity is shortened, and it may become difficult to pour the resin composition into the cavity in the mold.
本発明のエポキシ樹脂組成物は、例えば、エポキシ樹脂（Ａ）を含む主剤液と、チオール基含有硬化剤（Ｂ）を主成分（なお、ここでいう主成分とは、硬化剤液中において質量基準で最大量の成分であることを意味する。）として含む硬化剤液とを、それぞれ前述した配合量で配合しておき、使用直前に前述した配合量となるように、主剤液と硬化剤液を混合して得られる。前述した触媒（Ｃ）は、主剤液、硬化剤液のいずれに配合することもできるが、硬化剤液に含まれることがより好ましい態様である。
The epoxy resin composition of the present invention comprises, for example, a main component liquid containing an epoxy resin (A) and a thiol group-containing curing agent (B) as main components (the main component herein means the mass of the curing agent liquid). It means that it is the component with the maximum amount as a standard.) and the curing agent liquid contained in each of the above-mentioned amounts, and just before use, mix the main liquid and the curing agent so that the above-mentioned amounts are obtained. Obtained by mixing liquids. Although the catalyst (C) described above can be blended in either the main liquid or the curing agent liquid, it is more preferably contained in the curing agent liquid.
他の配合成分は、主剤液と硬化剤液のどちらに配合しても良く、あらかじめどちらかあるいは両方に混合して使用することができる。主剤液と硬化剤液は、混合前に、別々に加温しておくことが好ましく、成形型への注入など、使用の直前にミキサーを用いて混合して２液型エポキシ樹脂組成物を得ることが、樹脂の可使時間の点から好ましい。
Other compounding ingredients can be blended into either the main liquid or the hardener liquid, and can be used by mixing with either or both in advance. The main component liquid and the curing agent liquid are preferably heated separately before mixing, and are mixed using a mixer immediately before use such as injection into a mold to obtain a two-component epoxy resin composition. is preferable from the standpoint of the pot life of the resin.
本発明のエポキシ樹脂硬化物は、本発明のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物であって、４０℃以上のガラス転移点温度（Ｔｇ）を有する。このＴｇとは、後述の＜樹脂硬化板の作製＞に記載の方法で樹脂硬化板を作製し、後述の＜樹脂硬化物のガラス転移温度Ｔｇ測定＞に記載の方法によりＤＭＡ（動的粘弾性）を用いて観測される貯蔵弾性率のＯｎ Ｓｅｔから算出される値である。なお、ＤＭＡでＴｇが測定できないサンプルの場合は、ＤＳＣ（示差走査熱量計）にて観測されるベースラインの変位の中点から算出してもよい。エポキシ樹脂硬化物のＴｇは、より好ましくは５０℃以上である。Ｔｇが低く、常温でゴム状態にあるエポキシ樹脂硬化物は、不飽和結合を有していないエポキシ樹脂とチオール基含有硬化剤の硬化物であっても、副反応が起きやすくなるため、耐候性が落ち、紫外光による変色が起きやすくなる。また、本発明のエポキシ樹脂硬化物のＴｇは常温以上あるため、十分な硬度を有しており、被覆した成形品の取り扱い時に傷がつきにくい。常温での切削性も良いため、本発明のエポキシ樹脂硬化物で繊維強化樹脂成形品を被覆した被覆繊維強化樹脂成形品に塗装の前処理として被覆繊維強化樹脂成形品の表面を研磨する際、熱がこもっても柔らかくならないため、細かい番手のペーパーを使用しても、短時間で研磨できる。被覆繊維強化樹脂成形品の被覆樹脂の硬度は温度２３℃、湿度５０％の標準条件下で、鉛筆硬度のＨ以上あればより好ましい。
The epoxy resin cured product of the present invention is an epoxy resin cured product obtained by curing the epoxy resin composition of the present invention, and has a glass transition temperature (Tg) of 40°C or higher. This Tg means that a cured resin plate is prepared by the method described in <Preparation of cured resin plate> below, and DMA (dynamic viscoelasticity) is measured by the method described in <Measurement of glass transition temperature Tg of cured resin> below. ) is a value calculated from the On Set of the storage modulus observed using In the case of a sample whose Tg cannot be measured by DMA, it may be calculated from the midpoint of the baseline displacement observed by DSC (differential scanning calorimeter). The Tg of the cured epoxy resin is more preferably 50°C or higher. Epoxy resin cured products that have a low Tg and are in a rubbery state at room temperature are susceptible to side reactions, even if they are cured products of epoxy resins that do not have unsaturated bonds and thiol group-containing curing agents. and discoloration due to ultraviolet light is likely to occur. In addition, since the epoxy resin cured product of the present invention has a Tg higher than room temperature, it has sufficient hardness, and the coated molded product is less likely to be damaged during handling. Machinability at normal temperature is also good, so when polishing the surface of the coated fiber reinforced resin molded article as a pretreatment for coating the fiber reinforced resin molded article coated with the epoxy resin cured product of the present invention, Because it does not soften even when heat is trapped, it can be polished in a short time even with fine-grained paper. It is more preferable that the hardness of the coating resin of the coated fiber-reinforced resin molded product is H or higher than the pencil hardness under standard conditions of temperature of 23° C. and humidity of 50%.
本発明のエポキシ樹脂硬化物の耐候性はフロリダ暴露１年分相当の紫外線量（３０８ＭＪ／ｍ２）を高温環境下（４７℃）で浴びても変色が軽微であることが好ましい。具体的には、厚み２ｍｍのエポキシ樹脂硬化物の色差（ΔＥ）は３０以下が好ましく、２０以下がより好ましい。この板厚でこの色差であれば、エポキシ樹脂硬化物で被覆した繊維強化樹脂成形品に塗ってある紫外線吸収剤を含む塗料の膜厚が１０μｍ以上あれば、変色は軽微となる。また厚み２ｍｍのエポキシ樹脂硬化物の色差（ΔＥ）が４以下であれば、紫外線吸収剤を含む塗料がなくとも、変色は軽微となる。
Weather resistance of the epoxy resin cured product of the present invention is preferably such that discoloration is slight even when exposed to an ultraviolet dose (308 MJ/m 2 ) equivalent to one year exposure to Florida in a high temperature environment (47°C). Specifically, the color difference (ΔE) of a cured epoxy resin product having a thickness of 2 mm is preferably 30 or less, more preferably 20 or less. With this plate thickness and this color difference, if the film thickness of the paint containing the ultraviolet absorber applied to the fiber-reinforced resin molded product coated with the epoxy resin cured product is 10 μm or more, the discoloration will be slight. Further, if the color difference (ΔE) of the epoxy resin cured product having a thickness of 2 mm is 4 or less, discoloration is slight even without a coating containing an ultraviolet absorber.
本発明の被覆繊維強化樹脂成形品は、本発明のエポキシ樹脂硬化物を被覆層として繊維強化樹脂成形品の表面の少なくとも一部に被覆してなる。被覆される繊維強化樹脂成形品は、炭素繊維強化プラスチックであることが好ましい。炭素繊維強化プラスチックは軽量で高い剛性と強度を持ち、特に自動車や鉄道、航空機やドローン等に用いて軽量化することで、燃費や航続距離を延ばすことができる。また、表層に平織、綾織、朱子織といった織物を用いた炭素繊維強化樹脂成形品は審美性も要求され、本発明のエポキシ樹脂組成物を被覆する対象として好適である。使用する織物の炭素繊維目付は１８０ｇ／ｍ２以上が好ましく、２１５ｇ／ｍ２以上がより好ましい。炭素繊維目付が大きいほうが、クロスの凹凸が深く見え、より審美性が増す。この場合、全部または一部分有色塗装を施さずに、クリアー塗装を行い、織物自体を外部から視認可能とする製品の場合は、特に成形品の商品価値が高い。
The coated fiber-reinforced resin molded product of the present invention is obtained by coating at least part of the surface of the fiber-reinforced resin molded product with the cured epoxy resin of the present invention as a coating layer. The fiber-reinforced resin molded product to be coated is preferably carbon fiber-reinforced plastic. Carbon fiber reinforced plastics are lightweight, have high rigidity and strength, and can be used in automobiles, railways, aircraft, drones, etc. to reduce their weight, thereby increasing fuel efficiency and cruising range. In addition, carbon fiber reinforced resin molded articles using fabrics such as plain weave, twill weave, and satin weave for the surface layer are also required to be aesthetically pleasing, and are suitable as objects to be coated with the epoxy resin composition of the present invention. The fabric used has a carbon fiber basis weight of preferably 180 g/m 2 or more, more preferably 215 g/m 2 or more. The larger the carbon fiber basis weight, the deeper the unevenness of the cloth, and the more aesthetically pleasing. In this case, the commercial value of the molded article is particularly high in the case of a product in which the fabric itself is visible from the outside by applying a clear coating without applying a colored coating in whole or in part.
本発明の被覆繊維強化樹脂成形品に用いる炭素繊維は、特に限定されるものではないが、ポリアクリロニトリル系炭素繊維、レーヨン系炭素繊維およびピッチ系炭素繊維等が好ましく用いられる。中でも、引張強度の高いポリアクリロニトリル系炭素繊維が、特に好ましく用いられる。炭素繊維の形態としては、有撚糸、解撚糸および無撚糸等を使用することができる。
Although the carbon fiber used in the coated fiber-reinforced resin molded article of the present invention is not particularly limited, polyacrylonitrile-based carbon fiber, rayon-based carbon fiber, pitch-based carbon fiber, and the like are preferably used. Among them, polyacrylonitrile-based carbon fibers having high tensile strength are particularly preferably used. Twisted yarn, untwisted yarn, non-twisted yarn, and the like can be used as the form of the carbon fiber.
かかる炭素繊維は、引張弾性率が１８０～６００ＧＰａの範囲であることが好ましい。引張弾性率がこの範囲であれば、得られる繊維強化複合材料に剛性を持たせることができるため、得られる成形品を軽量化することができる。また一般に、炭素繊維は弾性率が高くなるほど強度が低下する傾向があるが、この範囲であれば炭素繊維自体の強度を保つことができる。より好ましい弾性率は、２００～４４０ＧＰａの範囲であり、さらに好ましくは２２０～３００ＧＰａの範囲である。上記の上限と下限のいずれを組み合わせた範囲であってもよい。ここで、炭素繊維の引張弾性率は、ＪＩＳ Ｒ７６０１－２００６に従い測定された値である。
Such carbon fibers preferably have a tensile modulus in the range of 180 to 600 GPa. If the tensile modulus is within this range, the obtained fiber-reinforced composite material can be given rigidity, so that the obtained molded article can be reduced in weight. In general, carbon fibers tend to have a lower strength as the modulus of elasticity increases, but within this range the strength of the carbon fibers themselves can be maintained. A more preferable elastic modulus is in the range of 200 to 440 GPa, more preferably in the range of 220 to 300 GPa. The range may be a combination of any of the above upper and lower limits. Here, the tensile modulus of carbon fiber is a value measured according to JIS R7601-2006.
炭素繊維の市販品としては、“トレカ（登録商標）”Ｔ３００（引張強度：３．５ＧＰａ、引張弾性率：２３０ＧＰａ）、“トレカ（登録商標）”Ｔ３００Ｂ（引張強度：３．５ＧＰａ、引張弾性率：２３０ＧＰａ）、“トレカ（登録商標）”Ｔ４００ＨＢ（引張強度：４．４ＧＰａ、引張弾性率：２５０ＧＰａ）、“トレカ（登録商標）”Ｔ７００ＳＣ（引張強度：４．９ＧＰａ、引張弾性率：２３０ＧＰａ）、“トレカ（登録商標）”Ｔ８００ＨＢ（引張強度：５．５ＧＰａ、引張弾性率：２９４ＧＰａ）、“トレカ（登録商標）”Ｔ８００ＳＣ（引張強度：５．９ＧＰａ、引張弾性率：２９４ＧＰａ）、“トレカ（登録商標）”Ｔ８３０ＨＢ（引張強度：５．３ＧＰａ、引張弾性率：２９４ＧＰａ）、“トレカ（登録商標）”Ｔ１０００ＧＢ－（引張強度：６．４ＧＰａ、引張弾性率：２９４ＧＰａ）、“トレカ（登録商標）”Ｔ１１００ＧＣ（引張強度：７．０ＧＰａ、引張弾性率：３２４ＧＰａ）、“トレカ（登録商標）”Ｍ３５ＪＢ（引張強度：４．７ＧＰａ、引張弾性率：３４３ＧＰａ）、“トレカ（登録商標）”Ｍ４０ＪＢ（引張強度：４．４ＧＰａ、引張弾性率：３７７ＧＰａ）、“トレカ（登録商標）”Ｍ４６ＪＢ（引張強度：４．２ＧＰａ、引張弾性率：４３６ＧＰａ）、“トレカ（登録商標）”Ｍ５５Ｊ（引張強度：４．０ＧＰａ、引張弾性率：５４０ＧＰａ）、“トレカ（登録商標）”Ｍ６０ＪＢ（引張強度：３．８ＧＰａ、引張弾性率：５８８ＧＰａ）、“トレカ（登録商標）”Ｍ３０ＳＣ（引張強度：５．５ＧＰａ、引張弾性率：２９４ＧＰａ）（以上、東レ（株）製）、ＰＸ３５（引張強度：４．１ＧＰａ、引張弾性率：２４２ＧＰａ）、（以上、ＺＯＬＴＥＫ社製）などを挙げることができる。
Commercially available carbon fibers include "Torayca (registered trademark)" T300 (tensile strength: 3.5 GPa, tensile modulus: 230 GPa), "Torayca (registered trademark)" T300B (tensile strength: 3.5 GPa, tensile modulus : 230 GPa), “Torayca (registered trademark)” T400HB (tensile strength: 4.4 GPa, tensile modulus: 250 GPa), “Torayca (registered trademark)” T700SC (tensile strength: 4.9 GPa, tensile modulus: 230 GPa), “Torayca (registered trademark)” T800HB (tensile strength: 5.5 GPa, tensile modulus: 294 GPa), “Torayca (registered trademark)” T800SC (tensile strength: 5.9 GPa, tensile modulus: 294 GPa), “Torayca (registered trademark)” Trademark) “T830HB (tensile strength: 5.3 GPa, tensile modulus: 294 GPa), “Torayca (registered trademark)” T1000GB- (tensile strength: 6.4 GPa, tensile elastic modulus: 294 GPa), “Torayca (registered trademark)” T1100GC (tensile strength: 7.0 GPa, tensile modulus: 324 GPa), "Torayca (registered trademark)" M35JB (tensile strength: 4.7 GPa, tensile elastic modulus: 343 GPa), "Torayca (registered trademark)" M40JB (tensile strength : 4.4 GPa, tensile modulus: 377 GPa), "Torayca (registered trademark)" M46JB (tensile strength: 4.2 GPa, tensile modulus: 436 GPa), "Torayca (registered trademark)" M55J (tensile strength: 4.0 GPa , tensile modulus: 540 GPa), “Torayca (registered trademark)” M60JB (tensile strength: 3.8 GPa, tensile elastic modulus: 588 GPa), “Torayca (registered trademark)” M30SC (tensile strength: 5.5 GPa, tensile elastic modulus : 294 GPa) (manufactured by Toray Industries, Inc.), PX35 (tensile strength: 4.1 GPa, tensile modulus: 242 GPa) (manufactured by ZOLTEK), and the like.
炭素繊維のフィラメント数としては、特に限定されるものではないが、本発明の被覆繊維強化樹脂成形品に後述の織物を用いる場合、製織生産性、要求される被覆繊維強化樹脂成形品の引張・曲げ弾性率や強度、プレートの意匠性の観点から、炭素繊維束は、１，０００～７０，０００フィラメントの範囲であることが好ましく、より好ましくは１，０００～６０，０００フィラメントで構成されたものである。
The number of filaments of the carbon fiber is not particularly limited, but when the woven fabric described later is used for the coated fiber-reinforced resin molded product of the present invention, the weaving productivity, the required tensile strength of the coated fiber-reinforced resin molded product, From the viewpoint of flexural modulus, strength, and plate design, the carbon fiber bundle preferably has a range of 1,000 to 70,000 filaments, more preferably 1,000 to 60,000 filaments. It is.
次に、本発明の被覆繊維強化樹脂成形品に用いる強化繊維の形態は、特に限定されるものではないが、前述の強化繊維を一つの方向に引き揃えて、後述のマトリックス樹脂と組み合わせた一方向繊維強化プラスチックや、前述の強化繊維を織物に加工した後に、後述のマトリックス樹脂と組み合わせた織物強化プラスチックを採用することが好ましく用いられる。
Next, the form of the reinforcing fibers used in the coated fiber-reinforced resin molded product of the present invention is not particularly limited, but the above reinforcing fibers are aligned in one direction and combined with the matrix resin described later. It is preferable to adopt a directional fiber reinforced plastic or a fabric reinforced plastic in which the above-mentioned reinforcing fibers are processed into a fabric and then combined with a matrix resin to be described later.
ここで、前述の織物について説明する。織物の織組織は、特に限定されるものではないが、平織り、斜文織り、朱子織り、うね織り、ななこ織り、はし巣織り、ハック織り、模しゃ織り、なし地織りが好ましく用いられる。斜文織りでは、３枚斜文、４枚斜文、５枚斜文、６枚斜文、伸び斜文、曲がり斜文、破れ斜文、飛び斜文、山形斜文、あじろ斜文、重ね斜文、よれ斜文、昼夜斜文、飾り斜文、ぼかし斜文を例示することができ、プレートに要求される意匠性に応じて選択することができる。また、朱子織りでは、５枚朱子、７枚朱子、８枚朱子、１０枚朱子、変則朱子、ひろげ朱子、重ね朱子、みかげ織り、昼夜朱子、ぼかし朱子を例示することができ、被覆繊維強化樹脂成形品に要求される意匠性に応じて選択することができる。また、うね織りでは、たてうね織り、よこうね織り、変化うね織りを例示することができ、被覆繊維強化樹脂成形品に要求される意匠性に応じて選択することができる。また、ななこ織りでは、正則ななこ織り、変化ななこ織り、不規則ななこ織り、変化ななこ織り、向いななこ織り、を例示することができ、被覆繊維強化樹脂成形品に要求される意匠性に応じて選択することができる。さらに、ここで、織物を構成する強化繊維としては、上記に例示した、ガラス繊維単一でもよいし、炭素繊維単一でもよく、複数の種類の異なる、ガラス繊維や炭素繊維を適用してもよく、また、性能・コスト・意匠性に優れることから、少なくとも１種類のガラス繊維と少なくとも１種類の炭素繊維を合わせて交織してもよい。
Here, the aforementioned fabric will be explained. The weave structure of the woven fabric is not particularly limited, but plain weave, twill weave, satin weave, ridge weave, satin weave, nest weave, huck weave, imitation weave, and pear weave are preferably used. . In the twill weave, 3-ply oblique, 4-ply oblique, 5-ply oblique, 6-ply oblique, stretched oblique, curved oblique, broken oblique, jump oblique, Yamagata oblique, Ajiro oblique, stacking Oblique text, twisted oblique text, day and night oblique text, decorative oblique text, and blurred oblique text can be exemplified, and can be selected according to the design required for the plate. In the satin weave, 5 satin, 7 satin, 8 satin, 10 satin, irregular satin, wide satin, layered satin, mikage weave, day and night satin, and shading satin can be exemplified. It can be selected according to the design property required for the resin molded product. The ridge weave can be exemplified by warp ridge weave, weft ridge weave, and variable ridge weave, and can be selected according to the design properties required for the coated fiber-reinforced resin molded product. In addition, the nanako weave includes regular nanako weave, variable nanako weave, irregular nanako weave, variable nanako weave, and counter nanako weave. can do. Furthermore, here, as the reinforcing fiber constituting the woven fabric, a single glass fiber, a single carbon fiber, or a plurality of different types of glass fibers and carbon fibers may be used. Alternatively, at least one type of glass fiber and at least one type of carbon fiber may be combined and woven together because of their excellent performance, cost and design.
被覆される繊維強化樹脂成形品内のマトリックス樹脂内には内部離型剤があることが好ましい。内部離型剤があると、被覆繊維強化樹脂成形品の量産性が改善される。
It is preferable that there is an internal release agent in the matrix resin in the fiber-reinforced resin molded article to be coated. The presence of the internal mold release agent improves the mass productivity of coated fiber reinforced resin moldings.
被覆される繊維強化樹脂プラスチックの成形法は、繊維強化プラスチックを成形するいかなる手法でも良いが、適当な長さにカットされた強化繊維束に熱硬化性樹脂を予め含浸させてシート状に形成した中間基材を成形型で加圧加熱して所定の形状に成形するＳＭＣ成形法や、適当な長さにカットされた強化繊維束と熱硬化性樹脂、充填材を混合しバルク状にした中間材料を成形型で加圧加熱して所定の形状に成形するＢＭＣ成形法、平行に引き揃えられたり、織物にされてシート状になった強化繊維束にマトリクス樹脂が含浸された中間基材であるプリプレグを、成形型に積層配置しプレスで加熱加圧したり、成形型に積層配置して真空バッグして加熱したり、オートクレーブで加圧加熱して成形するプリプレグ成形法、両面型からなる成形型の一方の型上に配置した織物やＮＣＦなどの強化繊維基材上に液状のマトリクス樹脂を供給し、両面型を閉じて加圧加熱するリキッドコンプレッション法、ＲＴＭ法（レジントランスファーモールディング法）等である。特にプリプレグを使用したプリプレグ成形法とＲＴＭ成形法は、織物の目乱れが少なく、審美性を要求される被覆繊維強化樹脂成形品の成形方法として好適である。
The fiber-reinforced resin plastic to be coated may be molded by any method for molding fiber-reinforced plastic, but the reinforcing fiber bundle cut to an appropriate length is pre-impregnated with a thermosetting resin and formed into a sheet. The SMC molding method, in which an intermediate base material is pressurized and heated in a molding die to mold it into a predetermined shape, and the intermediate material that is bulk-shaped by mixing reinforcing fiber bundles cut to an appropriate length, thermosetting resin, and filler. A BMC molding method in which a material is pressurized and heated in a molding die to mold it into a predetermined shape. An intermediate base material in which reinforcing fiber bundles that are arranged in parallel or woven into a sheet are impregnated with a matrix resin. A prepreg molding method in which a certain prepreg is laminated and arranged in a mold and heated and pressed with a press, laminated and arranged in a mold and vacuum bagged and heated, or molded by pressurizing and heating in an autoclave. Liquid compression method, RTM method (resin transfer molding method), etc., in which a liquid matrix resin is supplied onto a reinforcing fiber base material such as a fabric or NCF placed on one mold, and the double-sided mold is closed and pressurized and heated. is. In particular, the prepreg molding method using prepreg and the RTM molding method are suitable as molding methods for coated fiber-reinforced resin molded products that require less disturbance of the texture of the fabric and are required to be aesthetically pleasing.
被覆される繊維強化樹脂プラスチックのマトリックス樹脂は、熱可塑性樹脂、熱硬化性樹脂のいずれをも適宜適用することができる。マトリクス樹脂として、不飽和ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、ポリウレタン樹脂などの熱硬化性樹脂を用いると、機械的特性に優れる被覆繊維強化樹脂成形品を得られるため、好ましい。特に本発明のエポキシ樹脂組成物と同じ種類であるエポキシ樹脂であれば、相互に共有結合を取ることができ、より密着性が向上するため、より好ましい。また、耐熱性の観点から、マトリクス樹脂のガラス転移温度は１００℃以上であることが好ましい。
Both a thermoplastic resin and a thermosetting resin can be appropriately applied as the matrix resin of the fiber-reinforced resin plastic to be coated. Thermosetting resins such as unsaturated polyester resins, epoxy resins, phenolic resins, and polyurethane resins are preferably used as the matrix resin because they provide coated fiber-reinforced resin moldings with excellent mechanical properties. In particular, epoxy resins of the same type as the epoxy resin composition of the present invention are more preferable because covalent bonds can be formed with each other and adhesion is further improved. Moreover, from the viewpoint of heat resistance, the glass transition temperature of the matrix resin is preferably 100° C. or higher.
本発明のエポキシ樹脂組成物は、繊維強化樹脂成形品に低温かつ短時間、大膜厚で被覆できるため、本発明のエポキシ樹脂組成物を繊維強化樹脂成形品に被覆した被覆繊維強化樹脂成形品は、繊維強化樹脂成型品表面にある、繊維と樹脂の硬化収縮差と熱収縮差でできた凹みを埋めることができ、良好な表面品位を有する。被覆する繊維強化性樹脂成形品の表面粗さは、うねり曲線（Ｗｔ）が３μｍ以上であれば、従来の塗装方法では塗装後に塗装面を磨かないと、凹凸が消えないため、より効果が高い。
Since the epoxy resin composition of the present invention can coat a fiber reinforced resin molded article at a low temperature in a short time with a large film thickness, a coated fiber reinforced resin molded article obtained by coating a fiber reinforced resin molded article with the epoxy resin composition of the present invention can be obtained. can fill dents on the surface of a fiber-reinforced resin molded product due to the difference in cure shrinkage and heat shrinkage between the fiber and the resin, and has good surface quality. The surface roughness of the fiber-reinforced resin molded product to be coated is more effective if the undulation curve (Wt) is 3 μm or more, because the unevenness does not disappear unless the coated surface is polished after coating by the conventional coating method. .
繊維強化樹脂成形品に本発明のエポキシ樹脂組成物を被覆する方法としては、特許文献１に記載の方法や、片面型に本発明のエポキシ樹脂組成物を塗布し、そこに繊維強化樹脂成形品の意匠面を被せ、真空を引きつつ硬化させる方法も取ることができる。
As a method of coating a fiber-reinforced resin molded product with the epoxy resin composition of the present invention, there is a method described in Patent Document 1, or a single-sided mold is coated with the epoxy resin composition of the present invention, and a fiber-reinforced resin molded product is coated thereon. It is also possible to use a method of covering the design surface of , and curing while drawing a vacuum.
繊維強化樹脂成形品は、成形型から容易に離型できるように成形型に塗布した離型材が表面に転写されている場合や、あるいは、マトリクス樹脂に添加された内部離型材によって、被覆層との密着性が十分発揮できない場合があるため表面に被覆層を形成する面を研磨材等で研磨することで繊維強化樹脂成形品の表層のマトリクス樹脂や離型剤を除去する加工を施したり、あるいは化学的に密着性を向上させる表面処理を施してもよい。例えば、被覆層との密着性を向上させる前処理を施された繊維強化樹脂層の表面として、サンドペーパ等を用いて表面を研磨して最表層を除去または研磨痕を形成する前処理を行ってから、本発明のエポキシ樹脂組成物を被覆しても良い。これらの処理を行うことにより、繊維に起因する凹凸よりも成形品に生じ得る凹凸を小さくすることができる。
The fiber-reinforced resin molded product may have a release material applied to the mold that is transferred to the surface so that it can be easily released from the mold, or an internal mold release material added to the matrix resin. In some cases, the adhesion of the fiber-reinforced resin molded product may not be sufficiently exhibited, so the surface on which the coating layer is formed may be polished with an abrasive or the like to remove the matrix resin and mold release agent on the surface of the fiber-reinforced resin molded product. Alternatively, surface treatment may be applied to chemically improve adhesion. For example, as the surface of the fiber reinforced resin layer that has been pretreated to improve adhesion to the coating layer, the surface is polished with sandpaper or the like to remove the outermost layer or to form polishing marks. Therefore, the epoxy resin composition of the present invention may be coated. By performing these treatments, irregularities that may occur in the molded article can be made smaller than irregularities caused by fibers.
本発明のエポキシ樹脂組成物を繊維強化樹脂成形品に被覆した被覆繊維強化樹脂成形品に後加熱を行い、本発明のエポキシ樹脂組成物の硬化度を上げることが好ましい。後加熱を行うことで、反応性の悪い脂環式エポキシとチオールとの反応を進めることができ、繊維強化樹脂成形品のマトリックス樹脂と本発明のエポキシ樹脂組成物との反応を進めることができるため、より密着力が向上する。後加熱の温度は本発明のエポキシ樹脂組成物を被覆する温度以上で行っても良い。これは被覆したエポキシ樹脂硬化物は液状のエポキシ樹脂組成物よりも弾性率が高いため、後加熱によって発生する繊維強化樹脂成形品の表面凹凸部の熱収縮に対して追随しづらく、液状のエポキシ樹脂組成物を硬化させる温度よりも高い温度で後硬化させても、表面品位の悪化は軽微なものとなるためである。
It is preferable to increase the curing degree of the epoxy resin composition of the present invention by post-heating the coated fiber reinforced resin molded article obtained by coating the fiber reinforced resin molded article with the epoxy resin composition of the present invention. By performing post-heating, the reaction between the alicyclic epoxy having poor reactivity and the thiol can be promoted, and the reaction between the matrix resin of the fiber-reinforced resin molded article and the epoxy resin composition of the present invention can be promoted. Therefore, the adhesion is further improved. The post-heating temperature may be higher than the temperature at which the epoxy resin composition of the present invention is coated. This is because the coated epoxy resin cured product has a higher elastic modulus than the liquid epoxy resin composition, so it is difficult to follow the heat shrinkage of the surface irregularities of the fiber reinforced resin molded product caused by post-heating. This is because even if the resin composition is post-cured at a temperature higher than the temperature at which the resin composition is cured, deterioration in surface quality is slight.
後加熱の温度は本発明のエポキシ樹脂組成物の完全硬化Ｔｇに対して、好ましくは＋７０℃以下、より好ましくは＋６０℃以下であることが好ましい。＋７０℃より高い温度で後加熱をすると、エポキシ樹脂組成物が完全にゴム状態となり、線膨張係数の増加と弾性率の低下が著しく大きくなるため、後加熱によって発生する繊維強化樹脂成形品の表面凹凸部の熱収縮に追随し、後加熱後の表面品位が悪化する。本発明のエポキシ樹脂硬化物のＴｇに沿って、後加熱温度を徐々に上げるステップキュアを行うことで、後加熱による表面品位の悪化を軽微に抑えることができる。
The post-heating temperature is preferably +70°C or lower, more preferably +60°C or lower with respect to the complete curing Tg of the epoxy resin composition of the present invention. When post-heating at a temperature higher than +70 ° C., the epoxy resin composition becomes completely rubbery, and the linear expansion coefficient increases and the elastic modulus decreases significantly. The surface quality after post-heating deteriorates along with the heat shrinkage of the irregularities. By performing step curing by gradually increasing the post-heating temperature along the Tg of the epoxy resin cured product of the present invention, it is possible to minimize deterioration of the surface quality due to post-heating.
本発明の被覆繊維強化樹脂成形品の被覆層の厚さは、５０μｍ以上であることが好ましく、１００μｍ以上であることがより好ましい。また、本発明の被覆繊維強化樹脂成形品の被覆層の厚さは、６００μｍ以下であることが好ましく、５００μｍ以下であることがより好ましい。厚さを５０μｍ以上とすることにより、被覆層が欠落する部分が生じにくくなるほか、被覆繊維強化樹脂成形品の表面凹凸を緩和する効果が得やすい。一方で、厚さを６００μｍ以下とすることにより、被覆層の重量が大きくなることを抑制でき、軽量で機械的特性に優れるという繊維強化樹脂成形品の特徴が発揮しやすくなる。
The thickness of the coating layer of the coated fiber-reinforced resin molded product of the present invention is preferably 50 μm or more, more preferably 100 μm or more. The thickness of the coating layer of the coated fiber-reinforced resin molded product of the present invention is preferably 600 μm or less, more preferably 500 μm or less. By setting the thickness to 50 μm or more, it becomes difficult for the coating layer to be missing, and the effect of alleviating the surface unevenness of the coated fiber-reinforced resin molded product can be easily obtained. On the other hand, by setting the thickness to 600 μm or less, it is possible to suppress the weight of the coating layer from increasing, and the characteristics of the fiber-reinforced resin molded product, such as light weight and excellent mechanical properties, can be easily exhibited.
本発明の効果は、表面凹凸を数値化することで評価可能である。たとえば、その代表的な手段は、表面粗さ計を用いてはかる方法や、マイクロスコープ等を用いて、被覆繊維強化樹脂断面から求めることができる。たとえば、接触式の表面粗さ計を使用して、うねり曲線（Ｗｔ）から求めてもよいし、マイクロスコープを用いて断面から求めてもよい。被覆剤と繊維強化樹脂成形品の界面が見づらい場合はＸ線蛍光分析やＳＥＭ等を用いてもよい。
The effect of the present invention can be evaluated by quantifying surface unevenness. For example, typical means for this are a method of measuring using a surface roughness meter, or a cross section of the coated fiber reinforced resin using a microscope or the like. For example, it may be obtained from the waviness curve (Wt) using a contact-type surface roughness meter, or may be obtained from a cross section using a microscope. If it is difficult to see the interface between the coating agent and the fiber-reinforced resin molded product, X-ray fluorescence analysis, SEM, or the like may be used.
本発明の評価は、一定以上の光沢度が得られる場合には、写像鮮明度や塗装表面にうねりが見える（オレンジピールとも呼ばれる）現象を定量化することができる、ウェーブスキャン（ＷａｖｅＳｃａｎ）を用いて測定することもできる。自動車用途において、最も表面が良い状態は「クラスＡ」と呼ばれている。「クラスＡ」の統一的な基準は定められていないものの、一般に、表面の小さなピッチで出てくる凹凸量を示すショートウェーブ（ＳＷ）が２０以下、表面の大きなピッチで出てくる凹凸量を示すロングウェーブ（ＬＷ）が８以下であることが多い。好ましくは、ＳＷが２０以下、ＬＷが４以下である。これらの数字は、被覆繊維強化樹脂成形品を製造後、その上に、塗装を吹きかけた製品で達成する値である。
The evaluation of the present invention uses WaveScan, which can quantify the clarity of the image and the phenomenon that waviness appears on the painted surface (also called orange peel) when a certain level of glossiness is obtained. can also be measured. In automotive applications, the best surface condition is called "Class A". Although there is no unified standard for "Class A", in general, the short wave (SW), which indicates the amount of unevenness that appears at small pitches on the surface, is 20 or less, and the amount of unevenness that appears at large pitches on the surface is The long wave (LW) indicated is often 8 or less. Preferably, SW is 20 or less and LW is 4 or less. These figures are the values achieved with a coated fiber-reinforced resin molded product which is then sprayed with paint.
被覆繊維強化樹脂成形品の凹凸量を表面粗さとして示した場合、うねり曲線（Ｗｔ）において、好ましくは２μｍ以下、より好ましくは１μｍ以下である。２μｍ以下であると、１コートの塗装のみでクラスＡが達成可能となる。
When the amount of unevenness of the coated fiber-reinforced resin molded product is expressed as surface roughness, the waviness curve (Wt) is preferably 2 μm or less, more preferably 1 μm or less. If the thickness is 2 μm or less, class A can be achieved with only one coating.
被覆繊維強化樹脂成形品に有色塗装を施さずに、強化繊維基材自体を外部から視認可能とする製品の場合は、特に成形品の商品価値が高い。この場合は、織構造によって表現される独特の模様が意匠性に優れるため、平織り、綾織及び繻子織などの形態の織物が好んで用いられることがある。
In the case of products in which the reinforcing fiber base material itself is visible from the outside without applying a colored coating to the coated fiber reinforced resin molded product, the molded product has a particularly high commercial value. In this case, since the unique pattern expressed by the woven structure is excellent in design, plain weave, twill weave, satin weave, and the like are often preferred.
基材の目付けも、意匠性に影響を与える。織構造が外部から視認可能とする製品に用いる場合は、おおむね１００ｇ／ｍ２から３００ｇ／ｍ２程度の基材を用いることが好ましい。
The basis weight of the base material also affects the design. When used for a product whose woven structure is visible from the outside, it is preferable to use a base material of approximately 100 g/m 2 to 300 g/m 2 .
また、塗装も、強化繊維基材を視認できるよう、クリアー塗装を施すことが好ましい。
Also, it is preferable to apply a clear coating so that the reinforcing fiber base material can be seen.
次に、実施例により、本発明のエポキシ樹脂組成物と繊維強化複合材料について、さらに詳細に説明する。
Next, the epoxy resin composition and fiber-reinforced composite material of the present invention will be described in more detail with reference to examples.
＜樹脂原料＞
各実施例のエポキシ樹脂組成物を得るために、次の樹脂原料を用いた。表１中のエポキシ樹脂組成物の含有割合の単位は、特に断らない限り「質量部」を意味する。 <Resin raw material>
In order to obtain the epoxy resin composition of each example, the following resin raw materials were used. The unit of the content ratio of the epoxy resin composition in Table 1 means "parts by mass" unless otherwise specified.
各実施例のエポキシ樹脂組成物を得るために、次の樹脂原料を用いた。表１中のエポキシ樹脂組成物の含有割合の単位は、特に断らない限り「質量部」を意味する。 <Resin raw material>
In order to obtain the epoxy resin composition of each example, the following resin raw materials were used. The unit of the content ratio of the epoxy resin composition in Table 1 means "parts by mass" unless otherwise specified.
１．エポキシ樹脂
・Ｓｙｎａ Ｅｐｏｘｙ １８６（ＳＹＮＡＳＩＡ製）：４，５－エポキシヘキサヒドロフタル酸ジグリシジル、エポキシ当量１１０
・“セロキサイド”（登録商標）２０２１Ｐ（ダイセル（株）製）：３’，４’－エポキシシクロヘキシルメチル ３，４－エポキシシクロヘキサンカルボキシレート、エポキシ当量１３０
・ＥＨＰＥ３１５０（ダイセル（株）製）：２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物、エポキシ当量１８０
・ＨＢＥ－１００（新日本理化（株）製）：水添ビスフェノールＡ型エポキシ樹脂、エポキシ当量２１５
・ＲＤ １２９（ｅｐｏｔｅｃ製）：ペンタエリスリトールポリグリシジルエーテル、エポキシ当量１６０
２．チオール化合物
・“カレンズＭＴ”（登録商標）ＰＥ１（昭和電工（株）製）：ペンタエリスリトールテトラキス（３－メルカプトブチレート）
３．第四級ホスホニウム塩
・“ヒシコーリン”（登録商標）ＰＸ－４ＥＴ（日本化学工業（株）製）：テトラブチルホスホニウムｏ，ｏ－ジエチルホスホロジチオエート
＜被膜用樹脂組成物の調製＞
表１に記載した配合比により、エポキシ樹脂を配合し主剤液（Ａ）とした。表１に記載した配合比で、成分（Ｂ）（チオール化合物）と成分（Ｃ）（第四級ホスホニウム塩）、その他の物質を配合して硬化剤液とした。これらの主剤液と硬化剤液とを用い、これらを表１に記載した配合比で混合して、エポキシ樹脂組成物を調製した。 1. Epoxy resin Syna Epoxy 186 (manufactured by SYNASIA): diglycidyl 4,5-epoxyhexahydrophthalate, epoxy equivalent 110
- "Celoxide" (registered trademark) 2021P (manufactured by Daicel Corporation): 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, epoxy equivalent 130
EHPE3150 (manufactured by Daicel Corporation): 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxy equivalent 180
・ HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.): Hydrogenated bisphenol A type epoxy resin, epoxy equivalent 215
・ RD 129 (manufactured by epotec): pentaerythritol polyglycidyl ether, epoxy equivalent 160
2. Thiol compound ・"Karenzu MT" (registered trademark) PE1 (manufactured by Showa Denko Co., Ltd.): pentaerythritol tetrakis (3-mercaptobutyrate)
3. Quaternary phosphonium salt "Hishikorin" (registered trademark) PX-4ET (manufactured by Nippon Kagaku Kogyo Co., Ltd.): tetrabutylphosphonium o,o-diethylphosphorodithioate <Preparation of coating resin composition>
An epoxy resin was compounded according to the compounding ratio shown in Table 1 to prepare the main liquid (A). The component (B) (thiol compound), the component (C) (quaternary phosphonium salt) and other substances were blended at the blending ratio shown in Table 1 to prepare a curing agent liquid. An epoxy resin composition was prepared by using these base liquids and curing agent liquids and mixing them at the compounding ratios shown in Table 1.
・Ｓｙｎａ Ｅｐｏｘｙ １８６（ＳＹＮＡＳＩＡ製）：４，５－エポキシヘキサヒドロフタル酸ジグリシジル、エポキシ当量１１０
・“セロキサイド”（登録商標）２０２１Ｐ（ダイセル（株）製）：３’，４’－エポキシシクロヘキシルメチル ３，４－エポキシシクロヘキサンカルボキシレート、エポキシ当量１３０
・ＥＨＰＥ３１５０（ダイセル（株）製）：２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物、エポキシ当量１８０
・ＨＢＥ－１００（新日本理化（株）製）：水添ビスフェノールＡ型エポキシ樹脂、エポキシ当量２１５
・ＲＤ １２９（ｅｐｏｔｅｃ製）：ペンタエリスリトールポリグリシジルエーテル、エポキシ当量１６０
２．チオール化合物
・“カレンズＭＴ”（登録商標）ＰＥ１（昭和電工（株）製）：ペンタエリスリトールテトラキス（３－メルカプトブチレート）
３．第四級ホスホニウム塩
・“ヒシコーリン”（登録商標）ＰＸ－４ＥＴ（日本化学工業（株）製）：テトラブチルホスホニウムｏ，ｏ－ジエチルホスホロジチオエート
＜被膜用樹脂組成物の調製＞
表１に記載した配合比により、エポキシ樹脂を配合し主剤液（Ａ）とした。表１に記載した配合比で、成分（Ｂ）（チオール化合物）と成分（Ｃ）（第四級ホスホニウム塩）、その他の物質を配合して硬化剤液とした。これらの主剤液と硬化剤液とを用い、これらを表１に記載した配合比で混合して、エポキシ樹脂組成物を調製した。 1. Epoxy resin Syna Epoxy 186 (manufactured by SYNASIA): diglycidyl 4,5-epoxyhexahydrophthalate, epoxy equivalent 110
- "Celoxide" (registered trademark) 2021P (manufactured by Daicel Corporation): 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, epoxy equivalent 130
EHPE3150 (manufactured by Daicel Corporation): 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxy equivalent 180
・ HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.): Hydrogenated bisphenol A type epoxy resin, epoxy equivalent 215
・ RD 129 (manufactured by epotec): pentaerythritol polyglycidyl ether, epoxy equivalent 160
2. Thiol compound ・"Karenzu MT" (registered trademark) PE1 (manufactured by Showa Denko Co., Ltd.): pentaerythritol tetrakis (3-mercaptobutyrate)
3. Quaternary phosphonium salt "Hishikorin" (registered trademark) PX-4ET (manufactured by Nippon Kagaku Kogyo Co., Ltd.): tetrabutylphosphonium o,o-diethylphosphorodithioate <Preparation of coating resin composition>
An epoxy resin was compounded according to the compounding ratio shown in Table 1 to prepare the main liquid (A). The component (B) (thiol compound), the component (C) (quaternary phosphonium salt) and other substances were blended at the blending ratio shown in Table 1 to prepare a curing agent liquid. An epoxy resin composition was prepared by using these base liquids and curing agent liquids and mixing them at the compounding ratios shown in Table 1.
＜被膜用樹脂組成物の粘度の測定＞
ＩＳＯ ２８８４－１（１９９９）における円錐平板型回転粘度計を使用した測定方法に準拠し、エポキシ樹脂組成物の混合調製１分後の粘度を測定し、粘度安定性の指標とした。装置には、東機産業（株）製のＴＶＥ－３３Ｈ型を用いた。ここでローターは１゜３４’×Ｒ２４を用い、測定温度は２５℃、サンプル量は１ｃｍ３とした。 <Measurement of Viscosity of Coating Resin Composition>
According to ISO 2884-1 (1999), the viscosity of the epoxy resin composition was measured 1 minute after mixing and preparation, and used as an index of viscosity stability. As an apparatus, TVE-33H model manufactured by Toki Sangyo Co., Ltd. was used. Here, the rotor used was 1.34'×R24, the measurement temperature was 25.degree. C., and the sample amount was 1 cm.sup.3 .
ＩＳＯ ２８８４－１（１９９９）における円錐平板型回転粘度計を使用した測定方法に準拠し、エポキシ樹脂組成物の混合調製１分後の粘度を測定し、粘度安定性の指標とした。装置には、東機産業（株）製のＴＶＥ－３３Ｈ型を用いた。ここでローターは１゜３４’×Ｒ２４を用い、測定温度は２５℃、サンプル量は１ｃｍ３とした。 <Measurement of Viscosity of Coating Resin Composition>
According to ISO 2884-1 (1999), the viscosity of the epoxy resin composition was measured 1 minute after mixing and preparation, and used as an index of viscosity stability. As an apparatus, TVE-33H model manufactured by Toki Sangyo Co., Ltd. was used. Here, the rotor used was 1.34'×R24, the measurement temperature was 25.degree. C., and the sample amount was 1 cm.sup.3 .
＜樹脂硬化板の作製＞
プレス装置下面に、一辺５０ｍｍの正方形をくり抜いた、厚さ２ｍｍの銅製スペーサーを設置し、プレスの温度を５０℃に設定し、エポキシ樹脂組成物をスペーサーの内側に注ぎ、プレスを閉じた。１２０分保持した後、プレスを開け、樹脂硬化板を得た。その後、１０５℃３時間の熱処理を加えた。 <Preparation of resin cured plate>
A copper spacer with a thickness of 2 mm and a square with a side of 50 mm was cut out on the lower surface of the press, the temperature of the press was set at 50° C., the epoxy resin composition was poured inside the spacer, and the press was closed. After holding for 120 minutes, the press was opened to obtain a cured resin plate. After that, heat treatment was performed at 105° C. for 3 hours.
プレス装置下面に、一辺５０ｍｍの正方形をくり抜いた、厚さ２ｍｍの銅製スペーサーを設置し、プレスの温度を５０℃に設定し、エポキシ樹脂組成物をスペーサーの内側に注ぎ、プレスを閉じた。１２０分保持した後、プレスを開け、樹脂硬化板を得た。その後、１０５℃３時間の熱処理を加えた。 <Preparation of resin cured plate>
A copper spacer with a thickness of 2 mm and a square with a side of 50 mm was cut out on the lower surface of the press, the temperature of the press was set at 50° C., the epoxy resin composition was poured inside the spacer, and the press was closed. After holding for 120 minutes, the press was opened to obtain a cured resin plate. After that, heat treatment was performed at 105° C. for 3 hours.
＜樹脂硬化物のガラス転移温度Ｔｇ測定＞
樹脂硬化板から４０ｍｍ×１０ｍｍの試験片を切り出し、ＤＭＡ（動的粘弾性測定）装置（ＴＡインスツルメンツ社製ＡＲＥＳ－Ｇ２）を用いて、Ｔｇの測定を行った。測定条件は、昇温速度５℃／分である。－５０℃～１３０℃の温度範囲で測定し、貯蔵弾性率が変化した点（Ｏｎ ｓｅｔ）をガラス転移点とした。 <Measurement of glass transition temperature Tg of cured resin>
A test piece of 40 mm×10 mm was cut out from the cured resin plate, and Tg was measured using a DMA (dynamic viscoelasticity measurement) device (ARES-G2 manufactured by TA Instruments). The measurement conditions are a temperature increase rate of 5° C./min. Measurement was performed in the temperature range of -50°C to 130°C, and the point at which the storage modulus changed (On set) was defined as the glass transition point.
樹脂硬化板から４０ｍｍ×１０ｍｍの試験片を切り出し、ＤＭＡ（動的粘弾性測定）装置（ＴＡインスツルメンツ社製ＡＲＥＳ－Ｇ２）を用いて、Ｔｇの測定を行った。測定条件は、昇温速度５℃／分である。－５０℃～１３０℃の温度範囲で測定し、貯蔵弾性率が変化した点（Ｏｎ ｓｅｔ）をガラス転移点とした。 <Measurement of glass transition temperature Tg of cured resin>
A test piece of 40 mm×10 mm was cut out from the cured resin plate, and Tg was measured using a DMA (dynamic viscoelasticity measurement) device (ARES-G2 manufactured by TA Instruments). The measurement conditions are a temperature increase rate of 5° C./min. Measurement was performed in the temperature range of -50°C to 130°C, and the point at which the storage modulus changed (On set) was defined as the glass transition point.
＜硬化物着色＞
上記の樹脂硬化板について着色の有無を判断した。具体的には、樹脂硬化板から切り出した３０ｍｍ角、厚さ２ｍｍの試験片を使用し、分光測色計（ＣＭ－７００ｄ、コニカミノルタ（株）製）を用いて、硬化物の色調をＬ＊ａ＊ｂ＊表色系で表した。Ｌ＊ａ＊ｂ＊表色系は物質の色を表すのに用いられているもので、Ｌ＊により明度を表し、ａ＊とｂ＊により色度を表す。ここで、ａ＊は赤方向、－ａ＊は緑方向、ｂ＊は黄方向、－ｂ＊は青方向を示す。測定条件は波長３８０～７８０ｎｍの範囲において、Ｄ６５光源、１０°視野として、正反射光を含まない条件での分光透過率を測定した。このとき、｜ａ＊｜≦２であって、かつ｜ｂ＊｜≦５であるものは「着色無し」、それ以外を「着色有り」とした。 <Coloring of cured product>
The presence or absence of coloration was determined for the resin-cured plate. Specifically, a test piece of 30 mm square and 2 mm in thickness cut out from a cured resin plate is used, and a spectrophotometer (CM-700d, manufactured by Konica Minolta Co., Ltd.) is used to set the color tone of the cured product to L. *a*b* color system. The L*a*b* color system is used to represent the color of a substance, where L* represents lightness and a* and b* represent chromaticity. Here, a* indicates the red direction, -a* indicates the green direction, b* indicates the yellow direction, and -b* indicates the blue direction. Spectral transmittance was measured in a wavelength range of 380 to 780 nm, with a D65 light source and a 10° field of view, and without specular reflection. At this time, the case where |a*|≤2 and |b*|
上記の樹脂硬化板について着色の有無を判断した。具体的には、樹脂硬化板から切り出した３０ｍｍ角、厚さ２ｍｍの試験片を使用し、分光測色計（ＣＭ－７００ｄ、コニカミノルタ（株）製）を用いて、硬化物の色調をＬ＊ａ＊ｂ＊表色系で表した。Ｌ＊ａ＊ｂ＊表色系は物質の色を表すのに用いられているもので、Ｌ＊により明度を表し、ａ＊とｂ＊により色度を表す。ここで、ａ＊は赤方向、－ａ＊は緑方向、ｂ＊は黄方向、－ｂ＊は青方向を示す。測定条件は波長３８０～７８０ｎｍの範囲において、Ｄ６５光源、１０°視野として、正反射光を含まない条件での分光透過率を測定した。このとき、｜ａ＊｜≦２であって、かつ｜ｂ＊｜≦５であるものは「着色無し」、それ以外を「着色有り」とした。 <Coloring of cured product>
The presence or absence of coloration was determined for the resin-cured plate. Specifically, a test piece of 30 mm square and 2 mm in thickness cut out from a cured resin plate is used, and a spectrophotometer (CM-700d, manufactured by Konica Minolta Co., Ltd.) is used to set the color tone of the cured product to L. *a*b* color system. The L*a*b* color system is used to represent the color of a substance, where L* represents lightness and a* and b* represent chromaticity. Here, a* indicates the red direction, -a* indicates the green direction, b* indicates the yellow direction, and -b* indicates the blue direction. Spectral transmittance was measured in a wavelength range of 380 to 780 nm, with a D65 light source and a 10° field of view, and without specular reflection. At this time, the case where |a*|≤2 and |b*|
＜繊維強化複合材料の作製＞
繊維強化複合材料には、下記のＲＴＭ成形法によって作製したものを用いた。 <Production of fiber reinforced composite material>
The fiber-reinforced composite material used was produced by the following RTM molding method.
繊維強化複合材料には、下記のＲＴＭ成形法によって作製したものを用いた。 <Production of fiber reinforced composite material>
The fiber-reinforced composite material used was produced by the following RTM molding method.
３５０ｍｍ×７００ｍｍ×１．６ｍｍの板状キャビティを持つ金型のキャビティに、強化繊維として炭素繊維織物ＣＯ６３４３Ｂ（炭素繊維：Ｔ３００－３Ｋ、組織：平織、目付：１９８ｇ／ｍ２、東レ（株）製）を４枚とその中間層としてガラス繊維織物Ｍ３４０（ユニチカ株式会社）を配置し、プレス装置で型締めを行った。次に、１２０℃の温度（成形温度）に保持した金型内を、真空ポンプにより、大気圧－０．１ＭＰａに減圧し、エポキシ樹脂組成物（東レ（株）製ＴＲ－Ｃ３８）１００質量部にＩＣ－３５を１質量部加えた混合樹脂を、樹脂注入機を用いて注入した。混合樹脂の注入開始後１０分で金型を開き、脱型して、繊維強化複合材料を得た。得られた繊維強化複合材料の表面平滑性は、ＳＵＲＦ ＣＯＭ ４８０Ａ（ＡＣＣＲＥＴＥＣＨ社製）でろ「波うねり曲線」モード、測定長１０ｍｍ、カットオフ０．２５ｍｍ、織物の経糸と横糸の交点でできた樹脂のみの個所を通るように１０回測定し、その最大値は７．５μｍであった。
Carbon fiber fabric CO6343B (carbon fiber: T300-3K, texture: plain weave, basis weight: 198 g / m 2 , manufactured by Toray Industries, Inc.) was placed in the cavity of a mold having a plate-shaped cavity of 350 mm × 700 mm × 1.6 mm as a reinforcing fiber. ) and a glass fiber fabric M340 (Unitika Ltd.) as an intermediate layer were placed, and the mold was clamped with a press. Next, the inside of the mold held at a temperature of 120° C. (molding temperature) is evacuated to atmospheric pressure −0.1 MPa by a vacuum pump, and 100 parts by mass of an epoxy resin composition (TR-C38 manufactured by Toray Industries, Inc.) A mixed resin containing 1 part by mass of IC-35 was injected using a resin injection machine. Ten minutes after the start of injection of the mixed resin, the mold was opened and demolded to obtain a fiber-reinforced composite material. The surface smoothness of the obtained fiber-reinforced composite material was measured by SURF COM 480A (manufactured by ACCRETECH) in the "wave undulation curve" mode, measuring length 10 mm, cutoff 0.25 mm, resin made at the intersection of the warp and weft of the fabric. Measurements were taken 10 times so as to pass through the chisel, and the maximum value was 7.5 μm.
＜コーティング成形＞
３５０ｍｍ×３５０ｍｍ×１．９ｍｍの板状キャビティを持つ金型のキャビティ被膜用金型の温度を５０℃に調整し、下型に３５０ｍｍ×３５０ｍｍにカットした繊維強化複合材料を置き、繊維強化樹脂の上面両端に３５０ｍｍ×１０ｍｍ×０．３ｍｍｔのスペーサーを２枚配置し、上型を閉じた後、金型内を真空引きした。その後、表１の配合比に従い、エポキシ樹脂組成物を、樹脂注入機を用いて注入した。金型内に樹脂を流し込み、１０分後に上型を開け、表面に被膜が形成された繊維強化樹脂成形品を取り出した。その際、繊維強化樹脂成形品から被膜が剥がれることなく取り出せたものを「ｇｏｏｄ」、部分的に、あるいは全面にわたって被膜が剥がれたものを「ｎｏ ｇｏｏｄ」として脱型性を評価した。表１に記載の硬化条件で硬化しなかったものは、硬化温度５０℃で１２０分硬化させた。 <Coating molding>
The temperature of the cavity coating mold of a mold having a plate-shaped cavity of 350 mm × 350 mm × 1.9 mm is adjusted to 50 ° C., a fiber reinforced composite material cut into 350 mm × 350 mm is placed on the lower mold, and the fiber reinforced resin is produced. Two spacers of 350 mm×10 mm×0.3 mmt were placed on both ends of the upper surface, and after the upper mold was closed, the inside of the mold was evacuated. Then, according to the compounding ratio of Table 1, the epoxy resin composition was injected using a resin injection machine. The resin was poured into the mold, and after 10 minutes, the upper mold was opened and the fiber-reinforced resin molded product with the film formed on the surface was taken out. At that time, demoldability was evaluated as "good" when the film was removed from the fiber-reinforced resin molded product without peeling, and "no good" when the film was partially or entirely peeled off. Those that did not cure under the curing conditions shown in Table 1 were cured at a curing temperature of 50° C. for 120 minutes.
３５０ｍｍ×３５０ｍｍ×１．９ｍｍの板状キャビティを持つ金型のキャビティ被膜用金型の温度を５０℃に調整し、下型に３５０ｍｍ×３５０ｍｍにカットした繊維強化複合材料を置き、繊維強化樹脂の上面両端に３５０ｍｍ×１０ｍｍ×０．３ｍｍｔのスペーサーを２枚配置し、上型を閉じた後、金型内を真空引きした。その後、表１の配合比に従い、エポキシ樹脂組成物を、樹脂注入機を用いて注入した。金型内に樹脂を流し込み、１０分後に上型を開け、表面に被膜が形成された繊維強化樹脂成形品を取り出した。その際、繊維強化樹脂成形品から被膜が剥がれることなく取り出せたものを「ｇｏｏｄ」、部分的に、あるいは全面にわたって被膜が剥がれたものを「ｎｏ ｇｏｏｄ」として脱型性を評価した。表１に記載の硬化条件で硬化しなかったものは、硬化温度５０℃で１２０分硬化させた。 <Coating molding>
The temperature of the cavity coating mold of a mold having a plate-shaped cavity of 350 mm × 350 mm × 1.9 mm is adjusted to 50 ° C., a fiber reinforced composite material cut into 350 mm × 350 mm is placed on the lower mold, and the fiber reinforced resin is produced. Two spacers of 350 mm×10 mm×0.3 mmt were placed on both ends of the upper surface, and after the upper mold was closed, the inside of the mold was evacuated. Then, according to the compounding ratio of Table 1, the epoxy resin composition was injected using a resin injection machine. The resin was poured into the mold, and after 10 minutes, the upper mold was opened and the fiber-reinforced resin molded product with the film formed on the surface was taken out. At that time, demoldability was evaluated as "good" when the film was removed from the fiber-reinforced resin molded product without peeling, and "no good" when the film was partially or entirely peeled off. Those that did not cure under the curing conditions shown in Table 1 were cured at a curing temperature of 50° C. for 120 minutes.
表１に記載の硬化条件で硬化したものも、表１に記載の硬化条件で硬化せずに硬化温度５０℃で１２０分硬化させたものも、その後、さらに後硬化として１０５℃で３時間の熱処理を加えた。
Those cured under the curing conditions shown in Table 1, those cured under the curing conditions shown in Table 1 and cured at a curing temperature of 50°C for 120 minutes, and then further cured at 105°C for 3 hours as post-curing. A heat treatment was applied.
＜脱着時の密着力＞
３５０ｍｍ×３５０ｍｍにカットした繊維強化複合材料を熱板上に置き繊維強化複合材料の表面温度が５０℃になるよう熱板の温度を調整したのち、熱板上の繊維強化複合材料に、厚さ０．０５ｍｍの紙でくるんだ５０ｍｍ×２０ｍｍ×０．２ｍｍのスペーサーを１０ｍｍ離して長手方向が水平になるよう、２枚配置した。その後、エポキシ樹脂組成物を、対となるスペーサー間に１ｍｌ垂らし、２０ｍｍ×５ｍｍにカットしたうえで、非接着面にフックを張り付けた繊維強化複合材料を、スペーサーの橋になるよう、配置し、エポキシ樹脂組成物を接着した。表１に記載の硬化時間置いた後、フックにプッシュプルゲージ（イマダ製ＺＴＡ－５００Ｎ）をかけて、ゆっくり引き上げ、接着力を測定した。 <Adhesion strength when detaching>
A fiber reinforced composite material cut to 350 mm × 350 mm is placed on a hot plate, and the temperature of the hot plate is adjusted so that the surface temperature of the fiber reinforced composite material is 50 ° C., and then the fiber reinforced composite material on the hot plate is coated with a thickness Two spacers of 50 mm x 20 mm x 0.2 mm wrapped in 0.05 mm paper were arranged with a 10 mm separation between them so that the longitudinal direction was horizontal. After that, 1 ml of the epoxy resin composition is dropped between the paired spacers, cut into 20 mm × 5 mm, and the fiber reinforced composite material with hooks attached to the non-adhesive surface is arranged so as to form a bridge between the spacers, The epoxy resin composition was adhered. After setting for the curing time shown in Table 1, a push-pull gauge (ZTA-500N manufactured by Imada) was applied to the hook and pulled up slowly to measure the adhesive strength.
３５０ｍｍ×３５０ｍｍにカットした繊維強化複合材料を熱板上に置き繊維強化複合材料の表面温度が５０℃になるよう熱板の温度を調整したのち、熱板上の繊維強化複合材料に、厚さ０．０５ｍｍの紙でくるんだ５０ｍｍ×２０ｍｍ×０．２ｍｍのスペーサーを１０ｍｍ離して長手方向が水平になるよう、２枚配置した。その後、エポキシ樹脂組成物を、対となるスペーサー間に１ｍｌ垂らし、２０ｍｍ×５ｍｍにカットしたうえで、非接着面にフックを張り付けた繊維強化複合材料を、スペーサーの橋になるよう、配置し、エポキシ樹脂組成物を接着した。表１に記載の硬化時間置いた後、フックにプッシュプルゲージ（イマダ製ＺＴＡ－５００Ｎ）をかけて、ゆっくり引き上げ、接着力を測定した。 <Adhesion strength when detaching>
A fiber reinforced composite material cut to 350 mm × 350 mm is placed on a hot plate, and the temperature of the hot plate is adjusted so that the surface temperature of the fiber reinforced composite material is 50 ° C., and then the fiber reinforced composite material on the hot plate is coated with a thickness Two spacers of 50 mm x 20 mm x 0.2 mm wrapped in 0.05 mm paper were arranged with a 10 mm separation between them so that the longitudinal direction was horizontal. After that, 1 ml of the epoxy resin composition is dropped between the paired spacers, cut into 20 mm × 5 mm, and the fiber reinforced composite material with hooks attached to the non-adhesive surface is arranged so as to form a bridge between the spacers, The epoxy resin composition was adhered. After setting for the curing time shown in Table 1, a push-pull gauge (ZTA-500N manufactured by Imada) was applied to the hook and pulled up slowly to measure the adhesive strength.
＜被覆繊維強化樹脂成形品への塗装＞
繊維強化複合材料表面を研磨紙（３Ｍ社製スコッチ・ブライト＃７４４７）を用いて研磨・脱脂したのち、塗装膜厚が４０μｍになるようクリアー塗料（ＡｋｚｏＮｏｂｅｌ社製ＥＳＣ－２４４）を塗布し、所定の条件で焼き付けした。 <Coating on coated fiber reinforced resin moldings>
After polishing and degreasing the surface of the fiber-reinforced composite material with abrasive paper (Scotch Bright #7447 manufactured by 3M), clear paint (ESC-244 manufactured by AkzoNobel) is applied so that the coating film thickness is 40 μm. was baked under the conditions of
繊維強化複合材料表面を研磨紙（３Ｍ社製スコッチ・ブライト＃７４４７）を用いて研磨・脱脂したのち、塗装膜厚が４０μｍになるようクリアー塗料（ＡｋｚｏＮｏｂｅｌ社製ＥＳＣ－２４４）を塗布し、所定の条件で焼き付けした。 <Coating on coated fiber reinforced resin moldings>
After polishing and degreasing the surface of the fiber-reinforced composite material with abrasive paper (Scotch Bright #7447 manufactured by 3M), clear paint (ESC-244 manufactured by AkzoNobel) is applied so that the coating film thickness is 40 μm. was baked under the conditions of
＜表面平滑性＞
塗装した被覆繊維強化樹脂成形品の表面平滑性の評価は成形品表面のウェーブスキャン（ＷＳ）値で行った。ＷＳ値は自動車用途において、最も表面が良い状態は「クラスＡ」と呼ばれている。「クラスＡ」の統一的な基準は定められていないものの、一般に、表面の小さなピッチで出てくる凹凸量を示すショートウェーブ（ＳＷ）が２０以下、表面の大きなピッチで出てくる凹凸量を示すロングウェーブ（ＬＷ）が８以下であることが多い。塗装後の被膜層が形成された繊維強化樹脂成形品の表面を、ウェーブスキャン機器（ウェーブスキャンデュアル）を用いてＬＷ値を５回測定し、その平均値を、表１に記載した。 <Surface smoothness>
The surface smoothness of the coated coated fiber-reinforced resin molded product was evaluated by wave scan (WS) value of the surface of the molded product. The WS value is called "class A" when the surface is the best in automobile applications. Although there is no unified standard for "Class A", in general, the short wave (SW), which indicates the amount of unevenness that appears at small pitches on the surface, is 20 or less, and the amount of unevenness that appears at large pitches on the surface is The long wave (LW) indicated is often 8 or less. The LW value of the surface of the coated fiber-reinforced resin molded product on which the coating layer was formed was measured five times using a wave scan device (Wave Scan Dual), and the average value is shown in Table 1.
塗装した被覆繊維強化樹脂成形品の表面平滑性の評価は成形品表面のウェーブスキャン（ＷＳ）値で行った。ＷＳ値は自動車用途において、最も表面が良い状態は「クラスＡ」と呼ばれている。「クラスＡ」の統一的な基準は定められていないものの、一般に、表面の小さなピッチで出てくる凹凸量を示すショートウェーブ（ＳＷ）が２０以下、表面の大きなピッチで出てくる凹凸量を示すロングウェーブ（ＬＷ）が８以下であることが多い。塗装後の被膜層が形成された繊維強化樹脂成形品の表面を、ウェーブスキャン機器（ウェーブスキャンデュアル）を用いてＬＷ値を５回測定し、その平均値を、表１に記載した。 <Surface smoothness>
The surface smoothness of the coated coated fiber-reinforced resin molded product was evaluated by wave scan (WS) value of the surface of the molded product. The WS value is called "class A" when the surface is the best in automobile applications. Although there is no unified standard for "Class A", in general, the short wave (SW), which indicates the amount of unevenness that appears at small pitches on the surface, is 20 or less, and the amount of unevenness that appears at large pitches on the surface is The long wave (LW) indicated is often 8 or less. The LW value of the surface of the coated fiber-reinforced resin molded product on which the coating layer was formed was measured five times using a wave scan device (Wave Scan Dual), and the average value is shown in Table 1.
＜耐候性＞
耐候性は、樹脂硬化板２ｍｍ厚のものをメタリングウェザーメーター（スガ試験機（株）製Ｍ６Ｔ）中に置き、温度４７℃、湿度５０％、照射量１２５０Ｗ／ｍ２、積算照射量３０８ＭＪ／ｍ２で試験を実施した。静置前後で、分光測色計（ＣＭ－７００ｄ、コニカミノルタ（株）製）にて色差（ΔＥ）を測定した。 <Weather resistance>
Weather resistance was evaluated by placing a 2 mm thick resin cured plate in a metering weather meter (M6T manufactured by Suga Test Instruments Co., Ltd.), temperature 47° C., humidity 50%, irradiation amount 1250 W/m 2 , cumulative irradiation amount 308 MJ/. Tests were performed on m2 . Before and after standing, the color difference (ΔE) was measured with a spectrophotometer (CM-700d, manufactured by Konica Minolta, Inc.).
耐候性は、樹脂硬化板２ｍｍ厚のものをメタリングウェザーメーター（スガ試験機（株）製Ｍ６Ｔ）中に置き、温度４７℃、湿度５０％、照射量１２５０Ｗ／ｍ２、積算照射量３０８ＭＪ／ｍ２で試験を実施した。静置前後で、分光測色計（ＣＭ－７００ｄ、コニカミノルタ（株）製）にて色差（ΔＥ）を測定した。 <Weather resistance>
Weather resistance was evaluated by placing a 2 mm thick resin cured plate in a metering weather meter (M6T manufactured by Suga Test Instruments Co., Ltd.), temperature 47° C., humidity 50%, irradiation amount 1250 W/m 2 , cumulative irradiation amount 308 MJ/. Tests were performed on m2 . Before and after standing, the color difference (ΔE) was measured with a spectrophotometer (CM-700d, manufactured by Konica Minolta, Inc.).
（実施例１）
表１に示したように、一分子内にグリシジル構造を有するエポキシ基を２官能と脂環構造を有するエポキシ基を１官能有する「Ｓｙｎａ Ｅｐｏｘｙ １８６」１００質量部からなる主剤液を主剤タンクに、チオール化合物「カレンズＭＴ ＰＥ１」１２４質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた樹脂注入機を用いてエポキシ樹脂組成物を混合調製した。主剤タンクと硬化剤タンクはそれぞれ２５℃に温調したうえで、混合方法はスタティックミキサーを介して実施した。このエポキシ樹脂組成物は、２５℃の温度でも低粘度であり、上述の＜コーティング成形＞に記載の方法において、余裕をもって金型全体に注入することができた。また、主剤液と硬化剤液との混合状態も良好であった。５０℃１０分硬化でも繊維強化複合材料との密着性は良好で、問題なく金型から脱型できた。エポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表１に示す。 (Example 1)
As shown in Table 1, a main agent liquid consisting of 100 parts by mass of "Syna Epoxy 186" having two functional epoxy groups having a glycidyl structure in one molecule and one functional epoxy group having an alicyclic structure was added to the main agent tank. An epoxy resin composition was prepared using a resin injection machine in which a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved in 124 parts by mass of a thiol compound "Karenzu MT PE1" was placed in a curing agent tank. was prepared by mixing. The temperature of the main agent tank and the curing agent tank was controlled to 25° C., respectively, and mixing was performed via a static mixer. This epoxy resin composition had a low viscosity even at a temperature of 25° C., and could be injected into the entire mold with sufficient margin in the method described in <Coating Molding> above. In addition, the mixing state of the main component liquid and the curing agent liquid was also good. Even after curing at 50°C for 10 minutes, the adhesiveness to the fiber-reinforced composite material was good, and the mold could be demolded without any problems. The cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
表１に示したように、一分子内にグリシジル構造を有するエポキシ基を２官能と脂環構造を有するエポキシ基を１官能有する「Ｓｙｎａ Ｅｐｏｘｙ １８６」１００質量部からなる主剤液を主剤タンクに、チオール化合物「カレンズＭＴ ＰＥ１」１２４質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた樹脂注入機を用いてエポキシ樹脂組成物を混合調製した。主剤タンクと硬化剤タンクはそれぞれ２５℃に温調したうえで、混合方法はスタティックミキサーを介して実施した。このエポキシ樹脂組成物は、２５℃の温度でも低粘度であり、上述の＜コーティング成形＞に記載の方法において、余裕をもって金型全体に注入することができた。また、主剤液と硬化剤液との混合状態も良好であった。５０℃１０分硬化でも繊維強化複合材料との密着性は良好で、問題なく金型から脱型できた。エポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表１に示す。 (Example 1)
As shown in Table 1, a main agent liquid consisting of 100 parts by mass of "Syna Epoxy 186" having two functional epoxy groups having a glycidyl structure in one molecule and one functional epoxy group having an alicyclic structure was added to the main agent tank. An epoxy resin composition was prepared using a resin injection machine in which a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved in 124 parts by mass of a thiol compound "Karenzu MT PE1" was placed in a curing agent tank. was prepared by mixing. The temperature of the main agent tank and the curing agent tank was controlled to 25° C., respectively, and mixing was performed via a static mixer. This epoxy resin composition had a low viscosity even at a temperature of 25° C., and could be injected into the entire mold with sufficient margin in the method described in <Coating Molding> above. In addition, the mixing state of the main component liquid and the curing agent liquid was also good. Even after curing at 50°C for 10 minutes, the adhesiveness to the fiber-reinforced composite material was good, and the mold could be demolded without any problems. The cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
（実施例２）
「Ｓｙｎａ Ｅｐｏｘｙ １８６」１００質量部に、脂環構造を有するエポキシ基を２官能有する「セロキサイド２０２１Ｐ」を５０部加えて、主剤液を調合し、チオール化合物「カレンズＭＴ ＰＥ１」１１７質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。実施例１と比較して、より低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができた。脱型時の密着力は実施例１よりも低かったが、問題なく金型から脱型することができた。エポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表１に示す。 (Example 2)
To 100 parts by mass of "Syna Epoxy 186", 50 parts of "Celoxide 2021P" having a bifunctional epoxy group having an alicyclic structure was added to prepare a main liquid, and 117 parts by mass of the thiol compound "Karenz MT PE1" was added to the fourth. The procedure was carried out in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a grade phosphonium salt "Hishikorin PX-4ET" was dissolved was put into a curing agent tank. Compared with Example 1, it had a lower viscosity and could be quickly injected into the entire mold in the method described in <Coating Molding> above. Although the adhesive strength at demolding was lower than that of Example 1, the mold could be demolded without any problems. The cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
「Ｓｙｎａ Ｅｐｏｘｙ １８６」１００質量部に、脂環構造を有するエポキシ基を２官能有する「セロキサイド２０２１Ｐ」を５０部加えて、主剤液を調合し、チオール化合物「カレンズＭＴ ＰＥ１」１１７質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。実施例１と比較して、より低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができた。脱型時の密着力は実施例１よりも低かったが、問題なく金型から脱型することができた。エポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表１に示す。 (Example 2)
To 100 parts by mass of "Syna Epoxy 186", 50 parts of "Celoxide 2021P" having a bifunctional epoxy group having an alicyclic structure was added to prepare a main liquid, and 117 parts by mass of the thiol compound "Karenz MT PE1" was added to the fourth. The procedure was carried out in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a grade phosphonium salt "Hishikorin PX-4ET" was dissolved was put into a curing agent tank. Compared with Example 1, it had a lower viscosity and could be quickly injected into the entire mold in the method described in <Coating Molding> above. Although the adhesive strength at demolding was lower than that of Example 1, the mold could be demolded without any problems. The cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
（実施例３）
「Ｓｙｎａ Ｅｐｏｘｙ １８６」１００質量部に、脂環構造を有するエポキシ基を有する「セロキサイド２０２１Ｐ」を１２．５部、グリシジル構造を有するエポキシ基を有する「ＥＨＰＥ３１５０」を１２．５部加えて、主剤液を調合した。調合時は１２０℃に加熱し、「ＥＨＰＥ３１５０」を溶かしたうえで、常温に戻し、樹脂注入機の主剤タンクに移液した。チオール化合物「カレンズＭＴ ＰＥ１」１１７質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。 (Example 3)
To 100 parts by mass of "Syna Epoxy 186", 12.5 parts of "Celoxide 2021P" having an epoxy group having an alicyclic structure and 12.5 parts of "EHPE3150" having an epoxy group having a glycidyl structure were added to prepare a main component liquid. was mixed. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector. Example 1 was carried out in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved in 117 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
「Ｓｙｎａ Ｅｐｏｘｙ １８６」１００質量部に、脂環構造を有するエポキシ基を有する「セロキサイド２０２１Ｐ」を１２．５部、グリシジル構造を有するエポキシ基を有する「ＥＨＰＥ３１５０」を１２．５部加えて、主剤液を調合した。調合時は１２０℃に加熱し、「ＥＨＰＥ３１５０」を溶かしたうえで、常温に戻し、樹脂注入機の主剤タンクに移液した。チオール化合物「カレンズＭＴ ＰＥ１」１１７質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。 (Example 3)
To 100 parts by mass of "Syna Epoxy 186", 12.5 parts of "Celoxide 2021P" having an epoxy group having an alicyclic structure and 12.5 parts of "EHPE3150" having an epoxy group having a glycidyl structure were added to prepare a main component liquid. was mixed. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector. Example 1 was carried out in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved in 117 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
実施例１と同様に低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができた。脱型時の密着力も同様で、問題なく金型から脱型することができた。エポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表１に示す。
As with Example 1, it had a low viscosity and could be quickly injected into the entire mold by the method described in <Coating molding> above. The adhesive strength at the time of demolding was the same, and the mold could be demolded without any problem. The cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
（実施例４）
「Ｓｙｎａ Ｅｐｏｘｙ １８６」１００質量部に、グリシジル構造を有するエポキシ基を有する「ＥＨＰＥ３１５０」を２５部加えて、主剤液を調合した。調合時は１２０℃に加熱し、「ＥＨＰＥ３１５０」を溶かしたうえで、常温に戻し、樹脂注入機の主剤タンクに移液した。チオール化合物「カレンズＭＴ ＰＥ１」１１３質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。 (Example 4)
25 parts of "EHPE3150" having an epoxy group having a glycidyl structure was added to 100 parts by mass of "Syna Epoxy 186" to prepare a main component liquid. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector. Performed in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved in 113 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
「Ｓｙｎａ Ｅｐｏｘｙ １８６」１００質量部に、グリシジル構造を有するエポキシ基を有する「ＥＨＰＥ３１５０」を２５部加えて、主剤液を調合した。調合時は１２０℃に加熱し、「ＥＨＰＥ３１５０」を溶かしたうえで、常温に戻し、樹脂注入機の主剤タンクに移液した。チオール化合物「カレンズＭＴ ＰＥ１」１１３質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。 (Example 4)
25 parts of "EHPE3150" having an epoxy group having a glycidyl structure was added to 100 parts by mass of "Syna Epoxy 186" to prepare a main component liquid. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector. Performed in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved in 113 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
実施例１と同様に低粘度であり、上述の＜コーティング成形＞に記載の方法において、問題なく金型全体に注入することができた。脱型時の密着力は高く、問題なく金型から脱型することができた。エポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表１に示す。
As with Example 1, it had a low viscosity, and could be injected into the entire mold without any problems in the method described in <Coating molding> above. The adhesive strength at the time of demolding was high, and the mold could be demolded without any problem. The cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
（実施例５、６）
後硬化温度を、実施例５を８０℃、実施例６を１２５℃にしたこと以外は、実施例４と同様に実施した。後硬化の温度を変更してもエポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、後硬化の温度が低いほうが良好な表面平滑性を示しているが、温度が高くとも、十分良好な表面平滑性を有していた。また塗装後の表面平滑性も非常に良好であった。結果を表１に示す。 (Examples 5 and 6)
Example 4 was repeated except that the post-curing temperature was 80°C for Example 5 and 125°C for Example 6. Even when the post-curing temperature was changed, the cured product of the epoxy resin composition showed no coloration, slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film prepared using this epoxy resin composition exhibits better surface smoothness when the post-curing temperature is lower, but sufficiently good surface smoothness is exhibited even at a high temperature. had. The surface smoothness after coating was also very good. Table 1 shows the results.
後硬化温度を、実施例５を８０℃、実施例６を１２５℃にしたこと以外は、実施例４と同様に実施した。後硬化の温度を変更してもエポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、後硬化の温度が低いほうが良好な表面平滑性を示しているが、温度が高くとも、十分良好な表面平滑性を有していた。また塗装後の表面平滑性も非常に良好であった。結果を表１に示す。 (Examples 5 and 6)
Example 4 was repeated except that the post-curing temperature was 80°C for Example 5 and 125°C for Example 6. Even when the post-curing temperature was changed, the cured product of the epoxy resin composition showed no coloration, slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film prepared using this epoxy resin composition exhibits better surface smoothness when the post-curing temperature is lower, but sufficiently good surface smoothness is exhibited even at a high temperature. had. The surface smoothness after coating was also very good. Table 1 shows the results.
（実施例７）
「Ｓｙｎａ Ｅｐｏｘｙ １８６」１００質量部に、グリシジル構造を有するエポキシ基を有する「ＥＨＰＥ３１５０」を５０部加えて、主剤液を調合した。調合時は１２０℃に加熱し、「ＥＨＰＥ３１５０」を溶かしたうえで、常温に戻し、樹脂注入機の主剤タンクに移液した。チオール化合物「カレンズＭＴ ＰＥ１」１０８質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例４と同様に実施した。 (Example 7)
To 100 parts by mass of "Syna Epoxy 186" was added 50 parts of "EHPE3150" having an epoxy group having a glycidyl structure to prepare a main component liquid. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector. Example 4 was carried out in the same manner as in Example 4, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved in 108 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
「Ｓｙｎａ Ｅｐｏｘｙ １８６」１００質量部に、グリシジル構造を有するエポキシ基を有する「ＥＨＰＥ３１５０」を５０部加えて、主剤液を調合した。調合時は１２０℃に加熱し、「ＥＨＰＥ３１５０」を溶かしたうえで、常温に戻し、樹脂注入機の主剤タンクに移液した。チオール化合物「カレンズＭＴ ＰＥ１」１０８質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例４と同様に実施した。 (Example 7)
To 100 parts by mass of "Syna Epoxy 186" was added 50 parts of "EHPE3150" having an epoxy group having a glycidyl structure to prepare a main component liquid. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector. Example 4 was carried out in the same manner as in Example 4, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved in 108 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
実施例１より若干粘度が高いが、上述の＜コーティング成形＞に記載の方法において、問題なく金型全体に注入することができた。脱型時の密着力は非常に高く、問題なく金型から脱型することができた。エポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表１に示す。
Although the viscosity was slightly higher than that of Example 1, it could be injected into the entire mold without any problems in the method described in <Coating Molding> above. The adhesive strength at the time of demolding was very high, and the mold could be demolded without any problem. The cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 1 shows the results.
（比較例１）
脂肪族エポキシ樹脂「ＨＢＥ－１００」１００質量部からなる主剤液と、チオール化合物「カレンズＭＴ ＰＥ１」１０８質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は実施例１と同様に実施した。
実施例１と同様に低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができた。脱型時の密着力も同様で、問題なく金型から脱型することができた。エポキシ樹脂組成物の硬化物は、着色がないが、試験環境温度よりもＴｇが大きく低く、ゴム状態で紫外線が当たったため、大きく変色し、十分な耐候性を有していなかった。このエポキシ樹脂組成物を用いて作製した硬化被膜は柔らかく、塗装前の研磨を実施した際、硬化被膜が欠落し、スコッチブライドの表面に目詰まりが起きたため、研磨をするためには、実施例１と比較して時間と、必要なスコッチブライドの枚数が多くなった。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性は実施例１には劣るものの良好であった。結果を表２に示す。 (Comparative example 1)
A curing agent made by dissolving 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" in a main liquid consisting of 100 parts by mass of an aliphatic epoxy resin "HBE-100" and 108 parts by mass of a thiol compound "Karenzu MT PE1". The procedure was carried out in the same manner as in Example 1, except that the liquid was placed in the curing agent tank.
It had a low viscosity as in Example 1, and could be quickly injected into the entire mold in the method described in <Coating Molding> above. The adhesive strength at the time of demolding was the same, and the mold could be demolded without any problem. The cured product of the epoxy resin composition was not colored, but had a Tg much lower than the temperature of the test environment, was greatly discolored due to being exposed to ultraviolet rays in a rubber state, and did not have sufficient weather resistance. The cured film prepared using this epoxy resin composition was soft, and when polishing was performed before painting, the cured film was missing and clogging occurred on the surface of the Scotchbride. Compared to 1, the time and number of scotch brides required increased. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and although the surface smoothness after coating was inferior to that of Example 1, it was good. Table 2 shows the results.
脂肪族エポキシ樹脂「ＨＢＥ－１００」１００質量部からなる主剤液と、チオール化合物「カレンズＭＴ ＰＥ１」１０８質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は実施例１と同様に実施した。
実施例１と同様に低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができた。脱型時の密着力も同様で、問題なく金型から脱型することができた。エポキシ樹脂組成物の硬化物は、着色がないが、試験環境温度よりもＴｇが大きく低く、ゴム状態で紫外線が当たったため、大きく変色し、十分な耐候性を有していなかった。このエポキシ樹脂組成物を用いて作製した硬化被膜は柔らかく、塗装前の研磨を実施した際、硬化被膜が欠落し、スコッチブライドの表面に目詰まりが起きたため、研磨をするためには、実施例１と比較して時間と、必要なスコッチブライドの枚数が多くなった。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性は実施例１には劣るものの良好であった。結果を表２に示す。 (Comparative example 1)
A curing agent made by dissolving 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" in a main liquid consisting of 100 parts by mass of an aliphatic epoxy resin "HBE-100" and 108 parts by mass of a thiol compound "Karenzu MT PE1". The procedure was carried out in the same manner as in Example 1, except that the liquid was placed in the curing agent tank.
It had a low viscosity as in Example 1, and could be quickly injected into the entire mold in the method described in <Coating Molding> above. The adhesive strength at the time of demolding was the same, and the mold could be demolded without any problem. The cured product of the epoxy resin composition was not colored, but had a Tg much lower than the temperature of the test environment, was greatly discolored due to being exposed to ultraviolet rays in a rubber state, and did not have sufficient weather resistance. The cured film prepared using this epoxy resin composition was soft, and when polishing was performed before painting, the cured film was missing and clogging occurred on the surface of the Scotchbride. Compared to 1, the time and number of scotch brides required increased. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and although the surface smoothness after coating was inferior to that of Example 1, it was good. Table 2 shows the results.
（比較例２）
「Ｓｙｎａ Ｅｐｏｘｙ １８６」８０質量部に、脂環構造を有するエポキシ基を２官能有する「セロキサイド２０２１Ｐ」を１００質量部加えて、主剤液を調合し、チオール化合物「カレンズＭＴ ＰＥ１」１１４質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。実施例１と比較して、より低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができたが、脂環式エポキシの割合が多いため、１０分では十分硬化できず、脱型時にコーティングが剥離し、脱型時の密着力も低かった。エポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表２に示す。 (Comparative example 2)
To 80 parts by mass of "Syna Epoxy 186", 100 parts by mass of "Celoxide 2021P" having a bifunctional epoxy group having an alicyclic structure was added to prepare a main liquid, and 114 parts by mass of the thiol compound "Karenz MT PE1" was added. The procedure was carried out in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of the quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved was charged into the curing agent tank. Compared to Example 1, the viscosity was lower, and in the method described in <Coating Molding> above, it was possible to quickly inject the entire mold. The coating was peeled off when the mold was demolded, and the adhesion was low when the mold was demolded. The cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 2 shows the results.
「Ｓｙｎａ Ｅｐｏｘｙ １８６」８０質量部に、脂環構造を有するエポキシ基を２官能有する「セロキサイド２０２１Ｐ」を１００質量部加えて、主剤液を調合し、チオール化合物「カレンズＭＴ ＰＥ１」１１４質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。実施例１と比較して、より低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができたが、脂環式エポキシの割合が多いため、１０分では十分硬化できず、脱型時にコーティングが剥離し、脱型時の密着力も低かった。エポキシ樹脂組成物の硬化物は、着色がなく、紫外線を当てても変色は軽微であり、良好な耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表２に示す。 (Comparative example 2)
To 80 parts by mass of "Syna Epoxy 186", 100 parts by mass of "Celoxide 2021P" having a bifunctional epoxy group having an alicyclic structure was added to prepare a main liquid, and 114 parts by mass of the thiol compound "Karenz MT PE1" was added. The procedure was carried out in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of the quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved was charged into the curing agent tank. Compared to Example 1, the viscosity was lower, and in the method described in <Coating Molding> above, it was possible to quickly inject the entire mold. The coating was peeled off when the mold was demolded, and the adhesion was low when the mold was demolded. The cured product of the epoxy resin composition was free from coloration, showed slight discoloration even when exposed to ultraviolet rays, and exhibited good weather resistance. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 2 shows the results.
（比較例３）
脂環構造を有するエポキシ基を２官能有する「セロキサイド２０２１Ｐ」を１００質量部で主剤液を調合し、チオール化合物「カレンズＭＴ ＰＥ１」１００質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。実施例１と比較して、より低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができたが、脂環構造を有するエポキシ樹脂しか含まれないため、１０分では十分硬化できず、脱型時にコーティングが剥離し、脱型時の密着力も低かった。エポキシ樹脂組成物の硬化物は、着色がなかった。紫外線を当てると、若干変色したが、実用に耐えうる耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表２に示す。 (Comparative Example 3)
100 parts by mass of "Celoxide 2021P" having a bifunctional epoxy group with an alicyclic structure was prepared as the main component liquid, and 4 parts by mass of the quaternary phosphonium salt "Hishikorin PX-4ET" was added to 100 parts by mass of the thiol compound "Karenzu MT PE1". The procedure was carried out in the same manner as in Example 1, except that the curing agent liquid in which the parts were made compatible was put into the curing agent tank. Compared to Example 1, it has a lower viscosity and can be quickly injected into the entire mold in the method described in <Coating molding> above, but it contains only an epoxy resin having an alicyclic structure. Therefore, it was not sufficiently hardened in 10 minutes, the coating peeled off when demolded, and the adhesion was low when demolded. The cured epoxy resin composition was not colored. When exposed to ultraviolet rays, it discolored slightly, but it showed weather resistance that could withstand practical use. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 2 shows the results.
脂環構造を有するエポキシ基を２官能有する「セロキサイド２０２１Ｐ」を１００質量部で主剤液を調合し、チオール化合物「カレンズＭＴ ＰＥ１」１００質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。実施例１と比較して、より低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができたが、脂環構造を有するエポキシ樹脂しか含まれないため、１０分では十分硬化できず、脱型時にコーティングが剥離し、脱型時の密着力も低かった。エポキシ樹脂組成物の硬化物は、着色がなかった。紫外線を当てると、若干変色したが、実用に耐えうる耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表２に示す。 (Comparative Example 3)
100 parts by mass of "Celoxide 2021P" having a bifunctional epoxy group with an alicyclic structure was prepared as the main component liquid, and 4 parts by mass of the quaternary phosphonium salt "Hishikorin PX-4ET" was added to 100 parts by mass of the thiol compound "Karenzu MT PE1". The procedure was carried out in the same manner as in Example 1, except that the curing agent liquid in which the parts were made compatible was put into the curing agent tank. Compared to Example 1, it has a lower viscosity and can be quickly injected into the entire mold in the method described in <Coating molding> above, but it contains only an epoxy resin having an alicyclic structure. Therefore, it was not sufficiently hardened in 10 minutes, the coating peeled off when demolded, and the adhesion was low when demolded. The cured epoxy resin composition was not colored. When exposed to ultraviolet rays, it discolored slightly, but it showed weather resistance that could withstand practical use. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 2 shows the results.
（比較例４）
脂環構造を有するエポキシ基を２官能有する「セロキサイド２０２１Ｐ」１００質量部に、グリシジル構造を有するエポキシ基を有する「ＥＨＰＥ３１５０」を１２５部加えて、主剤液を調合した。調合時は１２０℃に加熱し、「ＥＨＰＥ３１５０」を溶かしたうえで、常温に戻し、樹脂注入機の主剤タンクに移液した。チオール化合物「カレンズＭＴ ＰＥ１」８８質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。 (Comparative Example 4)
125 parts of "EHPE3150" having an epoxy group having a glycidyl structure was added to 100 parts by mass of "Celoxide 2021P" having a bifunctional epoxy group having an alicyclic structure to prepare a main liquid. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector. Performed in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved in 88 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
脂環構造を有するエポキシ基を２官能有する「セロキサイド２０２１Ｐ」１００質量部に、グリシジル構造を有するエポキシ基を有する「ＥＨＰＥ３１５０」を１２５部加えて、主剤液を調合した。調合時は１２０℃に加熱し、「ＥＨＰＥ３１５０」を溶かしたうえで、常温に戻し、樹脂注入機の主剤タンクに移液した。チオール化合物「カレンズＭＴ ＰＥ１」８８質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。 (Comparative Example 4)
125 parts of "EHPE3150" having an epoxy group having a glycidyl structure was added to 100 parts by mass of "Celoxide 2021P" having a bifunctional epoxy group having an alicyclic structure to prepare a main liquid. At the time of preparation, the mixture was heated to 120° C. to dissolve “EHPE3150”, returned to room temperature, and transferred to the main agent tank of the resin injector. Performed in the same manner as in Example 1, except that a curing agent liquid in which 4 parts by mass of a quaternary phosphonium salt "Hishikorin PX-4ET" was dissolved in 88 parts by mass of the thiol compound "Karenzu MT PE1" was added to the curing agent tank. did.
実施例１より粘度が高く、上述の＜コーティング成形＞に記載の方法において、金型全体に注入しきるまでに時間がかかった。また、主剤内に含まれる「ＥＨＰＥ３１５０」は十分に反応していたものの、脂環構造を有する「セロキサイド２０２１Ｐ」が低分子の状態で残っていたため、１０分では十分硬化できず、脱型時にコーティングが剥離し、脱型時の密着力も低かった。エポキシ樹脂組成物の硬化物は、着色がなかった。紫外線を当てると、若干変色したが、実用に耐えうる耐候性を示した。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性も非常に良好であった。結果を表２に示す。
The viscosity was higher than in Example 1, and it took a long time to completely fill the entire mold in the method described in <Coating Molding> above. In addition, although "EHPE3150" contained in the main agent reacted sufficiently, "Celoxide 2021P", which has an alicyclic structure, remained in a low molecular state, so it could not be sufficiently cured in 10 minutes, and the coating was peeled off, and the adhesion at the time of demolding was low. The cured epoxy resin composition was not colored. When exposed to ultraviolet rays, it discolored slightly, but it showed weather resistance that could withstand practical use. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibited good surface smoothness, and the surface smoothness after coating was also very good. Table 2 shows the results.
（比較例５）
脂肪族エポキシ「ＲＤ１２９」１００質量部で主剤液を調合し、チオール化合物「カレンズＭＴ ＰＥ１」８６質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。実施例１と比較して、より低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができた。脱型時の密着力は低かったものの、金型から脱型することができた。エポキシ樹脂組成物の硬化物は、着色がないが、試験環境温度よりもＴｇが大きく低く、ゴム状態で紫外線が当たったため、大きく変色し、十分な耐候性を有していなかった。このエポキシ樹脂組成物を用いて作製した硬化被膜は柔らかく、塗装前の研磨を実施した際、硬化被膜が欠落し、スコッチブライドの表面に目詰まりが起きたため、研磨をするためには、実施例１と比較して時間と、必要なスコッチブライドの枚数が多くなった。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性は実施例１には劣るものの、使用に耐えるものであった。結果を表２に示す。 (Comparative Example 5)
Aliphatic epoxy "RD129" 100 parts by mass of the main component liquid was prepared, and 86 parts by mass of the thiol compound "Karenzu MT PE1" was mixed with 4 parts by mass of the quaternary phosphonium salt "Hishikorin PX-4ET" to prepare a curing agent solution. It was carried out in the same manner as in Example 1, except that it was placed in the curing agent tank. Compared with Example 1, it had a lower viscosity and could be quickly injected into the entire mold in the method described in <Coating Molding> above. Although the adhesive strength at demolding was low, it could be demolded from the mold. The cured product of the epoxy resin composition was not colored, but had a Tg much lower than the temperature of the test environment, was greatly discolored due to being exposed to ultraviolet rays in a rubber state, and did not have sufficient weather resistance. The cured film prepared using this epoxy resin composition was soft, and when polishing was performed before painting, the cured film was missing and clogging occurred on the surface of the Scotchbride. Compared to 1, the time and number of scotch brides required increased. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibits good surface smoothness, and although the surface smoothness after coating is inferior to that of Example 1, it is durable for use. rice field. Table 2 shows the results.
脂肪族エポキシ「ＲＤ１２９」１００質量部で主剤液を調合し、チオール化合物「カレンズＭＴ ＰＥ１」８６質量部に第四級ホスホニウム塩「ヒシコーリンＰＸ－４ＥＴ」４質量部を相溶させた硬化剤液を硬化剤タンクに入れた以外は、実施例１と同様に実施した。実施例１と比較して、より低粘度であり、上述の＜コーティング成形＞に記載の方法において、素早く金型全体に注入することができた。脱型時の密着力は低かったものの、金型から脱型することができた。エポキシ樹脂組成物の硬化物は、着色がないが、試験環境温度よりもＴｇが大きく低く、ゴム状態で紫外線が当たったため、大きく変色し、十分な耐候性を有していなかった。このエポキシ樹脂組成物を用いて作製した硬化被膜は柔らかく、塗装前の研磨を実施した際、硬化被膜が欠落し、スコッチブライドの表面に目詰まりが起きたため、研磨をするためには、実施例１と比較して時間と、必要なスコッチブライドの枚数が多くなった。このエポキシ樹脂組成物を用いて作製した硬化被膜を有する繊維強化複合材料は、良好な表面平滑性を示し、また塗装後の表面平滑性は実施例１には劣るものの、使用に耐えるものであった。結果を表２に示す。 (Comparative Example 5)
Aliphatic epoxy "RD129" 100 parts by mass of the main component liquid was prepared, and 86 parts by mass of the thiol compound "Karenzu MT PE1" was mixed with 4 parts by mass of the quaternary phosphonium salt "Hishikorin PX-4ET" to prepare a curing agent solution. It was carried out in the same manner as in Example 1, except that it was placed in the curing agent tank. Compared with Example 1, it had a lower viscosity and could be quickly injected into the entire mold in the method described in <Coating Molding> above. Although the adhesive strength at demolding was low, it could be demolded from the mold. The cured product of the epoxy resin composition was not colored, but had a Tg much lower than the temperature of the test environment, was greatly discolored due to being exposed to ultraviolet rays in a rubber state, and did not have sufficient weather resistance. The cured film prepared using this epoxy resin composition was soft, and when polishing was performed before painting, the cured film was missing and clogging occurred on the surface of the Scotchbride. Compared to 1, the time and number of scotch brides required increased. A fiber-reinforced composite material having a cured film produced using this epoxy resin composition exhibits good surface smoothness, and although the surface smoothness after coating is inferior to that of Example 1, it is durable for use. rice field. Table 2 shows the results.
本発明のエポキシ樹脂組成物は、繊維強化樹脂を成形した際、成形温度（硬化温度）と常温との温度差により生じる強化繊維の形態に伴って表面に生じる、表面凹凸を大幅に低減することができ、耐候性にも優れるため、特に外観品位を要求される自動車用途への繊維強化複合材料として好適に用いられる。その結果、自動車の更なる軽量化による燃費向上や、地球温暖化ガス排出削減への貢献が期待できる。
The epoxy resin composition of the present invention significantly reduces the surface unevenness that occurs on the surface due to the shape of the reinforcing fibers caused by the temperature difference between the molding temperature (curing temperature) and normal temperature when the fiber reinforced resin is molded. and excellent weather resistance, it is suitable for use as a fiber-reinforced composite material for automobile applications, which particularly require high appearance quality. As a result, it can be expected to contribute to the improvement of fuel efficiency by further reducing the weight of automobiles and the reduction of greenhouse gas emissions.
Claims (7)
- 単一または複数のエポキシ樹脂からなるエポキシ樹脂（Ａ）、チオール基含有硬化剤（Ｂ）、触媒（Ｃ）を少なくとも含むエポキシ樹脂組成物であって、エポキシ樹脂（Ａ）を構成するエポキシ樹脂のうち、重量比で５０％以上を占めるエポキシ樹脂（Ａ１）がグリシジル構造を有するエポキシ基を２官能以上、及び脂環構造を有するエポキシ基を１官能以上有するエポキシ樹脂組成物。 An epoxy resin composition containing at least an epoxy resin (A) consisting of a single or multiple epoxy resins, a thiol group-containing curing agent (B), and a catalyst (C), wherein the epoxy resin constituting the epoxy resin (A) An epoxy resin composition in which the epoxy resin (A1), which accounts for 50% or more by weight, has two or more functional epoxy groups having a glycidyl structure and one or more functional epoxy groups having an alicyclic structure.
- エポキシ樹脂（Ａ）に含まれるグリシジル構造を有するエポキシ基の官能基数［ＡＧ］と脂環構造を有するエポキシ基の官能基数［ＡＦ］の比が［ＡＧ］／［ＡＦ］＞０．７の関係を有する請求項１に記載のエポキシ樹脂組成物。 The ratio of the functional group number [AG] of the epoxy group having a glycidyl structure contained in the epoxy resin (A) to the functional group number [AF] of the epoxy group having an alicyclic structure is [AG]/[AF] > 0.7. The epoxy resin composition according to claim 1, having
- エポキシ樹脂（Ａ）およびチオール基含有硬化剤（Ｂ）のいずれにも炭素－炭素不飽和結合を含まない請求項１または２に記載のエポキシ樹脂組成物。 3. The epoxy resin composition according to claim 1, wherein neither the epoxy resin (A) nor the thiol group-containing curing agent (B) contains a carbon-carbon unsaturated bond.
- 請求項１～３のいずれかに記載のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物であって、４０℃以上のガラス転移点温度（Ｔｇ）を有するエポキシ樹脂硬化物。 A cured epoxy resin product obtained by curing the epoxy resin composition according to any one of claims 1 to 3, wherein the cured epoxy resin product has a glass transition temperature (Tg) of 40°C or higher.
- 請求項４に記載のエポキシ樹脂硬化物を被覆層として繊維強化樹脂成形品の表面の少なくとも一部に被覆してなる被覆繊維強化樹脂成形品。 A coated fiber-reinforced resin molded product obtained by coating at least part of the surface of a fiber-reinforced resin molded product with the epoxy resin cured product according to claim 4 as a coating layer.
- 前記繊維強化樹脂成形品が炭素繊維強化プラスチックである請求項５に記載の被覆繊維強化樹脂成形品。 The coated fiber-reinforced resin molded product according to claim 5, wherein the fiber-reinforced resin molded product is carbon fiber-reinforced plastic.
- 前記被覆層の表面にさらにクリアー塗装による塗膜を形成した構成である請求項５または６に記載の被覆繊維強化樹脂成形品。 7. The coated fiber-reinforced resin molded article according to claim 5, wherein the coating layer is further coated with a clear coating on the surface of the coating layer.
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