JPS6365108B2 - - Google Patents
Info
- Publication number
- JPS6365108B2 JPS6365108B2 JP56115315A JP11531581A JPS6365108B2 JP S6365108 B2 JPS6365108 B2 JP S6365108B2 JP 56115315 A JP56115315 A JP 56115315A JP 11531581 A JP11531581 A JP 11531581A JP S6365108 B2 JPS6365108 B2 JP S6365108B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- weight
- block copolymer
- parts
- cured product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920001400 block copolymer Polymers 0.000 claims description 66
- 229920005989 resin Polymers 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 49
- -1 vinyl aromatic compound Chemical class 0.000 claims description 42
- 229920000642 polymer Polymers 0.000 claims description 30
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- 229920001187 thermosetting polymer Polymers 0.000 claims description 21
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- 239000004640 Melamine resin Substances 0.000 claims description 8
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 7
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 7
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 6
- 229920001567 vinyl ester resin Polymers 0.000 claims description 6
- 229920000180 alkyd Polymers 0.000 claims description 5
- 239000007849 furan resin Substances 0.000 claims description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 description 32
- 239000000203 mixture Substances 0.000 description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 13
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical group OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000006482 condensation reaction Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 229920003244 diene elastomer Polymers 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- ITNADJKYRCCJNX-UHFFFAOYSA-N 3-(2,3-diaminophenyl)sulfonylbenzene-1,2-diamine Chemical compound NC1=CC=CC(S(=O)(=O)C=2C(=C(N)C=CC=2)N)=C1N ITNADJKYRCCJNX-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 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 1
- 238000012661 block copolymerization Methods 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、耐衝撃性、剛性にすぐれた熱硬化性
樹脂組成物に関する。更に詳しくは、本発明は、
ジアリルフタレート樹脂、フエノール樹脂、メラ
ミン樹脂、ユリア樹脂、エポキシ樹脂、ビニルエ
ステル樹脂、グアナミン樹脂、フラン樹脂、アル
キツド樹脂から選ばれる少くとも１種の樹脂と、
ビニル芳香族化合物重合体ブロツクＡとオレフイ
ン化合物重合体ブロツクＢとからなるブロツク共
重合体であつて、ブロツクＢの不飽和度が20％を
こえないブロツク共重合体に、カルボン酸基また
はその誘導体基を含有する分子単位が結合した変
性ブロツク共重合体とからなる熱硬化性樹脂組成
物に関する。
熱硬化性樹脂は機械的強度、耐熱性、電気絶縁
性、耐容剤性または接着性などに優れることか
ら、各種成形材料あるいは積層材料として広汎に
用いられている。
しかしながら熱硬化性樹脂は比較的脆いという
欠点、特に集中応力により簡単に破壊する欠点を
有しており、この脆さを補い衝撃に強い熱硬化性
樹脂を得ることが工業的に要望されている。
従来より熱硬化性樹脂の耐衝撃性を改良する試
みは種々なされており、ジエン系ゴムを添加する
方法もその一つとして公知である。
熱硬化性樹脂に添加されるジエン系ゴムの代表
的なものに、カルボキシル基、ビニル基、アミン
基を側鎖または末端にもつ液状のポリブタジエ
ン、スチレン−ブタジエン共重合体、アクリロニ
トリル−ブタジエン共重合体がある。なかでもハ
イカ−CTBNの商品名でグツドリツチ社から出
ている、カルボキシル基末端を有し、分子量5000
以下の液状ゴムであるアクリロニトリル−ブタジ
エン共重合体は、エポキシ樹脂、フエノール樹脂
などの耐衝撃性改良剤として使用しうることが知
られている。
しかし熱硬化性樹脂に上記液状ゴムを添加する
方法は実用上幾つかの問題点を抱えている。その
一つは、液状ゴムそのものが非常に粘稠な液であ
るため取扱い作業が煩雑となる点にある。今一つ
の問題は、得られる熱硬化性樹脂の耐衝撃性、特
にノツチ付きのアイゾツト衝撃で表わされる集中
応力に対する耐衝撃性の改良効果が乏しいこと、
更に熱硬化性樹脂の硬さあるいは剛性の低下が著
しいことなどを挙げることができる。
本発明は、上記液状ゴムを添加剤とする方法に
より得られる組成物がもつ幾つかの実用上の問題
点を完全に払拭しうる画期的な熱硬化性組成物を
提供するものである。
すなわち、本発明は、成分として
(a) ジアリルフタレート樹脂、フエノール樹脂、
メラミン樹脂、ユリア樹脂、エポキシ樹脂、ビ
ニルエステル樹脂、グアナミン樹脂、フラン樹
脂、アルキツド樹脂から選ばれる少くとも１種
の樹脂、99〜20重量部
(b) 少くとも１つのビニル芳香族化合物重合体ブ
ロツクＡと、少くとも１つの不飽和度が20％を
こえないオレフイン化合物重合体ブロツクＢと
からなり、ビニル芳香族化合物の含有量が10〜
90重量％であるブロツク共重合体に、カルボン
酸基またはその誘導体基を含有する分子単位が
ブロツク共重合体100重量部あたり0.05〜20重
量部結合した変性ブロツク共重合体、１〜80重
量部
の両成分を含んでなる熱硬化性樹脂組成物に関す
るものである。
本発明の組成物の特徴は、熱硬化性樹脂に添加
するジエン系ゴム、すなわち変性ブロツク共重合
体が常温で固体であり、取扱い易いこと、また、
その硬化物のアイゾツト衝撃で示される耐衝撃性
が極めて優れており、かつ硬さあるいは剛性の保
持率が良いことなどがある。
本発明の組成物を構成する変性ブロツク共重合
体は、加熱により溶融流動性を示すいわゆる熱可
塑性ゴムと称せられるものであり、更にカルボン
酸基またはその誘導体を分子中に結合しているた
め、反応性、接着性、相溶性に富む特性を有して
いる。これらの特性が本発明組成物の特徴発揮の
上で重要な役割を果たしているものと考えられ
る。
以下、本発明について詳しく述べる。
本発明の(a)成分を構成する熱硬化性樹脂は、ジ
アリルフタレート樹脂、フエノール樹脂、メラミ
ン樹脂、ユリア樹脂、エポキシ樹脂、グアナミン
樹脂、ビニルエステル樹脂、フラン樹脂、アルキ
ツド樹脂から選ばれる少くとも１種の樹脂であ
る。
本発明で用いるジアリルフタレート樹脂は、ジ
アリルフタレートを主成分とする硬化性のホモ重
合体又は共重合体である。共重合させるモノマー
としては、スチレン、α−メチルスチレン、アク
リル酸エステル、メタクリル酸エステルなどがあ
げられる。
本発明で用いるフエノール樹脂は、フエノール
類とアルデヒド類との縮合反応によつて得られる
重合体を主成分とする樹脂であり、フエノール、
ｍ−クレゾール、３，５−キシレノール、ｐ−ア
ルキルフエノール、レゾルシンなどと、ホルムア
ルデヒドから成るものが好適である。フエノール
樹脂は通常の酸性触媒又は塩基性触媒により縮合
反応でき、必要に応じてヘキサメチレンテトラミ
ンなどの硬化剤、木粉、パルプ、骨材等の充てん
剤を用いることもできる。
本発明で使用するメラミン樹脂は、メラミンと
アルデヒド類との付加縮合反応によつて得られる
重合体と主成分とする樹脂で、アルデヒド類とし
てはホルムアルデヒドが一般に用いられる。又、
メラミン樹脂には、尿素等と共縮合したものも含
まれる。メラミン樹脂は一般に熱により硬化され
るが、必要に応じて硬化剤を使うことも可能であ
る。
本発明で使用するユリア樹脂は、尿素とアルデ
ヒド類との縮合反応によつて得られる重合体を主
成分とする樹脂で、アルデヒド類としてはホルム
アルデヒドが一般に用いられる。又、ユリア系樹
脂にはチオ尿素、メラミン、フエノールなどと共
縮合したものも含まれる。
上記メラミン樹脂及びユリア樹脂は必要に応じ
てセルロース等を混在させることもできる。
本発明で用いるエポキシ樹脂は、一分子中に少
なくとも２個以上のエポキシ環を含んでいる化合
物を開環反応させて得られる重合体を主成分とす
る樹脂で、該化合物の一般的なものとしてはエピ
クロルヒドリンとビスフエノールＡとの縮合生成
物があげられる。硬化剤としては、エチレンジア
ミン、ジエチレントリアミン、トリエチレンテト
ラミン、テトラエチレンペンタミン、メタフエニ
レンジアミン、ジアミノフエニルスルホンなどの
アミン類、メチルナジツク酸無水物、ヘキサヒド
ロ酸無水物などの酸無水物の他、ユリア、メラミ
ン、フエノール樹脂なども用いることができる。
その他、エポキシ樹脂には、脂環式エポキシ樹
脂、臭素化エポキシ樹脂、脂肪族エポキシ樹脂、
多官能性エポキシ樹脂なども含まれる。
本発明で用いるグアナミン樹脂は、グアナミン
類とアルデヒド類との付加縮合反応によつて得ら
れる重合体を主成分とする樹脂で、ベンゾグアナ
ミンとホルムアルデヒドから成るものが一般的な
ものとしてあげられる。又、グアナミン樹脂には
ユリア、メラミン、チオユリアなどと共反応、共
縮合させたもの、ブタノール、メタノールなどで
エーテル化したものも含まれる。
本発明で用いるビニルエステル樹脂は、末端に
アクリル２重結合を有するエポキシ樹脂をスチレ
ン、アクリル酸エステル、メタクリル酸エステ
ル、多価不飽和酸エステル等のビニルモノマーと
共重合させたものである。
本発明で用いうるフラン樹脂は、フルフリルア
ルコール単独またはホルムアルデヒドとの縮合反
応によつて得られる重合体を主成分とする樹脂で
あり、例えば、フルフリルアルコール・フルフラ
ール共縮合樹脂、フルフリルアルコール樹脂、フ
ルフラール・フエノール共縮合樹脂、フルフラー
ル・ケトン共縮合樹脂、フルフリルアルコール・
尿素共重合樹脂、フルフリルアルコール・フエノ
ール共縮合樹脂などがあげられる。
本発明で用いるアルキド樹脂は、多塩基酸と多
価アルコールとの縮合反応によつて得られる重合
体を主成分とする樹脂で、多塩基酸としては無水
フタル酸、イソフタル酸、マレイン酸、脂肪油、
脂肪酸、ロジン、エステルロジンなどが、また多
価アルコールとしてはグリセリンが一般に用いら
れる。
本発明においては、上記熱硬化性樹脂の１種だ
けでなく、場合によつては２種以上を組み合わせ
て使用することも可能である。その他、不飽和ポ
リエステル、ポリウレタンなどの熱硬化性樹脂と
併用することもまた可能である。
本発明の(b)成分である変性ブロツク共重合体
は、一例として次のようにして合成される。即
ち、ビニル芳香族化合物重合体ブロツクと、共役
ジエン化合物を主体とする重合体ブロツクとから
構成されてなるブロツク共重合体に共役ジエン部
分の不飽和度が20％をこえない程度にまで選択的
に水添し、ビニル芳香族化合物重合体ブロツクＡ
と、不飽和度が20％を越えないオレフイン化合物
重合体ブロツクＢとからなるブロツク共重合体と
し、ついで、不飽和ジカルボン酸またはその誘導
体との付加反応により、変性ブロツク共重合体を
得る。
上記の水添する前のブロツク共重合体は、ビニ
ル芳香族化合物重合体ブロツクを少くとも１個、
好ましくは２個以上、共役ジエン化合物を主体と
する重合体ブロツクを少くとも１個含有するもの
である。ここで、共役ジエンを主体とする重合体
ブロツクは、ビニル芳香族化合物と共役ジエン化
合物との重量比が０／100〜50／50、好ましくは
０／100〜40／60の組成範囲からなる重合体ブロ
ツクであり、このブロツクにおけるビニル芳香族
化合物の分布は、ランダム、テーパー（分子鎖に
沿つてモノマー成分や増加または減少するもの）、
一部ブロツク状またはこれらの任意の組合せのい
ずれであつてもよい。なお、本発明における水添
する前のブロツク共重合体中には、ビニル芳香族
化合物重合体ブロツクと共役ジエン化合物を主体
とする重合体ブロツクとの遷移部等にビニル芳香
族化合物が50重量％を越えるビニル芳香族化合物
と共役ジエン化合物との共重合体部分が存在して
もよいが、かかる重合体部分は前記の共役ジエン
化合物を主体とする重合体ブロツクに含めるもの
とする。
上記ブロツク共重合体において、ビニル芳香族
化合物の含有量と共役ジエン化合物の含有量の重
量比は、10／90〜90／10の範囲であり、20／80〜
85／15の範囲が好ましい。
上記水添前のブロツク共重合体を構成するビニ
ル芳香族化合物としては、スチレン、α−メチル
スチレン、ビニルトルエン等のうちから１種また
は２種以上が選ばれ、中でもスチレンが特に好ま
しい。また、共役ジエン化合物としては、ブタジ
エン、イソプレン、１，３−ペンタジエン等のう
ちから１種または２種以上選ばれ、中でもブタジ
エンおよび／またはイソプレンが特に好ましい。
上記ブロツク共重合体は、数平均分子量が20000
〜500000の範囲であり、分子量分布（重量平均分
子量と数平均分子量の比）は、1.05〜10の範囲が
好ましい。またブロツク共重合体の分子構造は、
直鎖状、分岐状、放射状またはこれらの組合せな
どいずれでもよい。さらに、ブロツク共重合体に
おいて共役ジエン化合物として、ブタジエンを使
用した場合には、ブタジエン部分のミクロ構造の
１、２結合量が10〜80％の範囲が好ましい。変性
ブロツク共重合体にゴム弾性を持たせることを必
要とする場合には、１、２結合量は35〜55％の範
囲が特に好ましい。
上記ブロツク共重合体が、ビニル芳香族化合物
ブロツクまたは共役ジエン化合物を主体とするブ
ロツクを２個以上含有する場合においては、各ブ
ロツクは同一の構造であつてもよいし、モノマー
成分含有量、それらの分子鎖における分布、ブロ
ツクの分子量、ミクロ構造などの各構造が異なる
ものであつてもよい。
上記のブロツク共重合体は、通常、ベンゼン、
トルエン、ヘキサン、シクロヘキサン等の不活性
炭化水素溶媒中で、ブチルリチウム等の有機リチ
ウム化合物を触媒として、ビニル芳香族化合物と
共役ジエン化合物をモノマーとするアニオンリビ
ング重合法によつて得られる。さらに、上記方法
で得られたリチウム活性末端を有するブロツク共
重合体を、多官能性のカツプリング剤、例えば四
塩化炭素、四塩化ケイ素等と反応させることによ
り、分岐状、放射状のブロツク共重合体とするこ
とも可能である。本発明においては、いかなる重
合法で得られたものであつても、上記の範囲のも
のであれば使用可能である。更に、ブロツク共重
合体は、１種のみならず２種類以上の混合物とし
て使用することも可能である。
上記ブロツク共重合体を、公知の方法、例え
ば、特公昭42−8704号公報に記載の方法で水添す
ることにより、ビニル芳香族化合物ブロツクＡの
芳香族二重結合の20％をこえない部分及び共役ジ
エン化合物ブロツクＢの脂肪族二重結合の少くと
も80％が水素添加されている部分水素添加ブロツ
ク共重合体が合成される。
本発明でいうブロツクＢの不飽和度とは、ブロ
ツクＢに含まれる炭素−炭素二重結合の割のこと
であつて、これは、核磁気共鳴吸収スペクトル
（NMR）、赤外線吸収スペクトル（IR）等の機器
分析、ヨード滴定法等の化学分析により測定され
る。
部分水素添加ブロツク共重合体は、次いで、不
飽和カルボン酸またはその誘導体との付加反応に
より変性される。部分水素添加ブロツク共重合体
に付加される不飽和カルボン酸またはその誘導体
の例としては、マレイン酸、無水マレイン酸、フ
マル酸、イタコン酸、アクリル酸、クロトン酸、
シス−４−シクロヘキセン−１，２−ジカルボン
酸およびその無水物、エンド−シス−ビシクロ
〔２，２，１〕−５−ヘプテン−２，３−ジカルボ
ン酸およびその無水物、マレインイミド等が挙げ
られるが、これらの中では無水マレイン酸が特に
好ましい。これら不飽和カルボン酸またはその誘
導体は一種のみならず、二種以上混合しても使用
できる。
本発明の組成物の一成分である上記変性ブロツ
ク共重合体は、一例として部分水素添加ブロツク
共重合体に不飽和カルボン酸またはその誘導体
を、溶液状態または溶融状態において、ラジカル
開始剤を使用あるいは使用せずして付加せしめる
ことによつて得られる。これら変性ブロツク共重
合体の製造方法に関しては、本発明においては特
に限定はしないが、得られた変性ブロツク共重合
体がゲル等の好ましくない成分を含んだり、その
溶融粘度が著しく増大して加工性が悪化したりす
る製造方法は好ましくない。好ましい方法として
は、たとえば押出機中で、ラジカル開始剤存在下
で、未変性ブロツク共重合体と不飽和カルボン酸
またはその誘導体とを反応させる方法がある。不
飽和カルボン酸の誘題体は、誘導体のままブロツ
ク共重合体に付加させてもよく、また不飽和カル
ボン酸をブロツク共重合体に付加させた後、しか
るべき反応により対応する誘導体に変換してもよ
く、かかる反応は、熱硬化性樹脂と混合して組成
物にした後に実施することも可能である。
不飽和カルボン酸またはその誘導体のブロツク
共重合体への付加量は、ブロツク共重合体100重
量部あたり0.05〜20重量部であり、0.1〜10重量
部が好ましい。付加量が0.05重量部以下では組成
物として場合、熱硬化性樹脂との相溶性に劣り、
未変性の共役ジエン系重合体に比較して耐衝撃性
の改良効果がわずかであり、付加量が20重量部を
超えても、それ以下に比べて耐衝撃性の改良の増
加はほとんど見られない。この際、必要に応じて
ブロツク共重合体中に未反応の熱硬化性樹脂また
はその誘導体を残存させてもよい。
本発明の組成物における(a)成分と(b)成分の重量
比、99／１〜20／80、好ましくは98／２〜50／
50、更に好ましくは95／５〜70／30の範囲から選
ばれる。上記重量比が99／１よりも(b)成分が少く
なると耐衝撃性の改善が十分でなく、20／80より
も(b)成分が多くなると剛性の低下が著しいので好
ましくない。
本発明の組成物には、硬化剤、無機あるいは有
機の各種の充てん剤、無機あるいは有機の繊維強
化剤、ビニルモノマー、顔料、着色剤、滑剤、離
型剤、安定剤、難燃剤、カツプリング剤、熱可塑
性重合体などを添加することも可能である。
本発明の組成物の硬化は、硬化剤あるいは硬化
促進剤の存在下もしくは不存在下に、加熱あるい
は無加熱、もしくは紫外線照射などの方法によつ
て行うことが可能である。
本発明の組成物の硬化剤は、耐衝撃性に優れた
熱硬化性樹脂として、塗料、積層板、成形材料な
どに使用される。
以下、実施例を示すが、これは本発明をより具
体的に説明するものであつて、本発明の範囲を限
定するものではない。
実施例１、２及び比較例１〜３
(1) 水添ブロツク共重合体の調製
ｎ−ブチルリチウムを重合触媒とし、ｎ−ヘ
キサンまたはシクロヘキサン溶媒中で、テトラ
ヒドロフランをビニル含量調節剤として、ブタ
ジエンとスチレンとをアニオン・ブロツク共重
合することにより、表１に示したようなブロツ
ク共重合体を合成した。
The present invention relates to a thermosetting resin composition having excellent impact resistance and rigidity. More specifically, the present invention includes:
At least one resin selected from diallyl phthalate resin, phenol resin, melamine resin, urea resin, epoxy resin, vinyl ester resin, guanamine resin, furan resin, and alkyd resin,
A block copolymer consisting of a vinyl aromatic compound polymer block A and an olefin compound polymer block B, wherein the degree of unsaturation of block B does not exceed 20%, and a carboxylic acid group or its derivative The present invention relates to a thermosetting resin composition comprising a modified block copolymer to which molecular units containing groups are bonded. Thermosetting resins are widely used as various molding materials or laminated materials because they have excellent mechanical strength, heat resistance, electrical insulation, resistance to agents, adhesiveness, etc. However, thermosetting resins have the drawback of being relatively brittle, especially the drawback that they easily break due to concentrated stress, and there is an industrial need to compensate for this brittleness and obtain thermosetting resins that are resistant to impact. . Various attempts have been made to improve the impact resistance of thermosetting resins, and one known method is the addition of diene rubber. Typical diene rubbers added to thermosetting resins include liquid polybutadiene, styrene-butadiene copolymer, and acrylonitrile-butadiene copolymer, which have carboxyl groups, vinyl groups, and amine groups on side chains or ends. There is. Among them, it has a carboxyl group at the end and has a molecular weight of 5000, which is produced by Gutudoritsu under the trade name Hyka-CTBN.
It is known that the following liquid rubber acrylonitrile-butadiene copolymer can be used as an impact modifier for epoxy resins, phenolic resins, and the like. However, the method of adding the liquid rubber to the thermosetting resin has several practical problems. One of the problems is that the liquid rubber itself is a very viscous liquid, making handling work complicated. Another problem is that the effect of improving the impact resistance of the obtained thermosetting resin, especially against concentrated stress expressed by notched Izot impact, is poor.
Another problem is that the hardness or rigidity of the thermosetting resin is significantly reduced. The present invention provides an epoch-making thermosetting composition that can completely eliminate some of the practical problems of compositions obtained by the method using liquid rubber as an additive. That is, the present invention comprises (a) diallyl phthalate resin, phenol resin,
At least one resin selected from melamine resin, urea resin, epoxy resin, vinyl ester resin, guanamine resin, furan resin, and alkyd resin, 99 to 20 parts by weight (b) At least one vinyl aromatic compound polymer block A and an olefin compound polymer block B in which at least one degree of unsaturation does not exceed 20%, and the content of vinyl aromatic compounds is 10 to 10%.
A modified block copolymer in which 0.05 to 20 parts by weight of a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded to a block copolymer of 90% by weight, 1 to 80 parts by weight. The present invention relates to a thermosetting resin composition comprising both components. The composition of the present invention is characterized in that the diene rubber added to the thermosetting resin, that is, the modified block copolymer, is solid at room temperature and easy to handle;
The cured product has extremely excellent impact resistance as shown by Izot impact, and has good hardness or rigidity retention. The modified block copolymer constituting the composition of the present invention is a so-called thermoplastic rubber that exhibits melt fluidity when heated, and further has a carboxylic acid group or a derivative thereof bonded to the molecule. It has properties that are rich in reactivity, adhesiveness, and compatibility. It is believed that these properties play an important role in exerting the characteristics of the composition of the present invention. The present invention will be described in detail below. The thermosetting resin constituting component (a) of the present invention is at least one selected from diallyl phthalate resin, phenol resin, melamine resin, urea resin, epoxy resin, guanamine resin, vinyl ester resin, furan resin, and alkyd resin. Seed resin. The diallyl phthalate resin used in the present invention is a curable homopolymer or copolymer containing diallyl phthalate as a main component. Examples of monomers to be copolymerized include styrene, α-methylstyrene, acrylic esters, and methacrylic esters. The phenolic resin used in the present invention is a resin whose main component is a polymer obtained by a condensation reaction between phenols and aldehydes.
Those consisting of m-cresol, 3,5-xylenol, p-alkylphenol, resorcinol, etc., and formaldehyde are preferred. The phenol resin can be subjected to a condensation reaction using a conventional acidic or basic catalyst, and if necessary, a curing agent such as hexamethylenetetramine or a filler such as wood flour, pulp, or aggregate may be used. The melamine resin used in the present invention is a resin whose main component is a polymer obtained by an addition condensation reaction between melamine and an aldehyde, and formaldehyde is generally used as the aldehyde. or,
Melamine resins also include those co-condensed with urea and the like. Melamine resin is generally cured by heat, but it is also possible to use a curing agent if necessary. The urea resin used in the present invention is a resin whose main component is a polymer obtained by a condensation reaction of urea and aldehydes, and formaldehyde is generally used as the aldehyde. Further, urea resins include those co-condensed with thiourea, melamine, phenol, etc. The above melamine resin and urea resin may contain cellulose or the like, if necessary. The epoxy resin used in the present invention is a resin whose main component is a polymer obtained by ring-opening reaction of a compound containing at least two or more epoxy rings in one molecule. is a condensation product of epichlorohydrin and bisphenol A. Curing agents include amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, metaphenylenediamine, and diaminophenyl sulfone, acid anhydrides such as methylnadic anhydride, hexahydroanhydride, and urea. , melamine, phenolic resin, etc. can also be used.
In addition, epoxy resins include alicyclic epoxy resins, brominated epoxy resins, aliphatic epoxy resins,
Also included are polyfunctional epoxy resins. The guanamine resin used in the present invention is a resin whose main component is a polymer obtained by an addition condensation reaction of guanamines and aldehydes, and a common example is one consisting of benzoguanamine and formaldehyde. Guanamine resins also include those co-reacted or co-condensed with urea, melamine, thiourea, etc., and those etherified with butanol, methanol, etc. The vinyl ester resin used in the present invention is obtained by copolymerizing an epoxy resin having an acrylic double bond at the end with a vinyl monomer such as styrene, acrylic ester, methacrylic ester, or polyunsaturated acid ester. The furan resin that can be used in the present invention is a resin whose main component is furfuryl alcohol alone or a polymer obtained by a condensation reaction with formaldehyde. For example, furfuryl alcohol/furfural co-condensation resin, furfuryl alcohol resin , furfural/phenol cocondensation resin, furfural/ketone cocondensation resin, furfuryl alcohol/
Examples include urea copolymer resin and furfuryl alcohol/phenol cocondensation resin. The alkyd resin used in the present invention is a resin whose main component is a polymer obtained by a condensation reaction between a polybasic acid and a polyhydric alcohol. oil,
Fatty acids, rosin, ester rosin, etc. are generally used, and glycerin is generally used as the polyhydric alcohol. In the present invention, it is possible to use not only one type of the above thermosetting resin, but also a combination of two or more types in some cases. In addition, it is also possible to use it in combination with thermosetting resins such as unsaturated polyester and polyurethane. The modified block copolymer which is component (b) of the present invention is synthesized, for example, as follows. That is, a block copolymer composed of a vinyl aromatic compound polymer block and a polymer block mainly composed of a conjugated diene compound is selectively treated to an extent that the degree of unsaturation in the conjugated diene portion does not exceed 20%. Hydrogenated to produce vinyl aromatic compound polymer block A
and an olefin compound polymer block B having a degree of unsaturation not exceeding 20%.Then, by addition reaction with an unsaturated dicarboxylic acid or a derivative thereof, a modified block copolymer is obtained. The above block copolymer before hydrogenation contains at least one vinyl aromatic compound polymer block,
Preferably, it contains two or more polymer blocks, and at least one polymer block mainly composed of a conjugated diene compound. Here, the polymer block mainly composed of a conjugated diene is a polymer block having a composition in which the weight ratio of the vinyl aromatic compound and the conjugated diene compound is in the range of 0/100 to 50/50, preferably 0/100 to 40/60. It is a coalescing block, and the distribution of vinyl aromatic compounds in this block is random, tapered (monomer content increases or decreases along the molecular chain),
It may be partially block-shaped or any combination thereof. In addition, in the block copolymer before hydrogenation in the present invention, 50% by weight of the vinyl aromatic compound is contained in the transition region between the vinyl aromatic compound polymer block and the polymer block mainly composed of a conjugated diene compound. Although there may be a copolymer portion of a vinyl aromatic compound and a conjugated diene compound exceeding 100%, such a polymer portion shall be included in the polymer block mainly composed of the conjugated diene compound. In the above block copolymer, the weight ratio of the vinyl aromatic compound content to the conjugated diene compound content is in the range of 10/90 to 90/10, and 20/80 to
A range of 85/15 is preferred. As the vinyl aromatic compound constituting the block copolymer before hydrogenation, one or more compounds are selected from styrene, α-methylstyrene, vinyltoluene, etc. Among them, styrene is particularly preferred. The conjugated diene compound may be one or more selected from butadiene, isoprene, 1,3-pentadiene, etc., and butadiene and/or isoprene are particularly preferred.
The above block copolymer has a number average molecular weight of 20,000.
500,000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably in the range of 1.05 to 10. In addition, the molecular structure of the block copolymer is
It may be linear, branched, radial, or a combination thereof. Further, when butadiene is used as the conjugated diene compound in the block copolymer, the amount of 1 and 2 bonds in the microstructure of the butadiene portion is preferably in the range of 10 to 80%. When the modified block copolymer is required to have rubber elasticity, the amount of 1 and 2 bonds is particularly preferably in the range of 35 to 55%. When the above-mentioned block copolymer contains two or more blocks mainly composed of vinyl aromatic compound blocks or conjugated diene compounds, each block may have the same structure, and the monomer component content and their Each structure, such as the distribution in the molecular chain, the molecular weight of the block, and the microstructure, may be different. The above block copolymers usually contain benzene,
It is obtained by an anionic living polymerization method using an organic lithium compound such as butyllithium as a catalyst and a vinyl aromatic compound and a conjugated diene compound as monomers in an inert hydrocarbon solvent such as toluene, hexane, or cyclohexane. Furthermore, by reacting the block copolymer having a lithium active end obtained by the above method with a multifunctional coupling agent such as carbon tetrachloride, silicon tetrachloride, etc., a branched or radial block copolymer can be produced. It is also possible to do this. In the present invention, any polymer obtained by any polymerization method can be used as long as it falls within the above range. Furthermore, the block copolymers can be used not only as a single type but also as a mixture of two or more types. By hydrogenating the above block copolymer by a known method, for example, the method described in Japanese Patent Publication No. 42-8704, a portion not exceeding 20% of the aromatic double bonds of the vinyl aromatic compound block A can be obtained. and a partially hydrogenated block copolymer in which at least 80% of the aliphatic double bonds of the conjugated diene compound block B are hydrogenated is synthesized. In the present invention, the degree of unsaturation of block B refers to the proportion of carbon-carbon double bonds contained in block B, and this is determined by nuclear magnetic resonance absorption spectrum (NMR), infrared absorption spectrum (IR). It is measured by instrumental analysis such as, chemical analysis such as iodometry. The partially hydrogenated block copolymer is then modified by addition reaction with an unsaturated carboxylic acid or derivative thereof. Examples of unsaturated carboxylic acids or derivatives thereof to be added to the partially hydrogenated block copolymer include maleic acid, maleic anhydride, fumaric acid, itaconic acid, acrylic acid, crotonic acid,
Cis-4-cyclohexene-1,2-dicarboxylic acid and its anhydride, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid and its anhydride, maleimide, etc. Among these, maleic anhydride is particularly preferred. These unsaturated carboxylic acids or their derivatives can be used not only alone, but also as a mixture of two or more. The above-mentioned modified block copolymer, which is a component of the composition of the present invention, can be prepared by adding an unsaturated carboxylic acid or a derivative thereof to a partially hydrogenated block copolymer in a solution or melt state, using a radical initiator, or It can be obtained by adding it without using it. The method of producing these modified block copolymers is not particularly limited in the present invention, but the modified block copolymers obtained may contain undesirable components such as gels, or have a significantly increased melt viscosity and may be difficult to process. A manufacturing method that deteriorates properties is not preferred. A preferred method is, for example, a method in which an unmodified block copolymer is reacted with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical initiator in an extruder. The derivative of unsaturated carboxylic acid may be added to the block copolymer as a derivative, or it may be converted into the corresponding derivative by an appropriate reaction after adding the unsaturated carboxylic acid to the block copolymer. Such a reaction can also be carried out after mixing with a thermosetting resin to form a composition. The amount of unsaturated carboxylic acid or its derivative added to the block copolymer is 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the block copolymer. If the amount added is less than 0.05 parts by weight, the composition will have poor compatibility with the thermosetting resin,
Compared to unmodified conjugated diene polymers, the effect of improving impact resistance is small, and even if the amount added exceeds 20 parts by weight, there is almost no increase in impact resistance improvement compared to less than 20 parts by weight. do not have. At this time, unreacted thermosetting resin or its derivative may remain in the block copolymer, if necessary. Weight ratio of component (a) to component (b) in the composition of the present invention: 99/1 to 20/80, preferably 98/2 to 50/
50, more preferably from the range of 95/5 to 70/30. If the weight ratio is less than 99/1, the impact resistance will not be improved sufficiently, and if the weight ratio is more than 20/80, the rigidity will drop significantly, which is not preferable. The composition of the present invention includes a curing agent, various inorganic or organic fillers, inorganic or organic fiber reinforcing agents, vinyl monomers, pigments, colorants, lubricants, mold release agents, stabilizers, flame retardants, and coupling agents. It is also possible to add thermoplastic polymers, etc. The composition of the present invention can be cured in the presence or absence of a curing agent or curing accelerator, with or without heating, or by methods such as ultraviolet irradiation. The curing agent of the composition of the present invention is used as a thermosetting resin with excellent impact resistance in paints, laminates, molding materials, and the like. Examples are shown below, but these are intended to explain the present invention more specifically, and are not intended to limit the scope of the present invention. Examples 1, 2 and Comparative Examples 1 to 3 (1) Preparation of hydrogenated block copolymer N-butyllithium was used as a polymerization catalyst, and butadiene and tetrahydrofuran were used as vinyl content regulator in n-hexane or cyclohexane solvent. Block copolymers shown in Table 1 were synthesized by anionic block copolymerization with styrene.
【表】
ブタジエン部分のビニル含量はハンプトン法
で測定した。
次に、表１に示したブロツク共重合体を、ｎ
−ヘキサンおよびシクロヘキサンの混合溶媒中
で、ナフテン酸コバルトとトリエチルアルミニ
ウムを触媒として、水素圧７Kg／cm2、温度50℃
で５時間水素添加を行つて、ブタジエンブロツ
ク部分の二重結合の約90％が水素添加され、ス
チレンブロツク部分のベンゼン環はほとんど水
添されないで残つた、選択的に水添されたブロ
ツク共重合体を合成した。触媒残査の金属は塩
酸水溶液−メタノールで洗浄して除去した。
(2) 変性ブロツク共重合体の調製
上記(1)で合成した水添ブロツク共重合体100
重量部に対して2.5重量部の無水マレイン酸、
0.1重量部のパーヘキサ25B（日本油脂社製）を
均一に混合した後、窒素雰囲気下でスクリユー
型押出機（単軸、スクリユー直径20mm、Ｌ／Ｄ
＝24、フルフライト型スクリユー）に供給し、
シリンダー温度250℃でマレイン化反応を行つ
た。得られた変性ブロツク共重合体から、未反
応の無水マレイン酸を加熱減圧除去し、安定剤
として２，６−ジ−ターシヤリー−ブチル−４
−メチルフエノールを、重合体100重量部あた
り0.5重量部添加した。この変性ブロツク共重
合体を分析したところ、表２の結果が得られ
た。[Table] The vinyl content of the butadiene moiety was measured by the Hampton method. Next, the block copolymers shown in Table 1 were mixed with n
- In a mixed solvent of hexane and cyclohexane, using cobalt naphthenate and triethylaluminum as catalysts, hydrogen pressure 7 Kg/cm 2 and temperature 50°C.
After hydrogenation for 5 hours, about 90% of the double bonds in the butadiene block were hydrogenated, and the benzene rings in the styrene block remained almost unhydrogenated, resulting in a selectively hydrogenated block copolymer. Synthesized the union. The metal remaining on the catalyst was removed by washing with an aqueous hydrochloric acid solution and methanol. (2) Preparation of modified block copolymer Hydrogenated block copolymer 100 synthesized in (1) above
2.5 parts by weight of maleic anhydride,
After uniformly mixing 0.1 part by weight of Perhexa 25B (manufactured by NOF Corporation), a screw type extruder (single screw, screw diameter 20 mm, L/D
=24, full flight type screw),
The maleation reaction was carried out at a cylinder temperature of 250°C. From the obtained modified block copolymer, unreacted maleic anhydride was removed under reduced pressure and 2,6-di-tert-butyl-4 was added as a stabilizer.
- Methylphenol was added in an amount of 0.5 parts by weight per 100 parts by weight of the polymer. When this modified block copolymer was analyzed, the results shown in Table 2 were obtained.
【表】
無水マレイン酸の付加量は、ナトリウムメチ
ラートにより滴定により測定した。
(3) 組成物の調製
市販のエポキシ樹脂であるエピコート828（三
菱油化製）100重量部と、冷凍粉砕により80メ
ツシユ以下の粉状物とした変性ブロツク共重合
体（表２のＭ（）またはＭ（）10重量部とを
窒素雰囲気下、150℃で30分間撹拌混合した。
得られた混合物110重量部にアミノエチルピペ
ラジン硬化剤５重量部を添加混合し、200Kg／
cm2で90℃、１時間、次いで150℃、２時間の条
件で圧縮成形し硬化物Ｃ−１及びＣ−２を得
た。この硬化物の物性を測定した結果を実施例
１及び２として表３に示す。
変性ブロツク共重合体Ｍ（）またはＭ（）
のかわりに、表１のスチレン−ブタジエンブロ
ツク共重合体（）または（）を使用するこ
とをのぞいては、上記Ｃ−１及びＣ−２を得る
方法と全く同様な方法により硬化物Ｃ−３及び
Ｃ−４を得た。この硬化物の物性を比較例１及
び２として、表３に示す。また、ブロツク共重
合体のかわりに、市販の液状アクリロニトリル
−ブタジエン共重合体、ハイカーCTBNX
（グツドリツチ社製）を使用することをのぞい
ては、上記Ｃ−１及びＣ−２を得る方法と全く
同様な方法により、硬化物Ｃ−５を得た。この
硬化物の物性を比較例３として表３に示す。
表３より明らかなように、本発明の範囲内の
硬化物Ｃ−１及びＣ−２は、アイゾツト衝撃値
が高く、かつまげ弾性率の保持特性に優れてい
る。[Table] The amount of maleic anhydride added was determined by titration with sodium methylate. (3) Preparation of composition 100 parts by weight of Epicoat 828 (manufactured by Mitsubishi Yuka Co., Ltd.), a commercially available epoxy resin, and a modified block copolymer (M () in Table 2) made into a powder of 80 mesh or less by freeze-pulverization. Alternatively, 10 parts by weight of M() were stirred and mixed at 150° C. for 30 minutes under a nitrogen atmosphere.
5 parts by weight of an aminoethylpiperazine curing agent was added to 110 parts by weight of the obtained mixture, and the mixture was mixed to give 200Kg/
Compression molding was performed at 90° C. for 1 hour and then at 150° C. for 2 hours to obtain cured products C-1 and C-2. The results of measuring the physical properties of this cured product are shown in Table 3 as Examples 1 and 2. Modified block copolymer M() or M()
The cured product C-3 was obtained by the same method as that used to obtain C-1 and C-2 above, except that the styrene-butadiene block copolymer () or () shown in Table 1 was used instead. and C-4 were obtained. The physical properties of this cured product are shown in Table 3 as Comparative Examples 1 and 2. In addition, instead of the block copolymer, commercially available liquid acrylonitrile-butadiene copolymer, Hiker CTBNX
Cured product C-5 was obtained in exactly the same manner as the method for obtaining C-1 and C-2 above, except that C-1 (manufactured by Gutsudoritsu) was used. The physical properties of this cured product are shown in Table 3 as Comparative Example 3. As is clear from Table 3, the cured products C-1 and C-2 within the range of the present invention have a high Izot impact value and are excellent in retaining the elastic modulus.
【表】【table】
【表】
実施例 ３
ジアリルフタレート樹脂80重量部と実施例１で
使用した変性ブロツク共重合体（Ｍ（））20重量
部とを混合し、ジクミルパーオキサイド３重量部
を添加した後、射出成形（東芝機械IR−80A）し
て硬化物Ｃ−６を得た。
射出条件は、射出圧1300Kg／cm2、シリンダー温
度90℃、金型温度190℃、硬化時間60秒であつた。
この硬化物（Ｃ−６）のアイゾツト衝撃値は
3.5Kg・cm／cm（ノツチ付）であつた。
変性ブロツク共重合体を添加しない以外は硬化
物（Ｃ−６）を得た方法と同様にして硬化物（Ｃ
−７）を得た。この硬化物のアイゾツト衝撃値は
1.5Kg・cm／cm（ノツチ付）であつた。
変性ブロツク共重合体のかわりに液状のアクリ
ロニトリル−ブタジエン共重合体ハイカー
CTBNXを用い、硬化物（Ｃ−６）と同様にして
硬化物（Ｃ−８）を得た。この硬化物のアイゾツ
ト衝撃値は1.9Kg・cm／cm（ノツチ付）であつた。
実施例 ４
市販のフエノール樹脂であるスミコンPM−
400（住友ベークライト社製）90重量部と実施例１
で使用した変性ブロツク共重合体（Ｍ（））10重
量部を80℃でロール混合した。得られた混合物を
圧力200Kg／cm2、温度160℃、時間６分で圧縮成形
して硬化物（Ｃ−９）を得た。この硬化物のアイ
ゾツト衝撃値は5.8Kg・cm／cm（ノツチ付）であ
つた。
変性ブロツク共重合体を添加しない硬化物（Ｃ
−10）のアイゾツト衝撃値は1.9Kg・cm／cm（ノ
ツチ付）であつた。
変性ブロツク共重合体のかわりに液状のアクリ
ロニトリル−ブタジエン共重合体ハイカー
CTBNXを用いた硬化物（Ｃ−11）のアイゾツト
衝撃値は3.7Kg・cm／cm（ノツチ付）であつた。
実施例 ５
メラミン35重量部と30％の中性ホルマリン65重
量部を加熱撹拌してメラミン樹脂67重量部を得
た。得られたメラミン樹脂にセルロース粉末13重
量部と実施例２の変性ブロツク共重合体（Ｍ
（））10重量部を添加混合した。この混合物を乾
燥し、次いで圧力200Kg／cm2、温度180℃、時間４
分で圧射成形し、硬化物（Ｃ−12）を得た。
この硬化物のアイゾツト衝撃値は3.5Kg・cm／
cm（ノツチ付）であつた。また変性ブロツク共重
合体を添加しない硬化物（Ｃ−13）のアイゾツト
衝撃値は2.2Kg・cm／cm（ノツチ付）であつた。
実施例 ６
尿素１モルとホルムアルデヒド1.5モルを反応
させた得たユリア樹脂50重量部のセルロース粉末
40重量部と実施例１の変性ブロツク共重合体（Ｍ
（））10重量部を添加し、80℃でロール混合し
た。この混合物を圧力200Kg／cm3、温度180℃、時
間10分で圧縮成形して硬化物（Ｃ−14）を得た。
この硬化物のアイゾツト衝撃値は3.1Kg・cm／
cm（ノツチ付）であつた。また変性ブロツク共重
合体を添加しない硬化物（Ｃ−15）のアイゾツト
衝撃値は1.5Kg・cm／cm（ノツチ付）であつた。
実施例 ７
ビニルエステル樹脂（45重量％のスチレン溶
液）60重量部に実施例１の変性ブロツク共重合体
（Ｍ（））の30重量％スチレン溶液40重量部を添
加し、更に炭酸カルシウム150重量部およびｔ−
ブチルパーベンゾエート２重量部を加えた。この
混合物を圧力200Kg／cm2、温度160℃、時間６分で
圧縮成形して硬化物（Ｃ−16）を得た。この硬化
物のアイゾツト衝撃値は3.4Kg・cm／cm（ノツチ
付）であつた。変性ブロツク共重合体を添加しな
い硬化物（Ｃ−17）のアイゾツト衝撃値は2.3
Kg・cm／cm（ノツチ付）であつた。
実施例 ８
実施例１、２の変性ブロツク共重合体の調製に
用いたのと同じ水添ブロツク共重合体100重量部
に対して、2.5重量部のアクリル酸を含浸させ、
0.1重量部のパーヘキサ25Bを均一に混合した後、
窒素雰囲気下でスクリユー型押出機に供給し、シ
リンダー温度210℃で変性反応を行なつた。得ら
れた変性ブロツク共重合体から、未反応のアクリ
ル酸を加熱減圧除去し、安定剤として２，６−ジ
−ターシヤリー−ブチル−４−メチルフエノール
を、重合体100重量部あたり0.5重量部添加した。
この変性ブロツク共重合体を分析したところ、表
４の結果が得られた。[Table] Example 3 80 parts by weight of diallyl phthalate resin and 20 parts by weight of the modified block copolymer (M()) used in Example 1 were mixed, 3 parts by weight of dicumyl peroxide was added, and injection was carried out. A cured product C-6 was obtained by molding (Toshiba Machine IR-80A). The injection conditions were: injection pressure 1300 Kg/cm 2 , cylinder temperature 90°C, mold temperature 190°C, and curing time 60 seconds. The Izod impact value of this cured product (C-6) is
It was 3.5Kg・cm/cm (with notch). A cured product (C-6) was obtained in the same manner as the cured product (C-6) except that the modified block copolymer was not added.
-7) was obtained. The Izot impact value of this cured product is
It was 1.5Kg・cm/cm (with notch). Liquid acrylonitrile-butadiene copolymer hiker instead of modified block copolymer
A cured product (C-8) was obtained using CTBNX in the same manner as the cured product (C-6). The Izo impact value of this cured product was 1.9 kg·cm/cm (with notches). Example 4 Sumikon PM-, a commercially available phenolic resin
400 (manufactured by Sumitomo Bakelite) 90 parts by weight and Example 1
10 parts by weight of the modified block copolymer (M()) used in 1 were roll mixed at 80°C. The resulting mixture was compression molded at a pressure of 200 kg/cm 2 , a temperature of 160° C., and a time of 6 minutes to obtain a cured product (C-9). The Izo impact value of this cured product was 5.8 kg·cm/cm (with notches). Cured product without added modified block copolymer (C
-10) had an Izot impact value of 1.9Kg・cm/cm (with notch). Liquid acrylonitrile-butadiene copolymer hiker instead of modified block copolymer
The Izo impact value of the cured product (C-11) using CTBNX was 3.7 kg·cm/cm (with notches). Example 5 35 parts by weight of melamine and 65 parts by weight of 30% neutral formalin were heated and stirred to obtain 67 parts by weight of melamine resin. 13 parts by weight of cellulose powder and the modified block copolymer of Example 2 (M
()) was added and mixed. The mixture was dried, then at a pressure of 200 Kg/cm 2 and a temperature of 180°C for 4 hours.
The cured product (C-12) was obtained by pressure injection molding. The Izot impact value of this cured product is 3.5Kg・cm/
cm (with a notch). The cured product (C-13) to which no modified block copolymer was added had an Izot impact value of 2.2 kg·cm/cm (with notches). Example 6 Cellulose powder containing 50 parts by weight of urea resin obtained by reacting 1 mol of urea with 1.5 mol of formaldehyde
40 parts by weight and the modified block copolymer of Example 1 (M
()) was added and roll mixed at 80°C. This mixture was compression molded at a pressure of 200 kg/cm 3 , a temperature of 180° C., and a time of 10 minutes to obtain a cured product (C-14). The Izot impact value of this cured product is 3.1Kg・cm/
cm (with a notch). The cured product (C-15) to which no modified block copolymer was added had an Izot impact value of 1.5 kg·cm/cm (with notches). Example 7 40 parts by weight of a 30% by weight styrene solution of the modified block copolymer (M()) of Example 1 was added to 60 parts by weight of vinyl ester resin (45% by weight styrene solution), and further 150 parts by weight of calcium carbonate was added. part and t-
Two parts by weight of butyl perbenzoate were added. This mixture was compression molded at a pressure of 200 kg/cm 2 , a temperature of 160° C., and a time of 6 minutes to obtain a cured product (C-16). The Izo impact value of this cured product was 3.4 kg·cm/cm (with notches). The Izot impact value of the cured product (C-17) without the addition of modified block copolymer is 2.3
Kg・cm/cm (with notch). Example 8 100 parts by weight of the same hydrogenated block copolymer used in the preparation of the modified block copolymers in Examples 1 and 2 was impregnated with 2.5 parts by weight of acrylic acid,
After uniformly mixing 0.1 part by weight of Perhexa 25B,
The mixture was supplied to a screw type extruder under a nitrogen atmosphere, and a modification reaction was carried out at a cylinder temperature of 210°C. Unreacted acrylic acid was removed under reduced pressure from the obtained modified block copolymer, and 0.5 parts by weight of 2,6-di-tert-butyl-4-methylphenol was added as a stabilizer per 100 parts by weight of the polymer. did.
When this modified block copolymer was analyzed, the results shown in Table 4 were obtained.
【表】
アクリル酸の付加量は、ナトリウムメチラート
による滴定により測定した。
変性ブロツク共ブロツク共重合体としてＮ
（）、Ｎ（）を用いること以外は、実施例１、
２と同様にして、エピコト828との組成物から硬
化物（Ｃ−18、Ｃ−19）を得た。Ｎ（）から得
られた硬化物（Ｃ−18）のアイゾツト衝撃値は
4.3Kg・cm／cm（ノツチ付）、Ｎ（）から得られ
た硬化物（Ｃ−19）のアイゾツト衝撃値は4.5
Kg・cm／cm（ノツチ付）であつた。[Table] The amount of acrylic acid added was measured by titration with sodium methylate. N as a modified block copolymer
Example 1 except that () and N() are used,
In the same manner as in Example 2, cured products (C-18, C-19) were obtained from the composition with Epicoto 828. The Izot impact value of the cured product (C-18) obtained from N() is
4.3Kg・cm/cm (with notch), the Izot impact value of the cured product (C-19) obtained from N() is 4.5
Kg・cm/cm (with notch).
Claims (1)
脂、メラミン樹脂、ユリア樹脂、エポキシ樹
脂、ビニルエステル樹脂、グアナミン樹脂、フ
ラン樹脂、アルキツド樹脂から選ばれる少くと
も１種の樹脂、99〜20重量部 (b) 少くとも１つのビニル芳香族化合物重合体ブ
ロツクＡと、少くとも１つの不飽和度が20％を
こえないオレフイン化合物重合体ブロツクＢと
からなり、ビニル芳香族化合物の含有量が10〜
90重量％であるブロツク共重合体に、カルボン
酸基またはその誘導体基を含有する分子単位が
ブロツク共重合体100重量部あたり0.05〜20重
量部結合した変性ブロツク共重合体、１〜80重
量部 からなる熱硬化性樹脂組成物。[Scope of Claims] 1 (a) At least one resin selected from diallyl phthalate resin, phenol resin, melamine resin, urea resin, epoxy resin, vinyl ester resin, guanamine resin, furan resin, and alkyd resin, 99- 20 parts by weight (b) Consisting of at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B in which the degree of unsaturation does not exceed 20%, the content of vinyl aromatic compounds is 10~
A modified block copolymer in which 0.05 to 20 parts by weight of a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded to a block copolymer of 90% by weight, 1 to 80 parts by weight. A thermosetting resin composition consisting of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56115315A JPS5817160A (en) | 1981-07-24 | 1981-07-24 | Thermosetting resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56115315A JPS5817160A (en) | 1981-07-24 | 1981-07-24 | Thermosetting resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5817160A JPS5817160A (en) | 1983-02-01 |
| JPS6365108B2 true JPS6365108B2 (en) | 1988-12-14 |
Family
ID=14659568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56115315A Granted JPS5817160A (en) | 1981-07-24 | 1981-07-24 | Thermosetting resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5817160A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63319297A (en) * | 1987-06-19 | 1988-12-27 | Toray Ind Inc | Method and device for producing organic crystal |
| US5008334A (en) * | 1989-02-28 | 1991-04-16 | Basf Corporation | Resins of epoxy/aromatic diol copolymer and block copolymer of epoxy/aromatic diol copolymer and a epoxy-capped polybutadiene (co)polymer |
| US5349015A (en) * | 1989-12-08 | 1994-09-20 | Shell Oil Company | Melt blending acid or anhydride-crafted block copolymer pellets with epoxy resin |
| US5342885A (en) * | 1989-12-08 | 1994-08-30 | Shell Oil Company | Epoxy resin coating with COOH-grated hydrogenated block copolymer |
| US5115019A (en) * | 1990-03-30 | 1992-05-19 | Shell Oil Company | Carboxy-functional hydrogenated block copolymer dispersed in epoxy resin |
| USH1405H (en) * | 1992-04-09 | 1995-01-03 | Shell Oil Company | Epoxy resin composition |
| DE102004031189A1 (en) | 2004-06-28 | 2006-01-19 | Tesa Ag | Heat-activated and crosslinkable adhesive tape for the bonding of electronic components and printed conductors |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5560511A (en) * | 1978-10-31 | 1980-05-07 | Asahi Chem Ind Co Ltd | Modified block copolymer resin composition and its preparation |
| JPS55165731A (en) * | 1979-06-13 | 1980-12-24 | Natsume Seisakusho Kk | Gauge hanggdown method in pilot animal breeding shelf |
| JPS56115346A (en) * | 1980-02-15 | 1981-09-10 | Asahi Chem Ind Co Ltd | Thermosetting resin |
| JPS587443A (en) * | 1981-07-06 | 1983-01-17 | Asahi Chem Ind Co Ltd | Composition consisting of thermoplastic polymer |
-
1981
- 1981-07-24 JP JP56115315A patent/JPS5817160A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5560511A (en) * | 1978-10-31 | 1980-05-07 | Asahi Chem Ind Co Ltd | Modified block copolymer resin composition and its preparation |
| JPS55165731A (en) * | 1979-06-13 | 1980-12-24 | Natsume Seisakusho Kk | Gauge hanggdown method in pilot animal breeding shelf |
| JPS56115346A (en) * | 1980-02-15 | 1981-09-10 | Asahi Chem Ind Co Ltd | Thermosetting resin |
| JPS587443A (en) * | 1981-07-06 | 1983-01-17 | Asahi Chem Ind Co Ltd | Composition consisting of thermoplastic polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5817160A (en) | 1983-02-01 |
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