JPH03174424A - Radical-polymerizable unsaturated resin composition, molding material, shrinkage-lowering agent and their preparation - Google Patents
Radical-polymerizable unsaturated resin composition, molding material, shrinkage-lowering agent and their preparationInfo
- Publication number
- JPH03174424A JPH03174424A JP2253968A JP25396890A JPH03174424A JP H03174424 A JPH03174424 A JP H03174424A JP 2253968 A JP2253968 A JP 2253968A JP 25396890 A JP25396890 A JP 25396890A JP H03174424 A JPH03174424 A JP H03174424A
- Authority
- JP
- Japan
- Prior art keywords
- polymerizable unsaturated
- resin composition
- unsaturated resin
- radically polymerizable
- radical polymerization
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 28
- 239000012778 molding material Substances 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- 229920001400 block copolymer Polymers 0.000 claims abstract description 50
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 37
- 238000009833 condensation Methods 0.000 claims abstract description 34
- 230000005494 condensation Effects 0.000 claims abstract description 34
- 125000000524 functional group Chemical group 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 150000001993 dienes Chemical class 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 31
- 239000004793 Polystyrene Substances 0.000 claims description 27
- 229920002223 polystyrene Polymers 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000004417 polycarbonate Substances 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 17
- -1 azo compound Chemical group 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000515 polycarbonate Polymers 0.000 claims description 12
- 238000010526 radical polymerization reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229920001692 polycarbonate urethane Polymers 0.000 claims description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 150000002484 inorganic compounds Chemical class 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 9
- 229920006337 unsaturated polyester resin Polymers 0.000 abstract description 8
- 239000007869 azo polymerization initiator Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 28
- 239000000047 product Substances 0.000 description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000004412 Bulk moulding compound Substances 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 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 7
- 229920006305 unsaturated polyester Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 229920001610 polycaprolactone Polymers 0.000 description 5
- 239000004632 polycaprolactone Substances 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 229920002689 polyvinyl acetate Polymers 0.000 description 5
- 239000011118 polyvinyl acetate Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000001530 fumaric acid Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 229920002633 Kraton (polymer) Polymers 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000005474 octanoate group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-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
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- XPZBNIUWMDJFPW-UHFFFAOYSA-N 2,2,3-trimethylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1(C)C XPZBNIUWMDJFPW-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 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
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NBICYCZLCAMSBG-UHFFFAOYSA-L [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O NBICYCZLCAMSBG-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- HHZAIOOQYMFSFC-UHFFFAOYSA-L cobalt(2+);3-oxobutanoate Chemical compound [Co+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O HHZAIOOQYMFSFC-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 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 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FPCCSQOGAWCVBH-UHFFFAOYSA-N ketanserin Chemical compound C1=CC(F)=CC=C1C(=O)C1CCN(CCN2C(C3=CC=CC=C3NC2=O)=O)CC1 FPCCSQOGAWCVBH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- YZBNXQLCEJJXSC-UHFFFAOYSA-N miliacin Chemical compound C12CCC3C4=CC(C)(C)CCC4(C)CCC3(C)C1(C)CCC1C2(C)CCC(OC)C1(C)C YZBNXQLCEJJXSC-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 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
- WTNTZFRNCHEDOS-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylpropanamide Chemical compound CC(C)C(=O)NCCO WTNTZFRNCHEDOS-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 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
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229940040850 prosol Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ラジカル重合による硬化に際して収縮がなく
、表面平滑性の優れた成形品を与えることのできる成形
材料に適するラジカル重合性不飽和樹脂組成物、及びそ
のためのラジカル重合硬化低収縮剤として使用されるブ
ロック共重合体の製法に関するものであって、さらに詳
しくは上記低収縮剤として飽和ポリエステル、ポリエー
テル、ポリカーボネートあるいはポリウレタン等の縮合
系重合体とビニル系重合体とをブロック重合成分に有す
るブロック共重合体の製法を提供するとともに、この低
収縮剤を含有するラジカル重合性不飽和樹脂Ｍｉ或物を
提供し、さらにこれにポリスチレン、スチレン−共役ジ
エンブロック共重合体を併用できるようにしたものであ
る。Detailed Description of the Invention [Industrial Application Field] The present invention provides a radically polymerizable unsaturated resin that does not shrink when cured by radical polymerization and is suitable as a molding material that can provide molded products with excellent surface smoothness. The present invention relates to a composition and a method for producing a block copolymer used as a radical polymerization cured low-shrinkage agent for the composition, and more specifically, the low-shrinkage agent is a condensation polymer such as saturated polyester, polyether, polycarbonate, or polyurethane. In addition to providing a method for producing a block copolymer having a copolymer and a vinyl polymer as block polymerization components, the present invention also provides a radically polymerizable unsaturated resin (Mi) containing this low shrinkage agent, and further includes polystyrene, styrene, etc. - A conjugated diene block copolymer can be used in combination.
不飽和ポリエステル樹脂等のラジカル重合性樹脂組成物
は、低粘度で安価なために、種々の用途に用いられてい
るが、その通常の含有成分であるスチレンが重合すると
必然的に体積収縮をおこし、成形品にひけ、そり、クラ
ックを生じさせる原因になっている。この欠点を少なく
するために、不飽和ポリエステル樹脂を用いたシート・
モールディング・コンパウンド（ＳＭＣと略す）やバル
ク・モルディング・コンパウンド（ＢＭＣと略ス）には
、■ポリ酢酸ビニル、飽和ポリエステルのように相溶す
るもの、■ポリスチレン、ポリメチルメタクリレート、
スチレン−ブタジェンブロック共重合体のように、不飽
和ポリエステル樹脂組成物中のモノマーには溶解するが
、ポリマーに相溶せず、液滴分散しているもの、■ポリ
エチレン粉末のように固形のまま分散しているものなど
のタイプに分けられる。Radical polymerizable resin compositions such as unsaturated polyester resins are used for a variety of purposes because they have low viscosity and are inexpensive, but when styrene, which is a common ingredient in them, polymerizes, volumetric shrinkage inevitably occurs. This causes sink marks, warpage, and cracks in molded products. In order to reduce this drawback, sheets and
Molding compounds (abbreviated as SMC) and bulk molding compounds (abbreviated as BMC) include: ■ Compatible materials such as polyvinyl acetate and saturated polyester; ■ Polystyrene, polymethyl methacrylate,
Styrene-butadiene block copolymer, which dissolves in the monomer in the unsaturated polyester resin composition, but is not compatible with the polymer and is dispersed in droplets; It can be divided into different types, such as those that are dispersed.
〔発明が解決しようとする課題〕
しかしながら、これらの熱可塑性樹脂は一長一短がある
。すなわち、例えば■のポリ酢酸ビニルはラジカル硬化
時の収縮を抑制する、いわゆる低収縮付与効果が大きく
、平滑な表面が得られるけれども、機械的強度、着色性
、耐煮沸性が悪い。[Problems to be Solved by the Invention] However, these thermoplastic resins have advantages and disadvantages. That is, for example, polyvinyl acetate (3) has a large effect of suppressing shrinkage during radical curing, that is, a so-called low shrinkage imparting effect, and a smooth surface can be obtained, but it has poor mechanical strength, colorability, and boiling resistance.
また、■のポリスチレンは機械的強度、着色性、耐煮沸
性に優れるけれども、低収縮付与効果に劣る。ポリメチ
ルメタクリレートはポリスチレンとポリ酢酸ビニルの中
間の性能しか得られない。また、スチレン−ブタジェン
ブロック共重合体は低収縮付与効果に非常に優れ、平滑
な表面が得られるが、不飽和ポリエステル樹脂との相溶
性が悪いために、ＳＭＣ製造樹脂に配合物中で相分離を
起し、均質な成形品が得られない欠点がある。また、■
のポリエチレンの場合は、着色性は良好であるが、低収
縮付与効果が低く、塗装性が悪い。Furthermore, polystyrene (2) has excellent mechanical strength, colorability, and boiling resistance, but is inferior in the effect of imparting low shrinkage. Polymethyl methacrylate has performance that is between that of polystyrene and polyvinyl acetate. In addition, styrene-butadiene block copolymers have excellent low-shrinkage imparting effects and can provide smooth surfaces, but because they have poor compatibility with unsaturated polyester resins, they are not compatible with SMC-manufactured resins in formulations. There is a drawback that separation occurs and a homogeneous molded product cannot be obtained. Also,■
In the case of polyethylene, the colorability is good, but the effect of imparting low shrinkage is low and the paintability is poor.
このように、ラジカル重合硬化時に低収縮付与効果を与
える、いわゆる低収縮剤は、一長一短あるので、要求性
能や用途に応じて使い分けている。As described above, so-called low-shrinkage agents that impart a low-shrinkage imparting effect during radical polymerization curing have advantages and disadvantages, so they are used depending on the required performance and application.
〔課題を解決するための手段］
かかる実情に鑑み、本発明者らは鋭意研究した結果、従
来の低収縮剤の上記欠点を解決する重合体、即ちラジカ
ル重合性不飽和樹脂組成物に低収縮効果を付与し、さら
に不飽和樹脂と相溶性に乏しいポリスチレンやスチレン
−ブタジェンブロック共重合体などの均一分散性を向上
させるブロック共重合体を見出し、本発明を完成するに
いたったものである。[Means for Solving the Problems] In view of the above circumstances, the present inventors have conducted intensive research and have developed a polymer that solves the above-mentioned drawbacks of conventional low-shrinkage agents, that is, a radically polymerizable unsaturated resin composition with low-shrinkage properties. The present inventors discovered a block copolymer that can improve the uniform dispersibility of polystyrene and styrene-butadiene block copolymers, which have poor compatibility with unsaturated resins, and have completed the present invention. .
すなわち、本発明は、（Ａ）ラジカル重合性不飽和樹脂
と、（Ｂ）重合性不飽和単量体と、（Ｃ）縮合系重合ブ
ロックとビニル系重合ブロックとを有するブロック共重
合体とを含有することを特徴とするラジカル重合性不飽
和樹脂組成物、例えばブロック共重合体が、縮合系重合
体アゾ系ラジカル重合開始剤を用いてビニル系単量体を
重合させることにより得られるものであるラジカル重合
性不飽和樹脂組成物、縮合系重合体アゾ系ラジカル重合
開始剤が、官能基含有縮合系重合体と官能基含有アゾ系
ラジカル重合開始剤とを反応させることにより得られる
ものであるラジカル重合性不飽和樹脂組成物、官能基含
有縮合系重合体が、飽和ポリエステル、ポリエーテル及
びポリカーボネート、ポリウレタンから選ばれる少なく
とも１種の重合体であるラジカル重合性不飽和樹脂組成
物、特に組成比が、（Ａ）ラジカル重合性不飽和樹脂２
０〜５５重量部と、（Ｂ）重合性不飽和単量体３０〜６
０重量部と、（Ｃ）縮合系重合体とビニル系重合体とを
ブロック重合成分として有するブロック共重合体２〜２
５重量部とを含有するラジカル重合性不飽和樹脂組成物
、さらには、（Ｄ）ポリスチレン、スチレン−共役ジエ
ンブロック共重合体及びスチレン−水添共役ジエンブロ
ック共重合体の少なくとも１種を含有する底形材料用の
ラジカル重合性不飽和樹脂組成物を提供するものである
。That is, the present invention comprises (A) a radically polymerizable unsaturated resin, (B) a polymerizable unsaturated monomer, and (C) a block copolymer having a condensation polymer block and a vinyl polymer block. A radically polymerizable unsaturated resin composition, such as a block copolymer, is obtained by polymerizing a vinyl monomer using a condensation polymer azo radical polymerization initiator. A certain radically polymerizable unsaturated resin composition, a condensation polymer azo radical polymerization initiator, is obtained by reacting a functional group-containing condensation polymer with a functional group-containing azo radical polymerization initiator. A radically polymerizable unsaturated resin composition, a radically polymerizable unsaturated resin composition in which the functional group-containing condensation polymer is at least one polymer selected from saturated polyester, polyether, polycarbonate, and polyurethane, especially composition ratio However, (A) radically polymerizable unsaturated resin 2
0 to 55 parts by weight, and (B) 30 to 6 parts by weight of polymerizable unsaturated monomer
0 parts by weight, and (C) block copolymers 2 to 2 having a condensation polymer and a vinyl polymer as block polymerization components
5 parts by weight, and further contains (D) at least one of polystyrene, styrene-conjugated diene block copolymer, and styrene-hydrogenated conjugated diene block copolymer. The present invention provides a radically polymerizable unsaturated resin composition for bottom-shaped materials.
また、官能基含有縮合系重合体と官能基含有アゾ系ラジ
カル重合開始剤とを反応して得られる縮合系重合体含有
アゾラジカル重合開始剤を用い、好ましくは次いでビニ
ル系単量体に該ラジカル重合開始剤を溶解し、ビニル単
量体を重合反応させることを特徴とするラジカル重合性
不飽和樹脂組成物の低収縮剤の製造法を提供するもので
ある。Further, an azo radical polymerization initiator containing a condensation polymer obtained by reacting a functional group-containing condensation polymer with a functional group-containing azo radical polymerization initiator is preferably used, and then the vinyl monomer is subjected to the radical polymerization. The present invention provides a method for producing a low-shrinkage agent for a radically polymerizable unsaturated resin composition, which comprises dissolving an initiator and subjecting a vinyl monomer to a polymerization reaction.
（構成） 次に本発明の詳細な説明する。(composition) Next, the present invention will be explained in detail.
本発明のラジカル重合性不飽和樹脂（八）としては、不
飽和ポリエステル、ビニルエステル樹脂がポリマー成分
として挙げられる。ビニルエステル樹脂としては、エポ
キシ樹脂とアクリル酸又はメタクリル酸との反応により
得られるものが挙げられ、エポキシ樹脂としてはビスフ
ェノールＡ型、ノボラック型、グリシジルエステル型、
グリシジルアミン型、レゾルシン型などの樹脂が用いら
れる。Examples of the radically polymerizable unsaturated resin (8) of the present invention include unsaturated polyester and vinyl ester resins as polymer components. Examples of vinyl ester resins include those obtained by reacting epoxy resin with acrylic acid or methacrylic acid, and examples of epoxy resins include bisphenol A type, novolac type, glycidyl ester type,
Resins such as glycidylamine type and resorcin type are used.
また、不飽和ポリエステルとしては、２価以上のカルボ
ン酸及びその無水物と２価以上のアルコールから得られ
るポリエステルであり、一部エチレン系不飽和基を有す
るものである。カルボン酸の例としてはマレイン酸、無
水マレイン酸、フマール酸等の不飽和二塩基酸、フター
ル酸、無水フタール酸、イソフタール酸、テトラヒドロ
無水フタール酸、コハク酸、アジピン酸等の芳香族或い
は飽和二塩基酸が挙げられ、アルコール類の例としては
エチレングリコール、ジエチレングリコール、プロピレ
ングリコール、ジプロピレングリコール、１，３−又は
１，４−ブチレングリコール、ネオペンチルグリコール
、水添ビスフェノールＡ１グリセリン等が挙げられる。Further, the unsaturated polyester is a polyester obtained from a divalent or higher carboxylic acid and its anhydride and a divalent or higher alcohol, and partially has an ethylenically unsaturated group. Examples of carboxylic acids include unsaturated dibasic acids such as maleic acid, maleic anhydride, and fumaric acid; aromatic or saturated dibasic acids such as phthalic acid, phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, succinic acid, and adipic acid; Examples of the alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3- or 1,4-butylene glycol, neopentyl glycol, hydrogenated bisphenol A1 glycerin, and the like.
不飽和ポリエステルの分子量は、好ましくは２０００〜
５０００であり、また二重結合１個当りの分子量はプロ
ピレングリコ−ルーフマール酸型Ｆｍ合物の１５６を最
低としてできるかぎり低い方が表面平滑性が良好である
。その使用量は組成物１００重量部中２０〜５５重量部
であり、好ましくは３０〜４５重量部である。２０重量
部以下では機械的強度に劣り、また、５５重量部以上で
は組成物の粘度が高く、ＳＭＣ，ＢＭＣ製造時のガラス
繊維の含浸性が劣る。The molecular weight of the unsaturated polyester is preferably 2000 to 2000.
5000, and the surface smoothness is better when the molecular weight per double bond is as low as possible, with the minimum being 156 for the propylene glyco-roofmaric acid type Fm compound. The amount used is 20 to 55 parts by weight, preferably 30 to 45 parts by weight, based on 100 parts by weight of the composition. If it is less than 20 parts by weight, the mechanical strength will be poor, and if it is more than 55 parts by weight, the viscosity of the composition will be high and the impregnating properties of glass fibers during production of SMC and BMC will be poor.
重合性不飽和単量体（Ｂ）としては、スチレン、α−ス
チレン、ビニルトルエン、クロロスチレンの如き芳香族
ビニル、メチル（メタ）アクリレート、エチル（メタ）
アクリレート、ブチル（メタ）アクリレートの如き（メ
タ）アクリル酸エステル類が用いられる。好ましくはス
チレンである。Examples of the polymerizable unsaturated monomer (B) include aromatic vinyl such as styrene, α-styrene, vinyltoluene, and chlorostyrene, methyl (meth)acrylate, and ethyl (meth)acrylate.
(Meth)acrylic acid esters such as acrylate and butyl (meth)acrylate are used. Preferably it is styrene.
重合性不飽和単量体（Ｂ）の使用量は、組成物１００重
量部中３０〜６０重量部であり、好ましくは４０〜５５
重量部である。３０重量部以下では組成物の粘度が非常
に高く、ガラス繊維への浸透が悪い。また、６０重量部
以上では成形物の収縮が大きく、表面平滑性が劣る。The amount of the polymerizable unsaturated monomer (B) used is 30 to 60 parts by weight, preferably 40 to 55 parts by weight, based on 100 parts by weight of the composition.
Parts by weight. If it is less than 30 parts by weight, the viscosity of the composition is very high and penetration into glass fibers is poor. Moreover, if it exceeds 60 parts by weight, the molded product will shrink significantly and its surface smoothness will be poor.
本発明に用いられるブロック共重合体（Ｃ）は、縮合系
重合体アゾ系ラジカル重合開始剤を台底する工程、それ
を用いてビニル系単量体を重合させる工程とにより得ら
れるものである。その縮合系重合体アゾ系ラジカル重合
開始剤は、官能基含有縮合系重合体と官能基含有アゾ系
ラジカル重合開始剤とを反応させることにより得られる
ものである。官能基含有アゾ系ラジカル重合開始剤は、
活性水素含有アゾ化合物、またはＣＯＯＨ基含有アゾ化
合物が挙げられる。The block copolymer (C) used in the present invention is obtained by a step of adding a condensation polymer azo radical polymerization initiator and a step of polymerizing a vinyl monomer using the same. . The condensation polymer azo radical polymerization initiator is obtained by reacting a functional group-containing condensation polymer with a functional group-containing azo radical polymerization initiator. The functional group-containing azo radical polymerization initiator is
Examples include active hydrogen-containing azo compounds and COOH group-containing azo compounds.
官能基含有縮合系重合体とは、ポリブタジェン、シリコ
ン系ポリマー、飽和ポリエステル、ポリエーテル、ポリ
カーボネート、及びポリウレタン、好ましくは飽和ポリ
エステル、ポリエーテル、ポリカーボネート、及びポリ
ウレタンから選ばれる少なくとも１種の重合体で、主と
して脂肪族系原料の重合体である。The functional group-containing condensation polymer is polybutadiene, silicone polymer, saturated polyester, polyether, polycarbonate, and polyurethane, preferably at least one polymer selected from saturated polyester, polyether, polycarbonate, and polyurethane, It is mainly a polymer of aliphatic raw materials.
以下の方法で縮合系重合体アゾ系ラジカル重合開始剤を
調整する。A condensation polymer azo radical polymerization initiator is prepared by the following method.
■官能基含有縮合系重合体と官能基含有アゾ系ラジカル
重合開始剤との反応が、ＮＣＯ基を有するポリウレタン
と活性水素含有アゾ系ラジカル重合開始剤との反応によ
るもので、この反応が少量の溶媒の存在下で行われるも
のである。ポリウレタンは、飽和ポリエステル、ポリエ
ーテル、ポリカーボネート等のＯＨ基含有ポリマーの少
なくとも１種又はこれらの単独又は混合物とポリイソシ
アネート化合物との反応で鎖延長したポリウレタンの末
端ＯＨ基と、ＯＨ基含有アゾ化合物をポリイソシアネー
トで結合させるか、ポリウレタの末端ＮＣＯ基とＯＨ基
含有アゾ化合物との反応でポリウレタンアゾ系ラジカル
重合開始剤を使用する方法である。■The reaction between the functional group-containing condensation polymer and the functional group-containing azo radical polymerization initiator is due to the reaction between the NCO group-containing polyurethane and the active hydrogen-containing azo radical polymerization initiator. It is carried out in the presence of a solvent. Polyurethane is made by combining the terminal OH groups of polyurethane whose chain is extended by reacting at least one of OH group-containing polymers such as saturated polyester, polyether, polycarbonate, etc., or a mixture thereof with a polyisocyanate compound, and an OH group-containing azo compound. This method involves bonding with a polyisocyanate, or using a polyurethane azo radical polymerization initiator by reacting the terminal NCO group of the polyurethane with an OH group-containing azo compound.
■官能基含有縮合系重合体と官能基含有アゾ系ラジカル
重合開始剤との反応が、ＯＨ基を有するポリウレタ、Ｏ
Ｈ基を有するポリエステル、ＯＨ基を有するポリエーテ
ル及びＯＨ基を有するポリカーボネートから選ばれる少
なくとも１種とＣＯＯＨ基含有アゾ系ラジカル重合開始
剤をチオニルクロライドにより酸クロライド化したもの
とを結合させた高分子アゾ化合物ラジカル重合開始剤を
使用する方法である。その反応が溶媒の存在下で行われ
るものである。■The reaction between the functional group-containing condensation polymer and the functional group-containing azo radical polymerization initiator causes polyurethane containing OH groups, O
A polymer in which at least one selected from polyester having an H group, polyether having an OH group, and polycarbonate having an OH group is combined with a COOH group-containing azo radical polymerization initiator converted into acid chloride using thionyl chloride. This method uses an azo compound radical polymerization initiator. The reaction is carried out in the presence of a solvent.
■の方法は、Ｊ、Ａｐｐ口ｅｄ ｐｏｌｙｍｅｒ、 Ｓ
ｃｉ、、 ３１２１７１（１９８６）に記載されている
方法であり、ＯＨ基含有アゾ系ラジカル重合開始剤とし
ては、アゾビスシアノペンタノール、アゾビスシアノプ
ロパノール、アゾビス〔２−メチル−Ｎ−（２−ヒドロ
オキシエチル））プロピオンアミド〕が用いられる。■Method is J, App ed polymer, S
ci, 312171 (1986), and the OH group-containing azo radical polymerization initiator includes azobiscyanopentanol, azobiscyanopropanol, azobis[2-methyl-N-(2- hydroxyethyl)) propionamide] is used.
また、ポリイソシアネート化合物としては、ジフェニル
メタンジイソシアネート、トリレンジイソシアネート、
キシリレンジイソシアネート、ヘキサメチレンジイソシ
アネート、イソホロジイソシアネート、水添ジフェニル
メタンジイソシアネート、水添トリレンジイソシアネー
ト等が用いられる。In addition, as polyisocyanate compounds, diphenylmethane diisocyanate, tolylene diisocyanate,
Xylylene diisocyanate, hexamethylene diisocyanate, isophorodiisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, etc. are used.
また、■の方法は、Ｊ、Ａｐｐｌｉｅｄ ｐｏｌｙｍｅ
ｒ、 Ｓｃｉ。In addition, method ■ is based on J, Applied polyme
r, Sci.
Ｌ土４０５（１９８６）に記載されている方法であり、
アゾビスシアノペンクン酸をチオニルクロライドと反応
させて得られたアゾビスシアノベンクン酸クロライドを
縮合系重合体末端のＯＨ基と反応させることにより、縮
合系重合体アゾ系ラジカル重合開始剤が得られる。This is the method described in L Soil 405 (1986),
An azo radical polymerization initiator for condensed polymers is obtained by reacting azobiscyanobenconic acid chloride obtained by reacting azobiscyanobenconic acid with thionyl chloride with the OH group at the terminal of the condensed polymer. It will be done.
しかしながら、これら文献にみられる方法は、多量の溶
媒中で縮合系重合体アゾ系ラジカル重合開始剤を合威し
、沈澱液に沈澱させ、縮合系重合体アゾ系ラジカル重合
開始剤が分解しないように低温で真空乾燥しているため
、工業的に煩雑な方法である。However, the methods found in these documents combine the condensed polymer azo radical polymerization initiator in a large amount of solvent and precipitate it in a precipitation solution to prevent the condensed polymer azo radical polymerization initiator from decomposing. This method is industrially complicated, as it is vacuum-dried at low temperatures.
本発明■の方法では、こうした欠点を少量の溶媒の存在
下で反応すること、特にＮＣＯ基含有ポリウレタンに対
して１０重量％以下の存在下で反応を行いポリウレタン
アゾ系ラジカル重合開始剤を合或し、次いでビニル系単
量体に縮合系重合体アゾ系ラジカル重合開始剤を溶解し
、ビニル単量体を重合反応させブロック共重合体とする
のが好ましい。溶媒としては、アゾ系ラジカル重合開始
剤を溶解するもので、好ましくは、Ｎ−メチルピロリド
ン、アセトン、ジメチルホルムアミド等が挙げられる。In the method of the present invention (2), these drawbacks can be solved by performing the reaction in the presence of a small amount of solvent, particularly in the presence of 10% by weight or less with respect to the NCO group-containing polyurethane, to synthesize the polyurethane azo radical polymerization initiator. Then, it is preferable that a condensation polymer azo radical polymerization initiator is dissolved in the vinyl monomer, and the vinyl monomer is subjected to a polymerization reaction to form a block copolymer. The solvent is one that dissolves the azo radical polymerization initiator, and preferred examples include N-methylpyrrolidone, acetone, and dimethylformamide.
こうすることにより少量の溶媒を失うが短い反応時間で
縮合系重合体アゾ系ラジカル重合開始剤を得られる。こ
の反応は、ウレタン化反応中にアゾ基の分解を抑える必
要があるので、好ましくは１０°Ｃ以上でアゾ化合物の
１０時間半減期温度よりも１０’Ｃ低い温度以下の温度
範囲で、例えば密閉式加圧ニーダ−や高粘度用反応釜等
を用いて、反応系のＮＣ０％が０．０１％以下になるよ
うにするのが好ましい。By doing so, a condensation polymer azo radical polymerization initiator can be obtained in a short reaction time although a small amount of solvent is lost. Since it is necessary to suppress the decomposition of the azo group during the urethanization reaction, this reaction is preferably carried out in a temperature range of 10°C or higher and 10'C lower than the 10-hour half-life temperature of the azo compound, for example, under closed conditions. It is preferable to use a type pressure kneader, a high viscosity reaction vessel, etc. so that the NC0% of the reaction system is 0.01% or less.
縮合系重合体アゾ系ラジカル重合開始剤中のアゾ系ラジ
カル重合開始剤の量は、１〜１０重量％であり、好まし
くは２〜５重量％である。１重量％より少ないと重合性
不飽和単量体の重合を完了させることができず、また１
０重量％より多いとブロック共重合体のポリウレタン部
分の分子量が小さいものとなる。The amount of the azo radical polymerization initiator in the condensation polymer azo radical polymerization initiator is 1 to 10% by weight, preferably 2 to 5% by weight. If it is less than 1% by weight, the polymerization of the polymerizable unsaturated monomer cannot be completed;
If it is more than 0% by weight, the molecular weight of the polyurethane portion of the block copolymer will be small.
０Ｈ基含有ポリマーとしては、エチレングリコール、プ
ロピレングリコール、ブチレングリコール、ヘキサメチ
レンゲルコールなどのグリコールとアジピン酸、コハク
酸、アゼライン酸、セバシン酸、フタル酸などの２塩基
酸とを縮合した飽和ポリエステル、カプロラクトン、Ｔ
−ブチロラクトンなどを開環重合した飽和ポリエステル
、ポリエチレンオキサイド、ポリプロピレンオキサイド
などのポリエーテル類及び上記グリコールとジメチルカ
ーボネート、ジエチルカーボネートを反応させたポリカ
ーボネート、さらにこれらの飽和ポリエステル、ポリエ
ーテル、ポリカーボネートの１種又は２種以上の混合物
を上記ポリイソシアネート化合物で鎖延長したポリウレ
タンなどが用いられる。Examples of 0H group-containing polymers include saturated polyesters obtained by condensing glycols such as ethylene glycol, propylene glycol, butylene glycol, and hexamethylene gelcol with dibasic acids such as adipic acid, succinic acid, azelaic acid, sebacic acid, and phthalic acid; caprolactone, T
- Saturated polyesters obtained by ring-opening polymerization such as butyrolactone, polyethers such as polyethylene oxide and polypropylene oxide, and polycarbonates obtained by reacting the above glycols with dimethyl carbonate and diethyl carbonate, and one or more of these saturated polyesters, polyethers, and polycarbonates. A polyurethane obtained by chain-extending a mixture of two or more types with the above polyisocyanate compound is used.
上記■■の方法で得られた高分子アゾ化合物ラジカル重
合開始剤の存在下でスチレン、α−メチルスチレン、ビ
ニルトルエンの如き芳香族ビニル類、メチル（メタ）ア
クリレート、エチル（メタ）アクリレート、ブチル（メ
タ）アクリレートの如き（メタ）アクリル酸エステル、
酢酸ビニル、プロピオン酸ビニル、安息香酸ビニルの如
きビニルエステル類などのビニル系単量体を溶液重合、
懸濁重合、乳化重合、塊状重合などの公知の方法により
重合される。特に、ポリウレタンの場合、塊状重合でお
こなうのが好ましい。また、上記ビニル系単量体にアク
リル酸、メタクリル酸、イタコン酸等の酸基含有ビニル
系単量体を併用することにより酸化マグネシウム、水酸
化マグネシウムナどのアルカリ土類金属を併用すること
による増粘性の優れた重合物を与える。Aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylic acid ester such as (meth)acrylate,
Solution polymerization of vinyl monomers such as vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate.
Polymerization is carried out by known methods such as suspension polymerization, emulsion polymerization, and bulk polymerization. Particularly in the case of polyurethane, bulk polymerization is preferred. In addition, by using a vinyl monomer containing an acid group such as acrylic acid, methacrylic acid, or itaconic acid in combination with the above vinyl monomer, it is possible to increase the Provides a polymer with excellent viscosity.
ブロック共重合体は、縮合系重合体とビニル系重合体と
をブロック重合成分として有し、その構成比率（重量比
）は、好ましくは０．１１０．９〜０．９１０．１で、
特に好ましくは、０．３／’０．７〜０．７１０．３で
ある。The block copolymer has a condensation polymer and a vinyl polymer as block polymerization components, and the constituent ratio (weight ratio) thereof is preferably 0.110.9 to 0.910.1,
Particularly preferably, it is 0.3/'0.7 to 0.710.3.
本発明のラジカル重合性不飽和樹脂組成物中のブロック
重合体の使用量は、後述のポリスチレン等の低収縮剤を
併用しないときは２〜２５重量部、好ましくは１０〜２
０重量部、併用するときは２〜２０重量部、好ましくは
５〜１５重量部である。The amount of the block polymer used in the radically polymerizable unsaturated resin composition of the present invention is 2 to 25 parts by weight, preferably 10 to 25 parts by weight when a low shrinkage agent such as polystyrene described below is not used in combination.
When used together, the amount is 2 to 20 parts by weight, preferably 5 to 15 parts by weight.
２重量部より少ないと、ラジカル重合硬化低収縮剤とし
ての低収縮付与効果が顕著でなく、２５重量部より多い
と成形物の機械的特性が良くないことがある。ポリスチ
レン等を併用するときは、２重量部より少ないと、ポリ
スチレン、スチレン−共役ジエンブロック共重合体の分
散改良効果が顕著でなく、また、２０重量部より多いと
、成形物の機械的特性が悪くなることがある。If it is less than 2 parts by weight, the effect of imparting low shrinkage as a radical polymerization curing low shrinkage agent will not be significant, and if it is more than 25 parts by weight, the mechanical properties of the molded product may not be good. When using polystyrene, etc., if it is less than 2 parts by weight, the dispersion improvement effect of polystyrene and styrene-conjugated diene block copolymer will not be noticeable, and if it is more than 20 parts by weight, the mechanical properties of the molded product will deteriorate. It can get worse.
本発明においては、他のラジカル重合硬化低収縮剤を使
用することもできる。これに用いられるポリスチレンは
乳化重合、懸濁重合、溶液重合、塊状重合等の方法によ
り重合度５００〜６０００、好ましくは２０００〜４０
００のポリマーが好適に使用され、α−メチルスチレン
、メタクリル酸メチル等の共重合体であっても良い。Other radical polymerization curing low shrinkage agents can also be used in the present invention. The polystyrene used for this is produced by methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization to a degree of polymerization of 500 to 6000, preferably 2000 to 40.
00 polymer is preferably used, and copolymers of α-methylstyrene, methyl methacrylate, etc. may also be used.
また、スチレン−共役ジエン系ブロック共重合体は有機
金属触媒によってスチレンと共役ジエンを有機溶液中で
重合させて得られるスチレン成分と共役ジエン成分から
なるブロック共重合体であり、共役ジエンとしてブタジ
ェン、イソプレン、１．３−ペンタジェンなどが用いら
れる。さらに本発明においては、スチレン−共役ジエン
ブロック共重合体を水素添加して得られるスチレン−水
添共役ジエンブロック共重合体であっても良い。また、
ブロック共重合体の構成単位もスチレン−共役ジエン、
スチレン−共役ジエン−スチレン、共役ジエン−スチレ
ン−共役ジエンなどのスチレンと共役ジエンの繰り返し
単位のものも含まれる。Furthermore, the styrene-conjugated diene block copolymer is a block copolymer consisting of a styrene component and a conjugated diene component obtained by polymerizing styrene and a conjugated diene in an organic solution using an organometallic catalyst, and the conjugated diene includes butadiene, Isoprene, 1,3-pentadiene, etc. are used. Furthermore, in the present invention, a styrene-hydrogenated conjugated diene block copolymer obtained by hydrogenating a styrene-conjugated diene block copolymer may be used. Also,
The structural unit of the block copolymer is also styrene-conjugated diene,
Also included are repeating units of styrene and conjugated diene, such as styrene-conjugated diene-styrene and conjugated diene-styrene-conjugated diene.
これらの共重合体の使用量は組成物中３〜２０重量部、
好ましくは５〜１５重量部である。３重量部以下では低
収縮効果に顕著でな（，２０重量部以上では成形物の機
械的強度に劣ることがある。The amount of these copolymers used is 3 to 20 parts by weight in the composition,
Preferably it is 5 to 15 parts by weight. If it is less than 3 parts by weight, the shrinkage reduction effect is not significant (and if it is more than 20 parts by weight, the mechanical strength of the molded product may be poor.
本発明の組成物には、硬化触媒のほかに硬化促進剤、重
合禁止剤、充填剤、補強材、増粘剤、内部離型剤、顔料
等を目的に応じて加えることができる。In addition to the curing catalyst, a curing accelerator, a polymerization inhibitor, a filler, a reinforcing material, a thickener, an internal mold release agent, a pigment, etc. can be added to the composition of the present invention depending on the purpose.
硬化触媒としては、ベンゾイルパーオキサイド、Ｌ−ブ
チルパーベンゾエート、ｔ−ブチルパーオクトエート、
ジクミルパーオキサイド、ジーしブチルパーオサイド、
トリメチルシクロヘキサノンパーケタール等の有機過酸
物である。As a curing catalyst, benzoyl peroxide, L-butyl perbenzoate, t-butyl peroctoate,
dicumyl peroxide, dibutyl peroxide,
Organic peracids such as trimethylcyclohexanone perketal.
重合禁止剤としては、ハイドロキノン、バラベンゾキノ
ン、カテコール、トルハイドロドノン等であり、硬化促
進剤としては例えばナフテン酸コバルト、オクテン酸コ
バルト、コバルトアセチルアセテート、ジメチルアニリ
ンなどが用いられる。Examples of the polymerization inhibitor include hydroquinone, parabenzoquinone, catechol, and toluhydronone, and examples of the curing accelerator include cobalt naphthenate, cobalt octenoate, cobalt acetylacetate, and dimethylaniline.
充填剤としては、炭酸カルシウム、クレー、水和アルミ
ナ、石英砂、ガラスフレーク、ガラスバブル、マイカ粉
末等であり、補強材としてはロービング又はそれから得
られたチョツプドストラン及びそのマット状のガラス繊
維、炭素繊維、金属繊維、有機繊維等である。特に、補
強材の使用量は補強材を含めた組成物中２０〜３５重量
％が適当である。Fillers include calcium carbonate, clay, hydrated alumina, quartz sand, glass flakes, glass bubbles, mica powder, etc., and reinforcing materials include roving or chopped strands obtained therefrom, and glass fibers in the mat form thereof. , carbon fiber, metal fiber, organic fiber, etc. In particular, the appropriate amount of the reinforcing material used is 20 to 35% by weight of the composition including the reinforcing material.
内部離型剤としては、ステアリン酸亜鉛等の脂肪族金属
塩及びポリアルキレンエーテル等のワックスである。ま
た、増粘剤としては、酸化マグネシウム、水酸化マグネ
シウム、水酸化カルシウム等の土類金属類やイソシアネ
ート化合物が使用される。Internal mold release agents include aliphatic metal salts such as zinc stearate and waxes such as polyalkylene ethers. Further, as the thickener, earth metals such as magnesium oxide, magnesium hydroxide, calcium hydroxide, and isocyanate compounds are used.
本発明のラジカル重合性不飽和樹脂組成物は、例えば不
飽和ポリエステル樹脂を用いたＳＭＣ。The radically polymerizable unsaturated resin composition of the present invention is, for example, SMC using an unsaturated polyester resin.
ＢＭＣに好適に使用され、表面平滑性、塗装性、機械的
強度、着色性に優れた成形品を提供することができる。It is suitable for use in BMC, and can provide molded products with excellent surface smoothness, paintability, mechanical strength, and colorability.
また、これらの成形品は自動車のボンネット、ルーフ、
ドアー、テール、ゲート等の自動車外装品、浴槽、防水
パン、浄化層、タンク、クーリングタワー、キッチンカ
ウンター、洗面ボール等の大型成形品、椅子、テーブル
家の家具類、電気製品のケーシング、ハウジング等に使
用することができる。In addition, these molded products are used for automobile hoods, roofs,
For automotive exterior parts such as doors, tails, and gates, large molded products such as bathtubs, waterproof pans, purification layers, tanks, cooling towers, kitchen counters, and wash basins, chairs, tables, home furniture, casings and housings for electrical products, etc. can be used.
実施例
次に本発明の詳細な説明する。なお「部」は重量部であ
る。EXAMPLES Next, the present invention will be explained in detail. Note that "parts" are parts by weight.
（ラジカル重合硬化低収縮剤としてのブロック重合体の
製造）
実施例１
ポリカプロラクトンポリウレタン−ポリスチレンブロッ
ク共重合体の製造
ＬＬ４つ目フラスコにＯＨ基価５６ ｍｇＫＯＨ／ ｇ
のポリカプロラクトン１５０ｇを入れ、１００″Ｃに加
温した。スタナスオクトエートを１５■と、トリレンジ
イソシアネートを１７．４ ｇ入れ、窒素気流中で１時
間反応させると反応系の粘度が高くなった。この時点で
ジメチルホルムアミドを１５０ｇ添加した。さらに１時
間反応させた後、５０°Ｃに冷却シ、ジメチルホルムア
ごドを３００ ｇ （！ｌ：２．２’アヅビスロ２−メ
チル−Ｎ（２−ヒドロキシエチル）プロピオンアミド１
５ｇを添加し、８時間反応させた。ついで、スチレン２
２５ｇ加え、１００°Ｃに加温し、１０時間重合させた
後、大量のメタノールに沈澱させた。沈澱物を６０″Ｃ
にて２４時間乾燥すると、白色の重合体が３６５ｇ得ら
れた。(Production of block polymer as radical polymerization curing low shrinkage agent) Example 1 Production of polycaprolactone polyurethane-polystyrene block copolymer LL The fourth flask was charged with an OH group value of 56 mgKOH/g.
150g of polycaprolactone was added and heated to 100''C. 15g of stannous octoate and 17.4g of tolylene diisocyanate were added and reacted for 1 hour in a nitrogen stream, resulting in a high viscosity of the reaction system. At this point, 150 g of dimethylformamide was added. After further reaction for 1 hour, it was cooled to 50°C and 300 g of dimethylformamide (!l: 2.2'Azubislo 2-methyl-N(2 -Hydroxyethyl)propionamide 1
5 g was added and reacted for 8 hours. Then, styrene 2
25g was added, heated to 100°C, polymerized for 10 hours, and then precipitated in a large amount of methanol. Precipitate at 60″C
After drying for 24 hours, 365 g of a white polymer was obtained.
この共重合体の数平均分子量は２９，０００、重量平均
分子量は６３，０００であり、Ｃ，Ｈ，Ｏの元素分析よ
り、Ｃニア９．４％、Ｈ： ７．４％、Ｏ：１３．２％
であり４１％のポリカプロラクトンと５９％のポリエチ
レンからなるブロック共重合体であることがわかった。The number average molecular weight of this copolymer was 29,000, and the weight average molecular weight was 63,000. Elemental analysis of C, H, and O revealed that C-nia was 9.4%, H: 7.4%, and O: 13. .2%
It was found that it was a block copolymer consisting of 41% polycaprolactone and 59% polyethylene.
さらに下記の方法でプロ・ンク化率を測定したところブ
ロック化率９５％であった。これをブロック共重合体Ａ
とする。Furthermore, when the blocking rate was measured using the method described below, the blocking rate was 95%. This is block copolymer A
shall be.
実施例２
ポリエステルポリウレタンーボリスチレンブロ７り共重
合体の製造
２ Ｌ ４つロフラスコにメチルエチルケトン５００ｇ
を入れ、スタナスオクトエート５０ｍｇと２，２′アゾ
ビス（２−シアツブロバノール）１９．６ｇとトリレン
ジイソシアネート３６．５ ｇを入れ、４０’Ｃにて４
時間反応させた。ついで、ＯＨ基価（８，７■Ｋｏｊｉ
／ｇの１．４−ブタンジオールとアジピン酸とからなる
ポリエステルを６００ｇを入れ、８時間反応させた後、
減圧蒸留を行い、メチルエチルケトンを除去し、さらに
内容物を減圧乾燥した。Example 2 Production of polyester polyurethane-polystyrene bromide copolymer 2 500 g of methyl ethyl ketone was placed in a 4-L flask.
and 50 mg of stannath octoate, 19.6 g of 2,2'azobis(2-cyatuburobanol) and 36.5 g of tolylene diisocyanate, and heated at 40'C.
Allowed time to react. Next, the OH value (8,7■Koji
After adding 600 g of polyester consisting of /g of 1,4-butanediol and adipic acid and reacting for 8 hours,
Distillation was performed under reduced pressure to remove methyl ethyl ketone, and the contents were further dried under reduced pressure.
２Ｌ４つロフラスコにイオン交換水１２００ ｇと１０
％ポリアクリル酸共重合体水溶液１２ｇを入れさらに上
記減圧乾燥物１２０ｇをスチレン１８０ｇに溶解したも
のとメタクリル酸２ｇ、 ドデシルメルカプタン０．
５ｇを添加した。窒素気流中攪拌しなから７０°Ｃにて
４時間さらに８０°Ｃにて４時間重合させ、得られた懸
濁重合物を水洗し、８０°Ｃにて１６時間乾燥したとこ
ろ、２９０ｇの共重合体が得られた。この共重合体の数
平均分子量は７８．０００であり、ポリエステル４１％
とポリスチレン５９％からなるブロック共重合体であり
、ブロック化率９３％であった。これをブロック共重合
体Ｂとする。1200 g of ion-exchanged water and 10
% polyacrylic acid copolymer aqueous solution, and then 120 g of the above vacuum dried material dissolved in 180 g of styrene, 2 g of methacrylic acid, and 0.0 g of dodecyl mercaptan.
5g was added. Polymerization was carried out at 70°C for 4 hours without stirring in a nitrogen stream, and then at 80°C for 4 hours, and the resulting suspension polymer was washed with water and dried at 80°C for 16 hours, resulting in 290 g of copolymer. A polymer was obtained. The number average molecular weight of this copolymer was 78.000, and it was 41% polyester.
It was a block copolymer consisting of 59% polystyrene and 59% polystyrene, and the blocking rate was 93%. This is referred to as block copolymer B.
実施例３
ポリエーテルポリウレタン−ポリ酢酸ビニルブロック共
重合体の製造
ＬＬ４つロフラスコにＯＨ基価１１２ ｍｇＫＯＨ／
ｇのポリプロピレングリコール１５０ｇを入れ、８０°
Ｃに加熱し、ジブチル錫ジラウレート１５ｍｇ、イソホ
ロンジイソシネ−） ２７．８ ｇを添加し、窒素気流
中で反応させた。１時間後、クロロホルム２００ｇを加
え、５°Ｃに冷却した。次いでトリエチルアミン１０ｇ
を加えた後、４，４′ −アゾビス（４−シアノベンク
ン酸りロライド）８．０ｇをクロロホルム１００ｇに溶
解した溶液を少量づつ滴下し、５°Ｃにて４時間反応さ
せた後、反応溶液を５回水洗し、減圧乾燥した。Example 3 Production of polyether polyurethane-polyvinyl acetate block copolymer 4 LL flasks with OH group value of 112 mgKOH/
Add 150g of polypropylene glycol and heat at 80°.
15 mg of dibutyltin dilaurate and 27.8 g of isophorone diisocyanate were added, and the mixture was reacted in a nitrogen stream. After 1 hour, 200 g of chloroform was added and the mixture was cooled to 5°C. Then 10g of triethylamine
After adding , a solution of 8.0 g of 4,4'-azobis(4-cyanobencuonic acid chloride) dissolved in 100 g of chloroform was added dropwise little by little, and after reacting at 5°C for 4 hours, the reaction solution was added. It was washed with water five times and dried under reduced pressure.
乾燥物１５０ｇをトルエン３００ｇに溶解し、クロトン
酸１ｇ、酢酸ビニル１５０ｇを加え、窒素気流中攪拌し
なから７０°Ｃにて１２時間反応させた。反応液を多量
のヘキサン中に沈澱させ、沈澱物を５０″Ｃにて真空乾
燥した。得られたブロック共重合体は数平均分子量４８
．０００、重量平均分子１１８５．０００であり、ポリ
プロピレングリコール５２％、酢酸ビニル４８％からな
る共重合体が得られた。これをブロック共重合体Ｃとす
る。150 g of the dried product was dissolved in 300 g of toluene, 1 g of crotonic acid and 150 g of vinyl acetate were added, and the mixture was reacted at 70° C. for 12 hours with stirring in a nitrogen stream. The reaction solution was precipitated in a large amount of hexane, and the precipitate was vacuum dried at 50"C. The obtained block copolymer had a number average molecular weight of 48.
．． 000, a weight average molecular weight of 1185.000, and a copolymer consisting of 52% polypropylene glycol and 48% vinyl acetate was obtained. This will be referred to as block copolymer C.
実施例４
ポリカーボネートポリウレタン−ポリメチルメタクリレ
ートブロック共重合体の製造
１．６−ヘキサンジオールとジエチルカーボネートから
得られるＯＨ基価５６ ｍｇＫＯＩＩ／ ｇのポリカー
ボネー１〜２００ ｇを２Ｌ４つロフラスコに入れ、８
０″Ｃに加温し、スタナスオクトエート２０ｍｇ、ヘキ
サメチレンジイソシネート２３．９ ｇを添加し、２時
間反応させた後、メチルエチルケトン２００ｇに溶解さ
せた。温度を４０°Ｃに下げ、２，２′アゾビス（２−
シアツブロバノール）６．６ｇとメチルエチルケトン１
００ｇを加えて８時間反応させた。Example 4 Production of polycarbonate polyurethane-polymethyl methacrylate block copolymer 1. 1 to 200 g of polycarbonate with an OH group value of 56 mg KOII/g obtained from 6-hexanediol and diethyl carbonate was placed in four 2L flasks, and
The mixture was heated to 0"C, 20mg of stannous octoate and 23.9g of hexamethylene diisocyanate were added, and after reacting for 2 hours, it was dissolved in 200g of methyl ethyl ketone. The temperature was lowered to 40°C and ,2'Azobis(2-
6.6g (cyatubrobanol) and 1 methyl ethyl ketone
00g was added and reacted for 8 hours.
反応液を減圧乾燥し、乾燥物２００ｇ壱メタアクリル酸
５ｇ１ ドデシルメルカプタン２ｇを４７０ｇのメチル
メタアクリレートに溶解したものを、イオン交換水１５
０ｇとｌＯ％アクリル酸共重合体水溶液１８ｇを入れた
３Ｌ４つロフラスコに入れ、窒素気流中攪拌しなから７
５°Ｃにて８時間重合させた。重合物を７０°Ｃにて１
８時間乾燥すると６５０ｇの白色粒状物が得られた。こ
のものは数平均分子量３６，０００、重量平均分子！９
２．０００であり、ウレタン変性ポリカーボネート３１
％、ポリメチルメタアクリレート６９％からなるブロッ
ク共重合体であることがわかった。これをブロック共重
合体りとする。The reaction solution was dried under reduced pressure, and a solution of 200 g of dry matter, 5 g of methacrylic acid, and 2 g of dodecyl mercaptan dissolved in 470 g of methyl methacrylate was dissolved in 15 g of ion-exchanged water.
0g and 18g of 1O% acrylic acid copolymer aqueous solution were placed in a 3L four-bottle flask, and without stirring in a nitrogen stream,
Polymerization was carried out at 5°C for 8 hours. 1 at 70°C.
After drying for 8 hours, 650 g of white granules were obtained. This one has a number average molecular weight of 36,000 and a weight average molecular weight! 9
2.000, urethane-modified polycarbonate 31
%, and was found to be a block copolymer consisting of 69% polymethyl methacrylate. This is called a block copolymer.
実施例５
ポリエーテルポリウレタン−ポリスチレンブロック共重
合体の製造
１ｆ４つロフラスコに水酸基価１１２■ＫＯＨ／ ｇの
ポリプロピレングリコール１５０ｇを入れ、８０°Ｃに
加熱し、ジプチル錫ジラウレー）１５■、イソホロンジ
イソシネート２７．８ ｇを添加し、窒素気流中で反応
させた。１時間後、クロロホルム２００ｇを加え、５°
Ｃに冷却した。次いでトリエチルアミン１０ｇを加えた
後、４．４′ −アゾビス（４−シアノペンクン酸りロ
ライド）８．０ｇをクロロホルム１００ｇに溶解した溶
液を少量づつ滴下し、５°Ｃにて４時間反応させた後、
反応溶液を５回水洗し、減圧乾燥した。Example 5 Production of polyether polyurethane-polystyrene block copolymer 150 g of polypropylene glycol with a hydroxyl value of 112 ■KOH/g was placed in a 1F four-bottle flask, heated to 80°C, and dibutyltin dilaurate (15■), isophorone diisocyanate 27.8 g was added and reacted in a nitrogen stream. After 1 hour, add 200g of chloroform and stir at 5°.
Cooled to C. Next, after adding 10 g of triethylamine, a solution of 8.0 g of 4.4'-azobis(4-cyanopenconic acid chloride) dissolved in 100 g of chloroform was added dropwise little by little, and after reacting at 5°C for 4 hours,
The reaction solution was washed with water five times and dried under reduced pressure.
乾燥物１５０ｇをトルエン５００ｇに溶解し、メタアク
リル酸１ｇ２スチレン１５０ｇを加え、窒素気流中攪拌
しなから７５°Ｃにて１０時間反応させた。反応液を多
量のメタノール中に沈澱させ、沈澱物を８０°Ｃにて１
２時間乾燥した。２９０ｇの白色共重合体が得られ、数
平均分子１３９，７００、重量平均分子ｔ１８０，００
０であり、ポリエーテルポリウレタン成分５２％、ポリ
スチレン成分４８％からなる共重合体が得られた。これ
をブロック共重合体Ｅとする。150 g of the dried product was dissolved in 500 g of toluene, 1 g of methacrylic acid and 150 g of styrene were added, and the mixture was reacted at 75° C. for 10 hours with stirring in a nitrogen stream. The reaction solution was precipitated in a large amount of methanol, and the precipitate was incubated at 80°C for 1 hour.
It was dried for 2 hours. 290 g of white copolymer was obtained, number average molecule 139,700, weight average molecule t 180,00.
0, and a copolymer consisting of 52% polyether polyurethane component and 48% polystyrene component was obtained. This is referred to as block copolymer E.
実施例６
ポリカーボネートポリウレタン−ポリスチレンブロック
共重合体の製法
１．６ヘキサンジオールとジエチレンカーボネートから
得られる水酸基価５６■ＫＯＨ／ ｇのポリカーボネー
ト２００ｇを２Ｎ４つロフラスコに入れ、８０ ’Ｃに
加熱し、スタナスオクトエート２０■、ヘキサメチレン
ジイソシアネー） ２３．９ ｇを添加し、２時間反応
させた後、メチルエチルケトン２００ｇに溶解させた。Example 6 Process for producing polycarbonate polyurethane-polystyrene block copolymer 1.200 g of polycarbonate with a hydroxyl value of 56 KOH/g obtained from hexanediol and diethylene carbonate was placed in four 2N flasks, heated to 80'C, and placed in a stannous After adding 20 g of octoate and 23.9 g of hexamethylene diisocyanate and reacting for 2 hours, the mixture was dissolved in 200 g of methyl ethyl ketone.
温度を４０’Ｃに下げ、２．２′−アゾビス（２−アミ
ノプロパツール）６．６ｇとメチルエチルケトン１００
ｇを加えて８時間反応させた。反応液を減圧乾燥し、乾
燥物２００ｇをメタクリル酸５ｇ、ドデシルメルカプタ
ン２ｇ及びスチレン４７０ｇに溶解させたものを、予め
イオン交換水１５００ｇと１０％アクリル酸ポリマー水
溶液１８ｇを入れた３１４つロフラスコに入れ、窒素気
流中攪拌しなから７５°Ｃにて８時間重合させた。重合
物を７０℃にて１８時間加熱すると、６６０ｇの白色粒
状物が得られた。このものは数平均分子量３１，０００
、重量平均分子量８３、０００であり、ポリカーボネー
トポリウレタン３０％、ポリスチレン７０％からなるブ
ロック共重合体であることがわかった。この共重合体を
ブロック共重合体Ｆとする。Lower the temperature to 40'C and add 6.6 g of 2,2'-azobis(2-aminopropanol) and 100 g of methyl ethyl ketone.
g was added and reacted for 8 hours. The reaction solution was dried under reduced pressure, and 200 g of the dried product was dissolved in 5 g of methacrylic acid, 2 g of dodecyl mercaptan, and 470 g of styrene, and the solution was placed in a 314-bottle flask containing 1500 g of ion-exchanged water and 18 g of a 10% acrylic acid polymer aqueous solution in advance. Polymerization was carried out at 75°C for 8 hours without stirring in a nitrogen stream. The polymer was heated at 70° C. for 18 hours, yielding 660 g of white granules. This one has a number average molecular weight of 31,000
, a weight average molecular weight of 83,000, and was found to be a block copolymer consisting of 30% polycarbonate polyurethane and 70% polystyrene. This copolymer is referred to as block copolymer F.
なお、上記ブロック化率は以下のように測定した。In addition, the said blocking rate was measured as follows.
ブロック共重合体２０ｇをテトラヒドロフラン８０ｃｃ
に溶解させた溶液をメタノール６００ｃｃと、アセトン
３００ｃｃの混合液中に沈澱し、濾別する。20g of block copolymer in 80cc of tetrahydrofuran
The solution was precipitated in a mixture of 600 cc of methanol and 300 cc of acetone, and filtered.
濾、液を蒸発乾固してその重量を測定したのをＡとする
。また濾過残物を乾燥し、再度テトラヒドロフラン８０
ｃｃに？客層させ、アセトン８００ｃｃとメタノール１
００ｃｃの混合液中に沈澱し濾部する。Filter, evaporate the liquid to dryness, and measure its weight, which is referred to as A. In addition, dry the filtration residue and use 80% tetrahydrofuran again.
To cc? 800 cc of acetone and 1 ml of methanol
Precipitate in 00 cc of mixed solution and filter.
濾液を蒸発乾固してその重量を測定したものをＢとする
。また、濾過残物を乾燥し重量を測定したものをＣとす
る。下記Ｎ）式よりブロック化率を求めた。なお、赤外
線吸収スペクトルによりＡはブチレングリコールとアジ
ピン酸からなるボリウレタンであり、またＣはポリスチ
レンであることを確認した。The filtrate was evaporated to dryness and its weight was measured and designated as B. Further, the filtered residue was dried and its weight was measured and designated as C. The blocking rate was determined from the following formula N). In addition, it was confirmed by infrared absorption spectrum that A was polyurethane consisting of butylene glycol and adipic acid, and C was polystyrene.
（ラジカル重合性不飽和樹脂組成物の製造）実施例７〜
１０
上記実施例１〜４で得られた４種類のブロック共重合体
を固型分３０％になるようにスチレンに溶解させ、低収
縮剤溶液を得た。(Production of radically polymerizable unsaturated resin composition) Example 7~
10 The four types of block copolymers obtained in Examples 1 to 4 above were dissolved in styrene to give a solid content of 30% to obtain a low shrinkage agent solution.
プロピレングリコール１モル、フマール酸１モルからな
る不飽和ポリエステル７０％とスチレン３０％からなる
不飽和ポリエステル樹脂５０部と、上記それぞれの低収
縮剤溶液５０部、Ｌ−ブチルパーベンゾエート１部、ス
テアリン酸亜鉛４部、炭酸カルシウム１８０部、ポリト
ンブラックＰＴ５１５２ （大日本インキ化学工業■製
）１部を混合し、さらに酸化マグネシウム１重量部を加
え、良く混合した後、３５°Ｃにて一昼夜熟威し、増粘
させた。50 parts of an unsaturated polyester resin consisting of 70% unsaturated polyester consisting of 1 mol of propylene glycol, 1 mol of fumaric acid and 30% styrene, 50 parts of each of the above low shrinkage agent solutions, 1 part of L-butyl perbenzoate, and stearic acid. Mix 4 parts of zinc, 180 parts of calcium carbonate, and 1 part of Polyton Black PT5152 (manufactured by Dainippon Ink & Chemicals), add 1 part by weight of magnesium oxide, mix well, and leave to age at 35°C overnight. and thickened.
このようにして上記４種類のそれぞれの低収縮剤溶液を
含有するそれぞれ実施例７〜１０のラジカル重合性不飽
和樹脂組成物を得て、それぞれの組成物６５ｇをＪＩＳ
Ｋ−６９１１に規定された金型内に入れ、ｌ ４０ ’
Ｃにて５分間硬化させ、円板状の成形品を作威し、その
収縮率及び黒度（着色性）を測定した結果を表１に示す
。In this way, the radical polymerizable unsaturated resin compositions of Examples 7 to 10 containing each of the four types of low shrinkage agent solutions were obtained, and 65 g of each composition was
Place it in the mold specified in K-6911, l 40'
Table 1 shows the results of the shrinkage rate and blackness (coloring property) of the molded product.
また、上記実施例７〜１０のそれぞれのラジカル重合性
不飽和樹脂組成物をＳＭＣ製造機に供給し、ガラス含量
３０％になるようにガラス繊維を１インチに裁断しなが
ら加え、ＳＭＣを製造した。Further, each of the radically polymerizable unsaturated resin compositions of Examples 7 to 10 above was supplied to an SMC manufacturing machine, and glass fibers were added while cutting them into 1-inch pieces so that the glass content was 30%, thereby manufacturing SMC. .
このＳＭＣを、３５°Ｃ１２４時間熟戒後、３００肋Ｘ
５００帥の金型に入れ、１４０°Ｃ１１００ｋｇ／−の
圧力にて５分間成形し、厚さ３閣の平板を作成した。こ
れらのそれぞれについて相溶性、成形収縮率、平面平滑
性、曲げ強度、耐煮沸性、落球衝撃性を測定した結果を
表１に示す。After contemplating this SMC for 124 hours at 35°C, 300 ribs
The mixture was placed in a 500 mm mold and molded for 5 minutes at 140° C. and a pressure of 1100 kg/- to produce a flat plate with a thickness of 3 mm. Table 1 shows the results of measuring the compatibility, molding shrinkage rate, planar smoothness, bending strength, boiling resistance, and ball impact resistance for each of these.
比較例１〜３
数平均分子量２６０，０００のポリスチレン、数平均分
子１５０，０００のポリメチルメタクリレート、数平均
分子量３４．０００のポリ酢酸ビニルをそれぞれ固型分
３０重量％になるようにスチレンに溶解させてそれぞれ
の低収縮剤溶液を得た。これらのそれぞれの溶液を実施
例７〜ｌＯと同様にし使用して成形品を作威し、その収
縮率及び黒度を測定した結果を表１に示す。Comparative Examples 1 to 3 Polystyrene with a number average molecular weight of 260,000, polymethyl methacrylate with a number average molecular weight of 150,000, and polyvinyl acetate with a number average molecular weight of 34,000 were each dissolved in styrene to a solid content of 30% by weight. Each low shrinkage agent solution was obtained. Each of these solutions was used in the same manner as in Examples 7 to 10 to make molded products, and the shrinkage percentage and blackness of the molded products were measured. Table 1 shows the results.
また、上記実施例７〜１０と同様にガラス繊維を混合し
た平板を作威し、それぞれについて上記と同様に測定し
た結果を表１に示す。In addition, flat plates mixed with glass fiber were prepared in the same manner as in Examples 7 to 10 above, and the results of each measurement in the same manner as above are shown in Table 1.
（この頁以下余白） ア 表中、各測定項目の詳細は以下の通りである。(Margins below this page) a Details of each measurement item in the table are as follows.
収縮率：成形品３個の平均値（１個につき４ケ所測定）
黒 土：カラーメータによる成形品３個の平均値（数値
Ｏが純黒、１００が純白を示す）相溶性；不飽和ポリエ
ステル樹脂５０部と低収縮剤溶液５０部を混合し、−昼
夜放置観察した。Shrinkage rate: Average value of 3 molded products (measured at 4 locations for each product) Black Soil: Average value of 3 molded products measured by color meter (number O indicates pure black, 100 indicates pure white) Compatibility: Unsaturated polyester 50 parts of the resin and 50 parts of the low shrinkage agent solution were mixed and left to stand for observation day and night.
◎：骨分離ず
○：極く一部分離
△ニ一部分離
×：完全に分離
成形収縮率：４ケ所測定した平均値を示す。マイナスは
膨張をあられす。◎: No bone separation ○: Very partial separation △ △ Partial separation ×: Complete separation Molding shrinkage rate: The average value measured at 4 locations is shown. Minus hails expansion.
表面平滑性：東京貿易■装面歪測定機により、長さ２５
ｃｍを４ケ所測定し、社内試験
法によりロングウェーブ、ショート
ウェーブを算出した。ロングウェー
ブはうねりの度合いを示す数値であ
り、数値の小さいほどうねり程度が
低い。また、ショートウェーブは表
面粗さを示す数値であり、数値の小
さい程表面粗さが少ない。Surface smoothness: Length 25 by Tokyo Boeki's surface distortion measuring machine
cm was measured at four locations, and long waves and short waves were calculated using in-house testing methods. Long wave is a numerical value indicating the degree of waviness, and the smaller the value, the lower the degree of waviness. Further, the short wave is a numerical value indicating surface roughness, and the smaller the numerical value, the less the surface roughness.
曲げ強さ： ＪＩＳＫ−６９１１に準じる。Bending strength: According to JISK-6911.
耐煮沸性：、試験片（３ｃｍＸ１５ｃｍ）を９８℃の熱
水中に１週間浸漬後、表面に発生
する膨れ及び白化の度合を観察する。Boiling resistance: After immersing a test piece (3 cm x 15 cm) in hot water at 98°C for one week, observe the degree of blistering and whitening that occurs on the surface.
Ｏ：はとんど変化しない。O: hardly changes.
△：膨れ又は白化の変化が若干ある。△: There is some change in swelling or whitening.
×：膨れ又は白化の変化が著しい。×: Significant change in swelling or whitening.
落球衝撃性；試験片（１５ｃｍＸ １５ｃｍ）に５００
ｇの鋼球を５０ｃｍの高さから落とし、試験片の背面に
探傷剤を塗布し、ク
ランクの状態を観察する。Falling ball impact resistance: 500 on test piece (15cm x 15cm)
Drop a steel ball (g) from a height of 50 cm, apply a flaw detection agent to the back of the test piece, and observe the condition of the crank.
○：はとんどクラックなし。○: Almost no cracks.
Δ：クランクややあり。Δ: Slightly visible crank.
×：前面にクラックあり。×: There is a crack on the front.
表１に示すように実施例１〜４の低収縮剤を使用した成
形品は低収縮を示し、黒度も低いことを示す。黒度が低
いことは他の色に着色し易く着色性が良いことを示す。As shown in Table 1, the molded products using the low shrinkage agents of Examples 1 to 4 exhibit low shrinkage and low blackness. A low degree of blackness indicates that it is easy to be colored with other colors and has good coloring properties.
（低収縮剤を併用したラジカル重合性不飽和樹脂組成物
）
実施例１１〜１４
プロピレングリコール１モル、ネオペンチルグリコール
２モル、テレフタル酸１モル、フマール酸２モルからな
る不飽和ポリエステル（Ａ）６５％とスチレン３５％か
らなる不飽和ポリエステル樹脂６０部と重合度２５００
のポリスチレンの５０％スチレン溶液２０部と実施例１
．２．５．６で得られたブロック共重合体Ａ、Ｂ、Ｅ、
Ｆを固型分３０％になるようにスチレンに溶解した溶液
２０ 部、ｔ−７’チルバ一ベンゾエート１部、ステア
リン酸亜鉛４部、炭酸カルシウム１８０部、ポリトンブ
ランクＰＴ５１５２ （大日本インキ化学工業（掬製）
１部を混合し、さらに酸化マグネシウム１部を加え良く
混合後、−昼夜熟成し増粘させた。(Radical polymerizable unsaturated resin composition using a low shrinkage agent) Examples 11 to 14 Unsaturated polyester (A) 65 consisting of 1 mol of propylene glycol, 2 mol of neopentyl glycol, 1 mol of terephthalic acid, and 2 mol of fumaric acid % and 60 parts of unsaturated polyester resin consisting of 35% styrene and degree of polymerization 2500
20 parts of a 50% styrene solution of polystyrene and Example 1
．． Block copolymers A, B, E obtained in 2.5.6,
20 parts of a solution of F dissolved in styrene to a solid content of 30%, 1 part of t-7' tilba-benzoate, 4 parts of zinc stearate, 180 parts of calcium carbonate, Polyton Blank PT5152 (Dainippon Ink & Chemicals) (made by scooping)
After 1 part of the mixture was mixed, 1 part of magnesium oxide was added and mixed well, and the mixture was aged day and night to increase the viscosity.
この配合物６５ｇをＪＩＳＫ−６９１１に規定された金
型に入れ、１４０℃にて５分間硬化させ、円板状の成形
品を作成し、収縮率を表１の場合と同様に測定した結果
を表２に示す。65g of this compound was placed in a mold specified in JISK-6911 and cured at 140°C for 5 minutes to create a disc-shaped molded product.The shrinkage rate was measured in the same manner as in Table 1. It is shown in Table 2.
比較例４
実施例１で得られたブロック共重合体Ａを用いずに不飽
和ポリエステル樹脂６０部と重合度２５００のポリスチ
レンの５０％溶液を３２部とスチレン８部を使用した以
外は同様にして得た成形品について収縮率を測定した。Comparative Example 4 The same procedure was carried out except that block copolymer A obtained in Example 1 was not used, but 60 parts of unsaturated polyester resin, 32 parts of a 50% solution of polystyrene with a degree of polymerization of 2500, and 8 parts of styrene were used. The shrinkage rate of the obtained molded article was measured.
結果を表２に示す。The results are shown in Table 2.
）
／
／
／
表
実施例１５〜１８
プロピレングリコール１モル、フマール酸１モルからな
る不飽和ポリエステル（Ｂ）の７０％とスチレン３０％
からなる不飽和ポリエステル５゜部と、エチレンーブタ
ジエンブロソクボリマー（クレイトンＤ１３００Ｘ、シ
エルケξカルカンパニー製）の３０％スチレン溶液３０
部と、実施例１．２．５．６のブロック共重合体を固型
分３０％になるようにスチレンに溶解した溶液２０部、
ｔブチルバーベンジェ−１〜１部、ステアリン酸亜鉛４
部、炭酸カルシウム１５０部を混合し、さらに酸化マグ
ネシウム１部を加え、配合物をＳＭＣ製造機に供給し、
ガラス含量が３０％になるようにガラス繊維を１インチ
に裁断しながらＳＭＣを製作した。このＳＭＣを３５℃
、２４時間熟成後、３００＋＋ｎＸ ５００ｓｓＣＤ金
型に入れ、１４０”Ｃ１１００ｋｇ／ｃｄの圧力にて５
分間成形し、厚さ３市の平板を作成した。表３に表１と
同様に測定した結果を示す。) / / / Table Examples 15 to 18 70% of unsaturated polyester (B) consisting of 1 mol of propylene glycol and 1 mol of fumaric acid and 30% of styrene
30% of a 30% styrene solution of ethylene-butadiene broth polymer (Kraton D1300X, manufactured by Schierke Cal Company)
20 parts of a solution of the block copolymer of Example 1.2.5.6 dissolved in styrene to a solid content of 30%,
1 to 1 part of t-butyl barbenjee, 4 parts of zinc stearate
150 parts of calcium carbonate, further adding 1 part of magnesium oxide, and feeding the formulation to an SMC manufacturing machine,
SMC was manufactured by cutting glass fiber into 1-inch pieces so that the glass content was 30%. This SMC at 35℃
, After aging for 24 hours, it was placed in a 300++nX 500ssCD mold and heated at a pressure of 140"
It was molded for 3 minutes to create a flat plate with a thickness of 3 cm. Table 3 shows the results measured in the same manner as in Table 1.
比較例５
実施例１で得られたブロック共重合体Ａを使用せず、ス
チレンーブタジエンブロックポリマーの３０％スチレン
溶液５０部使用した以外、実施例１７〜２０と同様にし
て平板を作成した。その測定結果を表３に示す。Comparative Example 5 A flat plate was prepared in the same manner as Examples 17 to 20, except that block copolymer A obtained in Example 1 was not used, and 50 parts of a 30% styrene solution of the styrene-butadiene block polymer was used. The measurement results are shown in Table 3.
表
実施例１９〜２
実施例１７〜２０において、クレイトンＤ−１３００Ｘ
の代わりにスチレン−水添イソプレン（ＫＬ−２００３
、クラレ■製）を用いた以外は同様にして平板を作威し
た。実施例１７〜２０と同様に測定した結果を表３に示
す。Table Examples 19-2 In Examples 17-20, Kraton D-1300X
Styrene-hydrogenated isoprene (KL-2003
A flat plate was made in the same manner except that a material (manufactured by Kuraray ■) was used. Table 3 shows the results measured in the same manner as in Examples 17-20.
比較例６
比較例５のクレイトンＤ−１３００Ｘの代わりに、ＫＬ
２００３を用いた以外は同様にして平板を作成した。Comparative Example 6 Instead of Kraton D-1300X in Comparative Example 5, KL
A flat plate was prepared in the same manner except that 2003 was used.
これについても実施例１７〜２０と同様に測定した結果
を表４に示す。This was also measured in the same manner as in Examples 17 to 20, and the results are shown in Table 4.
ノ
／
表
実施例２
ビニルエステル樹脂として、
分子量８００のビ
スフェノールＡ型エポキシ樹脂と、メタアクリル酸を反
応させた後、スチレンで不揮発分６０％となるように希
釈したものを５０部と、実施例１で用いた低収縮剤溶液
５０部、ｔ−ブチルパーベンゾエート１部、ステアリン
酸亜鉛４部、炭酸カルシウム２５０部をニーダ−にて混
合し、さらに０、５インチのチョツプドガラス６３部を
添加した。/Table Example 2 As a vinyl ester resin, 50 parts of a bisphenol A type epoxy resin having a molecular weight of 800 and methacrylic acid were reacted and then diluted with styrene to have a non-volatile content of 60%. 50 parts of the low shrinkage agent solution used in 1, 1 part of t-butyl perbenzoate, 4 parts of zinc stearate, and 250 parts of calcium carbonate were mixed in a kneader, and 63 parts of 0.5 inch chopped glass was added.
得られたＢＭＣを実施例９と同様にして平板を作威し、
評価した。成形収縮率は−０，０１％、ロングウェーブ
３．２、ショートウェーブ３１０であった。A flat plate was prepared from the obtained BMC in the same manner as in Example 9,
evaluated. The molding shrinkage rate was -0.01%, the long wave was 3.2, and the short wave was 310.
比較例７
実施例２３で用いた実施例１の低収縮剤の代わりに比較
例４で用いたポリスチレンを使用した以外は同様にして
ＢＭＣを作成し、同様に平板の評価を行った。その結果
、成形収縮率０．１２％、ロングウェーブ９．７、ショ
ートウェーブ６３０であった。Comparative Example 7 A BMC was prepared in the same manner except that the polystyrene used in Comparative Example 4 was used in place of the low shrinkage agent of Example 1 used in Example 23, and the flat plate was evaluated in the same manner. As a result, the molding shrinkage rate was 0.12%, the long wave was 9.7, and the short wave was 630.
実施例２４
ビニルエステル樹脂として分子量８００のビスフェノー
ルＡ型エポキシ樹脂とメタアクリル酸を反応させた後、
スチレンで不揮発分６０％となるように希釈したものを
５０部、実施例１５で用いたスチレン−ブタジェンブロ
ックポリマーのスチレン溶液３０部、実施例１のポリカ
プロラクトンポリウレタン−ポリスチレンプロツクポリ
マーのスチレン溶液２０部、ｔ−ブチルパーベンゾエー
ト１部、ステアリン酸亜鉛４部、炭酸カルシウム２５０
部をニーグーにて混合し、さらに０．５インチのチョツ
プドガラス６３部を添加した。得られたＢＭＣを実施例
５と同様にして平板を作威し、その評価を行った。その
結果、成形収縮率−０，０９５％、ロングウェーブ２．
４０、ショートウェーブ２８０であった。Example 24 After reacting a bisphenol A type epoxy resin with a molecular weight of 800 as a vinyl ester resin with methacrylic acid,
50 parts of styrene diluted to a nonvolatile content of 60%, 30 parts of the styrene solution of the styrene-butadiene block polymer used in Example 15, and the styrene solution of the polycaprolactone polyurethane-polystyrene block polymer of Example 1. 20 parts, t-butyl perbenzoate 1 part, zinc stearate 4 parts, calcium carbonate 250 parts
63 parts of 0.5 inch chopped glass were added. A flat plate was prepared from the obtained BMC in the same manner as in Example 5, and the plate was evaluated. As a result, molding shrinkage rate -0,095%, long wave 2.
40, short wave 280.
比較例８
実施例２４で用いた実施例１のポリカプロラクトンポリ
ウレタンーポリスチレンブロックポリマーを使用せずに
、スチレンーブタジエンプロソクボリマーのスチレン溶
液３０部を５０部に変更した以外は同様にしてＢＭＣを
作成し、平板の評価を行った。その結果成形収縮率−０
，０４０％、ロングウェーブ３．９５、ショートウェー
ブ４７０であった・
〔発明の効果〕
本発明によれば、縮合系重合体とビニル系重合体とを有
するブロック共重合体からなる低収縮剤を含有させたラ
ジカル重合性不飽和樹脂組成物から得られる成形品を提
供することができるので、その成形品を得る際の重合硬
化時の収縮率を低くでき、したがって寸法安定性が良い
のみならず、各成分の相溶性も良く均質かつ表面平滑性
に優れた成形物を与えることができる。Comparative Example 8 BMC was produced in the same manner as in Example 24, except that the polycaprolactone polyurethane-polystyrene block polymer of Example 1 was not used, and the styrene solution of styrene-butadiene prosol polymer was changed from 30 parts to 50 parts. was created and the flat plate was evaluated. As a result, molding shrinkage rate -0
, 040%, long wave 3.95, and short wave 470. [Effects of the Invention] According to the present invention, a low shrinkage agent made of a block copolymer having a condensation polymer and a vinyl polymer is used. Since it is possible to provide a molded article obtained from a radically polymerizable unsaturated resin composition containing the above-mentioned radically polymerizable unsaturated resin composition, the shrinkage rate during polymerization and curing when obtaining the molded article can be lowered, and therefore not only has good dimensional stability but also , it is possible to provide a molded product with good compatibility of each component, homogeneity, and excellent surface smoothness.
また、ポリスチレンやスチレン−共役ブロックポリマー
等と本発明の低収縮剤を併用すると、これら樹脂の重合
性不飽和樹脂に対する相溶性が向上し、ラジカル重合性
不飽和樹脂組成物の成形時の硬化収縮を更に効果的に抑
制できる。Furthermore, when the low-shrinkage agent of the present invention is used in combination with polystyrene, styrene-conjugated block polymers, etc., the compatibility of these resins with polymerizable unsaturated resins improves, and the cure shrinkage during molding of radically polymerizable unsaturated resin compositions increases. can be suppressed even more effectively.
このように本発明を用いると、成形品の低収縮性、均質
性等が改善されるのみならず、機械的強度、着色性、耐
煮沸性等の性質も改善させることができる。As described above, when the present invention is used, not only the low shrinkage and homogeneity of the molded article can be improved, but also the properties such as mechanical strength, colorability, and boiling resistance can be improved.
Claims (1)
有するブロック共重合体と を含有する ことを特徴とするラジカル重合性不飽和樹脂組成物。 ２、ブロック共重合体が、縮合系重合体アゾ系ラジカル
重合開始剤を用いてビニル系単量体を重合させることに
より得られるものであることを特徴とする請求項１記載
のラジカル重合性不飽和樹脂組成物。 ３、縮合系重合体アゾ系ラジカル重合開始剤が、官能基
含有縮合系重合体と官能基含有アゾ系ラジカル重合開始
剤とを反応させることにより得られるものである請求項
２記載のラジカル重合性不飽和樹脂組成物。 ４、官能基含有縮合系重合体が、飽和ポリエステル、ポ
リエーテル及びポリカーボネート、ポリウレタンから選
ばれる少なくとも１種のポリマーである請求項３記載の
ラジカル重合性不飽和樹脂組成物。 ５、官能基含有アゾ系ラジカル重合開始剤が、活性水素
含有アゾ化合物、またはＣＯＯＨ基含有アゾ化合物であ
る請求項３記載のラジカル重合性不飽和樹脂組成物。 ６、官能基含有縮合系重合体と官能基含有アゾ系ラジカ
ル重合開始剤との反応が、ＮＣＯ基を有するポリウレタ
ンと活性水素含有アゾ系ラジカル重合開始剤との反応に
よるもので、この反応が少量の溶媒の存在下で行われる
ものであることを特徴とする請求項１、２、３のラジカ
ル重合性不飽和樹脂組成物。 ７、官能基含有縮合系重合体と官能基含有アゾ系ラジカ
ル重合開始剤との反応が、ＯＨ基を有するポリウレタン
、ＯＨ基を有するポリエステル、ＯＨ基を有するポリエ
ーテル及びＯＨ基を有するポリカーボネートから選ばれ
る少なくとも１種とＣＯＯＨ基含有アゾ系ラジカル重合
開始剤との反応によるもので、その反応が溶媒の存在下
で行われるものであることを特徴とする請求項１、２、
３のラジカル重合性不飽和樹脂組成物。 ８、活性水素含有アゾ系ラジカル重合開始剤が、ＯＨ基
含有アゾ化合物である請求項５のラジカル重合性不飽和
樹脂組成物。 ９、ポリウレタンが、飽和ポリエステル、ポリエーテル
及びポリカーボネートから選ばれる少なくとも１種のＯ
Ｈ基含有ポリマー及び／又はこれらの各々若しくは混合
物とポリイソシアネート化合物とを反応したものである
請求項４、６、７のラジカル重合性不飽和樹脂組成物。 １０、組成比が、（Ａ）ラジカル重合性不飽和樹脂２０
〜５５重量部と、（Ｂ）重合性不飽和単量体３０〜６０
重量部と、（Ｃ）縮合系重合体とビニル系重合体とをブ
ロック重合成分として有するブロック共重合体２〜２５
重量部とを含有することを特徴とする請求項１〜９記載
のラジカル重合性不飽和樹脂組成物。 １１、（Ｄ）ポリスチレン、スチレン−共役ジエンブロ
ック共重合体及びスチレン−水添共役ジエンブロック共
重合体の少なくとも１種を更に含有させたことを特徴と
する請求項１〜１０記載のラジカル重合性不飽和樹脂組
成物。 １２、（Ｄ）成分を３〜２０重量部含有させたことを特
徴とする請求項１０、１１記載のラジカル重合性不飽和
樹脂組成物。 １３、請求項１〜１２のラジカル重合性不飽和樹脂組成
物を用いたことを特徴とする成形材料。 １４、縮合系重合ブロックとビニル系重合ブロックとを
有するブロック共重合体からなり、ラジカル重合性不飽
和樹脂組成物に含有させて用いられる低収縮剤。 １５、官能基含有縮合系重合体と官能基含有アゾ系ラジ
カル重合開始剤とを反応して得られる縮合系重合体含有
アゾ系ラジカル重合開始剤を用い、ビニル系単量体を重
合反応することを特徴とするラジカル重合性不飽和樹脂
組成物の低収縮剤の製造法。[Claims] 1. A block copolymer having (A) a radically polymerizable unsaturated resin, (B) a polymerizable unsaturated monomer, and (C) a condensation polymer block and a vinyl polymer block. A radically polymerizable unsaturated resin composition comprising: 2. The radically polymerizable inorganic compound according to claim 1, wherein the block copolymer is obtained by polymerizing a vinyl monomer using a condensation polymer azo radical polymerization initiator. Saturated resin composition. 3. Radical polymerization according to claim 2, wherein the condensation polymer azo radical polymerization initiator is obtained by reacting a functional group-containing condensation polymer and a functional group-containing azo radical polymerization initiator. Unsaturated resin composition. 4. The radically polymerizable unsaturated resin composition according to claim 3, wherein the functional group-containing condensation polymer is at least one polymer selected from saturated polyester, polyether, polycarbonate, and polyurethane. 5. The radically polymerizable unsaturated resin composition according to claim 3, wherein the functional group-containing azo radical polymerization initiator is an active hydrogen-containing azo compound or a COOH group-containing azo compound. 6. The reaction between the functional group-containing condensation polymer and the functional group-containing azo radical polymerization initiator is due to the reaction between the NCO group-containing polyurethane and the active hydrogen-containing azo radical polymerization initiator. The radically polymerizable unsaturated resin composition according to claim 1, 2 or 3, characterized in that the polymerization is carried out in the presence of a solvent. 7. The reaction between the functional group-containing condensation polymer and the functional group-containing azo radical polymerization initiator is performed using a polyurethane having an OH group, a polyester having an OH group, a polyether having an OH group, and a polycarbonate having an OH group. Claims 1 and 2, characterized in that the reaction is carried out in the presence of a solvent, and the reaction is carried out in the presence of a solvent.
3. Radically polymerizable unsaturated resin composition. 8. The radically polymerizable unsaturated resin composition according to claim 5, wherein the active hydrogen-containing azo radical polymerization initiator is an OH group-containing azo compound. 9. The polyurethane is at least one O selected from saturated polyester, polyether and polycarbonate.
8. The radically polymerizable unsaturated resin composition according to claim 4, which is obtained by reacting an H group-containing polymer and/or each or a mixture thereof with a polyisocyanate compound. 10, composition ratio is (A) radically polymerizable unsaturated resin 20
~55 parts by weight, and (B) 30 to 60 parts by weight of polymerizable unsaturated monomer
parts by weight, and (C) block copolymers 2 to 25 having a condensation polymer and a vinyl polymer as block polymerization components.
The radically polymerizable unsaturated resin composition according to any one of claims 1 to 9, characterized in that it contains parts by weight. 11. The radical polymerizable material according to claims 1 to 10, further comprising (D) at least one of polystyrene, a styrene-conjugated diene block copolymer, and a styrene-hydrogenated conjugated diene block copolymer. Unsaturated resin composition. 12. The radically polymerizable unsaturated resin composition according to claims 10 and 11, which contains 3 to 20 parts by weight of component (D). 13. A molding material characterized by using the radically polymerizable unsaturated resin composition according to claims 1 to 12. 14. A low-shrinkage agent comprising a block copolymer having a condensation polymer block and a vinyl polymer block, which is used by being included in a radically polymerizable unsaturated resin composition. 15. Polymerizing a vinyl monomer using a condensation polymer-containing azo radical polymerization initiator obtained by reacting a functional group-containing condensation polymer with a functional group-containing azo radical polymerization initiator. A method for producing a low shrinkage agent for a radically polymerizable unsaturated resin composition, characterized by:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24520189 | 1989-09-22 | ||
| JP1-245201 | 1989-09-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03174424A true JPH03174424A (en) | 1991-07-29 |
| JP3000478B2 JP3000478B2 (en) | 2000-01-17 |
Family
ID=
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002201241A (en) * | 2000-12-28 | 2002-07-19 | Nippon Shokubai Co Ltd | Resin composition for waterproof coating, waterproof coated structure, and waterproofing coating method |
| US6555618B1 (en) | 1999-11-05 | 2003-04-29 | Dainippon Ink And Chemicals, Inc. | Compatibilizing agent, radical polymerizable resin composition, molding material, and molded article |
| US11518834B2 (en) | 2019-01-02 | 2022-12-06 | Polynt Composites USA, Inc. | Radically polymerizable compositions |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6555618B1 (en) | 1999-11-05 | 2003-04-29 | Dainippon Ink And Chemicals, Inc. | Compatibilizing agent, radical polymerizable resin composition, molding material, and molded article |
| US6897258B2 (en) | 1999-11-05 | 2005-05-24 | Dainippon Ink And Chemicals, Inc. | Compatibilizing agent, radical polymerizable resin composition, molding material, and molded article |
| JP2002201241A (en) * | 2000-12-28 | 2002-07-19 | Nippon Shokubai Co Ltd | Resin composition for waterproof coating, waterproof coated structure, and waterproofing coating method |
| US11518834B2 (en) | 2019-01-02 | 2022-12-06 | Polynt Composites USA, Inc. | Radically polymerizable compositions |
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