JP4374990B2 - Radical polymerizable resin composition - Google Patents
Radical polymerizable resin composition Download PDFInfo
- Publication number
- JP4374990B2 JP4374990B2 JP2003384961A JP2003384961A JP4374990B2 JP 4374990 B2 JP4374990 B2 JP 4374990B2 JP 2003384961 A JP2003384961 A JP 2003384961A JP 2003384961 A JP2003384961 A JP 2003384961A JP 4374990 B2 JP4374990 B2 JP 4374990B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- resin
- acrylate
- acid
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000011342 resin composition Substances 0.000 title claims description 29
- 229920005989 resin Polymers 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 29
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 20
- 238000007605 air drying Methods 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 87
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 55
- -1 dicyclopentadiene compound Chemical class 0.000 description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- 238000001723 curing Methods 0.000 description 22
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000003822 epoxy resin Substances 0.000 description 14
- 125000000524 functional group Chemical group 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 229920000647 polyepoxide Polymers 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000002516 radical scavenger Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical class C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000002000 scavenging effect Effects 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- 229940049920 malate Drugs 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- JFZHPFOXAAIUMB-UHFFFAOYSA-N Phenylethylmalonamide Chemical compound CCC(C(N)=O)(C(N)=O)C1=CC=CC=C1 JFZHPFOXAAIUMB-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 2
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 240000006240 Linum usitatissimum Species 0.000 description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 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
- 150000007513 acids Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 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 group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- NQPJDJVGBDHCAD-UHFFFAOYSA-N 1,3-diazinan-2-one Chemical compound OC1=NCCCN1 NQPJDJVGBDHCAD-UHFFFAOYSA-N 0.000 description 1
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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Description
本発明は、ホルムアルデヒド捕捉機能を有するラジカル重合性樹脂組成物に関するものである。 The present invention relates to a radical polymerizable resin composition having a formaldehyde scavenging function.
一般に用いられるラジカル重合性樹脂は、機械的物性、耐水性、耐薬品性等が良好であるため、成形品、塗料、接着剤等の様々な用途に幅広く用いられている。
ガラス繊維等の繊維強化材とラジカル重合性樹脂を積層硬化せしめて所謂、繊維強化プラスチック（ＦＲＰ）として、その優れた機械的強度、性能を活かし、防水パン、浴槽、カウンター、仕切板、壁材、車両部材、室内部材等、室内外用途含め、幅広く用いられている。
また、かかるラジカル硬化性樹脂に、フィラー、顔料等の充填剤、添加剤を混合させ、前記成形品、塗料、接着剤等として用いることができ、幅広い応用用途を有している。
しかしながら、かかるラジカル硬化性樹脂を重合硬化させるラジカル硬化剤により、重合性不飽和二重結合を有するラジカル重合性不飽和樹脂と反応性不飽和単量体とを反応させ硬化物を得る際に、硬化物からホルムアルデヒドが発生させることが知られている（例えば非特許文献１参照）。
Generally used radically polymerizable resins have good mechanical properties, water resistance, chemical resistance, and the like, and are therefore widely used in various applications such as molded articles, paints, and adhesives.
A fiber reinforced plastic (FRP) made by laminating and curing a fiber-reinforced material such as glass fiber and a radically polymerizable resin, making use of its excellent mechanical strength and performance, waterproof pan, bathtub, counter, partition plate, wall material Widely used for indoor and outdoor applications such as vehicle members and indoor members.
Moreover, fillers and additives such as fillers and pigments can be mixed with such radical curable resins and used as the molded products, paints, adhesives, and the like, and thus have a wide range of applications.
However, with a radical curing agent that polymerizes and cures such a radical curable resin, a radical polymerizable unsaturated resin having a polymerizable unsaturated double bond is reacted with a reactive unsaturated monomer to obtain a cured product. It is known that formaldehyde is generated from a cured product (see, for example, Non-Patent Document 1).
ホルムアルデヒドは、シックハウス等環境問題の原因物質とされ、その放散量が平成１５年７月より建築基準法により規制された。このため、硬化の際に発生するホルムアルデヒドをいかに削減させるかが、大きな問題となっている。この規制に対して、1)ホルムアルデヒドの放散量がある値より減少するまで硬化後の放置時間を長くする方法、2)高温での後硬化を行いホルムアルデヒドを強制的に揮散させ、硬化物中のホルムアルデヒドを放出させる方法、また3)ホルムアルデヒド捕捉材を後添加しホルムアルデヒドの放散を抑える方法が有用と考えられるが、実質有効な方法は、見いだされていないのが実状であった。
本発明の目的は、ラジカル重合し硬化する時に発生するホルムアルデヒドの捕捉機能を有し、硬化成形物からホルムアルデヒドの放散を抑えたラジカル重合性樹脂組成物を提供することである。 An object of the present invention is to provide a radically polymerizable resin composition that has a function of capturing formaldehyde generated during radical polymerization and curing, and suppresses formaldehyde emission from a cured molded product.
本発明者らは、これらの課題について鋭意研究の結果、硬化を阻害することなく、有効なホルムアルデヒド捕捉機能を有する化合物を見いだし、本発明を完成するに至ったものである。 As a result of intensive studies on these problems, the present inventors have found a compound having an effective formaldehyde scavenging function without inhibiting curing, and have completed the present invention.
即ち、本発明は、不飽和ポリエステル樹脂からなる１分子中に２個以上のエチレン性不飽和二重結合を有する樹脂（Ａ）と、分子中にエチレン性不飽和二重結合を有する単量体（Ｂ）と、エチレン尿素及びアジピン酸ジヒドラジドからなる群より選ばれる１種以上の化合物（Ｃ）とを含有してなり、前記化合物（Ｃ）が樹脂（Ａ）１００重量部に対して０．０１〜１．０重量部含まれるラジカル重合性樹脂組成物を提供するものである。
That is, the present invention relates to a resin (A) having two or more ethylenically unsaturated double bonds in one molecule comprising an unsaturated polyester resin, and a monomer having an ethylenically unsaturated double bond in the molecule. and (B), 1 or more compound selected from the group consisting of ethylene urea and adipic acid dihydrazide (C) and Ri greens contain the compound (C) is a resin (a) with respect to 100 parts by weight 0 The present invention provides a radical polymerizable resin composition contained in an amount of 0.01 to 1.0 part by weight.
本発明のラジカル重合性樹脂組成物は、特定のホルムアルデヒド捕捉剤を含むため、硬化時に発生するホルムアルデヒドを効率よく捕捉し、シックハウス対応型環境樹脂として非常に有用である。 Since the radically polymerizable resin composition of the present invention contains a specific formaldehyde scavenger, it efficiently captures formaldehyde generated during curing and is very useful as an environmental resin for sick houses.
次に本発明を詳細に説明する。
本発明に使用する１分子中に２個以上のエチレン性不飽和二重結合を有する樹脂（Ａ）［以下ラジカル硬化性樹脂（Ａ）という］としては、例えば、不飽和ポリエステル樹脂、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート等が挙げられる。これらの樹脂の数平均分子量は３００より大きいものであり、樹脂硬化物の物性の点で、５００〜５０００のものが好ましい。これらの樹脂は単独で使用しても良いし、必要に応じ２種以上併用しても良い。
Next, the present invention will be described in detail.
Examples of the resin (A) having two or more ethylenically unsaturated double bonds in one molecule used in the present invention (hereinafter referred to as radical curable resin (A)) include unsaturated polyester resins, epoxy (meta) ) Acrylate, urethane (meth) acrylate, polyester (meth) acrylate and the like. These resins have a number average molecular weight of more than 300, and preferably 500 to 5000 in terms of physical properties of the cured resin. These resins may be used alone or in combination of two or more as required.
これらのラジカル硬化性樹脂は、特に制限されないが、性能、用途面より選ばれる樹脂が好適であり、この点で不飽和ポリエステル樹脂が好ましい。
かかる不飽和ポリエステル樹脂とは、α，β−不飽和二塩基酸及び飽和二塩基酸を含む二塩基酸類と多価アルコ−ル類、必要によりジシクロペンタジエン系化合物との縮合反応で得られるものであり、好ましくは分子量５００〜５０００の範囲のものである。
These radically curable resins are not particularly limited, but resins selected from the viewpoints of performance and application are suitable, and unsaturated polyester resins are preferred in this respect.
The unsaturated polyester resin is obtained by a condensation reaction of α, β-unsaturated dibasic acid and dibasic acid containing saturated dibasic acid and polyhydric alcohol, and if necessary, dicyclopentadiene compound. Preferably, it is a thing of the range of molecular weight 500-5000.
不飽和ポリエステルを調製するにあたって使用されるα，β−不飽和二塩基酸としては、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸等を挙げることができる。また、飽和二塩基酸としては、フタル酸、無水フタル酸、ハロゲン化無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロフタル酸、ヘキサヒドロ無水フタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸、コハク酸、マロン酸、グルタル酸、アジピン酸、セバシン酸、１，１２−ドデカン２酸，２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸無水物、４，４'−ビフェニルジカルボン酸、またこれらのジアルキルエステル等を挙げることができる。これらは、単独でも２種類以上組み合わせて使用しても良い。 Examples of the α, β-unsaturated dibasic acid used in preparing the unsaturated polyester include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like. The saturated dibasic acids include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid. Acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3- Examples include naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof. These may be used alone or in combination of two or more.
多価アルコ−ル類としては、例えばエチレングリコ−ル、ジエチレングリコ−ル、トリエチレングリコ−ル、ポリエチレングリコ−ル、プロピレングリコ−ル、ジプロピレングリコ−ル、ポリプロピレングリコ−ル、２−メチル−１，３−プロパンジオ−ル、１，３−ブタンジオ−ル、ネオペンチルグリコ−ル、水素化ビスフェノ−ルＡ、１，４−ブタンジオ−ル、ビスフェノ−ルＡとプロピレンオキシド又はエチレンオキシドの付加物、１，２，３，４−テトラヒドロキシブタン、グリセリン、トリメチロ−ルプロパン、１，３−プロパンジオ−ル、１，２−シクロヘキサングリコ−ル、１，３−シクロヘキサングリコ−ル、１，４−シクロヘキサングリコ−ル、１，４−シクロヘキサンジメタノ−ル、パラキシレングリコ−ル、ビシクロヘキシル−４，４'−ジオ−ル、２，６−デカリングリコ−ル、２，７−デカリングリコ−ル等を挙げることができる。 Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl- 1,3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, bisphenol A and an adduct of propylene oxide or ethylene oxide 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4- Cyclohexane glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclo Cyclohexyl-4,4' Geo - le, 2,6-decalin glycolate - le, 2,7-decalin glyco - can be exemplified Le like.
かかる不飽和ポリエステル樹脂は、空乾性付与型の不飽和ポリエステル樹脂を用いることができる。
かかる空乾性付与型の不飽和ポリエステル樹脂としては、(1)二塩基酸成分として環状脂肪族不飽和多塩基酸及びその誘導体を含有する化合物を用いたもの、(2)多価アルコール成分として水酸基含有アリルエーテル化合物を用いたもの、(3)ジシクロペンタジエン系化合物を用いたもの、(4)乾性油としてアマニ油及び桐油を用いたもの等が挙げられる。
As the unsaturated polyester resin, an air-drying imparted unsaturated polyester resin can be used.
Such an air-drying imparted unsaturated polyester resin includes (1) a compound containing a cycloaliphatic unsaturated polybasic acid and a derivative thereof as a dibasic acid component, and (2) a hydroxyl group as a polyhydric alcohol component. And (3) those using dicyclopentadiene compounds, (4) those using linseed oil and tung oil as drying oils, and the like.
本発明に使用するエポキシ（メタ）アクリレートとは、エポキシ樹脂と、不飽和一塩基酸とを、エステル化触媒の存在下で、反応せしめて得られるものである。エポキシ樹脂としては、ビスフェノール・タイプのエポキシ樹脂、ノボラック・タイプのエポキシ樹脂等を挙げることができ、これらの1種又は２種以上を組み合わせて用いることができる。その平均エポキシ当量は、１５０〜４５０なる範囲内にあるようなものが好ましい。 The epoxy (meth) acrylate used in the present invention is obtained by reacting an epoxy resin and an unsaturated monobasic acid in the presence of an esterification catalyst. Examples of the epoxy resin include a bisphenol type epoxy resin, a novolac type epoxy resin, and the like, and these can be used alone or in combination. The average epoxy equivalent is preferably in the range of 150 to 450.
前記ビスフェノール・タイプのエポキシ樹脂としては、例えばビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡエチレンオキシド付加型エポキシ樹脂、ビスフェノールＡプロピレンオキシド付加型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂の、１，６−ナフタレン型エポキシ樹脂等を挙げることができる。 Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A ethylene oxide addition type epoxy resin, bisphenol A propylene oxide addition type epoxy resin, and bisphenol F type epoxy resin. , 6-naphthalene type epoxy resin.
また前記ノボラックタイプのエポキシ樹脂としては、例えばフェノール・ノボラック又はクレゾール・ノボラックと、エピクロルヒドリン又はメチルエピクロルヒドリンとの反応によって得られるエポキシ樹脂などを挙げることができる。 Examples of the novolac type epoxy resin include an epoxy resin obtained by a reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.
さらに、前記不飽和一塩基酸としては、例えばアクリル酸、メタクリル酸、桂皮酸、クロトン酸、ソルビン酸、モノメチルマレート、モノプロピルマレート、モノブチルマレート、又はモノ（２−エチルヘキシル）マレートなどが挙げられる。 Furthermore, examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, monomethyl malate, monopropyl malate, monobutyl malate, and mono (2-ethylhexyl) malate. Is mentioned.
これらの不飽和一塩基酸は、単独又は２種以上の併用して用いられる。
前記エポキシ樹脂と不飽和一塩基酸との反応は、好ましくは、６０〜１４０℃、特に好ましくは、８０〜１２０℃なる範囲内の温度において行われる。
These unsaturated monobasic acids are used alone or in combination of two or more.
The reaction between the epoxy resin and the unsaturated monobasic acid is preferably performed at a temperature in the range of 60 to 140 ° C., particularly preferably 80 to 120 ° C.
前記エステル化触媒としては、公知慣用の化合物を使用できるが、例えばトリエチルアミン、Ｎ，Ｎ−ジメチルベンジルアミン、Ｎ，Ｎ−ジメチルアニリンもしくはジアザビシクロオクタンの如き、各種の３級アミン類；又はジエチルアミン塩酸塩などが挙げられる。 As the esterification catalyst, known and conventional compounds can be used. For example, various tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane; or diethylamine Examples include hydrochloride.
かかるエポキシ（メタ）アクリレートの数平均分子量としては、好ましくは、４５０〜２，５００、特に好ましくは５００〜２，２００なる範囲内が適切である。分子量が４５０未満の場合には、得られる硬化物に粘着性が生じたり、強度物性が低下したりするようになるし、一方、２，５００を越えると、硬化時間が長くなり、生産性が劣る傾向にある。 The number average molecular weight of the epoxy (meth) acrylate is preferably in the range of 450 to 2,500, particularly preferably 500 to 2,200. If the molecular weight is less than 450, the resulting cured product will become sticky or the strength properties will decrease. On the other hand, if it exceeds 2,500, the curing time will be longer and the productivity will be increased. It tends to be inferior.
前記ウレタン（メタ）アクリレートは、通常ポリオール、ポリイソシアネート及び１分子中に１個以上の水酸基を有する（メタ）アクリレート［以下水酸基含有(メタ)アクリレートという］を反応させることにより得られるものであり、分子中に（メタ）アクリロイル基を有するものである。
前記ポリオールとしては、例えばポリプロピレンオキシド、ポリエチレンオキシド、ポリテトラメチレングリコール、ビスフェノールＡエチレンオキシド付加物、ビスフェノールＡプロピレンオキシド付加物等のポリエーテルポリオール、ポリブタジエンジオール、ポリイソプレンジオール、ポリエステルエーテルポリオール、ポリエステルポリオール等が挙げられる。
The urethane (meth) acrylate is usually obtained by reacting polyol, polyisocyanate and (meth) acrylate having one or more hydroxyl groups in one molecule [hereinafter referred to as hydroxyl group-containing (meth) acrylate], It has a (meth) acryloyl group in the molecule.
Examples of the polyol include polyether polyols such as polypropylene oxide, polyethylene oxide, polytetramethylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, polybutadiene diol, polyisoprene diol, polyester ether polyol, polyester polyol and the like. Can be mentioned.
ポリイソシアネートとしては、例えば２，４−トリレンジイソシアネート及びその異性体又は異性体の混合物（以下ＴＤＩと略す）、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、トリジンジイソシアネート、ナフタリンジイソシアネート、トリフェニルメタントリイソシアネート等が挙げられる。上記ポリイソシアネートのうちジイソシアネート、特にＴＤＩが好ましく用いられる。これらを単独又は２種以上で使用することができる。
ポリイソシアネートの市販品としては、例えばバーノックＤー７５０、クリスボンＮＸ（大日本インキ化学工業（株）製品）、デスモジュールＬ（住友バイエル（株）社製品）、コロネートＬ（日本ポリウレタン社製品）、タケネートＤ１０２（武田薬品工業（株）社製品）、イソネート１４３Ｌ（三菱化学（株）社製）等を挙げることができる。
Examples of the polyisocyanate include 2,4-tolylene diisocyanate and its isomer or a mixture of isomers (hereinafter abbreviated as TDI), diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexyl. Examples include methane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. Of the above polyisocyanates, diisocyanates, particularly TDI, are preferably used. These can be used alone or in combination of two or more.
Examples of commercially available polyisocyanates include Burnock D-750, Crisbon NX (Dainippon Ink Chemical Co., Ltd. product), Desmodur L (Sumitomo Bayer Co., Ltd. product), Coronate L (Nippon Polyurethane product), Takenate D102 (manufactured by Takeda Pharmaceutical Co., Ltd.), isonate 143L (manufactured by Mitsubishi Chemical Corporation), and the like.
水酸基含有（メタ）アクリレートとしては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシブチル（メタ）アクリレート；ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等の様な水酸基を２個有するアルコールのモノ（メタ）アクリレート類；α−オレフィンエポキサイドと（メタ）アクリル酸の付加物、カルボン酸グリシジルエステルと（メタ）アクリル酸の付加物；トリス（ヒドロキシエチル）イソシアヌル酸のジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等の様な３個以上の水酸基を有するアルコールの部分（メタ）アクリレート類が挙げられる。 Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( Mono (meth) acrylates of alcohols having two hydroxyl groups such as (meth) acrylate; adducts of α-olefin epoxide and (meth) acrylic acid, glycidyl esters of carboxylic acid and (meth) acrylic acid; Tris Examples thereof include partial (meth) acrylates of alcohol having three or more hydroxyl groups, such as di (meth) acrylate of (hydroxyethyl) isocyanuric acid and pentaerythritol tri (meth) acrylate.
また、前記ウレタン（メタ）アクリレートの製造において、水酸基含有（メタ）アクリレートの一部を、本発明の効果を損なわない程度の範囲で、水酸基含有アリールエーテル化合物や高級アルコール等で置換したものを用いることができる。 Further, in the production of the urethane (meth) acrylate, a part of the hydroxyl group-containing (meth) acrylate is substituted with a hydroxyl group-containing aryl ether compound or a higher alcohol within a range not impairing the effects of the present invention. be able to.
水酸基含有アリールエーテル化合物としては、例えばエチレングリコールモノアリールエーテル、ジエチレングリコールモノアリールエーテル、トリエチレングリコールモノアリールエーテル、ポリエチレングリコールモノアリールエーテル、プロピレングリコールモノアリールエーテル、ジプロピレングリコールモノアリールエーテル、トリプロピレングリコールモノアリールエーテル、ポリプロピレングリコールモノアリールエーテル、１，２−ブチレングリコールモノアリールエーテル、１，３−ブチレングリコールモノアリールエーテル、ヘキシレングリコールモノアリールエーテル、オクチレングリコールモノアリールエーテル、トリメチロールプロパンジアリールエーテル、グリセリンジアリールエーテル、ペンタエリスリトールトリアリールエーテル等の多価アルコール類のアリールエーテル化合物等が挙げられ、これらのうち、水酸基を１個有するアリールエーテル化合物が好ましい。 Examples of the hydroxyl group-containing aryl ether compound include ethylene glycol monoaryl ether, diethylene glycol monoaryl ether, triethylene glycol monoaryl ether, polyethylene glycol monoaryl ether, propylene glycol monoaryl ether, dipropylene glycol monoaryl ether, tripropylene glycol mono Aryl ether, polypropylene glycol monoaryl ether, 1,2-butylene glycol monoaryl ether, 1,3-butylene glycol monoaryl ether, hexylene glycol monoaryl ether, octylene glycol monoaryl ether, trimethylolpropane diaryl ether, glycerin Diaryl ether, pentaerythrito Aryl ether compounds of polyhydric alcohols such as triaryl ether. Of these, the aryl ether compounds having one hydroxyl group are preferred.
高級アルコールとしては、例えばデシルアルコール、ウンデシルアルコール、ラウリルアルコール、トリデシルアルコール、ステアリルアルコール等が挙げられる。 Examples of the higher alcohol include decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, stearyl alcohol, and the like.
ウレタン（メタ）アクリレートの製造方法としては、1)先ずポリイソシアネートとポリオールを好ましくはＮＣＯ／ＯＨ＝１．５〜２で反応させ、末端イソシアネート基を有する化合物を生成させ、次いでその化合物に水酸基含有（メタ）アクリレートをイソシアネート基に対して水酸基がほぼ等量になるように反応する方法と、2)ポリイソシアネート化合物と水酸基含有（メタ）アクリレートをＮＣＯ／ＯＨ＝２以上で反応させ、片末端にイソシアネート基を有する化合物を生成させ、次いでポリオールを加えて反応する方法等が挙げられる。得られるウレタン（メタ）アクリレートの数平均分子量は、５００〜３００００であることが好ましく、７００〜５０００であることが特に好ましい。 The production method of urethane (meth) acrylate is as follows: 1) First, a polyisocyanate and a polyol are preferably reacted at NCO / OH = 1.5 to 2 to form a compound having a terminal isocyanate group, and then the compound contains a hydroxyl group. A method of reacting (meth) acrylate with an isocyanate group so that the hydroxyl group is substantially equivalent, and 2) reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate at NCO / OH = 2 or more, Examples thereof include a method in which a compound having an isocyanate group is formed and then a polyol is added to react. The number average molecular weight of the obtained urethane (meth) acrylate is preferably 500 to 30000, and particularly preferably 700 to 5000.
前記のラジカル硬化性樹脂（Ａ）の一つであるポリエステル（メタ）アクリレートとは、１分子中に２個以上の（メタ）アクリロイル基を有する飽和ポリエステル樹脂もしくは不飽和ポリエステル樹脂をいい、飽和ポリエステル樹脂若しくは不飽和ポリエステル樹脂の末端に（メタ）アクリロイル基を有する化合物を反応させたものである。かかる樹脂の数平均分子量としては、好ましくは５００〜５０００、より好ましくは１０００〜５０００である。 The polyester (meth) acrylate which is one of the radical curable resins (A) means a saturated polyester resin or an unsaturated polyester resin having two or more (meth) acryloyl groups in one molecule. A compound having a (meth) acryloyl group at the terminal of a resin or unsaturated polyester resin is reacted. The number average molecular weight of the resin is preferably 500 to 5000, more preferably 1000 to 5000.
本発明に使用する分子中にエチレン性不飽和二重結合を有する単量体（以下重合性不飽和単量体という）としては、例えばスチレン、α-メチルスチレン、クロルスチレン、ジクロルスチレン、ジビニルベンゼン、t-ブチルスチレン、ビニルトルエン、酢酸ビニル、ジアリールフタレ-ト、トリアリールシアヌレ-ト、さらにアクリル酸エステル、メタクリル酸エステル等；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸トリデシル、ジシクロペンテニロキシエチル（メタ）アクリレート、エチレングリコールモノメチルエーテル（メタ）アクリレート、エチレングリコールモノエチルエーテル（メタ）アクリレート、エチレングリコールモノブチルエーテル（メタ）アクリレート、エチレングリコールモノヘキシルエーテル（メタ）アクリレート、エチレングリコールモノ２ーエチルヘキシルエーテル（メタ）アクリレート、ジエチレングリコールモノメチルエーテル（メタ）アクリレート、ジエチレングリコールモノエチルエーテル（メタ）アクリレート、ジエチレングリコールモノブチルエーテル（メタ）アクリレート、ジエチレングリコールモノヘキシルエーテル（メタ）アクリレート、ジエチレングリコールモノ２ーエチルヘキシルエーテル（メタ）アクリレート、ジプロピレングリコールモノメチルエーテル（メタ）アクリレート、ジプロピレングリコールモノエチルエーテル（メタ）アクリレート、ジプロピレングリコールモノブチルエーテル（メタ）アクリレート、ジプロピレングリコールモノヘキシルエーテル（メタ）アクリレート、ジプロピレングリコールモノ２ーエチルヘキシルエーテル（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコ-ルジ（メタ）アクリレ-ト、ＰＴＭＧのジメタアクリーレート、１，３−ブチレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、２−ヒドロキシ１，３ジメタクリロキシプロパン、２，２−ビス〔４−（メタクリロキシエトキシ）フェニル〕プロパン、２，２−ビス〔４−（メタクリロキシ・ジエトキシ）フェニル〕プロパン、２，２−ビス〔４−（メタクリロキシ・ポリエトキシ）フェニル〕プロパン、テトラエチレングリコールジアクリレート、ビスフェノールＡＥＯ変性（ｎ＝２）ジアクリレート、イソシアヌル酸ＥＯ変性（ｎ＝３）ジアクリレート、ペンタエリスリトールジアクリレートモノステアレート等の重合性不飽和単量体或いは不飽和オリゴマー等が挙げられる。これら重合性不飽和単量体は、単独でも２種類以上組み合わせて使用しても良い。 Examples of the monomer having an ethylenically unsaturated double bond (hereinafter referred to as polymerizable unsaturated monomer) used in the present invention include styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, and divinyl. Benzene, t-butyl styrene, vinyl toluene, vinyl acetate, diaryl phthalate, triaryl cyanurate, further acrylic ester, methacrylic ester, etc .; methyl (meth) acrylate, ethyl (meth) acrylate, N-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, Benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, disic Lopentenyloxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono 2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether ( Meth) acrylate, zip Pyrene glycol monomethyl ether (meth) acrylate, dipropylene glycol monoethyl ether (meth) acrylate, dipropylene glycol monobutyl ether (meth) acrylate, dipropylene glycol monohexyl ether (meth) acrylate, dipropylene glycol mono-2-ethylhexyl ether ( (Meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, PTMG dimethacrylate, 1,3-butylene glycol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, 2-hydroxy 1,3 dimethacryloxypropane, 2,2-bis [4- (methacryloxyate) Xyl) phenyl] propane, 2,2-bis [4- (methacryloxy / diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy / polyethoxy) phenyl] propane, tetraethylene glycol diacrylate, bisphenol AEO modified ( n = 2) Polymerizable unsaturated monomers or unsaturated oligomers such as diacrylate, isocyanuric acid EO-modified (n = 3) diacrylate, pentaerythritol diacrylate monostearate, and the like. These polymerizable unsaturated monomers may be used alone or in combination of two or more.
本発明のラジカル重合性樹脂組成物は、分子中にヒドラゾ基、尿素結合又はウレタン結合のいずれかの官能基を有する化合物（Ｃ）を含むものである。
かかる分子中にヒドラゾ基、尿素結合又はウレタン結合のいずれかの官能基を有する化合物（Ｃ）を用いることにより、ラジカル重合性樹脂組成物をラジカル重合させ硬化させる際、樹脂の硬化阻害等の問題がなく、効果的にホルムアルデヒド放散量を削減するものである。
かかる分子中にヒドラゾ基、尿素結合又はウレタン結合のいずれかの官能基を有する化合物（Ｃ）としては、分子中にヒドラゾ基、尿素結合又はウレタン結合のいずれかの官能基を有する化合物であれば包含されるが、一般式（１）で表される化合物が好ましい。
Ｒ−ＮＨ−Ｙ （１）
The radically polymerizable resin composition of the present invention contains a compound (C) having a functional group of any one of hydrazo group, urea bond or urethane bond in the molecule.
By using the compound (C) having a functional group of any one of hydrazo group, urea bond or urethane bond in the molecule, problems such as inhibition of resin curing when radically polymerizing and curing the radical polymerizable resin composition It effectively reduces formaldehyde emission.
The compound (C) having any functional group of hydrazo group, urea bond or urethane bond in the molecule is a compound having any functional group of hydrazo group, urea bond or urethane bond in the molecule. Although included, the compound represented by the general formula (1) is preferable.
R-NH-Y (1)
一般式（１）中、Ｒは、水素原子、アルキル基、アルケニル基、アルキニル基、水酸基で置換されたアルキル基、アミノ基で置換されたアルキル基、アルコキシ基で置換されたアルキル基、アミノ基、フェニル基、カルボキシル基、ウレタン結合を有する１価の官能基及び−ＮＨＮＨ−Ｒ１を表すものである。この場合、Ｒ１は水素原子、アルキル基である。またＹは、−ＮＨ−、−ＣＯ−ＮＨ−又は−ＣＯＯ−をいずれかを含む１価の官能基を表すものである。また、ＲとＹとが結合し、環を形成していてもよい。 In general formula (1), R is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkyl group substituted with a hydroxyl group, an alkyl group substituted with an amino group, an alkyl group substituted with an alkoxy group, an amino group , Phenyl group, carboxyl group, monovalent functional group having a urethane bond and —NHNH—R 1 . In this case, R 1 is a hydrogen atom or an alkyl group. Y represents a monovalent functional group containing any of —NH—, —CO—NH—, and —COO—. R and Y may be bonded to form a ring.
一般式（１）で表される化合物のうち、Ｒがアルキル基であり、かつＹが−ＣＯ−ＮＨを含む１価の官能基である化合物、Ｒが−ＮＨＮＨ−Ｒ１であり、かつＹが−ＮＨ−を含む１価の官能基である化合物、及びＲがウレタン結合を有する１価の官能基であり、かつＹが−ＣＯＯ−を含む１価の官能基である化合物であることが好ましい。
Ｒがアルキル基であり、かつＹが−ＣＯ−ＮＨ−を含む１価の官能基である一般式（１）で表される化合物（Ｃ）としては、例えば尿素、モノメチル尿素、モノメチロール尿素、ジメチロール尿素、ジメチル尿素、ジフェニル尿素、メチレン尿素、エチレン尿素、プロピレン尿素、アルコシキメチル尿素等が挙げられる。これらのうち、ホルムアルデヒド捕捉効果の大きい点でエチレン尿素が好ましい。
Among the compounds represented by the general formula (1), R is an alkyl group and Y is a monovalent functional group containing —CO—NH, R is —NHNH—R 1 , and Y Is a compound having a monovalent functional group containing —NH—, and R is a monovalent functional group having a urethane bond, and Y is a monovalent functional group containing —COO—. preferable.
Examples of the compound (C) represented by the general formula (1) in which R is an alkyl group and Y is a monovalent functional group containing —CO—NH— include, for example, urea, monomethylurea, monomethylolurea, Examples include dimethylol urea, dimethyl urea, diphenyl urea, methylene urea, ethylene urea, propylene urea, and alkoxymethyl urea. Of these, ethylene urea is preferred because of its large formaldehyde scavenging effect.
Ｒが−ＮＨＮＨ−Ｒ１であり、かつＹが−ＮＨ−を含む１価の官能基である一般式（１）で表される化合物（Ｃ）としては、例えばアジピン酸ジヒドラジド、コハク酸ジヒドラジド、ナフテン酸ジヒドラジド等が挙げられる。
さらにＲがウレタン結合を有する１価の官能基であり、かつＹが−ＣＯＯ−を含む１価の官能基を有する化合物（Ｃ）としては、ウレタン（メタ）アクリレート等のビニルウレタン化合物等が挙げられる。
Examples of the compound (C) represented by the general formula (1) in which R is —NHNH—R 1 and Y is a monovalent functional group containing —NH— include, for example, adipic acid dihydrazide, succinic acid dihydrazide, Examples thereof include naphthenic acid dihydrazide.
Furthermore, examples of the compound (C) in which R is a monovalent functional group having a urethane bond and Y has a monovalent functional group containing —COO— include vinyl urethane compounds such as urethane (meth) acrylate. It is done.
一般式（１）で表される化合物（Ｃ）の添加量は、ラジカル重合性樹脂組成物の硬化性を損なわない範囲であれば特に制限されないが、０．０１〜５０重量％の範囲で添加することが好ましい。添加量が０．０１重量％に満たないとホルムアルデヒド捕捉能力が十分でなく、また５０重量％を越えると、得られる硬化物の性能に悪影響を及ぼす場合がある。 The amount of the compound (C) represented by the general formula (1) is not particularly limited as long as it does not impair the curability of the radical polymerizable resin composition, but it is added in the range of 0.01 to 50% by weight. It is preferable to do. If the addition amount is less than 0.01% by weight, the formaldehyde scavenging ability is not sufficient, and if it exceeds 50% by weight, the performance of the resulting cured product may be adversely affected.
一般式（１）で表される化合物（Ｃ）は、ラジカル重合性樹脂組成物に含まれるものであってもよいし、ラジカル硬化性樹脂（Ａ）の骨格内に、一般式（１）で表される化合物と同様の構造を導入したものでもかまわない。 The compound (C) represented by the general formula (1) may be included in the radical polymerizable resin composition, or in the skeleton of the radical curable resin (A), the general formula (1) The same structure as the compound represented may be introduced.
本発明のラジカル重合性樹脂組成物には、通常硬化剤、すなわちラジカル重合開始剤、及び硬化促進剤、すなわちラジカル重合促進剤が添加される。 In general, a curing agent, that is, a radical polymerization initiator, and a curing accelerator, that is, a radical polymerization accelerator are added to the radical polymerizable resin composition of the present invention.
かかる硬化剤としては、熱硬化剤や光硬化剤が挙げられる。熱硬化剤としては、有機過酸化物が挙げられ、例えばジアシルパーオキサイド系、パーオキシエステル系、ハイドロパーオキサイド系、ジアルキルパーオキサイド系、ケトンパーオキサイド系、パーオキシケタール系、アルキルパーエステル系、パーカーボネート系等、公知公用のものが挙げられる。熱硬化剤の添加量は、本発明の目的を達成することのできる範囲であれば特に限定されるものではないが、好ましくは本発明に用いられる樹脂の合計量１００重量部に対して０．５〜５重量部であり、かかる範囲で使用することで可使時間、物性等の優れた樹脂組成物を得ることができる。 Examples of such curing agents include thermosetting agents and photocuring agents. Examples of thermosetting agents include organic peroxides such as diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peroxides, A publicly known thing, such as a percarbonate type, is mentioned. The addition amount of the thermosetting agent is not particularly limited as long as the object of the present invention can be achieved, but preferably it is 0.00% with respect to 100 parts by weight of the total amount of the resin used in the present invention. It is 5-5 weight part, By using it in this range, the resin composition excellent in pot life, physical properties, etc. can be obtained.
かかる光硬化剤としては、例としてベンゾインアルキルエーテルのようなベンゾインエーテル系、ベンゾフェノン、ベンジル、メチルオルソベンゾイルベンゾエートなどのベンゾフェノン系、ベンジルジメチルケタール、２，２−ジエトキシアセトフェノン、２−ヒドロキシ−２−メチルプロピオフェノン、４−イソプロピル−２−ヒドロキシ−２−メチルプロピオフェノン、１，１−ジクロロアセトフェノンなどのアセトフェノン系、２−クロロチオキサントン、２−メチルチオキサントン、２−イソプロピルチオキサントンなどのチオキサントン系等が挙げられる。光硬化剤の添加量は、好ましくは本発明に用いられる樹脂の合計量１００重量部に対して、０．１〜３重量部である。 Examples of such photocuring agents include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, and 2-hydroxy-2- Acetphenone series such as methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, thioxanthone series such as 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. Is mentioned. The addition amount of the photocuring agent is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the total amount of the resin used in the present invention.
また、硬化促進剤としては、例えばナフテン酸コバルト、オクチル酸コバルト、オクチル酸亜鉛、オクチル酸バナジウム、ナフテン酸銅、ナフテン酸バリウム等金属石鹸類、バナジウムアセチルアセテート、コバルトアセチルアセテート、鉄アセチルアセトネート等の金属キレート類、アニリン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン、ｐ−トルイジン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、Ｎ，Ｎ−ビス（２-ヒドロキシエチル）−ｐ−トルイジン、４-（Ｎ，Ｎ−ジメチルアミノ）ベンズアルデヒド、４−［Ｎ，Ｎ−ビス（２-ヒドロキシエチル）アミノ］ベンズアルデヒド、４−（Ｎ−メチル−Ｎ−ヒドロキシエチルアミノ）ベンズアルデヒド、Ｎ，Ｎ−ビス（２−ヒドロキシプロピル）−ｐ−トルイジン、Ｎ−エチル−ｍ−トルイジン、トリエタノールアミン、ｍ−トルイジン、ジエチレントリアミン、ピリジン、フェニリモルホリン、ピペリジン、Ｎ，Ｎ−ビス（ヒドロキシエチル）アニリン、ジエタノールアニリン等のＮ，Ｎ−置換アニリン、Ｎ，Ｎ−置換−ｐ−トルイジン、４-（Ｎ，Ｎ−置換アミノ）ベンズアルデヒド等のアミン類が挙げられる。これらの硬化促進剤のうち、アミン類、金属石鹸類が好ましい。これらの硬化促進剤は、単独又は２種以上の組み合わせで使用しても良い。またこれらの硬化促進剤は、予め樹脂に添加しておいても良いし、使用時に添加しても良い。硬化促進剤の添加量は、本発明の目的を達成することのできる範囲であれば特に限定されるものではないが、好ましくは本発明に用いられる樹脂の合計量１００重量部に対して０．１〜５重量部である。
またこれらアミン類は、本発明の効果を発現する上で併用することが好ましい。
Further, examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate, vanadium acetyl acetate, cobalt acetyl acetate, iron acetylacetonate and the like. Metal chelates, aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N- Bis (2-hydroxypropyl) -p-toluidine, N-ethyl- -N, N-substituted anilines such as toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, N, N-substituted-p -Toluidine, amines such as 4- (N, N-substituted amino) benzaldehyde. Of these curing accelerators, amines and metal soaps are preferred. These curing accelerators may be used alone or in combination of two or more. These curing accelerators may be added to the resin in advance or may be added at the time of use. The addition amount of the curing accelerator is not particularly limited as long as the object of the present invention can be achieved, but it is preferably 0.1% with respect to 100 parts by weight of the total amount of the resin used in the present invention. 1 to 5 parts by weight.
Further, these amines are preferably used in combination in order to exhibit the effects of the present invention.
さらに硬化速度を調整するため、重合禁止剤などを使用することができる。
重合禁止剤としては、例えばトリハイドロベンゼン、トルハイドロキノン、１４−ナフトキノン、パラベンゾキノン、ハイドロキノン、ベンゾキノン、ハイドロキノンモノメチルエーテル、ｐ−ｔｅｒｔ−ブチルカテコール、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール等を挙げることができる。重合禁止剤の添加量は、本発明に用いられる樹脂に対して１０〜１０００ｐｐｍ添加するのが好ましく、５０〜２００ｐｐｍ添加するのがさらに好ましい。かかる範囲で使用することで貯蔵安定性、作業性、強度発現性の優れた樹脂組成物を得ることができる。
Furthermore, a polymerization inhibitor or the like can be used to adjust the curing rate.
Examples of the polymerization inhibitor include trihydrobenzene, toluhydroquinone, 14-naphthoquinone, parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol. Etc. The addition amount of the polymerization inhibitor is preferably 10 to 1000 ppm, more preferably 50 to 200 ppm, based on the resin used in the present invention. By using in such a range, a resin composition excellent in storage stability, workability, and strength development can be obtained.
本発明のラジカル重合性樹脂組成物は、ホルムアルデヒド捕捉効果に優れるので、ラジカル重合性樹脂を用いる成形品、塗料、接着剤の種々の用途に有用である。 Since the radically polymerizable resin composition of the present invention has an excellent formaldehyde scavenging effect, it is useful for various uses of molded articles, paints, and adhesives using the radically polymerizable resin.
以下本発明を実施例によって更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。また、本文に「部」とあるのは、重量部を示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, “parts” in the text indicates parts by weight.
［ラジカル硬化性樹脂の調製］
（参考例１）不飽和ポリエステル樹脂の調製
撹拌機、還流冷却塔、不活性ガス導入管、温度計及び滴下装置を取り付けた２リットルの四口フラスコにジシクロペンタジエン７４６部、無水マレイン酸５５４部を仕込み、１２５℃まで昇温した後、水１０２部を１．５時間かけて滴下し、１２０〜１３０℃の温度で酸価が２２０となるまで反応した。次に、ジエチレングリコール３００部を仕込み、徐々に２０５℃まで昇温し、酸価が２０ＫＯＨｍｇ／ｇになったところで反応を終了した。このものに、ゲル化時間を調整するため、トルハイドロキノノン、ターシャリーブチルカテコールを仕込み、不飽和ポリエステル樹脂を得た。この不飽和ポリエステル樹脂をスチレンにより希釈し溶解させた。以下この不飽和ポリエステル樹脂を樹脂（１）という。
[Preparation of radical curable resin]
Reference Example 1 Preparation of Unsaturated Polyester Resin 746 parts of dicyclopentadiene and 554 parts of maleic anhydride in a 2 liter four-necked flask equipped with a stirrer, reflux cooling tower, inert gas introduction tube, thermometer and dropping device The mixture was heated to 125 ° C., and then 102 parts of water was added dropwise over 1.5 hours, and reacted at a temperature of 120 to 130 ° C. until the acid value became 220. Next, 300 parts of diethylene glycol was charged, the temperature was gradually raised to 205 ° C., and the reaction was terminated when the acid value reached 20 KOH mg / g. To this, tolugelquinone and tertiary butyl catechol were charged to adjust the gelation time, and an unsaturated polyester resin was obtained. This unsaturated polyester resin was diluted with styrene and dissolved. Hereinafter, this unsaturated polyester resin is referred to as resin (1).
（参考例２）不飽和ポリエステル樹脂の調製
窒素ガス導入管、還流コンデンサ、攪拌機を備えた２Ｌのガラス製フラスコに、プロピレングリコール３０４部、無水マレイン酸１９６部、無水フタル酸２９６部を仕込み窒素気流下、加熱を開始した。内温２００℃にて、常法にて脱水縮合反応を行い、ガードナー粘度がＱ〜Ｒ（樹脂固形分／スチレン＝７０／３０重量比率で希釈し固形分の縮合度を確認）、酸価が２４ＫＯＨｍｇ／ｇになったところで、１８０℃まで冷却し、参考例１と同様にトルハイドロキノン、ターシャリブチルカテコールを添加した。さらに１５０℃まで冷却して、不飽和ポリエステル樹脂を得た。この不飽和ポリエステル樹脂をスチレンで希釈し溶解させた。以下この不飽和ポリエステル樹脂を樹脂（２）という。
Reference Example 2 Preparation of Unsaturated Polyester Resin A 2 L glass flask equipped with a nitrogen gas inlet tube, a reflux condenser and a stirrer was charged with 304 parts of propylene glycol, 196 parts of maleic anhydride and 296 parts of phthalic anhydride, and a nitrogen stream Below, heating was started. Dehydration condensation reaction is carried out at an internal temperature of 200 ° C. by a conventional method, and the Gardner viscosity is Q to R (resin solid content / styrene = 70/30 weight ratio to confirm the degree of condensation of the solid content), the acid value is When it reached 24 KOH mg / g, it was cooled to 180 ° C., and toluhydroquinone and tertiary butyl catechol were added in the same manner as in Reference Example 1. Furthermore, it cooled to 150 degreeC and obtained the unsaturated polyester resin. This unsaturated polyester resin was diluted with styrene and dissolved. Hereinafter, this unsaturated polyester resin is referred to as resin (2).
（参考例３）空乾性付与型不飽和ポリエステル樹脂の合成
温度計、攪拌機、不活性ガス導入口、及び還流冷却器を備えた２リットルの四つ口フラスコに、ジエチレングリコール５７６部、無水フタル酸２８５部、無水マレイン酸８１部、ピペリレン・無水マレイン酸付加物４５７部を公知の条件で加熱脱水縮合させて酸価１０、空乾性付与成分の含有量が２４モル％の空乾性付与型の不飽和ポリエステル樹脂を得た。この樹脂を以下「空乾性ＵＰＥ」という。
(Reference Example 3) Synthesis of air-drying imparted unsaturated polyester resin In a 2-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 576 parts of diethylene glycol and 285 phthalic anhydride Part, maleic anhydride 81 parts, piperylene / maleic anhydride adduct 457 parts by heat dehydration condensation under known conditions to give an acid value of 10 and an air dryness imparting component content of 24 mol%. A polyester resin was obtained. This resin is hereinafter referred to as “air-drying UPE”.
（参考例４）ポリエステルメタクリレートの合成
温度計、攪拌機、ガス導入口、及び還流冷却器を備えた２リットルの四つ口フラスコに、トリエチレングリコール４６５部、ジエチレングリコール１７５部、無水フタル酸７４０部を仕込み、窒素雰囲気中２０５℃まで昇温し１２時間反応させ、固形分酸価２７．４になったところで１００℃まで冷却した。これにグリシジルメタクリレート８７．０部を加え、１３０℃で１．５時間反応させて、固形分酸価０．８０のポリエステルメタクリレートを得た。この樹脂を以下「ＰＥＭＡ」とする。
(Reference Example 4) Synthesis of polyester methacrylate A 2-liter four-necked flask equipped with a thermometer, stirrer, gas inlet, and reflux condenser was charged with 465 parts of triethylene glycol, 175 parts of diethylene glycol, and 740 parts of phthalic anhydride. The mixture was charged, heated to 205 ° C. in a nitrogen atmosphere, reacted for 12 hours, and cooled to 100 ° C. when the solid acid value reached 27.4. To this, 87.0 parts of glycidyl methacrylate was added and reacted at 130 ° C. for 1.5 hours to obtain a polyester methacrylate having a solid content acid value of 0.80. This resin is hereinafter referred to as “PEMA”.
［ホルムアルデヒド捕捉剤の調製］
（参考例５）ウレタンメタクリレートの合成
温度計、攪拌機、不活性ガス導入口、及び還流冷却器を備えた５リットルの四つ口フラスコに、ポリプロピレングリコール（数平均分子量３９９．３）１５９７部、トリレンジイソシアネート１３９２部を仕込み、窒素雰囲気中８０℃まで昇温し、２．５時間反応させ、ＮＣＯ当量３７０になったところで、５０℃まで冷却した後、窒素／空気（流量比１／１）混合気流下でトルハイドロキノン０．３０５部、２−ヒドロキシエチルメタクリレート１１００部を加え、９０℃まで再度昇温させた。３時間反応させ、残存ＮＣＯ量が０．０６４４％で２個のメタクリル基を含有するウレタンメタクリレートを得た。この化合物を以下「ＵＭＡ」という。
（実施例１）
参考例１で得られた樹脂(１)１００部に、硬化促進剤として６％ナフテン酸コバルト（大日本インキ化学製）０．５部、エチレン尿素（以下捕捉剤１という）０．２部（メタノールに加熱溶解添加）を配合し、混合攪拌した。
この混合物１００部に対し、パーメックＮ(ラジカル硬化剤、日本油脂（株）製)１．０部を配合し、ラジカル重合性樹脂組成物を得た。
（実施例２）
樹脂（１）を参考例２で得られた樹脂（２）を用いた以外は、実施例１と同様に操作を行い、ラジカル重合性樹脂組成物を得た。
（実施例３）
前記空乾性ＵＰＥ１０部と前記ＰＥＭＡ５６部を、反応希釈剤としてメチルメタクリレート３０部、２−エチルヘキシルメタクリレート４部にて希釈溶解させて、樹脂（３）を得た。この樹脂（３）１００部に対し６％ナフテン酸コバルト０．５部添加し、エチレン尿素０．４部添加混合し、さらに硬化剤としてベンゾイルパーオキサイド２部添加し、ラジカル重合性樹脂組成物を得た。
（実施例４）
エチレン尿素の代わりに、アジピン酸ジヒドラジド１．０部を用いた以外は、実施例３と同様に操作を行い、ラジカル重合性樹脂組成物を得た。
（比較例４）
前記空乾性ＵＰＥ５部と前記ＰＥＭＡソリッド２８部を、反応希釈剤としてメチルメタクリレート３５部、２−エチルヘキシルメタクリレート２部にて溶解させて、樹脂（４）を得た。この樹脂（４）にホルムアルデヒド捕捉剤としてＵＭＡ（以下捕捉剤３という）を３０部溶解し混合させ、促進剤として６％ナフテン酸コバルト０．５部添加混合し、硬化剤としてベンゾイルパーオキサイド２部添加して、ラジカル硬化性樹脂組成物を得た。
（比較例１）
実施例１の樹脂（１）にホルムアルデヒド捕捉剤としての化合物（Ｃ）を添加しない以外は、実施例１と同様に操作を行い、ラジカル重合性樹脂組成物を得た。
（比較例２）
実施例２で樹脂（２）にホルムアルデヒド捕捉剤としての化合物（Ｃ）を添加しない以外は、実施例２と同様に操作を行い、ラジカル重合性樹脂組成物を得た。
（比較例３）
実施例３で樹脂（３）にホルムアルデヒド捕捉剤としての化合物（Ｃ）を添加しない以外は、実施例３と同様に操作を行い、ラジカル重合性樹脂組成物を得た。
［評価方法及び評価基準］
前記実施例及び比較例で得られたラジカル重合性樹脂組成物について、硬化状態、ホルムアルデヒド放散量を測定し、評価した。測定方法及び評価基準は以下のとおりである。実施例１〜４および比較例１〜４の結果は、それぞれ表−１、表−２に示す。
[Preparation of formaldehyde scavenger]
Reference Example 5 A 5 liter four neck flask equipped with a urethane methacrylate synthesis thermometer, stirrer, inert gas inlet, and reflux condenser was charged with 1597 parts of polypropylene glycol (number average molecular weight 399.3), Charge 1392 parts of diisocyanate, heat up to 80 ° C. in nitrogen atmosphere, react for 2.5 hours, and when NCO equivalent 370 is reached, cool to 50 ° C., then mix nitrogen / air (flow rate ratio 1/1) Under an air stream, 0.305 part of toluhydroquinone and 1100 parts of 2-hydroxyethyl methacrylate were added, and the temperature was raised again to 90 ° C. The reaction was carried out for 3 hours to obtain urethane methacrylate containing two methacrylic groups with a residual NCO amount of 0.0644%. This compound is hereinafter referred to as “UMA”.
Example 1
To 100 parts of the resin (1) obtained in Reference Example 1, 0.5 part of 6% cobalt naphthenate (manufactured by Dainippon Ink & Chemicals) as a curing accelerator, 0.2 part of ethylene urea (hereinafter referred to as scavenger 1) ( The mixture was mixed with stirring.
To 100 parts of this mixture, 1.0 part of Parmec N (radical curing agent, manufactured by NOF Corporation) was blended to obtain a radical polymerizable resin composition.
(Example 2)
Except having used resin (2) obtained by the reference example 2 for resin (1), operation was performed like Example 1 and the radically polymerizable resin composition was obtained.
(Example 3)
10 parts of the air-drying UPE and 56 parts of the PEMA were diluted and dissolved with 30 parts of methyl methacrylate and 4 parts of 2-ethylhexyl methacrylate as a reaction diluent to obtain a resin (3). 0.5 parts of 6% cobalt naphthenate is added to 100 parts of this resin (3), 0.4 parts of ethylene urea is added and mixed, and 2 parts of benzoyl peroxide is further added as a curing agent, and a radical polymerizable resin composition is added. Obtained.
(Example 4)
A radical polymerizable resin composition was obtained in the same manner as in Example 3 except that 1.0 part of adipic acid dihydrazide was used instead of ethylene urea.
( Comparative Example 4 )
5 parts of the air-drying UPE and 28 parts of the PEMA solid were dissolved in 35 parts of methyl methacrylate and 2 parts of 2-ethylhexyl methacrylate as a reaction diluent to obtain a resin (4). To this resin (4), 30 parts of UMA (hereinafter referred to as scavenger 3) as a formaldehyde scavenger is dissolved and mixed, 0.5 part of 6% cobalt naphthenate is added and mixed as an accelerator, and 2 parts of benzoyl peroxide as a curing agent. This was added to obtain a radical curable resin composition.
(Comparative Example 1)
Except not adding the compound (C) as a formaldehyde scavenger to the resin (1) of Example 1, the same operation as in Example 1 was performed to obtain a radical polymerizable resin composition.
(Comparative Example 2)
Except not adding the compound (C) as a formaldehyde scavenger to the resin (2) in Example 2, the same operation as in Example 2 was performed to obtain a radical polymerizable resin composition.
(Comparative Example 3)
Except that the compound (C) as a formaldehyde scavenger was not added to the resin (3) in Example 3, the same operation as in Example 3 was performed to obtain a radical polymerizable resin composition.
[Evaluation method and evaluation criteria]
About the radically polymerizable resin composition obtained by the said Example and comparative example, the hardening state and the formaldehyde emission amount were measured and evaluated. The measurement method and evaluation criteria are as follows. The results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table-1 and Table-2, respectively.
＜硬化性評価＞
硬化状態は、ラジカル重合性樹脂組成物のゲルタイムの延長の有無により評価した。
「ゲルタイム」は、容量１００ｍｌのデスカップに各実施例で得られたラジカル重合性樹脂組成物を５０ｇ計量し、６％ナフテン酸コバルトを添加して２５℃温度に調整した後、パーメックＮ［メチルエチルケトンパーオキサイド（日本油脂社製）］あるいはベンゾイルパーオキサイドを混合添加した。これを２５℃の恒温槽に浸漬し、ゲルが発生して攪拌棒から樹脂が糸切れ状態になるまでの時間をゲルタイムとした。
ホルムアルデヒド捕捉剤を含まないラジカル重合性樹脂組成物である前記比較例でのゲルタイムに比較し著しいゲルタイムの延長がないか否かを確認した。著しいゲルタイムの延長がないものを「〇」とした。
<Curability evaluation>
The cured state was evaluated based on whether or not the gel time of the radical polymerizable resin composition was extended.
“Geltime” is obtained by weighing 50 g of the radical polymerizable resin composition obtained in each example in a 100-ml descup and adding 6% cobalt naphthenate to adjust the temperature to 25 ° C. Oxide (manufactured by NOF Corporation)] or benzoyl peroxide was mixed and added. This was immersed in a thermostatic bath at 25 ° C., and the time from when the gel was generated until the resin was broken from the stirring rod was taken as the gel time.
It was confirmed whether or not the gel time was not significantly extended as compared with the gel time in the comparative example which is a radical polymerizable resin composition containing no formaldehyde scavenger. The case where there was no significant gel time extension was marked as “◯”.
＜ホルムアルデヒド放散量評価＞
室温（２３℃）、湿度５０％の環境試験室内（４ｍ×４ｍ×２ｍ）で、大きさ１５０ｍｍ×１５０ｍｍのアルミ板に０．２５ｍｍのアプリケーターを用いて、実施例で得られたラジカル重合性樹脂組成物を塗布し、硬化させ、室温で２４時間放置して、ホルムアルデヒドの揮散量を測定した。測定法は、ＪＩＳ Ｋ ５６０１−４−１デシケーター法に準じて行った。
<Evaluation of formaldehyde emission>
Radical polymerizable resin obtained in the examples in an environmental test chamber (4 m x 4 m x 2 m) at room temperature (23 ° C) and humidity of 50% using an applicator of 0.25 mm on an aluminum plate of size 150 mm x 150 mm The composition was applied, cured, and allowed to stand at room temperature for 24 hours, and the volatilization amount of formaldehyde was measured. The measurement method was performed according to the JIS K 5601-4-1 desiccator method.
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| JP5066379B2 (en) * | 2007-03-27 | 2012-11-07 | パナソニック株式会社 | Thermosetting resin composition and thermosetting resin molded product |
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| CN104387817A (en) * | 2014-10-30 | 2015-03-04 | 青岛昌安达药业有限公司 | Glass film |
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| CN102858824B (en) * | 2010-11-19 | 2015-04-15 | Dic株式会社 | Radical-curable resin composition, coating material and civil engineering building structure each using radical-curable resin composition, and method for constructing civil engineering building structure |
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