JP4320590B2 - ラジカル重合性樹脂組成物 - Google Patents
ラジカル重合性樹脂組成物 Download PDFInfo
- Publication number
- JP4320590B2 JP4320590B2 JP2003419382A JP2003419382A JP4320590B2 JP 4320590 B2 JP4320590 B2 JP 4320590B2 JP 2003419382 A JP2003419382 A JP 2003419382A JP 2003419382 A JP2003419382 A JP 2003419382A JP 4320590 B2 JP4320590 B2 JP 4320590B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- resin composition
- radical polymerizable
- polymerizable resin
- 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 21
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 6
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 57
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 29
- -1 2-ethylhexyl Chemical group 0.000 description 26
- 150000003254 radicals Chemical class 0.000 description 18
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 238000001723 curing Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000000835 fiber Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000001993 wax Substances 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HNPDNOZNULJJDL-UHFFFAOYSA-N ethyl n-ethenylcarbamate Chemical class CCOC(=O)NC=C HNPDNOZNULJJDL-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000004992 toluidines Chemical class 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- JFZVSHAMRZPOPA-UHFFFAOYSA-N 1-[n-(2-hydroxypropyl)-4-methylanilino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)C1=CC=C(C)C=C1 JFZVSHAMRZPOPA-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- RKYJPYDJNQXILT-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C=C RKYJPYDJNQXILT-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 1
- SFUIQBAQBZTQLH-UHFFFAOYSA-N 2-methylprop-2-enoic acid;2-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]benzoic acid Chemical class CC(=C)C(O)=O.CC(=C)C(=O)OCCOC(=O)C1=CC=CC=C1C(O)=O SFUIQBAQBZTQLH-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- OSCBGQKPDGGHJP-UHFFFAOYSA-N 3-phenoxydodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCC(CCOC(=O)C(C)=C)OC1=CC=CC=C1 OSCBGQKPDGGHJP-UHFFFAOYSA-N 0.000 description 1
- JNRPOURQJNXRPA-UHFFFAOYSA-N 3-phenoxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOC1=CC=CC=C1 JNRPOURQJNXRPA-UHFFFAOYSA-N 0.000 description 1
- JRJNSEMUYTUGLA-UHFFFAOYSA-N 3-phenoxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC1=CC=CC=C1 JRJNSEMUYTUGLA-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- JOCUIVLSLBBESN-UHFFFAOYSA-N 4-[2-hydroxyethyl(methyl)amino]benzaldehyde Chemical compound OCCN(C)C1=CC=C(C=O)C=C1 JOCUIVLSLBBESN-UHFFFAOYSA-N 0.000 description 1
- YSDDPNWGLSGZRC-UHFFFAOYSA-N 4-[bis(2-hydroxyethyl)amino]benzaldehyde Chemical compound OCCN(CCO)C1=CC=C(C=O)C=C1 YSDDPNWGLSGZRC-UHFFFAOYSA-N 0.000 description 1
- FHQRDEDZJIFJAL-UHFFFAOYSA-N 4-phenylmorpholine Chemical compound C1COCCN1C1=CC=CC=C1 FHQRDEDZJIFJAL-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- DHNQMJPIVOCZMQ-UHFFFAOYSA-N C(C=C)(=O)O.[N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical compound C(C=C)(=O)O.[N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O DHNQMJPIVOCZMQ-UHFFFAOYSA-N 0.000 description 1
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
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- 229920002125 Sokalan® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
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- 239000006096 absorbing agent Substances 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
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- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 150000001408 amides Chemical class 0.000 description 1
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- 239000011324 bead Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-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
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
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- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
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- 239000000919 ceramic Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
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Description
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養生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、残存するホルムアルデヒドを放出させる方法、(3)乾燥した酸の条件下での、アルコールによるアセタール化によりホルムアルデヒドを捕捉する方法等が提案されているが、(1)については、JIS K 5970による養生期間7日以内では、ホルムアルデヒドの放散量が規制対象外まで低下しきれず、(2)及び(3)については、樹脂の硬化性に悪影響を及ぼしたり、ホルムアルデヒド捕捉機能が劣るなど、未だ満足できるものが得られていなかった。
(式中、R 1 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−R8を表す。Yは−NH−、−CO−NH−、又は−COO−のいずれかを含む官能基を表す。またR 1 とYとは結合して環を形成していてもよい。)
本発明に使用する(メタ)アクリル酸エステル系重合体(A)としては、(メタ)アクリル酸エステルを主たる成分とする重合性単量体を重合して得られものである。
アルキル基の炭素原子数が1〜4であるヒドロキシアルキル(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、2−ヒドロキシブチル(メタ)アクリレート等が挙げられる。
(式中、R 1 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−R8を表す。Yは−NH−、−CO−NH−、又は−COO−のいずれかを含む官能基を表す。またR 1 とYとは結合して環を形成していてもよい。)
本発明のラジカル重合性樹脂組成物は、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。
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。
攪拌機、温度計、環流コンデンサーを付した5リットルセパラブルフラスコにイオン交換水2500g、NaNO20.213g、「ジュリマーAC−10H」(ポリアクリル酸、日本純薬社製)18.8gを入れ攪拌し、窒素気流中で60℃まで加熱した。これにメチルメタクリレート1250g、連鎖移動剤としてラウリルメルカプタン7.5g、重合開始剤としてt−ブチルパーオキシ(2−エチルヘキサノエート)(日本油脂社製「パーブチルO」)12.5gの混合液を投入した。攪拌速度を200rpmにして、温度を80℃に保ち、3時間後、比重が1.13以上になったのを確認後、さらに3時間加熱攪拌した。反応中ブロッキング等の問題は生じなかった。冷却後、200メッシュの濾布で濾過、水洗後乾燥(40℃、10時間その後40℃で24時間真空乾燥)し、パール状のポリマーを得た。GPCによる分子量測定の結果Mn=32000であった。
参考例1で得られた重合体30部をメチルメタクリレート70部に溶解し、シラップ状のアクリル樹脂を得た。この樹脂100部に、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、パラトルイジンPO付加物0.3、ベンゾイルパーオキサイド2.0部を配合し、ラジカル重合性樹脂組成物を得た。
(実施例2)
エチレン尿素の代わりに、アジピン酸ジヒドラジド(以下補足剤2という)1.0部を用いた以外は、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。
(比較例1)
実施例1の樹脂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。
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、パラトルイジン0.15gを添加して25℃温度に調整した後、ベンゾイルパーオキサイド1g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。
温度23℃、湿度50%の環境試験室内(4m×4m×2m)で、150mm×150mmのアルミニウム板2枚のそれぞれに、各実施例及び比較例で得られたラジカル重合性被覆材料を刷毛にて約1.0kg/m2の厚さになるように塗布し、試験片とした。試験片はデシケーター中で1週間放置した後、この試験片を用い、JIS K 5601−4−1デシケーター法により測定した。
Claims (1)
- (メタ)アクリル酸エステル系重合体(A)と、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、アジピン酸ジヒドラジドからなる群から選ばれる少なくとも1種の化合物(C)0.01〜10重量%を含有してなるラジカル重合性樹脂組成物。
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