JPH08283589A - Curable resin composition and its use - Google Patents
Curable resin composition and its useInfo
- Publication number
- JPH08283589A JPH08283589A JP8216695A JP8216695A JPH08283589A JP H08283589 A JPH08283589 A JP H08283589A JP 8216695 A JP8216695 A JP 8216695A JP 8216695 A JP8216695 A JP 8216695A JP H08283589 A JPH08283589 A JP H08283589A
- Authority
- JP
- Japan
- Prior art keywords
- curable resin
- resin composition
- organic peroxide
- thiourea compound
- meth
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- -1 thiourea compound Chemical class 0.000 claims abstract description 44
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- DQMWMUMCNOJLSI-UHFFFAOYSA-N n-carbamothioylbenzamide Chemical compound NC(=S)NC(=O)C1=CC=CC=C1 DQMWMUMCNOJLSI-UHFFFAOYSA-N 0.000 claims description 6
- 150000003682 vanadium compounds Chemical class 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 239000005060 rubber Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 235000015073 liquid stocks Nutrition 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 229940126062 Compound A Drugs 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 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 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 2
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-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
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- FVIZARNDLVOMSU-UHFFFAOYSA-N ginsenoside K Natural products C1CC(C2(CCC3C(C)(C)C(O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O FVIZARNDLVOMSU-UHFFFAOYSA-N 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- KAJICSGLHKRDLN-UHFFFAOYSA-N 1,3-dicyclohexylthiourea Chemical compound C1CCCCC1NC(=S)NC1CCCCC1 KAJICSGLHKRDLN-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- OXGOEZHUKDEEKS-UHFFFAOYSA-N 3-tert-butylperoxy-1,1,5-trimethylcyclohexane Chemical compound CC1CC(OOC(C)(C)C)CC(C)(C)C1 OXGOEZHUKDEEKS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AFHIIJICYLMCSH-VOTSOKGWSA-N 5-amino-2-[(e)-2-(4-benzamido-2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C(C(=C1)S(O)(=O)=O)=CC=C1NC(=O)C1=CC=CC=C1 AFHIIJICYLMCSH-VOTSOKGWSA-N 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
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 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
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- MAXCWSIJKVASQC-UHFFFAOYSA-N n-methyl-n-phenylnitrous amide Chemical compound O=NN(C)C1=CC=CC=C1 MAXCWSIJKVASQC-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- WKEWCYHGACEYTR-UHFFFAOYSA-N tert-butyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(C)(C)C WKEWCYHGACEYTR-UHFFFAOYSA-N 0.000 description 1
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は室温下で短時間に硬化
し、しかも得られる硬化物がゴム弾性と強靱性を兼備し
ており、接着剤、コーティング剤およびシーリング剤等
に好適に利用できる硬化性樹脂組成物に関する。FIELD OF THE INVENTION The present invention is capable of curing at room temperature in a short time, and the cured product obtained has both rubber elasticity and toughness, and can be suitably used for adhesives, coating agents, sealing agents and the like. It relates to a curable resin composition.
【０００２】[0002]
【従来の技術】従来から室温下で容易に硬化して強靱な
硬化物を与える硬化性樹脂組成物は、注型用、接着用あ
るいはコーティング用に広く利用されている。その代表
的なものとしてエポキシ系およびアクリル系の二液型硬
化性樹脂組成物がある。このうち、アクリル系の二液型
硬化性樹脂組成物はエポキシ系二液型硬化性樹脂組成物
と比べて配合比の多少のずれによる硬化物の性能のばら
つきが少ないため、二液を正確に計量混合するという手
間が省けることと、室温下で短時間に硬化するという利
点を有している。しかしながら、エポキシ系二液型硬化
性樹脂組成物と同様に、一般的にその硬化物は硬く柔軟
性に劣っており、しかも耐衝撃性にも問題があるという
欠点を有していた。この欠点を改良するためにゴム等の
エラストマーを溶解させたり、重合性（メタ）アクリル
モノマーとしてポリオキシアルキレングリコールのモノ
（メタ）アクリレートやアルコキシポリオキシアルキレ
ングリコールのモノ（メタ）アクリレートのように分子
中に長鎖のエーテル基を含有する化合物を用いる工夫が
なされているが必ずしも十分とは言えなかった。2. Description of the Related Art Conventionally, a curable resin composition which is easily cured at room temperature to give a tough cured product has been widely used for casting, adhesion or coating. Typical examples thereof include epoxy-based and acrylic-based two-part curable resin compositions. Of these, the acrylic two-component curable resin composition has less variation in the performance of the cured product due to a slight deviation in the compounding ratio as compared with the epoxy two-component curable resin composition, and therefore the two-component curable composition It has the advantages that the trouble of measuring and mixing can be saved and that it can be cured at room temperature in a short time. However, like the epoxy-based two-pack type curable resin composition, the cured product is generally hard and inferior in flexibility, and has a problem that impact resistance is also problematic. In order to improve this drawback, an elastomer such as rubber is dissolved, or a molecule such as polyoxyalkylene glycol mono (meth) acrylate or alkoxypolyoxyalkylene glycol mono (meth) acrylate is used as a polymerizable (meth) acrylic monomer. A device using a compound containing a long-chain ether group therein has been devised, but it cannot be said to be sufficient.
【０００３】また、近年アクリル系モノマーと加水分解
性ケイ素基含有ポリマーを組み合わせた新しいタイプの
硬化性樹脂組成物が提案されている（特開平５−３３１
４４７号）。これは、それぞれの重合触媒としてラジカ
ル重合開始剤とイオン的重縮合触媒が配合されており、
アクリル系二液型硬化性組成物の優れた作業性と硬化物
の強靱性および加水分解性ケイ素基含有ポリマーの分子
構造に帰因する弾力性を兼ね備えたものである。しかし
ながら、加水分解性ケイ素基含有ポリマーが加水分解さ
れて生じるシラノール基間の重縮合触媒として用いられ
る有機錫化合物や酸性リン化合物は錫に基づく毒性やリ
ン酸基の作用により硬化物が解重合を起こす傾向を有し
ているため、更に優れた硬化触媒系が望まれていた。Further, in recent years, a new type of curable resin composition has been proposed in which an acrylic monomer and a hydrolyzable silicon group-containing polymer are combined (JP-A-5-331).
447). This contains a radical polymerization initiator and an ionic polycondensation catalyst as the respective polymerization catalysts,
It has both excellent workability of the acrylic two-pack type curable composition, toughness of the cured product and elasticity due to the molecular structure of the hydrolyzable silicon group-containing polymer. However, an organotin compound or an acidic phosphorus compound used as a polycondensation catalyst between silanol groups generated by hydrolysis of a hydrolyzable silicon group-containing polymer does not cause depolymerization of a cured product due to tin-based toxicity or the action of a phosphoric acid group. A better curing catalyst system has been desired because it tends to occur.
【０００４】[0004]
【発明が解決しようとする課題】本発明は室温下で短時
間に硬化するという優れた作業性を有し、更に、ゴム弾
性と強靱性を兼ね備えた硬化物を与える新規な硬化触媒
系を用いた（メタ）アクリルモノマーと加水分解性ケイ
素基含有ポリマーの複合系からなる硬化性樹脂組成物を
提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention uses a novel curing catalyst system which has excellent workability such that it cures at room temperature in a short time, and further provides a cured product having both rubber elasticity and toughness. An object of the present invention is to provide a curable resin composition composed of a composite system of a (meth) acrylic monomer and a hydrolyzable silicon group-containing polymer.
【０００５】[0005]
【課題を解決するための手段】本発明者等は加水分解性
ケイ素基含有ポリマーの反応性を検討した結果、有機過
酸化物とチオ尿素化合物からなる触媒系が重合性（メ
タ）アクリルモノマーのレドックス重合開始剤としての
作用のみならず、加水分解性ケイ素基含有ポリマーが加
水分解されて生じるシラノール基間で起こる重縮合反応
の触媒作用も呈すること、更に、該重縮合反応が室温下
で短時間に進行することを見出し本発明に至ったのであ
る。即ち、本発明によれば、加水分解性ケイ素基含有ポ
リマー、重合性（メタ）アクリルモノマー、有機過酸化
物、及び、チオ尿素化合物を必須成分とする硬化性樹脂
組成物において、該硬化性樹脂組成物の成分である有機
過酸化物とチオ尿素化合物が一液内に共存しないように
二液以上の形態で保存され、使用時複数の液を混合し、
有機過酸化物とチオ尿素化合物を共存せしめることによ
り硬化することを特徴とする硬化性樹脂組成物が提供さ
れ、また、より好ましくは、有機過酸化物がハイドロパ
ーオキサイド類であることを特徴とする硬化性樹脂組成
物が提供され、また、より好ましくは、チオ尿素化合物
がモノベンゾイルチオ尿素であることを特徴とする硬化
性樹脂組成物が提供され、また、より好ましくは、バナ
ジウム化合物が含まれることを特徴とする硬化性組成物
が提供され、更に、上記硬化性樹脂組成物を接着剤とし
て使用する用途が提供される。Means for Solving the Problems As a result of studies on the reactivity of a hydrolyzable silicon group-containing polymer, the present inventors have found that a catalyst system composed of an organic peroxide and a thiourea compound is a polymerizable (meth) acrylic monomer. Not only as a redox polymerization initiator, but also as a catalyst for a polycondensation reaction that occurs between silanol groups produced by hydrolysis of a hydrolyzable silicon group-containing polymer, and the polycondensation reaction is short at room temperature. The present invention has been found to progress in time and has led to the present invention. That is, according to the present invention, a curable resin composition containing a hydrolyzable silicon group-containing polymer, a polymerizable (meth) acrylic monomer, an organic peroxide, and a thiourea compound as essential components is used. The organic peroxide and the thiourea compound which are the components of the composition are stored in the form of two or more liquids so that they do not coexist in one liquid, and a plurality of liquids are mixed at the time of use,
Provided is a curable resin composition characterized by curing by allowing an organic peroxide and a thiourea compound to coexist, and more preferably, the organic peroxide is a hydroperoxide. A curable resin composition is provided, and more preferably, a curable resin composition characterized in that the thiourea compound is monobenzoylthiourea is provided, and more preferably, a vanadium compound is included. And a use of the curable resin composition as an adhesive.
【０００６】有機過酸化物とチオ尿素化合物からなる触
媒系を利用したアクリル系接着剤組成物は特開昭５０−
１４８４３２号および特公昭５５−１９５７号等多数あ
る。しかしながら、この触媒系は重合性（メタ）アクリ
ルモノマーのラジカル重合におけるレドックス触媒とし
て用いられており、本発明のように加水分解性ケイ素基
含有ポリマーが加水分解されて生じるシラノール基間で
起こる重縮合反応の触媒作用も呈することには全く触れ
られていない。An acrylic adhesive composition utilizing a catalyst system composed of an organic peroxide and a thiourea compound is disclosed in JP-A-50-
There are many such as No. 148432 and Japanese Patent Publication No. 55-1957. However, this catalyst system is used as a redox catalyst in radical polymerization of a polymerizable (meth) acrylic monomer, and polycondensation occurs between silanol groups produced by hydrolysis of a hydrolyzable silicon group-containing polymer as in the present invention. No mention is made that it also catalyzes the reaction.
【０００７】本発明における有機過酸化物およびチオ尿
素化合物の組み合せからなる触媒系は（メタ）アクリル
モノマーのラジカル重合に関与するだけでなく、加水分
解性ケイ素基含有ポリマーが加水分解されて生じるシラ
ノール基間で起こる重縮合反応にも触媒的に作用する結
果、得られる硬化物はポリマーアロイ化されているもの
と考えられる。これは本発明で初めて見出されたもので
ある。The catalyst system comprising a combination of an organic peroxide and a thiourea compound in the present invention not only participates in radical polymerization of a (meth) acrylic monomer, but also silanol produced by hydrolysis of a hydrolyzable silicon group-containing polymer. As a result of acting catalytically also on the polycondensation reaction occurring between the groups, it is considered that the obtained cured product is polymerized. This was first discovered in the present invention.
【０００８】本発明において必須成分として用いられる
重合性（メタ）アクリルモノマーとしては（メタ）アク
リル酸アルキルエステル、フェノキシエチル（メタ）ア
クリレート、シクロヘキシル（メタ）アクリレート、テ
トラヒドロフルフリル（メタ）アクリレート、イソボロ
ニル（メタ）アクリレート、（メタ）アクリル酸ヒドロ
キシアルキルエステル、多価アルコールのポリ（メタ）
アクリレート、エポキシ樹脂に（メタ）アクリル酸を付
加反応させて得られるエポキシ（メタ）アクリレート、
ウレタンポリ（メタ）アクリレート、ポリエステルポリ
（メタ）アクリレート、ビスフェノールＡのアルキレン
オキサイド付加物のジ（メタ）アクリレート等が挙げら
れる。The polymerizable (meth) acrylic monomer used as an essential component in the present invention includes (meth) acrylic acid alkyl ester, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and isobornyl. (Meth) acrylate, hydroxyalkyl ester of (meth) acrylic acid, poly (meth) of polyhydric alcohol
Acrylate, epoxy (meth) acrylate obtained by adding (meth) acrylic acid to an epoxy resin,
Examples thereof include urethane poly (meth) acrylate, polyester poly (meth) acrylate, and di (meth) acrylate of an alkylene oxide adduct of bisphenol A.
【０００９】次いで、有機過酸化物としてはｔ−ブチル
ハイドロパーオキサイド、ｐ−メンタンハイドロパーオ
キサイド、クメンハイドロパーオキサイド、ジイソプロ
ピルベンゼンハイドロパーオキサイド等のハイドロパー
オキサイド類、ｔ−ブチルパーオキシラウレート、ｔ−
ブチルパーオキシベンゾエート、ｔ−ブチルパーオキシ
デカノエート等のパーオキシエステル類、１，５−ジ−
ｔ−ブチルパーオキシ−３，３，５−トリメチルシクロ
ヘキサン等のパーオキシケタール類、アセト酢酸エチル
パーオキサイド等のケトンパーオキサイド類があげられ
るが、本発明の特徴の一つである短時間に硬化する点で
ハイドロパーオキサイド類が特に好ましい。Next, as organic peroxides, hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide and diisopropylbenzene hydroperoxide, t-butylperoxylaurate, t-
Peroxyesters such as butylperoxybenzoate and t-butylperoxydecanoate, 1,5-di-
Examples thereof include peroxyketals such as t-butylperoxy-3,3,5-trimethylcyclohexane, and ketone peroxides such as ethyl acetoacetate peroxide, which are one of the features of the present invention. Hydroperoxides are particularly preferable in that respect.
【００１０】更に、チオ尿素化合物としては例えばエチ
レンチオ尿素、ジエチルチオ尿素、テトラメチルチオ尿
素、モノアセチルチオ尿素、モノベンゾイルチオ尿素、
ジフェニルチオ尿素、ジシクロヘキシルチオ尿素等があ
げられるが、加水分解性ケイ素基含有ポリマーの重縮合
触媒作用の大きいモノベンゾイルチオ尿素が特に好まし
い。Further, as the thiourea compound, for example, ethylenethiourea, diethylthiourea, tetramethylthiourea, monoacetylthiourea, monobenzoylthiourea,
Examples thereof include diphenyl thiourea and dicyclohexyl thiourea, and monobenzoyl thiourea having a large polycondensation catalyst action of the hydrolyzable silicon group-containing polymer is particularly preferable.
【００１１】加水分解性ケイ素基含有ポリマーとしては
分子中にアルコキシシリル基のような加水分解性基を２
個以上有するものであり、例としてメチルジメトキシシ
リル基またはトリメトキシシリル基を末端に含有するポ
リプロピレンオキサイド系やポリシロキサン系の液状ポ
リマーがあげられる。前述したように、これらの加水分
解性ケイ素基含有ポリマーが水分と接触し、加水分解さ
れて生じるシラノール基間で重縮合反応が起こり、三次
元的な網目構造が形成される。この重縮合反応の触媒と
して有機過酸化物およびチオ尿素化合物の組み合せから
なる触媒系が有効に作用する。The hydrolyzable silicon group-containing polymer contains a hydrolyzable group such as an alkoxysilyl group in the molecule.
One or more of them is a liquid polymer of polypropylene oxide type or polysiloxane type having a methyldimethoxysilyl group or a trimethoxysilyl group at the end. As described above, these hydrolyzable silicon group-containing polymers are brought into contact with water to cause a polycondensation reaction between silanol groups generated by hydrolysis and form a three-dimensional network structure. A catalyst system composed of a combination of an organic peroxide and a thiourea compound effectively acts as a catalyst for this polycondensation reaction.
【００１２】また、より好ましくは本発明の硬化性樹脂
組成物にバナジウムアセチルアセトネート、バナジルア
セチルアセトネート、バナジルステアレート、バナジウ
ムナフテネート、バナジウムベンゾイルアセトネート、
五酸化バナジウム等のバナジウム化合物、銅アセチルア
セトネート、塩化銅、酢酸銅、ナフテン酸銅等の銅化合
物、中でもバナジウムアセチルアセトネート、バナジル
アセチルアセトネート等のバナジウムとアセチルアセト
ンのキレート化合物が単独で、或いは、組み合わされて
含まれていることが望ましい。これらの化合物が含まれ
ることによって加水分解性ケイ素基を有するポリマーの
硬化が更に促進される。More preferably, the curable resin composition of the present invention contains vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate,
Vanadium compounds such as vanadium pentoxide, copper acetylacetonate, copper chloride, copper acetate, copper compounds such as copper naphthenate, vanadium acetylacetonate, vanadium and acetylacetone chelate compounds such as vanadyl acetylacetonate alone or, , It is desirable that they are included in combination. By including these compounds, curing of the polymer having a hydrolyzable silicon group is further accelerated.
【００１３】次に本発明の硬化性樹脂組成物の必須成分
である上記４種の成分組成比について説明する。本発明
では二液以上の形態で保存された組成物を混合して得ら
れる硬化性樹脂組成物中の各成分の組成比をもって４種
の成分組成が説明される。即ち、二液以上の形態で保存
された組成物を混合して得られる組成物中の重合性（メ
タ）アクリルモノマー１００重量部に対して、有機過酸
化物は０．０５〜２０重量部、好ましくは０．１〜１０
重量部、チオ尿素化合物は０．０１〜１０重量部、好ま
しくは０．０５〜５重量部、加水分解性ケイ素基含有ポ
リマーは５〜２０００重量部、好ましくは１０〜１００
０重量部の範囲で使用する。各成分の組成がこの範囲に
とどまるのであれば、複数の液の混合比率の設定は柔軟
に行うことができる。更に、加水分解性ケイ素基を有す
るポリマーの硬化を促進する目的でバナジウム化合物、
銅化合物を添加する場合には、これらの化合物を重合性
（メタ）アクリルモノマー１００重量部に対して０．０
０５〜５重量部、好ましくは０．０１〜２重量部の範囲
で使用する。Next, the composition ratio of the above-mentioned four kinds of components, which are essential components of the curable resin composition of the present invention, will be explained. In the present invention, four kinds of component compositions will be explained by the composition ratio of each component in the curable resin composition obtained by mixing the compositions stored in the form of two or more liquids. That is, with respect to 100 parts by weight of the polymerizable (meth) acrylic monomer in the composition obtained by mixing the composition stored in the form of two or more liquids, the organic peroxide is 0.05 to 20 parts by weight, Preferably 0.1-10
0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, the hydrolyzable silicon group-containing polymer is 5 to 2000 parts by weight, preferably 10 to 100 parts by weight.
Used in the range of 0 parts by weight. If the composition of each component remains within this range, the mixing ratio of the plurality of liquids can be flexibly set. Furthermore, a vanadium compound for the purpose of promoting the curing of the polymer having a hydrolyzable silicon group,
When a copper compound is added, these compounds are added in an amount of 0.0 to 100 parts by weight of the polymerizable (meth) acrylic monomer.
It is used in the range of 05 to 5 parts by weight, preferably 0.01 to 2 parts by weight.
【００１４】その他本発明においては、重合性（メタ）
アクリルモノマーを含有する成分の保存安定性を高める
ものとして、２，６−ジ−ｔ−ブチル−４−メチルフェ
ール、２，２−メチレンビス（４−メチル−６−ｔ−ブ
チルフェノール）、ベンゾキノン、ハイドロキノン、メ
チルハイドロキノン、エチレンジアミン４酢酸４ナトリ
ウム、シュウ酸、Ｎ−メチル−Ｎ−ニトロソアニリン、
Ｎ−ニトロソジフェニルアミン等のラジカル重合禁止
剤、粘度調整および硬化物の硬化収縮を低減することを
目的とするアクリロニトリル−ブタジエン−スチレン共
重合体（ＡＢＳ樹脂）、メタクリル酸エステル−ブタジ
エン−スチレン共重合体（ＭＢＳ樹脂）、メタクリル酸
エステル−ブタジエン−アクリロニトリル−スチレン共
重合体（ＭＢＡＳ樹脂）等の熱可塑性樹脂および炭酸カ
ルシウム、酸化チタン、水酸化アルミニウム、シリカ等
の無機充填剤、加水分解性ケイ素基含有ポリマーの重縮
合反応の促進のための水、染料や顔料を添加することも
できる。Others In the present invention, the polymerizable (meth)
2,6-di-t-butyl-4-methylfeil, 2,2-methylenebis (4-methyl-6-t-butylphenol), benzoquinone, hydroquinone are used to enhance the storage stability of components containing an acrylic monomer. , Methylhydroquinone, ethylenediaminetetraacetic acid tetrasodium, oxalic acid, N-methyl-N-nitrosoaniline,
Radical polymerization inhibitors such as N-nitrosodiphenylamine, acrylonitrile-butadiene-styrene copolymer (ABS resin), methacrylic acid ester-butadiene-styrene copolymer for the purpose of adjusting viscosity and reducing curing shrinkage of the cured product. (MBS resin), thermoplastic resin such as methacrylic acid ester-butadiene-acrylonitrile-styrene copolymer (MBAS resin) and inorganic filler such as calcium carbonate, titanium oxide, aluminum hydroxide and silica, and hydrolyzable silicon group Water, dyes and pigments may be added to accelerate the polycondensation reaction of the polymer.
【００１５】次に、本発明の硬化性樹脂組成物を調製し
た後の保存形態について説明する。本発明の硬化性樹脂
組成物は基本的に有機過酸化物とチオ尿素化合物が共存
しないように製造され、そして二液以上の形態で保存さ
れる。この両者が共存するとたちまち重合性（メタ）ア
クリルモノマー、及び、加水分解性ケイ素基含有ポリマ
ーが重合を開始しゲル化する。従って、本発明の硬化性
樹脂組成物は二液以上の形態で有機過酸化物とチオ尿素
化合物が共存しないように分別して保存されなければな
らない。分別する液数は三液以上であっても差し支えな
いが、硬化性樹脂組成物を製造する工程の簡素化、充填
作業の簡素化、更には、硬化性樹脂組成物を使用する際
の混合作業の簡易化のために二液に分別して保存するの
がより好ましい。以下に本発明の硬化性樹脂組成物を二
液（甲、乙）に分別して保存する際に、各液に含まれる
成分の例を示す。 甲：重合性（メタ）アクリルモノマー、有機過酸化
物 乙：加水分解性ケイ素基含有ポリマー、チオ尿素化合物 甲：加水分解性ケイ素基含有ポリマー、有機過酸化
物 乙：重合性（メタ）アクリルモノマー、チオ尿素化合物 甲：重合性（メタ）アクリルモノマー、加水分解性
ケイ素基含有ポリマー、有機過酸化物 乙：チオ尿素化合物 甲：有機過酸化物 乙：重合性（メタ）アクリルモノマー、加水分解性ケイ
素基含有ポリマー、チオ尿素化合物 甲：加水分解性ケイ素基含有ポリマー、有機過酸化
物 乙：重合性（メタ）アクリルモノマー、加水分解性ケイ
素基含有ポリマー、チオ尿素化合物 甲：重合性（メタ）アクリルモノマー、加水分解性
ケイ素基含有ポリマー、有機過酸化物 乙：加水分解性ケイ素基含有ポリマー、チオ尿素化合物 甲：重合性（メタ）アクリルモノマー、有機過酸化
物 乙：重合性（メタ）アクリルモノマー、加水分解性ケイ
素基含有ポリマー、チオ尿素化合物 甲：重合性（メタ）アクリルモノマー、加水分解性
ケイ素基含有ポリマー、有機過酸化物 乙：重合性（メタ）アクリルモノマー、チオ尿素化合物 甲：重合性（メタ）アクリルモノマー、加水分解性
ケイ素基含有ポリマー、有機過酸化物 乙：重合性（メタ）アクリルモノマー、加水分解性ケイ
素基含有ポリマー、チオ尿素化合物 これらの組み合わせの中でもの組み合わせが、使用時
の混合比率のずれによる硬化物の性能のばらつきが特に
少なく、より好ましい。Next, the storage form after the curable resin composition of the present invention is prepared will be described. The curable resin composition of the present invention is basically prepared so that the organic peroxide and the thiourea compound do not coexist, and is stored in the form of two or more liquids. When both of these coexist, the polymerizable (meth) acrylic monomer and the hydrolyzable silicon group-containing polymer start to polymerize and gelate. Therefore, the curable resin composition of the present invention must be separately stored in the form of two or more liquids so that the organic peroxide and the thiourea compound do not coexist. The number of liquids to be separated may be three or more, but simplification of the process for producing the curable resin composition, simplification of the filling work, and further mixing work when using the curable resin composition It is more preferable to separate and store the two liquids for simplification. Examples of the components contained in each liquid when the curable resin composition of the present invention is separated and stored in two liquids (A and B) are shown below. Party A: Polymerizable (meth) acrylic monomer, organic peroxide B: Hydrolyzable silicon group-containing polymer, thiourea compound Party A: Hydrolyzable silicon group-containing polymer, organic peroxide B: Polymerizable (meth) acrylic monomer , Thiourea compound A: Polymerizable (meth) acrylic monomer, hydrolyzable silicon group-containing polymer, organic peroxide B: Thiourea compound A: Organic peroxide B: Polymerizable (meth) acrylic monomer, hydrolyzable Silicon group-containing polymer, thiourea compound K: Hydrolyzable silicon group-containing polymer, organic peroxide B: Polymerizable (meth) acrylic monomer, hydrolyzable silicon group-containing polymer, thiourea compound K: Polymerizable (meth) Acrylic monomer, hydrolyzable silicon group-containing polymer, organic peroxide B: Hydrolyzable silicon group-containing polymer, thiourea compound A: Heavy Polymerizable (meth) acrylic monomer, organic peroxide B: Polymerizable (meth) acrylic monomer, hydrolyzable silicon group-containing polymer, thiourea compound A: Polymerizable (meth) acrylic monomer, hydrolyzable silicon group-containing polymer, Organic peroxide B: Polymerizable (meth) acrylic monomer, thiourea compound A: Polymerizable (meth) acrylic monomer, hydrolyzable silicon group-containing polymer, organic peroxide B: Polymerizable (meth) acrylic monomer, water The combination of the degradable silicon group-containing polymer and the thiourea compound is more preferable because the variation of the performance of the cured product due to the deviation of the mixing ratio during use is particularly small.
【００１６】[0016]
【実施例】次に本発明を実施例、比較例および参考例に
よって、さらに詳細に説明する。また、これらの例にお
いて部は全て重量部を表すものとし、物性の測定は以下
のように行なった。更に、本実施例、比較例では硬化性
樹脂組成物を二液（Ａ剤、Ｂ剤）に分別して調製し、そ
れぞれの液甲、乙とした。The present invention will be described in more detail with reference to Examples, Comparative Examples and Reference Examples. In addition, all parts in these examples represent parts by weight, and the physical properties were measured as follows. Further, in this example and the comparative example, the curable resin composition was prepared by separating it into two liquids (agent A and agent B), which were used as respective solution A and B.
【００１７】［接着強度の測定］２３℃、５０％ＲＨの
室内でＡ剤、Ｂ剤をそれぞれ被着体（鋼板または鋼材）
の片方に薄く塗り、その後もう一方の被着体（鋼板また
は鋼材）を重ね合わせて接合し、７日後に以下の接着強
度を測定した。 引張剪断強度 ＡＳＴＭ Ｄ１００２−６４ 衝撃強度 ＡＳＴＭ Ｄ９５０−５４ 剥離強度 ＡＳＴＭ Ｄ１８７６−７２[Measurement of Adhesive Strength] Agent A and agent B are adhered (steel or steel) in a room at 23 ° C. and 50% RH, respectively.
Was thinly coated on one side, and then the other adherend (steel plate or steel material) was overlaid and bonded, and after 7 days, the following adhesive strength was measured. Tensile Shear Strength ASTM D1002-64 Impact Strength ASTM D950-54 Peel Strength ASTM D1876-72
【００１８】［硬化性及び硬化物の柔軟性の評価］２３
℃、５０％ＲＨの室内でＡ剤、Ｂ剤の等量を合成樹脂製
フィルム上に秤り取り混合する。そして７日間静置して
から硬化性及び硬化物の柔軟性を指触により評価した。[Evaluation of Curability and Flexibility of Cured Product] 23
Equivalent amounts of agent A and agent B are weighed and mixed on a synthetic resin film in a room at 50 ° C and 50% RH. After standing for 7 days, curability and flexibility of the cured product were evaluated by touch with fingers.
【００１９】［参考例］加水分解性ケイ素基含有ポリマ
ーとして鐘淵化学工業（株）製のメチルジメトキシシリ
ル基末端ポリプロピレンオキサイド（商品名サイリルＳ
ＡＴ２００）１００部に表１に示すごとく各化合物を添
加し、合成樹脂製フィルム上で硬化性及び硬化物の柔軟
性を評価した結果を表１に併せて示す。ＮＯ．１は有機
過酸化物とチオ尿素化合物を併用した例であり、室温で
徐々に増粘し始め、柔軟な硬化物を与える。[Reference Example] As a hydrolyzable silicon group-containing polymer, a methyldimethoxysilyl group-terminated polypropylene oxide (trade name Cyryl S manufactured by Kanegafuchi Chemical Industry Co., Ltd.)
Each compound is added to 100 parts of AT200) as shown in Table 1, and the results of evaluation of curability and flexibility of the cured product on a synthetic resin film are also shown in Table 1. NO. No. 1 is an example in which an organic peroxide and a thiourea compound are used in combination, and gradually begins to thicken at room temperature to give a flexible cured product.
【００２０】それに対して、ＮＯ．２〜３は有機過酸化
物とチオ尿素化合物を併用しない例であり、いずれも７
日後も硬化せず液状のままであった。On the other hand, NO. 2 to 3 are examples in which the organic peroxide and the thiourea compound are not used in combination, and all are 7
After the day, it did not cure and remained liquid.
【００２１】[0021]
【表１】 [Table 1]
【００２２】［実施例１〜４、比較例１］下記組成のＡ
剤およびＢ剤を調製し、接着強度の測定ならびに硬化性
及び硬化物の柔軟性の評価を行なった結果を表２に示
す。実施例１〜４は接着強度のバランスがとれており、
柔軟性に富み、折り曲げても割れにくい硬化物が得られ
た。それに対してチオ尿素化合物の代りにキレート化合
物を用いた比較例１は接着強度および硬化物の柔軟性と
もに劣っている。Ａ剤の組成 メチルジメトキシシリル基末端ポリプロピレンオキサイド1) ８０部 ヒドロキシプロピルメタクリレート ２０部 ｔ−ブチルハイドロパーオキサイド ３部 Ｂ剤の組成 アクリル変性ウレタンプレポリマー2) ６０部 ヒドロキシプロピルメタクリレート ４０部 ２，６−ジ−ｔ−ブチル−４−メチルフェノール ０．１部 水 ０．５部 チオ尿素化合物またはキレート化合物 表２に示す。 1)鐘淵化学工業（株）製「サイリルＳＡＴ０３０」 2)根上工業（株）製「アートレジンＵＮ１２５５ＴＭ」[Examples 1 to 4 and Comparative Example 1] A having the following composition
Agent and B agent are prepared, and measurement of adhesive strength and curability
Table 2 shows the results of evaluation of the flexibility of the cured product
You Examples 1 to 4 are well balanced in adhesive strength,
A cured product that is flexible and hard to break even when bent
Was. On the other hand, instead of thiourea compounds, chelation compounds
Comparative Example 1 using the cured product has excellent adhesive strength and flexibility of the cured product.
Inferior to mine.Composition of agent A Methyldimethoxysilyl group-terminated polypropylene oxide1) 80 parts Hydroxypropyl methacrylate 20 parts t-Butyl hydroperoxide 3 parts Composition of agent B Acrylic modified urethane prepolymer2) 60 parts Hydroxypropyl methacrylate 40 parts 2,6-Di-t-butyl-4-methylphenol 0.1 parts Water 0.5 parts Thiourea compound or chelate compound. 1) "Cyril SAT030" manufactured by Kanegafuchi Chemical Co., Ltd. 2) "Art Resin UN1255TM" manufactured by Negami Kogyo Co., Ltd.
【００２３】[0023]
【表２】 [Table 2]
【００２４】［実施例５〜７］下記組成のＡ剤およびＢ
剤を調製し、接着強度の測定ならびに硬化性及び硬化物
の柔軟性の評価を行なった結果を表３に示す。いずれ
も、接着強度と硬化物の柔軟性は良好であった。実施例
５にキレート化合物を加えた実施例６と７は、実施例５
よりも室温での硬化速度が速かった。Ａ剤の組成 メチルジメトキシシリル基末端ポリプロピレンオキサイド1) １００部 クメンハイドロパーオキサイド ４部Ｂ剤の組成 ヒドロキシエチルメタクリレート ５０部 ビスフェノールＡのエチレンオキサイド付加物のジメタクリレート3) １０部 ＭＢＳ樹脂4) ４０部 ハイドロキノン ０．１部 モノベンゾイルチオ尿素 １部 キレート化合物 表３に示す。 1)鐘淵化学工業（株）製「サイリルＳＡＴ０３０」 3)新中村化学（株）製「ＮＫエステルＢＰＥ１００」 4)日本合成ゴム（株）製「ＪＳＲ ＭＢＳ６１」[Examples 5 to 7] Agents A and B having the following compositions
Table 3 shows the results of preparing the agent, measuring the adhesive strength, and evaluating the curability and the flexibility of the cured product. In all cases, the adhesive strength and the flexibility of the cured product were good. Examples 6 and 7 in which a chelate compound is added to Example 5 are the same as Example 5.
The curing speed at room temperature was faster than that. Composition of agent A Methyldimethoxysilyl group-terminated polypropylene oxide 1) 100 parts Cumene hydroperoxide 4 parts Composition of agent B Hydroxyethyl methacrylate 50 parts Dimethacrylate of bisphenol A ethylene oxide adduct 3) 10 parts MBS resin 4) 40 parts Hydroquinone 0.1 part Monobenzoylthiourea 1 part Chelate compound Table 3 shows. 1) "Cyrill SAT030" manufactured by Kanegafuchi Chemical Co., Ltd. 3) "NK Ester BPE100" manufactured by Shin Nakamura Chemical Co., Ltd. 4) "JSR MBS61" manufactured by Nippon Synthetic Rubber Co., Ltd.
【００２５】[0025]
【表３】 [Table 3]
【００２６】［実施例８］加水分解性ケイ素基含有ポリ
マー（鐘淵化学工業（株）製サイリルＳＡＴ０３０）を
Ａ剤、Ｂ剤の両方に含有させた下記の組成を調製し、接
着強度の測定ならびに硬化性及び硬化物の柔軟性の評価
を行なった結果を表４に示す。Ａ剤の組成 メチルジメトキシシリル基末端ポリプロピレンオキサイド1) ２５部 ヒドロキシエチルメタクリレート ３７．５部 ビスフェノールＡのエチレンオキサイド付加物のジメタクリレート3)７．５部 ＭＢＳ樹脂4) ３０部 ベンゾキノン ０．１部 クメンハイドロパーオキサイド ４部 Ｂ剤の組成 メチルジメトキシシリル基末端ポリプロピレンオキサイド1) ２５部 ヒドロキシエチルメタクリレート ３７．５部 ビスフェノールＡのエチレンオキサイド付加物のジメタクリレート3)７．５部 ＭＢＳ樹脂4) ３０部 ハイドロキノン ０．１部 モノベンゾイルチオ尿素 １部 1)鐘淵化学工業（株）製「サイリルＳＡＴ０３０」 3)新中村化学（株）製「ＮＫエステルＢＰＥ１００」 4)日本合成ゴム（株）製「ＪＳＲ ＭＢＳ６１」Example 8 Hydrolyzable Silicon Group-Containing Poly
Mar (Kanebuchi Chemical Industry Co., Ltd. Cyril SAT030)
Prepare the following composition in both Agent A and Agent B, and
Measurement of adhesion strength and evaluation of curability and flexibility of cured products
The results obtained are shown in Table 4.Composition of agent A Methyldimethoxysilyl group-terminated polypropylene oxide1) 25 parts hydroxyethyl methacrylate 37.5 parts Dimethacrylate of ethylene oxide adduct of bisphenol A3)7.5 parts MBS resinFour) 30 parts Benzoquinone 0.1 parts Cumene hydroperoxide 4 parts Composition of agent B Methyldimethoxysilyl group-terminated polypropylene oxide1) 25 parts hydroxyethyl methacrylate 37.5 parts Dimethacrylate of ethylene oxide adduct of bisphenol A3)7.5 parts MBS resinFour) 30 parts Hydroquinone 0.1 part Monobenzoylthiourea 1 part 1) Kanefuchi Chemical Co., Ltd. "Cyryl SAT030" 3) Shin-Nakamura Chemical Co., Ltd. "NK Ester BPE100" 4) Nippon Synthetic Rubber Co., Ltd. "JSR MBS61"
【００２７】[0027]
【表４】 [Table 4]
【００２８】[0028]
【発明の効果】以上説明したように、本発明によれば、
室温下で短時間に硬化するという優れた作業性を有し、
更に、ゴム弾性と強靱性を兼ね備えた硬化物を与える硬
化性樹脂組成物が提供される。そして、該硬化性樹脂組
成物は、有機錫化合物や酸性リン化合物を触媒として用
いていないので、得られる硬化物は錫に基づく毒性や、
リン酸基の作用による解重合の心配がない。従って、本
発明の硬化性樹脂組成物は、接着剤、コーティング剤お
よびシーリング剤等の商品として社会に広く受け入れら
れるものである。As described above, according to the present invention,
It has excellent workability that it cures in a short time at room temperature,
Furthermore, a curable resin composition that provides a cured product having both rubber elasticity and toughness is provided. Since the curable resin composition does not use an organic tin compound or an acidic phosphorus compound as a catalyst, the resulting cured product has a tin-based toxicity or
There is no concern about depolymerization due to the action of the phosphate group. Therefore, the curable resin composition of the present invention is widely accepted by society as a product such as an adhesive, a coating agent and a sealing agent.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松田 ▲ひで▼明 香川県丸亀市中津町1515番地 大倉工業株 式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Matsuda ▲ Hide ▼ Akira 1515 Nakatsu-cho, Marugame-shi, Kagawa Okura Industrial Co., Ltd.
Claims (5)
性（メタ）アクリルモノマー、有機過酸化物、及び、チ
オ尿素化合物を必須成分とする硬化性樹脂組成物におい
て、該硬化性樹脂組成物の成分である有機過酸化物とチ
オ尿素化合物が一液内に共存しないように二液以上の形
態で保存され、使用時複数の液を混合し、有機過酸化物
とチオ尿素化合物を共存せしめることにより硬化するこ
とを特徴とする硬化性樹脂組成物。1. A curable resin composition containing a hydrolyzable silicon group-containing polymer, a polymerizable (meth) acrylic monomer, an organic peroxide, and a thiourea compound as essential components. The components, organic peroxide and thiourea compound, are stored in the form of two or more liquids so that they do not coexist in one liquid, and when used, multiple liquids are mixed to make the organic peroxide and thiourea compound coexist. A curable resin composition characterized by being cured by.
類であることを特徴とする請求項１に記載の硬化性樹脂
組成物。2. The curable resin composition according to claim 1, wherein the organic peroxide is a hydroperoxide.
素であることを特徴とする請求項１に記載の硬化性樹脂
組成物。3. The curable resin composition according to claim 1, wherein the thiourea compound is monobenzoylthiourea.
とする請求項１乃至３のいずれかに記載の硬化性組成
物。4. The curable composition according to claim 1, which contains a vanadium compound.
用する用途。5. Use of the curable resin composition as an adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8216695A JPH08283589A (en) | 1995-04-07 | 1995-04-07 | Curable resin composition and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8216695A JPH08283589A (en) | 1995-04-07 | 1995-04-07 | Curable resin composition and its use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08283589A true JPH08283589A (en) | 1996-10-29 |
Family
ID=13766855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8216695A Pending JPH08283589A (en) | 1995-04-07 | 1995-04-07 | Curable resin composition and its use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08283589A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000234061A (en) * | 1999-02-16 | 2000-08-29 | Okura Ind Co Ltd | Elastic curable resin composition of quick curing type |
| JP2008540740A (en) * | 2005-05-03 | 2008-11-20 | イリノイ トゥール ワークス インコーポレイティド | Adhesive for metal bonding applications |
| JP2011241342A (en) * | 2010-05-20 | 2011-12-01 | Okura Ind Co Ltd | Two-component curing type acrylic adhesive |
| JP2015522687A (en) * | 2012-06-27 | 2015-08-06 | ヘンケル ユーエス アイピー エルエルシー | Accelerator for two-step adhesive systems |
| WO2023282172A1 (en) * | 2021-07-09 | 2023-01-12 | 株式会社カネカ | Multi-component curable composition |
-
1995
- 1995-04-07 JP JP8216695A patent/JPH08283589A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000234061A (en) * | 1999-02-16 | 2000-08-29 | Okura Ind Co Ltd | Elastic curable resin composition of quick curing type |
| JP2008540740A (en) * | 2005-05-03 | 2008-11-20 | イリノイ トゥール ワークス インコーポレイティド | Adhesive for metal bonding applications |
| JP2011241342A (en) * | 2010-05-20 | 2011-12-01 | Okura Ind Co Ltd | Two-component curing type acrylic adhesive |
| JP2015522687A (en) * | 2012-06-27 | 2015-08-06 | ヘンケル ユーエス アイピー エルエルシー | Accelerator for two-step adhesive systems |
| WO2023282172A1 (en) * | 2021-07-09 | 2023-01-12 | 株式会社カネカ | Multi-component curable composition |
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