JP2005290271A - Curable composition, sealing material and adhesive - Google Patents
Curable composition, sealing material and adhesive Download PDFInfo
- Publication number
- JP2005290271A JP2005290271A JP2004109522A JP2004109522A JP2005290271A JP 2005290271 A JP2005290271 A JP 2005290271A JP 2004109522 A JP2004109522 A JP 2004109522A JP 2004109522 A JP2004109522 A JP 2004109522A JP 2005290271 A JP2005290271 A JP 2005290271A
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- curable composition
- compound
- polymer
- meth
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000003566 sealing material Substances 0.000 title claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 15
- 239000012945 sealing adhesive Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 33
- 239000000853 adhesive Substances 0.000 claims abstract description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 39
- 229920000570 polyether Polymers 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 22
- 125000002348 vinylic group Chemical group 0.000 abstract 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 40
- 239000000047 product Substances 0.000 description 34
- -1 polyethylene Polymers 0.000 description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 20
- 239000010410 layer Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 125000003342 alkenyl group Chemical group 0.000 description 17
- 239000004611 light stabiliser Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 238000001723 curing Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 125000005370 alkoxysilyl group Chemical group 0.000 description 13
- 229910052736 halogen Inorganic materials 0.000 description 12
- 150000002367 halogens Chemical class 0.000 description 12
- 230000003373 anti-fouling effect Effects 0.000 description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 description 10
- 239000011229 interlayer Substances 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000013008 thixotropic agent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 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
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- DQNSRQYYCSXZDF-UHFFFAOYSA-N 1,4-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1CCC(COC=C)CC1 DQNSRQYYCSXZDF-UHFFFAOYSA-N 0.000 description 1
- JOSFJABFAXRZJQ-UHFFFAOYSA-N 1,6-bis(ethenoxy)hexane Chemical compound C=COCCCCCCOC=C JOSFJABFAXRZJQ-UHFFFAOYSA-N 0.000 description 1
- UEIPWOFSKAZYJO-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-[2-(2-ethenoxyethoxy)ethoxy]ethane Chemical compound C=COCCOCCOCCOCCOC=C UEIPWOFSKAZYJO-UHFFFAOYSA-N 0.000 description 1
- UNMYKPSSIFZORM-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)butane Chemical compound CCCCOCCOC=C UNMYKPSSIFZORM-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
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- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- HZGIOLNCNORPKR-UHFFFAOYSA-N n,n'-bis(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCC[Si](OC)(OC)OC HZGIOLNCNORPKR-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical class CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229930014626 natural product Natural products 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
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- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
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- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
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- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
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Images
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- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、湿気により硬化する硬化性組成物に関し、より詳細には、架橋可能な加水分解性シリル基を含有するビニル系重合体を用いて構成されており、接着強度及び硬化物の弾力性に優れており、さらに硬化物表面のべたつきが少なく防汚性に優れた硬化物を与える硬化性組成物、並びに該硬化性組成物を用いたシーリング材及び接着剤に関する。 The present invention relates to a curable composition curable by moisture, and more specifically, is composed of a vinyl polymer containing a crosslinkable hydrolyzable silyl group, and has adhesive strength and elasticity of a cured product. In addition, the present invention relates to a curable composition that gives a cured product that is excellent in anti-fouling properties with less stickiness on the surface of the cured product, and a sealing material and an adhesive using the curable composition.
従来、アルコキシシリル基を有するビニル重合体は、雰囲気中の湿気により架橋し、耐久性、耐候性、透明性及び接着性に優れた硬化物を与えることが知られている（例えば、下記の特許文献１、特許文献２、特許文献３）。そのため、上記ビニル重合体を有する硬化性組成物は、塗料、コーティング剤、接着剤、感圧接着剤、シーラント及びシーリング材などの用途に広く用いられている。 Conventionally, a vinyl polymer having an alkoxysilyl group is known to be crosslinked by moisture in the atmosphere to give a cured product excellent in durability, weather resistance, transparency and adhesiveness (for example, the following patents) Literature 1, Patent Literature 2, Patent Literature 3). Therefore, the curable composition having the vinyl polymer is widely used for applications such as paints, coating agents, adhesives, pressure-sensitive adhesives, sealants, and sealants.
ところで、シーリング材や、外気に露出している部分に位置している接着剤硬化物は、雰囲気中を漂う湿気や塵埃などにより露出部分が汚れ、外観を損なうことが多々あった。そのため、従来、下記の特許文献４に記載の光硬化性化合物、特許文献５に記載の酸素反応性化合物などを添加する方法が用いられていた。また、下記の特許文献６に記載のように、ポリフルオロ基含有アクリル重合体を用いた硬化性組成物も提案されている。 By the way, the sealing material and the cured adhesive material located in the portion exposed to the outside air often have an exposed portion that is contaminated by moisture or dust drifting in the atmosphere, thereby impairing the appearance. Therefore, conventionally, a method of adding a photocurable compound described in Patent Document 4 below, an oxygen reactive compound described in Patent Document 5, or the like has been used. Further, as described in Patent Document 6 below, a curable composition using a polyfluoro group-containing acrylic polymer has also been proposed.
しかしながら、アルコキシシリル基含有ビニル重合体に対してこれらの化合物は共有結合を介して強固に結合されていない。従って、やはり硬化物表面が雰囲気の影響を受けて汚染されたり、経時によりこれらの化合物がブリードアウトしたりすることがあった。 However, these compounds are not firmly bonded to the alkoxysilyl group-containing vinyl polymer via a covalent bond. Accordingly, the surface of the cured product may be contaminated under the influence of the atmosphere, or these compounds may bleed out over time.
また、下記の特許文献７には、オルガノシロキサン成分を含有させた塗料用組成物が開示されているが、ここでは、加水分解性シリル基含有ビニル重合体への共有結合的な結合については言及されていない。 Further, Patent Document 7 below discloses a coating composition containing an organosiloxane component, but here, mention is made of a covalent bond to a hydrolyzable silyl group-containing vinyl polymer. It has not been.
他方、下記の特許文献８には、架橋可能な加水分解性シリル基を有する重合体と、空気硬化性化合物及び／または光硬化性化合物からなる室温硬化性組成物が開示されている。ここでは、空気硬化性化合物及び／または光硬化性化合物の配合により、硬化物表面のべたつきが抑制され、硬化性及び表面耐候性を高め得る旨が示されている。上記空気硬化性化合物としては、空気中の酸素により重合を化合物が好ましい旨、また上記光硬化性化合物としては、光の作用により硬化する種々の化合物を用いることができる旨が示されている。 On the other hand, Patent Document 8 below discloses a room temperature curable composition comprising a polymer having a crosslinkable hydrolyzable silyl group and an air curable compound and / or a photocurable compound. Here, it is shown that the stickiness of the surface of the cured product can be suppressed and the curability and surface weather resistance can be improved by blending the air curable compound and / or the photocurable compound. It is indicated that the air curable compound is preferably a compound that is polymerized by oxygen in the air, and the photo curable compound can be various compounds that are cured by the action of light.
他方、アルコキシシリル基含有ビニル系重合体の製造に際してアルコキシシリル基を導入する方法としては、（１）アルコキシシリル基を有する重合開始剤による重合を開始する方法、（２）アルコキシシリル基を有する連鎖移動剤を用いる方法、（３）アルコキシシリル基を有する共重合性モノマーを用いる方法などの重合と同時にアルコキシシリル基を導入する方法が知られている（例えば、特許文献９〜１２など）。あるいは、アルケニル基を有するビニル重合体を合成し、しかる後、ヒドロシリル化によりアルコキシシリル基を導入する方法も提案されている（例えば、特許文献１３，１４）。 On the other hand, as a method for introducing an alkoxysilyl group in the production of an alkoxysilyl group-containing vinyl polymer, (1) a method for initiating polymerization with a polymerization initiator having an alkoxysilyl group, and (2) a chain having an alkoxysilyl group. Methods for introducing an alkoxysilyl group simultaneously with polymerization such as a method using a transfer agent and (3) a method using a copolymerizable monomer having an alkoxysilyl group are known (for example, Patent Documents 9 to 12). Alternatively, a method of synthesizing a vinyl polymer having an alkenyl group and then introducing an alkoxysilyl group by hydrosilylation has been proposed (for example, Patent Documents 13 and 14).
上記先行技術に記載の方法で得られたアルコキシシリル基を有する（メタ）アクリル系重合体を主成分とする硬化性組成物において、透明な硬化物を得ようとした場合、充填剤や顔料のような添加物を入れずに硬化させればよい。しかしながら、先行技術に記載のアルコキシシリル基を有する（メタ）アクリル酸エステル系重合体を用いて透明な硬化物を得ようとした場合、目視的に透明な硬化物は得られるものの、経時により黄変するという問題があった。そのため、透明な硬化物を得たい場合や、淡色系の着色を施した場合に、安定な色合いを維持することが困難であることがあった。 In a curable composition containing as a main component a (meth) acrylic polymer having an alkoxysilyl group obtained by the method described in the above prior art, when trying to obtain a transparent cured product, What is necessary is just to harden | cure without adding such an additive. However, when an attempt is made to obtain a transparent cured product using the (meth) acrylic acid ester-based polymer having an alkoxysilyl group described in the prior art, a visually transparent cured product can be obtained. There was a problem of changing. For this reason, when it is desired to obtain a transparent cured product or when a light-colored coloring is applied, it may be difficult to maintain a stable hue.
本発明の目的は、上述した従来技術の現状に鑑み、雰囲気中の湿気により硬化し、弾力性に優れた硬化物を与えるだけでなく、硬化物表面のべたつきが少なく防汚性に優れているだけでなく、さらに硬化物の黄変が生じ難く、淡色の着色を施した場合でも安定的に色合いを維持することができ、あるいは透明性を維持することを可能とする、硬化性組成物、並びに該硬化性組成物を用いたシーリング材及び接着剤を提供することにある。 The object of the present invention is not only to give a cured product that is cured by moisture in the atmosphere and is excellent in elasticity, but also has excellent antifouling properties with less stickiness on the surface of the cured product in view of the current state of the prior art described above. In addition, it is difficult to cause further yellowing of the cured product, and even when lightly colored, it is possible to stably maintain the hue, or to maintain transparency, a curable composition, Another object is to provide a sealing material and an adhesive using the curable composition.
本発明に係る硬化性組成物は、式（１）で示される架橋性シリル基を末端に有するビニル系重合体（ａ）１００重量部と空気硬化性及び／又は光硬化性化合物（ｂ）５〜４０重量部とを含有してなる硬化性組成物である。
−［Ｓｉ（Ｒ1）2-b（Ｙ）bＯ］m−Ｓｉ（Ｒ2）3-a（Ｙ）a （１）
（式中、Ｒ1およびＲ2は、いずれも炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、または炭素数７〜２０のアラルキル基、または（Ｒ’）3Ｓｉ−（Ｒ’は炭素数１〜２０の１価の炭化水素基であって、３個のＲ’は同一であってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基を示し、Ｒ1またはＲ2が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｙは水酸基または加水分解性基を示し、Ｙが２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。ａは０，１，２，または３を、また、ｂは０，１，または２を示す。ｍは０〜１９の整数である。ただし、ａ＋ｍｂ≧１であることを満足するものとする。）
The curable composition according to the present invention comprises 100 parts by weight of a vinyl polymer (a) having a crosslinkable silyl group represented by the formula (1) at the terminal, and an air curable and / or photocurable compound (b) 5 It is a curable composition formed by containing ~ 40 parts by weight.
- [Si (R 1) 2 -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R 1 and R 2 are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) 3 Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R 1 Alternatively, when two or more R 2 are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)
本発明に係る硬化性組成物の他の特定の局面では、有機金属化合物からなる硬化促進剤がさらに配合される。
本発明に係る硬化性組成物のさらに別の特定の局面では、架橋可能な加水分解性シリル基を有するポリエーテル系重合体（ｃ）がさらに配合される。
In another specific aspect of the curable composition according to the present invention, a curing accelerator composed of an organometallic compound is further blended.
In yet another specific aspect of the curable composition according to the present invention, a polyether polymer (c) having a crosslinkable hydrolyzable silyl group is further blended.
本発明に係る硬化性組成物のさらに他の特定の局面では、層状珪酸塩（ｄ）がさらに配合される。
本発明に係るシーリング材及び接着剤は、それぞれ、本発明に従って構成された硬化性組成物からなることを特徴とする。
In still another specific aspect of the curable composition according to the present invention, a layered silicate (d) is further blended.
The sealing material and the adhesive according to the present invention are each characterized by comprising a curable composition constituted according to the present invention.
以下、本発明の詳細を説明する。
本発明の硬化性組成物には、式（１）を末端に有するビニル重合体（ａ）が含有される。
−［Ｓｉ（Ｒ3）2-b（Ｙ）bＯ］m−Ｓｉ（Ｒ4）3-a（Ｙ）a （１）
（式中、Ｒ1およびＲ2は、いずれも炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、または炭素数７〜２０のアラルキル基、または（Ｒ’）3Ｓｉ−（Ｒ’は炭素数１〜２０の１価の炭化水素基であって、３個のＲ’は同一であってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基を示し、Ｒ1またはＲ2が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｙは水酸基または加水分解性基を示し、Ｙが２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。ａは０，１，２，または３を、また、ｂは０，１，または２を示す。ｍは０〜１９の整数である。ただし、ａ＋ｍｂ≧１であることを満足するものとする。）
Details of the present invention will be described below.
The curable composition of the present invention contains a vinyl polymer (a) having the terminal formula (1).
- [Si (R 3) 2 -b (Y) b O] m -Si (R 4) 3-a (Y) a (1)
(In the formula, R 1 and R 2 are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) 3 Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R 1 Alternatively, when two or more R 2 are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)
上記Ｙで示される加水分解性基としては、特に限定されず、例えば、水素、ハロゲン原子、メトキシ基、エトキシ基などのアルコキシ基、アシルオキシド基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシド基などが好ましい例として挙げられ、取り扱いが容易で反応の際に有害な副生成物を生成しないアルコキシ基が特に好ましい。上記水酸基や加水分解性基は１個のケイ素原子に１〜３個の範囲で結合することができ、式（１）中における水酸基及び加水分解性基の総個数、すなわち、ａ＋ｍｂ、は１〜５の範囲であるのが好ましい。加水分解性基や水酸基が架橋性ケイ素基中に２個以上結合するときは、それらは同一であっても、異なっていてもよい。架橋性ケイ素化合物を構成するケイ素原子は１個でもよく、２個以上であってもよいが、シロキサン結合により連結されたケイ素原子の場合は２０個程度まであってもよい。 The hydrolyzable group represented by Y is not particularly limited, and examples thereof include an alkoxy group such as hydrogen, a halogen atom, a methoxy group, and an ethoxy group, an acyl oxide group, a ketoximate group, an amino group, an amide group, and an acid amide group. An aminooxy group, a mercapto group, an alkenyl oxide group and the like are preferable examples, and an alkoxy group that is easy to handle and does not generate harmful by-products during the reaction is particularly preferable. The hydroxyl group and hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3, and the total number of hydroxyl groups and hydrolyzable groups in the formula (1), that is, a + mb is 1 to 1 A range of 5 is preferred. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one or two or more. In the case of silicon atoms linked by a siloxane bond, up to about 20 silicon atoms may be used.
上記ビニル系重合体（ａ）を構成しているビニル重合体部分としては、ビニルモノマーを重合して得られる重合体であれば良く、例えば、ポリエチレン、ポリプロピレン、ポリイソブチレン、ポリ（メタ）アクリレート、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリブタジエン、ポリイソプレン、ポリ酢酸ビニル、ポリビニルアルコール、ポリビニルブチラール、ポリビニルエーテル等を挙げることができる。また、これらビニル重合体部分を有する共重合体であっても良い。好適には、凝集力や接着性とのバランスの良い数平均分子量７０００以上のポリ（メタ）アクリレートやその共重合体が良い。ここで、（メタ）アクリルとはメタクリルとアクリルをまとめて示した表現である。 The vinyl polymer part constituting the vinyl polymer (a) may be a polymer obtained by polymerizing a vinyl monomer, such as polyethylene, polypropylene, polyisobutylene, poly (meth) acrylate, Examples include polystyrene, polyvinyl chloride, polyvinylidene chloride, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, and polyvinyl ether. Moreover, the copolymer which has these vinyl polymer parts may be sufficient. Preferably, a poly (meth) acrylate having a number average molecular weight of 7000 or more and a copolymer thereof having a good balance between cohesive strength and adhesiveness are preferred. Here, (meth) acryl is an expression collectively showing methacryl and acryl.
ポリ（メタ）アクリレートやその共重合体を得るためのモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２ーブトキシエチル（メタ）アクリレート、２−フェノキシエチル（メタ）アクリレート、グリシジル（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、ヘキサンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリ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ールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールジ（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、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート、２−ヒドロキシエチル（メタ）アクリレート、３−ヒドロキシプロピル（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、４−ヒドロキシブチル（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、５−ヒドロキシペンチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、３−ヒドロキシー３ーメチルブチル（メタ）アクリレート、２−ヒドロキシー３ーフェノキシプロピル（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、２−［（メタ）アクリロイルオキシ］エチル２−ヒドロキシエチルフタル酸、２−［（メタ）アクリロイルオキシ］エチル２−ヒドロキシプロピルフタル酸、
［化合物１］
ＣＨ2＝ＣＨ−Ｃ（Ｏ）Ｏ−ＣＨ2ＣＨ2Ｏ−
［Ｃ（Ｏ）ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ2Ｏ］n−Ｈ
（ｎ＝１〜１０）
［化合物２］
ＣＨ2＝Ｃ（ＣＨ3）−Ｃ（Ｏ）Ｏ−ＣＨ2ＣＨ2Ｏ−
［Ｃ（Ｏ）ＣＨ2ＣＨ2ＣＨ2ＣＨ2ＣＨ2Ｏ］n−Ｈ
（ｎ＝１〜１０）
［化合物３］
ＣＨ2＝ＣＨ−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−Ｈ
（ｎ＝１〜１２）
［化合物４］
ＣＨ2＝Ｃ（ＣＨ3）−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−Ｈ
（ｎ＝１〜１２）
［化合物５］
ＣＨ2＝ＣＨ−Ｃ（Ｏ）Ｏ−［ＣＨ2ＣＨ（ＣＨ3）Ｏ］n−Ｈ
（ｎ＝１〜１２）
［化合物６］
ＣＨ2＝Ｃ（ＣＨ3）−Ｃ（Ｏ）Ｏ−［ＣＨ2ＣＨ（ＣＨ3）Ｏ］n−Ｈ
（ｎ＝１〜１２）
［化合物７］
ＣＨ2＝Ｃ（ＣＨ3）−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−
［ＣＨ2ＣＨ（ＣＨ3）Ｏ］m−Ｈ
（ｍ，ｎ＝１〜１２）
［化合物８］
ＣＨ2＝ＣＨ−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−
［ＣＨ2ＣＨ（ＣＨ3）Ｏ］m−Ｈ
（ｍ，ｎ＝１〜１２）
［化合物９］
ＣＨ2＝Ｃ（ＣＨ3）−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−
（ＣＨ2ＣＨ2ＣＨ2ＣＨ2Ｏ）mＨ
（ｍ，ｎ＝１〜１２）
［化合物１０］
ＣＨ2＝ＣＨ−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−
（ＣＨ2ＣＨ2ＣＨ2ＣＨ2Ｏ）mＨ
（ｍ，ｎ＝１〜１２）
［化合物１１］
ＣＨ2＝ＣＨ−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−ＣＨ3
（ｎ＝１〜１０）
［化合物１２］
ＣＨ2＝Ｃ（ＣＨ3）−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−ＣＨ3
（ｎ＝１〜３０）
［化合物１３］
ＣＨ2＝ＣＨ−Ｃ（Ｏ）Ｏ−［ＣＨ2ＣＨ（ＣＨ3）Ｏ］n−ＣＨ3
（ｎ＝１〜１０）
［化合物１４］
ＣＨ2＝Ｃ（ＣＨ3）−Ｃ（Ｏ）Ｏ−［ＣＨ2ＣＨ（ＣＨ3）Ｏ］n−ＣＨ3
（ｎ＝１〜１０）
［化合物１５］
ＣＨ2＝Ｃ（ＣＨ3）−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−
［ＣＨ2ＣＨ（ＣＨ3）Ｏ］m−Ｈ
（ｍ，ｎ＝１〜１０）
［化合物１６］
ＣＨ2＝ＣＨ−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−
［ＣＨ2ＣＨ（ＣＨ3）Ｏ］m−Ｈ
（ｍ，ｎ＝１〜１０）
［化合物１７］
ＣＨ2＝ＣＨ−Ｃ（Ｏ）Ｏ−［ＣＨ2ＣＨ（ＣＨ3）Ｏ］n
−Ｃ（Ｏ）−ＣＨ＝ＣＨ2
（ｎ＝１〜２０）
［化合物１８］
ＣＨ2＝Ｃ（ＣＨ3）−Ｃ（Ｏ）Ｏ−［ＣＨ2ＣＨ（ＣＨ3）Ｏ］n
−Ｃ（Ｏ）−Ｃ（ＣＨ3）＝ＣＨ2
（ｎ＝１〜２０）
［化合物１９］
ＣＨ2＝ＣＨ−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n−Ｃ（Ｏ）−ＣＨ＝ＣＨ2
（ｎ＝１〜２０）
［化合物２０］
ＣＨ2＝Ｃ（ＣＨ3）−Ｃ（Ｏ）Ｏ−（ＣＨ2ＣＨ2Ｏ）n
−Ｃ（Ｏ）−Ｃ（ＣＨ3）＝ＣＨ2
（ｎ＝１〜２０）等を挙げることができる。
Examples of the monomer for obtaining poly (meth) acrylate and its copolymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate , Isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydro Rufuryl (meth) acrylate, hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, Polyester acrylate, urethane acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropy (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-[(meth) acryloyloxy] ethyl 2-hydroxyethylphthalic acid, 2- [ (Meth) acryloyloxy] ethyl 2-hydroxypropylphthalic acid,
[Compound 1]
CH2 = CH-C (O) O-CH2CH2O-
[C (O) CH2CH2CH2CH2CH2O] n-H
(N = 1-10)
[Compound 2]
CH2 = C (CH3) -C (O) O-CH2CH2O-
[C (O) CH2CH2CH2CH2CH2O] n-H
(N = 1-10)
[Compound 3]
CH2 = CH-C (O) O- (CH2CH2O) n-H
(N = 1-12)
[Compound 4]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-H
(N = 1-12)
[Compound 5]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n-H
(N = 1-12)
[Compound 6]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n-H
(N = 1-12)
[Compound 7]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(M, n = 1-12)
[Compound 8]
CH2 = CH-C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(M, n = 1-12)
[Compound 9]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
(CH2CH2CH2CH2O) mH
(M, n = 1-12)
[Compound 10]
CH2 = CH-C (O) O- (CH2CH2O) n-
(CH2CH2CH2CH2O) mH
(M, n = 1-12)
[Compound 11]
CH2 = CH-C (O) O- (CH2CH2O) n-CH3
(N = 1-10)
[Compound 12]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-CH3
(N = 1-30)
[Compound 13]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n-CH3
(N = 1-10)
[Compound 14]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n-CH3
(N = 1-10)
[Compound 15]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(M, n = 1-10)
[Compound 16]
CH2 = CH-C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(M, n = 1-10)
[Compound 17]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n
-C (O) -CH = CH2
(N = 1-20)
[Compound 18]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n
-C (O) -C (CH3) = CH2
(N = 1-20)
[Compound 19]
CH2 = CH-C (O) O- (CH2CH2O) n-C (O) -CH = CH2
(N = 1-20)
[Compound 20]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n
-C (O) -C (CH3) = CH2
(N = 1 to 20).
その他のビニルモノマーとして、例えば、スチレン、インデン、αーメチルスチレン、ｐ−メチルスチレン、ｐ−クロロスチレン、ｐ−クロロメチルスチレン、ｐ−メトキシスチレン、ｐ−ｔｅｒｔ−ブトキシスチレン、ジビニルベンゼン等のスチレン誘導体；例えば、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、安息香酸ビニル、珪皮酸ビニル等のビニルエステル基を持つ化合物；無水マレイン酸、Ｎ−ビニルピロリドン、Ｎ−ビニルモルフォリン、（メタ）アクリロニトリル、（メタ）アクリルアミド、Ｎ−シクロヘキシルマレイミド、Ｎ−フェニルマレイミド、Ｎ−ラウリルマレイミド、Ｎ−ベンジルマレイミド、ｎ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテル、ｔｅｒｔ−ブチルビニルエーテル、ｔｅｒｔ−アミルビニルエーテル、シクロヘキシルビニルエーテル、２−エチルヘキシルビニルエーテル、ドデシルビニルエーテル、オクタデシルビニルエーテル、２−クロロエチルビニルエーテル、エチレングリコールブチルビニルエーテル、トリチレングリコールメチルビニルエーテル、安息香酸（４−ビニロキシ）ブチル、エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、テトラエチレングリコールジビニルエーテル、ブタン−１，４−ジオール−ジビニルエーテル、ヘキサン−１，６−ジオール−ジビニルエーテル、シクロヘキサン−１，４−ジメタノール−ジビニルエーテル、イソフタル酸ジ（４−ビニロキシ）ブチル、グルタル酸ジ（４−ビニロキシ）ブチル、コハク酸ジ（４−ビニロキシ）ブチルトリメチロールプロパントリビニルエーテル、２−ヒドロキシエチルビニルエーテル、４−ヒドロキシブチルビニルエーテル、６−ヒドロキシヘキシルビニルエーテル、シクロヘキサン−１，４−ジメタノール−モノビニルエーテル、ジエチレングリコールモノビニルエーテル３−アミノプロピルビニルエーテル、２−（Ｎ，Ｎ−ジエチルアミノ）エチルビニルエーテル、ウレタンビニルエーテル、ポリエステルビニルエーテル等のビニロキシ基を持つ化合物を挙げることができる。 Examples of other vinyl monomers include styrene derivatives such as styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, and divinylbenzene; For example, compounds having a vinyl ester group such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholine, (meta ) Acrylonitrile, (meth) acrylamide, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-benzylmaleimide, n-propylvinylether, n-butylvinylether, isobutylvinylether, ter -Butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, tritylene glycol methyl vinyl ether, benzoic acid (4-vinyloxy) butyl, ethylene Glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol-divinyl ether, hexane-1,6-diol-divinyl ether, cyclohexane-1,4-dimethanol -Divinyl ether, di (4-vinyloxy) butyl isophthalate, glu Di (4-vinyloxy) butyl tartrate, di (4-vinyloxy) butyl trimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-di succinate Mention may be made of compounds having a vinyloxy group such as methanol-monovinyl ether, diethylene glycol monovinyl ether 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, polyester vinyl ether and the like.
式（１）の架橋性シリル基を末端に有するビニル系重合体の製造方法としては、特に限定されず、例えば、有機ハロゲン化物、またはハロゲン化スルホニル化合物を開始剤、遷移金属錯体を触媒として上記ビニル系モノマーを重合することにより、式（２）で示す末端構造を有するビニル系重合体を製造し、式（２）のハロゲンを式（１）に示す架橋性シリル基含有置換基に変換する方法が挙げられる。
−Ｃ（Ｒ3）（Ｒ4）（Ｘ） （２）
（式中、Ｒ3は、Ｒ4はビニル系モノマーのエチレン性不飽和基に結合した基を表す。また、Ｘは塩素、臭素、またはヨウ素のハロゲン原子を表す。）
れる。
The method for producing a vinyl polymer having a crosslinkable silyl group of formula (1) at the terminal is not particularly limited. For example, the above-described method is performed using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. By polymerizing a vinyl monomer, a vinyl polymer having a terminal structure represented by formula (2) is produced, and the halogen of formula (2) is converted to a crosslinkable silyl group-containing substituent represented by formula (1). A method is mentioned.
-C (R 3 ) (R 4 ) (X) (2)
(In the formula, R 3, R 4 represents a group bonded to an ethylenically unsaturated group of a vinyl monomer. In addition, X represents chlorine, bromine, or halogen atom iodine,.)
It is.
上記式（２）のハロゲンを式（１）に示す架橋性シリル基含有置換基に変換する方法としては、特に限定されず、例えば、アルケニル基と架橋性シリル基とを有する化合物、シリル基と安定化カルバニオンを有する化合物等を反応させる方法、重合性アルケニル基とそれ以外のアルケニル基を有する化合物、アルケニル基を有する有機金属化合物、アルケニル基を有するカルボン酸金属塩、アルケニル基と安定化カルバニオンを有する化合物等を反応させて式（２）のハロゲンをアルケニル基に置換させた後に、該アルケニル基に架橋性シリル基を有するヒドロシランを反応させる方法等が挙げられる。 The method for converting the halogen of the above formula (2) into the crosslinkable silyl group-containing substituent represented by the formula (1) is not particularly limited. For example, a compound having an alkenyl group and a crosslinkable silyl group, a silyl group, A method of reacting a compound having a stabilized carbanion, a compound having a polymerizable alkenyl group and another alkenyl group, an organometallic compound having an alkenyl group, a carboxylic acid metal salt having an alkenyl group, an alkenyl group and a stabilized carbanion For example, a method in which a halogen compound represented by formula (2) is substituted with an alkenyl group and then a hydrosilane having a crosslinkable silyl group is reacted with the alkenyl group.
また、式（１）の架橋性シリル基を末端に有するビニル系重合体を製造する際に、架橋性シリル基を有する有機ハロゲン化物を開始剤として用いて、一方の端にハロゲンを有し他の端に架橋性シリル基を有する重合体を合成した後、ハロゲンとグリコール、ジアミン、ジカルボン酸等と反応させて両末端に架橋性シリル基を有する重合体を作成しても良いし、一方の端にハロゲンを有し他の端に架橋性シリル基を有する重合体を合成した後、
ハロゲンを上記反応により架橋性シリル基に変換させても良い。或いは、一方の端にハロゲンを有し他の端に架橋性シリル基を有する重合体を合成した後、先述の反応によりハロゲンをアルケニル基に変換した後に、さらに架橋性シリル基に変換しても良い。
In addition, when producing a vinyl polymer having a crosslinkable silyl group at the end of formula (1), an organic halide having a crosslinkable silyl group is used as an initiator, and a halogen is contained at one end. After synthesizing a polymer having a crosslinkable silyl group at one end, a polymer having a crosslinkable silyl group at both ends may be prepared by reacting with halogen and glycol, diamine, dicarboxylic acid, etc. After synthesizing a polymer having a halogen at one end and a crosslinkable silyl group at the other end,
Halogen may be converted to a crosslinkable silyl group by the above reaction. Alternatively, after synthesizing a polymer having a halogen at one end and a crosslinkable silyl group at the other end, the halogen may be converted to an alkenyl group by the above-described reaction, and then further converted to a crosslinkable silyl group. good.
また、式（１）の架橋性シリル基を末端に有するビニル系重合体を製造する際に、
アルケニル基を有する有機ハロゲン化物を開始剤として用いて、一方の端にハロゲンを有し他の端にアルケニル基を有する重合体を合成した後、ハロゲンをアルケニル基に変換した後に、アルケニル基を先述の方法で架橋性シリル基に変換する方法等が挙げられる。
Further, when producing a vinyl polymer having a terminal crosslinkable silyl group of formula (1),
After synthesizing a polymer having a halogen at one end and an alkenyl group at the other end using an organic halide having an alkenyl group as an initiator, the halogen is converted to an alkenyl group, And a method of converting to a crosslinkable silyl group by the above method.
（空気硬化性及び／又は光硬化性化合物（ｂ））
本発明においては、上記空気硬化性もしくは光硬化性化合物が硬化物の表面のべたつきを抑制するために配合されている。本発明においては、空気硬化性または光硬化性化合物（ｂ）が配合されておればよく、空気硬化性化合物及び光硬化性化合物の双方が配合されていてもよい。
(Air-curing and / or photo-curing compound (b))
In the present invention, the air curable or photocurable compound is blended in order to suppress stickiness of the surface of the cured product. In the present invention, it is sufficient that the air curable or photocurable compound (b) is blended, and both the air curable compound and the photocurable compound may be blended.
空気硬化性及び／又は光硬化性化合物（ｂ）の配合割合は、上記ビニル系重合体（ａ）１００重量部に対し、あるいは上記ビニル系重合体（ａ）と、後述の必要に応じて添加されるポリエーテル系重合体（ｃ）の合計１００重量部に対し、５〜４０重量部の割合で配合される。５重量部未満の場合には、硬化物表面のべたつきを抑制する作用が十分でなく、４０重量部を越えると所望とする硬化物の弾力性及び伸び特性を得ることができない。好ましくは、１０〜２０重量部の割合で配合される。 The blending ratio of the air-curing and / or photo-curing compound (b) is added to 100 parts by weight of the vinyl polymer (a) or the vinyl polymer (a), as described later. 5 to 40 parts by weight with respect to a total of 100 parts by weight of the polyether polymer (c). If the amount is less than 5 parts by weight, the effect of suppressing stickiness on the surface of the cured product is not sufficient, and if it exceeds 40 parts by weight, desired elasticity and elongation characteristics of the cured product cannot be obtained. Preferably, it mix | blends in the ratio of 10-20 weight part.
好ましい空気硬化性化合物及び光硬化性化合物としては、少なくとも沸点が１気圧で１００℃以上のものが好ましい。沸点が１００℃未満の場合には、硬化性組成物が硬化中に揮散し、空気硬化性化合物もしくは光硬化性化合物による効果を得ることができないことがある。 Preferable air curable compounds and photocurable compounds are those having at least a boiling point of 1 atm and 100 ° C. or higher. When the boiling point is less than 100 ° C., the curable composition volatilizes during the curing, and the effect of the air curable compound or the photocurable compound may not be obtained.
また、空気硬化性化合物及び光硬化性化合物としては、ビニル系重合体（ａ）と相分離しない化合物が好ましい。相分離が起きると、硬化性組成物の安定性が著しく低下したり、表面に空気硬化性化合物もしくは光硬化性化合物がブリードアウトし、硬化被膜がゴム的性質を示さないことがある。もっとも、相分離するような組み合わせであっても、適当な相溶化剤を添加することにより、相分離を抑制してもよい。 Moreover, as an air-curable compound and a photocurable compound, the compound which does not phase-separate with a vinyl type polymer (a) is preferable. When phase separation occurs, the stability of the curable composition may be significantly reduced, or the air curable compound or the photocurable compound may bleed out on the surface, and the cured coating may not exhibit rubbery properties. However, even in a combination that causes phase separation, phase separation may be suppressed by adding an appropriate compatibilizing agent.
本発明で用いられる空気硬化性物質とは、空気中の酸素により架橋し、硬化する化合物をいうものとする。このような空気硬化性化合物としては、大豆油、アマニ油、綿実油、菜種油、桐油、ケシ油等の乾性油、半乾性油及びこれらの変性物を挙げることができる。 The air curable substance used in the present invention refers to a compound that is crosslinked and cured by oxygen in the air. Examples of such air curable compounds include drying oils such as soybean oil, linseed oil, cottonseed oil, rapeseed oil, tung oil, and poppy oil, semi-drying oils, and modified products thereof.
光硬化性物質とは、可視光や紫外線等の光によって架橋硬化する化合物のことで、例えば、感光性の重合性不飽和基を持つモノマーやオリゴマーやこれら組成物を挙げることができる。重合性不飽和基として、（メタ）アクリロイル基、シンナモイル基、スチリル基等を挙げることができる。これら不飽和基を持つオリゴマーとしては、ポリエーテルオリゴマー、ポリエステルオリゴマー、ポリウレタンオリゴマー、ポリカーボネートオリゴマー、ポリオレフィンオリゴマー、ビニル重合体オリゴマー等に上記不飽和基を持つ化合物を適宜用いることができる。用いるオリゴマーとしては、配合が容易で、速やかに溶解させることができるポリスチレン換算数平均分子量５００００までのものが好ましい。 The photocurable substance is a compound that is crosslinked and cured by light such as visible light or ultraviolet light, and examples thereof include monomers and oligomers having a photosensitive polymerizable unsaturated group, and compositions thereof. Examples of the polymerizable unsaturated group include a (meth) acryloyl group, a cinnamoyl group, and a styryl group. As the oligomer having an unsaturated group, a compound having the unsaturated group in a polyether oligomer, a polyester oligomer, a polyurethane oligomer, a polycarbonate oligomer, a polyolefin oligomer, a vinyl polymer oligomer, or the like can be appropriately used. As the oligomer to be used, those having a polystyrene-reduced number average molecular weight of up to 50000, which can be easily blended and can be dissolved quickly, are preferable.
光硬化性化合物を添加する場合、硬化促進の為に各種、光ラジカル開始剤や光増感剤を添加しても良い。光ラジカル開始剤や光増感剤としては、例えば４−（２−ヒドロキシエトキシ）フェニル（２−ヒドロキシ−２−プロピル）ケトン、α−ヒドロキシ−α，α’−ジメチルアセトフェノン、メトキシアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン等のアセトフェノン誘導体化合物；ベンゾインエチルエーテル、ベンゾインプロピルエーテル等のベンゾインエーテル系化合物；ベンジルジメチルケタール等のケタール誘導体化合物；ハロゲン化ケトン；アシルフォスフィンオキシド；アシルフォスフォナート；２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−Ｎ，Ｎ−ジメチルアミノ−１−（４−モルフォリノフェニル）−１−ブタノン；ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキシドビス−（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルフォスフィンオキシド；エチルチオキサントン、イソプロピルチオキサントン、クロロチオキサントン等のチオキサントン誘導体；アントラセン、メトキシアントラセン、エトキシアントラセン等のアントラセン誘導体；ビス（η５−シクロペンタジエニル）−ビス（ペンタフルオロフェニル）−チタニウム、ビス（η５−シクロペンタジエニル）−ビス［２，６−ジフルオロ−３−（１Ｈ−ピリ−１−イル）フェニル］−チタニウムを挙げることができる。 When a photocurable compound is added, various photoradical initiators and photosensitizers may be added to accelerate curing. Examples of the photo radical initiator and photo sensitizer include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α′-dimethylacetophenone, methoxyacetophenone, 2, Acetophenone derivative compounds such as 2-dimethoxy-2-phenylacetophenone; Benzoin ether compounds such as benzoin ethyl ether and benzoin propyl ether; Ketal derivative compounds such as benzyldimethyl ketal; Halogenated ketones; Acylphosphine oxides; Acylphosphonates 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1 -Butanone; bis (2,4,6- Limethylbenzoyl) -phenylphosphine oxide bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; thioxanthone derivatives such as ethylthioxanthone, isopropylthioxanthone, chlorothioxanthone; anthracene, methoxyanthracene, Anthracene derivatives such as ethoxyanthracene; bis (η5-cyclopentadienyl) -bis (pentafluorophenyl) -titanium, bis (η5-cyclopentadienyl) -bis [2,6-difluoro-3- (1H-pyri -1-yl) phenyl] -titanium.
（ポリエーテル系重合体（ｃ））
本発明に係る硬化性組成物では、好ましくは、架橋可能な加水分解性シリル基を有するポリエーテル系重合体（ｃ）がさらに配合される。
(Polyether polymer (c))
In the curable composition concerning this invention, Preferably, the polyether polymer (c) which has a hydrolyzable silyl group which can be bridge | crosslinked is further mix | blended.
ポリエーテル系重合体（ｃ）としては、主鎖が本質的にポリエーテル重合体からなるもの、主鎖がポリエーテルと（メタ）アクリル酸エステルとからなる重合体等が挙げられる。この有機重合体を配合することにより、硬化物の耐水性を高めたり、シーリング材を構成した場合のゴム弾性を高めることができる。上記（メタ）アクリル酸エステル系重合体と、上記ポリエーテル系の有機重合体と併用する場合、その配合割合は、ビニル系重合体（ａ）１００重量部に対し、ポリエーテル系重合体（ｃ）を０．１〜１００重量部の割合で添加することが好ましく、より好ましくは０．５〜１００重量部である。 Examples of the polyether polymer (c) include those in which the main chain consists essentially of a polyether polymer, and polymers in which the main chain consists of polyether and (meth) acrylic acid ester. By blending this organic polymer, the water resistance of the cured product can be increased, and the rubber elasticity when a sealing material is formed can be increased. When the (meth) acrylic acid ester polymer and the polyether organic polymer are used in combination, the blending ratio of the polyether polymer (c) is 100 parts by weight of the vinyl polymer (a). ) Is preferably added at a ratio of 0.1 to 100 parts by weight, more preferably 0.5 to 100 parts by weight.
ポリエーテル系重合体（ｃ）の配合割合が０．１重量部未満では、接着性改善効果が小さくなることがあり、２００重量部を越えると、耐候性が低くなることがあり、かつ接着性向上効果がそれほど高くならないことがある。 When the blending ratio of the polyether polymer (c) is less than 0.1 parts by weight, the effect of improving the adhesiveness may be reduced, and when it exceeds 200 parts by weight, the weather resistance may be lowered and the adhesiveness may be decreased. The improvement effect may not be so high.
上記ポリエーテル系重合体（ｃ）とは、主鎖が本質的に、一般式〔−（Ｒ−Ｏ）n−、式中のＲは炭素数１〜４であるアルキレン基を示す。〕で表される化学的に結合された繰り返し単位を含み、かつ末端に架橋可能な加水分解性シリル基を含有する重合体をさす。 The polyether polymer (c) essentially represents a general formula [— (R—O) n—, wherein R represents an alkylene group having 1 to 4 carbon atoms. ] A polymer containing a hydrolyzable silyl group which can be cross-linked at the terminal.
上記ポリエーテル系重合体（ｃ）は、例えば、末端にアリル基を有するポリアルキレンオキサイドをVIII族遷移金属の存在化で下記化学式（３）により表されるヒドロシラン化合物を反応させることによって合成される。 The polyether polymer (c) is synthesized, for example, by reacting a polyalkylene oxide having an allyl group at a terminal with a hydrosilane compound represented by the following chemical formula (3) in the presence of a group VIII transition metal. .
（式中Ｒ5は１価の炭化水素基及びハロゲン化された１価の炭化水素基から選択される基、ａは０、１または２の整数、Ｘはハロゲン原子、アルコキシ基、アシルオキシ基及びケトキシメート基より選択される原子または基を意味する。）
上記重合体の主鎖であるポリアルキレンオキサイドとしては、例えば、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリブチレンオキサイド等が挙げられるが、室温硬化性組成物の硬化物が耐水性に優れ、かつシーリング材としての弾性を確保できるという点でポリプロピレンオキサイドが好ましい。
Wherein R 5 is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is an integer of 0, 1 or 2, X is a halogen atom, an alkoxy group, an acyloxy group, and Means an atom or group selected from a ketoximate group.)
Examples of the polyalkylene oxide that is the main chain of the polymer include polyethylene oxide, polypropylene oxide, polybutylene oxide, etc., but the cured product of the room temperature curable composition is excellent in water resistance and as a sealing material. Polypropylene oxide is preferable because it can ensure elasticity.
上記架橋可能な加水分解性シリル基としては、反応後有害な副生成物を生成しない物が好ましく、例えば、メトキシシリル基、エトキシシリル基等のアルコキシシリル基が挙げられる。 As the crosslinkable hydrolyzable silyl group, those which do not generate harmful by-products after the reaction are preferable, and examples thereof include alkoxysilyl groups such as methoxysilyl group and ethoxysilyl group.
ポリエーテル系重合体（ｃ）の数平均分子量が小さくなると、硬化物の伸びが十分でなくなり、目地面に対する追従性が低下し、大きくなると硬化前の粘度が高くなり、配合工程の作業性が悪くなる。従って、好ましくは、数平均分子量は、４０００〜３００００であり、さらに好ましくは１００００〜３００００であり、かつ分子量分布は１．６以下が望ましい。 If the number average molecular weight of the polyether polymer (c) is small, the cured product will not be sufficiently stretched, the followability to the ground will be reduced, and if it is large, the viscosity before curing will be high, and the workability of the blending process will be increased. Deteriorate. Therefore, the number average molecular weight is preferably 4,000 to 30,000, more preferably 10,000 to 30,000, and the molecular weight distribution is preferably 1.6 or less.
上記ポリエーテル系重合体（ｃ）としては、例えば、商品名「ＭＳポリマー」（鐘淵化学工業社製）として、ＭＳポリマーＳ−２０３、Ｓ−３０３など、商品名「サイリルポリマー」（鐘淵化学工業社製）として、サイリルＳＡＴ−２００、ＳＡＴ−３５０、ＳＡＴ−４００や、商品名「エクセスター」（旭硝子社製）として、エクセスターＥＳＳ−３６２０、ＥＳＳ−３４３０、ＥＳＳ−２４２０、ＥＳＳ−２４１０などが市販されている。 Examples of the polyether polymer (c) include the trade name “MS polymer” (manufactured by Kaneka Chemical Co., Ltd.), MS polymer S-203, S-303, etc. As Sakai Chemical Industry Co., Ltd.), Silyl SAT-200, SAT-350, SAT-400, and trade name "Exester" (manufactured by Asahi Glass Co., Ltd.), Exester ESS-3620, ESS-3430, ESS-2420, ESS -2410 and the like are commercially available.
（層状珪酸塩）
本発明で好ましくは用いられる層状珪酸塩とは、層間に交換性陽イオンを有する珪酸塩鉱物を意味する。本発明で用いられる層状珪酸塩としては特に限定されず、例えば、モンモリロナイト、サポナイト、ヘクトライト、バイデライト、スティブンサイト、ノントロナイト等のスメクタイト系粘土鉱物、バーミキュライト、ハロイサイト、膨潤性マイカ等が挙げられる。中でも、モンモリロナイト、膨潤性マイカが好ましい。上記層状珪酸塩は天然物または合成物のいずれであってもよく、これらの１種または２種以上を用い得る。
(Layered silicate)
The layered silicate preferably used in the present invention means a silicate mineral having exchangeable cations between layers. The layered silicate used in the present invention is not particularly limited, and examples thereof include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, and swelling mica. It is done. Among these, montmorillonite and swellable mica are preferable. The layered silicate may be a natural product or a synthetic product, and one or more of these may be used.
上記層状珪酸塩としては、下記式により定義される形状異方性効果が大きいスメクタイト類や膨潤性マイカを用いることが、硬化性組成物の機械強度向上やガスバリヤ性向上の点からより好ましい。なお、層状珪酸塩の結晶表面（Ａ）及び結晶端面（Ｂ）を図１に模式的に示す。 As the layered silicate, it is more preferable to use smectites or swelling mica having a large shape anisotropy effect defined by the following formula from the viewpoint of improving the mechanical strength and gas barrier property of the curable composition. In addition, the crystal | crystallization surface (A) and crystal | crystallization end surface (B) of layered silicate are typically shown in FIG.
形状異方性効果＝結晶表面（Ａ）の面積／結晶端面（Ｂ）の面積
図２に示すように、上記層状珪酸塩の層間に存在する交換性陽イオンとは、結晶表面上のナトリウム、カルシウム等のイオンであり、これらのイオンは、カチオン性物質とイオン交換性を有するので、カチオン性を有する種々の物質を上記層状珪酸塩の層間に捕捉（インターカレート）することができる。
Shape anisotropy effect = area of crystal surface (A) / area of crystal end face (B) As shown in FIG. 2, the exchangeable cation existing between the layers of the layered silicate is sodium on the crystal surface, These are ions such as calcium, and these ions have an ion exchange property with a cationic substance, so that various substances having a cationic property can be trapped (intercalated) between the layers of the layered silicate.
上記層状珪酸塩の陽イオン交換容量としては特に限定されないが、５０〜２００ミリ等量／１００ｇであるのが好ましい。５０ミリ等量／１００ｇ未満であると、イオン交換により結晶層間に捕捉（インターカレート）できるカチオン性界面活性剤の量が少なくなるので、層間が十分に非極性化されないことがある。一方、２００ミリ等量／１００ｇを超えると、層状珪酸塩の層間の結合力が強固となり、層状珪酸塩の各層を構成している結晶薄片間の距離を増大し難くなることがある。 Although it does not specifically limit as a cation exchange capacity | capacitance of the said layered silicate, It is preferable that it is 50-200 milliequivalent / 100g. If it is less than 50 milliequivalents / 100 g, the amount of the cationic surfactant that can be trapped (intercalated) between the crystal layers by ion exchange decreases, so the layers may not be sufficiently nonpolarized. On the other hand, when it exceeds 200 milliequivalents / 100 g, the bonding force between the layers of the layered silicate becomes strong, and it may be difficult to increase the distance between the crystal flakes constituting each layer of the layered silicate.
上記層状珪酸塩は、ベース樹脂１００重量部に対して、０.１〜１００重量部配合される。さらに好ましくは、０．５〜５０重量部、特に好ましくは、１〜１０重量部である。０.１重量部未満では硬化物の耐候性向上や難燃化などの作用が発現され難く、１０重量部を越えると、硬化性組成物の粘度が高くなり作業性、生産性が低下することがある。 The layered silicate is blended in an amount of 0.1 to 100 parts by weight with respect to 100 parts by weight of the base resin. More preferably, it is 0.5 to 50 parts by weight, and particularly preferably 1 to 10 parts by weight. When the amount is less than 0.1 part by weight, the effect of improving the weather resistance of the cured product and flame retardancy is hardly exhibited, and when the amount exceeds 10 parts by weight, the viscosity of the curable composition is increased and workability and productivity are reduced. There is.
なお、上記ベース樹脂とは、上記ビニル系重合体（ａ）と、必要に応じて添加されるポリエーテル系重合体（ｃ）の合計である。
上記層状珪酸塩は、広角Ｘ線回折測定法により測定した（００１）面の平均層間距離が３ｎｍ以上であり、５層以下で存在しているものを含んで分散しているものが好ましい。平均層間距離が３ｎｍ以上であり、５層以下で分散していると、硬化性組成物の耐候性、難燃性の性能発現に有利となる。
In addition, the said base resin is the sum total of the said vinyl polymer (a) and the polyether polymer (c) added as needed.
The layered silicate preferably has an average interlayer distance of (001) plane measured by wide-angle X-ray diffraction measurement method of 3 nm or more and dispersed including those existing in 5 layers or less. When the average interlayer distance is 3 nm or more and the dispersion is 5 layers or less, it is advantageous for the weather resistance and flame retardancy performance of the curable composition.
なお、本明細書において、層状珪酸塩の平均層間距離とは、微細薄片状結晶を層とした場合の平均の層間距離であり、Ｘ線回折ピーク及び透過型電子顕微鏡撮影により、すなわち、広角Ｘ線回折測定法により算出できるものである。３ｎｍ以上に層間が開裂し、５層以下で存在しているものを含んで分散している状態は、層状珪酸塩の積層体の一部または全てが分散していることを意味しており、層間の相互作用が弱まっていることによる。 In the present specification, the average interlayer distance of the layered silicate is an average interlayer distance when the fine flaky crystal is used as a layer, and is obtained by X-ray diffraction peak and transmission electron microscope photography, that is, wide-angle X It can be calculated by a line diffraction measurement method. The state where the layers are cleaved to 3 nm or more and dispersed including those existing in 5 layers or less means that a part or all of the layered silicate laminate is dispersed, This is because the interaction between layers is weakened.
さらに、層状珪酸塩の平均層間距離が６ｎｍ以上であると、難燃性、機械物性、耐熱性等の機能発現に特に有利である。平均層間距離が６ｎｍ以上であると、層状珪酸塩の結晶薄片層が層毎に分離し、層状珪酸塩の相互作用がほとんど無視できるほどに弱まるので、層状珪酸塩を構成する結晶薄片の樹脂中での分散状態が剥離安定化の方向に進行する。すなわち、層状珪酸塩が１枚づつ薄片状に乖離した状態で硬化性組成物中に安定化されて存在することとなる。 Furthermore, when the average interlayer distance of the layered silicate is 6 nm or more, it is particularly advantageous for expressing functions such as flame retardancy, mechanical properties, and heat resistance. If the average interlaminar distance is 6 nm or more, the lamellar silicate crystal flake layers separate into layers, and the interaction of the lamellar silicate weakens so that it can be almost ignored. The dispersion state in progresses in the direction of delamination stabilization. That is, the layered silicate is present in a stabilized state in the curable composition in a state where the layered silicates are separated in a flake form one by one.
層状珪酸塩の分散状態としては、ベースとなる樹脂中において層状珪酸塩の薄片状結晶が高度に分散していることが好ましい。より具体的には、層状珪酸塩の１０重量％以上が５層以下で存在している状態に分散されていることが好ましく、より好ましくは、層状珪酸塩の２０重量％以上が５層以下の状態で存在していることが望ましい。さらに、分散している薄片状結晶の積層数が５層以下であれば、層状珪酸塩の添加による効果が良好に得られるが、３層以下であればより好ましく、単層状に分散していることがさらに望ましい。 As a dispersion state of the layered silicate, it is preferable that the flaky crystals of the layered silicate are highly dispersed in the base resin. More specifically, it is preferable that 10% by weight or more of the layered silicate is dispersed in a state where it is present in 5 layers or less, more preferably, 20% by weight or more of the layered silicate is 5 layers or less. It is desirable to exist in a state. Furthermore, if the number of laminated flaky crystals is 5 or less, the effect of the addition of the layered silicate can be obtained satisfactorily, but if it is 3 or less, it is more preferable, and it is dispersed in a single layer. More desirable.
本発明の層状珪酸塩は、４級アンモニウム塩で処理されてなる層状珪酸塩であることが好ましい。４級アンモニウム塩で処理することにより、層状珪酸塩の上記ベース樹脂中への分散性を向上させることができるからである。また、４級アンモニウム塩は上記ビニル系重合体の架橋反応に対する触媒作用があることが知られており、層状珪酸塩と共に上記ベース樹脂中に分散することにより分散性の向上と共に硬化速度を促進させることも可能となる。 The layered silicate of the present invention is preferably a layered silicate treated with a quaternary ammonium salt. This is because the dispersibility of the layered silicate in the base resin can be improved by treating with a quaternary ammonium salt. Further, quaternary ammonium salts are known to have a catalytic action for the crosslinking reaction of the vinyl polymer, and disperse in the base resin together with the layered silicate to improve the dispersibility and accelerate the curing rate. It is also possible.
上記４級アンモニウム塩としては、例えば、ラウリルトリメチルアンモニウム塩、ステアリルトリメチルアンモニウム塩、トリオクチルアンモニウム塩、ジステアリルジメチルアンモニウム塩、ジ硬化牛脂ジメチルアンモニウム塩、ジステアリルジベンジルアンモニウム塩、Ｎ−ポリオキシエチレン−Ｎ−ラウリル−Ｎ，Ｎ−ジメチルアンモニウム塩等が挙げられ、これらの４級アンモニウム塩は、単独で用いられても良いし、２種類以上が併用されても良い。上記の中でも、良好な分散性が得られることから、炭素数６以上のアルキル鎖またはポリオキシアルキレン鎖を有する４級アルキルアンモニウムイオン塩が好ましい。 Examples of the quaternary ammonium salt include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, and N-polyoxyethylene. -N-lauryl-N, N-dimethylammonium salt and the like can be mentioned, and these quaternary ammonium salts may be used alone or in combination of two or more. Among them, a quaternary alkyl ammonium ion salt having an alkyl chain having 6 or more carbon atoms or a polyoxyalkylene chain is preferable because good dispersibility can be obtained.
層状珪酸塩の分散には各種攪拌機を用いることができるが、分散しにくい場合には３本ロール等の高剪断がかかる装置を用いて分散を行うと所望の分散状態を得やすい場合がある。 Various stirrers can be used to disperse the layered silicate, but if it is difficult to disperse, it may be easy to obtain a desired dispersion state by dispersing using a high shearing device such as a three roll.
（硬化促進剤）
本発明に係る硬化性組成物では、上記ビニル系重合体（ａ）の硬化促進剤として、好ましくは有機金属化合物がさらに配合され得る。
(Curing accelerator)
In the curable composition according to the present invention, an organometallic compound may be preferably further blended as a curing accelerator for the vinyl polymer (a).
好適に用いることの出来る有機金属化合物として、ゲルマニウム、錫、鉛、硼素、アルミニウム、ガリウム、インジウム、チタニウム、ジルコニウム等の金属元素と有機基を置換してなる有機金属化合物を挙げることが出来る。例えば、ジブチル錫ジラウレート、ジブチル錫オキサイド、ジブチル錫ジアセテート、ジブチル錫フタレート、ビス（ジブチル錫ラウリン酸）オキサイド、ジブチル錫ビスアセチルアセトナート、ジブチル錫ビス（モノエステルマレート）、オクチル酸錫、ジブチル錫オクトエート、ジオクチル錫オキサイド等の錫化合物、テトラ−ｎ−ブトキシチタネート、テトライソプロポキシチタネート等のチタネート系化合物等が挙げられ、これらは単独または２種以上を併用して使用することが出来る。 As an organic metal compound that can be suitably used, an organic metal compound obtained by substituting a metal element such as germanium, tin, lead, boron, aluminum, gallium, indium, titanium, and zirconium with an organic group can be given. For example, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin laurate) oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoester malate), tin octylate, dibutyl Examples thereof include tin compounds such as tin octoate and dioctyl tin oxide, and titanate compounds such as tetra-n-butoxy titanate and tetraisopropoxy titanate, and these can be used alone or in combination of two or more.
上記硬化促進剤は、好ましくは、ベース樹脂１００重量部に対して、０．１〜１０重量部の割合で配合される。０．１重量部未満では硬化促進効果が十分でないことがあり、１０重量部を越えると、硬化が早くなりすぎ、取り扱いが困難になる場合がある。 The curing accelerator is preferably blended at a ratio of 0.1 to 10 parts by weight with respect to 100 parts by weight of the base resin. If the amount is less than 0.1 parts by weight, the curing accelerating effect may not be sufficient. If the amount exceeds 10 parts by weight, curing may be too fast and handling may be difficult.
（紫外線吸収剤及び光安定剤）
本発明の硬化性組成物には、耐候性を向上させるために各種紫外線吸収剤や光安定剤を配合することが好ましい。層状珪酸塩との併用により、層状珪酸塩が各種紫外線吸収剤や光安定剤のブリードアウトを抑制するように作用するため、硬化物中にこれらが長期にわたって保持されるためである。
(Ultraviolet absorber and light stabilizer)
The curable composition of the present invention preferably contains various ultraviolet absorbers and light stabilizers in order to improve the weather resistance. This is because the layered silicate acts so as to suppress bleed-out of various ultraviolet absorbers and light stabilizers in combination with the layered silicate, so that these are retained in the cured product for a long time.
特に、前記ポリエーテル重合体（Ｃ）をさらに添加した硬化性組成物では、長期間の経過後に硬化物黄変等が発生し易いため有効となる。
上記紫外線吸収剤としては、ベンゾトリアゾール系、ベンゾフェノン系等の公知の紫外線吸収剤が挙げられ、中でもベンゾトリアゾール系紫外線吸収剤が紫外線吸収性能が高いので好ましい。上記紫外線吸収剤を配合する場合には、上記ベース樹脂１００重量部に対して、０．１〜２０重量部、より好ましくは、０.５〜１０重量部配合されているのが好ましい。０.１重量部よりも少ないと耐候性の向上効果が不十分であることがあり、２０重量部を越えると、呈色によりシーリング材としての外観を損なう等の問題を生じる。
In particular, a curable composition to which the polyether polymer (C) is further added is effective because yellowing of the cured product is likely to occur after a long period of time.
Examples of the UV absorber include known UV absorbers such as benzotriazole and benzophenone, and among them, a benzotriazole UV absorber is preferable because of its high UV absorption performance. When the ultraviolet absorber is blended, it is preferably blended in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the base resin. When the amount is less than 0.1 parts by weight, the effect of improving weather resistance may be insufficient. When the amount exceeds 20 parts by weight, problems such as deterioration of the appearance as a sealing material due to coloration occur.
上記光安定剤としては、例えばヒンダードアミン系光安定剤が用いられる。ヒンダードアミン系光安定剤は、一般に紫外線吸収剤と併用すると優れた効果を発揮する。上記ヒンダードアミン系光安定剤(以下、光安定剤)の中でも、下記一般式（Ａ）で示される構造を有する基を分子中に有するものが、層状珪酸塩と併用すると特に著しい効果がある。このようヒンダードアミン系光安定剤としては、例えば、、ビス（２，２，６，６−テトラメチル−４−ピペリジン）セバケート、ポリ［｛６−（１，１，３，３，−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル｝｛（２，２，６，６−テトラメチル−４−ピペリジン）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジン）イミノ｝］等が挙げられる。これらは単独で用いられてもよいし、２種以上併用されてもよい。 As the light stabilizer, for example, a hindered amine light stabilizer is used. A hindered amine light stabilizer generally exhibits an excellent effect when used in combination with an ultraviolet absorber. Among the hindered amine light stabilizers (hereinafter referred to as light stabilizers), those having a group having a structure represented by the following general formula (A) in the molecule are particularly effective when used in combination with a layered silicate. Examples of such a hindered amine light stabilizer include, for example, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, poly [{6- (1,1,3,3, -tetramethylbutyl). ) Amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidine) imino} hexamethylene {(2,2,6,6-tetramethyl) -4-piperidine) imino}] and the like. These may be used alone or in combination of two or more.
層状珪酸塩との併用による耐候性効果は、光安定剤のブリードアウト防止効果が主であると考えられる。すなわち層状珪酸塩が組成物中で光安定剤と相互作用し、光安定剤が系から散逸するのを防いでいる為であると考えられる。また、相互作用の中でも層状珪酸塩がブリードアウトを阻害する板のように作用することにより、光安定剤のブリードアウトが抑制されると考えられる。光安定剤の中でも下記一般式（Ａ）で示される構造を有する基を分子中に有するものが特にその効果が著しいのは、Ｎ原子に結合したＨ原子が関与しているものと推察される。 It is considered that the weather resistance effect by the combined use with the layered silicate is mainly due to the bleed-out prevention effect of the light stabilizer. That is, it is considered that the layered silicate interacts with the light stabilizer in the composition to prevent the light stabilizer from escaping from the system. In addition, it is considered that the bleedout of the light stabilizer is suppressed when the layered silicate acts like a plate that inhibits bleedout among the interactions. Among the light stabilizers, those having a group having the structure represented by the following general formula (A) in the molecule are considered to be particularly effective because the H atom bonded to the N atom is involved. .
上記光安定剤を配合する場合には、上記有機重合体１００重量部に対して、０.１〜２０重量部、より好ましくは０．５〜１０重量部配合されているのが好ましい。０.１重量部よりも少ないと、耐候性の向上効果が不十分であることがあり、２０重量部を越えると着色の問題が生じ、シーリング材としての外観を損なうことがある。 When the light stabilizer is blended, it is preferably blended in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the organic polymer. If the amount is less than 0.1 part by weight, the effect of improving the weather resistance may be insufficient. If the amount exceeds 20 parts by weight, coloring problems may occur and the appearance as a sealing material may be impaired.
（その他の添加物）
本発明の硬化性組成物には、本発明の目的より効果を阻害しない限り、ビニル系重合体（ａ）の硬化促進剤、組成物の粘性特性を調整する粘度調整剤、チキソトロープ剤、引張特性などを改善する物性調整剤、増量剤、補強剤、可塑剤、着色剤、難燃剤、紫外線吸収剤、光安定剤、酸化防止剤、たれ防止剤、老化防止剤、溶剤、香料、顔料、染料、脱水剤などを添加してもよい。
(Other additives)
In the curable composition of the present invention, unless the effect is hindered from the object of the present invention, a curing accelerator for the vinyl polymer (a), a viscosity modifier for adjusting the viscosity characteristics of the composition, a thixotropic agent, a tensile property Property modifiers, fillers, reinforcing agents, plasticizers, colorants, flame retardants, UV absorbers, light stabilizers, antioxidants, anti-sagging agents, anti-aging agents, solvents, fragrances, pigments, dyes Further, a dehydrating agent or the like may be added.
ビニル系重合体（ａ）の硬化促進剤としては、例えば、有機金属化合部を用いることができる。
粘度調整剤としては、例えば、ビニル系重合体（ａ）との相溶性の良い高分子化合物から選ばれ、配合される化合物から適宜選択される。例えば、アクリル系高分子、メタクリル系高分子、ポリビニルアルコール誘導体、ポリ酢酸ビニル、ポリスチレン誘導体、ポリエステル類、ポリエーテル類、ポリイソブテン、ポリオレフィン類、ポリアルキレンオキシド類、ポリウレタン類、ポリアミド類、天然ゴム、ポリブタジエン、ポリイソプレン、ＮＢＲ、ＳＢＳ、ＳＩＳ、ＳＥＢＳ、水添ＮＢＲ、水添ＳＢＳ、水添ＳＩＳ、水添ＳＥＢＳ等を挙げることができる。また、これら共重合体、官能基変成体を挙げることができし、これらを適宜組み合わせてもよい。
As a hardening accelerator of a vinyl polymer (a), an organometallic compound part can be used, for example.
The viscosity modifier is selected, for example, from a polymer compound having good compatibility with the vinyl polymer (a), and is appropriately selected from compounds to be blended. For example, acrylic polymers, methacrylic polymers, polyvinyl alcohol derivatives, polyvinyl acetate, polystyrene derivatives, polyesters, polyethers, polyisobutene, polyolefins, polyalkylene oxides, polyurethanes, polyamides, natural rubber, polybutadiene , Polyisoprene, NBR, SBS, SIS, SEBS, hydrogenated NBR, hydrogenated SBS, hydrogenated SIS, hydrogenated SEBS, and the like. Moreover, these copolymers and functional group modified products can be mentioned, and these may be combined as appropriate.
チキソトロープ剤としては、組成物がチキソトロピー性を発現するような物質から適宜選ばれる。例えば、コロイダルシリカ、ポリビニルピロリドン、疎水化炭酸カルシウム、ガラスバルーン、ガラスビーズ等を挙げることができる。チキソトロープ剤の選択については、ビニル系重合体（ａ）親和性の高い表面を有することが望ましい。 The thixotropic agent is appropriately selected from substances whose composition exhibits thixotropic properties. Examples thereof include colloidal silica, polyvinyl pyrrolidone, hydrophobized calcium carbonate, glass balloons, and glass beads. Regarding the selection of the thixotropic agent, it is desirable to have a surface having a high affinity for the vinyl polymer (a).
引っ張り特等を改善する物性調整剤としては、各種シランカップリング剤として、例えば、ビニルトリメトキシシラン、ジメチルジメトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、テトラメトキシシラン、テトラエトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルメチルジメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリエトキシシラン、Ｎ，Ｎ’−ビス−［３−（トリメトキシシリル）プロピル］エチレンジアミン、Ｎ，Ｎ’−ビス−［３−（トリエトキシシリル）プロピル］エチレンジアミン、Ｎ，Ｎ’−ビス−［３−（トリメトキシシリル）プロピル］ヘキサエチレンジアミン、Ｎ，Ｎ’−ビス−［３−（トリエトキシシリル）プロピル］ヘキサエチレンジアミン等を挙げられ、これらは単独または２種以上併用してもかまわない。 Examples of physical property modifiers that improve tensile properties include various silane coupling agents such as vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, and phenyltrimethoxy. Silane, diphenyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltriethoxysilane, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (triethoxysilyl) propyl] ethylene Amines, N, N′-bis- [3- (trimethoxysilyl) propyl] hexaethylenediamine, N, N′-bis- [3- (triethoxysilyl) propyl] hexaethylenediamine, and the like. Two or more types may be used in combination.
増量剤としては、本発明に係る組成物中に添加してチキソトロープ性を発現しないものが好適に利用でき、例えば、タルク、クレー、炭酸カルシウム、炭酸マグネシウム、無水珪素、含水珪素、ケイ酸カルシウム、二酸化チタン、カーボンブラック等を挙げられ、これらは単独または２種以上併用してもかまわない。 As the extender, those which are added to the composition according to the present invention and do not exhibit thixotropic properties can be suitably used. For example, talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrous silicon, calcium silicate, Examples thereof include titanium dioxide and carbon black, and these may be used alone or in combination of two or more.
可塑剤としては、例えば、リン酸トリブチル、リン酸トリクレジル等のリン酸エステル類、フタル酸ジオクチル等のフタル酸エステル類、グリセリンモノオレイル酸エステル等の脂肪酸-塩基酸エステル類、アジピン酸ジオクチル等の脂肪酸二塩基酸エステル類、ポリプロピレングリコール類等を挙げられ、これらは単独または２種以上併用してもかまわない。 Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate, phthalate esters such as dioctyl phthalate, fatty acid-basic acid esters such as glycerin monooleate, and dioctyl adipate. Examples thereof include fatty acid dibasic acid esters and polypropylene glycols, and these may be used alone or in combination of two or more.
（接着剤及びシーリング材）
本発明に係る硬化性組成物は、シーリング材または接着剤として好適に用いられる。本発明に係る硬化性組成物は、後述する実施例から明らかなように、雰囲気中の湿気により速やかに硬化し、柔軟性を有する硬化物を与え、良好な接着強度を発現する。さらに、上記空気硬化性もしくは光硬化性化合物（ｂ）が上記特定の割合で配合されているため、硬化物のべたつきが抑制され、防汚性も高められる。
(Adhesive and sealing material)
The curable composition according to the present invention is suitably used as a sealing material or an adhesive. As is clear from the examples described later, the curable composition according to the present invention is quickly cured by moisture in the atmosphere, gives a cured product having flexibility, and exhibits good adhesive strength. Furthermore, since the air-curable or photo-curable compound (b) is blended at the specific ratio, the stickiness of the cured product is suppressed and the antifouling property is improved.
従って、本発明によれば、透明や淡色の表面が求められるシーリング材や接着剤を提供することが可能となる。 Therefore, according to the present invention, it is possible to provide a sealing material or an adhesive that requires a transparent or light-colored surface.
本発明に係る硬化性組成物では、架橋性シリル基を含有するビニル系重合体（ａ）１００重量部に対し、空気硬化性及び／又は光硬化性化合物（ｂ）が５〜４０重量部の範囲で含有されているため、雰囲気中の湿気により硬化し、弾力性及び伸びに優れた硬化物が得られると共に、硬化物の表面のべとつきが抑制され、防汚性に優れた硬化物を得ることができる。
特に、本発明の架橋性シリル基含有ビニル重合体（ａ）は、上述のとおり末端に架橋性シリル基を有しているので、側鎖に架橋性シリル基を有している場合に比べて、硬化前は低粘度で糸引き等が少なく取り扱いが容易であるにもかかわらず、硬化物は優れた伸び、弾性を示す。
In the curable composition according to the present invention, the air-curable and / or photo-curable compound (b) is 5 to 40 parts by weight with respect to 100 parts by weight of the vinyl polymer (a) containing a crosslinkable silyl group. Since it is contained in a range, it is cured by moisture in the atmosphere, and a cured product excellent in elasticity and elongation is obtained, and the stickiness of the surface of the cured product is suppressed, and a cured product excellent in antifouling property is obtained. be able to.
In particular, the crosslinkable silyl group-containing vinyl polymer (a) of the present invention has a crosslinkable silyl group at the terminal as described above, so that it has a crosslinkable silyl group in the side chain. The cured product exhibits excellent elongation and elasticity despite its low viscosity before curing and easy handling with little stringing.
よって、本発明に係る硬化性組成物をシーリング材や接着剤として用いることにより、湿気硬化型であり、かつ硬化物の伸び物性に優れており、さらに硬化物の経時による汚染が生じ難く、かつ透明性や淡色の色合いを安定に保持し得る接着剤やシーリング材を提供することが可能となる。 Therefore, by using the curable composition according to the present invention as a sealing material or an adhesive, it is a moisture curable type and has excellent elongation properties of the cured product, and further, the cured product is hardly contaminated over time, and It is possible to provide an adhesive and a sealing material that can stably maintain transparency and light shades.
本発明の実施例及び比較例を以下において説明する。なお、本発明は、以下の実施例に限定されるものではない。 Examples of the present invention and comparative examples will be described below. The present invention is not limited to the following examples.
（実施例１）
（ビニル系重合体（ａ）の調製）
還流管をつけた１Ｌの三口丸底フラスコに臭化第一銅（６．２５ｇ、１５６ｍｍｏｌ）、アセトニトリル（５０ｍＬ）、及び、ペンタメチルジエチレントリアミン（９．１ｍＬ）を仕込み、窒素ガスで置換した。アクリル酸−ｎ−ブチル（５００ｍＬ、４４７ｇ、３．９ｍｏｌ）、及び、ジエチル−２，５−ジブロモアジペート（１５．７ｇ、４３．６ｍｍｏｌ）を添加し、７０℃で７時間加熱撹拌した。混合物を酢酸エチルで希釈し、活性アルミナで処理した。揮発分を減圧下留去し、末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）を３５０ｇ得た（重合収率８７％）。重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により１０７００、分子量分布は１．１５であった。
(Example 1)
(Preparation of vinyl polymer (a))
A 1 L three-necked round bottom flask equipped with a reflux tube was charged with cuprous bromide (6.25 g, 156 mmol), acetonitrile (50 mL), and pentamethyldiethylenetriamine (9.1 mL) and replaced with nitrogen gas. Acrylic acid-n-butyl (500 mL, 447 g, 3.9 mol) and diethyl-2,5-dibromoadipate (15.7 g, 43.6 mmol) were added, and the mixture was heated and stirred at 70 ° C. for 7 hours. The mixture was diluted with ethyl acetate and treated with activated alumina. Volatiles were distilled off under reduced pressure to obtain 350 g of poly (acrylic acid-n-butyl) having a halogen at the terminal (polymerization yield: 87%). The number average molecular weight of the polymer was 10700 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.15.
次に、還流管をつけた２Ｌの三口丸底フラスコに、上記のようにして得られた末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）（３５０ｇ）、製造例２で合成された４−ペンテン酸のカリウム塩（２２．３ｇ、１６１ｍｍｏｌ）、及び、ジメチルアセトアミド（３５０ｍＬ）を仕込み、窒素雰囲気下、７０℃で４時間反応させた。混合物を酢酸エチルで希釈し、２％塩酸、ブラインで洗浄した。有機層をＮａ2ＳＯ4で乾燥し、揮発分を減圧下留去することにより重合体を単離した。重合体と等量の珪酸アルミ（協和化学製：キョ−ワ−ド７００ＰＥＬ）を添加して１００℃で４時間撹拌し、末端にアルケニル基を有するポリ（アクリル酸ブチル）を得た。オリゴマ−１分子当たりに導入されたアルケニル基は、1Ｈ−ＮＭＲ分析より、１．８２個であった。 Next, in a 2 L three-necked round bottom flask equipped with a reflux tube, poly (acrylic acid-n-butyl) having halogen at the terminal obtained as described above (350 g), synthesized in Production Example 2 4 -A potassium salt of pentenoic acid (22.3 g, 161 mmol) and dimethylacetamide (350 mL) were charged and reacted at 70 ° C for 4 hours in a nitrogen atmosphere. The mixture was diluted with ethyl acetate and washed with 2% hydrochloric acid, brine. The organic layer was dried over Na 2 SO 4 and the polymer was isolated by removing the volatiles under reduced pressure. An equivalent amount of aluminum silicate (manufactured by Kyowa Chemical Co., Ltd .: Kyowaard 700PEL) was added to the polymer and stirred at 100 ° C. for 4 hours to obtain poly (butyl acrylate) having an alkenyl group at the terminal. According to 1 H-NMR analysis, 1.82 alkenyl groups were introduced per oligomer-1 molecule.
次に、２００ｍＬの耐圧ガラス反応容器に、上記重合体（１５０ｇ）、ジメトキシメチルヒドロシラン（１８ｍＬ、１４５ｍｍｏｌ）、オルトぎ酸ジメチル（２．６ｍＬ、２４．２ｍｍｏｌ）、及び、白金触媒を仕込んだ。ただし、白金触媒の使用量は、重合体のアルケニル基に対して、モル比で２×１０-4当量とした。反応混合物を１００℃で４時間加熱した。混合物の揮発分を減圧留去することにより、末端にシリル基を有するポリ（アクリル酸−ｎ−ブチル）を得た。オリゴマ−１分子当たりに導入されたシリル基は、1Ｈ−ＮＭＲ分析より、１．４６個であった。 Next, the polymer (150 g), dimethoxymethylhydrosilane (18 mL, 145 mmol), dimethyl orthoformate (2.6 mL, 24.2 mmol), and a platinum catalyst were charged into a 200 mL pressure-resistant glass reaction vessel. However, the amount of platinum catalyst used was 2 × 10 −4 equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 4 hours. The volatile component of the mixture was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a silyl group at the terminal. According to 1 H-NMR analysis, 1.46 silyl groups were introduced per oligomer-1 molecule.
（実施例１）
上記で得られたビニル系重合体１００ｇ、ポリプロピレングリコール（和光純薬社性、分子量３０００）５０ｇ、酢酸エチル１００ｇ、光硬化性化合物（東亞合成社製、アロニックスＭ６１００）２５ｇ、脂肪酸処理炭酸カルシウム３０ｇ、重質炭酸カルシウム７０ｇ及び硬化促進剤（ジブチル錫ジラウリレート）２ｇを加え、密封した攪拌機で均一になるまで混合し、脱溶剤をした後に、その後、１０分間減圧脱泡して白色ペースト状の硬化性組成物を得た。
(Example 1)
100 g of the vinyl polymer obtained above, 50 g of polypropylene glycol (Wako Pure Chemical Industries, Ltd., molecular weight 3000), 100 g of ethyl acetate, 25 g of photocurable compound (Aronix M6100, manufactured by Toagosei Co., Ltd.), 30 g of fatty acid-treated calcium carbonate, Add 70 g of heavy calcium carbonate and 2 g of hardening accelerator (dibutyltin dilaurate), mix until uniform with a sealed stirrer, remove the solvent, and then defoam under reduced pressure for 10 minutes to obtain a white paste-like curability. A composition was obtained.
得られた硬化性組成物をポリエチレン板上に、膜厚が２．５ｍｍとなる様に塗工し、その後、２０℃、相対湿度５０％の環境下で７日間養生して、ゴム状のシート皮膜を得た。シート皮膜のゴム物性を以下の要領で評価したところ、破断伸びは５５０％、破断応力は０．２５Ｎ／ｍｍ2であった。このシートを得るときのタックフリー時間は５時間であった。また、以下の要領で防汚性を評価した。結果を下記表１に示す。 The obtained curable composition was coated on a polyethylene plate so as to have a film thickness of 2.5 mm, and then cured for 7 days in an environment of 20 ° C. and 50% relative humidity. A film was obtained. When the rubber properties of the sheet film were evaluated as follows, the elongation at break was 550% and the stress at break was 0.25 N / mm 2. The tack-free time for obtaining this sheet was 5 hours. Moreover, antifouling property was evaluated in the following manner. The results are shown in Table 1 below.
（ゴム物性の評価）
２０℃及び相対湿度５０％の雰囲気下で７日間養生させた上記ゴム状のシート皮膜を、ＪＩＳ Ｋ ６３０１に準じ、３号ダンベル形状でクロスヘッド速度５００ｍｍ／分で引っ張り試験を行い、破断伸び（％）及び破断応力（Ｎ／ｍｍ2）を評価した。
(Evaluation of rubber properties)
The rubber-like sheet coating cured for 7 days in an atmosphere of 20 ° C. and 50% relative humidity was subjected to a tensile test at a cross head speed of 500 mm / min in a No. 3 dumbbell shape according to JIS K 6301, and elongation at break ( %) And breaking stress (N / mm 2 ).
（防汚性の評価）
ゴム物性を評価するのに用いたシートの一部を防汚性評価に用いた。評価に際しては、シートを屋外暴露（南方側、４５゜傾斜）し、外観の変化を観察した。暴露場所は、積水化学工業株式会社水口工場敷地内、国道一号線より距離約２０ｍの地点。
(Evaluation of antifouling properties)
A part of the sheet used for evaluating rubber physical properties was used for antifouling evaluation. In the evaluation, the sheet was exposed outdoors (south side, 45 ° inclination), and changes in appearance were observed. The location of exposure is within 20m from Sekisui Chemical Co., Ltd. Mizuguchi factory site.
（実施例２）
上記で実施例１で得られたビニル系重合体１００ｇ、ポリプロピレングリコール（和光純薬社性、分子量３０００）５０ｇ、酢酸エチル１００ｇ、光硬化性化合物（東亞合成社製、アロニックスＭ１６００）１０ｇ、脂肪酸処理炭酸カルシウム３０ｇ、重質炭酸カルシウム７０ｇ及び硬化促進剤（ジブチル錫ジラウリレート）２ｇを加え、密封した攪拌機で均一になるまで混合し、脱溶剤をした後に、１０分間減圧脱泡して白色ペースト状の硬化性組成物を得た。
(Example 2)
100 g of the vinyl polymer obtained in Example 1 above, 50 g of polypropylene glycol (Wako Pure Chemical Industries, Ltd., molecular weight 3000), 100 g of ethyl acetate, 10 g of photocurable compound (Aronix M1600, manufactured by Toagosei Co., Ltd.), fatty acid treatment Add 30 g of calcium carbonate, 70 g of heavy calcium carbonate, and 2 g of hardening accelerator (dibutyltin dilaurate), mix until uniform with a sealed stirrer, remove the solvent, and defoam under reduced pressure for 10 minutes. A curable composition was obtained.
得られた硬化性組成物を用い、実施例１と同様にして、シート皮膜のゴム物性を評価したところ、破断伸びは５５０％、破断応力は０．２５Ｎ／ｍｍ2であった。このシートを得るときのタックフリー時間は５時間であった。また、実施例１と同様にして、防汚性を評価した。表１に結果を示す。 Using the obtained curable composition, the rubber physical properties of the sheet film were evaluated in the same manner as in Example 1. As a result, the breaking elongation was 550% and the breaking stress was 0.25 N / mm2. The tack-free time for obtaining this sheet was 5 hours. Further, the antifouling property was evaluated in the same manner as in Example 1. Table 1 shows the results.
（実施例３）
参考例１で得たアルコキシシリル基含有アクリル系重合体の酢酸エチル溶液１００ｇにポリプロピレングリコール（和光純薬社性、分子量３０００）５０ｇ、光硬化性化合物（東亞合成社製、アロニックスＭ１６００）５ｇ、脂肪酸処理炭酸カルシウム３０ｇ、重質炭酸カルシウム７０ｇ、硬化促進剤（ジブチル錫ジラウリレート）２ｇを加え、密封した攪拌機で均一になるまで混合し、その後、１０分間減圧脱泡して白色ペースト状の硬化性組成物を得た。
(Example 3)
100 g of an ethyl acetate solution of an alkoxysilyl group-containing acrylic polymer obtained in Reference Example 1 is mixed with 50 g of polypropylene glycol (Wako Pure Chemical Industries, Ltd., molecular weight 3000), 5 g of a photocurable compound (Toagosei Co., Ltd., Aronix M1600), fatty acid 30g of treated calcium carbonate, 70g of heavy calcium carbonate and 2g of hardening accelerator (dibutyltin dilaurate) are added and mixed with a sealed stirrer until uniform, and then defoamed for 10 minutes under reduced pressure to form a white paste-like curable composition I got a thing.
得られた硬化性組成物を用い実施例１と同様にして、シート皮膜のゴム物性を評価したところ、破断伸びは５５０％、破断応力は０．２５Ｎ／ｍｍ2であった。このシートを得るときのタックフリー時間は５時間であった。また、実施例１と同様にして、防汚性を評価した。表１に結果を示す。 Using the obtained curable composition, the rubber physical properties of the sheet film were evaluated in the same manner as in Example 1. As a result, the elongation at break was 550% and the stress at break was 0.25 N / mm2. The tack-free time for obtaining this sheet was 5 hours. Further, the antifouling property was evaluated in the same manner as in Example 1. Table 1 shows the results.
（比較例１）
上記で実施例１で得られたビニル系重合体１００ｇ、ポリプロピレングリコール（和光純薬社性、分子量３０００）５０ｇ、酢酸エチル１００ｇ、脂肪酸処理炭酸カルシウム３０ｇ、重質炭酸カルシウム７０ｇ及び硬化促進剤（ジブチル錫ジラウリレート）２ｇを加え、密封した攪拌機で均一になるまで混合し、脱溶剤をした後に、１０分間減圧脱泡して白色ペースト状の硬化性組成物を得た。
(Comparative Example 1)
100 g of the vinyl polymer obtained in Example 1 above, 50 g of polypropylene glycol (Wako Pure Chemical Industries, Ltd., molecular weight 3000), 100 g of ethyl acetate, 30 g of fatty acid-treated calcium carbonate, 70 g of heavy calcium carbonate and a curing accelerator (dibutyl) 2 g of tin dilaurylate) was added and mixed with a sealed stirrer until uniform, and after removing the solvent, the mixture was degassed under reduced pressure for 10 minutes to obtain a white paste-like curable composition.
得られた硬化性組成物を用い、実施例１と同様にして、シート皮膜のゴム物性を評価したところ、破断伸びは５３０％、破断応力は０．２３Ｎ／ｍｍ2であった。このシートを得るときのタックフリー時間は８時間であった。また、実施例１と同様にして防汚性を評価した。結果を表１に示す。 Using the obtained curable composition, the rubber physical properties of the sheet film were evaluated in the same manner as in Example 1. As a result, the breaking elongation was 530% and the breaking stress was 0.23 N / mm 2. The tack-free time for obtaining this sheet was 8 hours. Further, the antifouling property was evaluated in the same manner as in Example 1. The results are shown in Table 1.
（実施例４）
実施例１の硬化性組成物を調製する際に、層状珪酸塩ソマシフＭＰＥ−１００（ポリオキシプロピレンジエチル４級アンモニウム塩で有機処理した膨潤性フッ素雲母、コープケミカル社製）１０ｇ、チヌビン７７０（ヒンダードアミン系光安定剤、チバスペシャリティーケミカルズ社製）５ｇ、チヌビン３２７（ベンゾトリアゾール系紫外線吸収剤、チバスペシャリティーケミカルズ社製）５ｇを加えたこと以外は実施例１と同様にして硬化性組成物を得た。
Example 4
When the curable composition of Example 1 was prepared, 10 g of stratified silicate somacif MPE-100 (swelling fluoromica organically treated with polyoxypropylene diethyl quaternary ammonium salt, manufactured by Co-op Chemical), tinuvin 770 (hindered amine) Curable composition in the same manner as in Example 1, except that 5 g of a light stabilizer based on Ciba Specialty Chemicals) and 5 g of TINUVIN 327 (benzotriazole ultraviolet absorber, Ciba Specialty Chemicals) were added. Obtained.
（層状珪酸塩の平均層間距離の測定）
実施例４で得られた硬化性組成物における層状珪酸塩の平均層間距離を以下のようにして測定した。
(Measurement of average interlayer distance of layered silicate)
The average interlayer distance of the layered silicate in the curable composition obtained in Example 4 was measured as follows.
Ｘ線回折測定装置（リガク社製、ＲＩＮＴ１１００）により、層状珪酸塩の積層面の回折により得られる回折ピークの２θを測定し、下記のブラックの回折式を用いて層状珪酸塩の（００１）面間隔を算出した。以下のｄを平均層間距離とし、平均層間距離が３ｎｍ以上と良好に分散していた。 Using a X-ray diffraction measurement device (RINT1100, manufactured by Rigaku Corporation), 2θ of the diffraction peak obtained by diffraction of the layered surface of the layered silicate is measured, and the (001) surface of the layered silicate using the following black diffraction equation The interval was calculated. The following d was defined as the average interlayer distance, and the average interlayer distance was well dispersed as 3 nm or more.
λ＝２ｄｓｉｎθ
なお、式中において、λ（ｎｍ）＝０．１５４、ｄ（ｎｍ）は層状珪酸塩の面間隔、θ（ｄｅｇｒｅｅ）は回折角である。
λ = 2 dsin θ
In the formula, λ (nm) = 0.154, d (nm) is the surface spacing of the layered silicate, and θ (degree) is the diffraction angle.
（層状珪酸塩の分散状態の確認）
透過型電子顕微鏡（ＴＥＭ 日本電子社製「ＪＥＭ−１２００ＥＸ ＩＩ」）写真により、硬化物中の層状珪酸塩の分散状態を観察して、５層以下で存在していた。
(Confirmation of dispersion state of layered silicate)
The dispersion state of the layered silicate in the cured product was observed with a transmission electron microscope (TEM “JEM-1200EX II” manufactured by JEOL Ltd.), and was present in 5 layers or less.
耐候性評価
（評価）
上記実施例１及び４で得られた硬化性組成物の下記方法で耐候性を評価した。各配合組成物を５０ｍｍ×１５０ｍｍ（厚み１ｍｍ）のステンレス板に０．５ｍｍ厚みで塗布し、２０℃×６０％ＲＨの雰囲気下で７日間（１６８時間）放置して養生硬化させた後、下記条件で、１５０時間及び４００時間光照射を行い、表面状態を目視で確認し、クラックの無いものを〇と判定した。結果を下記の表２に示す。
Weather resistance evaluation (Evaluation)
The weather resistance of the curable compositions obtained in Examples 1 and 4 was evaluated by the following method. Each compounded composition was applied to a stainless steel plate of 50 mm × 150 mm (thickness 1 mm) at a thickness of 0.5 mm, allowed to stand for 7 days (168 hours) in an atmosphere of 20 ° C. × 60% RH, and then cured and cured. Under the conditions, light irradiation was performed for 150 hours and 400 hours, and the surface state was visually confirmed. The results are shown in Table 2 below.
光照射条件
試験装置：アイスーパーＵＶテスター（ＳＵＶ−Ｆ１１型）、岩崎電気株式会社製
照射強度：１００ｍＷ／ｃｍ2 限定波長：２９５ｎｍ〜４５０ｎｍ
ブラックパネル温度：６３℃ 照射距離：２３５ｍｍ（光源と試料間）
（尚、アイスーパーＵＶテスターによる光照射評価は、材料系や試験条件によっても変動するので一概には言えないが、通常サンシャインウエザオメーターによる評価よりも、１０倍程度の過酷な促進効果があるとされている。）
Light irradiation conditions Test apparatus: Eye super UV tester (SUV-F11 type), manufactured by Iwasaki Electric Co., Ltd. Irradiation intensity: 100 mW / cm @ 2 Limited wavelength: 295 nm to 450 nm
Black panel temperature: 63 ° C Irradiation distance: 235mm (between light source and sample)
(Note that the light irradiation evaluation by the eye super UV tester varies depending on the material system and test conditions, so it cannot be said unconditionally. However, it is usually about 10 times as severe as that of the sunshine weatherometer. It is said that)
Claims (6)
−［Ｓｉ（Ｒ1）2-b（Ｙ）bＯ］m−Ｓｉ（Ｒ2）3-a（Ｙ）a （１）
（式中、Ｒ1およびＲ2は、いずれも炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、または炭素数７〜２０のアラルキル基、または（Ｒ’）3Ｓｉ−（Ｒ’は炭素数１〜２０の１価の炭化水素基であって、３個のＲ’は同一であってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基を示し、Ｒ1またはＲ2が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｙは水酸基または加水分解性基を示し、Ｙが２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。ａは０，１，２，または３を、また、ｂは０，１，または２を示す。ｍは０〜１９の整数である。ただし、ａ＋ｍｂ≧１であることを満足するものとする。） It contains 100 parts by weight of a vinyl polymer (a) having a crosslinkable silyl group represented by the formula (1) as a terminal and 5 to 40 parts by weight of an air curable and / or photocurable compound (b). A curable composition characterized by that.
- [Si (R 1) 2 -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R 1 and R 2 are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) 3 Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R 1 Alternatively, when two or more R 2 are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)
An adhesive comprising the curable composition according to any one of claims 1 to 4.
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| JP2004109522A JP2005290271A (en) | 2004-04-01 | 2004-04-01 | Curable composition, sealing material and adhesive |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008041768A1 (en) * | 2006-10-05 | 2008-04-10 | Kaneka Corporation | Curable composition |
| JP2019167471A (en) * | 2018-03-23 | 2019-10-03 | 富士ゼロックス株式会社 | Adhesive material, sheet for producing press-bonding printed matter, method for producing sheet for producing press-bonding printed matter, press-bonding printed matter, method for producing press-bonding printed matter, and apparatus for producing press-bonding printed matter |
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2004
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008041768A1 (en) * | 2006-10-05 | 2008-04-10 | Kaneka Corporation | Curable composition |
| JPWO2008041768A1 (en) * | 2006-10-05 | 2010-02-04 | 株式会社カネカ | Curable composition |
| US7977399B2 (en) | 2006-10-05 | 2011-07-12 | Kaneka Corporation | Curable composition |
| JP2019167471A (en) * | 2018-03-23 | 2019-10-03 | 富士ゼロックス株式会社 | Adhesive material, sheet for producing press-bonding printed matter, method for producing sheet for producing press-bonding printed matter, press-bonding printed matter, method for producing press-bonding printed matter, and apparatus for producing press-bonding printed matter |
| JP7081253B2 (en) | 2018-03-23 | 2022-06-07 | 富士フイルムビジネスイノベーション株式会社 | Adhesive material, crimp printed matter manufacturing sheet, crimp printed matter manufacturing sheet manufacturing method, crimp printed matter, crimp printed matter manufacturing method, and crimp printed matter manufacturing equipment |
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