JP4224420B2 - Curable composition, sealing material and adhesive - Google Patents
Curable composition, sealing material and adhesive Download PDFInfo
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- JP4224420B2 JP4224420B2 JP2004109518A JP2004109518A JP4224420B2 JP 4224420 B2 JP4224420 B2 JP 4224420B2 JP 2004109518 A JP2004109518 A JP 2004109518A JP 2004109518 A JP2004109518 A JP 2004109518A JP 4224420 B2 JP4224420 B2 JP 4224420B2
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- curable composition
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- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 71
- 239000003566 sealing material Substances 0.000 title claims description 12
- 230000001070 adhesive effect Effects 0.000 title claims description 7
- 239000012945 sealing adhesive Substances 0.000 title 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 47
- -1 triethoxysilyl group Chemical group 0.000 claims description 45
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 36
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 30
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 229920006222 acrylic ester polymer Polymers 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 40
- 239000010410 layer Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 238000003860 storage Methods 0.000 description 18
- 125000003342 alkenyl group Chemical group 0.000 description 16
- 239000004611 light stabiliser Substances 0.000 description 16
- 229920000570 polyether Polymers 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
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- 150000002367 halogens Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
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- 125000005370 alkoxysilyl group Chemical group 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
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- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012298 atmosphere Substances 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
- 125000004432 carbon atom Chemical group C* 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
- 238000004132 cross linking Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000013008 thixotropic agent Substances 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 229960000834 vinyl ether Drugs 0.000 description 3
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- 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
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- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
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- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 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
- 230000001771 impaired effect Effects 0.000 description 2
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- 239000012948 isocyanate Substances 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
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- 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
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- QMIREOCYHAFOPK-UHFFFAOYSA-N n,n'-bis(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCNCCC[Si](OCC)(OCC)OCC QMIREOCYHAFOPK-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
- 229920003052 natural elastomer Polymers 0.000 description 1
- 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 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
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 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
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 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
- 239000000565 sealant Substances 0.000 description 1
- 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
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002356 single layer Substances 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
- 230000006641 stabilisation Effects 0.000 description 1
- 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
- 150000003461 sulfonyl halides Chemical class 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 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
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-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
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、湿気により架橋し、耐久性に優れた硬化物を与える（メタ）アクリル酸エス
テル系重合体含有硬化性組成物に関し、特に貯蔵安定性及び速硬化性に優れた（メタ）アクリル酸エステル系重合体を含む硬化性組成物、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 is crosslinked by moisture, relates a cured product excellent in durability (meth) acrylic ester polymer containing perforated curable composition excellent in particular the storage stability and rapid curability (meth) acrylic The present invention relates to a curable composition containing an acid ester polymer, and a sealing material and an adhesive using the curable composition.
従来より、アルコキシシリル基を有する（メタ）アクリル重合体を主成分とする硬化性組成物が種々提案されている。（例えば、下記特許文献１〜３など）これらの硬化性組成物は、雰囲気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。そのため、上記硬化性組成物は、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様々な用途に用いられている。 Conventionally, various curable compositions based on a (meth) acrylic polymer having an alkoxysilyl group have been proposed. (For example, Patent Documents 1 to 3 below) These curable compositions are crosslinked by moisture in the atmosphere, and give a cured product excellent in durability, weather resistance, transparency, and adhesiveness. Therefore, the said curable composition is used for various uses, such as a coating material, a coating agent, an adhesive agent, a pressure sensitive adhesive, a sealant, and a sealing material.
しかしながら、上記アルコキシシリル基含有ビニル重合体は、湿気の作用により架橋し、硬化するため、貯蔵安定性が充分でないことがあった。そのため、貯蔵安定性を高めるため、下記の特許文献４及び５では、アクリルアミドとの共重合により、安定性の向上が図られていた。 However, since the alkoxysilyl group-containing vinyl polymer is crosslinked and cured by the action of moisture, the storage stability may not be sufficient. Therefore, in order to improve the storage stability, in Patent Documents 4 and 5 below, the stability is improved by copolymerization with acrylamide.
また、下記の特許文献６では、脱水を図るために、トリレンジイソシアネート（ＴＤＩ）のようなイソシアネートを添加する方法が開示されている。イソシアネート化合物が添加された場合、水との反応により、水素結合力が高いウレタンやウレアなどの結合が生成する。従って、組成物が濁ったり、有機凝集物が生成したりするという問題があった。また、アミド結合を用いる場合、硬化物に黄変が見られることがあった。 Patent Document 6 below discloses a method of adding an isocyanate such as tolylene diisocyanate (TDI) for dehydration. When an isocyanate compound is added, a bond such as urethane or urea having a high hydrogen bonding force is generated by reaction with water. Therefore, there has been a problem that the composition becomes cloudy or organic aggregates are generated. In addition, when an amide bond is used, yellowing may be observed in the cured product.
本発明の目的は、上述した従来技術の現状に鑑み、速度硬化性と貯蔵安定性とを両立し得る（メタ）アクリル酸エステル系重合体を用いた硬化性組成物、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。
SUMMARY OF THE INVENTION In view of the problems described above, may both speed curability and storage stability (meth) curable composition using an acrylic acid ester polymer, and the curable composition Another object is to provide a sealing material and an adhesive using the material .
本発明に係る硬化性組成物は、トリエトキシシリル基、ジエトキシシリル基及びジメトキシシリル基から選ばれる少なくとも１つの架橋可能な加水分解性シリル基を末端に有し、かつ前記加水分解性シリル基を１分子中に数平均で１．２〜４．０個の範囲で有する（メタ）アクリル酸エステル系重合体１００重量部と、ポリオキシアルキレン鎖を有する４級アンモニウム塩により処理されている層状ケイ酸塩０．１〜１００重量部とを含む。
The curable composition according to the present invention has at least one crosslinkable hydrolyzable silyl group selected from a triethoxysilyl group, a diethoxysilyl group and a dimethoxysilyl group at the end, and the hydrolyzable silyl group. the having at 1.2 to 4.0 or in the range average number per molecule (meth) layered acrylic acid ester polymer 100 parts by weight, and is processed by a quaternary ammonium salt having a polyoxyalkylene chain Including 0.1 to 100 parts by weight of silicate.
本発明に係る（メタ）アクリル酸エステル系重合体は、好ましくは、ポリスチレン換算の数平均分子量が５０００〜１０００００の範囲にある。 The (meth) acrylic acid ester polymer according to the present invention preferably has a polystyrene-equivalent number average molecular weight in the range of 5,000 to 100,000.
本発明に係る硬化性組成物では、好ましくは、前記硬化性組成物を６０℃で６０日間貯蔵した後の２５℃における粘度が、組成物を配合した５分後の２５℃における粘度の０．５〜１０倍の範囲とされている。 In the curable composition according to the present invention, preferably, the viscosity at 25 ° C. after the curable composition is stored at 60 ° C. for 60 days is 0. 5% of the viscosity at 25 ° C. after 5 minutes of blending the composition. The range is 5 to 10 times.
本発明に係る硬化性組成物では、好ましくは、硬化促進剤として、ジブチル錫ジアルキルカルボキシレートが添加され、それによってタックフリー時間が１２時間以下に短縮され得る。なお、タックフリー時間とは、硬化性組成物を適用した後貼り合わせを行い得る最大可使時間をいうものとする。 In the curable composition according to the present invention, dibutyltin dialkylcarboxylate is preferably added as a curing accelerator, whereby the tack-free time can be shortened to 12 hours or less. The tack-free time means the maximum pot life that can be bonded after applying the curable composition.
本発明に係る硬化性組成物では、好ましくは、さらに少なくとも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がさらに配合され、それによって硬化物の耐水性及び耐久性が高められる。 In the curable composition according to the present invention, preferably, a polyether polymer having at least a crosslinkable hydrolyzable silyl group is further blended, thereby improving the water resistance and durability of the cured product.
本発明に係る硬化性組成物では、層状珪酸塩が配合され、それによって硬化物の難燃性や強度が高められる。
本発明に係るシーリング材及び接着剤は、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。
The curable composition according to the present invention, engaged arrangement a layer-like silicate, it flame retardancy and strength of the cured product by is increased.
The sealing material and the adhesive according to the present invention are 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。
（（メタ）アクリル酸エステル系重合体（ａ））
本発明で用いられる（メタ）アクリル酸エステル系重合体は、トリエトキシシリル基、ジエトキシシリル基及びジメトキシシリル基から選ばれる少なくとも１つの架橋可能な加水分解性シリル基を末端に有し、かつ加水分解性シリル基を１分子中に数平均で１．２〜４．０個の範囲で有することを特徴とする、（メタ）アクリル酸エステル系重合体である。
Details of the present invention will be described below.
((Meth) acrylic acid ester polymer (a))
The (meth) acrylic acid ester polymer used in the present invention has at least one crosslinkable hydrolyzable silyl group selected from a triethoxysilyl group, a diethoxysilyl group and a dimethoxysilyl group at the end, and It is a (meth) acrylic acid ester polymer characterized by having a hydrolyzable silyl group in the range of 1.2 to 4.0 in terms of number average in one molecule.
アルコキシシリル基において、炭素数が３以上のプロポキシ基より大きなアルコキシ基が置換している場合、アルコキシシリル基が嵩高くなり、加水分解、縮合反応が著しく遅くなり、貯蔵安定性に優れるものの、実用に耐え得るほどの硬化速度を得ることが困難となる。一方、メトキシ基の場合には、アルコキシシリル基の嵩高さは小さくなり、実用に耐え得るほどの硬化速度を得ることができる。しかしながら、アルコキシシリル基が３個結合したトリアルコキシシリル基の場合、反応点が多くなり、貯蔵安定性に優れた組成物を得ることが困難な場合がある。また、モノアルコキシ基の場合は、反応点が極端に少なくなり、架橋ゴムの硬化皮膜を得ることが困難となる。従って、本発明では、トリエトキシシリル基、ジエトキシシリル基、ジメトキシシリル基が用いられる。 In the alkoxysilyl group, when an alkoxy group larger than a propoxy group having 3 or more carbon atoms is substituted, the alkoxysilyl group becomes bulky, the hydrolysis and condensation reactions become extremely slow, and the storage stability is excellent. It is difficult to obtain a curing rate sufficient to withstand On the other hand, in the case of a methoxy group, the bulk of the alkoxysilyl group is reduced, and a curing rate that can withstand practical use can be obtained. However, in the case of a trialkoxysilyl group in which three alkoxysilyl groups are bonded, the number of reaction points increases, and it may be difficult to obtain a composition having excellent storage stability. In the case of a monoalkoxy group, the number of reaction points is extremely reduced, making it difficult to obtain a cured film of a crosslinked rubber. Accordingly, in the present invention, a triethoxysilyl group, a diethoxysilyl group, and a dimethoxysilyl group are used.
上記（メタ）アクリル酸エステル系重合体（ａ）の数平均分子量（ゲルパーミエションクロマトグラフィー（ＧＰＣ）により求められたポリスチレン換算分子量）は、好ましくは５０００〜１０００００の範囲である。５０００未満の場合には、取り扱い易い液状の組成物を構成し得るが、硬化物の伸びが充分に得られないことがある。逆に、数平均分子量が１０００００を超えると、硬化物の伸び物性に優れた組成物を容易に得ることができるものの、糸引きが生じ易い液状組成物となることがある。従って、上記（メタ）アクリル酸エステル系重合体（ａ）を主成分とする硬化性組成物を構成した場合、硬化物の伸び特性が優れ、糸引きが生じ難い液状もしくはペースト状の組成物として用いる場合には、数平均分子量は上記範囲内であることが好ましい。硬化物の伸びに優れ、糸引きが生じ難い液状の組成物を得るには、より好ましくは、上記数平均分子量は、５０００〜５００００の範囲であり、さらに好ましくは８０００〜３００００の範囲であることが望ましい。 The number average molecular weight (polystyrene conversion molecular weight determined by gel permeation chromatography (GPC)) of the (meth) acrylic acid ester polymer (a) is preferably in the range of 5,000 to 100,000. When it is less than 5,000, a liquid composition that is easy to handle can be formed, but the elongation of the cured product may not be sufficiently obtained. On the other hand, when the number average molecular weight exceeds 100,000, a composition excellent in elongation property of the cured product can be easily obtained, but it may be a liquid composition in which stringing is likely to occur. Therefore, when a curable composition comprising the (meth) acrylic acid ester polymer (a) as a main component is constituted, as a liquid or paste-like composition having excellent elongation characteristics of the cured product and hardly causing stringing. When used, the number average molecular weight is preferably within the above range. More preferably, the number average molecular weight is in the range of 5000 to 50000, and more preferably in the range of 8000 to 30000, in order to obtain a liquid composition that is excellent in elongation of the cured product and hardly causes stringing. Is desirable.
本発明における架橋可能な加水分解性シリル基は、ＧＰＣにより求められたポリスチレン換算数平均分子量と、（メタ）アクリル酸エステル系重合体（ａ）を得るのに用いたシリル基含有化合物の添加量に基づき、計算によって求めた値である。 The crosslinkable hydrolyzable silyl group in the present invention includes the polystyrene-equivalent number average molecular weight determined by GPC and the amount of the silyl group-containing compound used to obtain the (meth) acrylate polymer (a). Based on the above, it is a value obtained by calculation.
本発明における加水分解性シリル基は、１分子中に数平均で１．２〜４．０個の範囲であることが必要である。この平均個数が１．２未満の場合には、貯蔵安定性に優れた硬化性組成物は得られるものの、硬化促進剤を添加したとしても硬化しない。他方、本発明における加水分解性シリル基の平均個数が４．０個を超える場合、貯蔵安定性が低下したり、硬化物の伸びが充分でなかったりする。より好ましくは、本発明における加水分解性シリル基の１分子中の平均個数は１．５〜３．５の範囲である。 The hydrolyzable silyl group in the present invention is required to be in the range of 1.2 to 4.0 in number average. When this average number is less than 1.2, a curable composition having excellent storage stability can be obtained, but it does not cure even when a curing accelerator is added. On the other hand, when the average number of hydrolyzable silyl groups in the present invention exceeds 4.0, the storage stability is lowered, or the elongation of the cured product is not sufficient. More preferably, the average number of hydrolyzable silyl groups in one molecule in the present invention is in the range of 1.5 to 3.5.
上記架橋可能な加水分解性シリル基を末端に有する（メタ）アクリル酸エステ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（メタ）アクリル酸エステル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（メタ）アクリル酸エステル系重合体系重合体を製造し、式（２）のハロゲンを上記架橋可能な加水分解性シリル基含有置換基に変換する方法が挙げられる。この際、二官能の有機ハロゲン化合物やハロゲン化スルホニルを用いることにより、分子末端に上記架橋可能な加水分解性シリル基を有するメタアクリル酸エステル系重合体が得られる。
−Ｃ（Ｒ3）（Ｒ4）（Ｘ） （２）
（式中、Ｒ3は、Ｒ4は（メタ）アクリル酸エステル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。）
The method for producing the (meth) acrylic acid ester polymer having a crosslinkable hydrolyzable silyl group at the end is not particularly limited. For example, an organic halide or a sulfonyl halide compound is used as an initiator, a transition metal. By polymerizing the (meth) acrylic acid ester monomer using the complex as a catalyst, a (meth) acrylic acid ester-based polymer having a terminal structure represented by the formula (2) is produced, and the halogen of the formula (2) is reduced. The method of converting into the said crosslinkable hydrolyzable silyl group containing substituent is mentioned. At this time, by using a bifunctional organic halogen compound or a sulfonyl halide, a methacrylic acid ester polymer having a crosslinkable hydrolyzable silyl group at the molecular end can be obtained.
-C (R 3 ) (R 4 ) (X) (2)
(In the formula, R 3, R 4 represents a group bonded to an ethylenically unsaturated group of the (meth) acrylic acid ester monomer. Further, X represents chlorine, bromine, or halogen atom iodine,.)
上記式（２）のハロゲンを上記架橋可能な加水分解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可能な加水分解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可能な加水分解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 expression halogen (2) a method of converting into the crosslinkable hydrolyzable silyl group-containing substituent is not particularly limited, for example, a compound having a crosslinkable hydrolyzable silyl group and an alkenyl group, A method of reacting a compound having a silyl group and 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, a stable alkenyl group and And a method of reacting a hydrosilane having a hydrolyzable silyl group capable of crosslinking with the alkenyl group after reacting a compound having a carbanion and the like to replace the halogen of formula (2) with an alkenyl group.
また、上記架橋可能な加水分解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、架橋可能な加水分解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可能な加水分解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可能な加水分解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可能な加水分解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可能な加水分解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可能な加水分解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、さらに架橋可能な加水分解性シリル基に変換しても良い。
In producing the vinyl polymer having the crosslinkable hydrolyzable silyl group at the end, with an organic halide having a crosslinkable hydrolyzable silyl group as an initiator, a halogen at one end After having synthesized a polymer having a hydrolyzable silyl group that can be cross-linked at the other end, it has a hydrolyzable silyl group that can be cross-linked at both ends by reacting with halogen, glycol, diamine, dicarboxylic acid, etc. A polymer may be prepared, or after synthesizing a polymer having a hydrolyzable silyl group having a halogen at one end and a crosslinkable at the other end, the hydrolyzable capable of crosslinking the halogen by the above reaction. It may be converted to a silyl group. Alternatively, after synthesizing a polymer having a hydrolyzable silyl group having a halogen at one end and a crosslinkable at the other end, the halogen can be converted into an alkenyl group by the above-described reaction, and then further hydrolyzable by hydrolysis. May be converted to a functional silyl group.
また、上記架橋可能な加水分解性シリル基を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可能な加水分解性シリル基に変換する方法等が挙げられる。
In producing the vinyl polymer to have a said crosslinkable hydrolyzable silyl group, by using an organic halide as an initiator having an alkenyl group, the other end having a halogen at one end Examples thereof include a method of synthesizing a polymer having an alkenyl group, converting a halogen to an alkenyl group, and then converting the alkenyl group to a hydrolyzable silyl group that can be crosslinked by the above-described method.
上記（メタ）アクリル酸エステルモノマーとしては、特に限定されるわけではないが、下記の化合物を挙げることができる。 Although it does not necessarily limit as said (meth) acrylic acid ester monomer, The following compound can be mentioned.
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−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−３−メチルブチル（メタ）アクリレート、２−ヒドロキシ−３−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）などを挙げることができる。
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, tetrahydrofurfuryl (meth) acrylate, hexanediol di (meth) acrylate, ethyl 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-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydride Xylbutyl (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).
また、本発明に係る（メタ）アクリル酸エステル系重合体（ａ）を得るにあたって用いられるモノマーとしは、上記（メタ）アクリル酸エステル系モノマーだけでなく、下記の共重合性モノマーを併用し、共重合してもよい。このような共重合性モノマーとしては、例えば、スチレン、インデン、α−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、ジビニルベンゼンなどのスチレン誘導体；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、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、珪皮酸ビニルなどのビニルエステル基を持つ化合物；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などのビニロキシ基を持つ化合物を挙げることができる。 Moreover, as a monomer used in obtaining the (meth) acrylic acid ester polymer (a) according to the present invention, not only the above (meth) acrylic acid ester monomer but also the following copolymerizable monomer is used in combination: It may be copolymerized. Examples of such copolymerizable monomers include styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinyl. Styrene derivatives such as benzene; maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-benzylmaleimide Compounds having a vinyl ester group such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether , Tert-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 Chill, di (4-vinyloxy) butyl glutarate, di (4-vinyloxy) butyl trimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl, vinyl ether, cyclohexane-1 Examples thereof include compounds having a vinyloxy group such as 4-dimethanol-monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, and polyester vinyl ether.
（硬化性組成物）
本発明に係る硬化性組成物は、上記（メタ）アクリル酸エステル系重合体（ａ）１００重量部と、ポリオキシアルキレン鎖を有する４級アンモニウムにより処理されている層状ケイ酸塩０．１〜１００重量部とを含む硬化性組成物である。
(Curable composition)
The curable composition according to the present invention is a layered silicate 0.1 to 100 treated by quaternary ammonium having a polyoxyalkylene chain and 100 parts by weight of the (meth) acrylic acid ester polymer (a). It is a curable composition containing 100 parts by weight .
（貯蔵安定性）
本発明に係る硬化性組成物は、好ましくは、６０℃で６０日間貯蔵した後の２５℃における粘度が、貯蔵前、すなわち配合した５分後の２５℃における粘度の０．５〜１０倍の範囲とされる。このように、６０℃の高温で６０日間貯蔵した場合であっても、粘度の上昇が充分に抑制される。すなわち、貯蔵安定性に優れている。なお、貯蔵後の２５℃における粘度が、配合直後の２５℃における粘度の０．５倍未満の場合には凝集力が不足し、たれることがあり、１０倍を超えるともはや塗工できないことがある。
(Storage stability)
The curable composition according to the present invention preferably has a viscosity at 25 ° C. after storage at 60 ° C. for 60 days of 0.5 to 10 times the viscosity at 25 ° C. before storage, that is, 5 minutes after compounding. Scope. Thus, even when stored at a high temperature of 60 ° C. for 60 days, the increase in viscosity is sufficiently suppressed. That is, it is excellent in storage stability. In addition, when the viscosity at 25 ° C. after storage is less than 0.5 times the viscosity at 25 ° C. immediately after blending, the cohesive force may be insufficient and may drip. There is.
（タックフリー時間）
本発明に係る硬化性組成物では、好ましくは、硬化促進剤として、ジブチル錫ジアルキルカルボキシレートを添加することにより、塗工直後から測定したタックフリー時間が１２時間以下とされる。タックフリー時間が１２時間を超える場合には、可使時間が長くなり過ぎ、速硬化性を得ることができない。
すなわち、本発明に係る硬化性組成物では、上記硬化促進剤の配合により、貯蔵安定性と速硬化性をより一層高度に両立することができる。
(Tack-free time)
In the curable composition according to the present invention, preferably, by adding dibutyltin dialkylcarboxylate as a curing accelerator, the tack-free time measured immediately after coating is 12 hours or less. If the tack-free time exceeds 12 hours, the pot life is too long, and fast curability cannot be obtained.
That is, in the curable composition according to the present invention, storage stability and fast curability can be achieved at a higher level by blending the curing accelerator.
（硬化促進剤）
本発明では、速やかな硬化を得るために、有機金属化合物からなる硬化促進剤をさらに加えてもよい。
(Curing accelerator)
In the present invention, a curing accelerator composed of an organometallic compound may be further added to obtain rapid curing.
好適に用いることの出来る有機金属化合物としては、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、ジブチル錫ジアルキルカルボキシレート、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などが挙げられ、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。 Examples of the organic metal compound that can be preferably used include 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. For example, dibutyltin dialkylcarboxylate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin laurate) oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoester maleate) , Tin compounds such as tin octylate, dibutyltin octoate and dioctyltin oxide, and titanate compounds such as tetra-n-butoxy titanate and tetraisopropoxy titanate. These may be used alone or in combination of two or more. I can do it.
好ましくは、硬化促進剤として、ジブチル錫ジアルキルカルボキシレートが用いられ、それによって、タックフリー時間を１２時間以内とすることができる。
上記硬化促進剤の配合割合は、好ましくは、（メタ）アクリル酸エステル系重合体（ａ）１００重量部に対し、０．０１〜１０重量部の範囲である。０．０１重量部未満では、硬化促進効果が十分でなく、１０重量部を越えると硬化が速くなりすぎることがあり、均一な硬化皮膜を得ることが困難となることがある。
Preferably, dibutyltin dialkylcarboxylate is used as the curing accelerator, whereby the tack-free time can be within 12 hours.
The blending ratio of the curing accelerator is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer (a). If it is less than 0.01 parts by weight, the effect of promoting curing is not sufficient, and if it exceeds 10 parts by weight, curing may become too fast, and it may be difficult to obtain a uniform cured film.
（層状珪酸塩）
本発明に係る硬化性組成物では、耐候性を高めるために層状珪酸塩が配合されている。
(Layered silicate)
The curable composition according to the present invention, the layered silicate is blended in order to improve the weather resistance.
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。 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. 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、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, more preferably 0.5 to 50 parts by weight, and particularly preferably 1 to 10 parts by weight with respect to 100 parts by weight of the base resin. 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、ベース樹脂とは、上記（メタ）アクリル酸エステル系重合体（ａ）、あるいは上記（メタ）アクリル酸エステル系重合体（ｂ）と必要に応じて添加される後述のポリエーテル系重合体（ｂ）の合計である。 The base resin refers to the (meth) acrylic acid ester polymer (a) or the (meth) acrylic acid ester polymer (b) and a later-described polyether polymer that is added as necessary. It is the sum of (b).
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。 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、ポリオキシアルキレン鎖を有する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。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。また、４級アンモニウム塩は上記有機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。
Layered silicate of the present invention, Ru layered silicate der consisting treated with quaternary ammonium salts having a polyoxyalkylene chain. By treatment with quaternary ammonium salts, Ru can improve the dispersibility of the above base resin of the layered silicate. Further, quaternary ammonium salts are known to have a catalytic action for the crosslinking reaction of the organic polymer, and disperse in the base resin together with the layered silicate to improve the dispersibility and accelerate the curing rate. 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、本発明では、ポリオキシアルキレン鎖を有する４級アンモニウム塩が用いられる。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. In the present invention, a quaternary ammonium salt having a polyoxyalkylene chain is used. 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.
（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.
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、上記有機重合体、ウレタン樹脂、エポキシ樹脂及び／または変性ポリサルファイド樹脂からなるベース樹脂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。 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, 0.1 to 20 parts by weight, more preferably 100 parts by weight of the base resin composed of the organic polymer, urethane resin, epoxy resin and / or modified polysulfide resin, It is preferable that 0.5-10 weight part is mix | blended. 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.
（ポリエーテル系重合体（ｂ））
本発明に係る硬化性組成物では、主鎖が本質的にポリエーテル系重合体からなり、架橋可能な加水分解性のシリル基を有するポリエーテル系重合体（ｂ）が配合されてもよい。ポリエーテル系重合体（ｂ）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。このポリエーテル系重合体（ｂ）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重合体（ｂ）と併用する場合、その配合割合は、（メタ）アクリル酸エステル系重合体（ａ）１００重量部に対し、ポリエーテル系重合体（ｂ）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。
(Polyether polymer (b))
In the curable composition according to the present invention, a polyether polymer (b) having a main chain essentially composed of a polyether polymer and having a crosslinkable hydrolyzable silyl group may be blended. Examples of the polyether polymer (b) 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 polyether polymer (b), 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 polymer (b) are used in combination, the blending ratio is calculated based on 100 parts by weight of the (meth) acrylic acid ester polymer (a). The ether polymer (b) is preferably added in a proportion 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（ｂ）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 (b) 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.
上記ポリエーテル重合体（ｂ）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 (b) is essentially 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.
上記重合体（ｂ）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 polymer (b) is synthesized, for example, by reacting a polyalkylene oxide having an allyl group at the terminal with a hydrosilane compound represented by the following chemical formula (3) in the presence of a group VIII transition metal.
（式中Ｒ1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 1 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 a ketoximate Means an atom or group selected from the 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（ｂ）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。 When the number average molecular weight of the polyether polymer (b) is small, the elongation of the cured product is insufficient, the followability to the joint surface is lowered, and when it is large, the viscosity before curing is increased, and the workability of the blending process is 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（ｂ）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 (b) include the trade name “MS polymer” (manufactured by Kaneka Chemical Industry 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.
本発明に係る硬化性組成物では、さらに、本発明の目的及び効果を阻害しない限り、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、引張特性を調整する物性調整剤、増量剤、補強剤、可塑剤、着色剤、難燃剤、タレ防止剤、酸化防止剤、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。 In the curable composition according to the present invention, as long as the objects and effects of the present invention are not impaired, a viscosity modifier that adjusts the viscosity characteristics of the composition, a thixotropic agent, a physical property modifier that adjusts tensile characteristics, a bulking agent, A reinforcing agent, plasticizer, colorant, flame retardant, anti-sagging agent, antioxidant, anti-aging agent, solvent, fragrance, pigment, dye, dehydrating agent, and the like may be added.
粘度調整剤としては、例えば、アルコキシシリル基を有する実質（メタ）アクリル酸エステルをモノマーとする繰り返し単位から成る重合体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など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。 The viscosity modifier is, for example, selected from a polymer compound having a good compatibility with a polymer composed of a repeating unit having a substantially (meth) acrylic acid ester having an alkoxysilyl group as a monomer, and appropriately selected from compounds to be blended Is done. 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、アルコキシシリル基を有する実質（メタ）アクリル酸エステルをモノマーとする繰り返し単位から成る重合体との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 high affinity with a polymer composed of a repeating unit having a substantially (meth) acrylic acid ester having an alkoxysilyl group as a monomer.
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などを挙げられ、これらは単独または２種以上併用してもかまわない。 As physical property modifiers, various silane coupling agents such as vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, 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] ethylenediamine, N, N '-Bi -[3- (trimethoxysilyl) propyl] hexaethylenediamine, N, N'-bis- [3- (triethoxysilyl) propyl] hexaethylenediamine and the like may be mentioned, and these may be used alone or in combination of two or more. Absent.
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、カーボンブラックなどを挙げられ、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 express 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などのリン酸エステル類、フタル酸ジオクチルなど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などの脂肪酸−塩基酸エステル類、アジピン酸ジオクチルなど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などを挙げられ、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 glycerol 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.
本発明に係る硬化性組成物は、雰囲気中の湿気と反応して硬化し、ゴム弾性を有する硬化物を与える。そして、効果速度、貯蔵安定性が優れている、従って、本発明に係る硬化性組成物を用いて、黄変が生じ難く、かつ着色状態が経時により変化し難い、シーリング材や接着剤を提供することができる。 The curable composition according to the present invention is cured by reacting with moisture in the atmosphere to give a cured product having rubber elasticity. And, the effect speed and storage stability are excellent, and therefore, the curable composition according to the present invention is used to provide a sealing material and an adhesive that hardly cause yellowing and the color state hardly changes over time. can do.
本発明に係る（メタ）アクリル酸エステル系重合体（ａ）は、少なくとも架橋可能な加水分解性シリル基として、トリエトキシシリル基、ジエトキシシリル基及びジメトキシシリル基から選ばれる少なくとも１つを有し、該加水分解性シリル基が、１分子中に数平均で１．２〜４．０個の範囲にあるため、貯蔵安定性に優れ、かつ糸引きが生じ難い硬化性組成物を構成することができる。 The (meth) acrylic acid ester polymer (a) according to the present invention has at least one selected from a triethoxysilyl group, a diethoxysilyl group and a dimethoxysilyl group as at least a crosslinkable hydrolyzable silyl group. In addition, since the hydrolyzable silyl group is in the range of 1.2 to 4.0 in number average in one molecule, it constitutes a curable composition having excellent storage stability and hardly causing stringing. be able to.
また、特に、硬化促進剤としてジブチル錫アルキルカルボキシレートが添加されている場合には、タックフリー時間を短縮することができ、貯蔵安定性と速硬化性とを高度に両立することができる。従って、貯蔵安定性に優れ、さらに硬化速度の速い接着剤やシーリング材を提供することが可能となる。 In particular, when dibutyltin alkylcarboxylate is added as a curing accelerator, tack-free time can be shortened, and storage stability and fast curability can be highly compatible. Accordingly, it is possible to provide an adhesive or a sealing material that is excellent in storage stability and has a fast curing rate.
以下、本発明の具体的な実施例及び比較例を挙げることにより、本発明を明らかにする。なお、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.
（（メタ）アクリル酸エステル系重合体（ａ１）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（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。
(Preparation of (meth) acrylic acid ester polymer (a1))
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 (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. 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）、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), potassium salt of 4-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（１４５ｍｍｏｌ）、オルトぎ酸ジメチル（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 (145 mmol), dimethyl orthoformate (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.
（（メタ）アクリル酸エステル系重合体（ａ２）の調製）
上記（メタ）アクリル酸エステル系重合体（ａ１）の調製において、ジメトキシメチルシランの代わりに、トリメトキシシランを用いる以外は同様にして（（メタ）アクリル酸エステル系重合体（ａ２）の調製）を得た。
(Preparation of (meth) acrylic acid ester polymer (a2))
In the preparation of the above (meth) acrylate polymer (a1), the same procedure was performed except that trimethoxysilane was used instead of dimethoxymethylsilane (preparation of (meth) acrylate polymer (a2)). Got.
（参考例１）
上記で得られた（メタ）アクリル酸エステル系重合体（ａ１）７０ｇと、ポリプロピレングリコール（ＰＰＧ、和光純薬社製、分子量３０００）３０ｇとを混合した後、ロータリーエバポレターを用いて溶剤を除いて、硬化性組成物を調製した。
（粘度測定）
得られた硬化性組成物を脱泡した後に、配合５分後、及び６０℃のオーブンで６０日養生した後、２５℃まで冷却して、粘度をＢ型回転粘度計（東京計器）を用い、回転数１０ｒｐｍ、評価温度２５℃で測定した。結果は表１に示した。
（ゴム物性）
上記で得られた硬化性組成物に更に、脂肪酸表面処理炭酸カルシウム２０ｇ、重質炭酸カルシウム５０ｇ、硬化促進剤（ジブチル錫ジラウリレート）３ｇ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状のペーストの室温硬化性組成物を得た。
( Reference Example 1)
After mixing 70 g of the (meth) acrylic acid ester polymer (a1) obtained above and 30 g of polypropylene glycol (PPG, manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 3000), the solvent was removed using a rotary evaporator. Thus, a curable composition was prepared.
(Viscosity measurement)
After defoaming the obtained curable composition, after 5 minutes of blending and curing in an oven at 60 ° C. for 60 days, the mixture was cooled to 25 ° C. and the viscosity was measured using a B-type rotational viscometer (Tokyo Keiki). The measurement was performed at a rotation speed of 10 rpm and an evaluation temperature of 25 ° C. The results are shown in Table 1.
(Rubber properties)
Further, 20 g of fatty acid surface-treated calcium carbonate, 50 g of heavy calcium carbonate and 3 g of a curing accelerator (dibutyltin dilaurylate) are added to the curable composition obtained above, and mixed with a sealed stirrer until uniform, Defoaming was performed under reduced pressure for 10 minutes to obtain a room temperature curable composition of a white paste.
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、ゴム状のシートを得た。得られたゴム状シートを用い、ＪＩＳ Ｋ ６３０１に準じて、３号ダンベル形状でクロスヘッドスピード５００ｍｍ／分で引っ張り試験を行い、破断伸び（％）と破断応力（Ｎ／ｍｍ2）を測定した。結果を表１に示した。 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. Got. Using the obtained rubber-like sheet, a tensile test was performed with a No. 3 dumbbell shape at a crosshead speed of 500 mm / min in accordance with JIS K 6301, and the breaking elongation (%) and breaking stress (N / mm 2 ) were measured. . The results are shown in Table 1.
（比較例１）
参考例１において、（メタ）アクリル酸エステル系重合体（ａ１）７０ｇの代わりに（メタ）アクリル酸エステル系重合体（ａ２）７０ｇを用いて同様に硬化性組成物を調製し、粘度測定、引っ張り試験を行った。結果を表１に示した。
(Comparative Example 1)
In Reference Example 1, a curable composition was similarly prepared using 70 g of (meth) acrylic acid ester polymer (a 2 ) instead of 70 g of (meth) acrylic acid ester polymer (a1), and viscosity measurement was performed. A tensile test was conducted. The results are shown in Table 1.
（実施例１）
参考例１において硬化性組成物調整の際に、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、参考例１と同様にして硬化性組成物を得た。
(Example 1 )
In the preparation of the curable composition in Reference Example 1, 10 g of stratified silicate somacif MPE-100 (swelling fluorinated mica organically treated with polyoxypropylene diethyl quaternary ammonium salt, manufactured by Co-op Chemical), tinuvin 770 (hindered amine series) A curable composition was prepared in the same manner as in Reference Example 1 except that 5 g of a light stabilizer (manufactured by Ciba Specialty Chemicals) and 5 g of tinuvin 327 (benzotriazole-based UV 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１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 1 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以上の場合を○と判定した。 The 2θ of the diffraction peak obtained by diffraction of the laminated surface of the layered silicate was measured with an X-ray diffraction measurement apparatus (RINT1100, manufactured by Rigaku Corporation), 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 a case where the average interlayer distance was 3 nm or more was determined as ◯.
λ＝２ｄｓｉｎθ
なお、式中において、λ（ｎｍ）＝０．１５４、ｄ（ｎｍ）二層状珪酸塩の面間隔、θ（度）は回折角である。
λ = 2 dsin θ
In the formula, λ (nm) = 0.154, d (nm) plane spacing of stratified silicate, θ (degree) is a 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るものを○と判定した。
[Confirmation of dispersion state of layered silicate]
With a transmission electron microscope (TEM, “JEM-1200EX II” manufactured by JEOL Ltd.) photograph, the dispersion state of the layered silicate in the cured product was observed, and those existing in 5 layers or less were judged as ◯. .
（耐候性評価）
〔評価〕
上記参考例１及び実施例１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％の相対湿度の雰囲気下で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、表面状態を目視で観察し、クラックの無いものを○と判定した。
(Weather resistance evaluation)
[Evaluation]
The weather resistance of the curable compositions obtained in Reference Example 1 and Example 1 was evaluated by the following method. After each compounding composition was applied to a 50 mm × 150 mm (thickness 1 mm) stainless steel plate with a thickness of 0.5 mm and left to stand for 7 days (168 hours) in an atmosphere of 20 ° C. × 60% relative humidity and cured and cured. The samples were irradiated with light for 150 hours and 400 hours under the following conditions, the surface state was visually observed, and those having no cracks were determined as ◯.
・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）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：２３５ｎｍ（光源と試料間）
なお、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。結果を下記の表２に示した。
Light irradiation condition 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: 235 nm (between light source and sample)
Although the light irradiation evaluation by the eye super UV tester varies depending on the material system and test conditions, it cannot be generally stated. However, it is usually 10 times more severe than the evaluation by the sunshine weatherometer. Has been. The results are shown in Table 2 below.
Claims (5)
ポリオキシアルキレン鎖を有する４級アンモニウムにより処理されている層状ケイ酸塩０．１〜１００重量部とを含む、硬化性組成物。 It has at least one crosslinkable hydrolyzable silyl group selected from a triethoxysilyl group, a diethoxysilyl group and a dimethoxysilyl group at the end, and the hydrolyzable silyl group has a number average of 1. 100 parts by weight of (meth) acrylic acid ester-based polymer having in the range of 2 to 4.0,
A curable composition comprising 0.1 to 100 parts by weight of a layered silicate treated with a quaternary ammonium having a polyoxyalkylene chain.
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