JP2008019300A - Curable composition excellent in property to be coated - Google Patents
Curable composition excellent in property to be coated Download PDFInfo
- Publication number
- JP2008019300A JP2008019300A JP2006190037A JP2006190037A JP2008019300A JP 2008019300 A JP2008019300 A JP 2008019300A JP 2006190037 A JP2006190037 A JP 2006190037A JP 2006190037 A JP2006190037 A JP 2006190037A JP 2008019300 A JP2008019300 A JP 2008019300A
- Authority
- JP
- Japan
- Prior art keywords
- crosslinkable silyl
- group
- silyl group
- polymer
- curable composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 102
- 229920000642 polymer Polymers 0.000 claims abstract description 95
- -1 acrylate ester Chemical class 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 229920000620 organic polymer Polymers 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- 239000003566 sealing material Substances 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000011109 contamination Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000003973 paint Substances 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 17
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 13
- 239000004014 plasticizer Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000000565 sealant Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical group SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 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
- 239000000047 product Substances 0.000 description 5
- 239000013008 thixotropic agent Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 238000004455 differential thermal analysis Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical group OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 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
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- KJYSXRBJOSZLEL-UHFFFAOYSA-N (2,4-ditert-butylphenyl) 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 KJYSXRBJOSZLEL-UHFFFAOYSA-N 0.000 description 1
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- ULINSPSZUQSNHZ-UHFFFAOYSA-N 1,3,6,6-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound O=C1N(C)C(=O)N(C)C11C(C)(C)CNCC1 ULINSPSZUQSNHZ-UHFFFAOYSA-N 0.000 description 1
- PTYXPKUPXPWHSH-UHFFFAOYSA-N 1-(butyltetrasulfanyl)butane Chemical compound CCCCSSSSCCCC PTYXPKUPXPWHSH-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- ATEDRLJNXRFXBZ-UHFFFAOYSA-N 2,2,6,6-tetramethyldecanedioic acid Chemical compound OC(=O)CCCC(C)(C)CCCC(C)(C)C(O)=O ATEDRLJNXRFXBZ-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- DMHHYBUEZRZGDK-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound NC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DMHHYBUEZRZGDK-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- TVWGHFVGFWIHFN-UHFFFAOYSA-N 2-hexadecan-2-yl-4,6-dimethylphenol Chemical compound CCCCCCCCCCCCCCC(C)C1=CC(C)=CC(C)=C1O TVWGHFVGFWIHFN-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UWRXMIQVSKQAIJ-UHFFFAOYSA-N 2-n-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1h-triazin-2-yl]-[2-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1h-triazin-2-yl]-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1h-triazin-2-yl]amino]propyl Chemical compound C=1C(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NN(NCCCN(CCN(CCCNN2N=C(C=C(N2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N2N=C(C=C(N2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N2N=C(C=C(N2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 UWRXMIQVSKQAIJ-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- MZWXWSVCNSPBLH-UHFFFAOYSA-N 3-(3-aminopropyl-methoxy-methylsilyl)oxypropan-1-amine Chemical compound NCCC[Si](C)(OC)OCCCN MZWXWSVCNSPBLH-UHFFFAOYSA-N 0.000 description 1
- YYBQKVULIKPELH-UHFFFAOYSA-N 3-(3-hydroxypropyltrisulfanyl)propan-1-ol Chemical compound OCCCSSSCCCO YYBQKVULIKPELH-UHFFFAOYSA-N 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- CRVZNBPFUFUUDI-UHFFFAOYSA-N 3-[dimethoxy(phenyl)silyl]propane-1-thiol Chemical compound SCCC[Si](OC)(OC)C1=CC=CC=C1 CRVZNBPFUFUUDI-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、硬化性組成物、シーリング材組成物、パテ組成物及び接着剤組成物に関し、さらに詳しくは塗料密着性、塗料非汚染性などの被塗装性に優れた硬化性組成物、シーリング材組成物、パテ組成物及び接着剤組成物に関する。 The present invention relates to a curable composition, a sealing material composition, a putty composition, and an adhesive composition. More specifically, the present invention relates to a curable composition and a sealing material excellent in coating properties such as paint adhesion and paint non-contamination. The present invention relates to a composition, a putty composition, and an adhesive composition.
反応性ケイ素基を有するポリオキシアルキレン系有機重合体をベースにした室温硬化性組成物は、例えば建築物のシーラント（変成シリコーン系シーリング材と呼ばれている）に利用でき、安価で優れた性能を有している。
これらは構造物の隙間（目地）等に充填施工し、硬化させ隙間をふさいで水密、気密を保つために用いられるものである。シーリング材硬化物の表面には塗料を塗布することが望まれる場合があるが、塗料とシーラント表面との密着力は必ずしも充分ではなく、特に溶剤系塗料を使用した場合は十分とは言えない問題点があった。
Room temperature curable compositions based on polyoxyalkylene organic polymers having reactive silicon groups can be used, for example, in building sealants (called modified silicone sealants) and are inexpensive and have excellent performance have.
These are used to fill a gap (joint) or the like of a structure and harden it to close the gap and maintain watertightness and airtightness. Although it may be desirable to apply paint to the surface of the cured sealant, the adhesion between the paint and the surface of the sealant is not always sufficient, especially when solvent-based paint is used. There was a point.
また、通常シーリング基材以外に充填剤、可塑剤、硬化促進剤、老化防止剤などが添加されている。このうち、可塑剤は主として作業性を向上するために添加され、通常ジオクチルフタレート、ジイソノニルフタレート等のフタル酸エステル系の可塑剤が用いられる。今や汎用的になっている変成シリコーンを基材としたシーリング材でもこれまでにこれらの可塑剤が主に用いられてきているが、これは施工後年月を経るとともに表面にブリードし、自己汚染・周辺汚染をするという問題があった。 Further, a filler, a plasticizer, a curing accelerator, an anti-aging agent and the like are usually added in addition to the sealing substrate. Among these, a plasticizer is mainly added to improve workability, and a phthalate ester plasticizer such as dioctyl phthalate or diisononyl phthalate is usually used. These plasticizers have been mainly used for sealing materials based on modified silicones, which are now widely used. However, this is a self-contamination that has bleeded to the surface as it has passed since construction.・ There was a problem of surrounding contamination.
一方、特許文献１は、特殊な重合触媒を用いた重合によって得られるアクリル系重合体や、その特殊なアクリル系重合体とシランカップリング剤とからなる硬化性組成物を開示している。しかしながら、これら硬化性組成物は、接着性やゴム物性、塗料との密着性等が充分ではなかった。特許文献２は架橋性シリル基含有有機重合体と特許文献１記載の特殊なアクリル系重合体を含む硬化性組成物を開示している。しかしながら、特許文献２記載の硬化性組成物は、接着性やゴム物性は優れているが、塗料との密着性は充分とはいえなかった。
本発明は、塗料密着性に優れ、塗料汚染の問題を解消した被塗装性に優れた硬化性組成物、及び良好な塗料密着性及び塗料非汚染性を有し、作業性に優れたシーリング材組成物、パテ組成物、及び接着剤組成物を提供することを目的とする。 The present invention relates to a curable composition having excellent paint adhesion and excellent paintability that solves the problem of paint contamination, and a sealing material having good paint adhesion and paint non-staining properties and excellent workability. It aims at providing a composition, a putty composition, and an adhesive composition.
上記課題を解決するために、本発明の硬化性組成物は、架橋性シリル基含有有機重合体（Ａ）、及びガラス転移温度が−１００℃〜−１０℃である、架橋性シリル基末端含有（メタ）アクリル酸エステル重合体（Ｂ）、を含有する硬化性組成物であって、前記（メタ）アクリル酸エステル重合体（Ｂ）が、下記式（１）で表されるメタロセン化合物及び架橋性シリル基含有チオール化合物の存在下に、重合性不飽和結合を有するアクリル系単量体を重合してなり、少なくとも１の末端に架橋性シリル基含有チオール化合物から水素原子が離脱した残基−Ｓ−Ｒ3（但し、Ｒ3は架橋性シリル基を有する基である）が結合している（メタ）アクリル酸エステル重合体であることを特徴とする。 In order to solve the above problems, the curable composition of the present invention comprises a crosslinkable silyl group-containing organic polymer (A), and a crosslinkable silyl group terminal containing a glass transition temperature of −100 ° C. to −10 ° C. A curable composition containing a (meth) acrylic acid ester polymer (B), wherein the (meth) acrylic acid ester polymer (B) is represented by the following formula (1) and a crosslink Residue formed by polymerizing an acrylic monomer having a polymerizable unsaturated bond in the presence of a polymerizable silyl group-containing thiol compound, and at least one terminal having a hydrogen atom removed from the crosslinkable silyl group-containing thiol compound It is a (meth) acrylic acid ester polymer to which S—R 3 (wherein R 3 is a group having a crosslinkable silyl group) is bonded.
前記架橋性シリル基含有有機重合体（Ａ）が、架橋性シリル基を末端に有するポリオキシアルキレン系重合体であることが好ましい。 The crosslinkable silyl group-containing organic polymer (A) is preferably a polyoxyalkylene polymer having a crosslinkable silyl group at the end.
前記（メタ）アクリル酸エステル重合体（Ｂ）における前記アクリル系単量体が、アクリル酸ブチル及び／又はアクリル酸２エチルヘキシルであることが好ましい。
前記（メタ）アクリル酸エステル重合体（Ｂ）が、重量平均分子量５００以上１００００以下であることが好ましく、５００以上５０００以下であることがより好ましい。
前記（メタ）アクリル酸エステル重合体（Ｂ）が、末端に１個の架橋性シリル基を有することが好ましい。
The acrylic monomer in the (meth) acrylic acid ester polymer (B) is preferably butyl acrylate and / or 2-ethylhexyl acrylate.
The (meth) acrylic acid ester polymer (B) preferably has a weight average molecular weight of 500 or more and 10,000 or less, and more preferably 500 or more and 5000 or less.
The (meth) acrylic acid ester polymer (B) preferably has one crosslinkable silyl group at the terminal.
本発明のシーリング材組成物は、前記本発明の硬化性組成物を主成分とすることを特徴とする。 The sealing material composition of the present invention is characterized by comprising the curable composition of the present invention as a main component.
本発明のパテ組成物は、前記本発明の硬化性組成物を主成分とすることを特徴とする。 The putty composition of the present invention is characterized by comprising the curable composition of the present invention as a main component.
本発明の接着剤組成物は、前記本発明の硬化性組成物を主成分とすることを特徴とする。 The adhesive composition of the present invention is characterized by comprising the curable composition of the present invention as a main component.
本発明によれば、塗料密着性に優れ、塗料汚染の問題を解消した被塗装性に優れた硬化性組成物、及び良好な塗料密着性及び塗料非汚染性を有し、作業性に優れたシーリング材組成物、パテ組成物、及び接着剤組成物を提供することができる。 According to the present invention, it has excellent paint adhesion, a curable composition with excellent paintability that has solved the problem of paint contamination, and good paint adhesion and paint non-staining properties, and excellent workability. Sealant compositions, putty compositions, and adhesive compositions can be provided.
以下に本発明の実施の形態を説明するが、これらは例示的に示されるもので、本発明の技術思想から逸脱しない限り種々の変形が可能なことはいうまでもない。 Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.
本発明の硬化性組成物は、成分（Ａ）架橋性シリル基含有有機重合体、及び成分（Ｂ）架橋性シリル基を末端に有する（メタ）アクリル酸エステル重合体を必須成分として含有するものである。
前記成分（Ａ）としては、珪素原子に結合した水酸基又は加水分解性基を有し、シロキサン結合を形成することにより架橋しうる珪素含有基、すなわち架橋性シリル基を含有する有機重合体が使用される。前記架橋性シリル基は、特に限定はないが、硬化性組成物の硬化性や硬化後の物性等の点から、分子内に１〜６個含まれるのが一般的である。架橋性シリル基の位置は特に限定されず、有機重合体分子鎖の末端あるいは内部にあってもよく、両方にあってもよいが、分子鎖末端にあることが好ましい。
The curable composition of the present invention contains component (A) a crosslinkable silyl group-containing organic polymer and component (B) a (meth) acrylic acid ester polymer having a crosslinkable silyl group at the terminal as essential components. It is.
As the component (A), a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond, that is, an organic polymer containing a crosslinkable silyl group is used. Is done. Although the said crosslinkable silyl group does not have limitation in particular, it is common that 1-6 pieces are contained in a molecule | numerator from points, such as sclerosis | hardenability of a curable composition, and the physical property after hardening. The position of the crosslinkable silyl group is not particularly limited and may be at the end or inside of the organic polymer molecular chain, or may be at both, but it is preferably at the end of the molecular chain.
更に、架橋性シリル基は、架橋しやすく製造しやすい下記一般式（２）で示されるものが好ましい。 Further, the crosslinkable silyl group is preferably one represented by the following general formula (2) which is easily crosslinked and easy to produce.
（式（２）中、Ｒ4は炭素数１〜２０の置換もしくは非置換の１価の有機基であり、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基が好ましく、メチル基が最も好ましい。Ｒ4が複数存在する場合、それらは同じであっても異なっていてもよい。Ｙは水酸基又は加水分解性基であり、ハロゲン原子、水素原子、水酸基、アルコキシ基、アシルオキシ基、ケトキシメート基、アミド基、酸アミド基、メルカプト基、アルケニルオキシ基及びアミノオキシ基から選択される基が好ましく、アルコキシ基がより好ましく、メトキシ基が最も好ましい。Ｙが複数存在する場合、それらは同じであっても異なっていてもよい。ｃは１、２又は３であり、速硬化性の点から３が最も好ましい。） (In the formula (2), R 4 is a monovalent organic group having a substituted or unsubstituted 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group or a carbon of 6 to 20 carbon atoms 7 An aralkyl group of ˜20 is preferred, and a methyl group is most preferred, and when a plurality of R 4 are present, they may be the same or different, Y is a hydroxyl group or a hydrolyzable group, a halogen atom, hydrogen A group selected from an atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group and an aminooxy group is preferred, an alkoxy group is more preferred, and a methoxy group is most preferred. When a plurality of Y are present, they may be the same or different, and c is 1, 2 or 3, and 3 is most preferable from the viewpoint of fast curing.
前記成分（Ａ）において、架橋性シリル基が複数存在する場合、これらは同じであっても異なっていても良く、さらに、前記式（２）中のｃの数も同じであっても異なっていても良い。例えば、下記式（３）で示される架橋性シリル基及び下記式（４）で示される架橋性シリル基を併有する有機重合体も用いることができる。また、下記一般式（３）で示される架橋性シリル基を含有する有機重合体と、下記一般式（４）で示される架橋性シリル基を含有する有機重合体との混合物も好適に用いられる。 In the component (A), when there are a plurality of crosslinkable silyl groups, these may be the same or different, and further, the number of c in the formula (2) may be the same or different. May be. For example, an organic polymer having both a crosslinkable silyl group represented by the following formula (3) and a crosslinkable silyl group represented by the following formula (4) can also be used. A mixture of an organic polymer containing a crosslinkable silyl group represented by the following general formula (3) and an organic polymer containing a crosslinkable silyl group represented by the following general formula (4) is also preferably used. .
上記成分（Ａ）としては、例えば、特公平1-58219号、特許第3062625号、特開平8-337713号、特開2003-138151号、特開平11-12480号、特開昭52-73998号、特開昭55-9669号、特開昭59-122541号、特開昭60-6747号、特開昭61-233043号、特開昭63-112642号、特開平3-79627号、特開平4-283259号、特開平5-70531号、特開平5-287186号、特開平11-80571号、特開平11-116763号、特開平11-130931号、特許第3313360号等に開示されているものを挙げることができ、具体的には、架橋性シリル基を含有する、主鎖がそれぞれオルガノシロキサンを含有していてもよい、ポリオキシアルキレン系重合体、ビニル変性ポリオキシアルキレン系重合体、ビニル系重合体、ポリエステル重合体、（メタ）アクリル酸エステル重合体、これらの共重合体や混合物等を挙げることができる。特に、硬化後の引張接着性、モジュラス等の物性の点から、架橋性シリル基を含有する、ポリオキシアルキレン系重合体、（メタ）アクリル変性ポリオキシアルキレン系重合体、ポリイソブチレン系重合体、（メタ）アクリル系重合体、これらの共重合体や混合物等が好ましく、架橋性シリル基を分子鎖末端に有するポリオキシアルキレン系重合体が更に好ましい。 Examples of the component (A) include Japanese Patent Publication No. 1-58219, Japanese Patent No. 3062625, Japanese Patent Application Laid-Open No. 8-337713, Japanese Patent Application Laid-Open No. 2003-138151, Japanese Patent Application Laid-Open No. 11-12480, and Japanese Patent Application Laid-Open No. 52-73998. JP, 55-9669, JP 59-122541, JP 60-6747, JP 61-233043, JP 63-112642, JP 3-79627, JP 4-283259, JP-A-5-70531, JP-A-5-287186, JP-A-11-80571, JP-A-11-116763, JP-A-11-130931, Patent 3313360, etc. Specifically, a polyoxyalkylene polymer, a vinyl-modified polyoxyalkylene polymer, which contains a crosslinkable silyl group, each main chain may contain an organosiloxane, Examples thereof include vinyl polymers, polyester polymers, (meth) acrylic acid ester polymers, copolymers and mixtures thereof. In particular, from the viewpoint of physical properties such as tensile adhesiveness after curing and modulus, a polyoxyalkylene polymer, a (meth) acryl-modified polyoxyalkylene polymer, a polyisobutylene polymer containing a crosslinkable silyl group, (Meth) acrylic polymers, copolymers and mixtures thereof are preferred, and polyoxyalkylene polymers having a crosslinkable silyl group at the end of the molecular chain are more preferred.
本発明の硬化性組成物において、上記成分（Ａ）の数平均分子量は、好ましくは１０００以上１０００００以下、より好ましくは３０００〜５００００で分子量分布の狭いものが、硬化前の粘度が低いので取り扱い易く、硬化後の強度、伸び、モジュラス等の物性が好適である。前記成分（Ａ）は１種のみで用いても良く、２種以上併用してもよい。 In the curable composition of the present invention, the number average molecular weight of the component (A) is preferably 1000 or more and 100,000 or less, more preferably 3000 to 50000, and a narrow molecular weight distribution is easy to handle because the viscosity before curing is low. Physical properties such as strength, elongation and modulus after curing are preferred. The component (A) may be used alone or in combination of two or more.
本発明において、成分（Ｂ）架橋性シリル基を末端に有する（メタ）アクリル酸エステル重合体のガラス転移温度は−１００℃以上−１０℃以下であり、−６０℃以上−２０℃以下がより好ましい。ガラス転移温度（Ｔｇ）の測定方法としては、一般的な測定方法、例えば、ＴＭＡ法、ＤＴＡ法、ＤＳＣ法、ＤＭＡ法を用いることができる。具体的な測定方法としては、例えば、示差熱分析（ＤＴＡ）、又は示差走査熱量計（ＤＳＣ）を使用し、サンプルを一定速度で昇温する。ＤＴＡ曲線、又はＤＳＣ曲線におけるベースラインの接線及びガラス転移による吸熱領域の急峻な下降位置の接線との交点を測定することによりサンプルのＴｇを導き出すことができる。 In the present invention, the glass transition temperature of the (meth) acrylic acid ester polymer having a terminal (B) crosslinkable silyl group is from -100 ° C to -10 ° C, and from -60 ° C to -20 ° C. preferable. As a measuring method of the glass transition temperature (Tg), a general measuring method such as a TMA method, a DTA method, a DSC method, or a DMA method can be used. As a specific measurement method, for example, a differential thermal analysis (DTA) or a differential scanning calorimeter (DSC) is used, and the sample is heated at a constant rate. The Tg of the sample can be derived by measuring the intersection of the DTA curve or the tangent of the baseline in the DSC curve and the tangent of the steeply descending position of the endothermic region due to the glass transition.
また、本発明において、成分（Ｂ）架橋性シリル基を末端に有する（メタ）アクリル酸エステル重合体は、特許文献１記載のメタロセン化合物を用いて製造される重合体であり、触媒として、下記式（１）で表されるメタロセン化合物及び架橋性シリル基含有チオール化合物を使用し、この触媒の存在下に、重合性不飽和結合を有するアクリル系単量体を重合して得られる重合体である。そして、この重合体には、少なくとも１の末端に触媒として使用した架橋性シリル基含有チオール化合物から水素原子が脱離した残基（−Ｓ−Ｒ3）が結合している。ここでは、Ｒ3は架橋性シリル基を有する基である。
前記重合触媒として使用されるメタロセン化合物は、下記式（１）で表すことができる。
In the present invention, the component (B) (meth) acrylic acid ester polymer having a crosslinkable silyl group at the end is a polymer produced using the metallocene compound described in Patent Document 1, and the catalyst is as follows. A polymer obtained by polymerizing an acrylic monomer having a polymerizable unsaturated bond in the presence of this catalyst using a metallocene compound represented by formula (1) and a crosslinkable silyl group-containing thiol compound. is there. In addition, a residue (—S—R 3 ) in which a hydrogen atom is eliminated from a crosslinkable silyl group-containing thiol compound used as a catalyst is bonded to at least one terminal of the polymer. Here, R 3 is a group having a crosslinkable silyl group.
The metallocene compound used as the polymerization catalyst can be represented by the following formula (1).
さらに、Ｒ1及びＲ2が共同して前記式（１）で表わされる化合物中の２個の５員環を結合していてもよい。また、前記式（１）において、ａ及びｂは、それぞれ独立に、１〜４の整数であり、Ｘは水素原子の少なくとも一部がハロゲン原子で置換されていることもある炭化水素基またはハロゲン原子であり、ｎは０又は金属Ｍの価数−２の整数である。
Further, R 1 and R 2 may be bonded to two 5-membered rings in the compound represented by the formula (1). In the formula (1), a and b are each independently an integer of 1 to 4, and X is a hydrocarbon group or halogen in which at least part of the hydrogen atoms may be substituted with halogen atoms. N is an integer of 0 or the valence-2 of the metal M.
前記メタロセン化合物としては、具体的には、ジシクロペンタジエン−Ｔｉ−ジクロライド、ジシクロペンタジエン−Ｔｉ−ビスフェニル、ジシクロペンタジエン−Ｔｉ−ビス−２，３，４，５，６−ペンタフルオロフェニ−１−イル、ジシクロペンタジエン−Ｔｉ−ビス−２，３，５，６−テトラフルオロフェニ−１−イル、ジシクロペンタジエン−Ｔｉ−ビス−２，５，６−トリフルオロフェニ−１−イル、ジシクロペンタジエン−Ｔｉ−ビス−２，６−ジフルオロフェニ−１−イル、ジシクロペンタジエン−Ｔｉ−ビス−２，４−ジフルオロフェニ−１−イル、ジメチルシクロペンタジエニル−Ｔｉ−ビス−２，３，４，５，６−ペンタフルオロフェニ−１−イル、ジメチルシクロペンタジエニル−Ｔｉ−ビス−２，３，５，６−テトラフルオロフェニ−１−イル、ジメチルシクロペンタジエニル−Ｔｉ−ビス−２，６−ジフルオロフェニ−１−イル、ジメチルシクロペンタジエニル−Ｔｉ−ビス−２，６−ジフルオロ−３−（ピル−１−イル）−フェニ−１−イルのようなチタノセン化合物；ジシクロペンタジエニル−Ｚｒ−ジクロライド、ジシクロペンタジエン−Ｚｒ−ビスフェニル、ジシクロペンタジエン−Ｚｒ−ビス−２，３，４，５，６−ペンタフルオロフェニ−１−イル、ジシクロペンタジエン−Ｚｒ−ビス−２，３，５，６−テトラフルオロフェニ−１−イル、ジシクロペンタジエン−Ｚｒ−ビス−２，５，６−トリフルオロフェニ−１−イル、ジシクロペンタジエン−Ｚｒ−ビス−２，６−ジフルオロフェニ−１−イル、ジシクロペンタジエン−Ｚｒ−ビス−２，４−ジフルオロフェニ−１−イル、ジメチルシクロペンタジエニル−Ｚｒ−ビス−２，３，４，５，６−ペンタフルオロフェニ−１−イル、ジメチルシクロペンタジエニル−Ｚｒ−ビス−２，３，５，６−テトラフルオロフェニ−１−イル、ジメチルシクロペンタジエニル−Ｚｒ−ビス−２，６−ジフルオロフェニ−１−イル、ジメチルシクロペンタジエニル−Ｚｒ−ビス−２，６−ジフルオロ−３−（ピル−１−イル）−フェニ−１−イル）のようなジルコノセン化合物；ジシクロペンタジエニル−Ｖ−クロライド、ビスメチルシクロペンタジエニル−Ｖ−クロライド、ビスペンタメチルシクロペンタジエニル−Ｖ−クロライド、ジシクロペンタジエニル−Ｒｕ−クロライド、ジシクロペンタジエニル−Ｃｒ−クロライドなどを挙げることができる。これらのメタロセン化合物は単独であるいは組み合わせて使用することができる。 Specific examples of the metallocene compound include dicyclopentadiene-Ti-dichloride, dicyclopentadiene-Ti-bisphenyl, dicyclopentadiene-Ti-bis-2,3,4,5,6-pentafluoropheny-. 1-yl, dicyclopentadiene-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadiene-Ti-bis-2,5,6-trifluorophen-1-yl, Dicyclopentadiene-Ti-bis-2,6-difluorophen-1-yl, dicyclopentadiene-Ti-bis-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2, 3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,5,6-teto Fluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluoro-3- (pyr-1 -Yl) -phen-1-yl-like titanocene compounds; dicyclopentadienyl-Zr-dichloride, dicyclopentadiene-Zr-bisphenyl, dicyclopentadiene-Zr-bis-2,3,4,5, 6-pentafluorophen-1-yl, dicyclopentadiene-Zr-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadiene-Zr-bis-2,5,6-trifluoro Pheni-1-yl, dicyclopentadiene-Zr-bis-2,6-difluorophen-1-yl, dicyclopentadiene-Zr-bis 2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis-2 , 3,5,6-tetrafluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis-2,6- Zirconocene compounds such as difluoro-3- (pyr-1-yl) -phen-1-yl); dicyclopentadienyl-V-chloride, bismethylcyclopentadienyl-V-chloride, bispentamethylcyclopenta Examples include dienyl-V-chloride, dicyclopentadienyl-Ru-chloride, and dicyclopentadienyl-Cr-chloride. be able to. These metallocene compounds can be used alone or in combination.
前記メタロセン化合物は、通常の触媒量で使用することができ、具体的には、重合させようとするアクリル系単量体１００質量部に対して、通常は１〜０．００１質量部、好ましくは０．０１〜０．００５質量部の量で使用される。 The metallocene compound can be used in a normal catalytic amount. Specifically, the metallocene compound is usually 1 to 0.001 parts by mass, preferably 100 parts by mass, preferably 100 parts by mass of the acrylic monomer to be polymerized. Used in an amount of 0.01 to 0.005 parts by mass.
また、本発明で前記メタロセン化合物と共に使用されるチオール化合物は、架橋性シリル基を有するチオール化合物であり、通常この架橋性シリル基含有チオール化合物は次の式ＨＳ−Ｒ3で表される化合物である。
ここでＲ3は架橋性シリル基を有する基であり、架橋性シリル基としては、成分（Ａ）の説明において例示した架橋性シリル基を同様に用いることができ、特に、ヒドロキシシリル基、メトキシシリル基、エトキシシリル基、プロポキシシリル基、クロロシリル基及びブロモシリル基よりなる群から選択された少なくとも１種の架橋性シリル基が好ましい。Ｒ3は、具体的には、３−メルカプトプロピル−トリメトキシシラン、３−メルカプトプロピル−トリエトキシシラン、３−メルカプトプロピル−モノメチルジメトキシシラン、３−メルカプトプロピル−モノフェニルジメトキシシラン、３−メルカプトプロピル−ジメチルモノメトキシシラン、３−メルカプトプロピル−モノメチルジエトキシシラン、４−メルカプトブチル−トリメトキシシランおよび３−メルカプトブチル−トリメトキシシラン等を挙げることができる。
Further, thiol compounds for use with the metallocene compound in the present invention is a thiol compound having a crosslinkable silyl group, usually a compound crosslinkable silyl group-containing thiol compound represented by the following formula HS-R 3 is there.
R 3 is a group having a crosslinkable silyl group, and as the crosslinkable silyl group, the crosslinkable silyl groups exemplified in the description of the component (A) can be used in the same manner. Preference is given to at least one crosslinkable silyl group selected from the group consisting of silyl groups, ethoxysilyl groups, propoxysilyl groups, chlorosilyl groups and bromosilyl groups. Specifically, R 3 is 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-mercaptopropyl-monomethyldimethoxysilane, 3-mercaptopropyl-monophenyldimethoxysilane, 3-mercaptopropyl. -Dimethylmonomethoxysilane, 3-mercaptopropyl-monomethyldiethoxysilane, 4-mercaptobutyl-trimethoxysilane, 3-mercaptobutyl-trimethoxysilane and the like.
前記架橋性シリル基含有チオール化合物の使用量は得ようとする重合体の特性を考慮して適宜設定することができる。即ち、反応系における架橋性シリル基含有チオール化合物の濃度が増大すると単位時間あたりの重合率が高くなり、また、到達重合率も高くなる。この際、メタロセン化合物の量が多くなると単位時間あたりの重合率が高くなるが、到達重合率には大きな影響を及ぼさない。また、メタロセン化合物の使用量は、得られる重合体の分子量に対してほとんど影響を与えないが、このメタロセン化合物を使用しないと、反応は有効には進行しない。さらに、チオール化合物の使用量を多くすると重合速度が高くなる。こうした傾向から、本発明の成分（Ｂ）で用いられる触媒において、メタロセン化合物が反応全体において活性化触媒的に作用し、チオール化合物は、重合開始作用がある（重合開始種的に作用する）と考えられる。このように本発明の成分（Ｂ）で用いられる触媒において、架橋性シリル基含有チオール化合物の使用量は、分子量、重合率の律則となっていると考えられる。
従って、架橋性シリル基含有チオール化合物の使用量は、得ようとする重合体の分子量、重合速度等を考慮して適宜設定することができるが、反応を円滑に進め、かつ反応を暴走させないためには、メタロセン化合物と架橋性シリル基含有チオール化合物とは通常は１００：１〜１：５００００の範囲内のモル比、好ましくは１０：１〜１：１００００のモル比で使用される。
The amount of the crosslinkable silyl group-containing thiol compound can be appropriately set in consideration of the characteristics of the polymer to be obtained. That is, when the concentration of the crosslinkable silyl group-containing thiol compound in the reaction system increases, the polymerization rate per unit time increases and the ultimate polymerization rate also increases. At this time, when the amount of the metallocene compound increases, the polymerization rate per unit time increases, but the ultimate polymerization rate is not greatly affected. The amount of the metallocene compound used has little effect on the molecular weight of the polymer obtained, but the reaction does not proceed effectively unless this metallocene compound is used. Furthermore, if the amount of the thiol compound used is increased, the polymerization rate increases. From this tendency, in the catalyst used in the component (B) of the present invention, the metallocene compound acts as an activated catalyst in the entire reaction, and the thiol compound has a polymerization initiating action (acts as a polymerization initiating species). Conceivable. Thus, in the catalyst used in the component (B) of the present invention, the amount of the crosslinkable silyl group-containing thiol compound is considered to be a rule of molecular weight and polymerization rate.
Accordingly, the amount of the crosslinkable silyl group-containing thiol compound can be appropriately set in consideration of the molecular weight of the polymer to be obtained, the polymerization rate, etc., but the reaction proceeds smoothly and does not run away. The metallocene compound and the crosslinkable silyl group-containing thiol compound are usually used in a molar ratio in the range of 100: 1 to 1: 50000, preferably in a molar ratio of 10: 1 to 1: 10000.
なお、この架橋性シリル基含有チオール化合物は、反応開始時に全量添加することもできるし、架橋性シリル基含有チオール化合物を最初に加えて、所望の時間反応させた後、さらに架橋性シリル基含有チオール化合物を追加添加することもできるし、架橋性シリル基含有チオール化合物とアクリル系単量体の両者を追加添加することもできる。このように架橋性シリル基含有チオール化合物の追加添加、あるいは、架橋性シリル基含有チオール化合物とアクリル系単量体との追加添加により、重合率が向上する。 The crosslinkable silyl group-containing thiol compound can be added in its entirety at the start of the reaction, or the crosslinkable silyl group-containing thiol compound is first added and reacted for a desired time. A thiol compound can be additionally added, or both a crosslinkable silyl group-containing thiol compound and an acrylic monomer can be additionally added. Thus, the addition rate of the crosslinkable silyl group-containing thiol compound or the addition of the crosslinkable silyl group-containing thiol compound and the acrylic monomer improves the polymerization rate.
本発明の成分（Ｂ）（メタ）アクリル酸エステル重合体は、前記特定の式（１）で表されるメタロセン化合物と架橋性シリル基含有チオール化合物とを用いてアクリル系単量体を反応させることにより得られるものであるが、この架橋性シリル基含有チオール化合物に加えて、本発明では、さらに、エチルメルカプタン、ブチルメルカプタン、ヘキシルメルカプタン、ターシャリードデシルメルカプタン、ノルマルドデシルメルカプタン、オクチルメルカプタン等のチオール基以外の官能基を有しないアルキルチオール類、フェニルメルカプタン、ベンジルメルカプタン等のチオール基以外の官能基を有しない芳香族系チオール類等のチオール化合物や、β−メルカプトプロピオン酸、メルカプトエタノール，チオフェノールなどのような、チオール基以外にも官能基含有チオール化合物、更には、トリチオグリセリンやペンタエリスリトールをβ−メルカプトプロピオン酸にてエステル化した多官能チオール化合物、また、ポリサルファイド系ポリマーのような活性のチオール基を有すポリマー型チオールを併用することも可能である。 Component (B) (meth) acrylic acid ester polymer of the present invention reacts an acrylic monomer using the metallocene compound represented by the specific formula (1) and a crosslinkable silyl group-containing thiol compound. In addition to the crosslinkable silyl group-containing thiol compound, the present invention further includes thiols such as ethyl mercaptan, butyl mercaptan, hexyl mercaptan, tar-lead decyl mercaptan, normal dodecyl mercaptan, and octyl mercaptan. Thiol compounds such as alkyl thiols having no functional groups other than thiol groups, aromatic mercaptan thiols having no functional groups other than thiol groups such as phenyl mercaptan and benzyl mercaptan, β-mercaptopropionic acid, mercaptoethanol, thiophenol Such as In addition to all groups, there are functional group-containing thiol compounds, polyfunctional thiol compounds obtained by esterifying trithioglycerin and pentaerythritol with β-mercaptopropionic acid, and active thiol groups such as polysulfide polymers. It is also possible to use a polymer type thiol in combination.
さらに、本発明では、重合開始触媒としての前記メタロセン化合物および架橋性シリル基含有チオール化合物以外に、重合速度や重合度を調整することを目的として、ジスルフィド化合物、トリスルフィド化合物、テトラスルフィド化合物を使用することができる。ここで使用することができる重合調整剤として使用されるジスルフィド化合物、トリスルフィド化合物、テトラスルフィド化合物の例としては、ジエチルトリスルフィド、ジブチルテトラスルフィド、ジフェニルジスルフィド、ビス（２−ヒドロキシエチル）ジスルフィド、ビス（４−ヒドロキシブチル）テトラスルフィド、ビス（３−ヒドロキシプロピル）トリスルフィド、ビス（３−カルボキシプロピル）トリスルフィド、ビス（３−カルボキシプロピル）テトラスルフィド、ビス（３−プロピルトリメトキシシラン）ジスルフィド、ビス（３−プロピルトリエトキシシラン）テトラスルフィドなどを挙げることができる。これらのスルフィド化合物は、単独であるいは組み合わせて使用することができる。このようなスルフィド化合物は、本発明の重合において、重合を失活させない程度に使用することができ、具体的には、重合させようとするアクリル系単量体１００質量部に対して、通常は５０〜０質量部、好ましくは２０〜０．００５質量部の量で使用される。 Furthermore, in the present invention, in addition to the metallocene compound and the crosslinkable silyl group-containing thiol compound as the polymerization initiation catalyst, a disulfide compound, a trisulfide compound, or a tetrasulfide compound is used for the purpose of adjusting the polymerization rate and degree of polymerization. can do. Examples of disulfide compounds, trisulfide compounds, and tetrasulfide compounds that can be used here include diethyl trisulfide, dibutyl tetrasulfide, diphenyl disulfide, bis (2-hydroxyethyl) disulfide, bis (4-hydroxybutyl) tetrasulfide, bis (3-hydroxypropyl) trisulfide, bis (3-carboxypropyl) trisulfide, bis (3-carboxypropyl) tetrasulfide, bis (3-propyltrimethoxysilane) disulfide, Examples thereof include bis (3-propyltriethoxysilane) tetrasulfide. These sulfide compounds can be used alone or in combination. In the polymerization of the present invention, such a sulfide compound can be used to such an extent that the polymerization is not deactivated. Specifically, with respect to 100 parts by mass of the acrylic monomer to be polymerized, usually, It is used in an amount of 50 to 0 parts by mass, preferably 20 to 0.005 parts by mass.
本発明の成分（Ｂ）（メタ）アクリル酸エステル重合体を形成する主鎖は、重合性不飽和結合を有するアクリル系単量体を各種重合法により（共）重合させることにより形成される。前記アクリル系単量体としては、アクリル酸ブチル、及びアクリル酸２エチルヘキシルが特に好ましい。前記アクリル系単量体は１種のみ使用してもよく、２種以上、例えば、アクリル酸ブチルとアクリル酸２エチルヘキシル、を併用し、共重合させてもよい。 The main chain forming the component (B) (meth) acrylic acid ester polymer of the present invention is formed by (co) polymerizing acrylic monomers having a polymerizable unsaturated bond by various polymerization methods. As the acrylic monomer, butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. The acrylic monomer may be used alone or in combination of two or more, for example, butyl acrylate and 2-ethylhexyl acrylate.
また、本発明の成分（Ｂ）（メタ）アクリル酸エステル重合体を製造するに際して、架橋性シリル基を有する重合性不飽和単量体を共重合させることができる。該架橋性シリル基としては、成分（Ａ）の説明において例示した架橋性シリル基を同様に用いることができ、特に、ヒドロキシシリル基、メトキシシリル基、エトキシシリル基、プロポキシシリル基、クロロシリル基及びブロモシリル基よりなる群から選択された少なくとも１種の架橋性シリル基が好ましい。 Moreover, when manufacturing the component (B) (meth) acrylic acid ester polymer of this invention, the polymerizable unsaturated monomer which has a crosslinkable silyl group can be copolymerized. As the crosslinkable silyl group, the crosslinkable silyl groups exemplified in the description of the component (A) can be used similarly, and in particular, a hydroxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a chlorosilyl group, and Preference is given to at least one crosslinkable silyl group selected from the group consisting of bromosilyl groups.
前記成分（Ｂ）（メタ）アクリル酸エステル重合体の重量平均分子量（Ｍｗ）は、好ましくは５００以上１００００以下、より好ましくは、５００以上５０００以下である。
前記（Ｂ）（メタ）アクリル酸エステル重合体に含有される架橋性シリル基の数は特に限定されないが、約１個が好ましい。
The component (B) (meth) acrylic acid ester polymer has a weight average molecular weight (Mw) of preferably 500 or more and 10,000 or less, and more preferably 500 or more and 5000 or less.
The number of crosslinkable silyl groups contained in the (B) (meth) acrylic acid ester polymer is not particularly limited, but is preferably about one.
成分（Ｂ）の配合割合は、特に限定はないが、成分（Ａ）１００質量部に対して、０．０１〜１００質量部用いることが好ましい。これらの（メタ）アクリル酸エステル重合体は、単独で使用しても良く、２種以上併用しても良い。 Although the compounding ratio of a component (B) does not have limitation in particular, It is preferable to use 0.01-100 mass parts with respect to 100 mass parts of components (A). These (meth) acrylic acid ester polymers may be used alone or in combination of two or more.
本発明の硬化性組成物は、上記した成分に加えて、必要に応じて、硬化触媒、接着付与剤、物性調整剤、充填剤、可塑剤、揺変剤、脱水剤（保存安定性改良剤）、粘着付与剤、垂れ防止剤、紫外線吸収剤、酸化防止剤、難燃剤、着色剤、ラジカル重合開始剤などの物質やトルエンやアルコール等の各種溶剤を配合してもよく、また相溶する他の重合体をブレンドしてもよい。 In addition to the above-described components, the curable composition of the present invention includes a curing catalyst, an adhesion-imparting agent, a physical property modifier, a filler, a plasticizer, a thixotropic agent, a dehydrating agent (a storage stability improving agent). ), Tackifiers, sag-preventing agents, ultraviolet absorbers, antioxidants, flame retardants, colorants, radical polymerization initiators, and various solvents such as toluene and alcohol may be blended and compatible. Other polymers may be blended.
前記硬化触媒としては、成分（Ａ）に対し硬化触媒の作用を示すものであれば、特に限定されないが、例えば、有機金属化合物やアミン類等が挙げられ、特にシラノール縮合触媒を用いることが好ましい。上記シラノール縮合触媒としては、例えば、スタナスオクトエート、ジブチル錫ジオクトエート、ジブチル錫ジラウレート、ジブチル錫マレエート、ジブチル錫ジアセテート、ジブチル錫ジアセチルアセトナート、ジブチル錫オキサイド、ジブチル錫ビストリエトキシシリケート、ジブチル錫ジステアレート、ジオクチル錫ジラウレート、ジオクチル錫ジバーサテート、オクチル酸錫及びナフテン酸錫等の有機錫化合物；ジブチル錫オキサイドとフタル酸エステルとの反応物等；テトラブチルチタネート、テトラプロピルチタネート等のチタン酸エステル類；アルミニウムトリスアセチルアセトナート、アルミニウムトリスエチルアセトアセテート、ジイソプロポキシアルミニウムエチルアセトアセテート等の有機アルミニウム化合物類；ジルコニウムテトラアセチルアセトナート、チタンテトラアセチルアセトナート等のキレート化合物類；オクチル酸鉛及びナフテン酸鉛等の有機酸鉛；オクチル酸ビスマス、ネオデカン酸ビスマス及びロジン酸ビスマス等の有機酸ビスマス；シラノール縮合触媒として公知のその他の酸性触媒及び塩基性触媒等が挙げられる。 The curing catalyst is not particularly limited as long as it exhibits the action of a curing catalyst on the component (A), and examples thereof include organometallic compounds and amines, and it is particularly preferable to use a silanol condensation catalyst. . Examples of the silanol condensation catalyst include stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate. Organotin compounds such as dioctyltin dilaurate, dioctyltin diversate, tin octylate and tin naphthenate; reactants of dibutyltin oxide and phthalate; titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum Organoaluminum compounds such as trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; Chelate compounds such as Konium tetraacetylacetonate and Titanium tetraacetylacetonate; Organic acid lead such as lead octylate and lead naphthenate; Bismuth acid bismuth, bismuth neodecanoate and bismuth rosinate; Silanol condensation Examples of the catalyst include other known acidic catalysts and basic catalysts.
前記接着付与剤としては、各種シランカップリング剤、例えば、アミノエチルアミノプロピルトリメトキシシラン、アミノエチルアミノプロピルメチルジメトキシシラン、アミノエチルアミノプロピルメチルメトキシシランなどのアミノシラン類、γ−グリシドキシプロピルトリメトキシシランなどのエポキシシラン類、γ−メタクリロキシプロピルトリメトキシシランなどのアクリルシラン類、γ−メルカプトプロピルトリメトキシシランなどのメルカプトシラン類、γ−イソシアネートプロピルトリメトキシシランなどのイソシアネートシラン類などが挙げられる。上記接着付与剤は単独で用いても良く、２種以上併用しても良い。 Examples of the adhesion imparting agent include various silane coupling agents such as aminosilanes such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethylmethoxysilane, and γ-glycidoxypropyltrimethyl. Examples include epoxy silanes such as methoxysilane, acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, and isocyanate silanes such as γ-isocyanatopropyltrimethoxysilane. It is done. The said adhesion grant agent may be used independently and may be used together 2 or more types.
前記物性調整剤は引っ張り物性を改善する目的で添加される。前記物性調整剤の例としては、１分子中にシラノール基を１個有するシリコン化合物があり、例えば、トリフェニルシラノール、トリアルキルシラノール、ジアルキルフェニルシラノール、ジフェニルアルキルシラノール等が挙げられ、その他にも加水分解して１分子中にシラノール基を１個有する化合物を生成するシリコン化合物等の各種シランカップリング剤が挙げられ、例えば、トリフェニルメトキシシラン、トリアルキルメトキシシラン、ジアルキルフェニルメトキシシラン、ジフェニルアルキルメトキシシラン、トリフェニルエトキシシラン、トリアルキルエトキシシラン等が挙げられる。前記物性調整剤は単独で用いても良く、２種以上併用しても良い。 The physical property modifier is added for the purpose of improving the tensile physical properties. Examples of the physical property modifier include a silicon compound having one silanol group in one molecule, and examples thereof include triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, diphenylalkylsilanol, and the like. Various silane coupling agents such as silicon compounds that can be decomposed to produce a compound having one silanol group in one molecule, such as triphenylmethoxysilane, trialkylmethoxysilane, dialkylphenylmethoxysilane, diphenylalkylmethoxy Silane, triphenylethoxysilane, trialkylethoxysilane, etc. are mentioned. The said physical property modifier may be used independently and may be used together 2 or more types.
前記充填剤として、例えば、炭酸カルシウム、炭酸マグネシウム、珪藻土含水ケイ酸、含水けい酸、無水ケイ酸、ケイ酸カルシウム、シリカ、二酸化チタン、クレー、タルク、カーボンブラック、スレート粉、マイカ、カオリン、ゼオライト等が挙げられ、このうち炭酸カルシウムが好ましく、脂肪酸処理炭酸カルシウムがより好ましい。また、ガラスビーズ、シリカビーズ、アルミナビーズ、カーボンビーズ、スチレンビーズ、フェノールビーズ、アクリルビーズ、多孔質シリカ、シラスバルーン、ガラスバルーン、シリカバルーン、サランバルーン、アクリルバルーン等を用いることもでき、これらの中で、組成物の硬化後の伸びの低下が少ない点からアクリルバルーンがより好ましい。前記充填剤は単独で用いても良く、２種以上併用しても良い。 Examples of the filler include calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, and zeolite. Of these, calcium carbonate is preferable, and fatty acid-treated calcium carbonate is more preferable. In addition, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, saran balloons, acrylic balloons, etc. can be used. Among them, an acrylic balloon is more preferable from the viewpoint that the decrease in elongation after curing of the composition is small. The fillers may be used alone or in combination of two or more.
前記可塑剤は硬化後の伸び物性を高めたり、低モジュラス化を可能とする目的で添加される。前記可塑剤として、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；ジオクチルフタレート（ＤＯＰ）、ジブチルフタレート、ブチルベンジルフタレートなどのフタル酸エステル類；グリセリンモノオレイン酸エステル等の脂肪酸一塩基酸エステル類；アジピン酸ジブチル、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等のグリコールエステル類；脂肪族エステル類；エポキシ可塑剤類；ポリエステル系可塑剤；ポリエーテル類；ポリスチレン類などが挙げられる。前記可塑剤は単独で用いても良く、または、２種類以上を併用しても良い。 The plasticizer is added for the purpose of enhancing the elongation physical properties after curing or enabling low modulus. Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate; phthalate esters such as dioctyl phthalate (DOP), dibutyl phthalate and butyl benzyl phthalate; fatty acid monobases such as glycerin monooleate Acid esters; fatty acid dibasic acid esters such as dibutyl adipate and dioctyl adipate; glycol esters such as polypropylene glycol; aliphatic esters; epoxy plasticizers; polyester plasticizers; polyethers; Is mentioned. The plasticizers may be used alone or in combination of two or more.
前記揺変剤としては、例えば、コロイダルシリカ、石綿粉等の無機揺変剤、有機ベントナイト、変性ポリエステルポリオール、脂肪酸アマイド等の有機揺変剤、水添ヒマシ油誘導体、脂肪酸アマイドワックス、ステアリル酸アルミニウム、ステアリル酸バリウム等が挙げられる。前記揺変剤は単独で使用しても良く、または、２種類以上を併用しても良い。 Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide, hydrogenated castor oil derivative, fatty acid amide wax, and aluminum stearylate. And barium stearylate. The thixotropic agent may be used alone or in combination of two or more.
前記脱水剤は保存中における水分を除去する目的で添加される。前記脱水剤として、例えば、ビニルトリメトキシシラン、ジメトルジメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン等のシラン化合物が挙げられる。 The dehydrating agent is added for the purpose of removing moisture during storage. Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimetholdimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.
前記酸化防止剤は、硬化シーリング材の酸化を防止して、耐候性を改善するために使用されるものであり、例えば、ヒンダードアミン系やヒンダードフェノール系の酸化防止剤等が挙げられる。ヒンダードアミン系酸化防止剤としては、例えば、Ｎ，Ｎ′，Ｎ″，Ｎ″′−テトラキス−（４，６−ビス（ブチル−（Ｎ−メチル−２，２，６，６−テトラメチルピペリジン−４−イル）アミノ）−トリアジン−２−イル）−４，７−ジアザデカン−１，１０−ジアミン、ジブチルアミン・１，３，５−トリアジン・Ｎ，Ｎ′−ビス−（２，２，６，６−テトラメチル−４−ピペリジル−１，６−ヘキサメチレンジアミン・Ｎ−（２，２，６，６−テトラメチル−４−ピペリジル）ブチルアミンの重縮合物、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−ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝］、コハク酸ジメチルと４−ヒドロキシ−２，２，６，６−テトラメチル−１−ピペリジンエタノールの重合体、［デカン二酸ビス（２，２，６，６−テトラメチル−１（オクチルオキシ）−４−ピペリジル）エステル、１，１−ジメチルエチルヒドロペルオキシドとオクタンの反応生成物（７０％）］−ポリプロピレン（３０％）、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ブチルマロネート、メチル１，２，２，６，６−ペンタメチル−４−ピペリジルセバケート、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケ−ト、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケ−ト、１−［２−〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ〕エチル］−４−〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ〕−２，２，６，６−テトラメチルピペリジン、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン、８−アセチル−３−ドデシル−７，７，９，９−テトラメチル−１，３，８−トリアザスピロ［４．５］デカン−２，４−ジオンなどが挙げられるが、これらに限定されるものではない。ヒンダードフェノール系酸化防止剤としては、例えば、ペンタエリストール−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、チオジエチレン−ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ′−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニルプロピオアミド］、ベンゼンプロパン酸３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシＣ７−Ｃ９側鎖アルキルエステル、２，４−ジメチル−６−（１−メチルペンタデシル）フェノール、ジエチル［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスホネート、３，３′，３″，５，５′，５″−ヘキサン−ｔｅｒｔ−ブチル−４−ａ，ａ′，ａ″−（メシチレン−２，４，６−トリル）トリ−ｐ−クレゾール、カルシウムジエチルビス［［［３，５−ビス−（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスホネート］、４，６−ビス（オクチルチオメチル）−ｏ−クレゾール、エチレンビス（オキシエチレン）ビス［３−（５−ｔｅｒｔ−ブチル−４−ヒドロキシ−ｍ−トリル）プロピオネート］、ヘキサメチレンビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、１，３，５−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）−１，３，５−トリアジン−２，４，６−（１Ｈ，３Ｈ，５Ｈ）−トリオン、Ｎ−フェニルベンゼンアミンと２，４，４−トリメチルペンテンとの反応生成物、２，６−ジ−ｔｅｒｔ−ブチル−４−（４，６−ビス（オクチルチオ）−１，３，５−トリアジン−２−イルアミノ）フェノールなどが挙げられるが、これらに限定されるものではない。前記酸化防止剤は単独で使用しても良く、または、２種類以上を併用しても良い。 The antioxidant is used to prevent oxidation of the cured sealant and improve weather resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine antioxidant include N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis- (2,2,6 , 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine · N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4- Peridyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis (2,2,6,6-tetramethyl-decanedioic acid) 1 (octyloxy) -4-piperidyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane (70%)]-polypropylene (30%), bis (1,2,2,6,6- Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba Kate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 1- [2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9- Examples include, but are not limited to, tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, etc. Examples of hindered phenol antioxidants include pentane. Erythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5-di-ter t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide), benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4 -Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 5 5 ', 5 "-hexane-tert-butyl-4-a, a', a"-(mesitylene-2,4,6-tolyl) tri-p-cresol, calci Mudiethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzenamine Product of 2,4,4-trimethylpentene with 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5 Triazin-2-ylamino) phenol and the like, but not limited thereto. The antioxidants may be used alone or in combination of two or more.
前記紫外線吸収剤は、硬化シーリング材の光劣化を防止して、耐候性を改善するために使用されるものであり、例えば、ベンゾトリアゾール系、トリアジン系、ベンゾフェノン系、ベンゾエート系等の紫外線吸収剤等が挙げられる。紫外線吸収剤としては、例えば、２，４−ジ−ｔｅｒｔ−ブチル−６−（５−クロロベンゾトリアゾール−２−イル）フェノール、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４，６−ジ−ｔｅｒｔ−ペンチルフェノール、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４−（１，１，３，３−テトラメチルブチル）フェノール、メチル３−（３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート／ポリエチレングリコール３００の反応生成物、２−（２Ｈ−ベンゾトリアゾール−２−イル）−６−（直鎖及び側鎖ドデシル）−４−メチルフェノール等のベンゾトリアゾール系紫外線吸収剤、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［（ヘキシル）オキシ］−フェノール等のトリアジン系紫外線吸収剤、オクタベンゾン等のベンゾフェノン系紫外線吸収剤、２，４−ジ−ｔｅｒｔ−ブチルフェニル−３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンゾエート等のベンゾエート系紫外線吸収剤などが挙げられるが、これらに限定されるものではない。前記紫外線吸収剤は単独で使用してもよく、又は、２種類以上を併用しても良い。 The ultraviolet absorber is used to improve the weather resistance by preventing photodegradation of the cured sealant, for example, an ultraviolet absorber such as benzotriazole, triazine, benzophenone, or benzoate. Etc. Examples of the ultraviolet absorber include 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazole-2) -Yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4 -Benzotriazole ultraviolet absorbers such as methylphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(he Sil) oxy] -phenol and the like triazine ultraviolet absorbers, benzophenone ultraviolet absorbers such as octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. Examples include, but are not limited to, benzoate ultraviolet absorbers. The said ultraviolet absorber may be used independently or may use 2 or more types together.
本発明の硬化性組成物は、塗料密着性、塗料非汚染性などの被塗装性に優れており、シーリング材組成物、パテ組成物及び接着剤組成物の主成分として特に好適に用いられる。 The curable composition of the present invention is excellent in coating properties such as paint adhesion and paint non-contamination, and is particularly suitably used as a main component of a sealing material composition, putty composition and adhesive composition.
以下に実施例をあげて本発明をさらに具体的に説明するが、これらの実施例は例示的に示されるもので限定的に解釈されるべきでないことはいうまでもない。 The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.
［実施例１〜８及び比較例１〜７］
（実施例１）
金属触媒であるメタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でアクリル酸ブチルを重合し、末端に１個の架橋性シリル基を有し、重量平均分子量（Ｍｗ）１３００、ガラス転移温度（Ｔｇ）が−６０℃の重合体Ｂ１を得た。なお、重量平均分子量はゲルパーミエーションクロマトグラフで測定し、ガラス転移温度はＴＭＡ法で測定した。
[Examples 1-8 and Comparative Examples 1-7]
(Example 1)
Ruthenocene dichloride is used as a metallocene compound as a metal catalyst, butyl acrylate is polymerized in the presence of 3-mercaptopropyltrimethoxysilane, has one crosslinkable silyl group at the end, and has a weight average molecular weight (Mw) 1300, a polymer B1 having a glass transition temperature (Tg) of −60 ° C. was obtained. The weight average molecular weight was measured by gel permeation chromatography, and the glass transition temperature was measured by the TMA method.
表１に示すように、成分（Ａ）架橋性シリル基末端含有有機重合体としてＳ２０３Ｈ［（株）カネカ製］、成分（Ｂ）架橋性シリル基含有（メタ）アクリル酸エステル重合体として前記得られた重合体Ｂ１、紫外線吸収剤、可塑剤、脱水処理剤、及び充填材をそれぞれ所定量ずつ仕込み、加熱減圧混合撹拌を行い、配合物質の脱水を行った。さらに、接着付与材及び硬化触媒を所定量ずつ添加し、撹拌配合して硬化性組成物を調整した。 As shown in Table 1, S203H [manufactured by Kaneka Corporation] as the component (A) crosslinkable silyl group terminal-containing organic polymer, and the component (B) obtained as the crosslinkable silyl group-containing (meth) acrylic acid ester polymer. A predetermined amount of each of the obtained polymer B1, ultraviolet absorber, plasticizer, dehydrating agent, and filler was charged, and the mixture was stirred under reduced pressure to dehydrate the compounded material. Furthermore, a predetermined amount of the adhesion-imparting material and the curing catalyst were added and mixed by stirring to prepare a curable composition.
（実施例２）
表１に示した如く、成分（Ａ）架橋性シリル基末端含有有機重合体としてＳ３０３Ｈ［（株）カネカ製］を用いた以外は実施例１と同様に硬化性組成物を調製した。
(Example 2)
As shown in Table 1, a curable composition was prepared in the same manner as in Example 1 except that S303H [manufactured by Kaneka Corporation] was used as the component (A) crosslinkable silyl group-containing organic polymer.
（実施例３）
表１に示した如く、成分（Ｂ）架橋性シリル基含有（メタ）アクリル酸エステル重合体の配合割合を変更した以外は実施例１と同様に硬化性組成物を調製した。
(Example 3)
As shown in Table 1, a curable composition was prepared in the same manner as in Example 1 except that the blending ratio of the component (B) crosslinkable silyl group-containing (meth) acrylic acid ester polymer was changed.
（実施例４）
メタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でアクリル酸ブチルを重合し、末端に１個の架橋性シリル基を有し、Ｍｗ４５００、Ｔｇが−６０℃の重合体Ｂ２を得た。
表１に示した如く、成分（Ｂ）架橋性シリル基含有（メタ）アクリル酸エステル重合体として前記得られた重合体Ｂ２を用いた以外は実施例１と同様に硬化性組成物を調製した。
Example 4
A polymer having ruthenocene dichloride as the metallocene compound, polymerized with butyl acrylate in the presence of 3-mercaptopropyltrimethoxysilane, having one crosslinkable silyl group at the end, Mw 4500, and Tg of −60 ° C. B2 was obtained.
As shown in Table 1, a curable composition was prepared in the same manner as in Example 1 except that the obtained polymer B2 was used as the component (B) crosslinkable silyl group-containing (meth) acrylic acid ester polymer. .
（実施例５）
メタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でアクリル酸ブチルを重合し、末端に１個の架橋性シリル基を有し、Ｍｗ７５００、Ｔｇが−６０℃の重合体Ｂ３を得た。
表１に示した如く、成分（Ｂ）架橋性シリル基含有（メタ）アクリル酸エステル重合体として前記得られた重合体Ｂ３を用いた以外は実施例１と同様に硬化性組成物を調製した。
(Example 5)
Ruthenocene dichloride as a metallocene compound, butyl acrylate is polymerized in the presence of 3-mercaptopropyltrimethoxysilane, a polymer having one crosslinkable silyl group at the end, Mw7500, Tg of −60 ° C. B3 was obtained.
As shown in Table 1, a curable composition was prepared in the same manner as in Example 1 except that the obtained polymer B3 was used as the component (B) crosslinkable silyl group-containing (meth) acrylic acid ester polymer. .
（実施例６）
メタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でアクリル酸ブチルを重合し、末端に１個の架橋性シリル基を有し、Ｍｗ１５０００、Ｔｇが−６０℃の重合体Ｂ４を得た。
表１に示した如く、成分（Ｂ）架橋性シリル基含有（メタ）アクリル酸エステル重合体として前記得られた重合体Ｂ４を用いた以外は実施例１と同様に硬化性組成物を調製した。
(Example 6)
Ruthenocene dichloride is used as the metallocene compound, butyl acrylate is polymerized in the presence of 3-mercaptopropyltrimethoxysilane, a polymer having one crosslinkable silyl group at the end, Mw 15000, and Tg of −60 ° C. B4 was obtained.
As shown in Table 1, a curable composition was prepared in the same manner as in Example 1 except that the obtained polymer B4 was used as the component (B) crosslinkable silyl group-containing (meth) acrylic acid ester polymer. .
（実施例７）
メタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でアクリル酸ブチルを重合し、末端に２個の架橋性シリル基を有し、Ｍｗ７０００、Ｔｇが−６０℃の重合体Ｂ５を得た。
表１に示した如く、成分（Ｂ）架橋性シリル基含有（メタ）アクリル酸エステル重合体として前記得られた重合体Ｂ５を用いた以外は実施例１と同様に硬化性組成物を調製した。
(Example 7)
Ruthenocene dichloride is used as the metallocene compound, butyl acrylate is polymerized in the presence of 3-mercaptopropyltrimethoxysilane, a polymer having two crosslinkable silyl groups at the end, Mw 7000, and Tg of −60 ° C. B5 was obtained.
As shown in Table 1, a curable composition was prepared in the same manner as in Example 1 except that the obtained polymer B5 was used as the component (B) crosslinkable silyl group-containing (meth) acrylic acid ester polymer. .
（実施例８）
メタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でアクリル酸２エチルヘキシルを重合し、末端に１個の架橋性シリル基を有し、Ｍｗ７０００、Ｔｇが−２０℃の重合体Ｂ６を得た。
表１に示した如く、成分（Ｂ）架橋性シリル基含有（メタ）アクリル酸エステル重合体として前記得られた重合体Ｂ６を用いた以外は実施例１と同様に硬化性組成物を調製した。
(Example 8)
Ruthenocene dichloride is used as the metallocene compound, and 2-ethylhexyl acrylate is polymerized in the presence of 3-mercaptopropyltrimethoxysilane, and has one crosslinkable silyl group at the end, Mw 7000, Tg is -20 ° C Combined B6 was obtained.
As shown in Table 1, a curable composition was prepared in the same manner as in Example 1 except that the obtained polymer B6 was used as the component (B) crosslinkable silyl group-containing (meth) acrylate polymer. .
（比較例１）
重合開始剤としてジターシャリーブチルパーオキサイドを用い、γ−メタクリロキシプロピルトリメトキシシランの存在下でアクリル酸ブチルを重合し、分子中に平均して１個の架橋性シリル基を有し、Ｍｗ６０００、Ｔｇが−６０℃の重合体１を得た。
表２に示した如く、成分（Ｂ）を配合せず、前記得られた重合体１を配合した以外は実施例１と同様に硬化性組成物を調製した。
(Comparative Example 1)
Ditertiary butyl peroxide is used as a polymerization initiator, butyl acrylate is polymerized in the presence of γ-methacryloxypropyltrimethoxysilane, and has an average of one crosslinkable silyl group in the molecule, Mw 6000, A polymer 1 having a Tg of −60 ° C. was obtained.
As shown in Table 2, a curable composition was prepared in the same manner as in Example 1 except that the component (B) was not blended and the obtained polymer 1 was blended.
（比較例２）
メタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でステアリルアクリレートを重合し、末端に１個の架橋性シリル基を有し、Ｍｗ６０００、Ｔｇが０℃の重合体２を得た。
表２に示した如く、成分（Ｂ）を配合せず、前記得られた重合体２を配合した以外は実施例１と同様に硬化性組成物を調製した。
(Comparative Example 2)
Using ruthenocene dichloride as the metallocene compound, polymerizing stearyl acrylate in the presence of 3-mercaptopropyltrimethoxysilane, having one crosslinkable silyl group at the end, Mw 6000, and Tg of 0 ° C. Polymer 2 Obtained.
As shown in Table 2, a curable composition was prepared in the same manner as in Example 1 except that the component (B) was not blended and the obtained polymer 2 was blended.
（比較例３）
メタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でアクリル酸メチルを重合し、末端に１個の架橋性シリル基を有し、Ｍｗ５８００、Ｔｇが７℃の重合体３を得た。
表２に示した如く、成分（Ｂ）を配合せず、前記得られた重合体３を配合した以外は実施例１と同様に硬化性組成物を調製した。
(Comparative Example 3)
Polymer 3 in which ruthenocene dichloride is used as the metallocene compound, methyl acrylate is polymerized in the presence of 3-mercaptopropyltrimethoxysilane, has one crosslinkable silyl group at the end, Mw5800, and Tg is 7 ° C. Got.
As shown in Table 2, a curable composition was prepared in the same manner as in Example 1 except that the component (B) was not blended and the obtained polymer 3 was blended.
（比較例４）
メタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でラウリルアクリレートを重合し、末端に１個の架橋性シリル基を有し、Ｍｗ６０００、Ｔｇが１５℃の重合体４を得た。
表２に示した如く、成分（Ｂ）を配合せず、前記得られた重合体４を配合した以外は実施例１と同様に硬化性組成物を調製した。
(Comparative Example 4)
Using ruthenocene dichloride as the metallocene compound, polymerizing lauryl acrylate in the presence of 3-mercaptopropyltrimethoxysilane, having one crosslinkable silyl group at the terminal, Mw 6000, and Tg of 15 ° C. Polymer 4 Obtained.
As shown in Table 2, a curable composition was prepared in the same manner as in Example 1 except that the component (B) was not blended and the obtained polymer 4 was blended.
（比較例５）
メタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でステアリルメタクリレートを重合し、末端に１個の架橋性シリル基を有し、Ｍｗ５２００、Ｔｇが３８℃の重合体５を得た。
表２に示した如く、成分（Ｂ）を配合せず、前記得られた重合体５を配合した以外は実施例１と同様に硬化性組成物を調製した。
(Comparative Example 5)
Ruthenocene dichloride is used as a metallocene compound, stearyl methacrylate is polymerized in the presence of 3-mercaptopropyltrimethoxysilane, one terminal crosslinkable silyl group is present, Mw 5200, and Tg is 38 ° C. Obtained.
As shown in Table 2, a curable composition was prepared in the same manner as in Example 1 except that the component (B) was not blended and the obtained polymer 5 was blended.
（比較例６）
メタロセン化合物としてルテノセンジクロライドを用い、３−メルカプトプロピルトリメトキシシランの存在下でメタクリル酸メチルを重合し、末端に１個の架橋性シリル基を有し、Ｍｗ５０００、Ｔｇが１０５℃の重合体６を得た。
表２に示した如く、成分（Ｂ）を配合せず、前記得られた重合体６を配合した以外は実施例１と同様に硬化性組成物を調製した。
(Comparative Example 6)
Polymer 6 in which ruthenocene dichloride is used as the metallocene compound, methyl methacrylate is polymerized in the presence of 3-mercaptopropyltrimethoxysilane, has one crosslinkable silyl group at the terminal, Mw 5000, and Tg is 105 ° C. Got.
As shown in Table 2, a curable composition was prepared in the same manner as in Example 1 except that the component (B) was not blended and the obtained polymer 6 was blended.
（比較例７）
表２に示した如く、成分（Ｂ）を配合しない点以外は実施例１と同様に硬化性組成物を調製した。
(Comparative Example 7)
As shown in Table 2, a curable composition was prepared in the same manner as in Example 1 except that the component (B) was not blended.
表１及び２における配合物質の配合量は質量部で示され、＊１〜２１は次の通りである。
＊１）重合体Ａ１：（株）カネカ製、商品名「Ｓ２０３Ｈ」（架橋性シリル基末端含有ポリオキシアルキレン系重合体）
＊２）重合体Ａ２：（株）カネカ製、商品名「Ｓ３０３Ｈ」（架橋性シリル基末端含有ポリオキシアルキレン系重合体）
＊３）重合体Ｂ１：メタロセン化合物を用いて得た、末端に架橋性シリル基を１個有するアクリル酸ブチルの重合体、Ｔｇ−６０℃、Ｍｗ１３００。
＊４）重合体Ｂ２：メタロセン化合物を用いて得た、末端に架橋性シリル基を１個有するアクリル酸ブチルの重合体、Ｔｇ−６０℃、Ｍｗ４５００。
＊５）重合体Ｂ３：メタロセン化合物を用いて得た、末端に架橋性シリル基を１個有するアクリル酸ブチルの重合体、Ｔｇ−６０℃、Ｍｗ７５００。
＊６）重合体Ｂ４：メタロセン化合物を用いて得た、末端に架橋性シリル基を１個有するアクリル酸ブチルの重合体、Ｔｇ−６０℃、Ｍｗ１５０００。
＊７）重合体Ｂ５：メタロセン化合物を用いて得た、末端に架橋性シリル基を２個有するアクリル酸ブチルの重合体、Ｔｇ−６０℃、Ｍｗ７０００。
＊８）重合体Ｂ６：メタロセン化合物を用いて得た、末端に架橋性シリル基を１個有するアクリル酸２エチルヘキシルの重合体、Ｔｇ−２０℃、Ｍｗ７０００。
＊９）紫外線吸収剤：旭電化工業（株）製、商品名ＬＡ３６。
＊１０）可塑剤：ＰＰＧ、旭硝子（株）製、商品名ＰＭＬ３０１２。
＊１１）脱水処理剤：ビニルトリエトキシシラン、信越化学工業（株）製、商品名「ＫＢＭ１００３」。
＊１２）充填材１：重質炭酸カルシウム、白石カルシウム工業（株）製、商品名「ホワイトンＳＢ」。
＊１３）充填材２：表面処理炭酸カルシウム、丸尾カルシウム（株）製、商品名「カルファイン５００」。
＊１４）接着付与材：シランカップリング材、信越化学工業（株）製、商品名「ＫＢＭ６０３」。
＊１５）硬化触媒：４価錫、日東化成（株）製、商品名「Ｕ−２２０」。
＊１６）重合体１：１分子中に平均して１個の架橋性シリル基を有するアクリル酸ブチルの重合体、Ｔｇ−６０℃、Ｍｗ５０００。
＊１７）重合体２：メタロセン化合物を用いて得た、末端に架橋性シリル基を１個有するステアリルアクリレートの重合体、Ｔｇ０℃。
＊１８）重合体３：メタロセン化合物を用いて得た、末端に架橋性シリル基を１個有するアクリル酸メチルの重合体、Ｔｇ７℃。
＊１９）重合体４：メタロセン化合物を用いて得た、末端に架橋性シリル基を１個有するラウリルアクリレートの重合体、Ｔｇ１５℃。
＊２０）重合体５：メタロセン化合物を用いて得た、末端に架橋性シリル基を１個有するステアリルメタクリレートの重合体、Ｔｇ３８℃。
＊２１）重合体６：メタロセン化合物を用いて得た、末端に架橋性シリル基を１個有するメタクリル酸メチルの重合体、Ｔｇ１０５℃。
The compounding amounts of the compounding substances in Tables 1 and 2 are shown in parts by mass, and * 1 to 21 are as follows.
* 1) Polymer A1: Product name “S203H” (manufactured by Kaneka Corporation) (crosslinkable silyl group terminal-containing polyoxyalkylene polymer)
* 2) Polymer A2: Product name “S303H” (manufactured by Kaneka Corporation) (crosslinkable silyl group terminal-containing polyoxyalkylene polymer)
* 3) Polymer B1: Polymer of butyl acrylate having one crosslinkable silyl group at the end, obtained using a metallocene compound, Tg-60 ° C., Mw 1300.
* 4) Polymer B2: A polymer of butyl acrylate having one crosslinkable silyl group at the end, obtained using a metallocene compound, Tg-60 ° C., Mw 4500.
* 5) Polymer B3: a polymer of butyl acrylate having one crosslinkable silyl group at the end, obtained using a metallocene compound, Tg-60 ° C., Mw 7500.
* 6) Polymer B4: Polymer of butyl acrylate having one crosslinkable silyl group at the end, obtained using a metallocene compound, Tg-60 ° C., Mw 15000.
* 7) Polymer B5: a polymer of butyl acrylate having two crosslinkable silyl groups at the end, obtained using a metallocene compound, Tg-60 ° C., Mw 7000.
* 8) Polymer B6: a polymer of 2-ethylhexyl acrylate having one crosslinkable silyl group at the end, obtained using a metallocene compound, Tg-20 ° C., Mw 7000.
* 9) Ultraviolet absorber: trade name LA36 manufactured by Asahi Denka Kogyo Co., Ltd.
* 10) Plasticizer: PPG, manufactured by Asahi Glass Co., Ltd., trade name PML3012.
* 11) Dehydration treatment agent: vinyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM1003”.
* 12) Filler 1: Heavy calcium carbonate, manufactured by Shiroishi Calcium Industry Co., Ltd., trade name “Whiteon SB”.
* 13) Filler 2: Surface treated calcium carbonate, manufactured by Maruo Calcium Co., Ltd., trade name “Calfine 500”.
* 14) Adhesion imparting material: Silane coupling material, manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM603”.
* 15) Curing catalyst: Tetravalent tin, manufactured by Nitto Kasei Co., Ltd., trade name “U-220”.
* 16) Polymer 1: 1 A polymer of butyl acrylate having an average of one crosslinkable silyl group in one molecule, Tg-60 ° C., Mw 5000.
* 17) Polymer 2: A stearyl acrylate polymer having one crosslinkable silyl group at the end, obtained using a metallocene compound, Tg 0 ° C.
* 18) Polymer 3: A polymer of methyl acrylate having one crosslinkable silyl group at the end, obtained using a metallocene compound, Tg 7 ° C.
* 19) Polymer 4: A lauryl acrylate polymer having one crosslinkable silyl group at the end, obtained using a metallocene compound, Tg 15 ° C.
* 20) Polymer 5: a polymer of stearyl methacrylate having one crosslinkable silyl group at the end, obtained using a metallocene compound, Tg 38 ° C.
* 21) Polymer 6: Methyl methacrylate polymer having one crosslinkable silyl group at the end, obtained using a metallocene compound, Tg 105 ° C.
前記得られた硬化性組成物を３ｍｍの厚さに延ばし、２３℃５０％相対湿度（ＲＨ）条件下において７日間の養生条件で硬化させた後、硬化物表面に塗料を刷毛で塗布し、２３℃５０％ＲＨの条件下で７日間、養生し、試験体とした。用いた塗料は表３に示したとおりである。 The obtained curable composition is stretched to a thickness of 3 mm, cured under curing conditions of 23 ° C. and 50% relative humidity (RH) for 7 days, and then a paint is applied to the cured product surface with a brush. The specimen was cured for 7 days under conditions of 23 ° C. and 50% RH to obtain a test specimen. The paint used is as shown in Table 3.
１．塗料密着性試験
前記試験体に対し、ニチバン（株）製のセロハンテープを用いて２ｍｍ間隔の碁盤目試験（２５個）を行った。全碁盤目数に対する硬化物表面に残存する碁盤目数の百分率（％）が４０％未満の場合を×、４０％以上８０％未満の場合を○、８０％以上の場合を◎として評価した。結果を表３に示す。
1. Paint Adhesion Test A cross-cut test (25 pieces) at intervals of 2 mm was performed on the test specimen using cellophane tape manufactured by Nichiban Co., Ltd. The case where the percentage (%) of the number of grids remaining on the cured product surface with respect to the total number of grids was less than 40% was evaluated as x, the case of 40% or more and less than 80% was evaluated as ◯, and the case of 80% or more was evaluated as ◎. The results are shown in Table 3.
２．塗料非汚染性試験
ａ）屋外暴露試験
前記試験体に対し、南面４５度で屋外暴露を６ヶ月行い、塗料の汚染の有無を目視にて調べた。全ての塗料に対して汚染がない場合を○、汚染が観察された場合を×として評価した。結果を表３に示した。
ｂ）促進試験
前記試験体を５０℃条件下において７日間、養生し、塗料促進を行った。その後、２３℃５０％ＲＨ条件下に取り出し、２４時間放置後、８号珪砂を塗料表面にふりかけ、１分後に９０°の傾斜により塗料表面の珪砂付着度を確認した。珪砂付着度が１０％未満の場合を○、１０％以上の場合を×として評価した。結果を表３に示した。
2. Paint non-contamination test a) Outdoor exposure test The test specimen was subjected to outdoor exposure at 45 degrees south for 6 months, and the presence or absence of contamination of the paint was visually examined. The case where there was no contamination with respect to all the paints was evaluated as ○, and the case where contamination was observed was evaluated as ×. The results are shown in Table 3.
b) Acceleration Test The test specimen was cured for 7 days under 50 ° C. conditions, and the paint was accelerated. Then, after taking out under conditions of 23 ° C. and 50% RH and leaving for 24 hours, No. 8 silica sand was sprinkled on the paint surface, and after 1 minute, the degree of silica sand adhesion on the paint surface was confirmed by a 90 ° inclination. The case where the silica sand adhesion degree was less than 10% was evaluated as ◯, and the case where it was 10% or more was evaluated as x. The results are shown in Table 3.
水系塗料２：菊水化学工業（株）製、商品名「スーパーＥ」
溶剤系塗料１：エスケー化研（株）製、商品名「ＥＸシーラー」
溶剤系塗料２：菊水化学工業（株）製、商品名「バンノウＳ」
弱溶剤系塗料：エスケー化研（株）製、商品名「クリーンマイルドウレタン」
Water-based paint 2: manufactured by Kikusui Chemical Co., Ltd., trade name “Super E”
Solvent-based paint 1: SK Kaken Co., Ltd., trade name “EX Sealer”
Solvent-based paint 2: manufactured by Kikusui Chemical Co., Ltd., trade name “Vannow S”
Weak solvent paint: SK Chemical Co., Ltd., trade name “Clean Mild Urethane”
表３に示した如く、実施例１〜８の本発明の硬化性組成物は、水系及び溶剤系のいずれの塗料に対しても塗料密着性及び塗料非汚染性に優れていたのに対し、成分（Ｂ）の代わりにメタロセン化合物を用いずに合成された架橋性シリル基含有有機重合体を配合した比較例１、成分（Ｂ）の代わりにガラス転移温度が−１０℃を超える架橋性シリル基含有有機重合体を配合した比較例２〜６、成分（Ｂ）を配合しなかった比較例７では、塗料密着性に問題があった。 As shown in Table 3, the curable compositions of the present invention of Examples 1 to 8 were excellent in paint adhesion and paint non-contamination for both water-based and solvent-based paints, Comparative Example 1 containing a crosslinkable silyl group-containing organic polymer synthesized without using a metallocene compound instead of component (B), and crosslinkable silyl having a glass transition temperature exceeding -10 ° C instead of component (B) In Comparative Examples 2 to 6 in which the group-containing organic polymer was blended and in Comparative Example 7 in which the component (B) was not blended, there was a problem in paint adhesion.
Claims (9)
An adhesive composition comprising the curable composition according to any one of claims 1 to 6 as a main component.
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| JP2013095861A (en) * | 2011-11-01 | 2013-05-20 | Cemedine Co Ltd | Non-solvent one component type moisture curable composition, sealing material made of the composition and solar cell module using the sealing material |
| JP2017160368A (en) * | 2016-03-10 | 2017-09-14 | セメダイン株式会社 | Easily detachable one liquid moisture curable adhesive |
| JP2021152171A (en) * | 2015-09-09 | 2021-09-30 | 綜研化学株式会社 | Method for producing (meth)acrylic polymer having substituent at one end |
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