JP2004124092A - Curable composition - Google Patents
Curable composition Download PDFInfo
- Publication number
- JP2004124092A JP2004124092A JP2003321989A JP2003321989A JP2004124092A JP 2004124092 A JP2004124092 A JP 2004124092A JP 2003321989 A JP2003321989 A JP 2003321989A JP 2003321989 A JP2003321989 A JP 2003321989A JP 2004124092 A JP2004124092 A JP 2004124092A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- acrylate
- curable composition
- group
- crosslinkable silyl
- 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 79
- -1 amine compound Chemical class 0.000 claims abstract description 90
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 45
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229920000620 organic polymer Polymers 0.000 claims abstract description 16
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 60
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 25
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000003860 storage Methods 0.000 abstract description 31
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract 4
- 238000007789 sealing Methods 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 41
- 238000001723 curing Methods 0.000 description 38
- 239000000178 monomer Substances 0.000 description 26
- 239000003566 sealing material Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000004014 plasticizer Substances 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 125000005375 organosiloxane group Chemical group 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000004658 ketimines Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000013008 thixotropic agent Substances 0.000 description 5
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- PJAKWOZHTFWTNF-UHFFFAOYSA-N (2-nonylphenyl) prop-2-enoate Chemical class CCCCCCCCCC1=CC=CC=C1OC(=O)C=C PJAKWOZHTFWTNF-UHFFFAOYSA-N 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 125000002704 decyl group Chemical group [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])* 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 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
- 229920001971 elastomer Polymers 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 125000001400 nonyl 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])[H] 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
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012945 sealing adhesive Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
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- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 238000007665 sagging Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005371 silicon functional group Chemical group 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、硬化性組成物に関し、さらに詳しくは、耐候性及び貯蔵安定性に優れ、貯蔵後の硬化特性の低下を防止し、且つ貯蔵後の耐水接着性が改善された硬化性組成物に関する。 The present invention relates to a curable composition, and more particularly, to a curable composition which has excellent weather resistance and storage stability, prevents deterioration of curing characteristics after storage, and has improved water resistance after storage. .
硬化性組成物は、各種のシーリング材や接着剤等に用いられており、例えば、変性シリコーンポリマーとアルコキシシリル基含有アクリル系ポリマーを主成分とする湿気硬化性組成物等がシーリング材として用いられている。しかしながら、上記組成物を建築用シーリング材や接着剤として使用する場合、柔軟性や作業性を付与するために、DOPやDINP、PPG等の可塑剤を添加して用いられていたが、接着性や耐候性に問題があった。耐候性を向上させるために、特許文献1では、変性シリコーンポリマーとアルコキシシリル基含有アクリル系ポリマーを主成分とし、常温液状の官能基を有さない無溶剤型アクリル系ポリマーを配合した湿気硬化性組成物を提供している。しかしながら、この組成物は、耐候性は向上するが、接着性、特に貯蔵後の耐水接着性に問題が生じる場合があった。 The curable composition is used for various sealing materials and adhesives, and for example, a moisture curable composition mainly containing a modified silicone polymer and an alkoxysilyl group-containing acrylic polymer is used as a sealing material. ing. However, when the above composition is used as a building sealant or an adhesive, a plasticizer such as DOP, DINP, or PPG has been used in order to impart flexibility and workability. And weather resistance. In order to improve the weather resistance, Patent Document 1 discloses a moisture-curing composition containing a modified silicone polymer and an alkoxysilyl group-containing acrylic polymer as main components, and a non-solvent acrylic polymer having no functional group in a liquid state at room temperature. A composition is provided. However, although the composition has improved weather resistance, it sometimes has a problem in adhesion, particularly water resistance after storage.
さらに、上記のような変性シリコーン系組成物を使用する場合、接着性を向上させるために、アミノシラン化合物を添加することが通常行われているが、変性シリコーン化合物とアクリル系ポリマーを含む硬化性組成物や、アルコキシシリル基含有アクリル系ポリマーを含有する硬化性組成物にアミノシラン化合物を添加すると、貯蔵後、硬化速度が遅くなる等、貯蔵後の硬化特性に悪影響が生じるといった問題があった。 Furthermore, when using the modified silicone composition as described above, it is usual to add an aminosilane compound in order to improve adhesion, but a curable composition containing the modified silicone compound and an acrylic polymer is usually used. When an aminosilane compound is added to a product or a curable composition containing an alkoxysilyl group-containing acrylic polymer, there is a problem in that the curing characteristics after storage are adversely affected, such as a decrease in curing speed after storage.
通常、シーリング材等の硬化性組成物は、製造後から使用されるまでの間、長時間保管されることが多く、使用者が該硬化性組成物を用いる際にも製造直後の性能が維持される必要があり、貯蔵後に接着性や硬化特性等の性能が大きく低減することは特に問題となる。
本発明は、シーリング材、接着剤及びコーティング材としての物性を損なうことなく、貯蔵安定性や耐候性に優れ、貯蔵後の硬化特性の低下を防止し且つ貯蔵後の耐水接着性が改善された硬化性組成物を提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention has excellent storage stability and weather resistance without impairing physical properties as a sealing material, an adhesive and a coating material, prevents a decrease in curing properties after storage, and has improved water resistance after storage. It is intended to provide a curable composition.
上記課題を解決するために、本発明の硬化性組成物の第1の態様は、(A)架橋性シリル基含有有機重合体、(B)アクリル系重合体、(C)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物、及び(D)硬化触媒を含有することを特徴とする。 In order to solve the above-mentioned problems, a first embodiment of the curable composition of the present invention comprises reacting (A) a crosslinkable silyl group-containing organic polymer, (B) an acrylic polymer, and (C) water. It is characterized by containing a compound producing an amine compound having at least one alkoxysilyl group in one molecule, and (D) a curing catalyst.
本発明の硬化性組成物の第2の態様は、(A)架橋性シリル基含有有機重合体、(B)アクリル系重合体、(C1)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物、(C2)カルボニル化合物、及び(D)硬化触媒を含有することを特徴とする。 The second embodiment of the curable composition of the present invention comprises (A) a crosslinkable silyl group-containing organic polymer, (B) an acrylic polymer, and (C1) at least one alkoxy group in one molecule by reacting with water. It is characterized by containing an amine compound having a silyl group, a (C2) carbonyl compound, and (D) a curing catalyst.
上記成分(A)として、架橋性シリル基含有ポリオキシアルキレン系重合体、架橋性シリル基含有アクリル変性ポリオキシアルキレン系重合体、及び/又は架橋性シリル基含有メタクリル変性ポリオキシアルキレン系重合体を用いることが好適である。 As the component (A), a crosslinkable silyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing acryl-modified polyoxyalkylene polymer, and / or a crosslinkable silyl group-containing methacryl-modified polyoxyalkylene polymer are used. It is preferred to use.
上記成分(A)として、(A1)架橋性シリル基含有アクリル系重合体を用いることにより、耐候性をより向上させることができ好ましい。 候 It is preferable to use (A1) a crosslinkable silyl group-containing acrylic polymer as the component (A) because the weather resistance can be further improved.
上記成分(B)として、(メタ)アクリル酸エステル−フルオロオレフィン共重合体を用いることが好適である。 と し て It is preferable to use a (meth) acrylate-fluoroolefin copolymer as the component (B).
本発明の硬化性組成物の第3の態様は、(A1)架橋性シリル基含有アクリル系重合体、(C)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物、及び(D)硬化触媒を含有することを特徴とする。 The third embodiment of the curable composition of the present invention comprises (A1) a crosslinkable silyl group-containing acrylic polymer, and (C) an amine compound having at least one alkoxysilyl group in one molecule by reacting with water. It contains a compound to be produced and (D) a curing catalyst.
本発明の硬化性組成物の第4の態様は、(A1)架橋性シリル基含有アクリル系重合体、(C1)一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物、(C2)カルボニル化合物、及び(D)硬化触媒を含有することを特徴とする。 A fourth embodiment of the curable composition of the present invention includes (A1) a crosslinkable silyl group-containing acrylic polymer, (C1) an amine compound having at least one alkoxysilyl group in one molecule, and (C2) a carbonyl compound. , And (D) a curing catalyst.
上記硬化性組成物の第1〜第4の態様に、(E)エポキシ樹脂をさらに添加することが、耐水性を向上させることができ好適である。 さ ら に It is preferable to further add (E) an epoxy resin to the first to fourth aspects of the curable composition because the water resistance can be improved.
本発明によれば、作業性や耐久性などのシーリング材、接着剤及びコーティング材として必要な物性を損なうことなく、貯蔵安定性や耐候性に優れ、貯蔵後の硬化特性の低下を防止し且つ貯蔵後の耐水接着性が改善された硬化性組成物を提供することができる。 According to the present invention, without impairing physical properties required as a sealing material such as workability and durability, an adhesive and a coating material, excellent storage stability and weather resistance, preventing a decrease in curing characteristics after storage, and A curable composition having improved water resistance after storage can be provided.
以下に本発明の実施の形態を説明するが、これらの実施の形態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 embodiments are illustratively shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.
本発明の硬化性組成物の第1の態様は、下記成分(A)、(B)、(C)及び(D)を含有する硬化性組成物である。
(A)架橋性シリル基含有有機重合体
(B)アクリル系重合体
(C)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物
(D)硬化触媒
A first embodiment of the curable composition of the present invention is a curable composition containing the following components (A), (B), (C) and (D).
(A) a crosslinkable silyl group-containing organic polymer (B) an acrylic polymer (C) a compound which reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule (D) a curing catalyst
本発明の硬化性組成物により、貯蔵後の硬化特性の低下を防止し、且つ貯蔵後の耐水接着性を改善することができる。なお、本発明において、貯蔵後の硬化速度、硬化物の硬さ及び厚み等の硬化特性の悪化を硬化特性の低下と称す。 (4) The curable composition of the present invention can prevent a decrease in curing characteristics after storage and can improve water resistance after storage. In the present invention, the deterioration of the curing characteristics such as the curing speed after storage and the hardness and thickness of the cured product is referred to as the deterioration of the curing characteristics.
本発明においては、(A)成分として用いられる架橋性シリル基含有有機重合体としては、従来公知のものを広く使用でき、分子内に、シロキサン結合を形成することによって架橋してゴム状硬化物を形成する、シリル基を1個以上含有する有機重合体であれば、特に限定されない。このような架橋性シリル基含有有機重合体(A)としては、例えば、特許文献2〜14中に開示されているものを挙げることができる。上記架橋性シリル基含有有機重合体(A)としては具体的には、分子内に1個以上の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、アクリル酸エステル重合体、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。架橋性シリル基は、シーリング材の硬化性や硬化後の物性等の点から、分子内に1〜5個含まれるのが好ましい。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(1)で示されるものが好ましい。 In the present invention, as the crosslinkable silyl group-containing organic polymer used as the component (A), conventionally known crosslinkable organic polymers can be widely used, and a rubber-like cured product which is crosslinked by forming a siloxane bond in the molecule is formed. Is not particularly limited as long as it is an organic polymer containing one or more silyl groups. Examples of such a crosslinkable silyl group-containing organic polymer (A) include those disclosed in Patent Documents 2 to 14. Specific examples of the crosslinkable silyl group-containing organic polymer (A) include a polyoxy group containing one or more crosslinkable silyl groups in the molecule, and a main chain each of which may contain an organosiloxane. Examples thereof include an alkylene polymer, a vinyl-modified polyoxyalkylene polymer, a vinyl polymer, a polyester polymer, an acrylate polymer, a methacrylate polymer, and copolymers and mixtures thereof. It is preferable that 1 to 5 crosslinkable silyl groups be contained in the molecule from the viewpoint of the curability of the sealing material, the physical properties after curing, and the like. Further, the crosslinkable silyl group is preferably a compound represented by the following general formula (1), which is easily crosslinked and easily produced.
(式中、R1は炭化水素基であり、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。Xで示される反応性基はハロゲン原子、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より選ばれる基であり、Xが複数の場合には、Xは同じ基であっても異なった基であってもよい。このうちXはアルコキシ基が好ましく、メトキシ基が最も好ましい。aは0、1又は2の整数であり、1が最も好ましい。) (Wherein, R 1 is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group shown is a group selected from a halogen atom, a hydrogen 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, and In the case of X, X may be the same or different groups, among which X is preferably an alkoxy group, most preferably a methoxy group, a is an integer of 0, 1 or 2, and 1 Is most preferred.)
架橋性シリル基含有有機重合体(A)の主鎖は、硬化後の引張接着性、モジュラス等の物性の点から、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及び/又はビニル変性ポリオキシアルキレン系重合体が好ましい。特に、成分(A)として、分子内に1個以上の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、アクリル変性ポリオキシアルキレン系重合体、及び/又はメタクリル変性ポリオキシアルキレン系重合体、並びにこれらの混合物が好ましく、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、ポリオキシプロピレン系重合体、アクリル変性ポリオキシプロピレン系重合体、及び/又はメタクリル変性ポリオキシプロピレン系重合体であるものが更に好ましい。 The main chain of the crosslinkable silyl group-containing organic polymer (A) may be a polyoxyalkylene polymer and / or a polyoxyalkylene polymer, which may contain an organosiloxane, from the viewpoint of physical properties such as tensile adhesion and modulus after curing. Vinyl-modified polyoxyalkylene polymers are preferred. In particular, as the component (A), a polyoxyalkylene-based polymer or an acryl-modified polyoxyalkylene-based polymer containing one or more crosslinkable silyl groups in the molecule and whose main chains may each contain an organosiloxane. A polymer and / or a methacryl-modified polyoxyalkylene polymer and a mixture thereof are preferable, and a polyoxypropylene polymer and an acryl-modified polyoxypropylene polymer whose main chains may each contain an organosiloxane. Those which are coalesced and / or methacryl-modified polyoxypropylene-based polymers are more preferred.
前記の分子内に1個以上の架橋性シリル基を含有する、オルガノシロキサンを含有していてもよいビニル変性ポリオキシアルキレン系重合体は、分子内に1個以上の架橋性シリル基を含有する、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の存在下で、ラジカル重合開始剤の添加あるいは紫外線照射などの通常のラジカル重合方法により、1種又は2種以上のビニル系単量体を重合させる等して得ることができる(特許文献15及び特許文献16等が参考として挙げられるが、これらに限定されるものではない)。 The above-mentioned vinyl-modified polyoxyalkylene-based polymer containing one or more crosslinkable silyl groups in the molecule and optionally containing an organosiloxane contains one or more crosslinkable silyl groups in the molecule. In the presence of a polyoxyalkylene polymer which may contain an organosiloxane, one or more vinyl monomers may be added by a conventional radical polymerization method such as addition of a radical polymerization initiator or ultraviolet irradiation. It can be obtained by polymerizing the product (Patent Documents 15 and 16 and the like are cited as reference, but are not limited thereto).
ビニル系単量体としては、分子内に1個以上の重合性不飽和結合を有する化合物であって、例えば、エチレン、プロピレン、イソブチレン、ブタジエン、クロロプレン、塩化ビニル、塩化ビニリデン、アクリル酸、メタクリル酸、酢酸ビニル、アクリロニトリル、スチレン、クロルスチレン、2−メチルスチレン、ジビニルベンゼン、アクリル酸メチル、アクリル酸エチル、アクリル酸イソブチル、アクリル酸2−エチルヘキシル、アクリル酸2−ヒドロキシエチル、アクリル酸ベンジル、グリシジルアクリレート、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソブチル、メタクリル酸2−エチルヘキシル、メタクリル酸2−ヒドロキシエチル、メタクリル酸ベンジル、グリシジルメタクリレート、アクリルアミド、メタクリルアミド、n−メチロールアクリルアミド、エトキシ化フェノールアクリレート、エトキシ化パラクミルフェノールアクリレート、エトキシ化ノニルフェノールアクリレート、プロポキシ化ノニルフェノールアクリレート、2−エチルヘキシルカルビトールアクリレート、N−ビニル−2−ピロリドン、イソボルニルアクリレート、エトキシ化ビスフェノールFジアクリレート、エトキシ化ビスフェノールAジアクリレート、エトキシ化イソシアヌル酸ジアクリレート、トリプロピレングリコールジアクリレート、ペンタエリスリトールジアクリレートモノステアレート、ポリエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート、エトキシ化イソシアヌル酸トリアクリレート、プロポキシ化トリメチロールプロパントリアクリレート、エトキシ化トリメチロールプロパントリアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、ジトリメチロールプロパンテトラアクリレート、ペンタエリスリトールテトラアクリレート、ポリウレタンジアクリレート、ω−カルボキシ−ポリカプロラクトンモノアクリレート、フタル酸モノヒドロキシエチルアクリレート、アクリル酸ダイマー、2−ヒドロキシ−3−フェノキシプロピルアクリレート、ポリエステルポリアクリレート、1,6−ヘキサンジオールジアクリレート、2−(2−エトキシエトキシ)エチルアクリレート、ステアリルアクリレート、テトラヒドロフルフリルアクリレート、ラウリルアクリレート、2−フェノキシアクリレート、イソデシルアクリレート、イソオクチルアクリレート、トリデシルアクリレート、カプロラクトンアクリレート、ジンクジアクリレート、1,3−ブタンジオールジアクリレート、1,4−ブタンジオールジアクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、プロポキシ化ネオペンチルグリコールジアクリレート、プロポキシ化グリセリントリアクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、ペンタアクリレートエステル、テトラヒドロフルフリルメタクリレート、シクロヘキシルメタクリレート、イソデシルメタクリレート、ラウリルメタクリレート、ポリプロピレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、エチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、1,4−ブタンジオールジメタクリレート、ジエチレングリコールジメタクリレート、1,6−ヘキサンジオールジメタクリレート、ネオペンチルグリコールジメタクリレート、1,3−ブタンジオールジメタクリレート、エトキシ化ビスフェノールAジメタクリレート、ジンクジメタクリレート、トリメチロールプロパントリメタクリレート、また、次の化学式(2)〜(25)で示される各化合物などが挙げられるが、これらに限定されるものではない。 The vinyl monomer is a compound having one or more polymerizable unsaturated bonds in the molecule, for example, ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid , Vinyl acetate, acrylonitrile, styrene, chlorostyrene, 2-methylstyrene, divinylbenzene, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, glycidyl acrylate , Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, glycidyl methacrylate, acrylamide, methacrylic acid Amide, n-methylol acrylamide, ethoxylated phenol acrylate, ethoxylated paracumyl phenol acrylate, ethoxylated nonyl phenol acrylate, propoxylated nonyl phenol acrylate, 2-ethylhexyl carbitol acrylate, N-vinyl-2-pyrrolidone, isobornyl acrylate, ethoxy Bisphenol F diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated isocyanuric acid diacrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate monostearate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, triacrylate Methylol propantria crele G, ethoxylated isocyanuric acid triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, polyurethane diacrylate Acrylate, ω-carboxy-polycaprolactone monoacrylate, monohydroxyethyl phthalate acrylate, dimer acrylic acid, 2-hydroxy-3-phenoxypropyl acrylate, polyester polyacrylate, 1,6-hexanediol diacrylate, 2- (2- Ethoxyethoxy) ethyl acrylate, stearyl acrylate, tetrahydroph Furyl acrylate, lauryl acrylate, 2-phenoxy acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone acrylate, zinc diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate Acrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, propoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate, pentaacrylate ester, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate , Lauryl methacryle G, polypropylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate , Neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, zinc dimethacrylate, trimethylolpropane trimethacrylate, and compounds represented by the following chemical formulas (2) to (25) And the like, but are not limited thereto.
ビニル系単量体は、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100重量部に対して、0.1〜1000重量部、更には1〜200重量部の範囲で使用するのが好ましい。なお、分子内に1個以上の架橋性シリル基を含有する、オルガノシロキサンを含有していてもよいビニル変性ポリオキシアルキレン系重合体としては、分子内に1個以上の架橋性シリル基を含有する、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と、前記ビニル系単量体の1種以上を重合して得られる重合体に架橋性シリル基を導入して得られる、架橋性シリル基含有ビニル系重合体とをブレンドしたものを使用することもできる。 The vinyl monomer is used in an amount of 0.1 to 1000 parts by weight, more preferably 1 to 200 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer which may contain an organosiloxane. Is preferred. The vinyl-modified polyoxyalkylene polymer having one or more crosslinkable silyl groups in the molecule and optionally containing the organosiloxane includes one or more crosslinkable silyl groups in the molecule. A polyoxyalkylene polymer which may contain an organosiloxane and a polymer obtained by polymerizing at least one of the vinyl monomers, and a crosslinkable polymer obtained by introducing a crosslinkable silyl group into the polymer. What blended with the hydrophilic silyl group-containing vinyl polymer can also be used.
また、成分(A)として(A1)架橋性シリル基含有アクリル系重合体を用いることにより、耐候性が向上し、好適である。(A1)架橋性シリル基含有アクリル系重合体としては、従来公知のものを広く使用でき、特に限定されないが、例えば、特許文献12及び17〜24中に開示されているものを挙げることができる。具体的には、分子内に1個以上の架橋性シリル基を有し、それぞれオルガノシロキサンを含有していてもよい、主鎖が本質的に(メタ)アクリル酸、(メタ)アクリル酸エステル、(メタ)アクリロニトリル、(メタ)アクリルアミド等のアクリル系単量体の1種以上を(共)重合して得られる重合体である化合物やそれらの混合物を主成分とする組成物が挙げられる。上記アクリル系単量体としては、特に限定されないが、(メタ)アクリル酸エステルが好ましい。 候 Also, by using (A1) a crosslinkable silyl group-containing acrylic polymer as the component (A), the weather resistance is improved, which is preferable. (A1) As the crosslinkable silyl group-containing acrylic polymer, conventionally known ones can be widely used and are not particularly limited, and examples thereof include those disclosed in Patent Documents 12 and 17 to 24. . Specifically, the main chain is essentially (meth) acrylic acid, (meth) acrylate, having one or more crosslinkable silyl groups in the molecule, each of which may contain an organosiloxane. Examples of the composition include a compound which is a polymer obtained by (co) polymerizing one or more acrylic monomers such as (meth) acrylonitrile and (meth) acrylamide, and a composition mainly containing a mixture thereof. The acrylic monomer is not particularly limited, but is preferably a (meth) acrylate.
上記アクリル酸エステルとしては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸−n−プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸−n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s−ブチル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸−n−ペンチル、(メタ)アクリル酸ネオペンチル、(メタ)アクリル酸−n−ヘキシル、(メタ)アクリル酸−n−ヘプチル、(メタ)アクリル酸−n−オクチル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸ノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸トリデシルおよび(メタ)アクリル酸ステアリル等の(メタ)アクリル酸アルキル;(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸イソボルニルおよび(メタ)アクリル酸トリシクロデシニル等のアクリル酸脂環式アルキル;(メタ)アクリル酸フェニル、(メタ)アクリル酸トルイル及び(メタ)アクリル酸ベンジル等の芳香族アクリル酸エステル類、(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸ヒドロキシブチル、(メタ)アクリル酸ヒドロキシプロピルおよび(メタ)アクリル酸ヒドロキシエチルのε−カプロラクトン付加反応物等の(メタ)アクリル酸ヒドロキシアルキル;(メタ)アクリル酸2−メトキシエチル、(メタ)アクリル酸3−メトキシブチル、(メタ)アクリル酸2−アミノエチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸クロロエチル、(メタ)アクリル酸トリフルオロエチル、(メタ)アクリル酸トリフルオロメチルメチル、および(メタ)アクリル酸テトラヒドロフルフリル等のヘテロ原子含有アクリル酸エステル類が挙げられるが、これらに限らない。また、これらの中の1種類または2種類以上を併用してもよい。上記(メタ)アクリル酸エステルの中でも、ガラス転移温度が低い重合体が得られるという理由から、アクリル酸ブチル、アクリル酸2−エチルヘキシルおよびアクリル酸2−メトキシエチルが好ましい。 Examples of the acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, -n- (meth) acrylate Hexyl, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic acid Isodecyl, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate and (meth) Alkyl (meth) acrylates such as stearyl acrylate; cycloaliphatic alkyl acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecynyl (meth) acrylate; phenyl (meth) acrylate , Aromatic acrylates such as toluyl (meth) acrylate and benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate and (meth) Hydroxyalkyl (meth) acrylate such as ε-caprolactone addition product of hydroxyethyl acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-aminoethyl (meth) acrylate , Dimethyl amide (meth) acrylate Heteroatom-containing acrylates such as noethyl, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate, trifluoromethylmethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. However, it is not limited to these. One or more of these may be used in combination. Among the above (meth) acrylates, butyl acrylate, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate are preferred because a polymer having a low glass transition temperature can be obtained.
なお、成分(A1)として、上記アクリル系単量体以外にこれと共重合可能な単量体を共重合させることも可能である。共重合可能な単量体としては、特に限定されないが、例えば、フルオロオレフィン類、α−オレフィン類、ビニルエステル類およびビニルエーテル類などのビニル系単量体が挙げられる。また、成分(A1)として、上記架橋性シリル基含有アクリル系重合体と他の重合体、例えば、上記したような架橋性シリル基含有ポリオキシアルキレン重合体や架橋性シリル基含有ビニル変性ポリオキシアルキレン重合体等、との混合物を用いることも可能であり、本発明に含まれる。架橋性シリル基含有アクリル系重合体と他の重合体との混合物を用いる場合、混合物中の架橋性シリル基含有アクリル系重合体の配合割合が30質量%以上であることが好ましい。 As the component (A1), it is also possible to copolymerize a monomer copolymerizable therewith in addition to the acrylic monomer. Examples of the copolymerizable monomer include, but are not particularly limited to, vinyl monomers such as fluoroolefins, α-olefins, vinyl esters, and vinyl ethers. As the component (A1), the crosslinkable silyl group-containing acrylic polymer and another polymer such as the crosslinkable silyl group-containing polyoxyalkylene polymer and the crosslinkable silyl group-containing vinyl-modified polyoxy as described above. It is also possible to use a mixture with an alkylene polymer or the like, which is included in the present invention. When a mixture of a crosslinkable silyl group-containing acrylic polymer and another polymer is used, the blending ratio of the crosslinkable silyl group-containing acrylic polymer in the mixture is preferably 30% by mass or more.
本発明において、上記架橋性シリル基含有有機重合体(A)の数平均分子量は1000以上、特に6000〜30000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。上記成分(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 present invention, the crosslinkable silyl group-containing organic polymer (A) having a number average molecular weight of 1,000 or more, particularly 6,000 to 30,000, and having a narrow molecular weight distribution is easy to handle because the viscosity before curing is low, and the strength after curing. Physical properties such as elongation, modulus and the like are suitable. The above component (A) may be used alone or in combination of two or more.
本発明において、上記(B)アクリル系重合体を含有させることにより、耐候性が向上する。上記成分(B)は、可塑剤として使用することもできる。成分(B)として用いられるアクリル系重合体としては、従来公知のものを広く使用でき、(メタ)アクリル酸、(メタ)アクリル酸エステル、(メタ)アクリロニトリル、(メタ)アクリルアミド等のアクリル系単量体から選ばれる1種以上を重合させたアクリル系(共)重合体であれば、特に限定されないが、好ましい例として、(メタ)アクリル酸エステル単量体を主成分としたものであり、エステル部分の炭素数が1〜20の(メタ)アクリル酸エステルが挙げられる。例えば、成分(A1)において上述したような(メタ)アクリル酸エステル単量体が挙げられるがこれらに限定されない。 候 In the present invention, by containing the acrylic polymer (B), the weather resistance is improved. The above component (B) can also be used as a plasticizer. As the acrylic polymer used as the component (B), conventionally known polymers can be widely used, and acrylic polymers such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, and (meth) acrylamide can be used. It is not particularly limited as long as it is an acrylic (co) polymer obtained by polymerizing one or more kinds selected from monomers, and as a preferred example, a (meth) acrylic acid ester monomer as a main component, (Meth) acrylic acid esters having 1 to 20 carbon atoms in the ester portion are exemplified. Examples include, but are not limited to, the (meth) acrylate monomers described above in component (A1).
アクリル系重合体(B)は、架橋性シリル基を含有していなくても架橋性シリル基を含有していてもよく、特に限定されないが、架橋性シリル基を含有しているものは、1分子中に平均して0.05個以上2.0個以下が好ましく、0.1個以上1.0個以下が特に好ましい。架橋性シリル基を有するアクリル系重合体としては、特に限定されないが、例えば、特許文献28及び特許文献29中に開示されているものが挙げられる。 The acrylic polymer (B) may not contain a crosslinkable silyl group or may contain a crosslinkable silyl group, and is not particularly limited. On average, the number is preferably 0.05 or more and 2.0 or less, more preferably 0.1 or more and 1.0 or less in the molecule. The acrylic polymer having a crosslinkable silyl group is not particularly limited, and examples thereof include those disclosed in Patent Documents 28 and 29.
また、アクリル系重合体(B)には、上記アクリル系単量体以外にこれと共重合可能な単量体を共重合させることも可能である。共重合可能な単量体としては、例えば、フルオロオレフィン類、α−オレフィン類、ビニルエステル類およびビニルエーテル類などのビニル系単量体が挙げられる。特に、(メタ)アクリル酸エステル単量体とフルオロオレフィン単量体を主構成単量体とする(メタ)アクリル酸エステル−フルオロオレフィン共重合体が好適に用いられる。(メタ)アクリル酸エステル−フルオロオレフィン共重合体としては、従来公知のものを広く使用でき、例えば、特許文献23〜27中に開示されているものを挙げることができる。フルオロオレフィン単量体としては、例えば、テトラフルオロエチレン、クロロトリフルオロエチレン、ヘキサフルオロプロピレン、ジクロロジフルオロエチレン、トリフルオロエチレン、フッ化ビニリデン、フッ化ビニルおよびパーフルオロ(アルキルビニルエーテル)等が挙げられ、これらの中でも、重合性の面よりテトラフルオロエチレン、クロロトリフルオロエチレン、ヘキサフルオロプロピレン及びトリフルオロエチレンが好ましく、更に好ましくはテトラフルオロエチレン、クロロトリフルオロエチレン及びトリフルオロエチレンである。 In addition, the acrylic polymer (B) may be copolymerized with a monomer copolymerizable therewith, in addition to the acrylic monomer. Examples of the copolymerizable monomer include vinyl monomers such as fluoroolefins, α-olefins, vinyl esters, and vinyl ethers. In particular, a (meth) acrylate-fluoroolefin copolymer containing a (meth) acrylate monomer and a fluoroolefin monomer as main constituent monomers is preferably used. As the (meth) acrylate-fluoroolefin copolymer, conventionally known ones can be widely used, and examples thereof include those disclosed in Patent Documents 23 to 27. Examples of the fluoroolefin monomer include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, dichlorodifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, and perfluoro (alkyl vinyl ether). Among these, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and trifluoroethylene are preferred from the viewpoint of polymerizability, and more preferred are tetrafluoroethylene, chlorotrifluoroethylene and trifluoroethylene.
上記アクリル系重合体(B)は、水性媒体中での懸濁重合や乳化重合、有機溶剤中での溶液重合、或いは塊状重合など通常の方法で製造することができる。有機溶剤としては、通常用いられるものが使用でき、例えば、テトラヒドロフランおよびジオキサン等の環状エーテル類;ベンゼン、トルエンおよびキシレン等の芳香族炭化水素化合物;酢酸エチルおよび酢酸ブチル等のエステル類;アセトン、メチルエチルケトンおよびシクロヘキサノン等のケトン類;メタノール、エタノールおよびイソプロパノール等のアルコール類等が挙げられ、これらの1種または2種以上を用いることができる。 The acrylic polymer (B) can be produced by a usual method such as suspension polymerization or emulsion polymerization in an aqueous medium, solution polymerization in an organic solvent, or bulk polymerization. As the organic solvent, commonly used organic solvents can be used, for example, cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone And ketones such as cyclohexanone; alcohols such as methanol, ethanol and isopropanol; and one or more of these can be used.
上記重合に用いるラジカル発生型重合開始剤としては、ジイソプロピルパーオキシジカーボネート、ターシャリーブチルパーオキシピバレート、ベンゾイルパーオキサイド、ラウロイルパーオキサイドおよびジターシャリーブチルパーオキサイド等の過酸化物、またはアゾビスイソブチロニトリル、アゾビスイソバレロニトリル等のアゾ化合物、過硫酸アンモニウム、過硫酸カリウム等の無機過酸化物が使用できる。また、連鎖移動剤は耐候性の低下につながるため、使用しないことが好ましい。 Examples of the radical-generating polymerization initiator used in the polymerization include peroxides such as diisopropyl peroxydicarbonate, tertiary butyl peroxypivalate, benzoyl peroxide, lauroyl peroxide, and ditertiary butyl peroxide, or azobisisopropane. Azo compounds such as butyronitrile and azobisisovaleronitrile, and inorganic peroxides such as ammonium persulfate and potassium persulfate can be used. It is preferable not to use a chain transfer agent because it leads to a decrease in weather resistance.
上記重合は、重合温度が20℃〜350℃、好ましくは150℃〜350℃、圧力が常圧〜10MPaで行い、加圧の場合は耐圧オートクレーブを用い、5分〜20時間の反応時間で行うことができる。重合方法はバッチ重合、セミバッチ重合、或いは連続重合でもよい。 The above polymerization is carried out at a polymerization temperature of 20 ° C. to 350 ° C., preferably 150 ° C. to 350 ° C., at a pressure of normal pressure to 10 MPa, and in the case of pressurization, using a pressure resistant autoclave for a reaction time of 5 minutes to 20 hours. be able to. The polymerization method may be batch polymerization, semi-batch polymerization, or continuous polymerization.
上記アクリル系重合体(B)のガラス転移温度は10℃以下が好ましく、より好ましくは0℃以下、さらにより好ましくは−10℃以下である。また、重量平均分子量は500以上20,000以下が好ましく、700以上10,000以下であることがより好ましい。ガラス転移温度が10℃より高いと、低温における作業性が悪くなる。また、重量平均分子量が20,000を越えると、十分な可塑性が発現されないため作業性が悪くなり、一方、500未満であると、低分子の重合体がブリードするため汚染性が低下する。 ガ ラ ス The glass transition temperature of the acrylic polymer (B) is preferably 10 ° C or lower, more preferably 0 ° C or lower, and even more preferably -10 ° C or lower. Further, the weight average molecular weight is preferably 500 or more and 20,000 or less, more preferably 700 or more and 10,000 or less. When the glass transition temperature is higher than 10 ° C., workability at a low temperature deteriorates. On the other hand, if the weight average molecular weight exceeds 20,000, sufficient plasticity will not be exhibited, resulting in poor workability. On the other hand, if the weight average molecular weight is less than 500, low molecular polymers will bleed, resulting in reduced contamination.
(B)成分の配合割合は、特に限定されるものではないが、(A)成分100重量部に対して、(B)成分を1〜400重量部用いることが好ましく、5〜200重量部用いることがより好ましい。上記アクリル系重合体は、単独で用いても良く、2種以上併用してもよい。 The blending ratio of the component (B) is not particularly limited, but the component (B) is preferably used in an amount of 1 to 400 parts by weight, more preferably 5 to 200 parts by weight, per 100 parts by weight of the component (A). Is more preferable. The acrylic polymers may be used alone or in combination of two or more.
上記(C)成分として用いられる水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物としては、具体的には、原料入手の容易性、貯蔵安定性、水との反応性などの点から、一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物のケチミン化合物、エナミン化合物、及び/又はアルジミン化合物が好適例として挙げられる。 As the compound which reacts with water used as the component (C) to produce an amine compound having at least one alkoxysilyl group in one molecule, specifically, the availability of raw materials, storage stability, water From the viewpoint of the reactivity with, a ketimine compound, an enamine compound, and / or an aldimine compound of an amine compound having at least one alkoxysilyl group in one molecule are preferred.
上記ケチミン化合物、エナミン化合物及びアルジミン化合物はそれぞれ、(C1)一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物と(C2)カルボニル化合物との脱水反応により得ることができる。上記成分(C)の製造方法は特に限定されず、公知の方法を用いることができる。 The ketimine compound, enamine compound, and aldimine compound can be obtained by a dehydration reaction between (C1) an amine compound having at least one alkoxysilyl group in one molecule and (C2) a carbonyl compound. The method for producing the component (C) is not particularly limited, and a known method can be used.
上記成分(C1)一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物と成分(C2)カルボニル化合物による脱水反応生成物について説明すれば、次の通りである。成分(C1)アルコキシシリル基を有するアミン化合物は、特に限定されないが、一分子中に少なくとも一個のアルコキシシリル基を有する第1級及び/又は第2級アミンが好適に用いられる。成分(C1)としては、例えば、下記一般式(26)で示されるものを挙げることができる。 The dehydration reaction product of the amine compound having at least one alkoxysilyl group in one molecule of the component (C1) and the carbonyl compound of the component (C2) will be described below. The component (C1) amine compound having an alkoxysilyl group is not particularly limited, but a primary and / or secondary amine having at least one alkoxysilyl group in one molecule is preferably used. Examples of the component (C1) include those represented by the following general formula (26).
[式(26)中、n=0,1,2、R2及びR3は同一又は異なって、それぞれ炭素数1〜4個の炭化水素基、R4は炭素数1〜10個の炭化水素基、Zは水素原子又は炭素数1〜4個のアミノアルキル基を意味する。] [In the formula (26), n = 0, 1, 2, R 2 and R 3 are the same or different and each is a hydrocarbon group having 1 to 4 carbon atoms, and R 4 is a hydrocarbon group having 1 to 10 carbon atoms. The group, Z, represents a hydrogen atom or an aminoalkyl group having 1 to 4 carbon atoms. ]
ここで、R2及びR3としては、メチル、エチル、プルピル、ブチルといったアルキル基、ビニル、アリル、プロペニル、ブテニルといったアルケニル基などが挙げられ、特にアルキル基が好ましい。R4としてはメチレン、エチレン、プロピレン、ブチレンなどのアルキレン基、フェニレンなどのアリーレン基やアルキレンアリーレン基等が挙げられるが、特にアルキレン基が好ましい。nは好ましくは0又は1である。 Here, examples of R 2 and R 3 include an alkyl group such as methyl, ethyl, propyl and butyl, and an alkenyl group such as vinyl, allyl, propenyl and butenyl, and an alkyl group is particularly preferable. Examples of R 4 include an alkylene group such as methylene, ethylene, propylene, and butylene, an arylene group such as phenylene, and an alkylene arylene group. An alkylene group is particularly preferred. n is preferably 0 or 1.
具体例としては、下記式(27)〜(34)で示される化合物や、N−(β−アミノエチル)−γ−アミノプロピルトリメトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルメチルジメトキシシラン等に代表されるアミノシラン類等を挙げることができる。これらの中では、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルメチルジメトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルトリメトキシシラン等が好ましい。 Specific examples include compounds represented by the following formulas (27) to (34), N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyl Examples thereof include aminosilanes represented by methyldimethoxysilane and the like. Among them, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and the like are preferable.
上記成分(C2)カルボニル化合物としては公知のものが含まれ、例えば、アセトアルデヒド、プロピオンアルデヒド、n−ブチルアルデヒド、イソブチルアルデヒド、n−アミルアルデヒド、イソヘキシルアルデヒド、ジエチルアセトアルデヒド、グリオキサール、ベンズアルデヒド、フェニルアセトアルデヒド等のアルデヒド類;シクロペンタノン、トリメチルシクロペンタノン、シクロヘキサノン、メチルシクロヘキサノン、トリメチルシクロヘキサノン等の環状ケトン類;アセトン、メチルエチルケトン、メチルプロピルケトン、メチルイソプロピルケトン、メチルイソブチルケトン、メチル−tert−ブチルケトン、ジエチルケトン、ジプロピルケトン、ジイソプロピルケトン、ジブチルケトン、ジイソブチルケトン等の脂肪族ケトン類;アセトフェノン、ベンゾフェノン、プロピオフェノン等の芳香族ケトン;及びアセチルアセトン、アセト酢酸メチル、アセト酢酸エチル、マロン酸ジメチル、マロン酸ジエチル、マロン酸メチルエチル、ジベンゾイルメタン等の下記一般式(35)で示されるβ−ジカルボニル化合物が挙げられるが、これらに限定されるものではない。このうち、メチルイソブチルケトン、ジプロピルケトン、フェニルアセトアルデヒド、及び活性メチレン基を有するβ−ジカルボニル化合物〔下記一般式(35)で示される化合物〕がより好ましい。 The component (C2) carbonyl compound includes known compounds such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-amylaldehyde, isohexylaldehyde, diethylacetaldehyde, glyoxal, benzaldehyde, and phenylacetaldehyde. Aldehydes; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, methylcyclohexanone, and trimethylcyclohexanone; acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl-tert-butyl ketone, and diethyl ketone , Dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, etc. Ketones; aromatic ketones such as acetophenone, benzophenone and propiophenone; and the following general formula (35) such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, methylethyl malonate, dibenzoylmethane, etc. )), But are not limited thereto. Among them, methyl isobutyl ketone, dipropyl ketone, phenylacetaldehyde, and a β-dicarbonyl compound having an active methylene group [compound represented by the following general formula (35)] are more preferable.
〔式中、R5及びR6は同一又は異なって、それぞれ炭素数1〜16個のアルキル基(例えば、メチル、エチル、プロピル、ブチル、ヘプチル、ヘキシル、オクチル、ノニル、デシル、ウンデシル、ヘキサデシル等)、炭素数6〜12個のアリール基(例えば、フェニル、トリル、ヘキシル、ナフチル等)、又は炭素数1〜4個のアルコキシル基(例えば、メトキシ、エトキシ、プロオキシ、プトキシ等)を意味する。〕 [Wherein, R 5 and R 6 are the same or different and each have an alkyl group having 1 to 16 carbon atoms (eg, methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, undecyl, hexadecyl, etc.) ), An aryl group having 6 to 12 carbon atoms (eg, phenyl, tolyl, hexyl, naphthyl, etc.) or an alkoxyl group having 1 to 4 carbon atoms (eg, methoxy, ethoxy, prooxy, butoxy, etc.). ]
上記(C)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物の製造方法は、どのような方法でも良いがモノマー純度が50〜95%で、かつアミノ基封鎖率が90%以上のものを製造するためには以下の方法が望ましい。アルコキシシリル基を有するアミン化合物とカルボニル化合物との反応はカルボニル化合物中に加熱下でアルコキシシリル基を有するアミン化合物を導入し、その導入中に生成した水をカルボニル化合物と共に共沸留去する。この際のアルコキシシリル基を有するアミン化合物に対し、過剰量のカルボニル化合物を反応させることが好ましい。 The method (C) for producing a compound which produces an amine compound having at least one alkoxysilyl group in one molecule by reacting with water may be any method, but it is preferable that the monomer purity is 50 to 95%, The following method is desirable for producing a product having a base blocking rate of 90% or more. In the reaction between the amine compound having an alkoxysilyl group and the carbonyl compound, an amine compound having an alkoxysilyl group is introduced into the carbonyl compound under heating, and water generated during the introduction is azeotropically distilled off together with the carbonyl compound. In this case, it is preferable to react an excess amount of the carbonyl compound with the amine compound having an alkoxysilyl group.
また、このアルコキシシリル基を有するアミン化合物の導入温度(反応温度)はカルボニル化合物と水との共沸温度付近からカルボニル化合物の還流温度付近までとすることが好ましく、アルコキシシリル基を有するアミン化合物はこの温度範囲で導入することが好ましい。例えば、カルボニル化合物をメチルイソブチルケトンとし、これをアルコキシシリル基を有するアミン化合物と反応させる場合には、メチルイソブチルケトンと水との共沸温度が80℃程度となり、このメチルイソブチルケトンの還流温度が130℃であることから、アルコキシシリル基を有するアミン化合物の導入温度は80〜130℃とすればよい。この反応のためのアルコキシシリル基を有するアミン化合物の導入方法は任意とされるが、これをカルボニル化合物と速やかに反応させるためには、これを液中に導入することが好ましい。この導入時間も任意とされるが、これは30分〜20時間程度とすることが好ましい。また、この反応は湿気があると反応生成物が加水分解してしまうために、反応は窒素、アルゴンなどの不活性ガス下で行うことが好ましく、カルボニル化合物中の水分もできるかぎり少なくすることが好ましい。 Further, the introduction temperature (reaction temperature) of the amine compound having an alkoxysilyl group is preferably from about the azeotropic temperature of the carbonyl compound to water to about the reflux temperature of the carbonyl compound. It is preferable to introduce in this temperature range. For example, when the carbonyl compound is methyl isobutyl ketone and this is reacted with an amine compound having an alkoxysilyl group, the azeotropic temperature of methyl isobutyl ketone and water becomes about 80 ° C., and the reflux temperature of this methyl isobutyl ketone becomes Since the temperature is 130 ° C., the introduction temperature of the amine compound having an alkoxysilyl group may be set to 80 to 130 ° C. The method of introducing the amine compound having an alkoxysilyl group for this reaction is optional, but it is preferable to introduce it into the liquid in order to react it with the carbonyl compound quickly. Although the introduction time is optional, it is preferably about 30 minutes to 20 hours. In addition, this reaction is preferably performed under an inert gas such as nitrogen or argon since the reaction product is hydrolyzed in the presence of moisture, and the water content in the carbonyl compound should be as small as possible. preferable.
この(C)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物の製造は、上記したように、カルボニル化合物に加熱下でアルコキシシリル基を有するアミン化合物を導入して反応させ、この導入中から生成した水をカルボニル化合物と共に共沸留去するものであるが、このアルコキシシリル基を有するアミン化合物の導入終了後も、系内の水分留去のためにはカルボニル化合物との共沸留去とすることが好ましい。 The production of the compound (C) which reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule is carried out by heating the carbonyl compound with an amine compound having an alkoxysilyl group under heating as described above. The reaction is carried out, and water generated during the introduction is azeotropically distilled off together with the carbonyl compound.However, even after the completion of the introduction of the amine compound having an alkoxysilyl group, water in the system is removed due to distillation. Is preferably azeotropically distilled with a carbonyl compound.
この留出温度はカルボニル化合物の還流温度まで上昇させ、還流温度になってから30分〜2時間程度留出を続けるか、或いはアルコキシシリル基を有するアミン化合物導入終了直後に減圧濃縮による系内から未反応カルボニル化合物を留去することが好ましい。なお、還流温度になってから30分〜2時間程度留去を続けると、系内に水分がなくなるために、これは安定で加水分解縮合の進行は生じにくいが、未反応カルボニル化合物はできるだけ速く系内から留去することが好ましい。このような方法で得た、目的とする水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物は、アルコキシ基の加水分解縮合で生成するアルコキシシランオリゴマーとの混合物として得られるが、オリゴマー量が従来の製造方法に比較して少なくなり、また残存アミノ基量も少ないものである。このものを高純度で得るためにはこの水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物を蒸留単離することもできるが、このように蒸留単離したものは、高コストとなり、また接着性も十分でないため、本発明の硬化性組成物に使用するのには望ましくない。 The distillation temperature is raised to the reflux temperature of the carbonyl compound, and the distillation is continued for about 30 minutes to 2 hours after the reflux temperature is reached, or the system is concentrated by vacuum concentration immediately after the completion of the introduction of the amine compound having an alkoxysilyl group. Preferably, unreacted carbonyl compounds are distilled off. In addition, if the distillation is continued for about 30 minutes to 2 hours after the reflux temperature is reached, water is not left in the system, and this is stable and progress of hydrolysis condensation does not easily occur. It is preferable to distill it out of the system. The compound obtained by such a method, which reacts with water of interest to form an amine compound having at least one alkoxysilyl group in one molecule, is combined with an alkoxysilane oligomer formed by hydrolytic condensation of an alkoxy group. Although it is obtained as a mixture, the amount of oligomer is smaller than that of a conventional production method, and the amount of residual amino groups is also smaller. In order to obtain this compound with high purity, a compound which reacts with water to form an amine compound having at least one alkoxysilyl group in one molecule can be isolated by distillation. These are not desirable for use in the curable compositions of the present invention because of their high cost and poor adhesion.
上記(C)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物として、上記の方法等によって得られる、モノマー純度が50〜95%、好ましくは70〜95%、更に好ましくは80〜95%で、かつアミノ基封鎖率が90%以上、好ましくは95%以上のものを使用することが好適である。モノマー純度が50%より低いと、組成物の保存安定性が悪く、95%より高いと組成物の接着性が悪くなり、またアミノ基封鎖率が90%より少ないと、組成物の保存安定性が悪くなるため好ましくない。 As the compound (C) which reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule, the monomer purity obtained by the above method or the like is 50 to 95%, preferably 70 to 95%. %, More preferably 80 to 95%, and the amino group blocking ratio is 90% or more, preferably 95% or more. When the monomer purity is lower than 50%, the storage stability of the composition is poor. When the monomer purity is higher than 95%, the adhesion of the composition is poor. When the amino group blocking ratio is lower than 90%, the storage stability of the composition is low. Is not preferred because it becomes worse.
上記成分(C)の配合割合は、特に限定されないが、成分(A)100重量部に対して、成分(C)0.01〜20重量部程度が好ましく、0.1〜10重量部がさらに好ましい。これらの水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物は、単独で使用しても良く、2種以上併用しても良い。 The mixing ratio of the component (C) is not particularly limited, but is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the component (A). preferable. These compounds which react with water to form an amine compound having at least one alkoxysilyl group in one molecule may be used alone or in combination of two or more.
上記成分(D)として用いられる硬化触媒としては、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;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。このうち高い架橋速度、毒性及び輝発性の比較的低い液体である点から、ジブチル錫ジアセチルアセトナートが特に好ましい。成分(D)の配合割合は、架橋速度、硬化物の物性などの点から、架橋性シリル基含有有機重合体(A)100重量部に対して、0.1〜30重量部、特に0.5〜20重量部用いることが好ましい。これらの硬化触媒は、単独で使用しても良く、2種以上併用しても良い。 The curing catalyst used as the component (D) is not particularly limited as long as it exhibits a function of the curing catalyst with respect to the component (A). Examples thereof include organometallic compounds and amines. It is preferable to use a condensation catalyst. Examples of the silanol condensation catalyst include, for example, stannas octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate Organic tin compounds such as dioctyltin dilaurate, dioctyltin diversate, tin octylate and tin naphthenate; reactants of dibutyltin oxide with phthalic esters; titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum Organic aluminum compounds such as trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; Co tetra acetylacetonate, chelate compounds such as titanium tetraacetyl acetonate; lead octylate; silanol condensation catalyst as known other acidic catalysts and basic catalysts, and the like. Of these, dibutyltin diacetylacetonate is particularly preferred because it is a liquid having a high crosslinking rate, toxicity and relatively low spontaneity. The mixing ratio of the component (D) is from 0.1 to 30 parts by weight, especially from 0.1 to 30 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing organic polymer (A) from the viewpoint of the crosslinking rate, the physical properties of the cured product, and the like. It is preferable to use 5 to 20 parts by weight. These curing catalysts may be used alone or in combination of two or more.
本発明の硬化性組成物には、耐水性向上の為に(E)エポキシ樹脂をさらに添加することが好適である。該(E)エポキシ樹脂としては、従来公知のものを広く使用でき、特に限定されないが、ビスフェノール型エポキシ樹脂やポリオキシアルキレン骨格を有するエポキシ樹脂を用いることがより好ましい。上記ポリオキシアルキレン骨格を有するエポキシ樹脂としては、ポリアルキレンオキシドを有するものであれば特に限定されないが、ビスフェノールA、ビスフェノールF、ビスフェノールADや、ノボラック等を含みポリオキシアルキレン単位を有するエポキシ樹脂がより好適な例として挙げられる。 硬化 It is preferable to further add (E) an epoxy resin to the curable composition of the present invention in order to improve water resistance. As the epoxy resin (E), conventionally known epoxy resins can be widely used and are not particularly limited, but it is more preferable to use a bisphenol-type epoxy resin or an epoxy resin having a polyoxyalkylene skeleton. The epoxy resin having a polyoxyalkylene skeleton is not particularly limited as long as it has a polyalkylene oxide.Bisphenol A, bisphenol F, bisphenol AD, and an epoxy resin having a polyoxyalkylene unit including novolak and the like are more preferable. A preferred example is given.
該(E)エポキシ樹脂の配合割合は、成分(A)100重量部に対して、1〜200重量部用いることが好ましく、3〜150重量部が更に好適である。該エポキシ樹脂は単独で用いても良く、2種以上を併用しても良い。 は The proportion of the epoxy resin (E) is preferably 1 to 200 parts by weight, more preferably 3 to 150 parts by weight, per 100 parts by weight of the component (A). The epoxy resins may be used alone or in combination of two or more.
上記成分(E)エポキシ樹脂を添加する場合、該エポキシ樹脂に対する硬化剤(エポキシ樹脂硬化剤)として、ケチミン類等を添加しても良い。上記硬化剤は、単独で使用してもよく、2種以上併用してもよい。また、成分(A)に対し硬化触媒作用を示し且つエポキシ樹脂の硬化剤となりうるものを上記硬化触媒(D)及び硬化剤として用いることも無論可能である。 (4) When the component (E) epoxy resin is added, ketimines and the like may be added as a curing agent (epoxy resin curing agent) for the epoxy resin. The above curing agents may be used alone or in combination of two or more. Of course, it is of course possible to use a curing catalyst which acts as a curing agent for the epoxy resin and has a curing catalytic action on the component (A) as the curing catalyst (D) and the curing agent.
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、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。 The curable composition of the present invention may further comprise, in addition to the components described above, an adhesion promoter, a physical property modifier, a filler, a plasticizer, a thixotropic agent, a dehydrating agent (storage stability improver), Substances such as imparting agents, anti-sagging agents, ultraviolet absorbers, antioxidants, flame retardants, coloring agents, radical polymerization initiators and various solvents such as toluene and alcohol may be blended, and other compatible heavy metals Coalescing may be blended.
上記の相溶する他の重合体としては各種ポリエーテルが特に好ましく、とりわけ、特許文献1及び30〜33で提案されている珪素官能基を有するポリエーテルなどが挙げられる。 As the other compatible polymer, various polyethers are particularly preferable, and in particular, polyethers having a silicon functional group proposed in Patent Documents 1 and 30 to 33 are exemplified.
上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, for example, aminosilanes such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethylmethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Epoxy silanes such as methoxysilane, acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate silanes such as γ-isocyanatopropyltrimethoxysilane, etc. Can be The above-mentioned adhesion imparting agents may be used alone or in combination of two or more.
上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。上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。上記物性調整剤は単独または、2種以上併用しても良い。 The above physical property modifier is added for the purpose of improving tensile properties. Examples of the physical property modifier include a silicon compound having one silanol group in one molecule. Examples thereof include triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, and diphenylalkylsilanol. Various silane coupling agents such as a silicon compound which decomposes to form a compound having one silanol group in one molecule, such as triphenylmethoxysilane, trialkylmethoxysilane, dialkylphenylmethoxysilane, and diphenylalkylmethoxy Examples include silane, triphenylethoxysilane, and trialkylethoxysilane. The physical property modifiers may be used alone or in combination of two or more.
上記充填剤は硬化物の補強の目的で添加される。上記充填剤として、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。上記充填剤は単独または、2種以上併用しても良い。 The above filler is added for the purpose of reinforcing the cured product. As the filler, for example, calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, silicic anhydride, calcium silicate, silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, zeolite And the like. Of these, calcium carbonate is preferred, and fatty acid-treated calcium carbonate is more preferred. Further, 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, and the like can also be used. Among them, an acrylic balloon is more preferable in that the decrease in elongation after curing of the composition is small. The above fillers may be used alone or in combination of two or more.
上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。本発明においては、上記(B)成分を可塑剤として用いることもできるが、必要に応じて、他の可塑剤を添加しても良い。他の可塑剤としては、例えば、リン酸トリブチル、リン酸トリクレジル等のリン酸エステル類;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。上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 above plasticizer is added for the purpose of enhancing elongation properties after curing and enabling reduction in modulus. In the present invention, the above component (B) can be used as a plasticizer, but other plasticizers may be added as necessary. Other plasticizers include, for example, phosphoric esters such as tributyl phosphate and tricresyl phosphate; phthalic esters such as dioctyl phthalate (DOP), dibutyl phthalate and butyl benzyl phthalate; fatty acids such as glycerin monooleate; Monobasic 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; And the like. The plasticizers may be used alone or in combination of two or more.
上記揺変剤としては、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。上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 colloidal silica, inorganic thixotropic agents such as asbestos powder, organic bentonite, modified polyester polyols, organic thixotropic agents such as fatty acid amides, hydrogenated castor oil derivatives, fatty acid amide wax, aluminum stearylate And barium stearylate. The thixotropic agents may be used alone or in combination of two or more.
上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。上記脱水剤として、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 above dehydrating agent is added for the purpose of removing water during storage. Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.
上記酸化防止剤は、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。上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 for preventing the cured sealing material from oxidizing and improving 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 Polycondensate of 2,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine.N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, 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-decandioate- 1 (octyloxy) -4-piperidyl) ester, reaction product of octane with 1,1-dimethylethyl hydroperoxide (70%)]-polypropylene (30%), bis (1,2,2,6,6- Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, 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 phenolic antioxidants include pentane Eristol-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), 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester of benzenepropanoic acid, 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, calcium M-diethyl bis [[[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-phenylbenzeneamine Reaction product of 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5 with 2,4,4-trimethylpentene Triazin-2-ylamino) phenol and the like, but not limited thereto. The above antioxidants may be used alone or in combination of two or more.
上記紫外線吸収剤は、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。上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 above-mentioned ultraviolet absorber is used for preventing the photo-deterioration of the cured sealing material and improving the weather resistance. For example, a benzotriazole-based, triazine-based, benzophenone-based, benzoate-based ultraviolet absorber, etc. And the like. Examples of the UV 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 branched dodecyl) -4 Benzotriazole-based ultraviolet absorbers such as -methylphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(f Triazine-based ultraviolet absorbers such as (sil) oxy] -phenol, benzophenone-based ultraviolet absorbers such as octabenzone, and 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; Examples include, but are not limited to, benzoate UV absorbers. The ultraviolet absorbers may be used alone or in combination of two or more.
本発明の硬化性組成物の第2の態様は、(A)架橋性シリル基含有有機重合体、(B)アクリル系重合体、(C1)一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物、(C2)カルボニル化合物、及び(D)硬化触媒を含有することを特徴とする。 The second embodiment of the curable composition of the present invention comprises (A) a crosslinkable silyl group-containing organic polymer, (B) an acrylic polymer, and (C1) an amine having at least one alkoxysilyl group in one molecule. It is characterized by containing a compound, a (C2) carbonyl compound, and (D) a curing catalyst.
上記成分(A)、(B)及び(D)は、本発明の硬化性組成物の第1の態様において上述した通りである。成分(B)及び(D)の配合割合もそれぞれ上記した本発明の硬化性組成物の第1の態様と同様に行えばよい。成分(C1)及び成分(C2)は、それぞれ本発明の硬化性組成物の第1の態様の成分(C)において挙げた一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物、及びカルボニル化合物を同様に用いることができる。本発明の硬化性組成物の第2の態様は、配合物中で成分(C1)及び(C2)を脱水反応させるものである。該脱水反応は、必要に応じて加熱処理等の反応処理を行っても良いが、特別な工程を行わずに、時間経過により進行させることが可能である。成分(C1)及び(C2)の配合割合は、特に限定されないが、成分(C1)及び(C2)が、成分(A)100重量部に対してそれぞれ0.05〜50重量部、特に0.1〜20重量部となるように配合するのが好ましい。さらに、[成分(C1)のモル量]/[成分(C2)のモル量]が0.1〜5.0の範囲であることが好ましく、0.5〜2.0の範囲であることがさらに好ましい。アルコキシシリル基を有するアミン化合物及びカルボニル化合物は、それぞれ単独で使用しても良く、2種以上併用しても良い。必要に応じて上記したような可塑剤を添加しても良い。上記成分以外の配合物についても第1の態様と同様である。 The components (A), (B) and (D) are as described above in the first embodiment of the curable composition of the present invention. The mixing ratio of the components (B) and (D) may be the same as in the above-described first embodiment of the curable composition of the present invention. Component (C1) and component (C2) are an amine compound having at least one alkoxysilyl group in one molecule and a carbonyl compound, respectively, as described in component (C) of the first embodiment of the curable composition of the present invention. Can be similarly used. A second embodiment of the curable composition of the present invention is one in which components (C1) and (C2) are subjected to a dehydration reaction in a formulation. The dehydration reaction may be subjected to a reaction treatment such as a heat treatment, if necessary, but can be allowed to proceed over time without performing a special step. The mixing ratio of the components (C1) and (C2) is not particularly limited, but the components (C1) and (C2) are each 0.05 to 50 parts by weight, particularly 0.1 to 100 parts by weight, based on 100 parts by weight of the component (A). It is preferable to mix them in an amount of 1 to 20 parts by weight. Further, [molar amount of component (C1)] / [molar amount of component (C2)] is preferably in the range of 0.1 to 5.0, and more preferably in the range of 0.5 to 2.0. More preferred. The amine compound having an alkoxysilyl group and the carbonyl compound may be used alone or in combination of two or more. If necessary, the above-described plasticizer may be added. The composition other than the above components is the same as in the first embodiment.
本発明の硬化性組成物の第3の態様は、成分(A1)架橋性シリル基含有アクリル系重合体、成分(C)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物、及び成分(D)硬化触媒を含有することを特徴とする。上記成分(A1)、(C)及び(D)は、本発明の硬化性組成物の第1の態様において上述した通りである。また、各成分の配合割合も上記した本発明の硬化性組成物の第1の態様と同様に行えばよい。必要に応じて上記したような可塑剤を添加しても良い。上記成分以外の配合物についても同様である。 A third embodiment of the curable composition of the present invention comprises a component (A1) a crosslinkable silyl group-containing acrylic polymer, a component (C) an amine having at least one alkoxysilyl group in one molecule by reacting with water. It is characterized by containing a compound producing a compound and a component (D) a curing catalyst. The components (A1), (C) and (D) are as described above in the first embodiment of the curable composition of the present invention. The mixing ratio of each component may be the same as in the above-described first embodiment of the curable composition of the present invention. If necessary, the above-described plasticizer may be added. The same applies to compounds other than the above components.
本発明の硬化性組成物の第4の態様は、成分(A1)架橋性シリル基含有アクリル系重合体、成分(C1)一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物、成分(C2)カルボニル化合物、及び成分(D)硬化触媒を含有することを特徴とする。上記成分(A1)及び(D)は、本発明の硬化性組成物の第1の態様において上述した通りであり、成分(D)の配合割合も上記した本発明の硬化性組成物の第1の態様と同様に行えばよい。上記成分(C1)及び(C2)は、本発明の硬化性組成物の第2の態様において上述した通りであり、成分(C1)及び(C2)の配合割合も上記した本発明の硬化性組成物の第2の態様と同様に行えばよい。必要に応じて上記したような可塑剤を添加しても良い。上記成分以外の配合物についても同様である。 The fourth embodiment of the curable composition of the present invention comprises a component (A1) a crosslinkable silyl group-containing acrylic polymer, a component (C1) an amine compound having at least one alkoxysilyl group in one molecule, and a component (C2). ) A carbonyl compound and a component (D) a curing catalyst. The components (A1) and (D) are as described above in the first embodiment of the curable composition of the present invention, and the mixing ratio of the component (D) is the same as that of the first embodiment of the curable composition of the present invention. This may be performed in the same manner as described above. The components (C1) and (C2) are as described above in the second embodiment of the curable composition of the present invention. What is necessary is just to carry out similarly to the 2nd aspect of a thing. If necessary, the above-described plasticizer may be added. The same applies to compounds other than the above components.
本発明の硬化性組成物は、必要に応じて1液型とすることもできるし、2液型とすることもできるが、特に1液型として好適に用いることができる。本発明の硬化性組成物は、シーリング材、接着剤及びコーティング材等として好適に用いられる。本発明の硬化性組成物は、基本性能を損なうことなく、貯蔵後の硬化特性や耐水接着性が低減されない、優れた貯蔵安定性、接着性及び耐候性を有しているため、特に、外壁用のシーリング材、接着剤に用いることが好ましいが、その他各種建築物用、自動車用、土木用、電気・電子分野用等に使用することができる。 硬化 The curable composition of the present invention can be of a one-pack type or a two-pack type as required, but it can be suitably used particularly as a one-pack type. The curable composition of the present invention is suitably used as a sealing material, an adhesive, a coating material, and the like. The curable composition of the present invention has excellent storage stability, adhesiveness and weather resistance, without impairing the basic properties, without reducing the curing properties and water-resistant adhesiveness after storage, and particularly, the outer wall. It is preferably used for sealing materials and adhesives for automobiles, but it can also be used for various other buildings, automobiles, civil engineering, electric / electronic fields, and the like.
以下に本発明の実施例を挙げてさらに具体的に説明するが、こ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。 す る Hereinafter, the present invention will be described in more detail with reference to Examples, but it is needless to say that the Examples are illustrative and should not be construed as limiting.
(合成例1)
架橋性シリル基含有アクリル系重合体(A1)として、下記方法に基づき、架橋性シリル基含有アクリル酸エステル−フルオロオレフィン共重合体を合成した。撹拌機を備えた2リットルのオートクレーブに、有機溶媒として酢酸ブチル135gおよびエタノール75g、単量体としてアクリル酸ブチルエステル6.9g、アクリル酸2−メトキシエチルエステル7.0gおよびビニルトリメトキシシラン1.0g、ならびにラジカル重合開始剤としてエトキシエチルパーオキシジカーボネート4.0gを仕込み、脱気と窒素置換を3回繰り返した後減圧脱気し、クロロトリフルオロエチレン510gを仕込んだ。50℃まで昇温して重合を開始させ、昇温1時間後、アクリル酸ブチルエステル62.4g、アクリル酸2−メトキシエチルエステル63.0gおよびビニルトリメトキシシラン9.0gの混合液を7時間に渡り一定速度でポンプを用いてオートクレーブ中に送り込んだ。重合開始8時間経過後、60℃まで昇温し重合を計10時間行った後、冷却した。反応終了後、未反応のクロロトリフルオロエチレンをパージし、オートクレーブを開放して共重合体溶液を得た。得られた溶液を濾過しほう酸ソーダを除いた後減圧乾燥させ、メタノール中に投入し、洗浄乾燥し245gの共重合体を得た。
(Synthesis example 1)
As a crosslinkable silyl group-containing acrylic polymer (A1), a crosslinkable silyl group-containing acrylate-fluoroolefin copolymer was synthesized based on the following method. In a 2-liter autoclave equipped with a stirrer, 135 g of butyl acetate and 75 g of ethanol as organic solvents, 6.9 g of butyl acrylate, 7.0 g of 2-methoxyethyl acrylate and vinyl trimethoxysilane as monomers. Then, 0 g and 4.0 g of ethoxyethyl peroxydicarbonate as a radical polymerization initiator were charged, and degassing and nitrogen replacement were repeated three times, followed by degassing under reduced pressure, and 510 g of chlorotrifluoroethylene. The temperature was raised to 50 ° C. to start the polymerization, and after 1 hour, a mixed solution of 62.4 g of butyl acrylate, 63.0 g of 2-methoxyethyl acrylate, and 9.0 g of vinyltrimethoxysilane was added for 7 hours. And fed into the autoclave using a pump at a constant speed. After a lapse of 8 hours from the start of the polymerization, the temperature was raised to 60 ° C., the polymerization was performed for a total of 10 hours, and then the system was cooled. After completion of the reaction, unreacted chlorotrifluoroethylene was purged, and the autoclave was opened to obtain a copolymer solution. The resulting solution was filtered to remove sodium borate, dried under reduced pressure, poured into methanol, washed and dried to obtain 245 g of a copolymer.
(実施例1)
表1に示したように、成分(A)架橋性シリル基含有有機重合体として架橋性シリル基含有ポリオキシプロピレン重合体、成分(B)アクリル系重合体として水酸基非含有アクリル系重合体、老化防止剤、炭酸カルシウム及びビニルトリメトキシシランをそれぞれ所定量ずつ仕込み、加熱減圧混合攪拌を110℃にて2時間行い、配合物質の脱水を行った。さらに、成分(C)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物としてケチミン構造含有アミノシラン及び成分(D)硬化触媒としてジブチル錫ジアセチルアセトナートを所定量ずつ添加し、攪拌配合して硬化性組成物を調製した。
(Example 1)
As shown in Table 1, as component (A) a crosslinkable silyl group-containing organic polymer, a crosslinkable silyl group-containing polyoxypropylene polymer, as component (B) an acrylic polymer, a hydroxyl group-free acrylic polymer, and aging Preventive agents, calcium carbonate, and vinyltrimethoxysilane were charged in predetermined amounts, respectively, and mixed under heating and reduced pressure at 110 ° C. for 2 hours to dehydrate the compounded substances. Further, a predetermined amount of a ketimine structure-containing aminosilane as a compound for producing an amine compound having at least one alkoxysilyl group in one molecule by reacting with component (C) water and dibutyltin diacetylacetonate as a curing catalyst for component (D). Were added and stirred to prepare a curable composition.
表1における各配合物質の配合量は(g)で示され、*1〜*13は次の通りである。
*1:架橋性シリル基含有ポリオキシプロピレン重合体(鐘淵化学工業(株)製、商品名:MSポリマーS303)
*2:架橋性シリル基含有アクリル変性ポリオキシプロピレン重合体(鐘淵化学工業(株)製、商品名:MSポリマーS903)
*3:合成例1で得た架橋性シリル基含有アクリル系重合体
*4:水酸基非含有アクリル系重合体(東亞合成(株)製、商品名:UP−1110)
*5:水酸基含有アクリル系重合体(東亞合成(株)製、商品名:UH−2000)
*6:アクリル酸エステル−フルオロオレフィン共重合体(東亞合成(株)製、商品名:XCS−3500)
*7:ケチミン構造含有アミノシラン(信越化学工業(株)製、商品名:X12−817)
*8:γ−アミノプロピルトリメトキシシラン(信越化学工業(株)製、商品名:KBM−903)
*9:N−β(アミノエチル)γ−アミノプロピルトリメトキシシラン
*10:メチルイソブチルケトン
*11:ジブチル錫ジアセチルアセトナート
*12:チバ・スペシャルティ・ケミカルズ(株)製の老化防止剤、商品名:チヌビンB75
*13:脂肪酸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200M)
The amount of each compounded substance in Table 1 is indicated by (g), and * 1 to * 13 are as follows.
* 1: Crosslinkable silyl group-containing polyoxypropylene polymer (manufactured by Kanegafuchi Chemical Industry Co., Ltd., trade name: MS Polymer S303)
* 2: Crosslinkable silyl group-containing acrylic-modified polyoxypropylene polymer (manufactured by Kaneka Chemical Co., Ltd., trade name: MS Polymer S903)
* 3: Crosslinkable silyl group-containing acrylic polymer obtained in Synthesis Example 1 * 4: Hydroxy group-free acrylic polymer (trade name: UP-1110, manufactured by Toagosei Co., Ltd.)
* 5: Hydroxyl group-containing acrylic polymer (Toagosei Co., Ltd., trade name: UH-2000)
* 6: Acrylate-fluoroolefin copolymer (trade name: XCS-3500, manufactured by Toagosei Co., Ltd.)
* 7: Aminosilane containing a ketimine structure (trade name: X12-817, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 8: γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903)
* 9: N-β (aminoethyl) γ-aminopropyltrimethoxysilane * 10: Methyl isobutyl ketone * 11: Dibutyltin diacetylacetonate * 12: Antiaging agent, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd. : Tinuvin B75
* 13: Calcium carbonate treated with fatty acid (Maruo Calcium Co., Ltd., trade name: Calfine 200M)
(実施例2及び3)
表1に示したように、架橋性シリル基含有ポリオキシプロピレン重合体の代わりに架橋性シリル基含有アクリル変性ポリオキシプロピレン重合体(A1)又は合成例1で得た共重合体(A1)を配合した以外は、実施例1と同様の方法により硬化性組成物を調製した。
(Examples 2 and 3)
As shown in Table 1, instead of the crosslinkable silyl group-containing polyoxypropylene polymer, a crosslinkable silyl group-containing acryl-modified polyoxypropylene polymer (A1) or the copolymer (A1) obtained in Synthesis Example 1 was used. A curable composition was prepared in the same manner as in Example 1 except that it was blended.
(実施例4及び5)
表1に示したように、水酸基非含有アクリル系重合体の代わりに水酸基含有アクリル系重合体又はアクリル酸エステル−フルオロオレフィン共重合体を配合した以外は、実施例1と同様の方法により硬化性組成物を調製した。
(Examples 4 and 5)
As shown in Table 1, curability was obtained in the same manner as in Example 1 except that a hydroxyl group-containing acrylic polymer or an acrylate-fluoroolefin copolymer was used instead of the hydroxyl group-free acrylic polymer. A composition was prepared.
(実施例6)
表1に示したように、成分(A1)架橋性シリル基含有アクリル系重合体として上記合成例1で得た共重合体、老化防止剤、炭酸カルシウム、ビニルトリメトキシシラン及びジオクチルフタレートをそれぞれ所定量ずつ仕込み、加熱減圧混合攪拌を110℃にて2時間行い、配合物質の脱水を行った。さらに、成分(C)としてケチミン構造含有アミノシラン及び成分(D)としてジブチル錫ジアセチルアセトナートを添加し、攪拌配合して硬化性組成物を調製した。
(Example 6)
As shown in Table 1, as the component (A1) crosslinkable silyl group-containing acrylic polymer, the copolymer obtained in Synthesis Example 1, an antioxidant, calcium carbonate, vinyl trimethoxysilane, and dioctyl phthalate were respectively used. A fixed amount was charged, and the mixture was heated and mixed under reduced pressure at 110 ° C. for 2 hours to dehydrate the compounded substance. Further, a ketimine structure-containing aminosilane was added as the component (C) and dibutyltin diacetylacetonate was added as the component (D), followed by stirring and blending to prepare a curable composition.
(実施例7)
表1に示したように、成分(A1)として、合成例1で得た共重合体100重量部の代わりに、合成例1で得た共重合体70重量部及び架橋性シリル基含有ポリオキシプロピレン重合体30重量部を配合した以外は、実施例6と同様の方法により、硬化性組成物を調製した。
(Example 7)
As shown in Table 1, instead of 100 parts by weight of the copolymer obtained in Synthesis Example 1, 70 parts by weight of the copolymer obtained in Synthesis Example 1 and polyoxysiloxane containing a crosslinkable silyl group were used as the component (A1). A curable composition was prepared in the same manner as in Example 6, except that 30 parts by weight of the propylene polymer was blended.
(実施例8)
表1に示したように、ケチミン構造含有アミノシランの代わりにアミノシラン化合物及びメチルイソブチルケトンを配合した以外は、実施例2と同様の方法により硬化性組成物を調製した。
(Example 8)
As shown in Table 1, a curable composition was prepared in the same manner as in Example 2 except that an aminosilane compound and methyl isobutyl ketone were added instead of the ketimine structure-containing aminosilane.
(実施例9)
表1に示したように、ケチミン構造含有アミノシランの代わりにアミノシラン化合物及びメチルイソブチルケトンを配合した以外は、実施例6と同様の方法により硬化性組成物を調製した。
(Example 9)
As shown in Table 1, a curable composition was prepared in the same manner as in Example 6, except that an aminosilane compound and methyl isobutyl ketone were added instead of the ketimine structure-containing aminosilane.
(比較例1)
表1に示したように、ケチミン構造含有アミノシランの代わりにアミノシラン化合物を配合した以外は、実施例1と同様の方法により硬化性組成物を調製した。
(Comparative Example 1)
As shown in Table 1, a curable composition was prepared in the same manner as in Example 1 except that an aminosilane compound was added instead of the ketimine structure-containing aminosilane.
[性能試験]
実施例1〜9及び比較例1にて得られた硬化性組成物について、下記の性能試験を行った。なお、50℃で28日間及び56日間は、常温(20℃)で6〜8ヶ月及び12〜16ヶ月に相当する。各性能の測定結果を表2に示す。
[performance test]
The following performance tests were performed on the curable compositions obtained in Examples 1 to 9 and Comparative Example 1. Note that 28 days and 56 days at 50 ° C. correspond to 6 to 8 months and 12 to 16 months at normal temperature (20 ° C.). Table 2 shows the measurement results of each performance.
1)引張接着性
JIS A1439:1997「建築用シーリング材の試験方法」の「4.21引張接着性試験」に準拠して試験した(試験温度23℃)。なお、試験体は、上記得られた(製造直後及び50℃で28日間、56日間保存後の)硬化性組成物を被着体としてアルマイトアルミに打設した試験体を23℃、50%相対湿度で14日間、30℃で14日間養生して作製した。また、耐水接着性については、上記条件にて作成された試験体を23℃水中に7日間浸漬したのちの破壊状態を評価し、接着性として示した。
接着性の判定基準:◎;凝集破壊、○;薄層凝集破壊が確認される場合、△;界面破壊が確認される場合。
1) Tensile Adhesion A test was conducted in accordance with JIS A1439: 1997 "4.21 Tensile adhesion test" of "Testing method for building sealing materials" (test temperature 23 ° C). The test piece was prepared by placing the curable composition obtained as described above (immediately after production and after storage at 50 ° C. for 28 days and 56 days) on anodized aluminum at 23 ° C. and 50% relative. Cured for 14 days at humidity and 14 days at 30 ° C. As for the water-resistant adhesiveness, the test piece prepared under the above conditions was immersed in water at 23 ° C. for 7 days, and the state of destruction was evaluated.
Adhesion evaluation criteria: ;: cohesive failure, 、: when thin layer cohesive failure is confirmed, Δ: when interfacial fracture is confirmed.
2)指触乾燥時間保持率
JIS A 1439 4.19により指触乾燥時間を測定した。判定方法は測定した結果の50℃で28日又は56日間保存後/製造直後が1.3未満を◎、1.3以上1.6未満を○、1.6以上1.9未満を△、1.9以上を×とした。
2) Touch dry time retention rate The touch dry time was measured in accordance with JIS A 1439 4.19. The determination method was as follows: after storage at 50 ° C. for 28 or 56 days / immediately after production: less than 1.3 ◎: 1.3 to less than 1.6 ○: 1.6 to less than 1.9: 1.9 or more was evaluated as x.
3)ゴム硬度保持率
23℃50%相対湿度雰囲気下24時間経過したものを試験体とし、厚さが5mm以上になるように積み重ね、JIS K 6301 5.2 スプリング式硬さ試験機A形を用いて測定した。判定方法は測定した結果の28日又は56日間保存後/製造直後が0.5未満を×、0.5以上0.7未満を△、0.7以上0.9未満を○、0.9以上1.0以下を◎とした。
3) Rubber Hardness Retention Rate The test specimens that had passed for 24 hours in an atmosphere of 23 ° C. and 50% relative humidity were used and stacked so that the thickness became 5 mm or more, and a JIS K 6301 5.2 spring type hardness tester A type was used. It measured using. Judgment method was as follows: less than 0.5 after storage / immediately after production / immediately after production for 28 or 56 days, Δ: 0.5 to less than 0.7, O: 0.7 to less than 0.9, 0.9 Not less than 1.0 and not more than ◎.
4)耐候性
JIS K6266:1996に準じてサンシャインウエザオメーターを用いて1000時間後、2000時間後、3000時間後、5000時間後、7000時間後のシーリング材の表面の状態を目視により判定した。
判定基準:○;シーリング材表面にヘアクラックなし、△;シーリング材表面にヘアクラック若干あり、×;シーリング材表面にヘアクラック多数あり。
4) Weather Resistance According to JIS K6266: 1996, the state of the surface of the sealing material after 1000 hours, 2000 hours, 3000 hours, 5000 hours, and 7000 hours was visually determined using a sunshine weatherometer.
Judgment criteria: ;: no hair crack on sealing material surface, Δ: slight hair crack on sealing material surface, x: many hair cracks on sealing material surface.
表2に示すように、実施例1〜9では、50℃で28日間及び56日間保存後の接着性が初期及び耐水試験後共に改善されており、且つ製造直後の指触乾燥時間及びゴム硬度が50℃で28日間及び56日間保存後も維持されていた。一方、比較例1では、製造直後の接着性は良好であったが、保存日数が経つにつれ接着性、特に耐水試験後の接着性が低減しており、且つ保存後の硬化特性も低下していた。実施例2、3及び6〜9は特に耐候性が向上していた。
As shown in Table 2, in Examples 1 to 9, the adhesiveness after storage at 50 ° C. for 28 days and 56 days was improved both at the initial stage and after the water resistance test, and the dry time to touch and the rubber hardness immediately after production. Was maintained after storage at 50 ° C. for 28 and 56 days. On the other hand, in Comparative Example 1, the adhesiveness immediately after the production was good, but the adhesiveness, particularly the adhesiveness after the water resistance test, decreased over the storage days, and the curing characteristics after the storage decreased. Was. In Examples 2, 3, and 6 to 9, the weather resistance was particularly improved.
Claims (8)
(B)アクリル系重合体、
(C)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物、及び
(D)硬化触媒を含有することを特徴とする硬化性組成物。 (A) a crosslinkable silyl group-containing organic polymer,
(B) an acrylic polymer,
A curable composition comprising (C) a compound which reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule, and (D) a curing catalyst.
(B)アクリル系重合体、
(C1)一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物、
(C2)カルボニル化合物、及び
(D)硬化触媒を含有することを特徴とする硬化性組成物。 (A) a crosslinkable silyl group-containing organic polymer,
(B) an acrylic polymer,
(C1) an amine compound having at least one alkoxysilyl group in one molecule,
A curable composition comprising (C2) a carbonyl compound and (D) a curing catalyst.
(C)水と反応して一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物を生成する化合物、及び
(D)硬化触媒を含有することを特徴とする硬化性組成物。 (A1) a crosslinkable silyl group-containing acrylic polymer,
A curable composition comprising (C) a compound which reacts with water to produce an amine compound having at least one alkoxysilyl group in one molecule, and (D) a curing catalyst.
(C1)一分子中に少なくとも一個のアルコキシシリル基を有するアミン化合物、
(C2)カルボニル化合物、及び
(D)硬化触媒を含有することを特徴とする硬化性組成物。 (A1) a crosslinkable silyl group-containing acrylic polymer,
(C1) an amine compound having at least one alkoxysilyl group in one molecule,
A curable composition comprising (C2) a carbonyl compound and (D) a curing catalyst.
The curable composition according to any one of claims 1 to 7, wherein (E) an epoxy resin is further added.
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JP2005319601A (en) * | 2004-05-06 | 2005-11-17 | Sustainable Titania Technology Inc | Hydrophilizing stainproof method of water repellent substrate and its use in artificial article |
JP4508717B2 (en) * | 2004-05-06 | 2010-07-21 | サスティナブル・テクノロジー株式会社 | Hydrophobic antifouling method for water repellent substrate and its use in artifacts |
WO2021157583A1 (en) * | 2020-02-04 | 2021-08-12 | 株式会社カネカ | Composition, curable composition, cured product, and storage method |
WO2021157584A1 (en) * | 2020-02-04 | 2021-08-12 | 株式会社カネカ | Curable composition and cured product |
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