JP2011178955A - Curable composition - Google Patents
Curable composition Download PDFInfo
- Publication number
- JP2011178955A JP2011178955A JP2010046783A JP2010046783A JP2011178955A JP 2011178955 A JP2011178955 A JP 2011178955A JP 2010046783 A JP2010046783 A JP 2010046783A JP 2010046783 A JP2010046783 A JP 2010046783A JP 2011178955 A JP2011178955 A JP 2011178955A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- group
- curable composition
- reactive silicon
- molecular weight
- 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 99
- 229920000642 polymer Polymers 0.000 claims abstract description 336
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 66
- 125000000962 organic group Chemical group 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims description 74
- 239000003999 initiator Substances 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 31
- 125000002947 alkylene group Chemical group 0.000 claims description 23
- 238000012644 addition polymerization Methods 0.000 claims description 17
- 238000007142 ring opening reaction Methods 0.000 claims description 16
- 239000003566 sealing material Substances 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 14
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 16
- 238000011109 contamination Methods 0.000 abstract description 16
- -1 methyldimethoxysilylpropyl groups Chemical group 0.000 description 57
- 238000004519 manufacturing process Methods 0.000 description 43
- 239000000047 product Substances 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 29
- 238000006884 silylation reaction Methods 0.000 description 29
- 239000004014 plasticizer Substances 0.000 description 28
- 239000003795 chemical substances by application Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 21
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 18
- 239000000945 filler Substances 0.000 description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 14
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 229920006158 high molecular weight polymer Polymers 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 150000003606 tin compounds Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 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
- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 239000013008 thixotropic agent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 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
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 102100035474 DNA polymerase kappa Human genes 0.000 description 2
- 101710108091 DNA polymerase kappa Proteins 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 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
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 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
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000012945 sealing adhesive Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 description 1
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VTPBXYSZYMYEMR-UHFFFAOYSA-N 2,2-bis(trimethylsilyloxymethyl)butoxy-trimethylsilane Chemical compound C[Si](C)(C)OCC(CC)(CO[Si](C)(C)C)CO[Si](C)(C)C VTPBXYSZYMYEMR-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- PARCMDAOZHNXLU-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O PARCMDAOZHNXLU-UHFFFAOYSA-N 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
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Landscapes
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、反応性ケイ素基を有する重合体を含有し、空気中の湿分により室温で硬化可能な硬化性組成物に関する。 The present invention relates to a curable composition containing a polymer having a reactive silicon group and curable at room temperature by moisture in the air.
反応性ケイ素基を有する重合体は、反応性ケイ素基が加水分解、縮合反応してシロキサン結合を形成することによって架橋する。したがって、室温下で空気中の湿分により硬化可能であり、硬化後はゴム弾性を有する硬化物となる。得られる硬化物は様々な被着体に対して優れた特性を有していることから、シーリング材、接着剤、被覆または密封用組成物の主剤等として広く用いられている。 The polymer having a reactive silicon group is crosslinked by the hydrolysis and condensation reaction of the reactive silicon group to form a siloxane bond. Therefore, it can be cured by moisture in the air at room temperature, and becomes a cured product having rubber elasticity after curing. Since the obtained cured product has excellent characteristics for various adherends, it is widely used as a base material for sealing materials, adhesives, coatings or sealing compositions.
一般にシーリング材、接着剤等に用いられる硬化性組成物は、その硬化物が柔軟であり、かつよく伸びることが好ましく、そのために硬化性組成物に可塑剤が配合されている。
該可塑剤としては、芳香族カルボン酸エステル類、脂肪族カルボン酸エステル類、グリコールエステル類、リン酸エステル類、エポキシ系可塑剤、塩素化パラフィン等が一般的に使用される。
また可塑剤として、アクリル系重合体、ポリエーテル系重合体を用いることも知られている(特許文献1)。
しかしながら、これらの可塑剤は移行性があるため硬化物から流出しやすく、シーリング部周辺の汚染、接着性への悪影響、表面塗装への汚染や密着性低下、等の問題がある。
In general, a curable composition used for a sealing material, an adhesive or the like is preferably a cured product that is flexible and stretches well. For this purpose, a plasticizer is blended in the curable composition.
As the plasticizer, aromatic carboxylic acid esters, aliphatic carboxylic acid esters, glycol esters, phosphate esters, epoxy plasticizers, chlorinated paraffins and the like are generally used.
It is also known to use an acrylic polymer or a polyether polymer as a plasticizer (Patent Document 1).
However, since these plasticizers have migratory properties, they easily flow out of the cured product, and there are problems such as contamination around the sealing portion, adverse effects on adhesion, contamination on the surface coating, and poor adhesion.
これに対して、移行性が低い可塑剤として反応性ケイ素基を有する低分子量の重合体を用いることが提案されている。例えば特許文献2には、1分子に平均1〜1.5個の反応性ケイ素基を有する分子量8,000〜5万の高分子量重合体(I)と、1分子に平均0.5〜1.5個の反応性ケイ素基を有する分子量300〜8,000の低分子量重合体(II)とを組み合わせた硬化性組成物が記載されている。特許文献2において、高分子量重合体(I)の実施例としては、1分子に平均1.2〜1.8個のメチルジメトキシシリルプロピル基を有する分子量18,000の重合体A〜Cが記載されている。 On the other hand, it has been proposed to use a low molecular weight polymer having a reactive silicon group as a plasticizer having low migration. For example, in Patent Document 2, a high molecular weight polymer (I) having a molecular weight of 8,000 to 50,000 having an average of 1 to 1.5 reactive silicon groups per molecule and an average of 0.5 to 1 per molecule. A curable composition is described in combination with a low molecular weight polymer (II) having 300 reactive molecular groups and a molecular weight of 300 to 8,000. In Patent Document 2, as examples of the high molecular weight polymer (I), polymers A to C having a molecular weight of 18,000 having an average of 1.2 to 1.8 methyldimethoxysilylpropyl groups per molecule are described. Has been.
ところで、優れた伸び物性を発現させるには、反応性ケイ素基を有する高分子量重合体として、従来の高分子量重合体よりもさらに高分子量であるものが好ましい。しかし、高分子量化した高分子量重合体は粘度が高く、その硬化物をシーリング材や接着剤として用いる場合に作業性が損なわれるという問題があった。高分子量化した高分子量重合体を用いて、シーリング材や接着剤用の硬化性組成物とするためには、より多くの可塑剤を必要とするが、前述の通り、移行性がある可塑剤ではシーリング部周辺の汚染、接着性への悪影響、表面塗装への汚染や密着性低下、等の問題が顕著に現れてしまうため、特に改良が求められていた。
また本発明者等の知見によると、移行性が低い可塑剤として反応性ケイ素基を有する低分子量重合体を用いる方法においても、硬化物の柔軟性、伸び、耐久性、または塗膜汚染性に劣る場合があり、改善が必要であることが判明した。
By the way, in order to develop excellent elongation properties, it is preferable that the high molecular weight polymer having a reactive silicon group has a higher molecular weight than the conventional high molecular weight polymer. However, the high molecular weight polymer has a high viscosity, and there is a problem that workability is impaired when the cured product is used as a sealing material or an adhesive. In order to obtain a curable composition for a sealing material or an adhesive by using a high molecular weight polymer, a larger amount of plasticizer is required. However, since problems such as contamination around the sealing portion, adverse effects on adhesiveness, contamination on the surface coating and lowering of adhesiveness appear remarkably, improvement has been particularly demanded.
In addition, according to the knowledge of the present inventors, even in a method using a low molecular weight polymer having a reactive silicon group as a plasticizer having low migration, the cured product has flexibility, elongation, durability, or coating contamination. It turned out to be inferior and needed to be improved.
本発明は前記事情に鑑みてなされたもので、硬化物の柔軟性、伸び及び耐久性が良好で、かつ塗膜汚染性のない硬化性組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable composition in which the cured product has good flexibility, elongation and durability and is free from coating film contamination.
本発明は、下記[1]〜[8]の発明である。
[1]直鎖状で、両末端に反応性ケイ素基を導入可能な前駆重合体(A’)に、下式(1)で表される反応性ケイ素基を導入して得られる重合体であって、数平均分子量が2万以上、4万以下である重合体(A)、および直鎖状で、片末端に反応性ケイ素基を導入可能な前駆重合体(B’)に、下式(1)で表される反応性ケイ素基を導入して得られる重合体であって、数平均分子量が3,000以上、2万以下であり、かつ前記前駆重合体(B’)の反応性ケイ素基を導入可能な末端基のうち前記反応性ケイ素基に置換された末端基の割合が60〜100モル%である重合体(B)を含有し、前記重合体(A)の含有量と前記重合体(B)の含有量の質量比(A/B)が、95/5〜5/95である、硬化性組成物。
−SiX1 2R1・・・(1)
[式中、R1は置換基を有していてもよい炭素数1〜20の1価の有機基(加水分解性基を除く。)を示し、X1は水酸基又は加水分解性基を示す。2個のX1は互いに同一でも異なっていてもよい。]
The present invention is the following [1] to [8].
[1] A polymer obtained by introducing a reactive silicon group represented by the following formula (1) into a linear precursor polymer (A ′) capable of introducing reactive silicon groups at both ends. And a polymer (A) having a number average molecular weight of 20,000 or more and 40,000 or less, and a linear precursor polymer (B ′) capable of introducing a reactive silicon group at one end, A polymer obtained by introducing the reactive silicon group represented by (1), having a number average molecular weight of 3,000 or more and 20,000 or less, and the reactivity of the precursor polymer (B ′) A polymer (B) in which the ratio of the terminal group substituted with the reactive silicon group in the terminal group capable of introducing a silicon group is 60 to 100 mol%, and the content of the polymer (A); The curable composition whose mass ratio (A / B) of content of the said polymer (B) is 95/5-5/95.
-SiX 1 2 R 1 (1)
[Wherein, R 1 represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X 1 represents a hydroxyl group or a hydrolyzable group. . Two X 1 may be the same or different from each other. ]
[2]前記重合体(A)の分子量分布(Mw/Mn)が1.0〜1.8である、[1]の硬化性組成物。
[3]前記重合体(B)の分子量分布(Mw/Mn)が1.0〜1.8である、[1]または[2]の硬化性組成物。
[4]前記重合体(A)において、前記前駆重合体(A’)の反応性ケイ素基を導入可能な末端基のうち前記反応性ケイ素基に置換された末端基の割合が、70〜100モル%である、[1]〜[3]の硬化性組成物。
[5]前記前駆重合体(A’)が、触媒の存在下で、活性水素を2個有する開始剤にアルキレンオキシドを開環付加重合させて製造した前駆重合体(A’1)である、[1]〜[4]の硬化性組成物。
[6]前記前駆重合体(A’)が、触媒の存在下で、活性水素を2個有する開始剤にアルキレンオキシドを開環付加重合させて製造した、両末端が水酸基である重合体の水酸基をアルコラート化して−OM(Mはアルカリ金属)とした後、不飽和基含有ハロゲン化炭化水素と反応させる方法で製造した前駆重合体(A’2)である、[1]〜[4]の硬化性組成物。
[2] The curable composition of [1], wherein the polymer (A) has a molecular weight distribution (Mw / Mn) of 1.0 to 1.8.
[3] The curable composition according to [1] or [2], wherein the polymer (B) has a molecular weight distribution (Mw / Mn) of 1.0 to 1.8.
[4] In the polymer (A), the ratio of terminal groups substituted with the reactive silicon group among the terminal groups into which the reactive silicon group of the precursor polymer (A ′) can be introduced is 70 to 100. Curable composition of [1]-[3] which is mol%.
[5] The precursor polymer (A ′) is a precursor polymer (A′1) produced by ring-opening addition polymerization of alkylene oxide to an initiator having two active hydrogens in the presence of a catalyst. [1]-[4] curable composition.
[6] Hydroxyl group of a polymer in which the precursor polymer (A ′) is produced by ring-opening addition polymerization of alkylene oxide to an initiator having two active hydrogens in the presence of a catalyst. Of [1] to [4], which is a precursor polymer (A′2) produced by a method in which is alcoholated to -OM (M is an alkali metal) and then reacted with an unsaturated group-containing halogenated hydrocarbon Curable composition.
[7]前記前駆重合体(B’)が、触媒の存在下で、活性水素を1個有する開始剤にアルキレンオキシドを開環付加重合させて製造した前駆重合体(B’1)である、[1]〜[6]の硬化性組成物。
[8]前記前駆重合体(B’)が、触媒の存在下で、活性水素を1個有する開始剤にアルキレンオキシドを開環付加重合させて製造した、片末端が水酸基である重合体の水酸基をアルコラート化して−OM(Mはアルカリ金属)とした後、不飽和基含有ハロゲン化炭化水素と反応させる方法で製造した前駆重合体(B’2)である、[1]〜[6]の硬化性組成物。
[9]シーリング材用または接着剤用である、[1]〜[8]の硬化性組成物。
[7] The precursor polymer (B ′) is a precursor polymer (B′1) produced by ring-opening addition polymerization of an alkylene oxide to an initiator having one active hydrogen in the presence of a catalyst. [1]-[6] curable composition.
[8] A hydroxyl group of a polymer in which the precursor polymer (B ′) is produced by ring-opening addition polymerization of alkylene oxide to an initiator having one active hydrogen in the presence of a catalyst, and one end of which is a hydroxyl group Of [1] to [6], which is a precursor polymer (B′2) produced by a method in which is alcoholated to -OM (M is an alkali metal) and then reacted with an unsaturated group-containing halogenated hydrocarbon Curable composition.
[9] The curable composition of [1] to [8], which is for a sealing material or an adhesive.
本発明の硬化性組成物によれば、硬化物において良好な柔軟性、伸び及び耐久性で、かつ塗膜汚染性がない硬化物を得ることができる。 According to the curable composition of the present invention, it is possible to obtain a cured product having good flexibility, elongation and durability in the cured product and having no coating film contamination.
本明細書における質量平均分子量(Mw、以下「Mw」とも記す。)および数平均分子量(Mn、以下「Mn」とも記す。)は、ゲル浸透クロマトグラフィ−(GPC)によって測定したポリスチレン換算分子量である。また本明細書における分子量分布(以下、「Mw/Mn」とも記す。)は、前記方法で測定したMw、Mnより算出した値であり、数平均分子量(Mn)に対する質量平均分子量(Mw)の比率(Mw/Mn)である。
本明細書において水酸基価から換算した分子量を「水酸基換算分子量MW(OH)」と記す。すなわち、水酸基価(重合体中に含まれる水酸基の量(単位:mgKOH/g))と水酸基換算分子量MW(OH)の関係は以下の式で表わされる。
水酸基換算分子量MW(OH)=重合体の開始剤として用いた化合物の一分子当たりの水酸基の数×56,100/水酸基価
本明細書における水酸基価は、JIS K 1557−1に準拠した方法で測定した値である。
本明細書における粘度の値(単位:mPa・s、またはPa・s)は、E型粘度計を用い25℃、No.4ローター(コーンロータ:3°×R14)、若しくはNo.1ローター(コーンロータ:1°34′×R24)を用いて測定した値である。
The mass average molecular weight (Mw, hereinafter also referred to as “Mw”) and the number average molecular weight (Mn, hereinafter also referred to as “Mn”) in the present specification are molecular weights in terms of polystyrene measured by gel permeation chromatography (GPC). . The molecular weight distribution in the present specification (hereinafter also referred to as “Mw / Mn”) is a value calculated from Mw and Mn measured by the above-described method, and is a mass average molecular weight (Mw) with respect to the number average molecular weight (Mn). The ratio (Mw / Mn).
In the present specification, the molecular weight converted from the hydroxyl value is referred to as “hydroxyl converted molecular weight MW (OH)”. That is, the relationship between the hydroxyl value (the amount of hydroxyl group contained in the polymer (unit: mg KOH / g)) and the hydroxyl equivalent molecular weight MW (OH) is represented by the following formula.
Hydroxyl equivalent molecular weight MW (OH) = number of hydroxyl groups per molecule of the compound used as the initiator of the polymer × 56,100 / hydroxyl value The hydroxyl value in the present specification is a method based on JIS K1557-1. It is a measured value.
The viscosity value (unit: mPa · s or Pa · s) in this specification is determined using an E-type viscometer at 25 ° C. 4 rotor (cone rotor: 3 ° × R14), or No. It is a value measured using one rotor (cone rotor: 1 ° 34 ′ × R24).
<重合体(A)>
本発明で用いられる重合体(A)は、上式(1)で表される反応性ケイ素基を有する。
式(1)において、R1は置換基を有していてもよい炭素数1〜20の1価の有機基(加水分解性基を除く。)を示す。R1は、炭素数8以下の炭化水素基が好ましい。具体例としてはメチル基、エチル基、プロピル基、ブチル基、ヘキシル基、シクロヘキシル基、フェニル基等が挙げられる。メチル基、フェニル基がより好ましく、特にメチル基が好ましい。
<Polymer (A)>
The polymer (A) used in the present invention has a reactive silicon group represented by the above formula (1).
In Formula (1), R 1 represents a monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group) which may have a substituent. R 1 is preferably a hydrocarbon group having 8 or less carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and a phenyl group. A methyl group and a phenyl group are more preferable, and a methyl group is particularly preferable.
式(1)において、X1は水酸基又は加水分解性基を示す。1分子中に存在する2個のX1は互いに同一でも異なっていてもよい。
加水分解性基とは、ケイ素原子に直結し、加水分解反応及び/又は縮合反応によってシロキサン結合を生じ得る置換基をいう。該加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基、アルケニルオキシ基が挙げられる。加水分解性基が炭素原子を有する場合、その炭素数は6以下であることが好ましく、4以下であることがより好ましい。X1としては、特に、炭素数4以下のアルコキシ基又は炭素数4以下のアルケニルオキシ基が好ましい。より具体的には、X1はメトキシ基又はエトキシ基であることが特に好ましい。
In the formula (1), X 1 represents a hydroxyl group or a hydrolyzable group. Two X 1 existing in one molecule may be the same as or different from each other.
The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. X 1 is particularly preferably an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms. More specifically, X 1 is particularly preferably a methoxy group or an ethoxy group.
重合体(A)は、直鎖状で、両末端に反応性ケイ素基を導入可能な前駆重合体(A’)に、反応性ケイ素基を導入して得られる重合体である。すなわち直鎖状の前駆重合体(A’)の両末端基の一部または全部が反応性ケイ素基で置換された重合体である。
重合体(A)の末端に反応性ケイ素基があると、硬化物の伸び物性、内部硬化性、表面硬化性が良好となりやすい。
The polymer (A) is a polymer obtained by introducing reactive silicon groups into a precursor polymer (A ′) that is linear and capable of introducing reactive silicon groups at both ends. That is, it is a polymer in which part or all of both terminal groups of the linear precursor polymer (A ′) are substituted with reactive silicon groups.
When there is a reactive silicon group at the terminal of the polymer (A), the elongation property, internal curability and surface curability of the cured product are likely to be good.
重合体(A)は、前駆重合体(A’)の両末端基が反応性を有し、該末端基と反応する基および反応性ケイ素基の両方を有する化合物(以下、「シリル化剤」ともいう。)と、前駆重合体(A’)とを反応させて反応性ケイ素基を導入する方法で得ることができる。
前駆重合体(A’)の両末端基が、それぞれ独立に、不飽和性の二重結合を含む1価基(以下、不飽和基という。)または水酸基であることが好ましい。
The polymer (A) is a compound in which both terminal groups of the precursor polymer (A ′) are reactive and has both a group that reacts with the terminal group and a reactive silicon group (hereinafter referred to as “silylating agent”). And a precursor polymer (A ′) can be reacted to introduce a reactive silicon group.
It is preferable that both terminal groups of the precursor polymer (A ′) are each independently a monovalent group (hereinafter referred to as an unsaturated group) or a hydroxyl group containing an unsaturated double bond.
重合体(A)は、活性水素を2個有する開始剤に、アルキレンオキシド単量体および/または(メタ)アクリル酸アルキルエステル単量体を付加重合させる工程を経て得られるものが好ましい。
すなわち、前駆重合体(A’)および重合体(A)における繰り返し単位は、アルキレンオキシド単量体単位および/または(メタ)アクリル酸アルキルエステル単量体単位を含むことが好ましい。少なくともアルキレンオキシド単量体単位の連鎖、すなわちポリオキシアルキレン鎖を有することが好ましい。
重合体(A)がポリオキシアルキレン鎖を有すると温度依存性が小さい、硬化物の柔軟性が良好となりやすい、価格面で優れる等の利点がある。
The polymer (A) is preferably obtained through a step of addition polymerization of an alkylene oxide monomer and / or a (meth) acrylic acid alkyl ester monomer to an initiator having two active hydrogens.
That is, it is preferable that the repeating unit in the precursor polymer (A ′) and the polymer (A) includes an alkylene oxide monomer unit and / or a (meth) acrylic acid alkyl ester monomer unit. It is preferable to have at least a chain of alkylene oxide monomer units, that is, a polyoxyalkylene chain.
When the polymer (A) has a polyoxyalkylene chain, there are advantages such as low temperature dependence, easy flexibility of the cured product, and excellent price.
または重合体(A)の一部または全部として、前駆重合体(A’)および重合体(A)における繰り返し単位が、(メタ)アクリル酸アルキルエステル単量体単位を含み、ポリオキシアルキレン鎖を有しないアクリル系重合体を用いてもよい。かかる重合体は硬化物の機械強度向上、ならびに硬化性組成物及び硬化物の耐候性向上に寄与する。
本明細書において、(メタ)アクリル酸アルキルエステル単量体単位とは、(メタ)アクリル酸アルキルエステルから誘導される繰り返し単位を意味する。(メタ)アクリル酸アルキルエステルとは、アクリル酸アルキルエステル、メタクリル酸アルキルエステルまたは両者の混合物を意味する。
Alternatively, as a part or all of the polymer (A), the repeating unit in the precursor polymer (A ′) and the polymer (A) includes a (meth) acrylic acid alkyl ester monomer unit, and a polyoxyalkylene chain. You may use the acrylic polymer which does not have. Such a polymer contributes to improving the mechanical strength of the cured product and improving the weather resistance of the curable composition and the cured product.
In this specification, the (meth) acrylic acid alkyl ester monomer unit means a repeating unit derived from a (meth) acrylic acid alkyl ester. (Meth) acrylic acid alkyl ester means acrylic acid alkyl ester, methacrylic acid alkyl ester or a mixture of both.
前駆重合体(A’)としては、ポリオキシアルキレン鎖を有し、両末端が水酸基である、直鎖状の前駆重合体(A’1);またはポリオキシアルキレン鎖を有し、両末端が不飽和基である、直鎖状の前駆重合体(A’2)が好ましい。
前駆重合体(A’1)は、触媒の存在下で、活性水素を2個有する開始剤にアルキレンオキシドを開環付加重合させて製造できる。
開始剤としては、水酸基を2個有する化合物が好ましい。具体例としてはエチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、ネオペンチルグリコール、1,4−ブタンジオール、1,6−ヘキサンジオールが挙げられる。これらのうちでプロピレングリコール、ジプロピレングリコールがより好ましい。また、これらの水酸基を2個有する化合物にアルキレンオキシドを開環付加重合させて得られる、水酸基換算分子量MW(OH)が190〜20,000のポリオキシアルキレンジオールを開始剤として用いることもできる。開始剤は1種単独で使用してもよく2種以上を併用してもよい。
As the precursor polymer (A ′), a linear precursor polymer (A′1) having a polyoxyalkylene chain and both ends being hydroxyl groups; or having a polyoxyalkylene chain and both ends being A linear precursor polymer (A′2) which is an unsaturated group is preferred.
The precursor polymer (A′1) can be produced by subjecting an alkylene oxide to ring-opening addition polymerization to an initiator having two active hydrogens in the presence of a catalyst.
As the initiator, a compound having two hydroxyl groups is preferable. Specific examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol. Of these, propylene glycol and dipropylene glycol are more preferable. Further, polyoxyalkylene diol having a hydroxyl equivalent molecular weight MW (OH) of 190 to 20,000 obtained by ring-opening addition polymerization of alkylene oxide to a compound having two hydroxyl groups can be used as an initiator. An initiator may be used individually by 1 type and may use 2 or more types together.
前駆重合体(A’1)または開始剤の合成に用いられるアルキレンオキシドは、炭素数が2〜20であることが好ましく、具体的にはプロピレンオキシド、ブチレンオキシド、エチレンオキシド等が挙げられる。プロピレンオキシドが特に好ましい。アルキレンオキシドは1種単独で使用してもよく2種以上を併用してもよい。ポリオキシアルキレン鎖が2種以上のオキシアルキレン単量体単位からなる場合、該単量体単位の並び方は、ブロック状でもよくランダム状でもよい。
触媒としては、アルカリ金属触媒、複合金属シアン化物錯体触媒、金属ポルフィリン等が挙げられる。特に重合体(A)の分子量分布が小さくなりやすい点で複合金属シアン化物錯体触媒が好ましい。
The alkylene oxide used for the synthesis of the precursor polymer (A′1) or the initiator preferably has 2 to 20 carbon atoms, and specific examples include propylene oxide, butylene oxide, ethylene oxide and the like. Propylene oxide is particularly preferred. An alkylene oxide may be used individually by 1 type, and may use 2 or more types together. When the polyoxyalkylene chain is composed of two or more oxyalkylene monomer units, the arrangement of the monomer units may be block or random.
Examples of the catalyst include an alkali metal catalyst, a double metal cyanide complex catalyst, and a metal porphyrin. In particular, a double metal cyanide complex catalyst is preferable because the molecular weight distribution of the polymer (A) tends to be small.
ポリオキシアルキレン鎖を有し、両末端が不飽和基である、直鎖状の前駆重合体(A’2)は、触媒の存在下で、活性水素を2個有する開始剤にアルキレンオキシドを開環付加重合させて製造した、両末端が水酸基である重合体、すなわち前駆重合体(A’1)の水酸基(−OH)をアルコラート化して−OM(Mはアルカリ金属)とした後、塩化アリルや塩化メタリル等の不飽和基含有ハロゲン化炭化水素と反応させる方法で製造できる。この方法は、一般的であり、また原料の入手のし易さや収率が高い点で好ましい。
または水酸基と反応しうる官能基および不飽和基を有する化合物を、前駆重合体(A’1)と反応させて、エステル結合、ウレタン結合、カーボネート結合などを介して不飽和基を導入する方法でも得られる。
In the presence of a catalyst, the linear precursor polymer (A′2) having a polyoxyalkylene chain and unsaturated groups at both ends opens an alkylene oxide to an initiator having two active hydrogens. A polymer produced by cycloaddition polymerization and having hydroxyl groups at both ends, that is, the hydroxyl group (—OH) of the precursor polymer (A′1) is alcoholated to -OM (M is an alkali metal), and then allyl chloride And a method of reacting with an unsaturated group-containing halogenated hydrocarbon such as methallyl chloride. This method is general and preferable in terms of easy availability of raw materials and high yield.
Alternatively, a compound having a functional group capable of reacting with a hydroxyl group and an unsaturated group is reacted with the precursor polymer (A′1) to introduce an unsaturated group via an ester bond, a urethane bond, a carbonate bond, or the like. can get.
前駆重合体(A’2)の末端の不飽和基に反応性ケイ素基を導入して重合体(A)を得る方法は公知の方法を用いることができる。例えば下記[1]または[2]の方法を用いることができる。
[1]末端の不飽和基と下式(2)で表される水素化ケイ素化合物を触媒の存在下で反応させる方法。ただし、式(2)中のX1、R1は上式(1)と同じである。
HSiX1 2R1・・・(2)
[2]末端の不飽和基と下式(3)で表されるケイ素化合物のメルカプト基とを反応させる方法。
W1R2−SiX1 2R1 …(3)
式(3)中のX1、R1は上式(1)と同じである。R2は2価の有機基であり、W1はメルカプト基である。
As a method for obtaining the polymer (A) by introducing a reactive silicon group into the terminal unsaturated group of the precursor polymer (A′2), a known method can be used. For example, the following method [1] or [2] can be used.
[1] A method of reacting a terminal unsaturated group with a silicon hydride compound represented by the following formula (2) in the presence of a catalyst. However, X 1 and R 1 in the formula (2) are the same as in the above formula (1).
HSiX 1 2 R 1 (2)
[2] A method of reacting a terminal unsaturated group with a mercapto group of a silicon compound represented by the following formula (3).
W 1 R 2 —SiX 1 2 R 1 (3)
X 1 and R 1 in the formula (3) are the same as those in the above formula (1). R 2 is a divalent organic group, and W 1 is a mercapto group.
前駆重合体(A’2)を経由せずに、前駆重合体(A’1)の末端の水酸基に反応性ケイ素基を導入して重合体(A)を得る方法は公知の方法を用いることができる。例えば下記[3]または[4]の方法を用いることができる。
[3]末端の水酸基と、下式(4)で表されるイソシアネートシラン化合物(U)とをウレタン化反応させる方法。この反応はウレタン化触媒の存在下に行ってもよい。
NCO−(CH2)n−SiX1 2R1 …(4)
式(4)中のX1、R1は上式(1)と同じである。nは1〜8の整数であり、好ましくは1〜3である。
イソシアネートシラン化合物(U)の好ましい例として、1−イソシアネートメチルジメトキシメチルシラン、1−イソシアネートメチルジエトキシエチルシラン、1−イソシアネートプロピルジメトキシメチルシラン、3−イソシアネートプロピルジメトキシメチルシラン、3−イソシアネートプロピルジエトキシエチルシラン等が挙げられる。
用いるウレタン化触媒は、特に限定されず、公知のウレタン化触媒を適宜用いることができる。例えば、有機錫化合物(ジブチル錫ジラウレート、ジオクチル錫ジラウレート等。)、ビスマス化合物等の金属触媒、有機アミン等の塩基触媒が用いられる。反応温度は、20〜200℃が好ましく、50〜150℃が特に好ましい。また、ウレタン化反応は、不活性ガス(窒素ガスが好ましい。)雰囲気下に行うのが好ましい。
A known method is used to obtain a polymer (A) by introducing a reactive silicon group into the terminal hydroxyl group of the precursor polymer (A′1) without going through the precursor polymer (A′2). Can do. For example, the following method [3] or [4] can be used.
[3] A method in which a terminal hydroxyl group and an isocyanate silane compound (U) represented by the following formula (4) are urethanated. This reaction may be performed in the presence of a urethanization catalyst.
NCO- (CH 2) n -SiX 1 2 R 1 ... (4)
X 1 and R 1 in the formula (4) are the same as in the above formula (1). n is an integer of 1 to 8, preferably 1 to 3.
Preferred examples of the isocyanate silane compound (U) include 1-isocyanate methyldimethoxymethylsilane, 1-isocyanatemethyldiethoxyethylsilane, 1-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyldiethoxy. Examples include ethylsilane.
The urethanization catalyst to be used is not specifically limited, A well-known urethanization catalyst can be used suitably. For example, organic tin compounds (dibutyltin dilaurate, dioctyltin dilaurate, etc.), metal catalysts such as bismuth compounds, and base catalysts such as organic amines are used. The reaction temperature is preferably 20 to 200 ° C, particularly preferably 50 to 150 ° C. The urethanization reaction is preferably performed in an inert gas (nitrogen gas is preferred) atmosphere.
[4]末端の水酸基と、トリレンジイソシアネートなどのポリイソシアネート化合物を反応させて末端をイソシアネート基とした後、該イソシアネート基に下式(5)で表されるケイ素化合物のW2で表わされる基を反応させる方法。
W2R3−SiX1 2R1 …(5)
式(5)中のX1、R1は上式(1)と同じである。R3は2価の有機基であり、W2は水酸基、カルボキシル基、メルカプト基およびアミノ基(1級または2級)から選ばれる活性水素含有基である。
[4] A group represented by W 2 of a silicon compound represented by the following formula (5) after reacting a terminal hydroxyl group with a polyisocyanate compound such as tolylene diisocyanate to convert the terminal to an isocyanate group. How to react.
W 2 R 3 -SiX 1 2 R 1 ... (5)
X 1 and R 1 in the formula (5) are the same as in the above formula (1). R 3 is a divalent organic group, and W 2 is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group, and an amino group (primary or secondary).
重合体(A)において、前駆重合体(A’)の、反応性ケイ素基を導入可能な末端基のうち反応性ケイ素基に置換された末端基の割合(以下、「シリル化率」ということもある。)は70〜100モル%が好ましい。
重合体(A)におけるシリル化率は、前駆重合体(A’)の末端基と、シリル化剤とを反応させる際の、該末端基と反応性ケイ素基とモル比によって制御できる。
本明細書におけるシリル化率の値は、NMR分析によって測定できる。または、通常、塩化メタリルを用いて製造した前駆重合体(A’)とシリル化剤との反応率はほぼ100%とみなすことができるため、前駆重合体(A’)の仕込量に対するシリル化剤の仕込量から計算される値を用いてもよい。塩化アリルを用いて製造した前駆重合体(A’)とシリル化剤の反応においては、副反応が起こる。塩化アリルを用いて製造した前駆重合体(A’)のおよそ10モル%のアリル基は、異性化し、シリル化されないため、100%のシリル化は困難である。しかしながら、およそシリル化率が90%までのシリル化においては、その反応率もほぼ100%とみなすことができる。よって、塩化アリルを用いて製造した前駆重合体(A’)とシリル化剤との反応により得ようとする重合体(A)のシリル化率が90%未満である場合には、重合体(A)におけるシリル化率の値として、前駆重合体(A’)の仕込量に対するシリル化剤の仕込量から計算される値を用いてもよい。
重合体(A)に該当する重合体を2種以上混合して用いる場合、混合した後の混合物におけるシリル化率が上記の範囲内であればよく、混合する前の重合体(A)の一部としてシリル化率が70%未満のものを用いてもよい。
後述する重合体(B)についても同様である。
In the polymer (A), the proportion of the terminal group of the precursor polymer (A ′) substituted with the reactive silicon group among the terminal groups capable of introducing the reactive silicon group (hereinafter referred to as “silylation rate”) Is also preferably 70 to 100 mol%.
The silylation rate in the polymer (A) can be controlled by the molar ratio between the terminal group and the reactive silicon group when the terminal group of the precursor polymer (A ′) is reacted with the silylating agent.
The value of the silylation rate in this specification can be measured by NMR analysis. Or, since the reaction rate between the precursor polymer (A ′) produced using methallyl chloride and the silylating agent can be regarded as almost 100%, silylation with respect to the charged amount of the precursor polymer (A ′). You may use the value calculated from the preparation amount of an agent. In the reaction between the precursor polymer (A ′) produced using allyl chloride and the silylating agent, a side reaction occurs. Approximately 10 mol% of the allyl group of the precursor polymer (A ′) produced using allyl chloride is isomerized and not silylated, so that 100% silylation is difficult. However, in a silylation with a silylation rate of up to 90%, the reaction rate can be regarded as almost 100%. Therefore, when the silylation rate of the polymer (A) to be obtained by the reaction between the precursor polymer (A ′) produced using allyl chloride and the silylating agent is less than 90%, the polymer ( As the value of the silylation rate in A), a value calculated from the charged amount of the silylating agent with respect to the charged amount of the precursor polymer (A ′) may be used.
When two or more kinds of polymers corresponding to the polymer (A) are mixed and used, the silylation rate in the mixture after mixing may be within the above range, and one of the polymers (A) before mixing. A part having a silylation rate of less than 70% may be used.
The same applies to the polymer (B) described later.
本発明の硬化性組成物において、重合体(B)の配合量がより多い方が低粘度になる。一方、重合体(A)に重合体(B)を配合し硬化させると、重合体(A)同士が架橋すると共に、重合体(A)の一部が重合体(B)と反応する。重合体(B)は片末端にのみ反応性ケイ素基を有するため、重合体(A)が重合体(B)と反応することにより、重合体(A)の架橋が阻害される。よって重合体(B)の配合量が多すぎると、硬化不良となり未硬化となる場合がある。
すなわち、硬化性組成物をより低粘度にし、かつ硬化不良にしないためには、重合体(B)の配合量が多く、かつ重合体(A)のシリル化率が高い方が有利である。重合体(A)のシリル化率が高いほど、重合体(B)を多く配合しても、量比の関係から架橋が阻害されにくく、未硬化となりにくい。
よって重合体(A)のシリル化率は、重合体(B)が配合された硬化性組成物において、良好な硬化性が得られる範囲であることが必要であり、シリル化率が高い方が、重合体(B)の添加量を増やすことができる。重合体(B)の配合量が多い方が、より低粘度となるため、シーリング材や接着剤用の硬化性組成物として作業性がより良好になる。
In the curable composition of the present invention, the higher the amount of the polymer (B), the lower the viscosity. On the other hand, when the polymer (B) is blended with the polymer (A) and cured, the polymers (A) are cross-linked and a part of the polymer (A) reacts with the polymer (B). Since the polymer (B) has a reactive silicon group only at one end, the polymer (A) reacts with the polymer (B) to inhibit the crosslinking of the polymer (A). Therefore, when there are too many compounding quantities of a polymer (B), it will be hardened | cured and may become uncured.
That is, in order to make the curable composition have a lower viscosity and not to cause poor curing, it is advantageous that the amount of the polymer (B) is large and the silylation rate of the polymer (A) is high. The higher the silylation rate of the polymer (A), the more the polymer (B) is blended, the more difficult the crosslinking is due to the quantitative ratio, and the harder it becomes uncured.
Therefore, the silylation rate of the polymer (A) needs to be in a range where good curability can be obtained in the curable composition in which the polymer (B) is blended, and the higher silylation rate is. The amount of the polymer (B) added can be increased. Since the one where there is much blending quantity of a polymer (B) becomes lower viscosity, workability | operativity becomes better as a curable composition for sealing materials and adhesives.
前駆重合体(A’)が、反応性ケイ素基を導入可能な末端基として水酸基を有する場合、該水酸基の全部のうち反応性ケイ素基に置換された末端基の割合(シリル化率)は、70モル%以上が好ましく、75モル%以上がより好ましい。70モル%未満であると、配合にもよるが硬化しないゲル状物となり、シーリング材、接着剤を製造できないおそれがある。該シリル化率は100モル%でもよい。
また、前駆重合体(A’)が反応性ケイ素基を導入可能な末端基として不飽和基を有する場合も、同様の理由で、シリル化率は70モル%以上が好ましく、75モル%以上がより好ましい。該シリル化率は100モル%でもよい。
When the precursor polymer (A ′) has a hydroxyl group as a terminal group into which a reactive silicon group can be introduced, the ratio of the terminal group substituted with the reactive silicon group (silylation rate) among all the hydroxyl groups is: 70 mol% or more is preferable, and 75 mol% or more is more preferable. If it is less than 70 mol%, it becomes a gel-like material that does not harden depending on the formulation, and there is a possibility that a sealing material and an adhesive cannot be produced. The silylation rate may be 100 mol%.
Further, when the precursor polymer (A ′) has an unsaturated group as a terminal group capable of introducing a reactive silicon group, for the same reason, the silylation rate is preferably 70 mol% or more, and 75 mol% or more. More preferred. The silylation rate may be 100 mol%.
重合体(A)の数平均分子量(Mn)は2万以上、4万以下であり、好ましくは2万以上、3万以下である。2万以上であると、硬化物から重合体(B)が流出するのが良好に抑制される。また硬化物の耐久性が良好となる。4万以下であると組成物が低粘度となりやすく、良好な作業性を得るうえで好ましい。特に硬化物の優れた伸びが得られやすい点で、2万以上、28,000以下が好ましい。
重合体(A)の分子量分布(Mw/Mn)は、1.0〜1.8が好ましく、1.0〜1.3がより好ましい。数平均分子量(Mn)が2万以上、4万以下のポリマーとして分子量分布(Mw/Mn)が上記の範囲内であると、数平均分子量(Mn)が100,000以上のものや少ないため重合体として粘度が低く、一方、粘度の低い低分子成分も少ないため硬化物として優れた伸びが得られやすく、硬化時の構造が均一な網目構造になり最大応力が高くなったり、接着強度が優れることが考えられるという点で、1.0〜1.2がさらに好ましい。
重合体(A)の分子量分布(Mw/Mn)は、触媒の種類や重合条件(温度、攪拌条件、圧力等)により制御できる。
重合体(A)に該当する重合体を2種以上混合して用いる場合、混合する前の重合体(A)のそれぞれにおける、末端当たりの数平均分子量(Mn)および分子量分布(Mw/Mn)が上記の範囲内となっていればよい。
後述する重合体(B)についても同様である。
The number average molecular weight (Mn) of the polymer (A) is 20,000 or more and 40,000 or less, preferably 20,000 or more and 30,000 or less. If it is 20,000 or more, the outflow of the polymer (B) from the cured product is satisfactorily suppressed. Moreover, durability of hardened | cured material becomes favorable. When the ratio is 40,000 or less, the composition tends to have a low viscosity, which is preferable for obtaining good workability. In particular, 20,000 or more and 28,000 or less are preferable in that excellent elongation of the cured product can be easily obtained.
1.0-1.8 are preferable and, as for molecular weight distribution (Mw / Mn) of a polymer (A), 1.0-1.3 are more preferable. If the molecular weight distribution (Mw / Mn) is within the above range as a polymer having a number average molecular weight (Mn) of 20,000 or more and 40,000 or less, the polymer has a number average molecular weight (Mn) of 100,000 or more and is heavy. The viscosity is low as a coalescence, but on the other hand, since there are few low molecular components with low viscosity, it is easy to obtain excellent elongation as a cured product. In view of this, 1.0 to 1.2 is more preferable.
The molecular weight distribution (Mw / Mn) of the polymer (A) can be controlled by the type of catalyst and polymerization conditions (temperature, stirring conditions, pressure, etc.).
When two or more kinds of polymers corresponding to the polymer (A) are used in combination, the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) per terminal in each of the polymers (A) before mixing. Should just be in said range.
The same applies to the polymer (B) described later.
重合体(A)は式(1)で表わされる反応性ケイ素基以外の反応性ケイ素基を有してもよいが、貯蔵安定性や伸び物性が優れるという点から、重合体(A)の反応性ケイ素基は式(1)で表わされる反応性ケイ素基のみであることが好ましい。
重合体(A)は1種単独でもよく、2種以上を併用してもよい。
重合体(A)に該当する2種以上の重合体が、硬化性組成物中に共存する場合、それらの反応性ケイ素基は互いに同じであってもよく、異なっていてもよい。
Although the polymer (A) may have a reactive silicon group other than the reactive silicon group represented by the formula (1), the reaction of the polymer (A) from the viewpoint of excellent storage stability and elongation property. The reactive silicon group is preferably only the reactive silicon group represented by the formula (1).
The polymer (A) may be used alone or in combination of two or more.
When two or more kinds of polymers corresponding to the polymer (A) coexist in the curable composition, their reactive silicon groups may be the same as or different from each other.
<重合体(B)>
重合体(B)は、上式(1)で表される反応性ケイ素基を有する。
硬化性組成物中に共存する重合体(A)の反応性ケイ素基と、重合体(B)の反応性ケイ素基は互いに同じであってもよく、異なっていてもよい。
<Polymer (B)>
The polymer (B) has a reactive silicon group represented by the above formula (1).
The reactive silicon group of the polymer (A) coexisting in the curable composition and the reactive silicon group of the polymer (B) may be the same or different from each other.
重合体(B)は、直鎖状で、片末端に反応性ケイ素基を導入可能な前駆重合体(B’)に、反応性ケイ素基を導入して得られる重合体である。
具体的には、前駆重合体(B’)の両末端のうちの一方の末端基が反応性を有する基、好ましくは水酸基または不飽和基であり、該末端基と反応する基および反応性ケイ素基を有する化合物と、前駆重合体(B’)とを反応させて反応性ケイ素基を導入することが好ましい。前駆重合体(B’)の他方の末端基は、前記反応性ケイ素基を有する化合物との反応性を有しない、不活性な有機基であることが好ましい。
The polymer (B) is a polymer obtained by introducing a reactive silicon group into a precursor polymer (B ′) that is linear and capable of introducing a reactive silicon group at one end.
Specifically, one terminal group of both ends of the precursor polymer (B ′) is a reactive group, preferably a hydroxyl group or an unsaturated group, a group that reacts with the terminal group, and reactive silicon. It is preferable to introduce a reactive silicon group by reacting a compound having a group with the precursor polymer (B ′). The other terminal group of the precursor polymer (B ′) is preferably an inert organic group that does not have reactivity with the compound having a reactive silicon group.
重合体(B)は、活性水素を1個有する開始剤に、アルキレンオキシド単量体および/または(メタ)アクリル酸アルキルエステル単量体を付加重合させる工程を経て得られるものが好ましい。
すなわち前駆重合体(B’)および重合体(B)における繰り返し単位は、アルキレンオキシド単量体単位および/または(メタ)アクリル酸アルキルエステル単量体単位を含むことが好ましい。少なくともアルキレンオキシド単量体単位の連鎖、すなわちポリオキシアルキレン鎖を有することが好ましい。
重合体(B)がポリオキシアルキレン鎖を有すると、重合体(A)との相溶性がよく貯蔵安定性がよいので好ましい。
または重合体(B)の一部または全部として、重前駆重合体(B’)および重合体(B)における繰り返し単位が、(メタ)アクリル酸アルキルエステル単量体単位を含み、ポリオキシアルキレン鎖を有しないアクリル系重合体を用いてもよい。かかる重合体は硬化物の耐候性や、硬化物表面と塗料との密着性や汚染性低減に寄与する。
The polymer (B) is preferably obtained by subjecting an initiator having one active hydrogen to an addition polymerization of an alkylene oxide monomer and / or a (meth) acrylic acid alkyl ester monomer.
That is, the repeating unit in the precursor polymer (B ′) and the polymer (B) preferably includes an alkylene oxide monomer unit and / or a (meth) acrylic acid alkyl ester monomer unit. It is preferable to have at least a chain of alkylene oxide monomer units, that is, a polyoxyalkylene chain.
It is preferable that the polymer (B) has a polyoxyalkylene chain because the compatibility with the polymer (A) is good and the storage stability is good.
Alternatively, as a part or all of the polymer (B), the repeating unit in the heavy precursor polymer (B ′) and the polymer (B) includes a (meth) acrylic acid alkyl ester monomer unit, and a polyoxyalkylene chain You may use the acrylic polymer which does not have. Such a polymer contributes to the weather resistance of the cured product, the adhesion between the cured product surface and the coating material, and the reduction of contamination.
前駆重合体(B’)としては、ポリオキシアルキレン鎖を有し、片末端が水酸基である、直鎖状の前駆重合体(B’1);ポリオキシアルキレン鎖を有し、片末端が不飽和基である、直鎖状の前駆重合体(B’2)が好ましい。
ポリオキシアルキレン鎖を有し、片末端が水酸基である、直鎖状の前駆重合体(B’1)は、触媒の存在下で、活性水素を1個有する開始剤にアルキレンオキシドを開環付加重合させて製造できる。
開始剤の具体例としては、炭素数1〜20の脂肪族モノオール、炭素数1〜20の脂環族モノオール、炭素数1〜20の芳香族モノオール、チオール、2級アミン、カルボン酸、または前記モノオールにアルキレンオキシドを開環付加重合させて得られる、水酸基換算分子量MW(OH)が300〜5,000のポリオキシアルキレンモノオールが挙げられる。より好ましいのは水酸基換算分子量MW(OH)が300〜3,300のポリオキシアルキレンモノオールである。またアリルアルコールのような、不飽和基含有モノヒドロキシ化合物も使用できる。開始剤は1種単独で使用してもよく2種以上を併用してもよい。
前駆重合体(B’1)または開始剤の合成に用いられるアルキレンオキシドおよび触媒は、上述の前駆重合体(A’1)の合成に用いられるアルキレンオキシドおよび触媒と、好ましい態様も含めて同様である。
前駆重合体(B’1)は、好ましくはポリオキシプロピレンモノオールである。
As the precursor polymer (B ′), a linear precursor polymer (B′1) having a polyoxyalkylene chain and one end being a hydroxyl group; having a polyoxyalkylene chain and having one end not A linear precursor polymer (B′2) which is a saturated group is preferred.
The linear precursor polymer (B'1), which has a polyoxyalkylene chain and one end is a hydroxyl group, undergoes ring-opening addition of alkylene oxide to an initiator having one active hydrogen in the presence of a catalyst. It can be produced by polymerization.
Specific examples of the initiator include an aliphatic monool having 1 to 20 carbon atoms, an alicyclic monool having 1 to 20 carbon atoms, an aromatic monool having 1 to 20 carbon atoms, a thiol, a secondary amine, and a carboxylic acid. Or a polyoxyalkylene monool having a hydroxyl equivalent molecular weight MW (OH) of 300 to 5,000 obtained by ring-opening addition polymerization of alkylene oxide to the monool. More preferred is a polyoxyalkylene monool having a hydroxyl equivalent molecular weight MW (OH) of 300 to 3,300. An unsaturated group-containing monohydroxy compound such as allyl alcohol can also be used. An initiator may be used individually by 1 type and may use 2 or more types together.
The alkylene oxide and catalyst used for the synthesis of the precursor polymer (B′1) or initiator are the same as the alkylene oxide and catalyst used for the synthesis of the precursor polymer (A′1) described above, including preferred embodiments. is there.
The precursor polymer (B′1) is preferably a polyoxypropylene monool.
ポリオキシアルキレン鎖を有し、片末端が不飽和基である、直鎖状の前駆重合体(B’2)は、片末端が水酸基である前駆重合体(B’1)の水酸基(−OH)をアルコラート化して−OM(Mはアルカリ金属)とした後、塩化アリル等の不飽和基含有ハロゲン化炭化水素と反応させる方法で製造できる。この方法は、一般的であり、原料の入手のし易さや反応収率が高い点で好ましい。
または水酸基と反応しうる官能基および不飽和基を有する化合物を、前駆重合体(B’1)と反応させて、エステル結合、ウレタン結合、カーボネート結合などを介して不飽和基を導入する方法でも得られる。
The linear precursor polymer (B′2) having a polyoxyalkylene chain and one end being an unsaturated group is a hydroxyl group (—OH) of the precursor polymer (B′1) having one end being a hydroxyl group. ) Is converted to -OM (M is an alkali metal) and then reacted with an unsaturated group-containing halogenated hydrocarbon such as allyl chloride. This method is general and is preferable in terms of easy availability of raw materials and high reaction yield.
Alternatively, a method in which a compound having a functional group capable of reacting with a hydroxyl group and an unsaturated group is reacted with the precursor polymer (B′1) to introduce an unsaturated group via an ester bond, a urethane bond, a carbonate bond, or the like. can get.
前駆重合体(B’2)の末端の不飽和基に反応性ケイ素基を導入して重合体(B)を得る方法は公知の方法を用いることができる.例えば上記[1]または[2]の方法を用いることができる。
前駆重合体(B’1)の末端の水酸基に反応性ケイ素基を導入して重合体(B)を得る方法は公知の方法を用いることができる。例えば上記[3]または[4]の方法を用いることができる。
As a method for obtaining the polymer (B) by introducing a reactive silicon group into the terminal unsaturated group of the precursor polymer (B′2), a known method can be used. For example, the above method [1] or [2] can be used.
As a method for obtaining the polymer (B) by introducing a reactive silicon group into the terminal hydroxyl group of the precursor polymer (B′1), a known method can be used. For example, the above method [3] or [4] can be used.
重合体(B)において、前駆重合体(B’)の、反応性ケイ素基を導入可能な末端基のうち反応性ケイ素基に置換された末端基の割合(シリル化率)は60〜100モル%である。
重合体(B)におけるシリル化率は、前駆重合体(B’)の末端の反応性を有する基と、反応性ケイ素基を有する化合物とを反応させる際の、該末端の反応性を有する基と反応性ケイ素基とモル比によって制御できる。
重合体(B)の片末端のシリル化率が60モル%以上であると可塑剤として移行性が低いものとなり、シーリング材部周辺の汚染、接着性が改善される。
特に、前駆重合体(B’)が、反応性ケイ素基を導入可能な末端基として水酸基を有する場合、該水酸基の全部のうち反応性ケイ素基に置換された末端基の割合(シリル化率)は上記の点から60モル%以上が好ましく、75モル%以上がより好ましい。
また同様に、前駆重合体(B’)が反応性ケイ素基を導入可能な末端基として不飽和基を有する場合も、同様の理由で、シリル化率は60モル%以上が好ましく、75モル%以上がより好ましい。該シリル化率は100モル%でもよい。
In the polymer (B), the ratio (silylation rate) of the terminal group substituted with the reactive silicon group among the terminal groups capable of introducing the reactive silicon group in the precursor polymer (B ′) is 60 to 100 mol. %.
The silylation rate in the polymer (B) is determined by reacting the terminal reactive group of the precursor polymer (B ′) with a compound having a reactive silicon group. And the reactive silicon group and the molar ratio can be controlled.
When the silylation rate at one end of the polymer (B) is 60 mol% or more, the plasticizer has low migration and the contamination around the sealing material portion and adhesion are improved.
In particular, when the precursor polymer (B ′) has a hydroxyl group as a terminal group capable of introducing a reactive silicon group, the ratio of the terminal group substituted with the reactive silicon group out of all the hydroxyl groups (silylation rate) Is preferably 60 mol% or more, more preferably 75 mol% or more from the above point.
Similarly, when the precursor polymer (B ′) has an unsaturated group as a terminal group capable of introducing a reactive silicon group, for the same reason, the silylation rate is preferably 60 mol% or more, preferably 75 mol%. The above is more preferable. The silylation rate may be 100 mol%.
重合体(B)の数平均分子量(Mn)は3,000以上、2万以下であり、好ましくは3,000以上、15,000以下であり、更に好ましくは、5,000以上、12,000以下である。該数平均分子量(Mn)が3,000以上であれば、重合体(B)が反応性ケイ素基を有していてもシーリング材部周辺の汚染がなく、接着性が改善され、硬化物が良好の物性を有する。2万以下であると重合体(B)の粘度が低くなり、可塑剤として有効に働く。
重合体(B)の分子量分布(Mw/Mn)は、1.0〜1.8が好ましく、1.0〜1.3がより好ましい。この範囲内であると製造しやすい。また、重合体としての粘度が低く硬化性組成物にしたときの作業性が良好となり、硬化時のべたつきも少なくなりうる。より好ましいMw/Mnは、1.0〜1.3である。
重合体(B)の分子量分布(Mw/Mn)は触媒の種類や重合条件(温度、攪拌条件、圧力等)により制御できる。
The number average molecular weight (Mn) of the polymer (B) is 3,000 or more and 20,000 or less, preferably 3,000 or more and 15,000 or less, more preferably 5,000 or more and 12,000. It is as follows. If the number average molecular weight (Mn) is 3,000 or more, even if the polymer (B) has a reactive silicon group, there is no contamination around the sealing material part, the adhesion is improved, and the cured product is Good physical properties. When it is 20,000 or less, the viscosity of the polymer (B) becomes low, and it works effectively as a plasticizer.
1.0-1.8 are preferable and, as for molecular weight distribution (Mw / Mn) of a polymer (B), 1.0-1.3 are more preferable. It is easy to manufacture in this range. Moreover, workability when the viscosity as a polymer is low and a curable composition is obtained is improved, and stickiness at the time of curing can be reduced. More preferable Mw / Mn is 1.0 to 1.3.
The molecular weight distribution (Mw / Mn) of the polymer (B) can be controlled by the type of catalyst and polymerization conditions (temperature, stirring conditions, pressure, etc.).
重合体(B)は、式(1)で表わされる反応性ケイ素基以外の反応性ケイ素基を有してもよいが、貯蔵安定性や伸び物性が優れるという点から、重合体(B)の反応性ケイ素基は式(1)で表わされる反応性ケイ素基のみであることが好ましい。
重合体(B)は1種単独でもよく、2種以上を併用してもよい。
重合体(B)に該当する2種以上の重合体が、硬化性組成物中に共存する場合、それらの反応性ケイ素基は互いに同じであってもよく、異なっていてもよい。
重合体(B)において、反応性ケイ素基以外の分子末端基は、不活性な有機基であることが好ましい。例えばアリルアルコールのような、不飽和基含有モノヒドロキシ化合物を開始剤として用いると、一方の末端基が水酸基で、他方の末端基が不飽和基である前駆重合体(B’1)が得られる。これの末端の不飽和基に反応性ケイ素基を導入して重合体(B)を得る場合、末端の水酸基は塩化ベンゾイルと反応させるなどの方法で不活性な有機基に変換することが好ましい。
The polymer (B) may have a reactive silicon group other than the reactive silicon group represented by the formula (1), but from the viewpoint of excellent storage stability and elongation property, the polymer (B) The reactive silicon group is preferably only the reactive silicon group represented by the formula (1).
A polymer (B) may be used individually by 1 type, and may use 2 or more types together.
When two or more kinds of polymers corresponding to the polymer (B) coexist in the curable composition, their reactive silicon groups may be the same as or different from each other.
In the polymer (B), the molecular end group other than the reactive silicon group is preferably an inert organic group. For example, when an unsaturated group-containing monohydroxy compound such as allyl alcohol is used as an initiator, a precursor polymer (B′1) is obtained in which one terminal group is a hydroxyl group and the other terminal group is an unsaturated group. . When a reactive silicon group is introduced into the terminal unsaturated group to obtain the polymer (B), the terminal hydroxyl group is preferably converted to an inert organic group by a method such as reacting with benzoyl chloride.
本発明の硬化性組成物は、重合体(A)と重合体(B)を含有する。重合体(A)の含有量と重合体(B)の含有量の質量比(A/B)は95/5〜5/95であり、好ましくは85/15〜50/50、より好ましくは80/20〜50/50である。
重合体(A)と重合体(B)の合計100質量%のうち、重合体(B)が5質量%以上であると充分な低粘度効果が得られ、95質量%以下であると硬化性組成物が硬化し、シーリング材、接着剤用の硬化性組成物として有用である。
The curable composition of this invention contains a polymer (A) and a polymer (B). The mass ratio (A / B) of the content of the polymer (A) and the content of the polymer (B) is 95/5 to 5/95, preferably 85/15 to 50/50, more preferably 80. / 20 to 50/50.
Of the total 100% by mass of the polymer (A) and the polymer (B), a sufficient low viscosity effect is obtained when the polymer (B) is 5% by mass or more, and the curability is 95% by mass or less. The composition is cured and is useful as a curable composition for sealing materials and adhesives.
<その他の成分>
本発明の硬化性組成物は、重合体(A)、(B)の他に、硬化性組成物において公知の成分を含むことができる。具体的には硬化触媒、充填材、添加剤、溶剤、可塑剤等である。また、任意成分として、重合体(A)、(B)以外の重合体として、物性を損なわない範囲で、耐候性や接着性向上のために、反応性ケイ素基を有する、アクリル系、ポリイソブチレン系、シリコン系またはポリウレタン系重合体を用いることができる。
<Other ingredients>
The curable composition of this invention can contain a well-known component in a curable composition other than a polymer (A) and (B). Specifically, a curing catalyst, a filler, an additive, a solvent, a plasticizer, and the like. In addition, as an optional component, a polymer other than the polymers (A) and (B) is an acrylic or polyisobutylene having a reactive silicon group in order to improve the weather resistance and adhesion as long as the physical properties are not impaired. , Silicon or polyurethane polymers can be used.
<硬化触媒>
硬化触媒としては下記の化合物が使用できる。
アルキルチタン酸塩、有機ケイ素チタン酸塩、ビスマストリス−2−エチルヘキソエート等の金属塩;リン酸、p−トルエンスルホン酸、フタル酸等の酸性化合物;ブチルアミン、ヘキシルアミン、オクチルアミン、デシルアミン、ラウリルアミン等の脂肪族モノアミン;、エチレンジアミン、ヘキサンジアミン等の脂肪族ジアミン;ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン等の脂肪族ポリアミン類;ピペリジン、ピペラジン等の複素環式アミン類;メタフェニレンジアミン等の芳香族アミン類;エタノールアミン類;トリエチルアミン、エポキシ樹脂の硬化剤として用いられる各種変性アミン等のアミン化合物。
ジオクチル酸錫(ビス(2−エチルヘキサン酸)スズ)、ジナフテン酸錫、ジステアリン酸錫等の2価の錫と、助触媒としての上記アミン類の混合物。
<Curing catalyst>
The following compounds can be used as the curing catalyst.
Metal salts such as alkyl titanates, organosilicon titanates, bismuth tris-2-ethylhexoate; acidic compounds such as phosphoric acid, p-toluenesulfonic acid, phthalic acid; butylamine, hexylamine, octylamine, decylamine Aliphatic diamines such as ethylenediamine and hexanediamine; aliphatic polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine; heterocyclic amines such as piperidine and piperazine; metaphenylene Amine compounds such as aromatic amines such as diamines; ethanolamines; various modified amines used as curing agents for triethylamine and epoxy resins.
A mixture of divalent tin such as tin dioctylate (bis (2-ethylhexanoate) tin), tin dinaphthenate and tin distearate and the above amines as a co-catalyst.
ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジオクチル錫ジラウレートおよび下記のカルボン酸型有機錫化合物;これらのカルボン酸型有機錫化合物と上記のアミン類との混合物。
(n−C4H9)2Sn(OCOCH=CHCOOCH3)2、
(n−C4H9)2Sn(OCOCH=CHCOOC4H9−n)2、
(n−C8H17)2Sn(OCOCH=CHCOOCH3)2、
(n−C8H17)2Sn(OCOCH=CHCOOC4H9−n)2、
(n−C8H17)2Sn(OCOCH=CHCOOC8H17−iso)2。
Dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate and the following carboxylic acid type organic tin compounds; a mixture of these carboxylic acid type organic tin compounds and the above amines.
(N-C 4 H 9) 2 Sn (OCOCH = CHCOOCH 3) 2,
(N-C 4 H 9) 2 Sn (OCOCH = CHCOOC 4 H 9 -n) 2,
(N-C 8 H 17) 2 Sn (OCOCH = CHCOOCH 3) 2,
(N-C 8 H 17) 2 Sn (OCOCH = CHCOOC 4 H 9 -n) 2,
(N-C 8 H 17) 2 Sn (OCOCH = CHCOOC 8 H 17 -iso) 2.
下記の含硫黄型有機錫化合物。
(n−C4H9)2Sn(SCH2COO)、
(n−C8H17)2Sn(SCH2COO)、
(n−C8H17)2Sn(SCH2CH2COO)、
(n−C8H17)2Sn(SCH2COOCH2CH2OCOCH2S)、
(n−C4H9)2Sn(SCH2COOC8H17−iso)2、
(n−C8H17)2Sn(SCH2COOC8H17−iso)2、
(n−C8H17)2Sn(SCH2COOC8H17−n)2、
(n−C4H9)2SnS。
The following sulfur-containing organotin compounds.
(N-C 4 H 9) 2 Sn (SCH 2 COO),
(N-C 8 H 17) 2 Sn (SCH 2 COO),
(N-C 8 H 17) 2 Sn (SCH 2 CH 2 COO),
(N-C 8 H 17) 2 Sn (SCH 2 COOCH 2 CH 2 OCOCH 2 S),
(N-C 4 H 9) 2 Sn (SCH 2 COOC 8 H 17 -iso) 2,
(N-C 8 H 17) 2 Sn (SCH2COOC 8 H 17 -iso) 2,
(N-C 8 H 17) 2 Sn (SCH2COOC 8 H 17 -n) 2,
(N-C 4 H 9) 2 SnS.
(n−C4H9)2SnO、(n−C8H17)2SnO等の有機錫オキシド;およびこれらの有機錫オキシドとエチルシリケート、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジオクチル、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジオクチル等のエステル化合物との反応生成物。 (N-C 4 H 9) 2 SnO, (n-C 8 H 17) 2 organotin oxide SnO or the like; and these organic tin oxide and ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, phthalic Reaction products with ester compounds such as dimethyl acid, diethyl phthalate and dioctyl phthalate.
下記のキレート錫化合物およびこれらの錫化合物とアルコキシシランとの反応生成物(ただし、acacはアセチルアセトナト配位子)。
(n−C4H9)2Sn(acac)2、
(n−C8H17)2Sn(acac)2、
(n−C4H9)2(C8H17O)Sn(acac)。
The following chelated tin compounds and reaction products of these tin compounds and alkoxysilanes (where acac is an acetylacetonato ligand).
(N-C 4 H 9) 2 Sn (acac) 2,
(N-C 8 H 17) 2 Sn (acac) 2,
(N-C 4 H 9) 2 (C 8 H 17 O) Sn (acac).
下記の錫化合物。
(n−C4H9)2(CH3COO)SnOSn(OCOCH3)(n−C4H9)2、
(n−C4H9)2(CH3O)SnOSn(OCH3)(n−C4H9)2。
The following tin compounds.
(N-C 4 H 9) 2 (CH 3 COO) SnOSn (OCOCH 3) (n-C 4 H 9) 2,
(N-C 4 H 9) 2 (CH 3 O) SnOSn (OCH 3) (n-C 4 H 9) 2.
<充填材>
充填材としてはたとえば下記の充填材が使用できる。
表面を脂肪酸または樹脂酸系有機物で表面処理した炭酸カルシウム、さらにこれを微粉末化した平均粒径1μm以下の膠質炭酸カルシウム、沈降法により製造した平均粒径1〜3μmの軽質炭酸カルシウム、平均粒径1〜20μmの重質炭酸カルシウム等の炭酸カルシウム、フュームシリカ、沈降性シリカ、無水ケイ酸、含水ケイ酸およびカーボンブラック、炭酸マグネシウム、ケイソウ土、焼成クレー、クレー、タルク、酸化チタン、ベントナイト、有機ベントナイト、有機樹脂バルーン、酸化第二鉄、酸化亜鉛、活性亜鉛華、シラスバルーン、木粉、パルプ、木綿チップ、マイカ、くるみ穀粉、もみ穀粉、グラファイト、アルミニウム微粉末、フリント粉末等の粉体状充填材。石綿、ガラス繊維、ガラスフィラメント、炭素繊維、ケブラー繊維、ポリエチレンファイバー等の繊維状充填材。
<Filler>
As the filler, for example, the following fillers can be used.
Calcium carbonate whose surface is treated with a fatty acid or resin acid organic substance, finely powdered colloidal calcium carbonate having an average particle size of 1 μm or less, light calcium carbonate having an average particle size of 1 to 3 μm and an average particle produced by a precipitation method Calcium carbonate such as heavy calcium carbonate having a diameter of 1 to 20 μm, fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, Organic bentonite, organic resin balloon, ferric oxide, zinc oxide, activated zinc white, shirasu balloon, wood flour, pulp, cotton chip, mica, walnut flour, rice flour, graphite, aluminum fine powder, flint powder, etc. Filler. Fibrous fillers such as asbestos, glass fiber, glass filament, carbon fiber, Kevlar fiber, polyethylene fiber.
充填材の使用量は重合体(A)と重合体(B)の合計100質量部に対して1〜1,000質量部が好ましく、50〜250質量部がより好ましい。これらの充填材は単独で用いてもよく、2種以上併用してもよい。 The amount of the filler used is preferably 1 to 1,000 parts by mass and more preferably 50 to 250 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the polymer (B). These fillers may be used alone or in combination of two or more.
<可塑剤>
重合体(B)のほかに可塑剤を含有してもよい。
可塑剤としては、たとえばフタル酸ジオクチル、フタル酸ジブチル、フタル酸ジイソノニル(ジイソノニルフタレート)、フタル酸ブチルベンジル等のフタル酸アルキルエステル類;アジピン酸ジオクチル、コハク酸ジイソデシル、セバシン酸ジブチル、オレイン酸ブチル等の脂肪族カルボン酸アルキルエステル類;ペンタエリスリトールエステル等のグルコールエステル類;リン酸トリオクチル、リン酸トリクレジル等のリン酸エステル類;エポキシ化大豆油、エポキシステアリン酸ベンジル等のエポキシ可塑剤;塩素化パラフィン;等が単独または2種以上の混合物で使用できる。
しかし、このような可塑剤のうち、低分子量の可塑剤は本発明の硬化性組成物の硬化後にブリードアウトしやすいという問題があるので、低分子量の可塑剤は使用しないことが好ましい。すなわち、本発明の硬化性組成物がさらに可塑剤を含有する場合は、その可塑剤として低分子量の可塑剤を含有しないことが好ましい。低分子量の可塑剤とは化合物自体が低分子量であり、かつ反応性基を有しない可塑剤を指す。たとえばフタル酸アルキルエステル類である。
また、ポリプロピレンポリオールなどのポリオキシアルキレンポリオールも可塑剤として用いることができる。該ポリオキシアルキレンポリオールの数平均分子量(Mn)は1,000〜20,000が好ましく、3,000〜15,000がより好ましい。
<Plasticizer>
A plasticizer may be contained in addition to the polymer (B).
Examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, diisononyl phthalate (diisononyl phthalate), phthalic acid alkyl esters such as butyl benzyl phthalate; dioctyl adipate, diisodecyl succinate, dibutyl sebacate, butyl oleate, etc. Aliphatic carboxylic acid alkyl esters; glycol esters such as pentaerythritol ester; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; Paraffin; etc. can be used alone or in a mixture of two or more.
However, among such plasticizers, there is a problem that a low molecular weight plasticizer tends to bleed out after curing of the curable composition of the present invention. Therefore, it is preferable not to use a low molecular weight plasticizer. That is, when the curable composition of the present invention further contains a plasticizer, it is preferable not to contain a low molecular weight plasticizer as the plasticizer. The low molecular weight plasticizer refers to a plasticizer whose compound itself has a low molecular weight and does not have a reactive group. For example, alkyl phthalates.
Polyoxyalkylene polyols such as polypropylene polyol can also be used as a plasticizer. The number average molecular weight (Mn) of the polyoxyalkylene polyol is preferably 1,000 to 20,000, more preferably 3,000 to 15,000.
<脱水剤>
硬化性組成物は、貯蔵安定性をさらに改良するために、硬化性や柔軟性に悪影響を及ぼさない範囲で少量の脱水剤を添加することできる。脱水剤としては、オルトギ酸メチル、オルトギ酸エチル等のオルトギ酸アルキル、オルト酢酸メチル、オルト酢酸エチル等のオルト酢酸アルキル、メチルトリメトキシシラン、ビニルトリメトキシシラン、テトラメトキシシラン、テトラエトキシシラン等の加水分解性有機シリコン化合物、加水分解性有機チタン化合物等が挙げられる。これらの中でも、ビニルトリメトキシシラン、テトラエトキシシランがコスト及び効果の点から特に好ましい。特に、硬化性組成物が、硬化触媒を含有した状態で防湿容器に充填された一液型の剤を用いることが有効である。
<Dehydrating agent>
In order to further improve the storage stability, a small amount of a dehydrating agent can be added to the curable composition as long as it does not adversely affect the curability and flexibility. Examples of the dehydrating agent include alkyl orthoformate such as methyl orthoformate and ethyl orthoformate, alkyl orthoacetate such as methyl orthoacetate and ethyl orthoacetate, methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane and tetraethoxysilane. Examples include hydrolyzable organic silicon compounds and hydrolyzable organic titanium compounds. Among these, vinyltrimethoxysilane and tetraethoxysilane are particularly preferable from the viewpoint of cost and effect. In particular, it is effective to use a one-pack type agent in which the curable composition contains a curing catalyst and is filled in a moisture-proof container.
<接着性付与剤>
接着性付与剤の具体例としては、ビニル基を有するシラン、エポキシ基を有するシラン、アミノ基を有するシラン、カルボキシ基を有するシラン等の有機シランカップリング剤;イソプロピルトリ(N−アミノエチル−アミノエチル)プロピルトリメトキシチタネート、3−メルカプトプロピルトリメトキチタネート等の有機金属カップリング剤;エポキシ樹脂が挙げられる。
エポキシ基を有するシランの具体例としては、3−グリシジルオキシプロピルトリメトキシシラン、3−グリシジルオキシプロピルメチルジメトキシシラン、3−グリシジルオキシプロピルトリエトキシシランが挙げられる。
アミノ基を有するシランの具体例としては、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、3−アミノプロピルメチルジメトキシシラン、N−(2−アミノエチル) −3−アミノプロピルトリメトキシシラン、N−(2−アミノエチル)−3−アミノプロピルメチルジメトキシシラン、N−(2−アミノエチル)−3−アミノプロピルトリエトキシシラン、3−ウレイドプロピルトリエトキシシラン、N−[(N−ビニルベンジル)−2−アミノエチル]−3−アミノプロピルトリメトキシシラン、3−アニリノプロピルトリメトキシシランなどが挙げられる。
<Adhesive agent>
Specific examples of the adhesion-imparting agent include organosilane coupling agents such as silane having a vinyl group, silane having an epoxy group, silane having an amino group, and silane having a carboxy group; isopropyltri (N-aminoethyl-amino) And organic metal coupling agents such as ethyl) propyltrimethoxytitanate and 3-mercaptopropyltrimethotitanate; and epoxy resins.
Specific examples of the silane having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropyltriethoxysilane.
Specific examples of the silane having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy. Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N-[(N- Vinylbenzyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane and the like.
<その他の添加剤>
本発明の硬化性組成物において、硬化物の物性や硬化性を調節する目的で分子量300未満の反応性ケイ素基含有化合物を任意に添加してもよい。そのような化合物としては具体的にはテトラメチルシリケート、ビニルトリメトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシランなどやこれらのメトキシ基がエトキシ基に置換された化合物などが例示できる。
その他の添加剤として、チクソ性付与剤;顔料;各種の安定剤;オリゴエステルアクリレートのような表面改質を目的とした光硬化性化合物等が挙げられる。また、粘度を調製する目的で溶剤を使用することもできる。
<Other additives>
In the curable composition of the present invention, a reactive silicon group-containing compound having a molecular weight of less than 300 may be optionally added for the purpose of adjusting the physical properties and curability of the cured product. Specific examples of such compounds include tetramethyl silicate, vinyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and the like, and compounds in which these methoxy groups are substituted with ethoxy groups.
Examples of other additives include a thixotropic agent; a pigment; various stabilizers; a photocurable compound for the purpose of surface modification such as an oligoester acrylate, and the like. A solvent can also be used for the purpose of adjusting the viscosity.
<モジュラス調整剤>
その他の添加剤として、モジュラス調整剤を用いてもよい。モジュラス調整剤とは、加水分解によりトリメチルシラノールを発生しうる化合物を言う。例えば、トリメチルシリルオキシ基を分子内に含有する化合物である。モジュラス調整剤が加水分解することにより発生したトリメチルシラノールは、前記重合体(A)や、重合体(B)と反応するため、当該硬化性組成物の機械物性を変化させることができる。
モジュラス調整剤の具体例としては、フェノキシトリメチルシラン、2,2−ビス[(トリメチルシロキシ)メチル]−1−(トリメチルシロキシ)ブタン等が挙げられる。1種単独で用いてもよく、2種以上を併用してもよい。
モジュラス調整剤としては、トリメチルシリルオキシ基など、トリメチルシラノールを発生しうる官能基を有していれば特に限定されないが、分子量2,000以下の化合物が好ましく、分子量500以下の化合物がより好ましい。また、トリメチルシラノールを発生しうる官能基の数が1分子中に平均0.5〜8.0個以下あるものが好ましく、平均0.9〜4.0個がより好ましい。
<Modulus modifier>
As other additives, a modulus adjusting agent may be used. The modulus modifier refers to a compound that can generate trimethylsilanol by hydrolysis. For example, a compound containing a trimethylsilyloxy group in the molecule. Trimethylsilanol generated by hydrolysis of the modulus modifier reacts with the polymer (A) or the polymer (B), and therefore the mechanical properties of the curable composition can be changed.
Specific examples of the modulus regulator include phenoxytrimethylsilane, 2,2-bis [(trimethylsiloxy) methyl] -1- (trimethylsiloxy) butane, and the like. 1 type may be used independently and 2 or more types may be used together.
The modulus modifier is not particularly limited as long as it has a functional group capable of generating trimethylsilanol, such as a trimethylsilyloxy group, but a compound having a molecular weight of 2,000 or less is preferable, and a compound having a molecular weight of 500 or less is more preferable. In addition, the average number of functional groups capable of generating trimethylsilanol is preferably 0.5 to 8.0 or less, and more preferably 0.9 to 4.0 on average.
モジュラス調整剤としては、メタノール、エタノール、2−エチルヘキサノール、フェノール等の1価のアルコール;エチレングリコール、プロパンジオール、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ソルビトール等の多価アルコール;などのアルコールの水酸基をトリメチルシリルオキシ化して得られる化合物が好ましい。トリメチルシリルオキシ化する化合物としては1 ,1,1,3,3,3−ヘキサメチルジシラザン、トリメチルクロロシランなどがある。
多価アルコールの全水酸基におけるトリメチルシリルオキシ化率は、任意に調整できるが、50%以上が好ましく、80%以上がより好ましい。実質的に全ての水酸基がトリメチルシリルオキシ化されていることが最も好ましい。
モジュラス調整剤の使用量は特に限定されるものではなく、目的とする硬化物の物性にあわせて使用量を自由に設定できる。通常は重合体(A)の100質量部に対して0.1〜10.0質量部が好ましく、0.1〜5.0質量部がより好ましい。また、硬化速度調整等の目的で、数種のモジュラス調整剤を併用して用いてもよい。
またモジュラス調整剤は、重合体Aと重合体Bの一方または両方にあらかじめ添加されていてもよいし、硬化性組成物を製造するときに添加してもよい。
Examples of the modulus regulator include monohydric alcohols such as methanol, ethanol, 2-ethylhexanol, and phenol; polyhydric alcohols such as ethylene glycol, propanediol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol; A compound obtained by trimethylsilyloxylation of is preferred. Examples of the compound to be trimethylsilyloxylated include 1,1,1,3,3,3-hexamethyldisilazane and trimethylchlorosilane.
Although the trimethylsilyloxylation rate in all the hydroxyl groups of a polyhydric alcohol can be adjusted arbitrarily, 50% or more is preferable and 80% or more is more preferable. Most preferably, substantially all hydroxyl groups are trimethylsilyloxylated.
The usage-amount of a modulus regulator is not specifically limited, A usage-amount can be freely set according to the physical property of the target hardened | cured material. Usually, 0.1-10.0 mass parts is preferable with respect to 100 mass parts of a polymer (A), and 0.1-5.0 mass parts is more preferable. In addition, for the purpose of adjusting the curing speed, several types of modulus adjusting agents may be used in combination.
Further, the modulus adjusting agent may be added in advance to one or both of the polymer A and the polymer B, or may be added when producing the curable composition.
<硬化性組成物>
本発明の硬化性組成物は、すべての配合成分を予め配合密封保存し、施工後空気中の湿気により硬化する1成分型として調製することも可能であり、重合体(A)および(B)を含む主剤とは別に、硬化剤組成物として、硬化触媒、充填材、水等の成分を配合しておき、該硬化剤組成物と主剤を使用前に混合する、2成分型として調製することもできる。
<Curable composition>
The curable composition of the present invention can be prepared as a one-component type in which all compounding components are preliminarily blended and stored and cured by moisture in the air after construction. Polymers (A) and (B) In addition to the main component containing, a curing agent composition is prepared as a two-component type in which components such as a curing catalyst, a filler, and water are blended, and the curing agent composition and the main component are mixed before use. You can also.
1成分型の場合、すべての配合成分が予め配合されるため、水分を含有する配合成分は予め脱水乾燥してから使用するか、また配合混練中に減圧などにより脱水するのが好ましい。
2成分型の場合、反応性ケイ素基を有する重合体を含有する主剤中に硬化触媒を配合する必要がないので、主剤中に若干の水分が含有されていてもゲル化の心配は少ないが、長期間の貯蔵安定性を必要とする場合には脱水乾燥するのが好ましい。
脱水、乾燥方法としては粉状などの固状物の場合は加熱乾燥法、液状物の場合は減圧脱水法または合成ゼオライト、活性アルミナ、シリカゲルなどを使用した脱水法が好適である。また、イソシアネート化合物を少量配合してイソシアネート基と水とを反応させて脱水してもよい。かかる脱水乾燥法に加えてメタノール、エタノールなどの低級アルコール;n−プロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルメチルジメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシランなどのアルコキシシラン化合物を添加することにより、さらに貯蔵安定性は向上する。
脱水剤、特にビニルトリメトキシシランなどの水と反応し得るケイ素化合物の使用量は重合体(A)と重合体(B)の合計量100質量部に対して、0.1〜20.0質量部が好ましく、0.5〜10.0質量部がより好ましい。
In the case of the one-component type, since all the blended components are blended in advance, it is preferable that the blended components containing moisture be used after being dehydrated and dried in advance or dehydrated under reduced pressure during blending and kneading.
In the case of the two-component type, since there is no need to blend a curing catalyst in the main agent containing a polymer having a reactive silicon group, there is little concern about gelation even if some moisture is contained in the main agent, When long-term storage stability is required, it is preferable to perform dehydration drying.
As the dehydration and drying method, a heat drying method is preferable in the case of a solid substance such as a powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel or the like is preferable in the case of a liquid material. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.
The amount of silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is 0.1 to 20.0 mass per 100 mass parts of the total amount of the polymer (A) and the polymer (B). Part is preferable, and 0.5 to 10.0 parts by mass is more preferable.
本発明の硬化性組成物は、シーリング材(建築用弾性シーリング材シーラント、複層ガラス用シーリング材等。);封止剤(ガラス端部の防錆・防水用封止剤、太陽電池裏面封止剤等。);電気絶縁材料(電線・ケーブル用絶縁被覆剤。)等の分野に用いられる接着剤;等として有用である。また、本発明の硬化性組成物は、粘着剤、塗料材料、フィルム材料、ガスケット材料、注型材料等の用途にも使用できる。 The curable composition of the present invention comprises a sealing material (an elastic sealing material sealant for construction, a sealing material for multi-layer glass, etc.); a sealing agent (a sealing agent for rust prevention and waterproofing at the glass edge, a solar cell back surface sealing It is useful as an adhesive used in fields such as electrical insulating materials (insulating coatings for electric wires and cables). Moreover, the curable composition of this invention can be used also for uses, such as an adhesive, a coating material, a film material, a gasket material, a casting material.
以下に本発明を具体的に説明するが、本発明は実施例のみに限定されない。例2〜5、7〜10、12〜15、21〜25、31〜33、35〜37、39〜42、51〜54が実施例、例1、6、11、26、34、38、43、55〜57が比較例である。
<製造例1:重合体(A−1)の製造>
プロピレングリコールにプロピレンオキシドを開環付加重合させて得られたポリオキシプロピレンジオール(水酸基換算分子量MW(OH)2,000)を開始剤(開始剤Aという)として用いた。
亜鉛ヘキサシアノコバルテートのt−ブタノール錯体触媒(0.03g)の存在下、開始剤A(64.1g)に、プロピレンオキシド(512.8g)を添加し、120℃にて反応系の圧力が下がらなくなるまで反応させた。これにより、ポリオキシプロピレン鎖を有し、かつ分子末端に水酸基を1分子あたり2個有する重合体(h1)を得た。重合体(h1)の25℃における粘度は17.4Pa・sであった。GPCで測定したMnは24,000、Mwは26,000、よってMw/Mnは1.1であった。
The present invention will be specifically described below, but the present invention is not limited to the examples. Examples 2-5, 7-10, 12-15, 21-25, 31-33, 35-37, 39-42, 51-54 are Examples, Examples 1, 6, 11, 26, 34, 38, 43 55 to 57 are comparative examples.
<Production Example 1: Production of polymer (A-1)>
Polyoxypropylene diol (hydroxyl equivalent molecular weight MW (OH) 2,000) obtained by ring-opening addition polymerization of propylene oxide to propylene glycol was used as an initiator (referred to as initiator A).
Propylene oxide (512.8 g) was added to initiator A (64.1 g) in the presence of a t-butanol complex catalyst (0.03 g) of zinc hexacyanocobaltate, and the pressure of the reaction system was lowered at 120 ° C. The reaction was continued until it disappeared. As a result, a polymer (h1) having a polyoxypropylene chain and having two hydroxyl groups per molecule at the molecular end was obtained. The viscosity of the polymer (h1) at 25 ° C. was 17.4 Pa · s. Mn measured by GPC was 24,000, Mw was 26,000, and thus Mw / Mn was 1.1.
得られた重合体(h1)に、重合体(h1)の水酸基量に対して1.05倍モルのナトリウムメトキシドを含むメタノール溶液を添加して、重合体(h1)をアルコラート化した。つぎに、加熱減圧によりメタノールを留去した後に、重合体(h1)の水酸基量に対して過剰量の塩化アリルを添加した。これにより、ポリオキシプロピレン鎖を有し、かつ分子末端にアリル基を有する重合体(v1)を得た。 To the obtained polymer (h1), a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl groups of the polymer (h1) was added to alcoholate the polymer (h1). Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl groups in the polymer (h1). As a result, a polymer (v1) having a polyoxypropylene chain and having an allyl group at the molecular end was obtained.
次に、塩化白金酸六水和物の存在下、得られた重合体(v1)の末端のアリル基量に対して0.6倍モルのジメトキシメチルシランを添加し、70℃にて5時間反応させた。これにより、ポリオキシプロピレン鎖を有し、かつ分子末端にジメトキシメチルシリル基を有する重合体(A−1)を得た。重合体(A−1)は、25℃における粘度が18.5Pa・sであった。GPCで測定したMnは24,000、Mwは27,000、よってMw/Mnは1.1であった。また、重合体(A−1)は、重合体(v1)の分子末端のアリル基の60%にジメトキシメチルシリル基が導入された重合体であった。
得られた重合体(A−1)の官能基数(開始剤の活性水素の数が重合体の官能基数になる。以下、同様。)、Mn、Mw/Mn、シリル化率(Si化率)、25℃における粘度を表1に示す(以下、同様。)。
Next, in the presence of chloroplatinic acid hexahydrate, 0.6 times moles of dimethoxymethylsilane is added to the terminal allyl group of the obtained polymer (v1), and the mixture is added at 70 ° C. for 5 hours. Reacted. As a result, a polymer (A-1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the molecular end was obtained. The viscosity of the polymer (A-1) at 25 ° C. was 18.5 Pa · s. Mn measured by GPC was 24,000, Mw was 27,000, and thus Mw / Mn was 1.1. The polymer (A-1) was a polymer in which a dimethoxymethylsilyl group was introduced into 60% of the allyl groups at the molecular terminals of the polymer (v1).
The number of functional groups of the obtained polymer (A-1) (the number of active hydrogens in the initiator becomes the number of functional groups of the polymer. The same applies hereinafter), Mn, Mw / Mn, silylation rate (Si conversion rate) The viscosity at 25 ° C. is shown in Table 1 (the same applies hereinafter).
<製造例2、3:重合体(A−2)、(A−3)の製造>
ジメトキシメチルシランの仕込量を調整した以外は、重合体(A−1)を合成したのと同様にして、重合体(A−2)、(A−3)を得た。
<Production Examples 2 and 3: Production of polymers (A-2) and (A-3)>
Except having adjusted the preparation amount of dimethoxymethylsilane, the polymer (A-2) and (A-3) were obtained like the synthesis | combination of the polymer (A-1).
<製造例4:重合体(A−4)の製造>
製造例1において開始剤A(64.1g)に反応させるプロピレンオキシドの量を641.0gに変更したほかは、製造例1と同様にして重合体(h2)を得た。重合体(h2)の粘度は28.5Pa・s、Mnは27,000、Mwは30,000、Mw/Mnは1.1であった。
<Production Example 4: Production of polymer (A-4)>
A polymer (h2) was obtained in the same manner as in Production Example 1 except that the amount of propylene oxide reacted with initiator A (64.1 g) in Production Example 1 was changed to 641.0 g. The viscosity of the polymer (h2) was 28.5 Pa · s, Mn was 27,000, Mw was 30,000, and Mw / Mn was 1.1.
続いて、製造例1と同様にして重合体(h2)から、、ポリオキシプロピレン鎖を有し、かつ分子末端にアリル基を有する重合体(v2)を得、これにジメトキシメチルシランを反応させて、ポリオキシプロピレン鎖を有し、かつ分子末端にジメトキシメチルシリル基を有する重合体(A−4)を得た。 Subsequently, in the same manner as in Production Example 1, a polymer (v2) having a polyoxypropylene chain and having an allyl group at the molecular end is obtained from the polymer (h2), and this is reacted with dimethoxymethylsilane. Thus, a polymer (A-4) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the molecular end was obtained.
<製造例5、6:重合体(A−5)、(A−6)の製造>
ジメトキシメチルシランの仕込量を調整した以外は、重合体(A−4)を合成したのと同様にして、重合体(A−5)、(A−6)を得た。
<Production Examples 5 and 6: Production of polymers (A-5) and (A-6)>
Except having adjusted the preparation amount of dimethoxymethylsilane, it carried out similarly to synthesize | combining a polymer (A-4), and obtained the polymer (A-5) and (A-6).
<製造例7:重合体(A−7)の製造>
製造例1において、開始剤A(64.1g)と反応させるプロピレンオキシドの量を705.1gに変更したほかは、製造例1と同様にして重合体(h3)を得た。重合体(h3)の25℃における粘度は38.0Pa・s、Mnは29,000、Mwは38,000、よってMw/Mnは1.3であった。
<Production Example 7: Production of polymer (A-7)>
In Production Example 1, a polymer (h3) was obtained in the same manner as in Production Example 1, except that the amount of propylene oxide reacted with initiator A (64.1 g) was changed to 705.1 g. The viscosity of the polymer (h3) at 25 ° C. was 38.0 Pa · s, Mn was 29,000, Mw was 38,000, and thus Mw / Mn was 1.3.
続いて、製造例1における亜鉛ヘキサシアノコバルテートのt−ブタノール錯体触媒の代わりに亜鉛ヘキサシアノコバルテートのグライム錯体触媒を用い、また、塩化アリルの代わりに塩化メタリルを用いたほかは、製造例1と同様にしてポリオキシプロピレン鎖を有し、かつ分子末端にメタリル基を有する重合体(v3)を得、これにジメトキシメチルシランを反応させて、ポリオキシプロピレン鎖を有し、かつ分子末端にジメトキシメチルシリル基を有する重合体(A−7)を得た。 Subsequently, except that a glyme complex catalyst of zinc hexacyanocobaltate was used instead of the t-butanol complex catalyst of zinc hexacyanocobaltate in Production Example 1, and methallyl chloride was used instead of allyl chloride, Production Example 1 and Similarly, a polymer (v3) having a polyoxypropylene chain and having a methallyl group at the molecular end is obtained, and this is reacted with dimethoxymethylsilane to have a polyoxypropylene chain and having dioxymethyl at the molecular end. A polymer (A-7) having a methylsilyl group was obtained.
<製造例8〜10:重合体(A−8)〜(A−10)の製造>
ジメトキシメチルシランの仕込量を調整した以外は、重合体(A−7)を合成したのと同様にして、重合体(A−8)〜(A−10)を得た。
<Production Examples 8 to 10: Production of polymers (A-8) to (A-10)>
Except having adjusted the preparation amount of dimethoxymethylsilane, it carried out similarly to synthesize | combining a polymer (A-7), and obtained the polymer (A-8)-(A-10).
<製造例11:重合体(B−1)の製造>
t−ブタノールにプロピレンオキシドを開環付加重合させて得られたポリオキシプロピレンモノオール(水酸基換算分子量MW(OH)2,000)を開始剤(開始剤Bという)として用いた。
亜鉛ヘキサシアノコバルテートのt−ブタノール錯体触媒(0.03g)の存在下、開始剤B(384g)に、プロピレンオキシド(249.6g)を添加し、120℃にて反応系の圧力が下がらなくなるまで反応させた。これにより、ポリオキシプロピレン鎖を有し、かつ分子末端に水酸基を1分子あたり1個有する重合体(h4)を得た。重合体(h4)は、25℃における粘度は0.45Pa・sであった。GPCで測定したMnは4,700、Mwは5,100、よってMw/Mnは1.08であった。
<Production Example 11: Production of polymer (B-1)>
Polyoxypropylene monool obtained by ring-opening addition polymerization of propylene oxide to t-butanol (hydroxyl equivalent molecular weight MW (OH) 2,000) was used as an initiator (referred to as initiator B).
Propylene oxide (249.6 g) is added to initiator B (384 g) in the presence of a zinc hexacyanocobaltate t-butanol complex catalyst (0.03 g) until the pressure of the reaction system does not drop at 120 ° C. Reacted. As a result, a polymer (h4) having a polyoxypropylene chain and having one hydroxyl group per molecule at the molecular end was obtained. The viscosity of the polymer (h4) at 25 ° C. was 0.45 Pa · s. Mn measured by GPC was 4,700, Mw was 5,100, and thus Mw / Mn was 1.08.
得られた重合体(h4)に、重合体(h4)の水酸基量に対して1.05倍モルのナトリウムメトキシドを含むメタノール溶液を添加して、重合体(h4)をアルコラート化した。つぎに、加熱減圧によりメタノールを留去した後に、重合体(h4)のヒドロキシ基量に対して過剰量の塩化アリルを添加した。これにより、ポリオキシプロピレン鎖を有し、かつ分子末端にアリル基を有する重合体(v4)を得た。 To the obtained polymer (h4), a methanol solution containing 1.05 times moles of sodium methoxide was added to the amount of hydroxyl groups of the polymer (h4) to alcoholate the polymer (h4). Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride relative to the amount of hydroxy groups of the polymer (h4) was added. Thereby, a polymer (v4) having a polyoxypropylene chain and having an allyl group at the molecular end was obtained.
次に、塩化白金酸六水和物の存在下、得られた重合体(v4)の末端のアリル基量に対して1.05倍モルのジメトキシメチルシランを添加し、70℃にて5時間反応させた。これにより、ポリオキシプロピレン鎖を有し、かつ分子末端にジメトキシメチルシリル基を有する重合体(B−1)を得た。
得られた重合体(B−1)の官能基数、Mn、Mw/Mn、シリル化率(Si化率)、25℃における粘度を表2に示す(以下、同様。)。
Next, in the presence of chloroplatinic acid hexahydrate, 1.05 times moles of dimethoxymethylsilane with respect to the amount of allyl group at the terminal of the obtained polymer (v4) was added, and the mixture was kept at 70 ° C. for 5 hours. Reacted. Thereby, a polymer (B-1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the molecular end was obtained.
The number of functional groups, Mn, Mw / Mn, silylation rate (Si conversion rate), and viscosity at 25 ° C. of the obtained polymer (B-1) are shown in Table 2 (the same applies hereinafter).
<製造例12:重合体(B−2)の製造>
製造例11において、亜鉛ヘキサシアノコバルテートのt−ブタノール錯体触媒を0.05gに変更し、開始剤B(384g)に反応させるプロピレンオキシドの量を576gに変更したほかは、製造例11と同様にして重合体(h5)を得た。重合体(h5)の25℃における粘度は1.20Pa・s、Mnは7,300、Mwは8,100、Mw/Mnは1.10であった。
続いて、製造例11と同様にして重合体(h5)から、ポリオキシプロピレン鎖を有し、かつ分子末端にアリル基を有する重合体(v5)を得、これにジメトキシメチルシランを反応させて、ポリオキシプロピレン鎖を有し、かつ分子末端にジメトキシメチルシリル基を有する重合体(B−2)を得た。
<Production Example 12: Production of polymer (B-2)>
In Production Example 11, the t-butanol complex catalyst of zinc hexacyanocobaltate was changed to 0.05 g, and the amount of propylene oxide reacted with initiator B (384 g) was changed to 576 g. Thus, a polymer (h5) was obtained. The viscosity of the polymer (h5) at 25 ° C. was 1.20 Pa · s, Mn was 7,300, Mw was 8,100, and Mw / Mn was 1.10.
Subsequently, a polymer (v5) having a polyoxypropylene chain and having an allyl group at the molecular end is obtained from the polymer (h5) in the same manner as in Production Example 11, and this is reacted with dimethoxymethylsilane. A polymer (B-2) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the molecular end was obtained.
<製造例13:重合体(B−3)の製造>
製造例11において、亜鉛ヘキサシアノコバルテートのt−ブタノール錯体触媒の使用量を0.07gに変更し、開始剤B(384g)に反応させるプロピレンオキシドの量を960gに変更したほかは、製造例11と同様にしてポリオキシプロピレン鎖を有し、かつ分子末端にヒドロキシ基を1分子あたり1個有する重合体(h6)を得た。重合体(h6)の25℃における粘度は3.3Pa・s、Mnは10,100、Mwは11,700、Mw/Mnは1.15であった。
<Production Example 13: Production of polymer (B-3)>
In Production Example 11, Production Example 11 except that the amount of zinc hexacyanocobaltate t-butanol complex catalyst used was changed to 0.07 g and the amount of propylene oxide reacted with initiator B (384 g) was changed to 960 g. In the same manner as above, a polymer (h6) having a polyoxypropylene chain and having one hydroxy group per molecule at the molecular end was obtained. The viscosity of the polymer (h6) at 25 ° C. was 3.3 Pa · s, Mn was 10,100, Mw was 11,700, and Mw / Mn was 1.15.
続いて、製造例11と同様にして重合体(h6)から、ポリオキシプロピレン鎖を有し、かつ分子末端にアリル基を有する重合体(v6)を得、これにジメトキシメチルシランを反応させて、ポリオキシプロピレン鎖を有し、かつ分子末端にジメトキシメチルシリル基を有する重合体(B−3)を得た。 Subsequently, a polymer (v6) having a polyoxypropylene chain and having an allyl group at the molecular end is obtained from the polymer (h6) in the same manner as in Production Example 11, and this is reacted with dimethoxymethylsilane. A polymer (B-3) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the molecular end was obtained.
<製造例14:重合体(B−4)の製造>
製造例11において、亜鉛ヘキサシアノコバルテートのt−ブタノール錯体触媒の使用量を0.09gに変更し、開始剤B(384g)に反応させるプロピレンオキシドの量を1440gに変更したほかは、製造例11と同様にして
、ポリオキシプロピレン鎖を有し、かつ分子末端にヒドロキシ基を1分子あたり1個有する重合体(h7)を得た。重合体(h7)の25℃における粘度は4.6Pa・s、Mnは14,100、Mwは16,000、Mw/Mnは1.14であった。
<Production Example 14: Production of polymer (B-4)>
In Production Example 11, Production Example 11 except that the amount of zinc hexacyanocobaltate t-butanol complex catalyst used was changed to 0.09 g and the amount of propylene oxide reacted with initiator B (384 g) was changed to 1440 g. In the same manner as above, a polymer (h7) having a polyoxypropylene chain and having one hydroxy group per molecule at the molecular end was obtained. The viscosity of the polymer (h7) at 25 ° C. was 4.6 Pa · s, Mn was 14,100, Mw was 16,000, and Mw / Mn was 1.14.
続いて、製造例11と同様にして重合体(h7)から、ポリオキシプロピレン鎖を有し、かつ分子末端にアリル基を有する重合体(v7)を得、これにジメトキシメチルシランを反応させて、ポリオキシプロピレン鎖を有し、かつ分子末端にジメトキシメチルシリル基を有する重合体(B−4)を得た。 Subsequently, a polymer (v7) having a polyoxypropylene chain and having an allyl group at the molecular end was obtained from the polymer (h7) in the same manner as in Production Example 11, and this was reacted with dimethoxymethylsilane. A polymer (B-4) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the molecular end was obtained.
<製造例15:比較重合体(C−1)の製造>
比較重合体(C−1)は、グリセリンにプロピレンオキシドを開環付加重合させて得られたポリオキシプロピレントリオール(水酸基換算分子量MW(OH)5,000)(開始剤Cという。)と、ジプロピレングリコールにプロピレンオキシドを開環付加重合させて得られたポリオキシプロピレンジオール(水酸基換算分子量MW(OH)3,200)(開始剤Dという。)とを、開始剤として用いた。
亜鉛ヘキサシアノコバルテートのグライム錯体触媒(0.23g)の存在下、開始剤C(64.1g)に、プロピレンオキシド(435.9g)を、120℃にて反応系の圧力が下がらなくなるまで反応させた。つぎに、開始剤C(58.3g)を添加し、プロピレンオキシド(291.7g)を、反応系の圧力が下がらなくなるまで反応させた。つづいて、開始剤D(57.6g)を添加し、プロピレンオキシド(392.4g)を、反応系の圧力が下がらなくなるまで反応させた。
さらに、開始剤D(44.4g)を添加し、プロピレンオキシド(205.6g)を、反応系の圧力が下がらなくなるまで反応させた。これにより、ポリオキシプロピレン鎖を有し、かつ分子末端に水酸基を1分子あたり2.4個有する重合体(h8)を得た。重合体(h8)は、25℃における粘度は17.4Pa・sであった。GPCで測定したMnは19,000、Mwは29,000、よってMw/Mnは1.5であった。
得られた重合体(h8)に、重合体(h8)の水酸基量に対して1.05倍モルのナトリウムメトキシドを含むメタノール溶液を添加して、重合体(h8)をアルコラート化した。つぎに、加熱減圧によりメタノールを留去した後に、重合体(h8)のヒドロキシ基量に対して過剰量の塩化アリルを添加した。これにより、ポリオキシプロピレン鎖を有し、かつ全末端にアリル基を有する重合体(v5)を得た。
次に、1,1,3,3−テトラメチルジビニルシロキサン白金錯体の存在下、得られた重合体(v5)の末端のアリル基量に対して0.84倍モルのジメトキシメチルシランを添加し、70℃にて5時間反応させた。これにより、ポリオキシプロピレン鎖を有し、かつ分子末端にジメトキシメチルシリル基を有する重合体(C−1)を得た。得られた比較重合体(C−1)の官能基数、Mn、Mw/Mn、シリル化率(Si化率)、25℃における粘度を表3に示す。なお、重合体(C−1)は2種の開始剤を用いて製造された重合体であるため、重合体の官能基数は平均官能基数で表す。該開始剤の活性水素の数の平均値が重合体の平均官能基数となる。
<Production Example 15: Production of comparative polymer (C-1)>
Comparative polymer (C-1) is a polyoxypropylene triol obtained by ring-opening addition polymerization of propylene oxide to glycerin (hydroxyl equivalent molecular weight MW (OH) 5,000) (referred to as initiator C), Polyoxypropylene diol (hydroxyl equivalent molecular weight MW (OH) 3,200) (referred to as initiator D) obtained by ring-opening addition polymerization of propylene oxide to propylene glycol was used as an initiator.
In the presence of a zinc hexacyanocobaltate glyme complex catalyst (0.23 g), initiator C (64.1 g) was reacted with propylene oxide (435.9 g) at 120 ° C. until the pressure of the reaction system was not lowered. It was. Next, initiator C (58.3 g) was added and propylene oxide (291.7 g) was reacted until the pressure in the reaction system did not drop. Subsequently, initiator D (57.6 g) was added, and propylene oxide (392.4 g) was reacted until the pressure in the reaction system did not drop.
Further, initiator D (44.4 g) was added, and propylene oxide (205.6 g) was reacted until the pressure in the reaction system did not drop. As a result, a polymer (h8) having a polyoxypropylene chain and having 2.4 hydroxyl groups per molecule at the molecular terminals was obtained. The viscosity of the polymer (h8) at 25 ° C. was 17.4 Pa · s. Mn measured by GPC was 19,000, Mw was 29,000, and thus Mw / Mn was 1.5.
To the obtained polymer (h8), a methanol solution containing 1.05 times moles of sodium methoxide was added to the polymer (h8) to form an alcoholate. Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxy groups of the polymer (h8). As a result, a polymer (v5) having a polyoxypropylene chain and having allyl groups at all terminals was obtained.
Next, in the presence of 1,1,3,3-tetramethyldivinylsiloxane platinum complex, 0.84 times mol of dimethoxymethylsilane was added to the amount of allyl group at the terminal of the obtained polymer (v5). And reacted at 70 ° C. for 5 hours. Thereby, a polymer (C-1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the molecular end was obtained. Table 3 shows the number of functional groups, Mn, Mw / Mn, silylation rate (Si conversion rate), and viscosity at 25 ° C. of the obtained comparative polymer (C-1). In addition, since a polymer (C-1) is a polymer manufactured using 2 types of initiators, the functional group number of a polymer is represented by an average functional group number. The average value of the number of active hydrogens in the initiator is the average number of functional groups of the polymer.
<製造例16:比較重合体(C−2)の製造>
亜鉛ヘキサシアノコバルテート錯体触媒(0.03g)の存在下、開始剤A(64.1g)に、プロピレンオキシド(320.5g)を添加し、120℃にて反応系の圧力が下がらなくなるまで反応させた。これにより、ポリオキシプロピレン鎖を有し、かつ分子末端に水酸基を1分子あたり2個有する重合体(h9)を得た。重合体(h9)の25℃における粘度は7.5Pa・sであった。GPCで測定したMnは17,000、Mwは19,000、よってMw/Mnは1.1であった。
得られた重合体(h9)に、重合体(h9)の水酸基量に対して1.05倍モルのナトリウムメトキシドを含むメタノール溶液を添加して、重合体(h9)をアルコラート化した。つぎに、加熱減圧によりメタノールを留去した後に、重合体(h9)の水酸基量に対して過剰量の塩化アリルを添加した。これにより、ポリオキシプロピレン鎖を有し、かつ全末端にアリル基を有する重合体(v6)を得た。
次に、塩化白金酸六水和物の存在下、得られた重合体(v6)の末端のアリル基量に対して0.84倍モルのジメトキシメチルシランを添加し、70℃にて5時間反応させた。これにより、ポリオキシプロピレン鎖を有し、かつ分子末端にジメトキシメチルシリル基を有する重合体(C−2)を得た。得られた比較重合体(C−2)の官能基数、Mn、Mw/Mn、シリル化率(Si化率)、25℃における粘度を表3に示す。
<Production Example 16: Production of comparative polymer (C-2)>
In the presence of zinc hexacyanocobaltate complex catalyst (0.03 g), propylene oxide (320.5 g) was added to initiator A (64.1 g) and allowed to react at 120 ° C. until the pressure of the reaction system did not drop. It was. As a result, a polymer (h9) having a polyoxypropylene chain and having two hydroxyl groups per molecule at the molecular end was obtained. The viscosity of the polymer (h9) at 25 ° C. was 7.5 Pa · s. Mn measured by GPC was 17,000, Mw was 19,000, and thus Mw / Mn was 1.1.
To the obtained polymer (h9), a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl group of the polymer (h9) was added to alcoholate the polymer (h9). Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl group in the polymer (h9). As a result, a polymer (v6) having a polyoxypropylene chain and having allyl groups at all terminals was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.84 moles of dimethoxymethylsilane was added to the terminal allyl group of the obtained polymer (v6), and the mixture was added at 70 ° C. for 5 hours. Reacted. Thus, a polymer (C-2) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the molecular end was obtained. Table 3 shows the number of functional groups, Mn, Mw / Mn, silylation rate (Si conversion rate), and viscosity at 25 ° C. of the obtained comparative polymer (C-2).
<その他の添加剤>
下記の例で用いた添加剤は、以下の通りである。
[可塑剤(1)]ジイソノニルフタレート(略称:DINP)(花王社製、商品名:ビニサイザー90)。
[可塑剤(2)]ポリプロピレングリコール(旭硝子社製、商品名:PREMINOL S4011、MW(OH)=10,000)。
[充填材(1)]膠質炭酸カルシウム(白石工業社製、商品名:白艶華CCR)。
[充填材(2)]重質炭酸カルシウム(白石カルシウム工業社製、商品名:ホワイトンSB、平均粒径1.78μm)
[充填材(3)]上記充填材(1)/上記充填材(2)=1/1(質量比)で混合したもの。
[充填材(4)]有機バルーン(松本油脂株式会社製、商品名:80−GCA)
[充填材(5)]カオリンクレー(竹原化学工業社製、商品名:グロマックスLL)
[充填材(6)]酸化チタン(石原産業社製、商品名:R820)。耐候性付与剤。
[チクソ性付与剤(1)]脂肪酸アマイド系チクソ性付与剤(楠本化成社製、商品名:ディスパロン#6500)。
[チクソ性付与剤(2)]水添ひまし油系チクソ性付与剤(楠本化成社製、商品名:ディスパロン#305)。
[モジュラス調整剤]トリメチロールプロパンのトリストリメチルシリル体。
[安定剤(1)]ベンゾトリアゾール系紫外線吸収剤(チバ・スペチャルテイー・ケミカル社製、商品名:チヌビン326)/ヒンダードフェノール系酸化防止剤(チバ・スペチャルテイー・ケミカル社製、商品名:イルガノックス1010)=1/1(質量比)で混合したもの。
[安定剤(2)]紫外線吸収剤・ヒンダードアミン・酸化防止剤の混合品(チバ・スペチャルテイー・ケミカル社製、商品名:チヌビンB75)。
[接着性付与剤]ビニル基含有シランカップリング剤(信越化学工業社製、商品名:KBM1003/アミノ基含有シランカップリング剤(信越化学工業社製、商品名:KBM603)/エポキシ基含有シランカップリング剤(信越化学工業社製、商品名:KBM403)=3/1/1(質量比)で混合したもの。
[光硬化性化合物]多官能アクリル基含有化合物(トリメチロールプロパントリアクリレート、東亞合成社製、商品名:アロニックス M−309)。
[1成分型配合用硬化剤]4価の有機スズ化合物(旭硝子社製:EXCESTAR C201)
[2成分型用硬化剤組成物]下記(a)〜(d)の混合物。
(a)硬化触媒としてのビス(2−エチルヘキサン酸)スズ(エーピーアイコーポレーション社製)と、助触媒としてのラウリルアミン(和光純薬工業社製)とを質量比(硬化触媒:助触媒)6:1で混合したものの4質量部。
(b)ジイソノニルフタレート(略称:DINP、上記可塑剤(1))の6質量部。
(c)重質炭酸カルシウム(商品名:ホワイトンSB、上記充填材(2))の15質量部。
(d)カオリンクレー(商品名:グロマックスLL、上記充填材(5))の5質量部。
<Other additives>
The additives used in the following examples are as follows.
[Plasticizer (1)] Diisononyl phthalate (abbreviation: DINP) (trade name: Vinicizer 90, manufactured by Kao Corporation).
[Plasticizer (2)] Polypropylene glycol (manufactured by Asahi Glass Co., Ltd., trade name: PREMINOL S4011, MW (OH) = 10,000).
[Filler (1)] Colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Baiyinhua CCR)
[Filler (2)] Heavy calcium carbonate (manufactured by Shiroishi Calcium Industry Co., Ltd., trade name: Whiten SB, average particle size 1.78 μm)
[Filler (3)] A mixture of the filler (1) / the filler (2) = 1/1 (mass ratio).
[Filler (4)] Organic balloon (Matsumoto Yushi Co., Ltd., trade name: 80-GCA)
[Filler (5)] Kaolin clay (manufactured by Takehara Chemical Industry Co., Ltd., trade name: Glomax LL)
[Filler (6)] Titanium oxide (Ishihara Sangyo Co., Ltd., trade name: R820). Weathering agent.
[Thixotropic agent (1)] Fatty acid amide type thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 6500).
[Thixotropic agent (2)] Hydrogenated castor oil-based thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 305).
[Modulus Modifier] Tristrimethylsilyl derivative of trimethylolpropane.
[Stabilizer (1)] Benzotriazole UV absorber (Ciba Specialty Chemicals, trade name: Tinuvin 326) / Hindered phenol antioxidant (Ciba Specialty Chemicals, product) Name: Irganox 1010) = 1/1 (mass ratio).
[Stabilizer (2)] A mixture of ultraviolet absorber, hindered amine and antioxidant (Ciba Specialty Chemicals, trade name: Tinuvin B75).
[Adhesiveness imparting agent] Vinyl group-containing silane coupling agent (Shin-Etsu Chemical Co., Ltd., trade name: KBM1003 / amino group-containing silane coupling agent (Shin-Etsu Chemical Co., Ltd., trade name: KBM603) / Epoxy group-containing silane cup Ring agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM403) = 3/1/1 (mass ratio).
[Photo-curable compound] Polyfunctional acrylic group-containing compound (trimethylolpropane triacrylate, manufactured by Toagosei Co., Ltd., trade name: Aronix M-309).
[One-component curing agent] Tetravalent organotin compound (Asahi Glass Co., Ltd .: EXCESTAR C201)
[Two-component curing agent composition] Mixtures (a) to (d) below.
(A) Mass ratio of bis (2-ethylhexanoic acid) tin (manufactured by API Corporation) as a curing catalyst and laurylamine (manufactured by Wako Pure Chemical Industries, Ltd.) as a cocatalyst (curing catalyst: cocatalyst) 4 parts by weight of 6: 1 mixture.
(B) 6 parts by mass of diisononyl phthalate (abbreviation: DINP, plasticizer (1)).
(C) 15 parts by mass of heavy calcium carbonate (trade name: Whiten SB, the filler (2)).
(D) 5 parts by mass of kaolin clay (trade name: Glomax LL, filler (5) above).
[例1〜15]
上記製造例で得た重合体を用い、表4に示す配合で各成分を混合し、得られた混合物の25℃における粘度を測定した。結果を表4に示す。
[Examples 1 to 15]
Using the polymer obtained in the above production example, each component was mixed according to the formulation shown in Table 4, and the viscosity at 25 ° C. of the obtained mixture was measured. The results are shown in Table 4.
表4の結果に示されるように、重合体(A)の粘度よりも、重合体(A)と重合体(B)との混合物の方が粘度が低い。例1の粘度よりも例2〜5の粘度が、例6の粘度よりも例7〜10の粘度が、例11の粘度よりも例12〜15の粘度が低い。すなわち、重合体(B)が可塑剤として働いていることが確認できる。 As shown in the results in Table 4, the viscosity of the mixture of the polymer (A) and the polymer (B) is lower than the viscosity of the polymer (A). The viscosity of Examples 2-5 is lower than the viscosity of Example 1, the viscosity of Examples 7-10 is lower than the viscosity of Example 6, and the viscosity of Examples 12-15 is lower than the viscosity of Example 11. That is, it can be confirmed that the polymer (B) works as a plasticizer.
[例21〜26、31〜43]
上記製造例で得た重合体を用い、表5、6に示す配合で各成分を混合して、1成分型の硬化性組成物を製造し、作業性および硬化物の引張特性を下記の方法で測定した。結果を表5、6に示す。
[Examples 21-26, 31-43]
Using the polymers obtained in the above production examples, the components shown in Tables 5 and 6 were mixed to produce a one-component curable composition, and workability and tensile properties of the cured product were determined by the following method. Measured with The results are shown in Tables 5 and 6.
(作業性)
各硬化性組成物を用いて硬化物の試験片を作成した時のヘラ切れ性や、取り扱いやすさを評価した。ヘラ切れ性とは、ペースト状である硬化前の硬化性組成物をヘラで扱った時の性状のことを言い、硬化性組成物が糸を引きやすいと取り扱いにくく、作業性が悪いことになる。取り扱いやすさとは、ペースト状である硬化前の硬化性組成物をヘラで混練した時の取り扱いやすさのことであり、硬化性組成物の粘度やチクソ性に影響される。ヘラ切れ性および取り扱いやすさが特に良好なものを「◎(優良)」で示し、双方ともに良好なものを「○(良好)」、片方が良好なものを「△(可)」で示し、いずれも良好でないものを「×(不良)」とした。
(Workability)
The spatability and ease of handling when a test piece of a cured product was prepared using each curable composition were evaluated. Spatility refers to the property when the paste-like curable composition before curing is handled with a spatula. If the curable composition easily pulls the yarn, it is difficult to handle and the workability is poor. . The ease of handling refers to the ease of handling when a paste-like curable composition before curing is kneaded with a spatula, and is affected by the viscosity and thixotropy of the curable composition. “◎ (excellent)” indicates that spatability and ease of handling are particularly good, “○ (good)” indicates that both are good, and “△ (possible)” indicates that one is good. Those that were not good in all were defined as “x (defect)”.
(引張特性)
各例で得られた硬化性組成物の硬化物からなる試験片を作製し、引張試験を行った。引張試験はJIS K 6251に準拠して行った。
具体的には、硬化性組成物を厚み2mmのシート状に成形し、23℃、湿度50%にて7日硬化養生した後、50℃、湿度65%にて7日間養生した。さらに、23℃、湿度50%にて24時間以上放置して硬化物を得た。得られたシート状の硬化物を3号ダンベル形状に打ち抜いて試験片とした。試験片の厚みを測定した後、テンシロン試験機を使用して、50%伸張した時の応力(M50、単位:N/mm2)、最大引張応力(Tmax、単位:N/mm2)、破断時の伸び量(E、単位:%)を測定した。
M50が低いほど柔軟性が高く、Tmaxが高いほど引張接着強さが高く、Eが高いほど伸びが良い。
(Tensile properties)
A test piece made of a cured product of the curable composition obtained in each example was prepared, and a tensile test was performed. The tensile test was performed according to JIS K 6251.
Specifically, the curable composition was formed into a sheet having a thickness of 2 mm, cured for 7 days at 23 ° C. and 50% humidity, and then cured for 7 days at 50 ° C. and 65% humidity. Furthermore, it was left to stand for 24 hours or more at 23 ° C. and 50% humidity to obtain a cured product. The obtained sheet-like cured product was punched into a No. 3 dumbbell shape to obtain a test piece. After measuring the thickness of the test piece, using a Tensilon tester, the stress at 50% elongation (M50, unit: N / mm 2 ), maximum tensile stress (Tmax, unit: N / mm 2 ), fracture The amount of elongation at the time (E, unit:%) was measured.
The lower the M50, the higher the flexibility, the higher the Tmax, the higher the tensile bond strength, and the higher the E, the better the elongation.
表5に示されるように、硬化性組成物が重合体(A)と重合体(B)とを含み、これらの質量比(A/B)が本発明の範囲内である例21〜25において、硬化性組成物の作業性が良好であり、硬化性組成物が硬化した硬化物の引張特性(柔軟性(M50)および伸び(E))も良好であることが確認された。特にM50が低く、伸び(E)が高かった。一方、重合体(B)を含まない例26は、例21〜25に比べて、特にM50が高く、伸び(E)が低い。
表6に示されるように、硬化性組成物が重合体(A)と重合体(B)とを含む例31〜33、35〜37、39〜42において、硬化性組成物の作業性が良好であり、硬化性組成物が硬化した硬化物の引張特性(柔軟性および伸び)も良好であることが確認された。
一方、重合体(B)を含まない例34、38、43は、例33、37、42とそれぞれ比べて、特にM50が高く、伸び(E)が低い。
また、重合体Aとして重合体(A−1)〜(A−6)を用いた例は、重合体(A−7)〜(A−10)を用いた例よりも作業性が良く、伸び(E)が優れている。
As shown in Table 5, in Examples 21 to 25 in which the curable composition contains a polymer (A) and a polymer (B), and their mass ratio (A / B) is within the scope of the present invention. It was confirmed that the workability of the curable composition was good, and the tensile properties (flexibility (M50) and elongation (E)) of the cured product obtained by curing the curable composition were also good. In particular, M50 was low and elongation (E) was high. On the other hand, Example 26 which does not contain a polymer (B) has especially high M50 and low elongation (E) compared with Examples 21-25.
As shown in Table 6, in Examples 31 to 33, 35 to 37, and 39 to 42 in which the curable composition contains the polymer (A) and the polymer (B), the workability of the curable composition is good. The tensile properties (flexibility and elongation) of the cured product obtained by curing the curable composition were also confirmed to be good.
On the other hand, Examples 34, 38 and 43 which do not contain the polymer (B) have a particularly high M50 and a low elongation (E) as compared with Examples 33, 37 and 42, respectively.
In addition, the examples using the polymers (A-1) to (A-6) as the polymer A have better workability and the elongation than the examples using the polymers (A-7) to (A-10). (E) is excellent.
[例51〜57]
上記製造例で得た重合体を用い、表7に示す配合で各成分を混合して、2成分型の硬化性組成物(主剤)を製造した。この主剤100質量部と、2成分型用硬化剤組成物10質量部とを混合し、この混合液を硬化させた硬化物について、H型物性・引張特性、塗膜汚染性、耐久性、表面べたつき性を以下の方法で評価した。結果を表7に示す。
(H型物性・引張特性)
被着体としてアルミニウムを使用し、JIS A 1439の建築用シーリング材の試験方法に準拠して引張特性試験を行った。引張特性試験では、テンシロン試験機を使用して、50%伸張した時の応力(M50、単位:N/mm2)、最大引張応力(Tmax、単位:N/mm2)、破断時の伸び量(E、単位:%)を測定した。
[Examples 51 to 57]
Using the polymer obtained in the above production example, the components shown in Table 7 were mixed to produce a two-component curable composition (main agent). About 100 parts by mass of the main agent and 10 parts by mass of the two-component curing agent composition, and curing the mixture, the H-type physical properties / tensile properties, coating film contamination, durability, surface The stickiness was evaluated by the following method. The results are shown in Table 7.
(H type physical properties and tensile properties)
Aluminum was used as the adherend, and a tensile property test was performed in accordance with the test method for architectural sealant of JIS A 1439. In the tensile property test, using a Tensilon tester, the stress at 50% elongation (M50, unit: N / mm 2 ), the maximum tensile stress (Tmax, unit: N / mm 2 ), and the elongation at break (E, unit:%) was measured.
(塗膜汚染性)
本発明の硬化性組成物の硬化物をシーリング材として用いる場合、上に塗料を塗ることがある。硬化物と塗料の密着性と共に、硬化物が塗料の硬化性能を低下させないことが必要である。塗膜汚染性とは、硬化物が塗料の硬化性能に与える影響を表す。アルミニウム板の上に縦50mm、横50mm、厚さ10mmの形状に硬化性組成物を施工し、23℃、湿度50%で48時間養生し硬化させた。その上から1液水性反応硬化形シリコン樹脂塗料(日本ペイント社製、商品名:オーデフレッシュSi100II)を塗布した。その後50℃で1週間養生したのち、23℃の条件で1日置いた後、よく乾燥させた汚染粉を表面全体にふりかけ10分静置した後、付着しなかった汚染粉をふるい落とした。汚染粉の付着がほとんどなく硬化性組成物の色合いを保っているものを「◎(優良)」、汚染粉がわずかに付着しているが、硬化性組成物の色合いを保っているものを「○(良好)」、汚染粉が多く付着しており、硬化性組成物の色合いが損なわれているものを「×(不良)」とした。なお、汚染粉にはJIS試験用粉体1,8種(関東ローム)(社団法人日本粉体工業技術協会製)を使用した。
(Coating contamination)
When using the hardened | cured material of the curable composition of this invention as a sealing material, a coating material may be applied on top. Along with the adhesion between the cured product and the paint, it is necessary that the cured product does not deteriorate the curing performance of the paint. The coating film contamination property represents the influence of the cured product on the curing performance of the paint. A curable composition was applied to an aluminum plate in a shape of 50 mm in length, 50 mm in width, and 10 mm in thickness, and cured and cured at 23 ° C. and 50% humidity for 48 hours. A one-component aqueous reaction-curable silicone resin paint (manufactured by Nippon Paint Co., Ltd., trade name: Odefresh Si100II) was applied thereon. Thereafter, after curing at 50 ° C. for 1 week, the sample was left for 1 day under the condition of 23 ° C., then the well-dried contaminated powder was sprinkled on the entire surface and allowed to stand for 10 minutes, and then the contaminated powder that did not adhere was screened off. “◎ (excellent)” indicates that the color of the curable composition is maintained with little adhesion of the contaminated powder, and “A (excellent)” indicates that the color of the curable composition is maintained even though the contaminated powder is slightly adhered. “Good (good)” means that a large amount of contaminating powder is adhered and the color of the curable composition is impaired. In addition, JIS test powders 1 and 8 (Kanto Loam) (manufactured by Japan Powder Industrial Technology Association) were used as contaminated powder.
(耐久性)
被着体としてアルミニウムを使用し、JIS A 1439の建築用シーリング材の試験方法に準拠して耐久試験を行った。伸縮試験を2,000回または4,000回行った。伸縮試験後に被着体と硬化した硬化性組成物との間に亀裂が生じたものを「×(不良)」。亀裂は生じていないが僅かにくぼみが生じているものを「○(良好)」。亀裂もくぼみも生じておらず、良好なものを「◎(優良)」とした。
(durability)
An endurance test was conducted in accordance with JIS A 1439 architectural sealing material test method using aluminum as the adherend. The stretch test was performed 2,000 times or 4,000 times. “X (defect)” indicates that a crack occurred between the adherend and the cured curable composition after the stretch test. “Good (good)” means that no cracks occurred but slight dents occurred. No cracks or dents were generated, and a good one was designated as “◎ (excellent)”.
(表面べたつき性)
ポリエチレンテレフタレート製フィルムの上におよそ縦150mm、横50mm、厚さ5mmの形状に硬化性組成物を施工し、23℃、湿度50%で8時間養生し硬化させ、表面のべたつきを指触で評価した。べたつきがないものを「○(良好)」、べたつくものを「×(不良)」とした。
(Surface stickiness)
A curable composition is applied to a polyethylene terephthalate film in a shape of approximately 150 mm in length, 50 mm in width, and 5 mm in thickness, cured and cured at 23 ° C. and 50% humidity for 8 hours, and the stickiness of the surface is evaluated by touch. did. A sample having no stickiness was designated as “◯ (good)”, and a sticky product was designated as “x (defective)”.
表7の結果より、硬化性組成物が重合体(A)と重合体(B)とを含む例51〜54では、H型物性・引張特性、塗膜汚染性、耐久性、および表面べたつき性のいずれも良好であった。また重合体(B)のうちでも分子量が高い重合体(B−3)、(B−4)を用いた例53、54は、特に塗膜に汚染粉が付着し難かった。
これに対して、重合体(A)を用いず、その代わりに、直鎖状でなく数平均分子量が20,000未満で、分子量分布が1.5である比較重合体(C−1)を用いた例55、56は、伸び(E)が低く、塗膜汚染性および表面べたつき性が不良であり、耐久性も劣る。
また、重合体(A)を用いず、その代わりに、直鎖状で数平均分子量が20,000未満で分子量分布が1.1である比較重合体(C−2)を用いた例57は、伸び(E)が低く、耐久性が劣っていた。
From the results of Table 7, in Examples 51 to 54, in which the curable composition contains the polymer (A) and the polymer (B), the H-type physical properties / tensile properties, the film contamination property, the durability, and the surface stickiness Both were good. Further, in Examples 53 and 54 using the polymers (B-3) and (B-4) having a high molecular weight among the polymers (B), it was particularly difficult for the contaminated powder to adhere to the coating film.
On the other hand, the polymer (A) is not used, and instead, a comparative polymer (C-1) which is not linear but has a number average molecular weight of less than 20,000 and a molecular weight distribution of 1.5. In Examples 55 and 56 used, the elongation (E) is low, the coating film contamination property and the surface stickiness are poor, and the durability is also inferior.
In addition, Example 57 using a comparative polymer (C-2) that does not use the polymer (A) but instead has a linear shape, a number average molecular weight of less than 20,000, and a molecular weight distribution of 1.1 is The elongation (E) was low and the durability was poor.
Claims (9)
直鎖状で、片末端に反応性ケイ素基を導入可能な前駆重合体(B’)に、下式(1)で表される反応性ケイ素基を導入して得られる重合体であって、数平均分子量が3,000以上、2万以下であり、かつ前記前駆重合体(B’)の反応性ケイ素基を導入可能な末端基のうち前記反応性ケイ素基に置換された末端基の割合が60〜100モル%である重合体(B)を含有し、前記重合体(A)の含有量と前記重合体(B)の含有量の質量比(A/B)が、95/5〜5/95である、硬化性組成物。
−SiX1 2R1・・・(1)
[式中、R1は置換基を有していてもよい炭素数1〜20の1価の有機基(加水分解性基を除く。)を示し、X1は水酸基又は加水分解性基を示す。2個のX1は互いに同一でも異なっていてもよい。] A polymer obtained by introducing a reactive silicon group represented by the following formula (1) into a linear precursor polymer (A ′) capable of introducing a reactive silicon group at both ends, A polymer (A) having a number average molecular weight of 20,000 or more and 40,000 or less, and a linear precursor polymer (B ′) capable of introducing a reactive silicon group at one end are represented by the following formula (1) Wherein the number average molecular weight is 3,000 or more and 20,000 or less, and the precursor silicon (B ′) has a reactive silicon group. It contains a polymer (B) in which the proportion of terminal groups substituted with the reactive silicon group among the terminal groups that can be introduced is 60 to 100 mol%, and the content of the polymer (A) and the polymer The curable composition whose mass ratio (A / B) of content of (B) is 95 / 5-5 / 95.
-SiX 1 2 R 1 (1)
[Wherein, R 1 represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X 1 represents a hydroxyl group or a hydrolyzable group. . Two X 1 may be the same or different from each other. ]
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011202157A (en) * | 2010-03-03 | 2011-10-13 | Asahi Glass Co Ltd | Curable composition |
WO2012117902A1 (en) * | 2011-03-02 | 2012-09-07 | 株式会社カネカ | Curable composition |
JP5953234B2 (en) * | 2010-10-27 | 2016-07-20 | 株式会社カネカ | Curable composition |
JP2018104670A (en) * | 2016-12-27 | 2018-07-05 | 旭硝子株式会社 | Curable composition and production method thereof, cured product, and sealing material |
JP2019104789A (en) * | 2017-12-11 | 2019-06-27 | 積水フーラー株式会社 | Adhesive composition |
JP2019199581A (en) * | 2018-05-18 | 2019-11-21 | Agc株式会社 | Curable composition and production method of the same, and cured product and sealing material |
JPWO2020066551A1 (en) * | 2018-09-26 | 2021-08-30 | Agc株式会社 | Curable composition and cured product and sealant |
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