JP2015145506A - aqueous adhesive composition - Google Patents
aqueous adhesive composition Download PDFInfo
- Publication number
- JP2015145506A JP2015145506A JP2015077354A JP2015077354A JP2015145506A JP 2015145506 A JP2015145506 A JP 2015145506A JP 2015077354 A JP2015077354 A JP 2015077354A JP 2015077354 A JP2015077354 A JP 2015077354A JP 2015145506 A JP2015145506 A JP 2015145506A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- group
- adhesive composition
- hydrolyzable
- organic
- 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
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 241
- 125000000962 organic group Chemical group 0.000 claims abstract description 41
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 24
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 16
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 13
- 239000000057 synthetic resin Substances 0.000 claims abstract description 13
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims abstract description 4
- 125000003544 oxime group Chemical group 0.000 claims abstract description 4
- -1 nitrile compound Chemical class 0.000 claims description 57
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 150000002483 hydrogen compounds Chemical class 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 10
- 239000000839 emulsion Substances 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- 238000013329 compounding Methods 0.000 description 13
- 239000005056 polyisocyanate Substances 0.000 description 13
- 229920001228 polyisocyanate Polymers 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 229920000058 polyacrylate Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229920000126 latex Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 125000000346 malonyl group Chemical group C(CC(=O)*)(=O)* 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920005749 polyurethane resin Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 238000007718 adhesive strength test Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000002562 thickening agent Substances 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
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WVWYODXLKONLEM-UHFFFAOYSA-N 1,2-diisocyanatobutane Chemical compound O=C=NC(CC)CN=C=O WVWYODXLKONLEM-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- PQDIQKXGPYOGDI-UHFFFAOYSA-N 1,3,5-triisocyanatobenzene Chemical compound O=C=NC1=CC(N=C=O)=CC(N=C=O)=C1 PQDIQKXGPYOGDI-UHFFFAOYSA-N 0.000 description 1
- HUFIHLDYTVSJID-UHFFFAOYSA-N 1,3,5-tris(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC(CN=C=O)=CC(CN=C=O)=C1 HUFIHLDYTVSJID-UHFFFAOYSA-N 0.000 description 1
- BVWZWQNKNHMPLQ-UHFFFAOYSA-N 1,3-diethyl-4-phenylpyrrole-2,5-dione Chemical compound O=C1N(CC)C(=O)C(CC)=C1C1=CC=CC=C1 BVWZWQNKNHMPLQ-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- UFXYYTWJETZVHG-UHFFFAOYSA-N 1,3-diisocyanatobutane Chemical compound O=C=NC(C)CCN=C=O UFXYYTWJETZVHG-UHFFFAOYSA-N 0.000 description 1
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 description 1
- HJXDYZHSBKUFMA-UHFFFAOYSA-N 1,3-diisocyanatocyclopentane Chemical compound O=C=NC1CCC(N=C=O)C1 HJXDYZHSBKUFMA-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- WSJAAYDOXKEWNC-UHFFFAOYSA-N 1,4-bis(2-isocyanatoethyl)benzene Chemical compound O=C=NCCC1=CC=C(CCN=C=O)C=C1 WSJAAYDOXKEWNC-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- ZMRQAAYTICWWOJ-UHFFFAOYSA-N 1-(2-isocyanatoethyl)-2-(isocyanatomethyl)-3-(3-isocyanatopropyl)bicyclo[2.2.1]heptane Chemical compound O=C=NCCCC1C2CCC(CCN=C=O)(C2)C1CN=C=O ZMRQAAYTICWWOJ-UHFFFAOYSA-N 0.000 description 1
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 1
- IQXXEPZFOOTTBA-UHFFFAOYSA-N 1-benzylpiperazine Chemical compound C=1C=CC=CC=1CN1CCNCC1 IQXXEPZFOOTTBA-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- SUVCZZADQDCIEQ-UHFFFAOYSA-N 1-isocyanato-2-methoxybenzene Chemical compound COC1=CC=CC=C1N=C=O SUVCZZADQDCIEQ-UHFFFAOYSA-N 0.000 description 1
- RQBUVIFBALZGPC-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanatophenyl)benzene Chemical group C1=CC(N=C=O)=CC=C1C1=CC=C(N=C=O)C=C1 RQBUVIFBALZGPC-UHFFFAOYSA-N 0.000 description 1
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
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- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
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- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052719 titanium Chemical group 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は水性接着剤組成物に関し、特に、貯蔵安定性、常態接着性及び耐水接着性に優れた水性接着剤組成物に関する。 The present invention relates to an aqueous adhesive composition, and more particularly to an aqueous adhesive composition excellent in storage stability, normal adhesiveness and water-resistant adhesiveness.
近年、水性接着剤は溶剤型接着剤と比べ、労働安全衛生上の問題、環境問題、省資源に適するなどの種々の利点を有するため、接着剤分野において急速に溶剤型接着剤から水性接着剤に転換される傾向にある。 In recent years, water-based adhesives have various advantages such as occupational safety and health problems, environmental problems, and resource saving compared with solvent-based adhesives. Tend to be converted to
硬化性重合体の水性エマルジョン化方法として、特許文献１は、加水分解性シリル基を有するラジカル重合性単量体、該単量体と共重合可能な単量体および油溶性ラジカル重合開始剤からなる溶液を、ＨＬＢが１．５〜２０の界面活性剤およびＰＨ緩衝剤を含有する水性媒体中に乳化分散させる工程（１）と、該工程（１）で得られた水性乳化分散体を、攪拌下の水性媒体中に連続的または間欠的に供給し、該媒体中で前記単量体を重合させる工程（２）からなる硬化性重合体エマルジョンの製造方法を開示している。しかしながら、特許文献１記載の重合体エマルジョンの製造方法においては、使用する水性乳濁液が単量体混合物の粒子径の小さい乳濁液を調製する必要があるため、工業的に重合体エマルジョンを製造するためには、高せん断力を有する特殊な分散装置が必要となったり、操作が煩雑となるという問題があった。 As a method for emulsifying a curable polymer in water, Patent Document 1 discloses a radical polymerizable monomer having a hydrolyzable silyl group, a monomer copolymerizable with the monomer, and an oil-soluble radical polymerization initiator. And emulsifying and dispersing the resulting solution in an aqueous medium containing a surfactant having a HLB of 1.5 to 20 and a PH buffer, and the aqueous emulsified dispersion obtained in the step (1), It discloses a method for producing a curable polymer emulsion comprising a step (2) of continuously or intermittently supplying an aqueous medium under stirring and polymerizing the monomer in the medium. However, in the method for producing a polymer emulsion described in Patent Document 1, it is necessary to prepare an emulsion having a small particle size of the monomer mixture as the aqueous emulsion to be used. In order to manufacture, there existed a problem that the special dispersion apparatus which has high shear force was needed, and operation became complicated.
また、特許文献２は、水性接着剤組成物として、水溶性高分子水溶液、水性ラテックス、水性エマルジョンの１種または２種以上からなる主剤と、２，４’−ジフェニルメタンジイソシアネートを含むイソシアネート化合物からなる硬化剤と、特定のイミド構造を有する化合物とを含む高度耐水性接着剤組成物を開示している。しかしながら、特許文献２記載の接着剤組成物は、２液型であるため混合工程が必要であり、混合不良が発生する等の問題があった。 Patent Document 2 includes, as an aqueous adhesive composition, a main agent composed of one or more of a water-soluble polymer aqueous solution, an aqueous latex, and an aqueous emulsion, and an isocyanate compound containing 2,4′-diphenylmethane diisocyanate. A highly water-resistant adhesive composition comprising a curing agent and a compound having a specific imide structure is disclosed. However, since the adhesive composition described in Patent Document 2 is a two-component type, a mixing step is required, and there is a problem that mixing failure occurs.
本発明は、常態接着性及び耐水接着性等の接着性に優れ、且つ貯蔵安定性及び作業性に優れた水性接着剤組成物を提供することを目的とする。 An object of the present invention is to provide an aqueous adhesive composition having excellent adhesion such as normal adhesion and water-resistant adhesion, and excellent storage stability and workability.
本発明者らは上記課題を解決するために鋭意研究を行った結果、合成樹脂の水分散液と特定の加水分解性基含有化合物を含有することにより、特に常態接着性や耐水性を有する水性接着剤組成物が得られることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the inventors of the present invention include an aqueous dispersion of a synthetic resin and a specific hydrolyzable group-containing compound. The present inventors have found that an adhesive composition can be obtained and completed the present invention.
本発明の水性接着剤組成物は、合成樹脂の水分散液（Ａ）と、加水分解性基含有化合物（Ｂ）と、を含む水性接着剤組成物であって、前記加水分解性基含有化合物（Ｂ）が、一級アミノ基、二級アミノ基、メルカプト基、（メタ）アクリロイル基及びエポキシ基からなる群から選択される１種以上の有機基を有し且つアルコキシ基、アセトキシ基及びオキシム基からなる群から選ばれる１種以上の加水分解性基が直接１〜１０個の珪素原子若しくはチタン原子に結合した化合物（ａ）と、前記有機基と反応し得る有機化合物（ｂ）とを反応させて、その１分子内に該加水分解性基が直接１〜１０個の珪素原子若しくはチタン原子に結合した化合物であることを特徴とする。 The aqueous adhesive composition of the present invention is an aqueous adhesive composition comprising an aqueous dispersion (A) of a synthetic resin and a hydrolyzable group-containing compound (B), wherein the hydrolyzable group-containing compound (B) has one or more organic groups selected from the group consisting of primary amino groups, secondary amino groups, mercapto groups, (meth) acryloyl groups and epoxy groups, and alkoxy groups, acetoxy groups and oxime groups. A compound (a) in which one or more hydrolyzable groups selected from the group consisting of these are directly bonded to 1 to 10 silicon atoms or titanium atoms and an organic compound (b) capable of reacting with the organic group are reacted. The hydrolyzable group is a compound in which 1 to 10 silicon atoms or titanium atoms are directly bonded in one molecule.
前記加水分解性基含有化合物（Ｂ）は、前記加水分解性基がアルコキシ基であり、該アルコキシ基が直接珪素原子に結合した化合物であることが好適である。 The hydrolyzable group-containing compound (B) is preferably a compound in which the hydrolyzable group is an alkoxy group and the alkoxy group is directly bonded to a silicon atom.
前記化合物（ａ）が、前記有機基が一級アミノ基及び／又は二級アミノ基である化合物（ａ−１）及び前記有機基がメルカプト基である化合物（ａ−２）からなる群から選択される１種以上であり、前記化合物（ｂ）が、α，β−不飽和カルボニル化合物（ｂ−１）、α，β−不飽和ニトリル化合物（ｂ−２）、カーボネート化合物（ｂ−３）、２個以上のイソシアネート基を有する化合物と分子中にイソシアネート基と反応し得る１〜２個の活性水素を有する化合物とを反応させて得たその分子中に２個未満のイソシアネート基を持つ化合物（ｂ−４）、モノイソシアネート化合物（ｂ−５）、エポキシ基を有する化合物（ｂ−６）及びアリル基を有する化合物（ｂ−７）からなる群から選択される１種以上であることが好ましい。
前記分子中にイソシアネート基と反応し得る１〜２個の活性水素を有する化合物が、モノアルコール、モノ一級アミン、モノ二級アミン、モノマロニル化合物、モノカルボン酸及びモノチオールからなる群から選択される１種以上であることが好ましい。
また、前記化合物（ａ）が前記化合物（ａ−１）であり且つ前記加水分解性基が直接珪素原子に結合した化合物であり、前記化合物（ｂ）が前記化合物（ｂ−１）であることが好適である。
The compound (a) is selected from the group consisting of a compound (a-1) in which the organic group is a primary amino group and / or a secondary amino group and a compound (a-2) in which the organic group is a mercapto group. And the compound (b) is an α, β-unsaturated carbonyl compound (b-1), an α, β-unsaturated nitrile compound (b-2), a carbonate compound (b-3), A compound having less than 2 isocyanate groups in the molecule obtained by reacting a compound having 2 or more isocyanate groups with a compound having 1 to 2 active hydrogens capable of reacting with isocyanate groups in the molecule ( It is preferably at least one selected from the group consisting of b-4), monoisocyanate compound (b-5), compound having epoxy group (b-6) and compound having allyl group (b-7). .
The compound having 1 to 2 active hydrogens capable of reacting with an isocyanate group in the molecule is selected from the group consisting of monoalcohol, monoprimary amine, monosecondary amine, monomalonyl compound, monocarboxylic acid and monothiol. One or more are preferable.
Further, the compound (a) is the compound (a-1), the hydrolyzable group is directly bonded to a silicon atom, and the compound (b) is the compound (b-1). Is preferred.
また、前記化合物（ａ）が、前記有機基が（メタ）アクリロイル基である化合物（ａ−３）であり、前記化合物（ｂ）が、一級アミノ基及び／又は二級アミノ基を有する化合物（ｂ−８）及びメルカプト基を有する化合物（ｂ−９）からなる群から選択される１種以上であることが好ましい。なお、本発明において、アクリロイル基とメタクリロイル基をあわせて（メタ）アクリロイル基と称する。
前記化合物（ａ）が前記化合物（ａ−３）であり且つ前記加水分解性基が直接珪素原子に結合した化合物であり、前記化合物（ｂ）が前記化合物（ｂ−８）であることが好適である。
Further, the compound (a) is a compound (a-3) in which the organic group is a (meth) acryloyl group, and the compound (b) is a compound having a primary amino group and / or a secondary amino group ( It is preferably at least one selected from the group consisting of b-8) and a compound (b-9) having a mercapto group. In the present invention, the acryloyl group and the methacryloyl group are collectively referred to as a (meth) acryloyl group.
Preferably, the compound (a) is the compound (a-3), the hydrolyzable group is directly bonded to a silicon atom, and the compound (b) is the compound (b-8). It is.
また、前記化合物（ａ）が、前記有機基がエポキシ基である化合物（ａ−４）であり、前記化合物（ｂ）が、活性水素を含有する化合物（ｂ−１０）であることが好適である。前記化合物（ａ−４）が、前記加水分解性基が直接珪素原子に結合した化合物であり、前記化合物（ｂ−１０）がアミノ基含有化合物であることが好ましい。 The compound (a) is preferably a compound (a-4) in which the organic group is an epoxy group, and the compound (b) is a compound (b-10) containing active hydrogen. is there. It is preferable that the compound (a-4) is a compound in which the hydrolyzable group is directly bonded to a silicon atom, and the compound (b-10) is an amino group-containing compound.
前記合成樹脂の水分散液（Ａ）の固形分１００質量部に対して、前記加水分解性基含有化合物（Ｂ）を０．１〜１５質量部配合することが好ましい。 It is preferable to blend 0.1 to 15 parts by mass of the hydrolyzable group-containing compound (B) with respect to 100 parts by mass of the solid content of the aqueous dispersion (A) of the synthetic resin.
本発明の水性接着剤組成物は、貯蔵安定性及び通常条件下での接着力に優れ、且つ常態接着性や耐水接着性、貯蔵後の接着性に優れており、さらに、有機溶剤やフタル酸系可塑剤等を含まないため、シックハウス症候群等の環境問題に懸念が無いという甚大な効果を奏するものである。
本発明の水性接着剤組成物は、用途に制限はなく、例えば、建築用途、工業用途、プライマー、コーティング材等、幅広く使用できる。また、本発明の水性接着剤組成物は、１液型及び２液型のいずれでも使用できる為、作業性に優れている。
The aqueous adhesive composition of the present invention is excellent in storage stability and adhesion under normal conditions, and is excellent in normal adhesion, water-resistant adhesion, and adhesion after storage. Since it does not contain a plasticizer or the like, it has a great effect that there is no concern about environmental problems such as sick house syndrome.
The water-based adhesive composition of the present invention is not limited in use, and can be widely used, for example, for architectural use, industrial use, primer, coating material and the like. Moreover, since the aqueous | water-based adhesive composition of this invention can be used by either 1 liquid type and 2 liquid type, it is excellent in workability | operativity.
以下に本発明の実施の形態を説明するが、これらは例示的に示されるもので、本発明の技術思想から逸脱しない限り種々の変形が可能なことはいうまでもない。 Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.
本発明の水性接着剤組成物は、合成樹脂の水分散液（Ａ）と、特定の加水分解性基含有化合物（Ｂ）と、を含むものである。 The aqueous adhesive composition of the present invention comprises an aqueous dispersion (A) of a synthetic resin and a specific hydrolyzable group-containing compound (B).
前記合成樹脂の水分散液（Ａ）としては、公知の合成樹脂の水分散液を用いることができるが、アクリル系重合体エマルジョン、ゴム系ラテックスおよび合成樹脂系エマルジョンからなる群より選ばれる１種又は２種以上を用いることが好ましい。 As the synthetic resin aqueous dispersion (A), known synthetic resin aqueous dispersions can be used, but one type selected from the group consisting of acrylic polymer emulsions, rubber latexes and synthetic resin emulsions. Or it is preferable to use 2 or more types.
前記アクリル系重合体エマルジョンは特に限定はなく、各種公知のものを使用できる。該アクリル系重合体エマルジョンは、（メタ）アクリル酸エステルを一括仕込み重合法、モノマー逐次添加重合法、乳化モノマー逐次添加重合法、シード重合法などの公知の乳化重合法により容易に製造することが出来る。 The acrylic polymer emulsion is not particularly limited, and various known ones can be used. The acrylic polymer emulsion can be easily produced by a known emulsion polymerization method such as a batch charging polymerization method, a monomer sequential addition polymerization method, an emulsion monomer sequential addition polymerization method, or a seed polymerization method. I can do it.
使用される（メタ）アクリル酸エステルとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、グリシジル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート等をあげることができ、これらを単独または２種以上を混合して用いることができる。また、得られるアクリル系重合体エマルジョンに貯蔵安定性を付与するため、前記（メタ）アクリル酸エステルに換えて（メタ）アクリル酸を少量使用してもよい。さらに所望により（メタ）アクリル酸エステル重合体の接着特性を損なわない程度で、たとえば、酢酸ビニル、スチレン等の共重合可能なビニル系単量体を併用してもよい。なお、アクリル系重合体エマルジョンに用いられる乳化剤としては、アニオン性乳化剤、ノニオン性乳化剤、部分ケン化ポリビニルアルコール等の各種公知のものを使用でき、その使用量は重合体１００質量部に対して０．１〜５質量部程度が好ましく、０．５〜３質量部がより好ましい。 Examples of the (meth) acrylic acid ester used include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and 2-hydroxyethyl. (Meth) acrylates can be used, and these can be used alone or in admixture of two or more. Further, in order to impart storage stability to the resulting acrylic polymer emulsion, a small amount of (meth) acrylic acid may be used instead of the (meth) acrylic acid ester. Further, if desired, a copolymerizable vinyl monomer such as vinyl acetate or styrene may be used in combination so long as the adhesive properties of the (meth) acrylic acid ester polymer are not impaired. In addition, as an emulsifier used for acrylic polymer emulsion, various well-known things, such as an anionic emulsifier, a nonionic emulsifier, and partially saponified polyvinyl alcohol, can be used, and the usage-amount is 0 with respect to 100 mass parts of polymers. About 1-5 mass parts is preferable, and 0.5-3 mass parts is more preferable.
前記ゴム系ラテックスは特に限定はなく、各種公知のものを使用できる。該ゴム系ラテックスとしては、例えば、天然ゴムラテックス、スチレン−ブタジエン共重合体ラテックス、クロロプレンラテックス等が挙げられる。 The rubber latex is not particularly limited, and various known ones can be used. Examples of the rubber latex include natural rubber latex, styrene-butadiene copolymer latex, and chloroprene latex.
前記合成樹脂系エマルジョンは特に限定はなく、各種公知のものを使用できる。該合成樹脂系エマルジョンとしては、例えば、酢酸ビニル系エマルジョン、エチレン−酢酸ビニル共重合体エマルジョン、ポリウレタン樹脂系エマルジョン等が挙げられる。 The synthetic resin emulsion is not particularly limited, and various known ones can be used. Examples of the synthetic resin emulsion include vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, polyurethane resin emulsion and the like.
本発明で用いられる前記加水分解性基含有化合物（Ｂ）は、一級アミノ基、二級アミノ基、メルカプト基、（メタ）アクリロイル基及びエポキシ基からなる群から選択される１種以上の有機基を有し且つアルコキシ基、アセトキシ基及びオキシム基からなる群から選ばれる１種以上の加水分解性基が直接１〜１０個の珪素原子若しくはチタン原子に結合した化合物（ａ）と、前記有機基と反応し得る有機化合物（ｂ）とを反応させて、その１分子内に該加水分解性基が直接１〜１０個の珪素原子若しくはチタン原子に結合した化合物である。 The hydrolyzable group-containing compound (B) used in the present invention is one or more organic groups selected from the group consisting of primary amino groups, secondary amino groups, mercapto groups, (meth) acryloyl groups and epoxy groups. A compound (a) having at least one hydrolyzable group selected from the group consisting of an alkoxy group, an acetoxy group and an oxime group directly bonded to 1 to 10 silicon atoms or titanium atoms, and the organic group Is a compound in which the hydrolyzable group is directly bonded to 1 to 10 silicon atoms or titanium atoms in one molecule.
前記加水分解性基含有化合物（Ｂ）は、前記加水分解性基がアルコキシ基であり、該アルコキシ基が直接珪素原子に結合したアルコキシシラン化合物であることが好適である。 The hydrolyzable group-containing compound (B) is preferably an alkoxysilane compound in which the hydrolyzable group is an alkoxy group and the alkoxy group is directly bonded to a silicon atom.
前記加水分解性基含有化合物（Ｂ）は、１種単独で使用してもよく、２種以上併用してもよい。前記加水分解性基含有化合物（Ｂ）の配合割合は特に限定されないが、合成樹脂の水分散液（Ａ）の固形分１００質量部に対して０．１〜１５質量部配合することが好ましく、０．５〜１０質量部配合することがより好ましい。 The hydrolyzable group-containing compound (B) may be used alone or in combination of two or more. The blending ratio of the hydrolyzable group-containing compound (B) is not particularly limited, but is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the solid content of the synthetic resin aqueous dispersion (A). It is more preferable to blend 0.5 to 10 parts by mass.
前記化合物（ａ）は１種のみでもよく、２種以上組み合わせて用いてもよい。また、前記化合物（ｂ）も１種のみでもよく、２種以上組み合わせて用いてもよい。前記化合物（ａ）と前記化合物（ｂ）との反応は、１種又は２種以上の化合物（ａ）及び１種又は２種以上の化合物（ｂ）を、−２０℃〜１５０℃程度の温度で０．５〜１０００時間同時又は逐次的に反応させて、１〜１０個の前記加水分解性基が直接珪素原子若しくはチタン原子に結合した加水分解性基含有化合物（Ｂ）を合成することが好適である。該反応は、有機溶媒等の媒体の存在下行っても良く、１０００時間を超えて行っても何ら問題はない。化合物（ａ）及び化合物（ｂ）の使用割合は、化合物（ａ）中の前記有機基と、化合物（ｂ）中の前記化合物（ａ）の前記有機基と反応する有機基とが１個以上反応する範囲とすることが好ましい。また、化合物（ｂ）を過剰に使用して接着剤組成物中に残留させ、可塑剤として作用させても良いが、本発明の接着剤組成物の性能を阻害するほど多く用いることは好ましくない。なお、化合物（ｂ）が、α，β−不飽和カルボニル化合物及びα，β−不飽和ニトリル化合物等の光硬化開始剤等によって重合する化合物の場合は、光硬化開始剤と併用して硬化させるのであれば、化合物（ｂ）を過剰に使用しても問題はない。 The compound (a) may be used alone or in combination of two or more. Moreover, the said compound (b) may be only 1 type, and may be used in combination of 2 or more type. The reaction between the compound (a) and the compound (b) is performed at a temperature of about −20 ° C. to 150 ° C. using one or more compounds (a) and one or more compounds (b). For 0.5 to 1000 hours simultaneously or sequentially to synthesize a hydrolyzable group-containing compound (B) in which 1 to 10 hydrolyzable groups are directly bonded to a silicon atom or a titanium atom. Is preferred. The reaction may be performed in the presence of a medium such as an organic solvent, and there is no problem if it is performed for more than 1000 hours. The compound (a) and the compound (b) are used in a proportion of one or more of the organic group in the compound (a) and the organic group that reacts with the organic group of the compound (a) in the compound (b). It is preferable to make it the range which reacts. Further, the compound (b) may be used excessively and left in the adhesive composition to act as a plasticizer. However, it is not preferable to use the compound (b) so much as to hinder the performance of the adhesive composition of the present invention. . In the case where the compound (b) is a compound that is polymerized by a photocuring initiator such as an α, β-unsaturated carbonyl compound and an α, β-unsaturated nitrile compound, the compound (b) is cured in combination with the photocuring initiator. In this case, there is no problem even if the compound (b) is used in excess.
前記化合物（ａ）としては、例えば、前記有機基が一級アミノ及び／又は二級アミノ基である化合物（ａ−１）、前記有機基がメルカプト基である化合物（ａ−２）、前記有機基が（メタ）アクリロイル基である化合物（ａ−３）、及び前記有機基がエポキシ基である化合物（ａ−４）等が好ましい。 Examples of the compound (a) include a compound (a-1) in which the organic group is a primary amino and / or secondary amino group, a compound (a-2) in which the organic group is a mercapto group, and the organic group. Is a (meth) acryloyl group (a-3), and the organic group is an epoxy group (a-4).
前記有機基が一級アミノ基及び／又は二級アミノ基である化合物（ａ−１）とは、即ち、前記有機基が１個以上の一級アミノ基である化合物、前記有機基が１個以上の二級アミノ基である化合物、及び前記有機基が１個以上の一級アミノ基及び１個以上の二級アミノ基である化合物からなる群から選択される１種又は２種以上の化合物である。該化合物（ａ−１）としては、例えば、３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルメチルジエトキシシラン、３−アミノプロピルメチルジメトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、Ｎ−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、この他特殊アミノシランである信越化学工業社製、商品名：ＫＢＭ６０６３、Ｘ−１２−８９６、ＫＢＭ５７６、Ｘ−１２−５６５、Ｘ−１２−５８０、Ｘ−１２−８０６、Ｘ−１２−６６６、Ｘ−１２−５２６３、ＫＢＭ６１２３、Ｘ−１２−５７７、Ｘ−１２−５７５、Ｘ−１２−５６３Ｂ、Ｘ−１２−５６２等のアミノシラン化合物やイソプロポキシトリス[２−（２−アミノエチル）アミノエトキシ]チタン等のアミノ基含有チタン化合物が挙げられ、アミノシラン化合物が好ましい。これらは単独で用いてもよく２種以上併用してもよい。 The compound (a-1) in which the organic group is a primary amino group and / or a secondary amino group means that the organic group is one or more primary amino groups, and the organic group is one or more organic groups. A compound that is a secondary amino group, and one or more compounds selected from the group consisting of compounds in which the organic group is one or more primary amino groups and one or more secondary amino groups. Examples of the compound (a-1) include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, and N-phenyl-3. -Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl)- 3-aminopropylmethyldimethoxysilane, other special aminosilanes manufactured by Shin-Etsu Chemical Co., Ltd., trade names: KBM6063, X-12-896, KBM576, X-12-565, X-12-580, X-12-806 , X-12-666, X-12-5263, KBM6123, X-12-5 7, aminosilane compounds such as X-12-575, X-12-563B, X-12-562, and amino group-containing titanium compounds such as isopropoxytris [2- (2-aminoethyl) aminoethoxy] titanium. An aminosilane compound is preferred. These may be used alone or in combination of two or more.
前記有機基がメルカプト基である化合物（ａ−２）としては、例えば、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピルメチルジエトキシシラン等が挙げられる。これらは単独で用いてもよく２種以上併用してもよい。 Examples of the compound (a-2) in which the organic group is a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldiethoxy. Silane etc. are mentioned. These may be used alone or in combination of two or more.
前記有機基が（メタ）アクリロイル基である化合物（ａ−３）としては、例えば、３−アクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−アクリロキシプロピルメチルジメトキシシラン等の（メタ）アクリロキシシラン化合物が挙げられる。これらは単独で用いてもよく２種以上併用してもよい。 Examples of the compound (a-3) in which the organic group is a (meth) acryloyl group include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane. A (meth) acryloxysilane compound is mentioned. These may be used alone or in combination of two or more.
前記有機基がエポキシ基である化合物（ａ−４）としては、例えば、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン等のエポキシシラン化合物が挙げられる。これらは単独で用いてもよく２種以上併用してもよい。 Examples of the compound (a-4) in which the organic group is an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl. Epoxysilane compounds such as triethoxysilane and 3-glycidoxypropylmethyldiethoxysilane are exemplified. These may be used alone or in combination of two or more.
前記化合物（ｂ）は、前記化合物（ａ）中の前記有機基と反応し得る有機化合物であれば特に制限はなく、化合物（ａ）に応じて適宜選択すればよい。 The compound (b) is not particularly limited as long as it is an organic compound that can react with the organic group in the compound (a), and may be appropriately selected according to the compound (a).
具体的には、前記化合物（ａ）として、前記有機基が一級アミノ基及び／又は二級アミノ基である化合物（ａ−１）及び前記有機基がメルカプト基である化合物（ａ−２）からなる群から選択される１種以上を用いた場合における好適な化合物（ｂ）としては、例えば、α，β−不飽和カルボニル化合物（ｂ−１）、α，β−不飽和ニトリル化合物（ｂ−２）、カーボネート化合物（ｂ−３）、２個以上のイソシアネート基を有する化合物と分子中にイソシアネート基と反応し得る１〜２個の活性水素を有する化合物とを反応させて得たその分子中に２個未満のイソシアネート基を持つ化合物（ｂ−４）、モノイソシアネート化合物（ｂ−５）、エポキシ基を有する化合物（ｂ−６）及びアリル基を有する化合物（ｂ−７）からなる群から選択される１種以上が挙げられる。前記化合物（ａ）が化合物（ａ−１）であり、前記化合物（ｂ）が化合物（ｂ−１）であることが好適である。 Specifically, as the compound (a), a compound (a-1) in which the organic group is a primary amino group and / or a secondary amino group and a compound (a-2) in which the organic group is a mercapto group. As a suitable compound (b) in the case of using one or more selected from the group consisting of, for example, α, β-unsaturated carbonyl compound (b-1), α, β-unsaturated nitrile compound (b- 2) In the molecule obtained by reacting a carbonate compound (b-3), a compound having two or more isocyanate groups and a compound having one or two active hydrogens capable of reacting with an isocyanate group in the molecule. And (b-4), monoisocyanate compound (b-5), compound (b-6) having an epoxy group and compound (b-7) having an allyl group. Choice One or more members, and the like. It is preferable that the compound (a) is the compound (a-1) and the compound (b) is the compound (b-1).
前記化合物（ａ）として、化合物（ａ−１）及び（ａ−２）からなる群から選択される１種又は２種以上を用い、前記化合物（ｂ）として、化合物（ｂ−１）、（ｂ−２）、（ｂ−３）、（ｂ−４）、（ｂ−５）、（ｂ−６）及び（ｂ−７）からなる群から選択される１種又は２種以上を用いる場合、両者を−２０℃〜１２０℃で０．５〜１０００時間程度混合反応を行うことが好適である。両者の反応は、室温〜１２０℃でよいが、必要に応じて冷却してもよい。該反応時における化合物（ａ−１）及び（ａ−２）と、化合物（ｂ−１）、（ｂ−２）、（ｂ−３）、（ｂ−４）、（ｂ−５）、（ｂ−６）及び（ｂ−７）との配合比は、化合物（ａ−１）及び（ａ−２）１モル中の活性水素をγ個とし、化合物（ｂ−１）、（ｂ−２）、（ｂ−３）、（ｂ−４）、（ｂ−５）、（ｂ−６）及び（ｂ−７）の１モル中の（ａ）の前記有機基と反応する有機基数をδ個とした場合、化合物（ａ−１）及び（ａ−２）１モルに対して化合物（ｂ−１）、（ｂ−２）、（ｂ−３）、（ｂ−４）、（ｂ−５）、（ｂ−６）及び（ｂ−７）を１／δ〜γモルの範囲となるようにすることが好ましい。 As the compound (a), one or more selected from the group consisting of the compounds (a-1) and (a-2) is used, and the compound (b-1), ( When using one or more selected from the group consisting of b-2), (b-3), (b-4), (b-5), (b-6) and (b-7) It is preferable that the two are mixed at -20 ° C to 120 ° C for about 0.5 to 1000 hours. Both reactions may be performed at room temperature to 120 ° C., but may be cooled as necessary. Compounds (a-1) and (a-2) at the time of the reaction, and compounds (b-1), (b-2), (b-3), (b-4), (b-5), ( The compounding ratio of (b-6) and (b-7) is γ active hydrogens in 1 mol of the compounds (a-1) and (a-2), and the compounds (b-1) and (b-2) ), (B-3), (b-4), (b-5), (b-6) and (b-7) in 1 mol, the number of organic groups which react with the organic group of (a) is represented by δ In this case, the compounds (b-1), (b-2), (b-3), (b-4), (b-) with respect to 1 mol of the compounds (a-1) and (a-2). 5), (b-6) and (b-7) are preferably in the range of 1 / δ to γ mol.
前記α，β−不飽和カルボニル化合物（ｂ−１）としては、α，β−不飽和カルボキシ化合物、α，β−不飽和ケトン化合物、及びα，β−不飽和アルデヒド化合物等が好ましく、具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタジエニル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ｎ−ステアリル（メタ）アクリレート、２−シアノアクリル酸エチル等の（メタ）アクリル酸エステル、ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、ペンタエリスリトールトリアクリレート、２−ヒドロキシ−３−フェノキシプロピルアクリレート等のヒドロキシ基含有（メタ）アクリル酸エステル、東亞合成（株）製の商品名：アロニックス（登録商標）Ｍ−１０１、Ｍ−１０２、Ｍ−１１０、Ｍ−１１１、Ｍ−１１３、Ｍ−１１７、Ｍ−１２０、Ｍ−１５６、Ｍ−５３００、Ｍ−５４００、Ｍ−５６００、Ｍ−５７００等の単官能特殊アクリレート、ダイセル化学工業（株）製の商品名：ＰＬＡＣＣＥＬ（登録商標）ＦＡ−２Ｄ等、３−（メタ）アクリロキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピルメチルジメトキシシラン等の（メタ）アクリロキシシラン化合物、Ｎ−シクロヘキシルマレイミド、Ｎ−フェニルマレイミド、Ｎ−ラウリルマレイミド、ジエチルフェニルマレイミド等のモノマレイミド化合物、Ｎ−（４−ヒドロキシフェニル）マレインイミド等のヒドロキシ基含有モノマレイミド化合物、無水マレイン酸、マレイン酸ジエチル、マレイン酸ジブチル、マレイン酸ジ−ｎ−ブチル等マレイン酸エステル、フマル酸ジエチル等のフマル酸エステルなどが好適な例として挙げられる。これらは単独で用いてもよく２種以上併用してもよい。 The α, β-unsaturated carbonyl compound (b-1) is preferably an α, β-unsaturated carboxy compound, an α, β-unsaturated ketone compound, an α, β-unsaturated aldehyde compound, or the like. Are methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, n-stearyl (Meth) acrylate, 2- (Meth) acrylic acid ester such as ethyl cyanoacrylate, hydroxy group-containing (meth) acrylic acid ester such as hydroxyethyl acrylate, hydroxypropyl acrylate, pentaerythritol triacrylate, 2-hydroxy-3-phenoxypropyl acrylate, Toagosei ( Product name: Aronix (registered trademark) M-101, M-102, M-110, M-111, M-113, M-117, M-120, M-156, M-5300, M- Monofunctional special acrylates such as 5400, M-5600, M-5700, etc., trade names manufactured by Daicel Chemical Industries, Ltd .: PLACEL (registered trademark) FA-2D, 3- (meth) acryloxypropyltrimethoxysilane, 3 -(Meth) acryloxypropylmethyldimethoxysilane and the like ( T) Acryloxysilane compound, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, monomaleimide compound such as diethylphenylmaleimide, hydroxy group-containing monomaleimide compound such as N- (4-hydroxyphenyl) maleimide, Suitable examples include maleic anhydride, diethyl maleate, dibutyl maleate, maleic acid esters such as di-n-butyl maleate, and fumaric acid esters such as diethyl fumarate. These may be used alone or in combination of two or more.
前記α，β−不飽和ニトリル化合物（ｂ−２）としては、ヒドロキシ基を含まないものを使用することが好ましく、例えば、２−シアノアクリレート、２−シアノアクリル酸エチル、（メタ）アクリロニトリル等が挙げられる。これらは単独で用いてもよく２種以上併用してもよい。 As the α, β-unsaturated nitrile compound (b-2), those not containing a hydroxy group are preferably used. For example, 2-cyanoacrylate, ethyl 2-cyanoacrylate, (meth) acrylonitrile, etc. Can be mentioned. These may be used alone or in combination of two or more.
前記カーボネート化合物（ｂ−３）としては、例えば、プロピレンカーボネート、エチレンカーボネート等が挙げられる。これらは単独で用いてもよく２種以上併用してもよい。 Examples of the carbonate compound (b-3) include propylene carbonate and ethylene carbonate. These may be used alone or in combination of two or more.
前記その分子中に２個未満のイソシアネート基を持つ化合物（ｂ−４）は、２個以上のイソシアネート基を有する化合物（ポリイソシアネート化合物）と、分子中にイソシアネート基と反応し得る１〜２個の活性水素を有する化合物とを反応させることにより得られる。該反応は、−２０℃〜１５０℃程度の温度で０．５〜１０００時間行うことが好適である。該反応時におけるポリイソシアネート化合物と、活性水素を有する化合物との配合比は、ポリイソシアネート化合物中のイソシアネート基の数をκとした場合、ポリイソシアネート化合物１モルに対して、活性水素を有する化合物を（κ−１）×（０．１〜１．７）モルとすることが好ましい。 The compound (b-4) having less than two isocyanate groups in the molecule is a compound having two or more isocyanate groups (polyisocyanate compound) and one or two that can react with the isocyanate groups in the molecule. It can be obtained by reacting with a compound having active hydrogen. The reaction is preferably performed at a temperature of about −20 ° C. to 150 ° C. for 0.5 to 1000 hours. The compounding ratio of the polyisocyanate compound and the compound having active hydrogen at the time of the reaction is such that when the number of isocyanate groups in the polyisocyanate compound is κ, the compound having active hydrogen with respect to 1 mol of the polyisocyanate compound. It is preferable to set it as ((kappa) -1) * (0.1-1.7) mol.
前記化合物（ｂ−４）を合成する際に用いられる２個以上のイソシアネート基を有する化合物としては、公知のポリイソシアネート化合物を用いることができる。これらは単独で用いてもよく２種以上併用してもよい。ジイソシアネート化合物としては、例えば、脂肪族ジイソシアネート化合物、脂環式ジイソシアネート化合物、芳香脂肪族ジイソシアネート化合物、芳香族ジイソシアネート化合物等が挙げられる。
脂肪族ジイソシアネート化合物としては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、プロパン−１，２−ジイルビスイソシアネート、ブタン−１，２−ジイルビスイソシアネート、ブタン−２，３−ジイルビスイソシアネート、ブタン−１，３−ジイルビスイソシアネート、２，４，４−又は２，２，４−トリメチルヘキサメチレンジイソシアネート、リシンジイソシアネート等が挙げられる。
脂環式ジイソシアネート化合物としては、例えば、１，３−シクロペンタンジイルジイソシアネート、シクロヘキサン−１，４−ジイルジイソシアネート、シクロヘキサン−１，３−ジイルジイソシアネート、イソホロンジイソシアネート、４，４′−メチレンビス（イソシアナトシクロヘキサン）、１−メチルシクロヘキサン−２，４−ジイルジイソシアネート、２−メチル−１，３−シクロヘキシレンジイソシアネート、１，３−ビス（イソシアネートメチル）シクロヘキサン、１，４−ビス（イソシアネートメチル）シクロヘキサン等が挙げられる。
芳香脂肪族ジイソシアネート化合物としては、例えば、１，３−若しくは１，４−キシリレンジイソシアネート又はそれらの混合物、１，４−フェニレンビス（エチレン）ジイソシアネート、１，３−若しくは１，４−ビス（１−イソシアネート−１−メチルエチル）ベンゼン又はそれらの混合物等が挙げられる。
芳香族ジイソシアネート化合物としては、例えば、ｍ−フェニレンジイソシアネート、ｐ−フェニレンジイソシアネート、４，４′−ジイソシアナトビフェニル、１，５−ナフタレンジイソシアネート、４，４′−ジフェニルメタンジイソシアネート、２，４−又は２，６−トリレンジイソシアネート、トリジンジイソシアネート、ジフェニルエーテル−４，４′−ジイソシアネート等が挙げられる。
A known polyisocyanate compound can be used as the compound having two or more isocyanate groups used when the compound (b-4) is synthesized. These may be used alone or in combination of two or more. Examples of the diisocyanate compound include an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, an araliphatic diisocyanate compound, and an aromatic diisocyanate compound.
Examples of the aliphatic diisocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, propane-1,2-diyl bisisocyanate, butane-1,2-diyl bisisocyanate, butane-2,3. -Diyl bisisocyanate, butane-1,3-diyl bisisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and the like.
Examples of the alicyclic diisocyanate compound include 1,3-cyclopentanediyl diisocyanate, cyclohexane-1,4-diyl diisocyanate, cyclohexane-1,3-diyl diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (isocyanatocyclohexane). ), 1-methylcyclohexane-2,4-diyl diisocyanate, 2-methyl-1,3-cyclohexylene diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, etc. It is done.
Examples of the araliphatic diisocyanate compound include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,4-phenylenebis (ethylene) diisocyanate, 1,3- or 1,4-bis (1 -Isocyanate-1-methylethyl) benzene or a mixture thereof.
Examples of the aromatic diisocyanate compound include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diisocyanatobiphenyl, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4- or 2 , 6-tolylene diisocyanate, tolidine diisocyanate, diphenyl ether-4,4'-diisocyanate and the like.
ジイソシアネート化合物を除くポリイソシアネート化合物としては、例えば、脂肪族、脂環式ポリイソシアネート化合物、芳香脂肪族ポリイソシアネート化合物、芳香族ポリイソシアネート化合物等が挙げられる。
脂肪族ポリイソシアネート化合物としては、例えば、リジンエステルトリイソシアネート、１，４，８−トリイソシアネートオクタン、１，６，１１−トリイソシアネートウンデカン、１，８−ジイソシアネート−４−イソシアネートメチルオクタン、１，３，６−トリイソシアネートヘキサン、２，５，７−トリメチル−１，８−ジイソシアネート−５−イソシアネートメチルオクタン等が挙げられる。
脂環式ポリイソシアネート化合物としては、例えば、１，３，５−トリイソシアネートシクロヘキサン、１，３，５−トリメチルイソシアネートシクロヘキサン、３−イソシアネートメチル−３，３，５−トリメチルシクロヘキシルイソシアネート、２−（３−イソシアネートプロピル）−２，５−ジ（イソシアネートメチル）−ビシクロ［２，２，１］ヘプタン、２−（３−イソシアネートプロピル）−２，６−ジ（イソシアネートメチル）−ビシクロ［２，２，１］ヘプタン、３−（３−イソシアネートプロピル）−２，５−ジ（イソシアネートメチル）−ビシクロ［２，２，１］ヘプタン、５−（２−イソシアネートエチル）−２−イソシアネートメチル−３−（３−イソシアネートプロピル）−ビシクロ［２，２，１］ヘプタン、６−（２−イソシアネートエチル）−２−イソシアネートメチル−３−（３−イソシアネートプロピル）−ビシクロ［２，２，１］ヘプタン、５−（２−イソシアネートエチル）−２−イソシアネートメチル−２−（３−イソシアネートプロピル）−ビシクロ［２，２，１］ヘプタン、６−（２−イソシアネートエチル）−２−イソシアネートメチル−２−（３−イソシアネートプロピル）−ビシクロ［２，２，１］ヘプタン等が挙げられる。
芳香脂肪族ポリイソシアネート化合物としては、例えば、１，３，５−トリ（イソシアネートメチル）ベンゼン等が挙げられる。
芳香族ポリイソシアネート化合物としては、例えば、トリフェニルメタン−４，４′，４″−トリイソシアネート、ベンゼン−１，３，５−トリイルトリイソシアネート、１，３，５−トリイソシアナト−２−メチルベンゼン等が挙げられる。
Examples of the polyisocyanate compound excluding the diisocyanate compound include aliphatic, alicyclic polyisocyanate compounds, araliphatic polyisocyanate compounds, and aromatic polyisocyanate compounds.
Examples of the aliphatic polyisocyanate compound include lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3. , 6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, and the like.
Examples of the alicyclic polyisocyanate compound include 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 3-isocyanatemethyl-3,3,5-trimethylcyclohexylisocyanate, 2- (3 -Isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo [2,2, 1] Heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatemethyl) -bicyclo [2,2,1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- ( 3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6 (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3- Isocyanate) -bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, and the like. .
Examples of the araliphatic polyisocyanate compound include 1,3,5-tri (isocyanatomethyl) benzene.
Examples of the aromatic polyisocyanate compound include triphenylmethane-4,4 ′, 4 ″ -triisocyanate, benzene-1,3,5-triyltriisocyanate, and 1,3,5-triisocyanato-2-methyl. Examples include benzene.
前記化合物（ｂ−４）を合成する際に用いられる分子中にイソシアネート基と反応し得る１〜２個の活性水素を有する化合物としては、モノアルコール、モノ一級アミン、モノ二級アミン、モノマロニル化合物、モノカルボン酸及びモノチオールからなる群から選択される１種又は２種以上が好適である。 Examples of the compound having 1 to 2 active hydrogens capable of reacting with an isocyanate group in the molecule used when synthesizing the compound (b-4) include monoalcohols, monoprimary amines, monosecondary amines, and monomalonyl compounds. One or more selected from the group consisting of monocarboxylic acid and monothiol are preferred.
前記モノアルコールとしては、ＲＯＨの一般式で表される化合物の中で，一級アミノ基、二級アミノ基、カルボキシル基、マロニル基若しくはメルカプト基等、ヒドロキシ基以外のイソシアネート基と反応する基を持たないモノアルコールが挙げられる。ジエチレングリコールモノブチルエステル等ポリエステルジオールのモノエステル類、フェノール等の芳香族系化合物を用いてもよい。
前記モノ一級アミンとしては、ＲＮＨ２の一般式で表される化合物の中で、ヒドロキシ基、二級アミノ基、カルボキシ基、マロニル基若しくはメルカプト基等、一級アミノ基以外のイソシアネート基と反応する基を持たないモノ一級アミンが挙げられる。３−アミノプロピルトリメトキシシラン等のアミノシラン等やアニリン、ベンジルアミン等の芳香族系化合物を用いてもよい。
モノ二級アミンとしては、ＲＮＨＲ′の一般式で表される化合物の中で、ヒドロキシ基、一級アミノ基、カルボキシ基、マロニル基若しくはメルカプト基等、二級アミノ基以外のイソシアネート基と反応する基を持たないモノ二級アミンが挙げられる。Ｎ−フェニル−３−アミノプロピルトリメトキシシラン等のアリールアミノシラン等やピペリジン等の複素環状化合物を用いてもよい。
モノマロニル化合物としては、ＲＣＯＣＨ２ＣＯＲ′の一般式で示される化合物の中で、ヒドロキシ基、一級アミノ基、二級アミノ基、カルボキシ基若しくはメルカプト基等、マロニル基以外のイソシアネート基と反応する基を持たないモノマロニル化合物が挙げられる。マロン酸エステル類、アセチルアセトン等を用いてもよい。
モノカルボン酸としては、ＲＣＯＯＨの一般式で示される化合物の中で、ヒドロキシ基、一級アミノ基、二級アミノ基、マロニル基若しくはメルカプト基等、カルボキシ基以外のイソシアネート基と反応する基を持たないモノカルボン酸化合物が挙げられる。安息香酸等芳香族化合物を用いてもよい。
モノチオールとしては、ＲＳＨの一般式で表される化合物の中で、ヒドロキシ基、一級アミノ基、二級アミノ基、カルボキシ基若しくはマロニル基等、メルカプト基以外のイソシアネート基と反応する基を持たないモノチオールが挙げられる。３−メルカプトプロピルトリメトキシシラン等を用いてもよい。
The monoalcohol has a group that reacts with an isocyanate group other than a hydroxy group, such as a primary amino group, a secondary amino group, a carboxyl group, a malonyl group, or a mercapto group, among the compounds represented by the general formula of ROH. There are no monoalcohols. Monoesters of polyester diol such as diethylene glycol monobutyl ester and aromatic compounds such as phenol may be used.
Examples of the mono-primary amines, among the compounds represented by formula of RNH 2, hydroxy groups, secondary amino group, carboxy group, malonyl group or a mercapto group, groups which react with isocyanate groups other than primary amino groups And mono-primary amines that do not have. Aminosilanes such as 3-aminopropyltrimethoxysilane and aromatic compounds such as aniline and benzylamine may be used.
The mono-secondary amine is a group that reacts with an isocyanate group other than the secondary amino group, such as a hydroxy group, a primary amino group, a carboxy group, a malonyl group, or a mercapto group, among the compounds represented by the general formula of RNHR ′. And mono-secondary amines that do not have. An arylaminosilane such as N-phenyl-3-aminopropyltrimethoxysilane or a heterocyclic compound such as piperidine may be used.
As the monomalonyl compound, among the compounds represented by the general formula RCOCH 2 COR ′, a group that reacts with an isocyanate group other than a malonyl group, such as a hydroxy group, a primary amino group, a secondary amino group, a carboxy group, or a mercapto group. Examples thereof include monomalonyl compounds that do not have them. Malonic acid esters, acetylacetone and the like may be used.
The monocarboxylic acid has no group that reacts with an isocyanate group other than a carboxyl group, such as a hydroxy group, a primary amino group, a secondary amino group, a malonyl group, or a mercapto group, among the compounds represented by the general formula of RCOOH. A monocarboxylic acid compound is mentioned. Aromatic compounds such as benzoic acid may be used.
Monothiol does not have a group that reacts with an isocyanate group other than a mercapto group, such as a hydroxy group, a primary amino group, a secondary amino group, a carboxy group, or a malonyl group, among the compounds represented by the general formula of RSH. A monothiol is mentioned. 3-mercaptopropyltrimethoxysilane or the like may be used.
前記モノイソシアネート化合物（ｂ−５）としては、例えば、エチルイソシアネート、ラウリルイソシアネート、トシルイソシアネート、ヘキシルイソシアネート、ベンジルイソシアネート、２−メトキシフェニルイソシアネート等のＲ−ＮＣＯの一般式で示される化合物の他、信越化学工業（株）製、商品名：ＫＢＥ９００７等のイソシアネートシラン等が挙げられる。これらは単独で用いてもよく２種以上併用してもよい。 Examples of the monoisocyanate compound (b-5) include compounds represented by the general formula of R-NCO such as ethyl isocyanate, lauryl isocyanate, tosyl isocyanate, hexyl isocyanate, benzyl isocyanate and 2-methoxyphenyl isocyanate, as well as Shin-Etsu. Examples include isocyanate silanes manufactured by Chemical Industry Co., Ltd. and trade names: KBE9007. These may be used alone or in combination of two or more.
前記エポキシ基を有する化合物（ｂ−６）としては、エポキシ基を１個以上含有する化合物を広く使用することができ、特に制限はないが、例えば、メチルフェニルグリシジルエーテル、ｐ−ｔｅｒｔブチルフェニルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、長鎖脂肪族グリシジルエーテル、フェニルグリシジルエーテル、アリルグリシジルエーテル、ブチルグリシジルエーテル、クレゾールグリシジルエーテルその他各種アルキルグリシジルエーテル、アルキルフェニルグリシジルエーテル、スチレンオキシド、シクロヘキセンオキシド等のモノエポキシ化合物、前述した有機基がエポキシ基である化合物（ａ−４）等が好適に用いられる。これらは単独で用いてもよく２種以上併用してもよい。 As the compound (b-6) having an epoxy group, a compound containing one or more epoxy groups can be widely used, and is not particularly limited. For example, methylphenyl glycidyl ether, p-tertbutylphenylglycidyl Ether, 2-ethylhexyl glycidyl ether, long-chain aliphatic glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, cresol glycidyl ether and other various epoxy glycidyl ethers, alkylphenyl glycidyl ethers, styrene oxide, cyclohexene oxide and other monoepoxy A compound, the compound (a-4) whose organic group mentioned above is an epoxy group, etc. are used suitably. These may be used alone or in combination of two or more.
前記アリル基を有する化合物（ｂ−７）としては、アリル基を１個以上含有する化合物を広く使用することができ、特に制限はないが、例えば、アリルアルコール、アリルフェノール、ペンタエリスリトールトリアリルエーテル等の１個のアリル基を有する化合物等が好適に用いられる。これらは単独で用いてもよく２種以上併用してもよい。 As the compound (b-7) having an allyl group, a compound containing one or more allyl groups can be widely used, and is not particularly limited. For example, allyl alcohol, allylphenol, pentaerythritol triallyl ether The compound etc. which have one allyl group, such as these, are used suitably. These may be used alone or in combination of two or more.
前記化合物（ａ）として、有機基が（メタ）アクリロイル基である化合物（ａ−３）を用いた場合における好適な化合物（ｂ）としては、一級アミノ基及び／又は二級アミノ基を有する化合物（ｂ−８）及びメルカプト基を有する化合物（ｂ−９）からなる群から選択される１種以上が挙げられる。前記化合物（ａ）が化合物（ａ−３）であり、前記化合物（ｂ）が化合物（ｂ−８）であることが好適である。 As the compound (a), a compound having a primary amino group and / or a secondary amino group is preferable as the compound (b) when the compound (a-3) in which the organic group is a (meth) acryloyl group is used. One or more selected from the group consisting of (b-8) and a compound (b-9) having a mercapto group may be mentioned. It is preferable that the compound (a) is the compound (a-3) and the compound (b) is the compound (b-8).
前記化合物（ａ）として、化合物（ａ−３）を用い、前記化合物（ｂ）として、化合物（ｂ−８）及び（ｂ−９）からなる群から選択される１種又は２種以上を用いる場合、両者を−２０℃〜１５０℃で０．５〜１０００時間程度求核付加反応を行うことが好ましい。該反応における化合物（ａ−３）と、化合物（ｂ−８）及び（ｂ−９）との配合比は、化合物（ａ−３）１モル中の（メタ）アクリロイル基をε個とし、化合物（ｂ−８）、（ｂ−９）中の活性水素をζ個とした場合、化合物（ａ−３）１モルに対して化合物（ｂ−８）、（ｂ−９）を１／ζ〜εモルの範囲となるようにすることが好ましい。 Compound (a-3) is used as compound (a), and one or more selected from the group consisting of compounds (b-8) and (b-9) is used as compound (b). In this case, it is preferable to carry out a nucleophilic addition reaction at -20 ° C to 150 ° C for about 0.5 to 1000 hours. The compounding ratio of the compound (a-3) to the compounds (b-8) and (b-9) in the reaction is such that the number of (meth) acryloyl groups in 1 mol of the compound (a-3) is ε. When the number of active hydrogens in (b-8) and (b-9) is ζ, compounds (b-8) and (b-9) are added to 1 / ζ to 1 mol of compound (a-3). It is preferable to be in the range of ε mol.
前記一級アミノ基及び／又は二級アミノ基を有する化合物（ｂ−８）としては、一級アミノ基及び二級アミノ基からなる群から選択されるアミノ基を１個以上含有するアミノ基含有化合物を広く使用することができ、特に制限はないが、例えば、前述した有機基が一級アミノ基及び／又は二級アミノ基である化合物（ａ−１）や、エチルアミン、アリルアミン、イソプロピルアミン、２−エチルヘキシルアミン、２−エチルヘキシルオキシルプロピルアミン、３−エトキシプロピルアミン、ｔ−ブチルアミン、ｓｅｃ−ブチルアミン、プロピルアミン、３−メトキシプロピルアミン、ステアリルアミン、２−フェニルエチルアミン等のモノ１級アミン化合物、ジイソプロピルアミン、ジエチルアミン、ジイソブチルアミン、ジ（２−エチルヘキシル）アミン、２−ピロリドン、各種イミダゾール化合物、ピロリジン、ピペリジン、１−ベンジルピペラジン等の２級アミン化合物、３−ジエチルアミノプロピルアミン、ジブチルアミノプロピルアミン、３−（ジメチルアミノ）プロピルアミン等の１級及び２級アミノ基を有する化合物等が好適に用いられる。これらは単独で用いてもよく２種以上併用してもよい。 The compound (b-8) having a primary amino group and / or a secondary amino group is an amino group-containing compound containing at least one amino group selected from the group consisting of a primary amino group and a secondary amino group. Although it can be widely used and is not particularly limited, for example, the compound (a-1) in which the organic group is a primary amino group and / or a secondary amino group, ethylamine, allylamine, isopropylamine, 2-ethylhexyl. Mono primary amine compounds such as amine, 2-ethylhexyloxylpropylamine, 3-ethoxypropylamine, t-butylamine, sec-butylamine, propylamine, 3-methoxypropylamine, stearylamine, 2-phenylethylamine, diisopropylamine, Diethylamine, diisobutylamine, di (2-ethyl Sil) amine, 2-pyrrolidone, various imidazole compounds, secondary amine compounds such as pyrrolidine, piperidine, 1-benzylpiperazine, primary such as 3-diethylaminopropylamine, dibutylaminopropylamine, 3- (dimethylamino) propylamine And compounds having a secondary amino group are preferably used. These may be used alone or in combination of two or more.
前記メルカプト基を有する化合物（ｂ−９）としては、メルカプト基を１個以上含有する化合物を広く使用することができ、特に制限はないが、例えば、前述した有機基がメルカプト基である化合物（ａ−２）や、ラウリルメルカプタン、ステアリルメルカプタン、アリルメルカプタン、フェネチルメルカプタン等が好適に用いられる。これらは単独で用いてもよく２種以上併用しても良い。 As the compound (b-9) having a mercapto group, compounds containing one or more mercapto groups can be widely used, and there is no particular limitation. For example, a compound in which the organic group described above is a mercapto group ( a-2), lauryl mercaptan, stearyl mercaptan, allyl mercaptan, phenethyl mercaptan and the like are preferably used. These may be used alone or in combination of two or more.
前記化合物（ａ）として、有機基がエポキシ基である化合物（ａ−４）を用いた場合における好適な化合物（ｂ）としては、例えば、活性水素を含有する化合物（ｂ−１０）等が挙げられる。 As the compound (a), when the compound (a-4) in which the organic group is an epoxy group is used, examples of the suitable compound (b) include a compound (b-10) containing active hydrogen. It is done.
前記化合物（ａ）として、化合物（ａ−４）を用い、前記化合物（ｂ）として、化合物（ｂ−１０）を用いる場合、両者を−２０℃〜１５０℃で０．５〜１０００時間程度混合反応させることが好ましい。該反応における化合物（ａ−４）と、化合物（ｂ−１０）との配合比は、化合物（ａ−４）１モル中のエポキシ基をη個とし、化合物（ｂ−１０）中の活性水素をθ個とした場合、化合物（ａ−４）１モルに対して化合物（ｂ−１０）を１／θ〜ηモルの範囲となるようにすることが好ましい。 When the compound (a-4) is used as the compound (a) and the compound (b-10) is used as the compound (b), both are mixed at −20 ° C. to 150 ° C. for about 0.5 to 1000 hours. It is preferable to react. The compounding ratio of the compound (a-4) and the compound (b-10) in the reaction is such that the number of epoxy groups in 1 mol of the compound (a-4) is η and the active hydrogen in the compound (b-10) Is θ, the compound (b-10) is preferably in the range of 1 / θ to ηmol with respect to 1 mol of the compound (a-4).
前記活性水素を含有する化合物（ｂ−１０）としては、公知の分子内に１個以上の活性水素を有する化合物を広く使用することができ、特に制限はないが、アミノ基含有化合物が好ましい。前記化合物（ｂ−１０）としては、例えば、前記化合物（ａ−１）において述べたアミノシラン化合物や前記化合物（ａ−２）において述べたメルカプトシラン化合物等の各種シラン化合物、アリル尿素、前記化合物（ｂ−８）において述べたアミノ基含有化合物等が好適な例として挙げられる。また、シラン化合物と他の化合物との反応生成物等を用いてもよい。これらは単独で用いてもよく２種以上併用してもよい。 As the compound (b-10) containing active hydrogen, a compound having one or more active hydrogens in a known molecule can be widely used, and there is no particular limitation, but an amino group-containing compound is preferable. Examples of the compound (b-10) include various silane compounds such as the aminosilane compound described in the compound (a-1) and the mercaptosilane compound described in the compound (a-2), allyl urea, and the compound ( Preferred examples include the amino group-containing compounds described in b-8). Moreover, you may use the reaction product etc. of a silane compound and another compound. These may be used alone or in combination of two or more.
本発明の水性接着剤組成物における水の含有量は、水性接着剤組成物中の固形分濃度が１０〜８０質量％となるように調整することが好ましく、固形分濃度が３０〜７０質量％となるように調整することがより好ましい。 The water content in the aqueous adhesive composition of the present invention is preferably adjusted so that the solid content concentration in the aqueous adhesive composition is 10 to 80% by mass, and the solid content concentration is 30 to 70% by mass. It is more preferable to adjust so that.
本発明の水性接着剤組成物は、前記成分（Ａ）及び（Ｂ）に加えて、必要に応じて、充填剤、安定剤、分散剤、消泡剤、防腐剤、増粘剤、可塑剤等の各種添加剤を配合してもよい。本発明の水性接着剤組成物は、必要に応じて１液型とすることもできるし、２液型とすることもできるが、特に１液型として好適に用いることができる。
本発明の水性接着剤組成物は常温で硬化することが可能であり、常温硬化型水性接着剤組成物として好適に用いられるが、必要に応じて、適宜、加熱により硬化を促進させてもよい。
In addition to the components (A) and (B), the aqueous adhesive composition of the present invention includes a filler, a stabilizer, a dispersant, an antifoaming agent, a preservative, a thickener, and a plasticizer as necessary. You may mix | blend various additives, such as. The aqueous adhesive composition of the present invention can be made into a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type.
The aqueous adhesive composition of the present invention can be cured at room temperature and is suitably used as a room temperature curable aqueous adhesive composition. However, curing may be accelerated by heating as necessary. .
充填剤としては、一般に水性接着剤組成物に使用される公知の充填剤を広く使用することができる。例えば、炭酸カルシウム、炭酸マグネシウム、珪砂、硫酸カルシウム、硫酸バリウム、タルク、水酸化アルミニウム、カオリン、クレー、マイカ、ケイソウ土、ガラス、酸化亜鉛、酸化マグネシウム、酸化チタン、カーボンブラック、合成繊維、ガラス繊維、アルミナ繊維、炭素繊維、各種ウィスカーなどが挙げられる。これらは単独で使用してもよく、２種以上が併用されてもよい。また、上記充填剤の平均粒子径は、好ましくは１〜５０μｍ、さらに好ましくは１０〜４０μｍの範囲である。充填剤の平均粒子径を前記範囲とすることにより、接着強度に優れ且つ水性接着剤組成物の粘度の増加やゲル化を抑えることができる。 As the filler, known fillers generally used in aqueous adhesive compositions can be widely used. For example, calcium carbonate, magnesium carbonate, silica sand, calcium sulfate, barium sulfate, talc, aluminum hydroxide, kaolin, clay, mica, diatomaceous earth, glass, zinc oxide, magnesium oxide, titanium oxide, carbon black, synthetic fiber, glass fiber , Alumina fibers, carbon fibers, and various whiskers. These may be used alone or in combination of two or more. The average particle diameter of the filler is preferably in the range of 1 to 50 μm, more preferably 10 to 40 μm. By setting the average particle diameter of the filler within the above range, the adhesive strength is excellent, and an increase in viscosity and gelation of the aqueous adhesive composition can be suppressed.
安定剤としては、例えば、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレンポリオキシプロピレンブロックコポリマーなどが挙げられる。
分散剤としては、例えば、トリポリリン酸塩、ピロリン酸塩などの無機系分散剤、ポリカルボン酸塩などの高分子分散剤などが挙げられる。
消泡剤としては、例えば、鉱物油系ノニオン系界面活性剤や、ポリジメチルシロキサンオイル、エチレンオキサイドまたはプロピレンオキサイド変性の、ジメチルシリコーンまたはジメチルシリコーンエマルジョンなどのシリコーン系消泡剤、鉱物油、アセチレンアルコールなどのアルコール系消泡剤などが挙げられる。
防腐剤としては、例えば、環状窒素系化合物、環状窒素硫黄系化合物などが挙げられる。
増粘剤としては、例えば、ポリアクリル酸塩、ヒドロキシエチルセルロース、水溶性ウレタン樹脂、などが挙げられる。
Examples of the stabilizer include polyoxyalkylene alkyl ether and polyoxyethylene polyoxypropylene block copolymer.
Examples of the dispersant include inorganic dispersants such as tripolyphosphate and pyrophosphate, and polymer dispersants such as polycarboxylate.
Examples of antifoaming agents include mineral oil-based nonionic surfactants, polydimethylsiloxane oils, silicone-based antifoaming agents such as dimethyl silicone or dimethyl silicone emulsion modified with ethylene oxide or propylene oxide, mineral oil, and acetylene alcohol. And alcohol-based antifoaming agents.
Examples of the preservative include cyclic nitrogen compounds and cyclic nitrogen sulfur compounds.
Examples of the thickener include polyacrylate, hydroxyethyl cellulose, water-soluble urethane resin, and the like.
可塑剤としては、フタル酸系可塑剤以外の可塑剤を用いることが好ましく、例えば、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などの(ポリ)アルキレングリコール類、更にこれらの誘導体として、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテルなどの(ポリ)アルキレングリコールモノアルキルエーテル類及び、エチレングリコールモノメチルアセテート、ジエチレングリコールモノエチルアセテートなどの(ポリ)アルキレングリコールモノアルキルアセテート類、ジ(2-エチルヘキシル)アジペート、ジイソデシルアジペートなどのアジピン酸誘導体、ジn-ブチルセバケート、ジ(2-エチルヘキシル)セバケートなどのセバシン酸誘導体、クエン酸エステル、グリセリンエステル等が挙げられる。 As the plasticizer, it is preferable to use a plasticizer other than the phthalic acid plasticizer. For example, (poly) alkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol, and further derivatives thereof include ethylene glycol monobutyl ether and diethylene glycol. (Poly) alkylene glycol monoalkyl ethers such as monomethyl ether and (poly) alkylene glycol monoalkyl acetates such as ethylene glycol monomethyl acetate and diethylene glycol monoethyl acetate, adipic acid such as di (2-ethylhexyl) adipate and diisodecyl adipate Derivatives, di-n-butyl sebacate, sebacic acid derivatives such as di (2-ethylhexyl) sebacate, citric acid ester, glycerin ester, etc. It is done.
以下に実施例をあげて本発明をさらに具体的に説明するが、これらの実施例は例示的に示されるもので限定的に解釈されるべきでないことはいうまでもない。 The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.
（合成例１）アクリル系重合体の水分散液Ａ１の合成
容器にイオン交換水５０質量部、ドデシル硫酸ナトリウム３質量部、アクリル酸３質量部、２−エチルヘキシルアクリレート５２質量部、メチルメタクリレート４５質量部、１０％過硫酸アンモニウム水溶液２質量部を秤量・攪拌し、モノマー乳化液を調整した。撹拌機、ジムロート冷却器、窒素導入管及び温度計を備えた４つ口フラスコに、イオン交換水５０質量部を仕込み、攪拌しながら内温を７５℃に加温し、モノマー乳化液１０質量部と１０％過硫酸アンモニウム水溶液を０．５質量部添加した。同温で残りのモノマー乳化液を滴下し３時間重合反応を行った。内温を保ちながら１時間後重合反応を行った。後重合反応終了後、室温に冷却し２５％アンモニア水溶液を３質量部加えて中和し、粘度１５００ｍＰａ・ｓ、不揮発分５０．７％のアクリル系重合体の水分散液Ａ１を得た。
(Synthesis Example 1) Synthesis of Acrylic Polymer Aqueous Dispersion A1 In a container, 50 parts by mass of ion-exchanged water, 3 parts by mass of sodium dodecyl sulfate, 3 parts by mass of acrylic acid, 52 parts by mass of 2-ethylhexyl acrylate, 45 parts by mass of methyl methacrylate Part of a 10% aqueous solution of ammonium persulfate was weighed and stirred to prepare a monomer emulsion. A four-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube and a thermometer was charged with 50 parts by mass of ion-exchanged water, and while stirring, the internal temperature was raised to 75 ° C., and 10 parts by mass of the monomer emulsion And 0.5 part by mass of 10% ammonium persulfate aqueous solution was added. The remaining monomer emulsion was dropped at the same temperature, and a polymerization reaction was performed for 3 hours. The polymerization reaction was carried out after 1 hour while maintaining the internal temperature. After completion of the post-polymerization reaction, the mixture was cooled to room temperature and neutralized by adding 3 parts by mass of a 25% aqueous ammonia solution to obtain an aqueous dispersion A1 of an acrylic polymer having a viscosity of 1500 mPa · s and a nonvolatile content of 50.7%.
（合成例２）ポリウレタン樹脂の水分散液Ａ２の合成
撹拌機、ジムロート冷却器、窒素導入管及び温度計を備えた４つ口フラスコに、分子量２，０００のポリエステルポリオール（（株）クラレ製、Ｐ−２０１０）１００質量部を投入し、窒素気流下１１０℃にて脱水し、脱水後、６０℃まで冷却を行った。その後、２，２−ジメチロールプロピオン酸１．６質量部、イソホロンジイソシアネート（ヒュルス社製、ＶＥＳＴＡＮＴ ＩＰＤＩ）１７．５質量部、アセトン７０質量部を順次投入し、７０〜９０℃にて所定のイソシアネート含量となるまで反応を行った。その後、４０℃以下まで冷却し、トリエチルアミン１．２質量部を添加し中和を行いポリウレタンプレポリマー溶液を調整した。
(Synthesis Example 2) Synthesis of aqueous dispersion A2 of polyurethane resin Polyester polyol having a molecular weight of 2,000 (manufactured by Kuraray Co., Ltd.) was added to a four-necked flask equipped with a stirrer, Dimroth cooler, nitrogen inlet tube and thermometer. P-2010) 100 parts by mass were charged, dehydrated at 110 ° C. under a nitrogen stream, and cooled to 60 ° C. after dehydration. Thereafter, 1.6 parts by mass of 2,2-dimethylolpropionic acid, 17.5 parts by mass of isophorone diisocyanate (manufactured by Huls, VESTANT IPDI) and 70 parts by mass of acetone were sequentially added, and a predetermined isocyanate was obtained at 70 to 90 ° C. The reaction was carried out until the content was reached. Then, it cooled to 40 degrees C or less, added 1.2 mass parts of triethylamine, neutralized, and prepared the polyurethane prepolymer solution.
前記調整したポリウレタンプレポリマー溶液を撹拌しながら、蒸留水２８１質量部を徐々に添加し、乳白色のポリウレタンプレポリマー水分散液を得た、その後、速やかに、Ｎ−（２−アミノエチル）エタノールアミン（日本乳化剤（株）製、アミノアルコールＥＡ）１．５質量部を滴下して、鎖伸長反応させた。なお、この鎖伸長反応では、反応温度を３０℃以下に調整した。次いで、常温で１時間撹拌を続けた後、減圧下４０〜５０℃にてアセトンを除去し、不揮発分３０重量％、粘度５０ｍＰａ・ｓのポリウレタン樹脂の水分散液Ａ２を得た。 While stirring the prepared polyurethane prepolymer solution, 281 parts by mass of distilled water was gradually added to obtain a milky white polyurethane prepolymer aqueous dispersion. Thereafter, N- (2-aminoethyl) ethanolamine was promptly added. 1.5 parts by mass (manufactured by Nippon Emulsifier Co., Ltd., amino alcohol EA) was added dropwise to cause chain elongation reaction. In this chain extension reaction, the reaction temperature was adjusted to 30 ° C. or lower. Next, after stirring at room temperature for 1 hour, acetone was removed at 40 to 50 ° C. under reduced pressure to obtain an aqueous dispersion A2 of polyurethane resin having a nonvolatile content of 30% by weight and a viscosity of 50 mPa · s.
（合成例３〜１０）
表１及び表２に示した割合で各配合物質を室温で混合し、８０℃で３日間反応させ、加水分解性基含有化合物Ｂ１〜Ｂ８を得た。
(Synthesis Examples 3 to 10)
Each compounding substance was mixed at room temperature in the ratio shown in Table 1 and Table 2, and reacted at 80 ° C. for 3 days to obtain hydrolyzable group-containing compounds B1 to B8.
表１及び表２において、各配合物質の詳細は下記の通りである。
ＫＢＭ９０３；信越化学工業（株）製、３−アミノプロピルトリメトキシシラン
ＫＢＭ６０３；信越化学工業（株）製、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
ＫＢＭ６０２；信越化学工業（株）製、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
ＭＡ；メチルアクリレート
２ＥＨＡ；２−エチルヘキシルアクリレート
ＭＭＡ；メチルメタクリレート
ＫＢＭ８０３；信越化学工業（株）製、３−メルカプトプロピルトリメトキシシラン
ＫＢＭ５０３；信越化学工業（株）製、３−メタクリロキシプロピルトリメトキシシラン
ＫＢＭ４０３；信越化学工業（株）製、３−グリシドキシプロピルトリメトキシシラン
In Tables 1 and 2, details of each compounding substance are as follows.
KBM903; Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane KBM603; Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -3-aminopropyltrimethoxysilane KBM602; Shin-Etsu Chemical Co., Ltd. N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane MA; methyl acrylate 2EHA; 2-ethylhexyl acrylate MMA; methyl methacrylate KBM803; manufactured by Shin-Etsu Chemical Co., Ltd., 3-mercaptopropyltrimethoxysilane KBM503: Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltrimethoxysilane KBM403: Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane
（実施例１〜１１）
表３に示した割合で各配合物質を混合撹拌し、本発明の水性接着剤組成物を調整した。
(Examples 1 to 11)
Each compounding substance was mixed and stirred at the ratio shown in Table 3 to prepare the aqueous adhesive composition of the present invention.
表３において、各配合物質の配合量は質量部で示され、各配合物質の詳細は下記の通りである。
アクリル系重合体の水分散液Ａ１；合成例１で合成したアクリル系重合体の水分散液Ａ１
ポリウレタン樹脂の水分散液Ａ２；合成例２で合成したポリウレタン樹脂の水分散液Ａ２
ＳＢＲラテックス；商品名：旭化成ラテックスＳＢ系Ｌ−７４３０、旭化成ケミカルズ（株）製
加水分解性基含有化合物Ｂ１〜Ｂ８；合成例３〜１０で合成した加水分解性基含有化合物Ｂ１〜Ｂ８
In Table 3, the compounding quantity of each compounding substance is shown by a mass part, and the detail of each compounding substance is as follows.
Acrylic polymer aqueous dispersion A1; acrylic polymer aqueous dispersion A1 synthesized in Synthesis Example 1
Aqueous dispersion A2 of polyurethane resin; aqueous dispersion A2 of polyurethane resin synthesized in Synthesis Example 2
Product name: Asahi Kasei Latex SB L-7430, manufactured by Asahi Kasei Chemicals Corporation Hydrolyzable group-containing compounds B1 to B8; Hydrolyzable group-containing compounds B1 to B8 synthesized in Synthesis Examples 3 to 10
前記得られた水性接着剤組成物に対して、下記試験を行った。結果を表４に示した。
１．接着強度試験
ＪＩＳＫ６８５０「接着剤−剛性被着材の引張せん断接着強さ試験方法」に準拠し、接着強度を測定した。即ち、米栂（５．５×２５×１００ｍｍ）の両面に接着剤を１００ｇ／ｍ２ウェットで塗布し貼り合わせた。常態強度は、試験体を２３℃、５０％ＲＨで１６８時間養生した後に５０ｍｍ／ｍｉｎの引張り速度で試験を行ったものであり、水中浸せき強度は、試験体を２３℃、５０％ＲＨで１６８時間養生した後、水に３時間浸せきした後５０ｍｍ／ｍｉｎの引張り速度で試験を行ったものである。
The following test was done with respect to the obtained aqueous adhesive composition. The results are shown in Table 4.
1. Adhesive strength test The adhesive strength was measured in accordance with JIS K6850 "Adhesive-Test method for tensile shear adhesive strength of rigid adherend". That is, the adhesive was applied to both sides of rice bran (5.5 × 25 × 100 mm) with 100 g / m 2 wet and bonded. The normal strength was obtained by curing the test specimen at 23 ° C. and 50% RH for 168 hours, and then conducting a test at a tensile rate of 50 mm / min. The immersion strength in water was 168 at 23 ° C. and 50% RH. After curing for a period of time, the test was carried out at a tensile speed of 50 mm / min after being immersed in water for 3 hours.
２．貯蔵安定性試験
接着剤を密閉容器に入れ５０℃雰囲気下で１週間置き、貯蔵前からの増粘率を測定した。評価基準は下記の通りである。
○：１．５倍未満、△：１．５以上２．０倍未満、×：２倍以上。
2. Storage stability test The adhesive was placed in a sealed container and placed in a 50 ° C atmosphere for 1 week, and the thickening rate before storage was measured. The evaluation criteria are as follows.
○: Less than 1.5 times, Δ: 1.5 or more and less than 2.0 times, ×: 2 or more times.
３．貯蔵後性能試験
前記２．貯蔵安定性試験と同様の方法で接着剤を貯蔵した後、該貯蔵後の接着剤に対して、前記１．接着強度試験と同様の試験を行った。
3. Post-storage performance test 2. After the adhesive is stored in the same manner as in the storage stability test, the above-mentioned 1. A test similar to the adhesive strength test was performed.
（比較例１〜８）
表５に示した組成に変更した以外は実施例１と同様の方法で水性接着剤組成物を調整し、各試験を行った。結果を表６に示した。なお、比較例２，３及び６は、各配合質を混合直後にゲル物が発生した。
(Comparative Examples 1-8)
Except having changed into the composition shown in Table 5, the water-based adhesive composition was prepared in the same manner as in Example 1, and each test was performed. The results are shown in Table 6. In Comparative Examples 2, 3, and 6, gels were generated immediately after mixing the ingredients.
表５において、各配合物質の配合量は質量部で示され、各配合物質の詳細は表１、表２及び表３と同じである。 In Table 5, the compounding quantity of each compounding substance is shown by a mass part, and the detail of each compounding substance is the same as Table 1, Table 2, and Table 3.
Claims (10)
加水分解性基含有化合物（Ｂ）と、を含む水性接着剤組成物であって、
前記加水分解性基含有化合物（Ｂ）が、
一級アミノ基、二級アミノ基、メルカプト基、（メタ）アクリロイル基及びエポキシ基からなる群から選択される１種以上の有機基を有し且つアルコキシ基、アセトキシ基及びオキシム基からなる群から選ばれる１種以上の加水分解性基が直接１〜１０個の珪素原子若しくはチタン原子に結合した化合物（ａ）と、前記有機基と反応し得る有機化合物（ｂ）とを反応させて、その１分子内に該加水分解性基が直接１〜１０個の珪素原子若しくはチタン原子に結合した化合物であることを特徴とする水性接着剤組成物。 An aqueous dispersion (A) of a synthetic resin;
A hydrolyzable group-containing compound (B), and an aqueous adhesive composition comprising:
The hydrolyzable group-containing compound (B) is
It has one or more organic groups selected from the group consisting of primary amino group, secondary amino group, mercapto group, (meth) acryloyl group and epoxy group, and selected from the group consisting of alkoxy group, acetoxy group and oxime group The compound (a) in which one or more hydrolyzable groups directly bonded to 1 to 10 silicon atoms or titanium atoms is reacted with the organic compound (b) capable of reacting with the organic group, A water-based adhesive composition characterized in that the hydrolyzable group is directly bonded to 1 to 10 silicon atoms or titanium atoms in the molecule.
前記化合物（ｂ）は、α，β−不飽和カルボニル化合物（ｂ−１）、α，β−不飽和ニトリル化合物（ｂ−２）、カーボネート化合物（ｂ−３）、２個以上のイソシアネート基を有する化合物と分子中にイソシアネート基と反応し得る１〜２個の活性水素を有する化合物とを反応させて得たその分子中に２個未満のイソシアネート基を持つ化合物（ｂ−４）、モノイソシアネート化合物（ｂ−５）、エポキシ基を有する化合物（ｂ−６）及びアリル基を有する化合物（ｂ−７）からなる群から選択される１種以上であることを特徴とする請求項１又は２記載の水性接着剤組成物。 The compound (a) is selected from the group consisting of the compound (a-1) in which the organic group is a primary amino group and / or a secondary amino group and the compound (a-2) in which the organic group is a mercapto group. One or more
The compound (b) includes an α, β-unsaturated carbonyl compound (b-1), an α, β-unsaturated nitrile compound (b-2), a carbonate compound (b-3), and two or more isocyanate groups. A compound having less than two isocyanate groups in the molecule (b-4), monoisocyanate, obtained by reacting a compound having 1 and 2 active hydrogen compounds capable of reacting with an isocyanate group in the molecule 3. One or more selected from the group consisting of compound (b-5), compound (b-6) having an epoxy group and compound (b-7) having an allyl group, The aqueous adhesive composition as described.
前記化合物（ｂ）は、前記化合物（ｂ−１）であることを特徴とする請求項３記載の水性接着剤組成物。 The compound (a) is the compound (a-1) and a compound in which the hydrolyzable group is directly bonded to a silicon atom,
4. The aqueous adhesive composition according to claim 3, wherein the compound (b) is the compound (b-1).
前記化合物（ｂ）は、一級アミノ基及び／又は二級アミノ基を有する化合物（ｂ−８）及びメルカプト基を有する化合物（ｂ−９）からなる群から選択される１種以上であることを特徴とする請求項１又は２記載の水性接着剤組成物。 The compound (a) is a compound (a-3) in which the organic group is a (meth) acryloyl group,
The compound (b) is at least one selected from the group consisting of a compound (b-8) having a primary amino group and / or a secondary amino group and a compound (b-9) having a mercapto group. The aqueous adhesive composition according to claim 1 or 2, characterized in that
前記化合物（ｂ）は、前記化合物（ｂ−８）であることを特徴とする請求項６記載の水性接着剤組成物。 The compound (a) is the compound (a-3) and the hydrolyzable group is directly bonded to a silicon atom,
The water-based adhesive composition according to claim 6, wherein the compound (b) is the compound (b-8).
前記化合物（ｂ）は、活性水素を含有する化合物（ｂ−１０）であることを特徴とする請求項１又は２記載の水性接着剤組成物。 The compound (a) is a compound (a-4) in which the organic group is an epoxy group,
The aqueous adhesive composition according to claim 1, wherein the compound (b) is a compound (b-10) containing active hydrogen.
前記化合物（ｂ−１０）は、アミノ基含有化合物であることを特徴とする請求項８記載の水性接着剤組成物。 The compound (a-4) is a compound in which the hydrolyzable group is directly bonded to a silicon atom,
The aqueous adhesive composition according to claim 8, wherein the compound (b-10) is an amino group-containing compound.
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| JPS61287977A (en) * | 1985-06-14 | 1986-12-18 | Kyoritsu Kagaku Sangyo Kk | Aqueous polyurethane adhesive composition |
| JPH08188764A (en) * | 1995-01-06 | 1996-07-23 | Sunstar Eng Inc | Two liquid crosslinking type aqueous adhesive |
| JP2004300402A (en) * | 2003-03-20 | 2004-10-28 | Konishi Co Ltd | Silylated urethane-based aqueous composition, adhesive for aqueous wrapping and aqueous contact type adhesive |
| JP5737563B2 (en) * | 2010-03-31 | 2015-06-17 | セメダイン株式会社 | One-component water-based adhesive composition |
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| JPS61287977A (en) * | 1985-06-14 | 1986-12-18 | Kyoritsu Kagaku Sangyo Kk | Aqueous polyurethane adhesive composition |
| JPH08188764A (en) * | 1995-01-06 | 1996-07-23 | Sunstar Eng Inc | Two liquid crosslinking type aqueous adhesive |
| JP2004300402A (en) * | 2003-03-20 | 2004-10-28 | Konishi Co Ltd | Silylated urethane-based aqueous composition, adhesive for aqueous wrapping and aqueous contact type adhesive |
| JP5737563B2 (en) * | 2010-03-31 | 2015-06-17 | セメダイン株式会社 | One-component water-based adhesive composition |
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