JP2009155407A - Curable resin composition and adhesive composition - Google Patents
Curable resin composition and adhesive composition Download PDFInfo
- Publication number
- JP2009155407A JP2009155407A JP2007333389A JP2007333389A JP2009155407A JP 2009155407 A JP2009155407 A JP 2009155407A JP 2007333389 A JP2007333389 A JP 2007333389A JP 2007333389 A JP2007333389 A JP 2007333389A JP 2009155407 A JP2009155407 A JP 2009155407A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- group
- curable resin
- resin composition
- molecule
- 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.)
- Ceased
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- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- 239000000853 adhesive Substances 0.000 title claims description 22
- 230000001070 adhesive effect Effects 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 158
- 125000005587 carbonate group Chemical group 0.000 claims abstract description 28
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 22
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 22
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims abstract description 18
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract description 14
- 239000002981 blocking agent Substances 0.000 claims abstract description 9
- -1 aminosilane compound Chemical class 0.000 claims description 44
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920000768 polyamine Polymers 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000466 oxiranyl group Chemical group 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 125000003277 amino group Chemical group 0.000 abstract description 5
- 229940126062 Compound A Drugs 0.000 abstract 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 150000003077 polyols Chemical class 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000004721 Polyphenylene oxide Substances 0.000 description 11
- 229920000570 polyether Polymers 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000005676 cyclic carbonates Chemical group 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012948 isocyanate Substances 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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- ANOPCGQVRXJHHD-UHFFFAOYSA-N 3-[3-(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]propan-1-amine Chemical compound C1OC(CCCN)OCC21COC(CCCN)OC2 ANOPCGQVRXJHHD-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 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
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- NXTLMBKGEDJACS-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)-3-methylbenzene Chemical compound CC1=CC=CC(CN=C=O)=C1CN=C=O NXTLMBKGEDJACS-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
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- GNDOBZLRZOCGAS-JTQLQIEISA-N 2-isocyanatoethyl (2s)-2,6-diisocyanatohexanoate Chemical compound O=C=NCCCC[C@H](N=C=O)C(=O)OCCN=C=O GNDOBZLRZOCGAS-JTQLQIEISA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-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
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Chemical group C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- DEAZRROVIZAXKE-UHFFFAOYSA-N OCCNCCCN.NCCCOCCCN Chemical compound OCCNCCCN.NCCCOCCCN DEAZRROVIZAXKE-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Chemical group O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000003180 beta-lactone group Chemical group 0.000 description 1
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 description 1
- ULEAQRIQMIQDPJ-UHFFFAOYSA-N butane-1,2-diamine Chemical compound CCC(N)CN ULEAQRIQMIQDPJ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- XMMDVXFQGOEOKH-UHFFFAOYSA-N n'-dodecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCNCCCN XMMDVXFQGOEOKH-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002917 oxazolidines Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000013008 thixotropic agent Substances 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Chemical group OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、硬化性樹脂組成物及びそれを成分とする接着剤組成物に関し、特定の化学構造・硬化機構を有する硬化性樹脂組成物からなる接着性に優れた硬化性樹脂組成物及びそれを用いた接着剤組成物に関する。より詳細には、分子内に五員環カーボネート基を有する硬化性樹脂を配合した硬化性樹脂組成物に関する。 The present invention relates to a curable resin composition and an adhesive composition containing the curable resin composition, and relates to a curable resin composition excellent in adhesiveness and comprising a curable resin composition having a specific chemical structure and curing mechanism. It relates to the adhesive composition used. More specifically, the present invention relates to a curable resin composition containing a curable resin having a five-membered ring carbonate group in the molecule.
従来、各種プラスチック同士又は各種プラスチックと金属等の異種材料を貼り合わせる接着剤としては、変成シリコーン／エポキシ系接着剤、２液型ウレタン系接着剤、ＳＧＡ（第２世代アクリル）系接着剤などが主に用いられていた。
ここで、異種材料を貼り合わせるための接着剤には、主に次のような性能が求められる。すなわち、（１）各種被着材に対して良好な接着性を有すること、（２）被着材が多孔質、非多孔質に関わらず良好な硬化性を有すること、（３）互いに熱膨張係数が異なる材料同士の貼り合わせであっても応力を緩和できる強靱且つ柔軟な硬化皮膜を形成すること、等である。このような性能を満足すべく、様々な検討が行われている（例えば、特許文献１〜３参照）。しかしながら、これらの要求性能を考えた場合に、従来の接着剤ではそれぞれ以下のような問題点があった。
変成シリコーン／エポキシ系接着剤は、その硬化機構の一部（具体的には変成シリコーン樹脂の硬化機構）が湿気硬化機構であるため、貼り合わせ面積が比較的大きく、中でも被着材が非多孔質である場合には、貼り合わせ後湿気が供給されにくい被着材中央部の硬化性（内部硬化性）が悪い、という問題があった。また、貯蔵中に混入した水分により変成シリコーン樹脂が反応して増粘する、等の問題もあった。
二液混合反応型であるウレタン系接着剤では、柔軟な皮膜が得られにくい、混入した湿気とイソシアネート基との反応による発泡によって皮膜強度が低下する、貯蔵中に混入した水分によりイソシアネート化合物が反応して増粘する、等の問題があった。
ＳＧＡ系接着剤ではそのような問題はないものの、独特の臭気がある、等の問題を抱えていた。そこで、これら従来型の接着剤に替わる新たな硬化機構を有する接着剤が求められていた。
また、分子末端に環状カーボネート基を有する化合物が提案されている（特許文献４）。しかしながら、これらの提案では環状カーボネート化合物をポリウレタンの原料として使用されているにすぎなかった。
Conventionally, as adhesives for bonding various plastics or different plastics and different materials such as metal, modified silicone / epoxy adhesives, two-component urethane adhesives, SGA (second generation acrylic) adhesives, etc. It was mainly used.
Here, the following performance is mainly required for the adhesive for bonding different materials. (1) Good adhesion to various adherends; (2) Good adherence regardless of whether the adherend is porous or non-porous; and (3) Thermal expansion of each other For example, a tough and flexible cured film that can relieve stress even when materials having different coefficients are bonded together. Various studies have been made to satisfy such performance (for example, see Patent Documents 1 to 3). However, when considering these required performances, the conventional adhesives have the following problems.
The modified silicone / epoxy adhesive has a relatively large bonding area because a part of its curing mechanism (specifically, the curing mechanism of the modified silicone resin) is a moisture curing mechanism, and in particular, the adherend is non-porous. In the case of a high quality, there is a problem that the curability (internal curability) of the center portion of the adherend where it is difficult to supply moisture after bonding is poor. In addition, there is a problem that the modified silicone resin reacts and thickens due to moisture mixed during storage.
With urethane adhesives that are two-component mixed reaction type, it is difficult to obtain a flexible film, the film strength decreases due to foaming caused by the reaction between mixed moisture and isocyanate groups, and the isocyanate compound reacts with moisture mixed during storage. Then, there was a problem such as thickening.
Although the SGA adhesive does not have such a problem, it has problems such as a unique odor. Therefore, there has been a demand for an adhesive having a new curing mechanism that replaces these conventional adhesives.
In addition, a compound having a cyclic carbonate group at the molecular end has been proposed (Patent Document 4). However, these proposals only use a cyclic carbonate compound as a raw material for polyurethane.
そこで、本発明者らは、分子内に五員環カーボネート基を有する硬化性樹脂に関する研究を進め、それらの問題を克服した（特願２００６−１７２２２８）。該硬化性組成物は、貯蔵時に湿気の影響を受けないため湿分管理の必要がなく、大面積の非多孔質材料同士を貼り合わせた際も良好な内部硬化性を示すうえ臭気の問題のない、接着性に優れた硬化性樹脂組成物である。しかし、より高度な要求性能である耐水性については未だ満足できなかったという問題があり、改善を検討してきた。 Therefore, the present inventors proceeded with research on a curable resin having a five-membered cyclic carbonate group in the molecule and overcame those problems (Japanese Patent Application No. 2006-172228). The curable composition is not affected by moisture at the time of storage, so there is no need for moisture management, and it exhibits good internal curability even when non-porous materials of a large area are bonded to each other. It is a curable resin composition excellent in adhesiveness. However, there is a problem that water resistance, which is a higher performance requirement, has not been satisfied yet, and improvements have been studied.
すなわち、本発明は、貯蔵時に湿気の影響を受けないため湿分管理の必要がなく、大面積の非多孔質材料同士を貼り合わせた際も良好な内部硬化性を示すうえ臭気の問題のない、接着性に優れた硬化性樹脂組成物であって、さらに耐水性が高い硬化性樹脂組成物及び該硬化性樹脂を主体とする上記性能に優れた接着剤組成物を提供するものである。 That is, since the present invention is not affected by moisture during storage, there is no need for moisture management, and when the non-porous materials of large areas are bonded together, they exhibit good internal curability and are free from odor problems. The present invention provides a curable resin composition excellent in adhesiveness, and further having a high water resistance and an adhesive composition excellent in the above performance mainly composed of the curable resin.
このような問題を解決するために、本発明者らは、鋭意研究の結果、上述の五員環カーボネート基を含有する硬化性樹脂組成物にブロックドポリイソシアネート化合物を配合することにより、硬化物の耐水性がさらに向上することを見出し、本発明を完成させるに至った。本発明は次の第１〜８の発明から構成される。 In order to solve such a problem, as a result of intensive studies, the present inventors have found that a cured product by blending a blocked polyisocyanate compound with the above-described curable resin composition containing a five-membered cyclic carbonate group. The water resistance of the water was further improved, and the present invention was completed. The present invention is composed of the following first to eighth inventions.
すなわち、第１の発明は、分子内に下記一般式（１）で示される五員環カーボネート基を有する化合物（Ａ）と、分子内に第１級及び／又は第２級アミノ基を有するポリアミン化合物（Ｂ）と、ブロック剤で保護されたイソシアネート基を有するブロックドポリイソシアネート化合物（Ｃ）とを含有することを特徴とする硬化性樹脂組成物に関するものである。
（ただし、式中のＸは化合物（Ａ）の残基を表す）
That is, the first invention is a compound (A) having a five-membered ring carbonate group represented by the following general formula (1) in the molecule, and a polyamine having a primary and / or secondary amino group in the molecule. The present invention relates to a curable resin composition comprising a compound (B) and a blocked polyisocyanate compound (C) having an isocyanate group protected with a blocking agent.
(However, X in the formula represents a residue of compound (A))
また、第２の発明は、五員環カーボネート基を有する化合物（Ａ）が、分子内に下記一般式（２）で示される基を有することを特徴とする請求項１に記載の硬化性樹脂組成物に関するものである。
（ただし、式中のＲは分子量１，０００未満の２価の有機基であり、Ｙは化合物（Ａ）の残基を表す）
In the second invention, the compound (A) having a five-membered ring carbonate group has a group represented by the following general formula (2) in the molecule. It relates to a composition.
(In the formula, R is a divalent organic group having a molecular weight of less than 1,000, and Y represents a residue of the compound (A)).
また、第３の発明は、五員環カーボネート基を有する化合物（Ａ）又はブロックドポリイソシアネート化合物（Ｃ）の主鎖がオキシアルキレン重合体であることを特徴とする、第１又は第２のいずれかの発明に係る硬化性樹脂組成物に関するものである。 The third invention is characterized in that the main chain of the compound (A) having a five-membered ring carbonate group or the blocked polyisocyanate compound (C) is an oxyalkylene polymer, The present invention relates to a curable resin composition according to any one of the inventions.
また、第４の発明は、五員環カーボネート基を有する化合物（Ａ）の残基Ｘ又はＹが、オキシエチレン基（−ＯＣＨ２ＣＨ２−）を繰り返し構成単位として含有することを特徴とする、第３の発明に係る硬化性樹脂組成物に関するものである。 The fourth invention is characterized in that the residue X or Y of the compound (A) having a five-membered ring carbonate group contains an oxyethylene group (—OCH 2 CH 2 —) as a repeating structural unit. The present invention relates to a curable resin composition according to the third invention.
また、第５の発明は、五員環カーボネート基を有する化合物（Ａ）の残基Ｘ又はＹの分子量が５００以上であることを特徴とする、第１〜第４のいずれかの発明に係る硬化性樹脂組成物に関するものである。 The fifth invention relates to any one of the first to fourth inventions, wherein the molecular weight of the residue X or Y of the compound (A) having a five-membered ring carbonate group is 500 or more. The present invention relates to a curable resin composition.
また、第６の発明は、さらに、分子内に第１級及び／又は第２級アミノ基、並びに架橋可能な反応性珪素基を有するアミノシラン化合物（Ｄ）を含有することを特徴とする、第１〜第５のいずれかの発明に係る硬化性樹脂組成物に関するものである。 The sixth invention further comprises an aminosilane compound (D) having a primary and / or secondary amino group and a crosslinkable reactive silicon group in the molecule. The present invention relates to a curable resin composition according to any one of the first to fifth inventions.
また、第７の発明は、さらに、分子内にオキシラン環を有するエポキシ樹脂（Ｅ）を含有することを特徴とする、第１〜第６のいずれかの発明に係る硬化性樹脂組成物に関するものである。 The seventh invention further relates to a curable resin composition according to any one of the first to sixth inventions, further comprising an epoxy resin (E) having an oxirane ring in the molecule. It is.
また、第８の発明は、第１〜第７のいずれかの発明に係る硬化性樹脂組成物を主体とする接着剤組成物に関するものである。 The eighth invention relates to an adhesive composition mainly comprising the curable resin composition according to any one of the first to seventh inventions.
本発明に係る硬化性樹脂組成物は、ブロックドポリイソシアネート化合物を配合することにより、特定の五員環カーボネート基を有する硬化性樹脂組成物の耐水性がさらに向上するという効果を奏するものである。 The curable resin composition according to the present invention has an effect that the water resistance of the curable resin composition having a specific five-membered cyclic carbonate group is further improved by blending the blocked polyisocyanate compound. .
以下、本発明の実施するための最良の形態を、詳細に説明する。なお、本発明はこれらの例示にのみ限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々の変更を加え得ることは勿論である。 Hereinafter, the best mode for carrying out the present invention will be described in detail. In addition, this invention is not limited only to these illustrations, Of course, a various change can be added in the range which does not deviate from the summary of this invention.
［五員環カーボネート基を有する化合物（Ａ）について］
本発明における、五員環カーボネート基を有する化合物（Ａ）（以下、単に「化合物（Ａ）」と表記することがある）は、上記一般式（１）で示される五員環カーボネート基を有する化合物である。
化合物（Ａ）は、例えば、ジオールとホスゲンとの反応（参考文献、Ｂ．Ｍ．Ｔｒｏｓｔ ａｎｄ Ｄ．Ｍ．Ｔ．Ｃｈａｎ．，Ｊ．Ｏｒｇ．Ｃｈｅｍ．，４８，３３４６（１９８３）他）、オキシランとβラクトンとの反応（Ｔ．Ｎｉｓｈｉｋｕｂｏ，Ｔ．Ｉｉｚｕｋａ，Ｍ．Ｉｉｄａ ａｎｄ Ｎ．Ｉｓｏｂｅ，Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔ．，２７，３７４１（１９８６））、オキシランと二酸化炭素による反応（Ｗ．Ｊ．Ｐｅｐｐｅｌ，Ｉｎｄ．Ｅｎｇ．Ｃｈｅｍ．，５０，７６７（１９５８）、Ｎ．Ｋｉｈａｒａ ａｎｄ Ｔ．Ｅｎｄｏ，Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，２５，４８２４（１９９２））等の反応を用いて合成することができる。
[Compound (A) having a five-membered ring carbonate group]
In the present invention, the compound (A) having a five-membered ring carbonate group (hereinafter sometimes simply referred to as “compound (A)”) has a five-membered ring carbonate group represented by the general formula (1). A compound.
Compound (A) can be prepared, for example, by reaction of diol with phosgene (reference, B. M. Trost and D. M. T. Chan., J. Org. Chem., 48, 3346 (1983), etc.), oxirane, etc. Reaction with β-lactone (T. Nishikubo, T. Iizuka, M. Iida and N. Isobe, Tetrahedron Lett., 27, 3741 (1986)), reaction with oxirane and carbon dioxide (WJ Peppel, Ind. Eng. Chem., 50, 767 (1958), N. Kihara and T. Endo, Macromolecules, 25, 4824 (1992)) and the like.
また、上記化合物（Ａ）のうち、上記一般式（２）で示される、分子内にウレタン結合及び五員環カーボネート基を有するものは、イソシアネート基含有ウレタンプレポリマー（ａ１）とグリセリンカーボネート（下記一般式（３））との反応により、合成することもできる。
［イソシアネート基含有ウレタンプレポリマー（ａ１）について］
イソシアネート基含有ウレタンプレポリマー（ａ１）は、ポリオール化合物（ｉ）とポリイソシアネート化合物（ｉｉ）から従来公知の定法により合成することができる。
[Isocyanate group-containing urethane prepolymer (a1)]
The isocyanate group-containing urethane prepolymer (a1) can be synthesized from the polyol compound (i) and the polyisocyanate compound (ii) by a conventionally known method.
［ポリオール化合物（ｉ）について］
ポリオール化合物（ｉ）としては、ポリエーテルポリオール、ポリエステルポリオール、ポリオレフィンポリオール等の従来公知のポリオール化合物が例示される。これらポリオールは、一種単独を用いてもよく、必要に応じて二種以上を併用してもよい。
[About Polyol Compound (i)]
Examples of the polyol compound (i) include conventionally known polyol compounds such as polyether polyol, polyester polyol, and polyolefin polyol. These polyols may be used individually by 1 type, and may use 2 or more types together as needed.
さらに具体的に説明すれば、ポリエーテルポリオールとしては、数平均分子量５００〜３０，０００のものが好ましく、１，０００〜２０，０００のものが特に好ましい。また、官能基数が２以上のポリエーテルポリオールが好ましく、その具体例としては、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン、ポリオキシヘキシレン、ポリオキシテトラメチレン等の単独重合体、並びにエチレンオキシド、プロピレンオキシド、ブチレンオキシド、ヘキシレンオキシド及びテトラヒドロフランよりなる群から選ばれた二種以上のモノエポキシドを開環共重合させてなる共重合体が挙げられる。 More specifically, the polyether polyol preferably has a number average molecular weight of 500 to 30,000, and particularly preferably 1,000 to 20,000. Further, polyether polyols having 2 or more functional groups are preferred, and specific examples thereof include homopolymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene, ethylene oxide, Examples thereof include a copolymer obtained by ring-opening copolymerization of two or more kinds of monoepoxides selected from the group consisting of propylene oxide, butylene oxide, hexylene oxide and tetrahydrofuran.
ポリエーテルポリオールの市販品としては、株式会社ＡＤＥＫＡ製；アデカポリエーテルシリーズ、旭硝子株式会社製；ＰＭＬシリーズ、住化バイエルウレタン株式会社製；スミフェンシリーズ、三井化学ポリウレタン株式会社製；アクトコールシリーズ（以上、いずれも商品名）等が例示される。 Commercially available polyether polyols include: ADEKA Corporation; Adeka Polyether Series, Asahi Glass Co., Ltd .; PML Series, Sumika Bayer Urethane Co., Ltd .; Sumifen Series, Mitsui Chemicals Polyurethanes Co., Ltd .; As described above, the trade names are all exemplified.
ポリエステルポリオールとしては、マレイン酸、アジピン酸、セバシン酸、フタル酸等のジカルボン酸類の一種又は二種以上と、ジオール類の一種又は二種以上とを重縮合して得られる重合体、ε−カプロラクタム、バレロラクトン等を開環重合させてなる開環重合物、活性水素を２個以上有するひまし油等の活性水素化合物が例示される。通常、分子量５０〜２５，０００のものが用いられる。 As the polyester polyol, a polymer obtained by polycondensation of one or more dicarboxylic acids such as maleic acid, adipic acid, sebacic acid and phthalic acid and one or more diols, ε-caprolactam Examples thereof include ring-opening polymers obtained by ring-opening polymerization of valerolactone and the like, and active hydrogen compounds such as castor oil having two or more active hydrogens. Usually, those having a molecular weight of 50 to 25,000 are used.
ポリオレフィンポリオールとしては、エチレン・α−オレフィン骨格を有するポリオール、ポリイソブチレン骨格を有するポリオール等が例示される。 Examples of the polyolefin polyol include a polyol having an ethylene / α-olefin skeleton and a polyol having a polyisobutylene skeleton.
この他、ポリオール化合物（ｉ）の主鎖骨格は、アクリル骨格を有するポリオール化合物、フッ素原子、珪素原子、硫黄原子又はロジン骨格を有する有機基を含有するポリオール化合物、ジエン系モノマーを重合して得られるポリブタジエン骨格及び／又はポリイソプレン骨格などを有するポリオール化合物が挙げられ、使用目的や求める性能に応じて、適宜のポリオール化合物を用いればよい。 In addition, the main chain skeleton of the polyol compound (i) is obtained by polymerizing a polyol compound having an acrylic skeleton, a polyol compound containing an organic group having a fluorine atom, a silicon atom, a sulfur atom or a rosin skeleton, or a diene monomer. Polyol compounds having a polybutadiene skeleton and / or a polyisoprene skeleton, and the like, and an appropriate polyol compound may be used depending on the purpose of use and the required performance.
以上例示したポリオール化合物の中でも、上記化合物（Ａ）の主鎖骨格（すなわち残基Ｘ又はＹ）としては、ポリオキシアルキレンであることが、得られる硬化皮膜の柔軟性を向上させ、さらに各種基材との密着性が向上するため、好ましい。さらに、ポリエチレンオキサイド、すなわち、エチレンオキサイドの開環重合体（具体的には、オキシエチレン基（−ＯＣＨ２ＣＨ２−））をその繰り返し構成単位として含有するものであることによって、アクリル系基材等への接着性が大幅に向上するため、特に好ましい。
また、上記化合物（Ａ）の主鎖骨格（すなわち残基Ｘ又はＹ）の分子量が５００以上となるようなポリオール化合物（ｉ）を選択することが、これらの効果をさらに明確するのでさらに好ましい。
Among the polyol compounds exemplified above, the main chain skeleton (that is, the residue X or Y) of the compound (A) is polyoxyalkylene, which improves the flexibility of the resulting cured film, and various groups. This is preferable because adhesion to the material is improved. Furthermore, by containing polyethylene oxide, that is, a ring-opening polymer of ethylene oxide (specifically, an oxyethylene group (—OCH 2 CH 2 —)) as its repeating structural unit, an acrylic base material is obtained. This is particularly preferable because the adhesion to the resin is greatly improved.
In addition, it is more preferable to select the polyol compound (i) such that the molecular weight of the main chain skeleton (that is, the residue X or Y) of the compound (A) is 500 or more because these effects are further clarified.
［ポリイソシアネート化合物（ｉｉ）について］
ポリイソシアネート化合物（ｉｉ）としては、分子内に少なくとも２個以上のイソシアネート基（あるいはイソチオシアネート基）を有する化合物及びその変性物である。具体例としては、脂肪族ポリイソシアネート化合物、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例示される。さらに具体的には、ヘキサメチレンジイソシアネート、イソホロ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、４，４′−ジフェニルメタンジイソシアネート、１，３−若しくは１，４−キシリレンジイソシアネート、ｍ−テトラメチルキシリレンジイソシアネート、リジンジイソシアネート、リジントリイソシアネート、フェニルジイソチオシアネート、及び、それらの変性三量体等が挙げられるが、これらに限定されるわけではない。
[About Polyisocyanate Compound (ii)]
The polyisocyanate compound (ii) is a compound having at least two isocyanate groups (or isothiocyanate groups) in the molecule and a modified product thereof. Specific examples include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, araliphatic polyisocyanate compounds, and aromatic polyisocyanate compounds. More specifically, hexamethylene diisocyanate, isophorone diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3- or 1,4-xylylene diisocyanate, m-tetra Examples include, but are not limited to, methylxylylene diisocyanate, lysine diisocyanate, lysine triisocyanate, phenyl diisothiocyanate, and modified trimers thereof.
［ポリアミン化合物（Ｂ）について］
本発明におけるポリアミン化合物（Ｂ）（以下、単に「化合物（Ｂ）」と表記することがある）は、分子内に第１級及び／又は第２級アミノ基を複数有する化合物であり、従来公知のポリアミン化合物を使用することができる。また、これらポリアミン化合物とカルボニル化合物との脱水縮合反応により生成するポリイミン化合物やポリオキサゾリジン化合物も、加水分解反応によってポリアミン化合物を再生するため本発明のポリアミン化合物（Ｂ）に包含される。具体例としては、エチレンジアミン、ジエチレントリアミン、トリエチレンジアミン、ペンタエチレンジアミン、１，２−ジアミノプロパン、１，３−ジアミノプロパン、１，２−ジアミノブタン、１，４−ジアミノブタン、１，９−ジアミノノナン、ノルボルナンジアミン、ビスアミノメチルシクロヘキサン、イソフォロンジアミン、ＡＴＵ（３，９−ビス（３−アミノプロピル）−２，４，８，１０−テトラオキサスピロ［５．５］ウンデカン）、ヘキサメチレンジアミン、ｍ−キシリレンジアミン、ビス（アミノプロピル）ピペラジン、Ｎ−（３−アミノプロピル）−１，３−プロパンジアミン、ビス（３−アミノプロピル）エーテル２−ヒドロキシエチルアミノプロピルアミン、ラウリルアミノプロピルアミン、式 Ｈ２Ｎ（Ｃ２Ｈ４ＮＨ）ｎＨ（ｎ≧５)で表わされる化合物（商品名：ポリエイト、東ソー株式会社製）、サンテクノジャパン株式会社製商品名ジェファーミンシリーズ等の分子末端に第１級アミノ基を有するポリオキシプロピレン、日本触媒株式会社製商品名エポミンシリーズ等のポリエチレンイミン、日本触媒株式会社製商品名ポリメントシリーズ等のアミノエチル化アクリルポリマー、上記のポリアミン化合物における第１級アミノ基とケトン類との反応生成物であるケチミン化合物、第１級アミノ基とアルデヒド類との反応生成物であるアルジミン化合物、β−アミノアルコール化合物とケトン類との反応生成物であるオキサゾリジン化合物等が挙げられるが、これらに限定されるわけではない。
[About polyamine compound (B)]
The polyamine compound (B) in the present invention (hereinafter sometimes simply referred to as “compound (B)”) is a compound having a plurality of primary and / or secondary amino groups in the molecule, and is conventionally known. These polyamine compounds can be used. In addition, polyimine compounds and polyoxazolidine compounds produced by dehydration condensation reaction of these polyamine compounds and carbonyl compounds are also included in the polyamine compound (B) of the present invention in order to regenerate the polyamine compounds by hydrolysis reaction. Specific examples include ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, 1,9-diaminononane, norbornane. Diamine, bisaminomethylcyclohexane, isophoronediamine, ATU (3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane), hexamethylenediamine, m- Xylylenediamine, bis (aminopropyl) piperazine, N- (3-aminopropyl) -1,3-propanediamine, bis (3-aminopropyl) ether 2-hydroxyethylaminopropylamine, laurylaminopropylamine, formula H 2 N (C 2 4 NH) compounds represented by n H (n ≧ 5) (trade name: Porieito, manufactured by Tosoh Corporation), polyoxy having a primary amino group at the molecular terminal, such as San Techno Japan Co., Ltd. trade name Jefferies Pharmingen Series Propylene, polyethyleneimine such as Nippon Shokubai Co., Ltd. trade name Epomin series, aminoethylated acrylic polymer such as Nippon Shokubai Co., Ltd. trade name Polyment series, primary amino group and ketones in the above polyamine compounds Examples include ketimine compounds that are reaction products, aldimine compounds that are reaction products of primary amino groups and aldehydes, and oxazolidine compounds that are reaction products of β-amino alcohol compounds and ketones. It is not limited to.
上記化合物（Ｂ）は、上記化合物（Ａ）の五員環カーボネート基と反応することから、硬化物の皮膜凝集力をさらに一段と向上させることができ、硬化性樹脂組成物を効果的に硬化させる。上記化合物（Ｂ）は、所望の硬化皮膜物性を得るために適宜選択すればよく、さらにこれらは１種又は２種以上使用してもよい。上記化合物（Ｂ）の配合量は特に限定されないが、上記化合物（Ａ）の五員環カーボネート基１モルに対して、上記化合物（Ｄ）中の第１級及び／又は第２級アミノ基が０．０１〜３．０モルであるのが好ましく、０．１〜２．０モルであるのがさらに好ましく、０．２〜１．０モルであるのが特に好ましい。上記化合物（Ｄ）の添加量が、上記化合物（Ｃ）の五員環カーボネート基１モルに対して０．０１モルを下回ると上記化合物（Ｂ）を添加する効果が十分でないことがあり、３．０モルを上回ると上記化合物（Ａ）が十分硬化しないことがある。 Since the compound (B) reacts with the five-membered ring carbonate group of the compound (A), the film cohesion of the cured product can be further improved, and the curable resin composition is effectively cured. . The compound (B) may be appropriately selected in order to obtain desired cured film properties, and these may be used alone or in combination of two or more. Although the compounding quantity of the said compound (B) is not specifically limited, The primary and / or secondary amino group in the said compound (D) with respect to 1 mol of 5-membered ring carbonate groups of the said compound (A). The amount is preferably from 0.01 to 3.0 mol, more preferably from 0.1 to 2.0 mol, particularly preferably from 0.2 to 1.0 mol. When the addition amount of the compound (D) is less than 0.01 mol with respect to 1 mol of the five-membered carbonate group of the compound (C), the effect of adding the compound (B) may not be sufficient. When the amount exceeds 0.0 mol, the compound (A) may not be sufficiently cured.
［ブロックドポリイソシアネート化合物（Ｃ）について］
本発明におけるブロックドポリイソシアネート化合物（Ｃ）（以下、単に「化合物（Ｃ）」と表記することがある）は、ポリイソシアネートのイソシアネート基末端前駆体の遊離のイソシアネート基を活性水素基含有化合物（ブロック剤）と反応させて、不活性としたものであり、解離温度以上になると活性なイソシアネート基が再生されて架橋反応を起こす化合物である。また、解離温度以下であっても、第１級アミノ基及び／又は第２級アミノ基含有化合物が共存する条件ではイソシアネート基が再生されるブロックドポリイソシアネート化合物もあり、これらを使用することもできる。
ブロックドイソシアネート化合物は、ブロック剤が解離した際に、ブロック剤以外の水酸基含有化合物、第１級アミノ基及び／又は第２級アミノ基含有化合物、メルカプタン化合物等に代表されるようなイソシアネート基と反応性を有する化合物が系中に共存した場合、それらの化合物と反応する。
[About blocked polyisocyanate compound (C)]
The blocked polyisocyanate compound (C) in the present invention (hereinafter, sometimes simply referred to as “compound (C)”) is a compound containing an active hydrogen group containing a free isocyanate group of an isocyanate group terminal precursor of polyisocyanate ( It is a compound that is inactivated by reacting with a blocking agent, and when the dissociation temperature is reached, the active isocyanate group is regenerated to cause a crosslinking reaction. There are also blocked polyisocyanate compounds in which isocyanate groups are regenerated under conditions where primary amino groups and / or secondary amino group-containing compounds coexist even at a dissociation temperature or lower, and these may be used. it can.
When the blocking agent is dissociated, the blocked isocyanate compound has a hydroxyl group-containing compound other than the blocking agent, a primary amino group and / or a secondary amino group-containing compound, a mercaptan compound and the like as represented by When reactive compounds coexist in the system, they react with these compounds.
上記化合物（Ｃ）におけるブロック剤には、フェノール、クレゾール等のアルコール系化合物、メチルエチルケトオキシム等のオキシム系化合物、アミン系化合物、アミド系化合物、ε−カプロラクタム等のラクタム系化合物、アセト酢酸エチル，マロン酸エチル等の活性メチレン系化合物等が挙げられるが、これらに限定されるわけではない。 The blocking agent in the compound (C) includes alcohol compounds such as phenol and cresol, oxime compounds such as methyl ethyl ketoxime, amine compounds, amide compounds, lactam compounds such as ε-caprolactam, ethyl acetoacetate, and malon. Examples include, but are not limited to, active methylene compounds such as ethyl acid.
上記化合物（Ｃ）の具体例としては、デュラネート１７Ｂ−６０ＰＸ、デュラネートＴＰＡ−Ｂ８０Ｘ、デュラネートＭＦ−Ｂ６０Ｘ、デュラネートＭＦ−Ｋ６０Ｘ、デュラネートＥ４０２−Ｂ８０Ｔ（以上は旭化成ケミカルズ株式会社製／商品名）、アデカレジンＱＲ９４２５、アデカレジンＱＲ９３６３、アデカレジンＱＲ９２７６、アデカレジンＱＲ９２９９（以上は株式会社ＡＤＥＫＡ製／商品名）等が挙げられるが、これらに限定されるわけではない。 Specific examples of the compound (C) include DURANATE 17B-60PX, DURANATE TPA-B80X, DURANATE MF-B60X, DURANATE MF-K60X, DURANATE E402-B80T (the above are manufactured by Asahi Kasei Chemicals Corporation / trade name), Adeka Resin QR9425. , Adeka Resin QR9363, Adeka Resin QR9276, Adeka Resin QR9299 (the above is ADEKA Co., Ltd./trade name) and the like, but are not limited thereto.
［分子内に第１級アミノ基及び／又は第２級アミノ基、並びに架橋可能な反応性珪素基を有するアミノシラン化合物（Ｄ）について］
本発明における、アミノシラン化合物（Ｄ）（以下、単に「化合物（Ｄ）」と表記することがある）は、分子内に第１級及び／又は第２級アミノ基、並びに架橋可能な反応性珪素基を有する化合物である。
[Aminosilane compound (D) having a primary amino group and / or a secondary amino group and a crosslinkable reactive silicon group in the molecule]
In the present invention, the aminosilane compound (D) (hereinafter sometimes simply referred to as “compound (D)”) includes a primary and / or secondary amino group in the molecule and a crosslinkable reactive silicon. A compound having a group.
上記化合物（Ｄ）としては、下記一般式（４）で示される化合物（ｄ１）、化合物（ｄ１）の縮合生成物、又は、化合物（ｄ１）と下記一般式（５）で示される化合物（ｄ２）との縮合反応生成物が挙げられる。これらの中では、化合物（ｄ１）の縮合生成物、及び、化合物（ｄ１）と下記一般式（５）で示される化合物（ｄ２）との縮合反応生成物がより好ましく、化合物（ｄ１）の縮合生成物、及び、化合物（ｄ１）と下記一般式（４）で示される化合物（ｄ２）との縮合反応生成物のうち２個以上の化合物（ｄ１）と１個以上の化合物（ｄ２）との縮合反応生成物が特に好ましい。その理由は、上記縮合生成物はその分子内に第１級アミノ基を複数個有しているため、上記化合物（Ａ）及び上記化合物（Ｃ）との反応確率が向上するからである。 As the compound (D), a compound (d1) represented by the following general formula (4), a condensation product of the compound (d1), or a compound (d2) represented by the following general formula (5) and the compound (d1) ) And a condensation reaction product. Among these, the condensation product of the compound (d1) and the condensation reaction product of the compound (d1) and the compound (d2) represented by the following general formula (5) are more preferable, and the condensation of the compound (d1) Of the product and the condensation reaction product of the compound (d1) and the compound (d2) represented by the following general formula (4), two or more compounds (d1) and one or more compounds (d2) A condensation reaction product is particularly preferred. The reason is that since the condensation product has a plurality of primary amino groups in the molecule, the reaction probability with the compound (A) and the compound (C) is improved.
（ただし、式中、Ｒ１はフェニル基及び炭素数１〜６のアルキル基から選ばれる一種以上の官能基を、Ｒ２は第２級アミノ基を含んでいてもよい二価の有機基を、Ｗはフェノキシ基及び炭素数１〜６のアルコキシ基から選ばれる一種以上の基を、ｎは０、１又は２を、それぞれ表す）
（ただし、式中、Ｒ３、Ｒ４、Ｒ５は、フェニル基、分子量５００以下のアルキル基、フェノキシ基、及び、炭素数１〜６のアルコキシ基から選ばれる一種以上の基をそれぞれ表し、Ｒ６は、フェニル基、及び、炭素数１〜６のアルキル基から選ばれる一種以上の基をそれぞれ表す）
(Wherein, R 1 represents one or more functional groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms, and R 2 represents a divalent organic group that may contain a secondary amino group. W represents one or more groups selected from a phenoxy group and an alkoxy group having 1 to 6 carbon atoms, and n represents 0, 1 or 2, respectively.
(However, in the formula, R 3 , R 4 and R 5 each represent one or more groups selected from a phenyl group, an alkyl group having a molecular weight of 500 or less, a phenoxy group, and an alkoxy group having 1 to 6 carbon atoms, R 6 represents one or more groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms.
［化合物（ｄ１）について］
化合物（ｄ１）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−アミノプロピルメチルジメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルメチルジエトキシシラン、Ｎ−（２−アミノエチル）−３−プロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−プロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−プロピルトリエトキシシラン、Ｎ−（２−アミノエチル）−３−プロピルメチルジエトキシシラン、４−アミノ−３−ジメチルブチルトリメトキシシラン、４−アミノ−３−ジメチルブチルメチルジメトキシシラン、４−アミノ−３−ジメチルブチルトリエトキシシラン、４−アミノ−３−ジメチルブチルメチルジエトキシシラン、［２−アミノエチル−（２′−アミノエチル）］−３−アミノプロピルトリメトキシシラン等の第１級アミノ基含有アミノシラン化合物等が例示される。また、３−トリエトキシシリル−Ｎ−（１，３−ジメチル-ブチリデン）プロピルアミン等のケチミンシラン化合物も、湿気により第１級アミノ基が生成するため実質的に含まれる。なかでも、３−アミノプロピルトリメトキシシラン、又は、Ｎ−（２−アミノエチル）−３−プロピルトリメトキシシランを用いることが、入手が容易であるという観点から好ましい。
[Compound (d1)]
Specific examples of the compound (d1) include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl). ) -3-propyltrimethoxysilane, N- (2-aminoethyl) -3-propylmethyldimethoxysilane, N- (2-aminoethyl) -3-propyltriethoxysilane, N- (2-aminoethyl)- 3-propylmethyldiethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, 4-amino-3- Dimethylbutylmethyldiethoxysilane, [2-aminoethyl- (2 ′ Aminoethyl)] - primary amino group-containing aminosilane compound such as 3-aminopropyltrimethoxysilane and the like. Further, ketimine silane compounds such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine are substantially contained because primary amino groups are generated by moisture. Of these, it is preferable to use 3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-propyltrimethoxysilane from the viewpoint of easy availability.
［化合物（ｄ２）について］
化合物（ｄ２）の具体例としては、メチルトリメトキシシラン、ジメチルジメトキシシラン、ヘキシルトリメトキシシラン、デシルトリメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−ウレイドプロピルトリメトキシシラン等が例示される。なかでも、メチルトリメトキシシラン、ジメチルジメトキシシランを用いることが、化合物（ｄ１）との縮合反応の容易性の観点から好ましい。
[Compound (d2)]
Specific examples of the compound (d2) include methyltrimethoxysilane, dimethyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, 3-mercaptopropyltrimethoxy. Examples include silane and 3-ureidopropyltrimethoxysilane. Of these, methyltrimethoxysilane and dimethyldimethoxysilane are preferably used from the viewpoint of easy condensation reaction with the compound (d1).
化合物（ｄ１）単独、あるいは、化合物（ｄ１）と化合物（ｄ２）との縮合生成物は、従来公知の定法により合成すればよい。具体的には、化合物（ｄ１）を水と反応させる方法、あるいは、化合物（ｄ１）及び化合物（ｄ２）を水と反応させる方法が挙げられる。化合物（ｄ１）単独、あるいは、化合物（ｄ１）と化合物（ｄ２）との縮合生成物は市販されており、本発明ではそれらを用いることができる。市販品としては、ＭＳ３３０１（チッソ株式会社製／商品名）、ＭＳ３３０２（チッソ株式会社製／商品名）、Ｘ−４０−２６５１（信越化学工業株式会社製／商品名）等のアミノシランのシリル基を単独あるいはその他のアルコキシシラン化合物と一部縮合させた化合物が挙げられる。 The compound (d1) alone or the condensation product of the compound (d1) and the compound (d2) may be synthesized by a conventionally known method. Specifically, a method of reacting compound (d1) with water or a method of reacting compound (d1) and compound (d2) with water can be mentioned. The compound (d1) alone or the condensation product of the compound (d1) and the compound (d2) is commercially available, and they can be used in the present invention. Examples of commercially available products include aminosilane silyl groups such as MS3301 (manufactured by Chisso Corporation / brand name), MS3302 (manufactured by Chisso Corporation / brand name), X-40-2651 (manufactured by Shin-Etsu Chemical Co., Ltd./brand name), and the like. Examples thereof include a single compound or a partially condensed compound with other alkoxysilane compounds.
上記化合物（Ｄ）は、所望の硬化皮膜物性を得るために適宜選択すればよい。また、上記化合物（Ｄ）は１種単独又は２種以上併用してもよい。上記化合物（Ｄ）の配合量は特に限定されないが、上記化合物（Ａ）中の五員環カーボネート基及び上記化合物中のブロックドイソシアネート基の合計１．０モルに対して、０．００１〜１０モルが好ましく、０．０５〜５．０モルがより好ましく、０．１〜１．０モルが特に好ましい。 The compound (D) may be appropriately selected in order to obtain desired cured film properties. Moreover, the said compound (D) may be used individually by 1 type or in combination of 2 or more types. Although the compounding quantity of the said compound (D) is not specifically limited, 0.001-10 with respect to the total 1.0 mol of the five-membered-ring carbonate group in the said compound (A) and the blocked isocyanate group in the said compound. Mol is preferable, 0.05 to 5.0 mol is more preferable, and 0.1 to 1.0 mol is particularly preferable.
上記化合物（Ｄ）の分子中の第１級アミノ基及び／又は第２級アミノ基は、上記化合物（Ａ）の五員環カーボネート基又は上記化合物（Ｃ）からブロック化剤が脱離して生成した遊離イソシアネート基と反応する。また、一方で上記化合物（Ｄ）の反応性珪素基も架橋可能であるため、いわば上記化合物（Ａ）及び上記化合物（Ｃ）の硬化剤として働き、硬化性樹脂組成物を効果的に硬化させる。また、上記化合物（Ａ）及び上記化合物（Ｃ）と反応せずに残った上記化合物（Ｄ）は、金属や無機材料への密着性付与剤として働くことができる。 The primary amino group and / or secondary amino group in the molecule of the compound (D) is generated by elimination of the blocking agent from the five-membered carbonate group of the compound (A) or the compound (C). Reacts with free isocyanate groups. On the other hand, since the reactive silicon group of the compound (D) can also be cross-linked, it acts as a curing agent for the compound (A) and the compound (C), and effectively cures the curable resin composition. . Moreover, the said compound (A) and the said compound (D) which remained without reacting with the said compound (C) can work | function as an adhesive imparting agent to a metal or an inorganic material.
［分子内にオキシラン環を有するエポキシ樹脂（Ｅ）について］
本発明におけるエポキシ樹脂（Ｅ）は、分子内にオキシラン環を有する従来公知のエポキシ樹脂である。具体例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ノボラック型エポキシ樹脂、アミンをエポキシ化したエポキシ樹脂、複素環を有するエポキシ樹脂、脂環式エポキシ樹脂、ウレタン結合を有するウレタン変性エポキシ樹脂等の一分子中に一個以上のオキシラン環を含有する化合物等の従来公知のエポキシ基含有化合物が挙げられる。また、市販品としては、エピクロンシリーズ（大日本インキ化学工業株式会社製／商品名）、セロキサイドシリーズ、エポリードシリーズ、ＥＨＰＥシリーズ、サイクロマーシリーズ（ダイセル化学工業株式会社製／商品名）、エピコートシリーズ（ジャパンエポキシレジン株式会社製／商品名）、Ｄ．Ｅ．Ｒ．シリーズ（ダウケミカル日本株式会社製／商品名）等が挙げられるが、これらに限定されるわけではない。
エポキシ樹脂（Ｅ）は、化合物（Ｂ）及び／又は化合物（Ｄ）が有する第１級アミノ基及び／又は第２級アミノ基と反応することができる。従って、エポキシ樹脂（Ｅ）を本発明の硬化性樹脂組成物に配合することによって、その硬化皮膜をより強固なものとすることができる。エポキシ樹脂（Ｅ）の配合量は、五員環カーボネート基を有する化合物（Ａ）１００質量部に対して１〜１０００質量部が好ましく、１０〜５００質量部がより好ましく、５０〜２００質量部が特に好ましい。
[Epoxy resin (E) having an oxirane ring in the molecule]
The epoxy resin (E) in the present invention is a conventionally known epoxy resin having an oxirane ring in the molecule. Specific examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, epoxy resin in which amine is epoxidized, epoxy resin having a heterocyclic ring, fat Conventionally known epoxy group-containing compounds such as a compound containing one or more oxirane rings in one molecule such as a cyclic epoxy resin and a urethane-modified epoxy resin having a urethane bond may be mentioned. Commercially available products include the Epicron series (Dainippon Ink Chemical Co., Ltd./trade name), Celoxide series, Epolide series, EHPE series, Cyclomer series (Daicel Chemical Industries, Ltd./ trade name). , Epicote series (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) E. R. Series (made by Dow Chemical Japan Co., Ltd./trade name) and the like can be mentioned, but are not limited thereto.
An epoxy resin (E) can react with the primary amino group and / or secondary amino group which a compound (B) and / or a compound (D) have. Therefore, the cured film can be made stronger by blending the epoxy resin (E) into the curable resin composition of the present invention. As for the compounding quantity of an epoxy resin (E), 1-1000 mass parts is preferable with respect to 100 mass parts of compounds (A) which have a five-membered ring carbonate group, 10-500 mass parts is more preferable, and 50-200 mass parts is. Particularly preferred.
［その他の成分について］
本発明に係る硬化性樹脂組成物及び接着剤組成物には、従来公知の任意の化合物乃至物質を配合することができる。例えば、エポキシ樹脂、硬化促進剤、親水性又は疎水性シリカ系粉体、炭酸カルシウム粉体、クレイ粉体、アクリル系等の有機系粉体、有機系・無機系のバルーン等の充填材、フェノール樹脂等の粘着付与剤、アマイドワックス等の揺変剤、酸化カルシウム等の脱水剤、希釈剤、可塑剤、難燃剤、機能性オリゴマー、ヒンダードアミン系化合物、ヒンダードフェノール系化合物、３−（２，２，６，６−テトラメチルピペリジ−４−イルオキシ）プロピルトリエトキシシラン等の老化防止剤、ベンゾトリアゾール系化合物等の紫外線吸収剤、顔料、チタネートカップリング剤、アルミニウムカップリング剤、３−グリシドキシプロピルトリメトキシシラン等のシランカップリング剤、乾性油等を配合することができる。
[Other ingredients]
Any conventionally known compound or substance can be added to the curable resin composition and the adhesive composition according to the present invention. For example, epoxy resin, curing accelerator, hydrophilic or hydrophobic silica powder, calcium carbonate powder, clay powder, acrylic organic powder, organic / inorganic balloon fillers, phenol, etc. Tackifiers such as resins, thixotropic agents such as amide wax, dehydrating agents such as calcium oxide, diluents, plasticizers, flame retardants, functional oligomers, hindered amine compounds, hindered phenol compounds, 3- (2, Anti-aging agents such as 2,6,6-tetramethylpiperidi-4-yloxy) propyltriethoxysilane, UV absorbers such as benzotriazole compounds, pigments, titanate coupling agents, aluminum coupling agents, 3-glycols Silane coupling agents such as Sidoxypropyltrimethoxysilane, drying oil and the like can be blended.
本発明にかかる硬化性樹脂組成物は、上記化合物（Ａ）の五員環カーボネート基と上記化合物（Ｂ）のアミノ基との反応による反応生成物で形成されるネットワーク（ＮＡ）、及び、上記化合物（Ｂ）のアミノ基と上記化合物（Ｃ）に由来するイソシアネート基都の反応による反応生成物で形成されるネットワーク（ＮＢ）が相互に入り組んだ高次構造を取っていると推察される。さらには、上記化合物（Ｂ）は複数のアミノ基を有するので、上記化合物（Ｂ）によって上記化合物（Ａ）と上記化合物（Ｃ）とが連結されることにより、上記ネットワーク（ＮＡ）と上記ネットワーク（ＮＢ）が架橋されていると推察される。また、ネットワーク（ＮＡ）は上記化合物（Ａ）の五員環カーボネート基と上記化合物（Ｂ）のアミノ基とが反応した際に生成する水酸基を有している。この水酸基と上記化合物（Ｃ）とは反応可能であり、これらが反応することにより、より緻密な架橋ネットワークが形成されているものと推察される。さらに、上記化合物（Ｄ）を配合した際には、反応性珪素基の架橋も起こるため、さらに緻密な架橋ネットワークが形成されているものと推察される。また、上記化合物（Ｅ）を配合した際にも架橋ネットワークが強化される。このような理由から、本発明における硬化性樹脂組成物は耐水性が極めて向上したものと推察されるのである。
つまり、本発明は、上記化合物（Ａ）と上記化合物（Ｂ）とから構成されるもの、あるいは、上記化合物（Ｂ）と上記化合物（Ｃ）とから構成されるものとは全く異なり、従来に類を見ない硬化機構並びに硬化ネットワークを形成するものであると認識されるべきである。上記化合物（Ｃ）はブロック化剤でイソシアネート基の反応性が大きく低下しているため、上記化合物（Ａ）、上記化合物（Ｂ）、上記化合物（Ｃ）を同時に混合してもすぐには反応が進行しないことから、十分な可使時間が確保されるため極めて作業性が高いのである。
The curable resin composition according to the present invention includes a network (NA) formed by a reaction product obtained by a reaction between a five-membered carbonate group of the compound (A) and an amino group of the compound (B), and It is presumed that the network (NB) formed by the reaction product of the reaction of the amino group of the compound (B) and the isocyanate group derived from the compound (C) has a higher order structure. Further, since the compound (B) has a plurality of amino groups, the compound (A) and the compound (C) are connected by the compound (B), whereby the network (NA) and the network are connected. It is inferred that (NB) is crosslinked. The network (NA) has a hydroxyl group that is generated when the five-membered carbonate group of the compound (A) reacts with the amino group of the compound (B). The hydroxyl group and the compound (C) can react with each other, and it is assumed that a denser cross-linked network is formed by the reaction. Furthermore, when the compound (D) is blended, reactive silicon groups are also cross-linked, so that it is presumed that a denser cross-linked network is formed. Moreover, when the said compound (E) is mix | blended, a crosslinked network is strengthened. For these reasons, it is presumed that the water resistance of the curable resin composition in the present invention has been greatly improved.
That is, the present invention is completely different from the one composed of the compound (A) and the compound (B), or the one composed of the compound (B) and the compound (C). It should be recognized that it forms a unique cure mechanism as well as a cure network. Since the compound (C) is a blocking agent and the reactivity of the isocyanate group is greatly reduced, the compound (A), the compound (B), and the compound (C) react immediately even if they are mixed at the same time. Therefore, workability is extremely high because sufficient pot life is secured.
本発明に係る硬化性樹脂組成物は、たとえば、接着剤、シーリング材、塗料、コーティング材、目止め材、注型材、被覆材等として用いることができる。
また、本発明に係る硬化性樹脂組成物は、一液型としても二液型としても、場合によっては三液以上を混合して使用することもできる。一液型として使用される場合は、互いに密封状態では不活性な化合物を選択し、保管乃至搬送中は、空気（空気中の水分）と接触しないよう、気密に密封した状態で取り扱われる。そして、使用時には開封して任意の箇所に適用すればよい。
また、二液型（又は三液以上）として使用される場合には、適宜、化合物（Ａ）、ポリアミン化合物（Ｂ）ブロックドイソシアネート化合物（Ｃ）とが、第一液及び第二液（又はさらに第三液）として個別に包装されて提供されるが、その組み合わせは任意である。そして、使用時にこれら第一液と第二液（又はさらに第三液以上）とを混合して任意の箇所に適用すればよい。
The curable resin composition according to the present invention can be used as, for example, an adhesive, a sealing material, a paint, a coating material, a sealing material, a casting material, a coating material, and the like.
Moreover, the curable resin composition according to the present invention can be used as a one-component type or a two-component type, or in some cases, by mixing three or more components. When used as a one-pack type, compounds that are inert in a sealed state are selected and handled in a hermetically sealed state so as not to come into contact with air (water in the air) during storage or transportation. And it should just open and use for arbitrary places at the time of use.
Further, when used as a two-component type (or three or more components), the compound (A), the polyamine compound (B) and the blocked isocyanate compound (C) are appropriately mixed with the first solution and the second solution (or Furthermore, the third liquid is provided by being individually packaged, but the combination thereof is arbitrary. And what is necessary is just to mix these 1st liquids and 2nd liquids (or 3rd liquid or more) at the time of use, and to apply to arbitrary places.
以下、本発明を実施例に基づいて詳細に説明するが、本発明は実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.
［五員環カーボネート基を有する化合物（Ａ）の調製］
（合成例１）
アデカポリエーテルＰＲ−５００７（株式会社ＡＤＥＫＡ製商品名、ポリエーテルポリオール、分子量５，０００、オキシプロピレン／オキシエチレン質量比（以下「ＰＯ／ＥＯ」と表記する）＝３０／７０）を３５質量部、アクトコールＰ−２８（三井化学ポリウレタン株式会社製商品名、ポリエーテルポリオール、分子量５，０００、ＰＯ／ＥＯ＝１００／０）を７００質量部、及び、イソホロンジイソシアネートを８２．７質量部（ＮＣＯ／ＯＨ＝２．０）を窒素雰囲気下にて撹拌混合しながら、ポリオール化合物に対して５０ｐｐｍのスズ触媒の存在下９０℃で５時間反応させた。その後グリセリンカーボネート（宇部興産株式会社製）を５１．０質量部加え同温度でさらに３時間反応させることで、分子内に五員環カーボネート基を有する化合物Ａ−１を得た。反応後ＩＲ測定を行ったところイソシアネート基に帰属される吸収（２２６５ｃｍ−１）は観察されなかった。
[Preparation of Compound (A) Having Five-membered Ring Carbonate Group]
(Synthesis Example 1)
35 parts by mass of ADEKA polyether PR-5007 (trade name, polyether polyol, molecular weight 5,000, oxypropylene / oxyethylene mass ratio (hereinafter referred to as “PO / EO”) = 30/70, manufactured by ADEKA Corporation) , Actol P-28 (trade name, polyether polyol, molecular weight 5,000, PO / EO = 100/0) manufactured by Mitsui Chemicals Polyurethane Co., Ltd., 700 parts by mass, and isophorone diisocyanate 82.7 parts by mass (NCO /OH=2.0) while stirring and mixing in a nitrogen atmosphere, the polyol compound was reacted at 90 ° C. for 5 hours in the presence of 50 ppm of a tin catalyst. Thereafter, 51.0 parts by mass of glycerin carbonate (manufactured by Ube Industries) was added and reacted at the same temperature for 3 hours to obtain Compound A-1 having a 5-membered ring carbonate group in the molecule. When IR measurement was performed after reaction, the absorption (2265cm < -1 >) attributed to an isocyanate group was not observed.
（合成例２）
アデカポリエーテルＰＲ−５００７（株式会社ＡＤＥＫＡ製商品名、ポリエーテルポリオール、分子量５，０００、ＰＯ／ＥＯ＝３０／７０）を１００質量部、アクトコールＰ−２８（三井化学ポリウレタン株式会社製商品名、ポリエーテルポリオール、分子量５，０００、ＰＯ／ＥＯ＝１００／０）を５００質量部、及び、イソホロンジイソシアネートを６７．６質量部（ＮＣＯ／ＯＨ＝２．０）を窒素雰囲気下にて撹拌混合しながら、ポリオール化合物に対して５０ｐｐｍのスズ触媒の存在下９０℃で５時間反応させた。その後グリセリンカーボネート（宇部興産株式会社製）を３８．３質量部加え同温度でさらに３時間反応させることで、分子内に五員環カーボネート基を有する化合物Ａ−２を得た。反応後ＩＲ測定を行ったところイソシアネート基に帰属される吸収（２２６５ｃｍ−１）は観察されなかった。
(Synthesis Example 2)
100 parts by mass of ADEKA polyether PR-5007 (trade name, polyether polyol, molecular weight 5,000, PO / EO = 30/70, manufactured by ADEKA Corporation), Actol P-28 (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) , Polyether polyol, molecular weight 5,000, PO / EO = 100/0) 500 parts by mass and isophorone diisocyanate 67.6 parts by mass (NCO / OH = 2.0) under nitrogen atmosphere However, the reaction was performed at 90 ° C. for 5 hours in the presence of 50 ppm of tin catalyst with respect to the polyol compound. Thereafter, 38.3 parts by mass of glycerin carbonate (manufactured by Ube Industries) was added and reacted at the same temperature for further 3 hours to obtain Compound A-2 having a five-membered carbonate group in the molecule. When IR measurement was performed after reaction, the absorption (2265cm < -1 >) attributed to an isocyanate group was not observed.
［硬化性樹脂組成物の調製］
（実施例１）
化合物Ａ−１を４０質量部、化合物Ａ−２を１０質量部、エピコート８２８（ジャパンエポキシレジン株式会社製商品名、ビスフェノールＡ型エポキシ樹脂）を４０質量部、ノルボルナンジアミンを２０質量部、及び、アデカレジンＱＲ−９４２５（株式会社ＡＤＥＫＡ製商品名、ブロックドポリイソシアネート）１０質量部を混ぜ合わせ、硬化性樹脂組成物を調製した。
（実施例２）
さらに３−アミノプロピルトリメトキシシランを１．０重量部配合した以外は実施例１と同様に、硬化性樹脂組成物を調製した。
（比較例１）
アデカレジンＱＲ−９４２５（株式会社ＡＤＥＫＡ製商品名、ブロックドポリイソシアネート）を配合しない以外は実施例１と同様に、硬化性樹脂組成物を調製した。
（比較例２）
アデカレジンＱＲ−９４２５（株式会社ＡＤＥＫＡ製商品名、ブロックドポリイソシアネート）を配合しない以外は実施例２と同様に、硬化性樹脂組成物を調製した。
[Preparation of curable resin composition]
Example 1
40 parts by mass of Compound A-1, 10 parts by mass of Compound A-2, 40 parts by mass of Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin), 20 parts by mass of norbornanediamine, and 10 parts by mass of Adeka Resin QR-9425 (trade name, blocked polyisocyanate manufactured by ADEKA Corporation) was mixed to prepare a curable resin composition.
(Example 2)
Furthermore, a curable resin composition was prepared in the same manner as in Example 1 except that 1.0 part by weight of 3-aminopropyltrimethoxysilane was added.
(Comparative Example 1)
A curable resin composition was prepared in the same manner as in Example 1 except that Adeka Resin QR-9425 (trade name, manufactured by ADEKA, blocked polyisocyanate) was not blended.
(Comparative Example 2)
A curable resin composition was prepared in the same manner as in Example 2 except that Adeka Resin QR-9425 (trade name, manufactured by ADEKA, blocked polyisocyanate) was not blended.
［接着強さ測定］
被着材として、ステンレス板（厚さ１．５ｍｍ、幅２５ｍｍ、長さ１００ｍｍ）、木材（アサダ材、厚さ３ｍｍ、幅２５ｍｍ、長さ１００ｍｍ）を準備した。ステンレス板に、各硬化性樹脂生成物（約０．１ｇ）を２５ｍｍ×２５ｍｍの面積に均一に塗布し、１２．５ｍｍ×２５ｍｍの面積で木材をはり合わせた。各はり合わせ試験体を２３℃相対湿度５０％で７日間養生した後、引張りせん断接着強さ（Ｎ／ｍｍ２）をＪＩＳ Ｋ ６８５０に準じて測定した（耐水性試験前）。
［耐水性比較］
接着強さ測定と同様にはり合わせ試験体を作成した。各はり合わせ試験体を２３℃相対湿度５０％で７日間養生した後、さらに、２３℃で水に７日間浸せきした（耐水性試験後）。その後、２３℃相対湿度５０％で１日間静置し、引張りせん断接着強さ（Ｎ／ｍｍ２）をＪＩＳ Ｋ ６８５０に準じて測定した。実施例１、２及び比較例１、２の硬化性樹脂組成物に関して、耐水性試験前の引張せん断接着強さ及び耐水性試験後の引張せん断接着強さを表１に示す。
[Adhesive strength measurement]
Stainless steel plates (thickness 1.5 mm, width 25 mm, length 100 mm) and wood (asada material, thickness 3 mm, width 25 mm, length 100 mm) were prepared as adherends. Each curable resin product (about 0.1 g) was uniformly applied to a stainless plate with an area of 25 mm × 25 mm, and wood was pasted with an area of 12.5 mm × 25 mm. Each bonded specimen was cured at 23 ° C. and 50% relative humidity for 7 days, and then the tensile shear bond strength (N / mm 2 ) was measured according to JIS K 6850 (before the water resistance test).
[Water resistance comparison]
A bonded specimen was prepared in the same manner as the adhesive strength measurement. Each bonded specimen was cured at 23 ° C. and 50% relative humidity for 7 days, and further immersed in water at 23 ° C. for 7 days (after the water resistance test). Then, it left still at 23 degreeC relative humidity 50% for 1 day, and measured the tensile shear bond strength (N / mm < 2 >) according to JISK6850. Table 1 shows the tensile shear bond strength before the water resistance test and the tensile shear bond strength after the water resistance test for the curable resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2.
表１
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
耐水性試験前 耐水性試験後
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１ ３．４０ （ＣＦ８０ＡＦ２０） １．１０ （ＣＦ６０ＡＦ４０）
実施例２ ４．１８ （ＣＦ９０ＡＦ１０） １．５０ （ＣＦ７０ＡＦ３０）
比較例１ ３．５８ （ＣＦ８０ＡＦ２０） ０．１２ （ＡＦ１００）
比較例２ ３．９８ （ＣＦ８０ＡＦ２０） ０．０９ （ＡＦ１００）
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
＊単位：Ｎ／ｍｍ２、ＣＦ：凝集破壊、ＡＦ：界面破壊、ＣＦ及びＡＦの後ろの数字は
それぞれの破壊状態の割合を示す。
Table 1
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Before water resistance test After water resistance test ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 3.40 (CF80AF20) 1.10 (CF60AF40)
Example 2 4.18 (CF90AF10) 1.50 (CF70AF30)
Comparative Example 1 3.58 (CF80AF20) 0.12 (AF100)
Comparative Example 2 3.98 (CF80AF20) 0.09 (AF100)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
* Unit: N / mm 2 , CF: cohesive failure, AF: interfacial failure, numbers after CF and AF indicate the ratio of each fractured state.
表１の結果から明らかなように、本発明に係る硬化性樹脂組成物（実施例１及び２）は、耐水性試験後の接着強さ及び破壊状態の低下が少ない。一方、比較例１及び２の硬化性樹脂組成物は、耐水性試験後の接着強さ及び破壊状態が大きく低下し接着性を維持していない。以上のことから、本発明に係る硬化性樹脂組成物は、ブロックドポリイソシアネートが配合されているため、耐水性が向上していることが分かる。 As is clear from the results in Table 1, the curable resin compositions according to the present invention (Examples 1 and 2) have little decrease in adhesion strength and fracture state after the water resistance test. On the other hand, in the curable resin compositions of Comparative Examples 1 and 2, the adhesive strength and the fracture state after the water resistance test are greatly reduced and the adhesiveness is not maintained. From the above, it can be seen that the curable resin composition according to the present invention has improved water resistance since the blocked polyisocyanate is blended therein.
本発明に係る硬化性樹脂組成物は、たとえば、接着剤、シーリング材、塗料、コーティング材、目止め材、注型材、被覆材等として用いることができる。 The curable resin composition according to the present invention can be used as, for example, an adhesive, a sealing material, a paint, a coating material, a sealing material, a casting material, a coating material, and the like.
Claims (8)
（ただし、式中のＸは化合物（Ａ）の残基を表す） A compound (A) having a five-membered carbonate group represented by the following general formula (1) in the molecule, a polyamine compound (B) having a primary and / or secondary amino group in the molecule, and a blocking agent A blocked polyisocyanate compound (C) having an isocyanate group protected with a curable resin composition.
(However, X in the formula represents a residue of compound (A))
（ただし、式中のＲは分子量１，０００未満の２価の有機基であり、Ｙは化合物（Ａ）の残基を表す） The curable resin composition according to claim 1, wherein the compound (A) having a five-membered ring carbonate group has a group represented by the following general formula (2) in the molecule.
(In the formula, R is a divalent organic group having a molecular weight of less than 1,000, and Y represents a residue of the compound (A)).
An adhesive composition mainly comprising the curable resin composition according to claim 1.
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