JP6883558B2 - Two-component mixed curable resin composition - Google Patents
Two-component mixed curable resin composition Download PDFInfo
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- JP6883558B2 JP6883558B2 JP2018153781A JP2018153781A JP6883558B2 JP 6883558 B2 JP6883558 B2 JP 6883558B2 JP 2018153781 A JP2018153781 A JP 2018153781A JP 2018153781 A JP2018153781 A JP 2018153781A JP 6883558 B2 JP6883558 B2 JP 6883558B2
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- curable silicone
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- 239000011342 resin composition Substances 0.000 title claims description 96
- 229920002050 silicone resin Polymers 0.000 claims description 59
- 239000003822 epoxy resin Substances 0.000 claims description 38
- 229920000647 polyepoxide Polymers 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000000853 adhesive Substances 0.000 claims description 28
- 230000001070 adhesive effect Effects 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 21
- 150000003606 tin compounds Chemical class 0.000 claims description 15
- -1 amine compound Chemical class 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- UZFVQGTYOXJWTF-UHFFFAOYSA-L [octadecanoyloxy(dioctyl)stannyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCCCCCCCC UZFVQGTYOXJWTF-UHFFFAOYSA-L 0.000 claims description 8
- 229920000193 polymethacrylate Polymers 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 3
- 238000005524 ceramic coating Methods 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 claims 1
- 239000002648 laminated material Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 125000005370 alkoxysilyl group Chemical group 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical group N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000002947 alkylene 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
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、二液を混合後、速やかに硬化するとともに内部硬化性及び貯蔵安定性に優れた二液混合型硬化性樹脂組成物に関するものである。 The present invention relates to a two-component mixed curable resin composition which cures quickly after mixing two liquids and has excellent internal curability and storage stability.
エポキシ樹脂系接着剤は、その硬化物の凝集力が高く、溶剤を用いずに使用できることから、主に建築物等の比較的高い構造強度が求められる用途における接着剤、コーティング剤等として広く用いられている。
しかし一方で、硬化した皮膜が一般的に硬くなるため、線膨張係数が異なる異種材料の接着など、硬化物にある程度の伸びや曲げ強度が必要とされる箇所への接着には必ずしも適していない。また、引張り（垂直方向）やせん断方向の力に対しては強いものの、はく離方向の力に対して弱いという欠点を有している。
Epoxy resin adhesives are widely used as adhesives, coating agents, etc. mainly in applications where relatively high structural strength is required, such as buildings, because the cured product has high cohesive power and can be used without using a solvent. Has been done.
However, on the other hand, since the cured film is generally hard, it is not always suitable for adhesion to places where the cured product requires a certain degree of elongation and bending strength, such as adhesion of different materials having different coefficients of linear expansion. .. Further, it has a drawback that it is strong against a force in a tensile (vertical direction) or a shearing direction, but weak against a force in a peeling direction.
そこで、このようなエポキシ樹脂系接着剤の欠点を改良するために、エポキシ樹脂にアルコキシシリル基含有樹脂（これらは一般に変成シリコーン樹脂と呼ばれる）を組み合わせた二液混合型硬化性樹脂組成物が従来知られている（例えば特許文献１、２）。この種の樹脂組成物は、そのゴム特性を生かし、歪みや応力を繰り返し受ける接着箇所に使用されて、接着信頼性の向上や接着耐久性の向上に多大の寄与をしている。
しかし、これらの樹脂組成物は、上述のような優れた特性を持つ反面、基本的には空気中の湿気によって反応性シリル基含有樹脂が硬化していくため、例えば大面積の非多孔質被着体同士の接着など湿気の入りにくい箇所での接着では内部硬化が悪く、強度発現までに長い時間を要するという問題があった。これを解決するための技術として、特許文献３に開示されるように、予め接着剤中に水を配合することがなされている。
Therefore, in order to improve the drawbacks of such epoxy resin-based adhesives, a two-component mixed curable resin composition in which an epoxy resin is combined with an alkoxysilyl group-containing resin (these are generally called modified silicone resins) has been conventionally used. It is known (for example, Patent Documents 1 and 2). Taking advantage of its rubber properties, this type of resin composition is used in adhesive places that are repeatedly subjected to strain and stress, and contributes greatly to the improvement of adhesive reliability and adhesive durability.
However, while these resin compositions have the above-mentioned excellent properties, the reactive silyl group-containing resin is basically cured by the humidity in the air, so that, for example, a large-area non-porous cover is used. Adhesion in places where moisture does not easily enter, such as adhesion between bodies, has a problem that internal curing is poor and it takes a long time to develop strength. As a technique for solving this problem, as disclosed in Patent Document 3, water is mixed in the adhesive in advance.
しかし、上記特許文献３のように、反応性シリル基含有樹脂と水とを同一組成物中に共存させると、硬化触媒が存在しない状態といえども貯蔵中に徐々に硬化反応が進行し、貯蔵安定性が確保できないという問題があった。一方で、反応性シリル基含有樹脂の硬化触媒である有機スズ化合物と水とを共存させた場合には、経時的に有機スズ化合物の触媒活性が低下し、使用時（混合時）に所望の硬化速度が発現しないという問題もあった。
すなわち、本発明が解決しようとする課題は、二液を混合後、速やかに硬化するとともに内部硬化性及び貯蔵安定性ともに優れる二液混合型硬化性樹脂組成物を提供することである。
However, as in Patent Document 3, when the reactive silyl group-containing resin and water coexist in the same composition, the curing reaction gradually proceeds during storage even in the absence of a curing catalyst, and the storage There was a problem that stability could not be ensured. On the other hand, when the organic tin compound, which is a curing catalyst for the reactive silyl group-containing resin, and water coexist, the catalytic activity of the organic tin compound decreases with time, which is desired at the time of use (mixing). There was also a problem that the curing rate did not develop.
That is, an object to be solved by the present invention is to provide a two-component mixed curable resin composition which cures quickly after mixing the two liquids and is excellent in both internal curability and storage stability.
本発明者らは、鋭意検討を重ねた結果、特定の有機スズ化合物は水と共存しても、その活性が経時的に変化しないことを見出し、上記課題を解決できることを見出し、本発明を完成させるに至った。本発明は、概要以下の発明から構成される。 As a result of diligent studies, the present inventors have found that the activity of a specific organotin compound does not change with time even if it coexists with water, and finds that the above problems can be solved, and completes the present invention. I came to let you. The present invention is composed of the following inventions.
（１）下記樹脂組成物（Ｉ）と、下記樹脂組成物（ＩＩ）とからなる二液混合型硬化性樹脂組成物であって、
樹脂組成物（Ｉ）：架橋性シリル基を分子内に有し、主鎖骨格がポリオキシアルキレン及び／又はポリ（メタ）アクリレートである硬化性シリコーン系樹脂（Ａ）及び下記エポキシ樹脂（Ｃ）の硬化剤（Ｂ）を含有する樹脂組成物、
樹脂組成物（ＩＩ）：エポキシ樹脂（Ｃ）、上記硬化性シリコーン系樹脂（Ａ）の硬化触媒である、常温で固体であり且つジオクチルスズジステアレート及び／又はジオクチルスズマレートポリマーよりなる有機スズ化合物（Ｄ）及び水（Ｅ）を含有する樹脂組成物とからなり、
前記エポキシ樹脂（Ｃ）と前記硬化剤（Ｂ）の質量比は、前記エポキシ樹脂（Ｃ）：前記硬化剤（Ｂ）＝１００：０．１〜１００：３００であること、
前記硬化性シリコーン系樹脂（Ａ）と前記エポキシ樹脂（Ｃ）の質量比は、前記硬化性シリコーン系樹脂（Ａ）：前記エポキシ樹脂（Ｃ）＝１５：８５〜９５：５であること、
前記硬化性シリコーン系樹脂（Ａ）１００質量部に対して、前記有機スズ化合物（Ｄ）は０．１〜２０質量部であること及び
前記硬化性シリコーン系樹脂（Ａ）１００質量部に対して、前記水（Ｅ）は０．１〜２０質量部であることを特徴とする二液混合型硬化性樹脂組成物。
(1) A two-component mixed curable resin composition comprising the following resin composition (I) and the following resin composition (II).
Resin composition (I): a crosslinkable silyl group possess in the molecule, the main chain skeleton polyoxyalkylene and / or poly (meth) acrylate is a curable silicone resin (A) and the following epoxy resin (C) Resin composition containing the curing agent (B) of
Resin composition (II): An organic composition of an epoxy resin (C), a curing catalyst for the curable silicone resin (A) , a solid at room temperature, and a dioctyltin distearate and / or a dioctyltinmalate polymer. It is composed of a resin composition containing a tin compound (D) and water (E) .
The mass ratio of the epoxy resin (C) to the curing agent (B) is that the epoxy resin (C): the curing agent (B) = 100: 0.1 to 100: 300.
The mass ratio of the curable silicone resin (A) to the epoxy resin (C) is such that the curable silicone resin (A): the epoxy resin (C) = 15: 85 to 95: 5.
The amount of the organotin compound (D) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the curable silicone resin (A).
A two-component mixed curable resin composition, wherein the amount of water (E) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the curable silicone resin (A).
（２）前記樹脂組成物（ＩＩ）において、常温で固体の有機スズ化合物（Ｄ）が、融点２０℃以上であることを特徴とする、（１）に記載の二液混合型硬化性樹脂組成物。 (2) The two-component mixed curable resin composition according to (1), wherein the organotin compound (D), which is solid at room temperature, has a melting point of 20 ° C. or higher in the resin composition (II). Stuff.
（３）前記樹脂組成物（Ｉ）において、硬化剤（Ｂ）がアミン化合物であることを特徴とする、（１）又は（２）に記載の二液混合型硬化性樹脂組成物。
（４）（１）〜（３）のいずれかに記載の二液混合型硬化性樹脂組成物を層間接着剤として用いたことを特徴とする自動車用積層部材。
（５）前記自動車用積層部材において、積層部材材料の少なくとも一層がセラミックコーティング層であることを特徴とする（４）に記載の自動車用積層部材。
( 3 ) The two-component mixed curable resin composition according to (1) or (2) , wherein the curing agent (B) is an amine compound in the resin composition (I).
( 4 ) A laminated member for an automobile, wherein the two-component mixed curable resin composition according to any one of (1) to ( 3) is used as an interlayer adhesive.
(5) In the automotive laminated member, automotive laminated member according to (4) that at least one layer of the laminate member material is a ceramic coating layer.
本発明は、樹脂組成物（Ｉ）と樹脂組成物（ＩＩ）とを混合した場合、速やかに硬化するとともに内部硬化性及び貯蔵安定性ともに優れる二液混合型硬化性樹脂組成物が得られるという優れた効果を奏するものであり、その理由としては、例えば、以下のことを挙げることができる。
本発明は、硬化性シリコーン系樹脂（Ａ）の硬化触媒として常温で固体のジオクチルスズジステアレート及び／又はジオクチルスズマレートポリマーよりなる有機スズ化合物を用いるものであり、これらの有機スズ化合物は、水と共存させても触媒活性が経時で変化しないため、水との共存時間にかかわらず所望の硬化速度を得ることができるとともに、樹脂組成物中に水を予め配合できるために硬化性にも優れ、内部硬化性及び貯蔵安定性の両方に優れた二液混合型硬化性樹脂組成物を得ることができる。
According to the present invention, when the resin composition (I) and the resin composition (II) are mixed, a two-component mixed curable resin composition that cures quickly and has excellent internal curability and storage stability can be obtained. It has an excellent effect, and the reasons for this can be as follows, for example.
The present invention uses an organic tin compound composed of dioctyltin distearate and / or dioctyltinmalate polymer which is solid at room temperature as a curing catalyst of the curable silicone resin (A), and these organic tin compounds are used. Since the catalytic activity does not change with time even when coexisting with water, a desired curing rate can be obtained regardless of the coexistence time with water, and water can be premixed in the resin composition to make the resin composition curable. It is also possible to obtain a two-component mixed curable resin composition which is excellent in both internal curability and storage stability.
以下、本発明を実施するための形態を、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, embodiments for carrying out the present invention will be described in detail. It should be noted that the present invention is not limited to these examples, and it goes without saying that various modifications can be made without departing from the gist of the present invention.
［二液混合型硬化性樹脂組成物について］
本発明の二液混合型硬化性樹脂組成物は、下記樹脂組成物（Ｉ）と、下記樹脂組成物（ＩＩ）とからなるものである。ここで、樹脂組成物（Ｉ）は、架橋性シリル基を分子内に有し、主鎖骨格がポリオキシアルキレン及び／又はポリ（メタ）アクリレートである硬化性シリコーン系樹脂（Ａ）及び下記エポキシ樹脂（Ｃ）の硬化剤（Ｂ）（以下、単に「硬化剤（Ｂ）」と記載することがある）を含有する樹脂組成物である。また、樹脂組成物（ＩＩ）は、オキシラン環を分子内に含有するエポキシ樹脂（Ｃ）、上記硬化性シリコーン系樹脂（Ａ）の硬化触媒である、常温で固体であり且つジオクチルスズジステアレート及び／又はジオクチルスズマレートポリマーよりなる有機スズ化合物（Ｄ）及び上記硬化性シリコーン系樹脂（Ａ）の硬化剤としての水（Ｅ）を含有する樹脂組成物である。常温で固体であり且つジオクチルスズジステアレート及び／又はジオクチルスズマレートポリマーよりなる有機スズ化合物（Ｄ）は、水（Ｅ）と共存しても、その触媒活性が経時で変化しないために、二液を混合後、速やかに硬化することが可能であり、さらに、内部硬化性及び貯蔵安定性ともに優れる二液混合型硬化性樹脂組成物を得ることができる。
[About two-component mixed curable resin composition]
The two-component mixed curable resin composition of the present invention comprises the following resin composition (I) and the following resin composition (II). Here, the resin composition (I), a crosslinkable silyl group possess in the molecule, the main chain skeleton is a polyoxyalkylene and / or poly (meth) acrylate curable silicone resin (A) and the following epoxy It is a resin composition containing a curing agent (B) of the resin (C) (hereinafter, may be simply referred to as "curing agent (B)"). The resin composition (II) is an epoxy containing an oxirane ring in the molecule resin (C), a curing catalyst for the curable silicone resin (A), the solid at normal temperature and dioctyltin distearate And / or a resin composition containing an organic tin compound (D) made of a dioctyl tinmalate polymer and water (E) as a curing agent for the curable silicone resin (A). The organotin compound (D), which is solid at room temperature and is composed of dioctyltin distearate and / or dioctyltinmalate polymer , does not change its catalytic activity over time even when coexisting with water (E). After mixing the two liquids, it can be cured quickly, and a two-component mixed curable resin composition having excellent internal curability and storage stability can be obtained.
樹脂組成物（Ｉ）と樹脂組成物（ＩＩ）とを混合した時点で、樹脂組成物（Ｉ）に含有される硬化性シリコーン系樹脂（Ａ）が、樹脂組成物（ＩＩ）に含有される常温で固体の有機スズ化合物（Ｄ）によって活性化されるとともに、同じく樹脂組成物（ＩＩ）に含有される水（Ｅ）によって加水分解縮合反応が起こることにより硬化する。また、これと同時に、樹脂組成物（ＩＩ）に含有されるエポキシ樹脂（Ｃ）が、樹脂組成物（Ｉ）に含有される硬化剤（Ｂ）と反応して硬化する。その結果、最終的な硬化物は、これらが相互に入り組んだ高次構造となっているものと推察される。
樹脂組成物（Ｉ）と樹脂組成物（ＩＩ）の混合比率は、組成物（Ｉ）中の硬化性シリコーン系樹脂（Ａ）：組成物（ＩＩ）中のエポキシ樹脂（Ｃ）＝１５：８５〜９５ :５（質量比）の範囲である。
When the resin composition (I) and the resin composition (II) are mixed, the curable silicone-based resin (A) contained in the resin composition (I) is contained in the resin composition (II). It is activated by the organic tin compound (D) which is solid at room temperature, and is cured by a hydrolysis condensation reaction caused by water (E) also contained in the resin composition (II). At the same time, the epoxy resin (C) contained in the resin composition (II) reacts with the curing agent (B) contained in the resin composition (I) to be cured. As a result, it is inferred that the final cured product has a higher-order structure in which these are intertwined with each other.
The mixing ratio of the resin composition (I) and the resin composition (II) is such that the curable silicone resin (A) in the composition (I): the epoxy resin (C) in the composition (II) = 15:85. It is in the range of ~ 95: 5 (mass ratio).
以下、各組成物及び構成成分について説明する。
［硬化性シリコーン系樹脂（Ａ）について］
本発明における硬化性シリコーン系樹脂（Ａ）は、下記一般式（１）で表される架橋性シリル基を分子内に有する硬化性シリコーン系樹脂である。本発明で使用される硬化性シリコーン系樹脂（Ａ）は、作業性などの面から、室温で液状であることが好ましい。また、硬化性シリコーン系樹脂（Ａ）は、所望の性能に合わせて、１種単独で使用してもよいし２種以上併用してもよい。
−ＳｉＲ１ ３−ｘ（ＯＲ２）ｘ ・・・式（１）
（但し、Ｒ１、Ｒ２は炭素数１〜１０個の炭化水素基を、ｘは１、２又は３を、それぞれ示す）
Hereinafter, each composition and constituent components will be described.
[About curable silicone resin (A)]
The curable silicone resin (A) in the present invention is a curable silicone resin having a crosslinkable silyl group represented by the following general formula (1) in the molecule. The curable silicone resin (A) used in the present invention is preferably liquid at room temperature from the viewpoint of workability and the like. Further, the curable silicone resin (A) may be used alone or in combination of two or more, depending on the desired performance.
−SiR 1 3-x (OR 2 ) x・ ・ ・ Equation (1)
(However, R 1 and R 2 indicate hydrocarbon groups having 1 to 10 carbon atoms, and x indicates 1, 2 or 3, respectively).
上記アルコキシシリル基は、上記一般式（１）で表されるように、ケイ素原子に対して炭化水素基（Ｒ１）が２〜０個結合すると共に、アルコキシ基（Ｒ２）が１〜３個結合しているものである。そして、このケイ素原子には、後述する結合官能基を介して主鎖が結合している。前記炭化水素基（Ｒ１）としては、メチル基、エチル基、プロピル基、ブチル基、フェニル基であることが好ましく、メチル基、エチル基、プロピル基、ブチル基であることがより好ましく、メチル基、エチル基であることが特に好ましい。前記アルコキシ基（Ｒ２）としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基であるのが好ましく、メトキシ基又はエトキシ基であるのがより好ましい。 As represented by the general formula (1), the alkoxysilyl group has 2 to 0 hydrocarbon groups (R 1 ) bonded to the silicon atom and 1 to 3 alkoxy groups (R 2). It is an individual combination. A main chain is bonded to this silicon atom via a bond functional group described later. The hydrocarbon group (R 1 ) is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. It is particularly preferable that the group is an ethyl group. The alkoxy group (R 2 ) is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and more preferably a methoxy group or an ethoxy group.
前記アルコキシ基の数としては、硬化速度を高めたい場合は３個（ｘ＝３）が好ましく、密着性を高めたい場合は２個（ｘ＝２）又は１個（ｘ＝１）が好ましい。アルコキシ基の数については、二液混合型硬化性樹脂組成物に求められる性能によって、適宜比率を調整すればよいが、特に、アルコキシシリル基としてトリアルコキシシリル基（ｘ＝３）、好ましくはトリメトキシシリル基又はトリエトキシシリル基、より好ましくはトリメトキシシリル基を含有すると、さらに良好な初期硬化性を得ることができる。
硬化性シリコーン系樹脂（Ａ）の主鎖骨格は、ポリオキシアルキレン及び／又はポリ（メタ）アクリレートである。
The number of alkoxy groups is preferably 3 (x = 3) when the curing rate is to be increased, and 2 (x = 2) or 1 (x = 1) is preferable when the adhesion is to be increased. Regarding the number of alkoxy groups, the ratio may be appropriately adjusted according to the performance required for the two-component mixed curable resin composition, and in particular, the trialkoxysilyl group (x = 3) as the alkoxysilyl group, preferably tri. When a methoxysilyl group or a triethoxysilyl group, more preferably a trimethoxysilyl group is contained, even better initial curability can be obtained.
The main chain skeleton of the curable silicone resin (A) is polyoxyalkylene and / or poly (meth) acrylate.
硬化性シリコーン系樹脂（Ａ）の主鎖骨格は、ポリオキシアルキレン又はポリ（メタ）アクリレートが含まれていてもよいし、ポリオキシアルキレン及びポリ（メタ）アクリレートの２種が含まれていてもよい。
硬化性シリコーン系樹脂（Ａ）は、主鎖骨格がポリオキシアルキレンである硬化性シリコーン樹脂（ａ１）と、主鎖骨格がポリ（メタ）アクリレートある硬化性シリコーン樹脂（ａ２）とからなる混合物であってもよい。混合物にすると、粘度、耐熱性、被着材料に対する密着性のバランスの良い接着剤を得ることができる。硬化性シリコーン樹脂（ａ１）は適度な粘度で作業性が良いことが特徴であり、硬化性シリコーン樹脂（ａ２）は耐熱性が高いことが特徴である。
The main chain skeleton of the curable silicone resin (A) may be contained polyoxyalkylene or poly (meth) acrylates, also contain two or polyoxyalkylene and poly (meth) acrylate Good.
The curable silicone resin (A) is a mixture of a curable silicone resin (a1) having a polyoxyalkylene main chain skeleton and a curable silicone resin (a2) having a poly (meth) acrylate main chain skeleton. may I Oh. If you to the mixture, it is possible to obtain the viscosity, heat resistance, good adhesive balance of adhesion to adherends material. The curable silicone resin (a1) is characterized by having an appropriate viscosity and good workability, and the curable silicone resin (a2) is characterized by having high heat resistance.
硬化性シリコーン系樹脂（Ａ）の分子量は特に制限されないが、１，０００〜８０，０００が好ましく、１，５００〜６０，０００がより好ましく、２，０００〜４０，０００が特に好ましい。分子量が１，０００を下回ると、架橋密度が高くなり過ぎることから得られる硬化物が脆い物性となる場合があり、分子量が８０，０００を上回ると、粘度が高くなり作業性が悪くなるため溶剤や希釈剤が多量に必要になるなど配合が制限される場合がある。 The molecular weight of the curable silicone resin (A) is not particularly limited, but is preferably 1,000 to 80,000, more preferably 1,500 to 60,000, and particularly preferably 2,000 to 40,000. If the molecular weight is less than 1,000, the cured product obtained from the excessively high crosslink density may have brittle physical properties, and if the molecular weight exceeds 80,000, the viscosity becomes high and the workability deteriorates, so that the solvent is used. In some cases, the formulation may be restricted, such as the need for a large amount of diluent.
硬化性シリコーン系樹脂（Ａ）のアルコキシシリル基と主鎖骨格とは、結合官能基を介して結合されている。結合官能基は主鎖骨格に対してアルコキシシリル基を導入する際の化学反応によって生じるものであり、主鎖骨格とアルコキシシリル基以外の化学構造部分を指す。結合官能基としては、例えばメチレン基、エチレン基、プロピレン基等のアルキレン基、フェニレン基、ウレタン結合、尿素結合、置換尿素結合、カーボネート基等、これらの複数及びこれら以外の化学構造を含む２価の化学結合が挙げられる。 The alkoxysilyl group of the curable silicone resin (A) and the main chain skeleton are bonded via a bonding functional group. The bond functional group is generated by a chemical reaction when an alkoxysilyl group is introduced into the main chain skeleton, and refers to a chemical structural part other than the main chain skeleton and the alkoxysilyl group. Examples of the bond functional group include alkylene groups such as methylene group, ethylene group and propylene group, phenylene group, urethane bond, urea bond, substituted urea bond, carbonate group and the like, and divalent including a plurality of these and chemical structures other than these. Chemical bond of.
また、本発明では、硬化性シリコーン系樹脂（Ａ）として、分子内にアルコキシシリル基を有し、かつ、分子内（特に好ましくは結合官能基内）に特定の極性基を含有する硬化性樹脂を好適に用いることができる。ここで、特定の極性基とは、ウレタン結合基、チオウレタン結合基、尿素結合基、チオ尿素結合基、置換尿素結合基、置換チオ尿素結合基、アミド結合基、スルフィド結合基、ヒドロキシ基、第一級アミノ基、第二級アミノ基及び第三級アミノ基等の酸素原子、窒素原子、硫黄原子を含有する結合基又は官能基等を指す。このような極性基を加水分解性ケイ素基の近傍に導入すると、硬化性樹脂自体の硬化能が高まるため好ましい。 Further, in the present invention, as the curable silicone resin (A), a curable resin having an alkoxysilyl group in the molecule and containing a specific polar group in the molecule (particularly preferably in the binding functional group). Can be preferably used. Here, the specific polar groups include urethane-binding groups, thiourethane-binding groups, urea-binding groups, thiourea-binding groups, substituted urea-binding groups, substituted thiourea-binding groups, amide-binding groups, sulfide-binding groups, hydroxy groups, and the like. It refers to a bonding group or a functional group containing an oxygen atom, a nitrogen atom, a sulfur atom, etc. such as a primary amino group, a secondary amino group and a tertiary amino group. Introducing such a polar group in the vicinity of the hydrolyzable silicon group is preferable because the curable ability of the curable resin itself is enhanced.
特に、これらの特定極性基の中では、ウレタン結合基、チオウレタン結合基、尿素結合基、チオ尿素結合基、置換尿素結合基、置換チオ尿素結合基、アミド結合基、第一級アミノ基、第二級アミノ基及び第三級アミノ基等の含窒素極性基を有するものが好ましく、ウレタン結合基（−ＮＨＣＯＯ−）、尿素結合基（−ＮＨＣＯＮＨ−）、置換尿素結合基（−ＮＨＣＯＮＲ−；Ｒ＝有機基）を有するものであることが最も好ましい。硬化性樹脂自体の硬化能が高まる理由としては、硬化性樹脂の分子内に存在する特定極性基同士がドメインを形成し、その結果、硬化性樹脂の加水分解性ケイ素基同士のカップリング反応がさらに促進されるためであると考えられる。 In particular, among these specific polar groups, urethane-binding group, thiourethane-binding group, urea-binding group, thiourea-binding group, substituted urea-binding group, substituted thiourea-binding group, amide-binding group, primary amino group, Those having a nitrogen-containing polar group such as a secondary amino group and a tertiary amino group are preferable, and a urethane-binding group (-NHCOO-), a urea-binding group (-NHCONH-), and a substituted urea-binding group (-NHCONR-; Most preferably, it has R (organic group). The reason why the curable ability of the curable resin itself is enhanced is that the specific polar groups existing in the molecule of the curable resin form a domain, and as a result, the coupling reaction between the hydrolyzable silicon groups of the curable resin occurs. It is thought that this is because it is further promoted.
硬化性シリコーン系樹脂（Ａ）の市販品としては、変成シリコーン樹脂として多数販売されている。例えば、カネカ社製のサイリルシリーズ、カネカＭＳポリマーシリーズ、ＭＡシリーズ、ＥＰシリーズ、ＳＡシリーズ、ＯＲシリーズ、旭硝子社製のエクセスターシリーズ、ＷａｃｋｅｒＣｈｅｍｉｅＡＧ製のＧＥＮＩＯＳＩＬＳＴＰ−Ｅ１０、ＧＥＮＩＯＳＩＬＳＴＰ−Ｅ３０、エボニックジャパン社製のシラン変性ポリアルファオレフィン、信越化学工業社製のＫＣシリーズ、ＫＲシリーズ、Ｘ−４０シリーズ、東亞合成社製のＸＰＲシリーズ、綜研化学社製のアクトフローシリーズ等が挙げられるが、これらに限定されるわけではない。 As a commercially available product of the curable silicone resin (A), many are sold as modified silicone resins. For example, Kaneka's Cyril series, Kaneka MS polymer series, MA series, EP series, SA series, OR series, Asahi Glass's Excelter series, Wacker Chemie AG's GENESILSTP-E10, GENESILSTP-E30, Evonik Japan's Silane-modified polyalphaolefins, KC series, KR series, X-40 series manufactured by Shin-Etsu Chemical Co., Ltd., XPR series manufactured by Toagosei Co., Ltd., Actflow series manufactured by Soken Kagaku Co., Ltd., etc., but are limited to these. Not that.
また、分子内に極性基を含有する硬化性シリコーン系樹脂は、従来公知の方法で合成すればよい。例えば、イソシアネート基末端ポリマーにアミノ基含有アルコキシシラン化合物（あるいはメルカプト基含有アルコキシシラン化合物）を反応させる方法や、水酸基末端有機重合体にイソシアネート基含有アルコキシシラン化合物を反応させる方法等が知られている。より具体的には、特許第３０３００２０号公報、特許第３３４３６０４号公報、特開２００５−５４１７４号公報、特表２００４−５１８８０１号公報、特表２００４−５３６９５７号公報、特表２００５−５０１１４６号公報等に記載の方法で容易に合成することができる。 Further, the curable silicone resin containing a polar group in the molecule may be synthesized by a conventionally known method. For example, a method of reacting an isocyanate group-terminated polymer with an amino group-containing alkoxysilane compound (or a mercapto group-containing alkoxysilane compound), a method of reacting a hydroxyl group-terminal organic polymer with an isocyanate group-containing alkoxysilane compound, and the like are known. .. More specifically, Japanese Patent No. 3030020, Japanese Patent No. 3343604, Japanese Patent Application Laid-Open No. 2005-54174, Japanese Patent Application Laid-Open No. 2004-518801, Japanese Patent Application Laid-Open No. 2004-536957, Japanese Patent Application Laid-Open No. 2005-501146, etc. Can be easily synthesized by the method described in 1.
上述のとおり、上記硬化性シリコーン系樹脂（Ａ）は、その主鎖がポリオキシアルキレンである硬化性シリコーン樹脂（ａ１）と、その主鎖がポリ（メタ）アクリレートである硬化性シリコーン樹脂（ａ２）とからなる二液混合型硬化性樹脂組成物も本発明の好ましい態様である。
硬化性シリコーン系樹脂（Ａ）が上記組成のものであると、接着耐久性が向上する。
また、上記硬化性シリコーン樹脂（ａ１）及び／又は硬化性シリコーン樹脂（ａ２）が有する架橋性シリル基として、トリメトキシシリル基を含有するものである態様も、本発明の好ましい態様である。架橋性シリル基がトリメトキシシリル基を含有するものであると、速硬化性が得られ作業効率が向上するため好ましい。
As described above, the curable silicone resin (A) is a curable silicone resin (a1) whose main chain is polyoxyalkylene and a curable silicone resin (a2) whose main chain is poly (meth) acrylate. ) Is also a preferred embodiment of the present invention.
When the curable silicone resin (A) has the above composition, the adhesive durability is improved.
Further, an embodiment in which the curable silicone resin (a1) and / or the curable silicone resin (a2) contains a trimethoxysilyl group as the crosslinkable silyl group is also a preferred embodiment of the present invention. It is preferable that the crosslinkable silyl group contains a trimethoxysilyl group because quick curing is obtained and work efficiency is improved.
［硬化剤（Ｂ）について］
本発明における、エポキシ樹脂（Ｃ）の硬化剤（Ｂ）（以下、単に「硬化剤（Ｂ）」ということがある）としては、エポキシ樹脂を硬化させ得る従来公知の化合物乃至物質を用いることができる。硬化剤（Ｂ）としては特に限定されないが、具体例を挙げれば、トリエチレンテトラミン、ジエチレントリアミン、メタキシリレンジアミン、メタフェニレンジアミン、ジアミノジフェニルメタン、イソホロンジアミン、２，４，６−トリス（ジメチルアミノメチル）フェノール、等のアミン類；３級アミン塩；ポリアミド樹脂；イミダゾール類；無水フタル酸等のカルボン酸無水物等の化合物が用いられ得る。
本発明の硬化性樹脂組成物は、硬化反応の速い脂肪族アミン系硬化剤、特に３級アミンを用いることが好ましい。また、活性アミンがブロックされていて、空気中の水分で活性化するケチミン等の潜在型硬化剤を用いてもよい。これらアミン類は単独で使用してもよく、２種以上併用してもよい。
[About curing agent (B)]
As the curing agent (B) of the epoxy resin (C) in the present invention (hereinafter, may be simply referred to as "curing agent (B)"), a conventionally known compound or substance capable of curing the epoxy resin may be used. it can. The curing agent (B) is not particularly limited, and specific examples thereof include triethylenetetramine, diethylenetriamine, m-xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, isophoronediamine, 2,4,6-tris (dimethylaminomethyl). ) Amines such as phenol; tertiary amine salts; polyamide resins; imidazoles; compounds such as carboxylic acid anhydrides such as phthalic anhydride can be used.
In the curable resin composition of the present invention, it is preferable to use an aliphatic amine-based curing agent having a fast curing reaction, particularly a tertiary amine. Alternatively, a latent curing agent such as ketimine, which has the active amine blocked and is activated by the moisture in the air, may be used. These amines may be used alone or in combination of two or more.
［エポキシ樹脂（Ｃ）について］
本発明における、エポキシ樹脂（Ｃ）としては、オキシラン環を分子内に含有する従来公知の化合物乃至物質を用いることができる。エポキシ樹脂（Ｃ）としては特に限定されないが、具体例を挙げれば、従来公知のビスフェノール型エポキシ樹脂；ビフェニル型エポキシ樹脂；脂環式エポキシ樹脂；テトラグリシジルアミノジフェニルメタン等の多官能性グリシジルアミン樹脂；テトラフェニルグリシジルエーテルエタン等の多官能性グリシジルエーテル樹脂；フェノールノボラック型エポキシ樹脂やクレゾールノボラック型エポキシ樹脂等があり、種々のグレードのエポキシ樹脂が市販されているため、これらを利用することができる。作業性の点からは、分子量が３００〜５００程度のものが好ましく、常温で液状のビスフェノールＡ型液状樹脂が特に好ましい。これらのエポキシ樹脂は単独で使用してもよく、２種以上併用してもよい。
[About epoxy resin (C)]
As the epoxy resin (C) in the present invention, a conventionally known compound or substance containing an oxylane ring in the molecule can be used. The epoxy resin (C) is not particularly limited, and specific examples thereof include conventionally known bisphenol type epoxy resins; biphenyl type epoxy resins; alicyclic epoxy resins; polyfunctional glycidylamine resins such as tetraglycidylaminodiphenylmethane; Polyfunctional glycidyl ether resin such as tetraphenyl glycidyl ether ethane; there are phenol novolac type epoxy resin, cresol novolac type epoxy resin and the like, and various grades of epoxy resin are commercially available, and these can be used. From the viewpoint of workability, those having a molecular weight of about 300 to 500 are preferable, and bisphenol A type liquid resin which is liquid at room temperature is particularly preferable. These epoxy resins may be used alone or in combination of two or more.
樹脂組成物（ＩＩ）中のエポキシ樹脂（Ｃ）と、樹脂組成物（Ｉ）中の硬化剤（Ｂ）の配合割合は、（Ｃ）：（Ｂ）＝１００：０．１〜１００：３００であり、１００：０．５〜１００：１５０であることが好ましく、１００：１〜１００：１００であることが特に好ましい。（Ｃ）：（Ｂ）＝１００：０．１よりも（Ｂ）の割合が少なくなると、エポキシ樹脂の硬化が不十分となることから不都合であり、（Ｃ）：（Ｂ）＝１００：３００よりも（Ｂ）の割合が多くなると（Ｂ）成分はブリードして被着材を汚染する点で不都合である。 The mixing ratio of the epoxy resin (C) in the resin composition (II) and the curing agent (B) in the resin composition (I) is (C) :( B) = 100: 0.1 to 100: 300. der is, 100: 0.5 to 100: is preferably 150, 100: 1 to 100: particularly preferably 100. If the ratio of (B) is smaller than (C): (B) = 100: 0.1, it is inconvenient because the epoxy resin is insufficiently cured, and (C): (B) = 100: 300. If the proportion of (B) is larger than that of (B), the component (B) is inconvenient in that it bleeds and contaminates the adherend.
また、上記樹脂組成物（Ｉ）中の硬化性シリコーン系樹脂（Ａ）と、上記樹脂組成物（ＩＩ）中のエポキシ樹脂（Ｃ）の配合割合は、質量比で（Ａ）：（Ｃ）＝１５：８５〜９５：５であり、２０：８０〜９０：１０であることが好ましく、３０：７０〜８０：２０であることが特に好ましい。（Ａ）：（Ｃ）＝１５：８５よりも（Ａ）の割合が少なくなると、硬く脆くなる点で不都合であり、（Ａ）：（Ｃ）＝９５：５よりも（Ａ）の割合が多くなると強靭性が不足することから不都合である。 The mixing ratio of the curable silicone resin (A) in the resin composition (I) and the epoxy resin (C) in the resin composition (II) is the mass ratio of (A): (C). = 15: 85 to 95: 5 der is, 20: 80-90: is preferably 10, 30: 70-80: and particularly preferably 20. If the ratio of (A) is smaller than (A): (C) = 15:85, it is inconvenient in that it becomes hard and brittle, and the ratio of (A) is larger than (A): (C) = 95: 5. If it increases, it is inconvenient because the toughness is insufficient.
［常温で固体の有機スズ化合物（Ｄ）について］
本発明では硬化性シリコーン系樹脂（Ａ）の硬化触媒として、常温で固体の有機スズ化合物（Ｄ）（以下、単に「硬化触媒（Ｄ）」と記載することがある）を用いる。常温で固体の有機スズ化合物（Ｄ）は、硬化性シリコーン系樹脂（Ａ）を活性化し、硬化性シリコーン系樹脂（Ａ）が有するアルコキシシリル基の加水分解反応を促進し、結果として樹脂組成物（II）中の水（Ｅ）及び／又は雰囲気中の湿気によって硬化性シリコーン系樹脂（Ａ）を硬化させる役割を有するものである。
[About the organotin compound (D) that is solid at room temperature]
In the present invention, as the curing catalyst of the curable silicone resin (A), an organotin compound (D) solid at room temperature (hereinafter, may be simply referred to as “curing catalyst (D)”) is used. The organotin compound (D), which is solid at room temperature, activates the curable silicone resin (A) and promotes the hydrolysis reaction of the alkoxysilyl group of the curable silicone resin (A), resulting in a resin composition. It has a role of curing the curable silicone resin (A) by the water (E) in (II) and / or the moisture in the atmosphere.
常温で固体の有機スズ化合物（Ｄ）としては融点が２０℃以上のものを好ましく用いることができ、さらに、融点が２３℃以上のジオクチルスズジステアレート又はジオクチルスズマレートポリマーを好ましく用いることができる。それらの化合物は試薬又は工業品として入手できるものを用いればよい。工業品としては、日東化成株式会社製「ネオスタンＵ−５００」、「ＳＣＡＴ−４７」、「ＳＴＡＮＮＤＯＴＯ」、「ＳＴＡＮＮＯＤＣ」等がある。
一方、融点が２０℃未満の従来の汎用硬化触媒ジブチルスズジラウレート（「ネオスタンＵ−１００」融点：１０〜１３℃）は常温で固体にはなりにくく、本発明の効果を得ることが困難な場合が多い。
なお、常温で固体の有機スズ化合物（Ｄ）の融点に幅がある場合は、溶け始める温度が２０℃以上のものを好ましく使用できる。また、本発明での融点の測定は融点測定装置（固体粉末の融点を目視によって測定する装置）を用いて行う。
As the organic tin compound (D) solid at room temperature, a compound having a melting point of 20 ° C. or higher can be preferably used, and further, a dioctyl tin distearate or a dioctyl tin malate polymer having a melting point of 23 ° C. or higher can be preferably used. it can. As those compounds, those available as reagents or industrial products may be used. Examples of industrial products include "Neostan U-500", "SCAT-47", "STANNDOTO", and "STANNODC" manufactured by Nitto Kasei Co., Ltd.
On the other hand, the conventional general-purpose curing catalyst dibutyltin dilaurate (“Neostan U-100” melting point: 10 to 13 ° C.) having a melting point of less than 20 ° C. does not easily become a solid at room temperature, and it may be difficult to obtain the effects of the present invention. There are many.
When the melting point of the organic tin compound (D) solid at room temperature varies, those having a melting temperature of 20 ° C. or higher can be preferably used. Further, the melting point in the present invention is measured by using a melting point measuring device (a device for visually measuring the melting point of a solid powder).
上述したとおり樹脂組成物（ＩＩ）中において、ジオクチルスズジステアレート及び／又はジオクチルスズマレートポリマーの常温で固体の有機スズ化合物（Ｄ）を用いると、二液を混合後、速やかに硬化するとともに内部硬化性及び貯蔵安定性ともに優れる二液混合型硬化性樹脂組成物を得ることができるが、上記硬化性シリコーン系樹脂（Ａ）１００質量部に対して、常温で固体の有機スズ化合物（Ｄ）が０．１〜２０質量部であり、０ .５〜１５質量部であるのが好ましく、１ .０〜１０質量部であるのが特に好ましい。 As described above, when the organotin compound (D) solid at room temperature of the dioctyltin distearate and / or the dioctyltinmalate polymer is used in the resin composition (II), the two liquids are mixed and then cured quickly. A two-component mixed curable resin composition having excellent internal curability and storage stability can be obtained together with the above-mentioned curable silicone resin (A), which is a solid organotin compound at room temperature with respect to 100 parts by mass. D) is Ri 0.1 to 20 parts by mass der, from 0.5 to 15 is preferably a mass parts, particularly preferably from 1.0 to 10 parts by weight.
常温で固体の有機スズ化合物（Ｄ）の配合量が２０質量部を超えると、硬化物の物性を低下させることがあり好ましくない。また、配合量が０．１質量部未満であると、硬化性シリコーン系樹脂（Ａ）の硬化が不十分となり、硬化不良等の不具合が生じることがある。 If the blending amount of the organic tin compound (D) solid at room temperature exceeds 20 parts by mass, the physical properties of the cured product may be deteriorated, which is not preferable. On the other hand, if the blending amount is less than 0.1 parts by mass, the curable silicone resin (A) is not sufficiently cured, and problems such as poor curing may occur.
［水（Ｅ）について］
本発明における水（Ｅ）は、硬化性シリコーン系樹脂（Ａ）の硬化剤としての役割を果たし、樹脂組成物（II）中に配合される。硬化性シリコーン系樹脂（Ａ）は、樹脂組成物
（II）中の水（Ｅ）及び／又は雰囲気中の湿気によって加水分解縮合反応により硬化するが、仮に大面積の非多孔質被着材の貼り合わせなど、雰囲気中からの湿気の供給がなかったとしても本発明の二液混合型硬化性樹脂組成物はしっかりと内部まで硬化することができる。
[About water (E)]
The water (E) in the present invention serves as a curing agent for the curable silicone-based resin (A) and is blended in the resin composition (II). The curable silicone resin (A) is cured by the hydrolysis condensation reaction due to the water (E) in the resin composition (II) and / or the moisture in the atmosphere, but it is assumed that the non-porous adherend has a large area. The two-component mixed curable resin composition of the present invention can be firmly cured to the inside even if there is no supply of moisture from the atmosphere such as bonding.
硬化性シリコーン系樹脂（Ａ）に対する、水（Ｅ）の配合比率は、硬化性シリコーン系樹脂（Ａ）１００質量部に対して水（Ｅ）が０．１〜２０質量部であり、好ましくは０．２〜１５質量部、特に好ましくは０.５〜１０質量部である。水（Ｅ）の配合量が０．１質量部を下回ると内部硬化性が低下する不具合が生じる場合があり、２０質量部を上回るとブリードアウトによる接着阻害などの不具合を生じる場合がある。
硬化性シリコーン系樹脂（Ａ）と、水（Ｅ）の配合比率が上記範囲内であると、本発明の効果を最大限に発揮することができる。
The mixing ratio of water (E) to the curable silicone resin (A) is 0.1 to 20 parts by mass of water (E) with respect to 100 parts by mass of the curable silicone resin (A), preferably 0.1 to 20 parts by mass. It is 0.2 to 15 parts by mass, particularly preferably 0.5 to 10 parts by mass. If the blending amount of water (E) is less than 0.1 parts by mass, a problem may occur in which the internal curability is lowered, and if it exceeds 20 parts by mass, a problem such as adhesion inhibition due to bleed-out may occur.
When the blending ratio of the curable silicone resin (A) and the water (E) is within the above range, the effect of the present invention can be maximized.
［その他成分について］
本発明の二液混合型硬化性樹脂組成物は、上記（Ａ）〜（Ｅ）の各成分を有効成分とするものであるが、本発明の効果を損なわない範囲内において、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、有機金属系化合物、三フッ化ホウ素系化合物等の硬化促進剤、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、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、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。シランカップリング剤としては、特に分子内にアミノ基と架橋性シリル基とを有する、いわゆるアミノシラン化合物が好ましい。
[About other ingredients]
The two-component mixed curable resin composition of the present invention contains each of the above components (A) to (E) as an active ingredient, but is optionally known as long as the effects of the present invention are not impaired. Compounds or substances can be blended. For example, curing accelerators such as organic metal compounds and boron trifluoride compounds, hydrophilic or hydrophobic silica powders, calcium carbonate powders, clay powders, acrylic powders and other organic powders, organic powders, etc. Fillers such as inorganic balloons, tackifiers such as phenolic resins, rocking agents such as amide wax, dehydrating agents, diluents, plasticizers, flame retardants, functional oligomers, hindered amine compounds, hindered phenolic compounds , 3- (2,2,6,6-tetramethylpiperidi-4-yloxy) anti-aging agents such as propyltriethoxysilane, UV absorbers such as benzotriazole compounds, pigments, titanate coupling agents, aluminum cups A ring agent, a silane coupling agent, a drying oil and the like can be blended. As the silane coupling agent, a so-called aminosilane compound having an amino group and a crosslinkable silyl group in the molecule is particularly preferable.
上記可塑剤としては、ジオクチルフタレート、ジブチルフタレート等のフタル酸エステル類、アジピン酸ジオクチル、セバチン酸ジブチル等の脂肪族カルボン酸エステル等を用いることができる。
上記希釈剤としては、上記二液混合型硬化性樹脂組成物と相溶性がよく、樹脂組成物（Ｉ）に配合される場合には、水分含有量が５００ｐｐｍ以下であればいずれを用いても良い。
上記脱水剤としては、樹脂組成物（Ｉ）に配合されるものであるが、生石灰、オルト珪酸エステル、無水硫酸ナトリウム、ゼオライト、メチルシリケート、エチルシリケート、各種アルキルアルコキシシラン、各種ビニルアルコキシシラン等が挙げられる。
As the plasticizer, phthalates such as dioctyl phthalate and dibutyl phthalate, and aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sevacinate can be used.
As the diluent, any one can be used as long as it has good compatibility with the two-component mixed curable resin composition, and when blended in the resin composition (I), the water content is 500 ppm or less. good.
Examples of the dehydrating agent include those blended in the resin composition (I), such as fresh lime, orthosilicic acid ester, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, various alkylalkoxysilanes, and various vinylalkoxysilanes. Can be mentioned.
［用途・使用方法について］
本発明の二液混合型硬化性樹脂組成物は、様々な被着材料に対して良好な接着性を有するため広範な用途の積層部材に使用することができるが、はり合わせから被着積層部材の移動までの時間を短縮することが求められる、工業、産業分野でのインライン用接着剤として好適に使用することができる。なかでも、ラインスピードの向上と高い接着信頼性が求められる自動車用部材や電気・電子材料の接着用途に対して、本発明の二液混合型硬化性樹脂組成物は特に好適に使用することができる。
[Usage / Usage]
The two-component mixed curable resin composition of the present invention can be used for a laminated member for a wide range of applications because it has good adhesiveness to various adherend materials. It can be suitably used as an in-line adhesive in the industrial and industrial fields where it is required to shorten the time required for moving the plastic. In particular, the two-component mixed curable resin composition of the present invention can be particularly preferably used for bonding automobile members and electrical / electronic materials, which require improved line speed and high bonding reliability. it can.
自動車用部材のはり合わせを例にとって積層部材を説明すると、自動車のフロント、サイド、リアのガラスに対する、各種センサー類の取付け用ブラケット、パワーウィンドウのホルダー、インナーミラーの取付け用ミラーベース、モール、プロテクター、位置決め用基準ピン、ヒンジ等の各種部材の接着等に、本発明の二液混合型硬化性樹脂組成物は好
適に使用することができる。被着材料の材質としては、黒色セラミックコーティングガラス、カチオン電着塗装された金属材料、ポリブチレンテレフタレート（ＰＢＴ）、ポリアクリルアミド（ＰＡＡ）等のプラスチック材料が挙げられる。
To explain the laminated members by taking the bonding of automobile members as an example, brackets for mounting various sensors, power window holders, mirror bases for mounting inner mirrors, moldings, and protectors for the front, side, and rear glass of automobiles. The two-component mixed curable resin composition of the present invention can be suitably used for bonding various members such as positioning reference pins and hinges. Examples of the material of the adherend include black ceramic coated glass, cationic electrodeposition-coated metal material, and plastic materials such as polybutylene terephthalate (PBT) and polyacrylamide (PAA).
本発明の二液混合型硬化性樹脂組成物の使用方法としては、ブラケット等の部材に適正量を塗布し、他方の被着材料・部材にはり合わせ、圧着すればよい。塗布量は、被着材料・部材の質量や形状等に応じて適宜変更可能である。その後、エポキシ樹脂の接着硬化反応が完了し、非常に強固な接着力を有し、かつ、耐振動性、耐候性、耐衝撃性、耐水性、耐熱性等の各種特性に優れた接着硬化層が形成される。本発明の二液混合型硬化性樹脂組成物は、プライマー処理や後処理は必ずしも必要ではないが、加熱・加湿等の後処理を適宜行ってもよい。
塗布方法は公知の方法のいずれも採用できる。特にインラインにおいては、二液を混合しつつ塗布することができる、スタティックミキサーを用いるのが好適である。
As a method of using the two-component mixed curable resin composition of the present invention, an appropriate amount may be applied to a member such as a bracket, and the resin composition may be bonded to the other adherend material / member and crimped. The coating amount can be appropriately changed according to the mass and shape of the adherend material / member. After that, the adhesive curing reaction of the epoxy resin is completed, and the adhesive curing layer has very strong adhesive strength and is excellent in various properties such as vibration resistance, weather resistance, impact resistance, water resistance, and heat resistance. Is formed. The two-component mixed curable resin composition of the present invention does not necessarily require primer treatment or post-treatment, but post-treatment such as heating and humidification may be appropriately performed.
Any known method can be adopted as the coating method. Especially in the in-line, it is preferable to use a static mixer that can apply the two liquids while mixing them.
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。
本発明の二液混合型硬化性樹脂組成物は、樹脂組成物（I）と樹脂組成物（II）とからなるものである、樹脂組成物（I）は、架橋性シリル基を分子内に有する硬化性変性シリコーン系樹脂（Ａ）及びエポキシ樹脂（Ｃ）の硬化剤(Ｂ)を含有する樹脂組成物であり、また、樹脂組成物（II）は、オキシラン環を分子内に含有するエポキシ樹脂（Ｃ）、硬化性シリコーン系樹脂（Ａ）の硬化触媒である常温で固体の有機スズ化合物（Ｄ）及び硬化性シリコーン系樹脂（Ａ）の硬化剤としての水（Ｅ）を含有する樹脂組成物である。
Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples.
The two-component mixed curable resin composition of the present invention comprises a resin composition (I) and a resin composition (II). The resin composition (I) has a crosslinkable silyl group in the molecule. It is a resin composition containing a curable modified silicone resin (A) and a curing agent (B) of an epoxy resin (C), and the resin composition (II) is an epoxy containing an oxylan ring in the molecule. A resin containing a resin (C), an organic tin compound (D) solid at room temperature as a curing catalyst for the curable silicone resin (A), and water (E) as a curing agent for the curable silicone resin (A). It is a composition.
［実施例１］
硬化性シリコーン系樹脂として、カネカ社製「ＳＡＸ５８０」を用い、を用い、エポキシ樹脂の硬化剤としてエボニックジャパン社製のアミン化合物「アンカミンＫ５４」を用い、無機充填材として表面処理炭酸カルシウム（白石カルシウム社製「白艶華ＣＣＲ−Ｂ」）、炭酸カルシウム（日東粉化工業社製「ＮＳ＃４００」）を用い、表１に示す配合割合にて樹脂組成物（Ｉ）を調製した。
[Example 1]
Kaneka's "SAX580" is used as the curable silicone resin, Ebonic Japan's amine compound "Ancamine K54" is used as the epoxy resin curing agent, and surface-treated calcium carbonate (Shiraishi calcium) is used as the inorganic filler. The resin composition (I) was prepared at the blending ratios shown in Table 1 using "Shiroshinka CCR-B" manufactured by Shiro Gloss Flower CCR-B) and calcium carbonate ("NS # 400" manufactured by Nitto Flour Chemical Co., Ltd.).
一方、エポキシ樹脂として三菱ケミカル社製ビスＡ型エポキシ樹脂「ｊＥＲ８２８」を用い、硬化性シリコーン系樹脂の硬化触媒として有機スズ化合物：Ｕ−８３０，Ｕ−５００，ＳＣＡＴ−４７を用い、水として工業用水を用い、無機充填材として表面処理炭酸カルシウム（白石カルシウム社製「白艶華ＣＣＲ−Ｂ」）、未処理の炭酸カルシウム（日東粉化工業社製「ＮＳ＃４００」）を用い、表１に示す配合割合にて樹脂組成物（II）を調製した。
なお、Ｕ−８３０，Ｕ−５００，ＳＣＡＴ−４７は、全て日東化成社製の以下のジオクチルスズ化合物である。
Ｕ-８３０：ジオクチルスズジバーサテート 融点：０℃以下
Ｕ-５００：ジオクチルスズジステアレート 融点：２４−４２℃
ＳＣＡＴ−４７：ジオクチルスズマレートポリマー 融点：８０−１００℃
こうして樹脂組成物（I）と樹脂組成物（II）からなる室温硬化性２液混合型接着剤を調製した。
On the other hand, Mitsubishi Chemical's screw A type epoxy resin "jER828" is used as the epoxy resin, and organic tin compounds: U-830, U-500, SCAT-47 are used as the curing catalyst of the curable silicone resin, and industrialized as water. Table 1 shows surface-treated calcium carbonate (“Shiraishi CCR-B” manufactured by Shiraishi Calcium Co., Ltd.) and untreated calcium carbonate (“NS # 400” manufactured by Nitto Flour Chemical Co., Ltd.) as an inorganic filler using irrigation water. The resin composition (II) was prepared in a blending ratio.
U-830, U-500, and SCAT-47 are all the following dioctyltin compounds manufactured by Nitto Kasei Co., Ltd.
U-830: Dioctyl tin diversate Melting point: 0 ° C or less U-500: Dioctyl tin stearate Melting point: 24-42 ° C
SCAT-47: Dioctyl sumalate polymer Melting point: 80-100 ° C
In this way, a room temperature curable two-component mixed adhesive composed of the resin composition (I) and the resin composition (II) was prepared.
［実施例１〜２及び比較例１〜２］
樹脂組成物（I）及び樹脂組成物（II）の構成成分のうち、有機スズ化合物の種類及び配合割合を表１に示すとおりに変更して、実施例１〜２及び比較例１〜２の接着剤を調製した。
[Examples 1 and 2 and Comparative Examples 1 and 2]
Among the constituents of the resin composition (I) and the resin composition (II), the types and blending ratios of the organotin compounds were changed as shown in Table 1, and Examples 1 and 2 and Comparative Examples 1 and 2 were changed. Adhesive was prepared.
［性能試験］
（貯蔵安定性）
表１に記載の配合処方に基づき、樹脂組成物（Ｉ）としてＡ剤（Ａ−１）、樹脂組成物（IＩ）としてＢ剤（Ｂ−１〜Ｂ−４）の各成分を混合調整し、それぞれを５０℃で所定期間貯蔵した後、２３℃、５０％ＲＨの雰囲気下で両者を混合し、硬化するまでの所要時間（皮ばり時間）を測定した。
その状態を指触観察によって評価し、その評価結果を表２に示す。
観察の評価基準は下記の通りである。
○：促進後の皮張り時間が促進前の皮張り時間の２倍未満
×：促進後の皮張り時間が促進前の皮張り時間の２倍以上
[performance test]
(Storage stability)
Based on the formulation shown in Table 1, each component of agent A (A-1) as the resin composition (I) and agent B (B-1 to B-4) as the resin composition (II) was mixed and adjusted. After storing each at 50 ° C. for a predetermined period, both were mixed in an atmosphere of 23 ° C. and 50% RH, and the time required for curing (peeling time) was measured.
The state is evaluated by finger touch observation, and the evaluation results are shown in Table 2.
The evaluation criteria for observation are as follows.
◯: The skinning time after promotion is less than twice the skinning time before promotion ×: The skinning time after promotion is more than twice the skinning time before promotion
（接着強さの立ち上がり）
表１に記載の配合処方に基づき、樹脂組成物（Ｉ）としてＡ剤（Ａ−１）、樹脂組成物（IＩ）としてＢ剤（Ｂ−１〜Ｂ−４）の各成分を混合調整した後、両者を混合し４種類の接着剤を製造した。
それらの接着剤を用い２５ｍｍ×１００ｍｍ（厚さ３．８ｍｍ）の黒色セラミックコーティングガラスと２５ｍｍ×１００ｍｍ（厚さ１．６ｍｍ）のカチオン電着塗装鋼板を接着（接着面積２５ｍｍ×１０ｍｍ、接着層厚さ０．６ｍｍ）し、２３℃、５０％ＲＨの雰囲気下で所定時間経過後の接着強さを測定した。
(Rise of adhesive strength)
Based on the formulation shown in Table 1, each component of agent A (A-1) as the resin composition (I) and agent B (B-1 to B-4) as the resin composition (II) was mixed and adjusted. After that, both were mixed to produce four kinds of adhesives.
Using these adhesives, a 25 mm x 100 mm (thickness 3.8 mm) black ceramic coated glass and a 25 mm x 100 mm (thickness 1.6 mm) cationic electrodeposition coated steel sheet are bonded (bonding area 25 mm x 10 mm, adhesive layer thickness). The adhesive strength was measured after a lapse of a predetermined time in an atmosphere of 23 ° C. and 50% RH.
その接着強さによって３段階で評価し、その評価結果を表３に示す。
観察の評価基準は下記の通りである。
○：接着強さ接着強さ［Ｎ/ｍｍ２］ ２．０以上
△：接着強さ接着強さ［Ｎ/ｍｍ２］ １．５以上、２．０未満
×：接着強さ接着強さ［Ｎ/ｍｍ２］ １．５未満
Evaluation is made in three stages according to the adhesive strength, and the evaluation results are shown in Table 3.
The evaluation criteria for observation are as follows.
◯: Adhesive strength Adhesive strength [N / mm 2 ] 2.0 or more Δ: Adhesive strength Adhesive strength [N / mm 2 ] 1.5 or more, less than 2.0 ×: Adhesive strength Adhesive strength [ N / mm 2 ] Less than 1.5
（表中の成分）
ＳＡＸ５８０：硬化性シリコーン系樹脂（Ａ）
アンカミンＫ５４：硬化剤（Ｂ）
ｊＥＲ８２８：エポキシ樹脂（Ｃ）
ネオスタンＵ-８３０：常温で液体の有機スズ化合物（Ｄ）
ネオスタンＵ-５００、ＳＣＡＴ-４７：常温で固体の有機スズ化合物（Ｄ）
(Ingredients in the table)
SAX580: Curable silicone resin (A)
Ancamine K54: Hardener (B)
jER828: Epoxy resin (C)
Neostan U-830: Organic tin compound (D) that is liquid at room temperature
Neostan U-500, SCAT-47: Organic tin compound (D) solid at room temperature
上記の実験結果から、本願発明では、常温で固体の有機スズ化合物（Ｄ）を用いることにより、有機スズ化合物（Ｄ）が水（Ｅ）と共存しても、その触媒活性が経時で変化せず、その結果、二液を混合後、内部硬化性に優れ、水を配合していない系に比較して強度発現までに要する時間が明らかに短く、且つ、貯蔵安定性にも優れた二液混合型硬化性樹脂組成物を得られることが確認できる。 From the above experimental results, in the present invention, by using the organotin compound (D) which is solid at room temperature, even if the organotin compound (D) coexists with water (E), its catalytic activity changes with time. As a result, after mixing the two liquids, the two liquids have excellent internal curability, the time required for developing strength is clearly shorter than that of a system not containing water, and the two liquids are also excellent in storage stability. It can be confirmed that a mixed curable resin composition can be obtained.
本発明は、二液を混合後、速やかに硬化するとともに内部硬化性及び貯蔵安定性ともに優れる二液混合型硬化性樹脂組成物であり、産業上極めて有用である。 The present invention is a two-component mixed curable resin composition that cures quickly after mixing two liquids and is excellent in both internal curability and storage stability, and is extremely useful in industry.
Claims (5)
樹脂組成物（Ｉ）：架橋性シリル基を分子内に有し、主鎖骨格がポリオキシアルキレン及び／又はポリ（メタ）アクリレートである硬化性シリコーン系樹脂（Ａ）及び下記エポキシ樹脂（Ｃ）の硬化剤（Ｂ）を含有する樹脂組成物、
樹脂組成物（ＩＩ）：エポキシ樹脂（Ｃ）、上記硬化性シリコーン系樹脂（Ａ）の硬化触媒である、常温で固体であり且つジオクチルスズジステアレート及び／又はジオクチルスズマレートポリマーよりなる有機スズ化合物（Ｄ）及び水（Ｅ）を含有する樹脂組成物とからなり、
前記エポキシ樹脂（Ｃ）と前記硬化剤（Ｂ）の質量比は、前記エポキシ樹脂（Ｃ）：前記硬化剤（Ｂ）＝１００：０．１〜１００：３００であること、
前記硬化性シリコーン系樹脂（Ａ）と前記エポキシ樹脂（Ｃ）の質量比は、前記硬化性シリコーン系樹脂（Ａ）：前記エポキシ樹脂（Ｃ）＝１５：８５〜９５：５であること、
前記硬化性シリコーン系樹脂（Ａ）１００質量部に対して、前記有機スズ化合物（Ｄ）は０．１〜２０質量部であること及び
前記硬化性シリコーン系樹脂（Ａ）１００質量部に対して、前記水（Ｅ）は０．１〜２０質量部であることを特徴とする二液混合型硬化性樹脂組成物。 A two-component mixed curable resin composition comprising the following resin composition (I) and the following resin composition (II) .
Resin composition (I): a crosslinkable silyl group possess in the molecule, the main chain skeleton polyoxyalkylene and / or poly (meth) acrylate is a curable silicone resin (A) and the following epoxy resin (C) Resin composition containing the curing agent (B) of
Resin composition (II): an epoxy resin (C), a curing catalyst for the curable silicone resin (A), the consisting solid at and dioctyltin distearate and / or dioctyltin maleate polymer at room temperature the organic It is composed of a resin composition containing a tin compound (D) and water (E) .
The mass ratio of the epoxy resin (C) to the curing agent (B) is that the epoxy resin (C): the curing agent (B) = 100: 0.1 to 100: 300.
The mass ratio of the curable silicone resin (A) to the epoxy resin (C) is that the curable silicone resin (A): the epoxy resin (C) = 15: 85 to 95: 5.
The amount of the organotin compound (D) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the curable silicone resin (A).
A two-component mixed curable resin composition, wherein the amount of water (E) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the curable silicone resin (A).
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| JP2862898B2 (en) * | 1989-04-19 | 1999-03-03 | 鐘淵化学工業株式会社 | Curable composition |
| JP3516798B2 (en) * | 1996-04-11 | 2004-04-05 | 積水化学工業株式会社 | Room temperature curable two-part mixed type composition |
| JP4287071B2 (en) * | 2001-04-16 | 2009-07-01 | 株式会社カネカ | Two-component curable composition |
| JP5205006B2 (en) * | 2007-08-08 | 2013-06-05 | 株式会社カネカ | COATING METHOD AND COATED PRODUCT USING CURABLE COMPOSITION |
| JP6162480B2 (en) * | 2013-05-17 | 2017-07-12 | 株式会社カネカ | Curable composition |
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2018
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