JP2010132753A - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
- Publication number
- JP2010132753A JP2010132753A JP2008309075A JP2008309075A JP2010132753A JP 2010132753 A JP2010132753 A JP 2010132753A JP 2008309075 A JP2008309075 A JP 2008309075A JP 2008309075 A JP2008309075 A JP 2008309075A JP 2010132753 A JP2010132753 A JP 2010132753A
- Authority
- JP
- Japan
- Prior art keywords
- component
- compound
- prepolymer
- molecule
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000004359 castor oil Substances 0.000 claims abstract description 32
- 235000019438 castor oil Nutrition 0.000 claims abstract description 32
- 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 claims abstract description 32
- 229920000768 polyamine Polymers 0.000 claims abstract description 31
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 17
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000001730 thiiranyl group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 29
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 4
- 229920000570 polyether Polymers 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 29
- 239000000047 product Substances 0.000 description 23
- 238000003860 storage Methods 0.000 description 16
- -1 isocyanate compound Chemical class 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 150000002513 isocyanates Chemical group 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 235000004443 Ricinus communis Nutrition 0.000 description 4
- 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 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 150000003141 primary amines Chemical group 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 150000003335 secondary amines Chemical group 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- LGGSPSCANPXHOD-UHFFFAOYSA-N 2-[[4-[1,1-bis[4-(thiiran-2-ylmethoxy)cyclohexyl]ethyl]cyclohexyl]oxymethyl]thiirane Chemical compound C1CC(OCC2SC2)CCC1C(C1CCC(CC1)OCC1SC1)(C)C(CC1)CCC1OCC1CS1 LGGSPSCANPXHOD-UHFFFAOYSA-N 0.000 description 2
- AQRQEXKPVGHATN-UHFFFAOYSA-N 2-[[4-[1,1-bis[4-(thiiran-2-ylmethoxy)phenyl]ethyl]phenoxy]methyl]thiirane Chemical compound C=1C=C(OCC2SC2)C=CC=1C(C=1C=CC(OCC2SC2)=CC=1)(C)C(C=C1)=CC=C1OCC1CS1 AQRQEXKPVGHATN-UHFFFAOYSA-N 0.000 description 2
- TZVVBCSGSIKYCY-UHFFFAOYSA-N 2-[[4-[2-[4-(thiiran-2-ylmethoxy)cyclohexyl]propan-2-yl]cyclohexyl]oxymethyl]thiirane Chemical compound C1CC(OCC2SC2)CCC1C(C)(C)C(CC1)CCC1OCC1CS1 TZVVBCSGSIKYCY-UHFFFAOYSA-N 0.000 description 2
- FBYXHYIBMHFFCM-UHFFFAOYSA-N 2-[[4-[2-[4-(thiiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]thiirane Chemical compound C=1C=C(OCC2SC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CS1 FBYXHYIBMHFFCM-UHFFFAOYSA-N 0.000 description 2
- QHJSEAYVVMLPME-UHFFFAOYSA-N 2-[[4-[[4-(thiiran-2-ylmethoxy)cyclohexyl]methyl]cyclohexyl]oxymethyl]thiirane Chemical compound C1SC1COC(CC1)CCC1CC(CC1)CCC1OCC1CS1 QHJSEAYVVMLPME-UHFFFAOYSA-N 0.000 description 2
- VWIZSZPDQCQHBF-UHFFFAOYSA-N 2-[[4-[[4-(thiiran-2-ylmethoxy)phenyl]methyl]phenoxy]methyl]thiirane Chemical compound C1SC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CS1 VWIZSZPDQCQHBF-UHFFFAOYSA-N 0.000 description 2
- LSNKFBWUVAWOGE-UHFFFAOYSA-N 2-butyl-3-[2-[6-[2-(3-butylthiiran-2-yl)ethoxy]hexoxy]ethyl]thiirane Chemical compound CCCCC1SC1CCOCCCCCCOCCC1C(CCCC)S1 LSNKFBWUVAWOGE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 238000013008 moisture curing Methods 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000003553 thiiranes Chemical class 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 1
- RDMFEHLCCOQUMH-UHFFFAOYSA-N 2,4'-Diphenyldiamine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1N RDMFEHLCCOQUMH-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- XQRUEDXXCQDNOT-UHFFFAOYSA-N 2,5-diaminophenol Chemical compound NC1=CC=C(N)C(O)=C1 XQRUEDXXCQDNOT-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- HOLGXWDGCVTMTB-UHFFFAOYSA-N 2-(2-aminophenyl)aniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1N HOLGXWDGCVTMTB-UHFFFAOYSA-N 0.000 description 1
- UYINXWLEUKYMEC-UHFFFAOYSA-N 2-(2-hydrazinyl-2-oxoethoxy)acetohydrazide;4-[1-(4-hydroxyphenyl)ethyl]phenol Chemical compound NNC(=O)COCC(=O)NN.C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 UYINXWLEUKYMEC-UHFFFAOYSA-N 0.000 description 1
- RBUQDANCHIQPAD-UHFFFAOYSA-N 2-(naphthalen-1-yloxymethyl)thiirane Chemical compound C=1C=CC2=CC=CC=C2C=1OCC1CS1 RBUQDANCHIQPAD-UHFFFAOYSA-N 0.000 description 1
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 description 1
- SEDUWVYYKOAFPW-UHFFFAOYSA-N 2-[[5-(thiiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]thiirane Chemical compound C1SC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CS1 SEDUWVYYKOAFPW-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- GRWFFFOEIHGUBG-UHFFFAOYSA-N 3,4-Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclo-hexanecarboxylate Chemical compound C1C2OC2CC(C)C1C(=O)OCC1CC2OC2CC1C GRWFFFOEIHGUBG-UHFFFAOYSA-N 0.000 description 1
- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- AXNUJYHFQHQZBE-UHFFFAOYSA-N 3-methylbenzene-1,2-diamine Chemical compound CC1=CC=CC(N)=C1N AXNUJYHFQHQZBE-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- DGRGLKZMKWPMOH-UHFFFAOYSA-N 4-methylbenzene-1,2-diamine Chemical compound CC1=CC=C(N)C(N)=C1 DGRGLKZMKWPMOH-UHFFFAOYSA-N 0.000 description 1
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- LUTQTJVPOVFVEK-UHFFFAOYSA-N C(=CCCCCC=CCCC=CCCCCCCC(=O)NN)C(=O)NN Chemical compound C(=CCCCCC=CCCC=CCCCCCCC(=O)NN)C(=O)NN LUTQTJVPOVFVEK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-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
- 239000002253 acid 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
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- GXGMLHLXTNVBOQ-UHFFFAOYSA-N benzene-1,3-diol;2-(2-hydrazinyl-2-oxoethoxy)acetohydrazide Chemical compound OC1=CC=CC(O)=C1.NNC(=O)COCC(=O)NN GXGMLHLXTNVBOQ-UHFFFAOYSA-N 0.000 description 1
- VQXDIDTUGQJUFE-UHFFFAOYSA-N benzene-1,4-diol;2-(2-hydrazinyl-2-oxoethoxy)acetohydrazide Chemical compound OC1=CC=C(O)C=C1.NNC(=O)COCC(=O)NN VQXDIDTUGQJUFE-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- ATJCASULPHYKHT-UHFFFAOYSA-N hexadecane-1,16-diamine Chemical compound NCCCCCCCCCCCCCCCCN ATJCASULPHYKHT-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 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 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- QQWAKSKPSOFJFF-UHFFFAOYSA-N oxiran-2-ylmethyl 2,2-dimethyloctanoate Chemical compound CCCCCCC(C)(C)C(=O)OCC1CO1 QQWAKSKPSOFJFF-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- MSVPBWBOFXVAJF-UHFFFAOYSA-N tetradecane-1,14-diamine Chemical compound NCCCCCCCCCCCCCCN MSVPBWBOFXVAJF-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、硬化性組成物に関するものであり、加熱および／または湿気により短時間で硬化し、広い温度範囲での弾性および耐熱性、耐湿性に優れた硬化型樹脂組成物に関するものであり、接着剤、シール剤、コーティング剤、注型剤等に広く応用が可能なものである。 The present invention relates to a curable composition, relates to a curable resin composition that is cured in a short time by heating and / or moisture, and is excellent in elasticity, heat resistance, and moisture resistance in a wide temperature range, It can be widely applied to adhesives, sealants, coating agents, casting agents and the like.
従来より、１分子中に２以上のイソシアネート基を有する化合物の中に、常温で固体のポリアミン化合物の粉末を硬化剤として分散または混合した一液型樹脂組成物が知られている。（以下、ポリアミン化合物の粉末をポリアミン粉と呼ぶ。）ポリアミン化合物の融点以上の加熱により、ポリアミン化合物が溶解し速やかにイソシアネート基と反応するため、加熱硬化型組成物として有用であることが知られている。しかしながら、ポリアミン粉をそのままイソシアネート基を有する化合物に添加すると増粘やゲル化を伴い保存安定性が著しく低下してしまうため、実用的な一液化が困難であった。特に、１００μｍ以下の微粉末状のポリアミン粉では比表面積が高くなるため、さらに保存性低下を招くことが知られている。 Conventionally, one-component resin compositions are known in which a polyamine compound powder that is solid at room temperature is dispersed or mixed as a curing agent in a compound having two or more isocyanate groups in one molecule. (Hereinafter, the polyamine compound powder is referred to as polyamine powder.) It is known that the polyamine compound dissolves and reacts quickly with an isocyanate group when heated to a temperature equal to or higher than the melting point of the polyamine compound, and thus is useful as a thermosetting composition. ing. However, when polyamine powder is added as it is to a compound having an isocyanate group, the storage stability is remarkably reduced due to thickening and gelation, so that it is difficult to make a practical one-component solution. In particular, it is known that a fine powdery polyamine powder of 100 μm or less has a high specific surface area, which further reduces storage stability.
保存性を改善するため、種々の方法で表面を処理したポリアミン粉を分散または混合させる方法が知られている。特許文献１において段落００４０に示されている実施例では、流動パラフィンで処理したポリアミン粉をイソシアネート基末端プレポリマーに添加すると保存性を維持することができると記述されている。一方、段落００４３の比較例ではポリアミン粉を流動パラフィンにより表面処理を実施せずにポリアミン粉をイソシアネート基末端プレポリマーに添加すると保存性が著しく低下することが示されている。この様に保存性を維持するためにはポリアミン粉の表面処理は不可欠であることがわかる。 In order to improve the storage stability, a method of dispersing or mixing the polyamine powder whose surface has been treated by various methods is known. In the example shown in paragraph 0040 in Patent Document 1, it is described that the preservability can be maintained when polyamine powder treated with liquid paraffin is added to an isocyanate group-terminated prepolymer. On the other hand, in the comparative example of paragraph 0043, it is shown that when the polyamine powder is not surface-treated with liquid paraffin and the polyamine powder is added to the isocyanate group-terminated prepolymer, the storage stability is significantly lowered. Thus, it can be seen that the surface treatment of the polyamine powder is indispensable for maintaining the storage stability.
公知になっている他の表面処理方法としては、特許文献２の様な２μｍ以下の無機または有機微粉体を物理的に固着させて被覆する方法や、特許文献３の様なあらかじめ特定の割合のイソシアネート化合物で固形ポリアミン表面を反応表面処理させる方法や、特許文献４の様なパラトルエンスルホニルイソシアネートとオルソギ酸メチルエステルの反応物で固体ポリアミン表面をコーティングする方法が知られている。しかしながら、これらの手法は、工程の多段階化に伴う品質低下や加工賃の増加によるコストアップを伴う。 Other known surface treatment methods include a method in which inorganic or organic fine powders of 2 μm or less as in Patent Document 2 are physically fixed and coated, or a specific ratio in advance as in Patent Document 3 There are known a method in which a solid polyamine surface is subjected to a reactive surface treatment with an isocyanate compound, and a method in which the solid polyamine surface is coated with a reaction product of paratoluenesulfonyl isocyanate and orthoformate methyl ester as in Patent Document 4. However, these methods are accompanied by a cost reduction due to a decrease in quality accompanying an increase in the number of processes and an increase in processing costs.
ポリオール化合物とイソシアネート化合物をウレタン結合させて、末端にイソシアネート基を有する常温で液状のポリマーが知られている。（以下、常温で液状の末端にイソシアネート基を有するポリマーをプレポリマーと呼ぶ。）該ポリオール化合物には、ポリエステル骨格やポリエーテル骨格を有している事が多い。しかしながら、特許文献５の段落０００４に示されている通り、これらの硬化物は信頼性試験（１００℃の高温試験、８５℃×８５％ＲＨの耐湿試験など）により硬化物が堅くなる傾向（柔軟性が低下する）が見られ、被着体からの剥離や硬化物にクラックが入る等の問題点が従来から知られていた。 Polymers that are liquid at room temperature are known in which a polyol compound and an isocyanate compound are urethane-bonded and have an isocyanate group at the terminal. (Hereinafter, a polymer having an isocyanate group at the liquid end at normal temperature is called a prepolymer.) The polyol compound often has a polyester skeleton or a polyether skeleton. However, as shown in paragraph 0004 of Patent Document 5, these cured products tend to become hardened by reliability tests (100 ° C high temperature test, 85 ° C x 85% RH moisture resistance test, etc.). Have been known for some time, such as peeling from the adherend and cracks in the cured product.
従来は硬化剤の表面を処理することにより保存性を安定化させると共に、硬化性に優れた組成物が得られていた。しかしながら、ポリアミン粉の表面処理の製造工程が煩雑であり、品質安定化や加工賃の増加に問題を抱えていた。さらに、従来用いられているプレポリマーの多くはポリエステル骨格、ポリエーテル骨格を有し、その骨格を有する硬化物では柔軟性、耐熱性、耐湿性を同時に満足するものはなかった。 Conventionally, by preserving the preservability by treating the surface of the curing agent, a composition having excellent curability has been obtained. However, the manufacturing process of the surface treatment of polyamine powder is complicated, and there are problems in stabilizing the quality and increasing the processing fee. Furthermore, many of the prepolymers conventionally used have a polyester skeleton and a polyether skeleton, and no cured product having such a skeleton satisfies the flexibility, heat resistance and moisture resistance at the same time.
本発明者らは上記目的を達成するべく鋭意検討した結果、粉末状の硬化剤を分散または混合するプレポリマーとして、水素添加ヒマシ油系ポリオールとポリイソシアネート化合物を反応させて得られる末端にイソシアネート基を含有したプレポリマーを使用することにより、表面処理されていない粉末状の硬化剤でも充分安定した保存性を有する一液型組成物が得られ、加熱により容易に硬化し柔軟で耐熱性と耐湿性に優れる硬化物が得られることを見いだした。 As a result of diligent investigations to achieve the above object, the present inventors have found that a prepolymer in which a powdery curing agent is dispersed or mixed as an isocyanate group at the terminal obtained by reacting a hydrogenated castor oil-based polyol with a polyisocyanate compound. By using a prepolymer containing, a one-part composition having sufficiently stable storage stability even with a powdery curing agent that has not been surface-treated is obtained, which is easily cured by heating and is flexible, heat resistant and moisture resistant. It has been found that a cured product having excellent properties can be obtained.
本発明の要旨を次に説明する。本発明の第一の実施態様は、（Ａ）成分と（Ｂ）成分からなる硬化性樹脂組成物である。
（Ａ）成分：（ａ−１）成分と（ａ−２）成分を反応させて得られる末端にイソシアネート基を有するプレポリマー
（ａ−１）成分：水素添加ヒマシ油系ポリオール
（ａ−２）成分：１分子内に２以上のイソシアネート基を有する化合物
（Ｂ）成分：１分子内に２以上の一級アミン基および／または二級アミン基を有する化合物の粉体
The gist of the present invention will be described next. The first embodiment of the present invention is a curable resin composition comprising a component (A) and a component (B).
(A) Component: Prepolymer having an isocyanate group at the terminal obtained by reacting (a-1) component with (a-2) component (a-1) Component: Hydrogenated castor oil-based polyol (a-2) Component: Compound (B) having two or more isocyanate groups in one molecule Component: Powder of a compound having two or more primary amine groups and / or secondary amine groups in one molecule
本発明の第二の実施態様は、（Ｃ）成分として１分子中に１以上のイソシアネート基を有する化合物を含む請求項１の硬化性樹脂組成物である。 2nd embodiment of this invention is curable resin composition of Claim 1 containing the compound which has a 1 or more isocyanate group in 1 molecule as (C) component.
本発明の第三の実施態様は、（Ｄ）成分として１分子内に１以上のエポキシ基および／またはチイラン基を有する化合物を含む請求項１〜２に記載の硬化性樹脂組成物である。 The third embodiment of the present invention is the curable resin composition according to claim 1 or 2, wherein the component (D) includes a compound having one or more epoxy groups and / or thiirane groups in one molecule.
本発明の第四の実施態様は、前記（Ｂ）成分が脂肪族ポリアミン化合物および／またはヒドラジド化合物である請求項１〜３に記載の硬化性樹脂組成物である。 The fourth embodiment of the present invention is the curable resin composition according to claims 1 to 3, wherein the component (B) is an aliphatic polyamine compound and / or a hydrazide compound.
本発明の第五の実施態様は、請求項１〜４に記載の硬化性樹脂組成物を熱および／または湿気により硬化させる硬化方法と該硬化方法により得られた硬化物である。 The fifth embodiment of the present invention is a curing method for curing the curable resin composition according to claims 1 to 4 with heat and / or moisture and a cured product obtained by the curing method.
本発明は、加熱または空気中の湿分により速やかに硬化し、弾性および耐熱性、耐湿性に優れた硬化物を形成し、電気電子分野、輸送機器分野、一般接着等広い分野で接着剤、シール剤、注型剤等として広く応用が可能である。 The present invention quickly cures by heating or moisture in the air to form a cured product having excellent elasticity, heat resistance and moisture resistance, and is used in a wide range of fields such as electric and electronic fields, transportation equipment fields, general bonding, Widely applicable as sealant, casting agent, etc.
本発明の詳細を次に説明する。本発明で（Ａ）成分として使用することができる末端にイソシアネート基を有するプレポリマーとは、（ａ−１）成分：水素添加ヒマシ油系ポリオールと、（ａ−２）成分：１分子中に２以上のイソシアネート基を有する化合物を反応させたプレポリマーであれば限定されない。 Details of the present invention will be described below. In the present invention, the prepolymer having an isocyanate group at the terminal which can be used as the component (A) includes (a-1) component: hydrogenated castor oil-based polyol, and (a-2) component: in one molecule. It is not limited as long as it is a prepolymer obtained by reacting a compound having two or more isocyanate groups.
合成方法としては、（ａ−１）成分に過剰量の（ａ−２）成分をイソシアネート基／水酸基の当量比が１．２〜３．５となるように反応させることにより製造することができる。反応は、無溶媒かつ無触媒の条件化で通常２０℃〜９０℃で１〜２４時間の条件で撹拌することによって行うことができるが、必要に応じて酢酸エチル、トルエン、キシレンなどの溶媒および、ジブチル錫ジラウレート等の有機錫系触媒、オクチル酸ビスマス等のビスマス系触媒、チタンアルコキシド等のチタン系触媒、１，４−ジアザ［２．２．２］ビシクロオクタン等の三級アミン系触媒などの重合触媒を用いても良い。 As a synthesis method, it can be produced by reacting the component (a-1) with an excess amount of the component (a-2) so that the equivalent ratio of isocyanate group / hydroxyl group is 1.2 to 3.5. . The reaction can be carried out by stirring at 20 ° C. to 90 ° C. for 1 to 24 hours under solvent-free and catalyst-free conditions. If necessary, a solvent such as ethyl acetate, toluene, xylene and the like , Organotin catalysts such as dibutyltin dilaurate, bismuth catalysts such as bismuth octylate, titanium catalysts such as titanium alkoxide, tertiary amine catalysts such as 1,4-diaza [2.2.2] bicyclooctane, etc. The polymerization catalyst may be used.
前記（ａ−１）成分におけるヒマシ油系ポリオールとは、ヒマシ油またはヒマシ油誘導体からなる広義の意味のものとする。ヒマシ油とはヒマの種子から得られる油を精製したものであり、リシノール酸を主成分とする脂肪酸のグリセリンエステルである。ヒマシ油系ポリオールの中でもヒマシ油が好適に用いられ、ヒマシ油誘導体としては、ヒマシ油と多価アルコールとのエステル交換反応物、部分脱水ヒマシ油、部分アシル化ヒマシ油（部分アセチル化ヒマシ油等）、ヒマシ油のアルキレンオキシド付加物、ヒマシ油のエポキシ化物、ヒマシ油のハロゲン化物、ビスフェノール類アルキレンオキサイド付加物のヒマシ油脂肪酸モノまたはジエステル、ダイマー酸とヒマシ油系ポリオールとのエステル化物、重合ヒマシ油のエステル交換反応物とカプロラクトンとの反応物、ヒマシ油脂肪酸の２量体以上の縮合体またはその縮合体と多価アルコールとのエステルなども用いられるが、例示したもの以外のものであって差し支えない。また、２種以上を併用しても差し支えない。 The castor oil-based polyol in the component (a-1) has a broad meaning made of castor oil or a castor oil derivative. Castor oil is refined oil obtained from castor seeds, and is a glycerin ester of fatty acid mainly composed of ricinoleic acid. Among castor oil-based polyols, castor oil is preferably used, and castor oil derivatives include transesterification products of castor oil and polyhydric alcohol, partially dehydrated castor oil, partially acylated castor oil (partially acetylated castor oil, etc. ), Castor oil alkylene oxide adduct, castor oil epoxidized product, castor oil halide, castor oil fatty acid mono- or diester of bisphenol alkylene oxide adduct, esterified product of dimer acid and castor oil-based polyol, polymerized castor A reaction product of a transesterification product of oil and caprolactone, a condensate of dimers or more of castor oil fatty acid, or an ester of the condensate with a polyhydric alcohol, etc. may be used. There is no problem. Two or more kinds may be used in combination.
前記（ａ−１）成分における水素添加とは、化合物内に存在する不飽和二重結合を飽和結合化したものであり、その方法には限定されない。水素添加ヒマシ油系ポリオールを使用する場合、ヒマシ油ポリオールを使用するよりも長期耐熱性が優れている。 The hydrogenation in the component (a-1) is obtained by saturation bonding of unsaturated double bonds present in the compound, and is not limited to the method. When using a hydrogenated castor oil-based polyol, long-term heat resistance is superior to using a castor oil polyol.
水素添加ヒマシ油は商業的に容易に入手することができる。例えば、伊藤製油株式会社製のヒマシ硬化油Ａ、ヒマシ硬化油Ｂ、川研ファインケミカル（株）製のＫ−３−ワックス、Ｋ−３−ワックス−５００、日本油脂（株）製のカスターワックスなどが挙げられる。また、水素添加ヒマシ油誘導体も商業的に容易に入手することができる。例えば、伊藤製油株式会社製のＵＲＩＣＰＨ−５００１、ＰＨ−５００２、ＰＨ−６０００、ＵＲＩＣ１８１５Ｕ、ＵＲＩＣ１８８６Ｕ、豊国製油株式会社社製のＨＳ−３Ｇ−５００Ｂ、等が挙げられる。 Hydrogenated castor oil is readily available commercially. For example, castor hardened oil A, castor hardened oil B manufactured by Ito Oil Co., Ltd., K-3-wax manufactured by Kawaken Fine Chemical Co., Ltd., K-3-wax-500, castor wax manufactured by Nippon Oil & Fats Co., Ltd., etc. Is mentioned. Hydrogenated castor oil derivatives can also be easily obtained commercially. Examples thereof include URICPH-5001, PH-5002, PH-6000, URIC1815U, URIC1886U manufactured by Ito Oil Co., Ltd., HS-3G-500B manufactured by Toyokuni Oil Co., Ltd., and the like.
前記（ａ−２）成分は１分子中にイソシアネート基を２つ以上含有する化合物であればよく、芳香族、鎖状脂肪族または環状脂肪族に属する任意のものが使用できる。具体的には、トリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、３，３′−ジメチル−４，４′−ビフェニレンジイソシアネート、１，４−フェニレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフチレンジイソシアネート、ジシクロヘキシルメタン−４，４′−ジイソシアネート、粗製ＴＤＩ、ポリメチレン・ポリフェニルイソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、水素化キシリレンジイソシアネート、これらの異性体、イソシアヌレート化物、カルボジイミド化物、ビューレット化物等が挙げられるがこれらに限定されるものではない。また、これらの１種または２種以上の混合物を使用に供してよい。 The component (a-2) may be any compound containing two or more isocyanate groups in one molecule, and any of those belonging to aromatic, chain aliphatic or cycloaliphatic can be used. Specifically, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,4-phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, Naphthylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, crude TDI, polymethylene polyphenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isomers thereof, isocyanurates, carbodiimides, burettes However, it is not limited to these. Moreover, you may use for the use of these 1 type, or 2 or more types of mixtures.
本発明で使用することができる（Ｂ）成分は分子内に２個以上の一級アミン基および／または二級アミン基を有する化合物の粉末である。（以下、一級アミン基および／または二級アミン基を有する化合物の粉末をポリアミン粉と呼ぶ。）具体例としては、４，４′−ジアミノジフェニルメタン、２，４′−ジアミノジフェニルメタン、３，３′−ジアミノジフェニルメタン、３，４′−ジアミノジフェニルメタン、２，２′−ジアミノビフェニル、２，４′−ジアミノビフェニル、３，３′−ジアミノビフェニル、２，４−ジアミノフェノール、２，５−ジアミノフェノール、ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、２，３−トリレンジアミン、２，４−トリレンジアミン、２，５−トリレンジアミン、２，６−トリレンジアミン、３，４−トリレンジアミン等の芳香族ポリアミン化合物、１，１２−ドデカンジアミン、１，１０−デカンジアミン、１，９−ノナンジアミン、１，１４−テトラデカンジアミン、１，１６−ヘキサデカンジアミン等の脂肪族ポリアミン化合物、アジピン酸ジヒドラジド、セバチン酸ジヒドラジド、イソフタール酸ジヒドラジド、１，３−ビス−（ヒドラジノカルボエチル）−５−イソプロピルヒダントインエイコサン二酸ジヒドラジド、ハイドロキノンジグリコール酸ジヒドラジド、レゾルシノールジグリコール酸ジヒドラジド、４，４′−エチリデンビスフェノールジグリコール酸ジヒドラジド、７，１１−オクタデカジエン−１，１８−ジカルボヒドラジド、３，３’−（４−イソプロピル−２，５−ジオキソ−１，３−ジアゾリジン−１，３−ジイル）ジプロピオノヒドラジド等のヒドラジド化合物が挙げられるがこれに限定されない。これらは１種または２種以上を混合して用いることができる。保存性の観点から脂肪族ポリアミン化合物とヒドラジド化合物を使用することが好ましい。また、工程数の多段階化、加工賃の増加などを考慮しなければ、必要に応じて粒子表面が不活性化処理されているポリアミン化合物を用いても良い。これら不活性化処理されたアミンを用いることで、さらに保存安定性の向上した組成物となる。 The component (B) that can be used in the present invention is a powder of a compound having two or more primary amine groups and / or secondary amine groups in the molecule. (Hereinafter, a powder of a compound having a primary amine group and / or a secondary amine group is referred to as a polyamine powder.) As specific examples, 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 3,3 ′ -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine, etc. Aromatic polyamine compounds, 1,12-dodecanediamine, 1,10-decanediamine, 1,9-nona Aliphatic polyamine compounds such as diamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, 1,3-bis- (hydrazinocarboethyl) -5-isopropyl Hydantoin eicosanedioic acid dihydrazide, hydroquinone diglycolic acid dihydrazide, resorcinol diglycolic acid dihydrazide, 4,4'-ethylidenebisphenol diglycolic acid dihydrazide, 7,11-octadecadienene-1,18-dicarbohydrazide, 3,3 Examples include, but are not limited to, hydrazide compounds such as'-(4-isopropyl-2,5-dioxo-1,3-diazolidine-1,3-diyl) dipropionohydrazide. These can be used alone or in combination of two or more. From the viewpoint of storage stability, it is preferable to use an aliphatic polyamine compound and a hydrazide compound. Moreover, if the number of steps is not taken into account and the increase in processing cost is not taken into consideration, a polyamine compound in which the particle surface is inactivated may be used as necessary. By using these inactivated amines, a composition having further improved storage stability is obtained.
（Ｂ）成分の平均粒径としては、１００μｍ以下、好ましくは４０μｍ以下、より好ましくは０．１〜２０μｍに調整する。１００μｍを越える中心粒径では、加熱硬化物の不均一性が大きく所望の物性が得られない傾向となる。粒子の調整の手法は特に限定されず、任意の化学的手法および機械的粉砕手法を用いることができる。 (B) As an average particle diameter of a component, 100 micrometers or less, Preferably it is 40 micrometers or less, More preferably, it adjusts to 0.1-20 micrometers. When the center particle diameter exceeds 100 μm, the non-uniformity of the heat-cured product tends to be large and desired physical properties cannot be obtained. The method for adjusting the particles is not particularly limited, and any chemical method and mechanical grinding method can be used.
粉砕方法としてはジェットミル、遊星ボールミル、ハンマーミル等が知られる。化合物の融点が低い場合は、凍結粉砕が有効である。一方、平均粒径の確認方法としては、レーザー回折散乱式やマイクロソーティング制御方式の粒度・形状分布測定器、光学顕微鏡、電子顕微鏡等の画像解析がある。 Known pulverization methods include a jet mill, a planetary ball mill, and a hammer mill. When the melting point of the compound is low, freeze pulverization is effective. On the other hand, as a method for confirming the average particle diameter, there are image analysis such as a particle size / shape distribution measuring instrument of a laser diffraction scattering method or a microsorting control method, an optical microscope, an electron microscope and the like.
本発明に使用することができる（Ｃ）成分は、１分子内に１以上のイソシアネート基を有する化合物を添加することができる。具体例としては、前記（ａ−２）成分であるイアネート化合物の他、フェニルイソシアネート、ｐ−トルエンスルホニルイソシアネート、イソシアネートエチルメタクリレート、３−イソプロペニル−α，α′−ジメチルベンジルイソシアネート、３−イソシアネートプロピルトリエトキシシランなど使用することができるがこれに限定されない。これらは１種または２種以上を混合して用いることができる。（Ｃ）成分を添加することで、粘度の調製ができる事と接着性が向上する効果がある。（以下、１分子内に１以上のイソシアネート基を有する化合物をイソシアネート化合物と呼ぶ。）（Ｃ）成分の添加量としては、（Ａ）成分１００重量部に対し（Ｃ）成分が０．１〜２０重量部の範囲で添加される事が最も好ましい。 (C) component which can be used for this invention can add the compound which has a 1 or more isocyanate group in 1 molecule. Specific examples include, in addition to the ianate compound as component (a-2), phenyl isocyanate, p-toluenesulfonyl isocyanate, isocyanate ethyl methacrylate, 3-isopropenyl-α, α'-dimethylbenzyl isocyanate, 3-isocyanatopropyl. Although triethoxysilane etc. can be used, it is not limited to this. These can be used alone or in combination of two or more. By adding the component (C), the viscosity can be adjusted and the adhesiveness is improved. (Hereinafter, a compound having one or more isocyanate groups in one molecule is referred to as an isocyanate compound.) (C) Component (C) is added in an amount of 0.1 to 100 parts by weight of component (A). Most preferably, it is added in the range of 20 parts by weight.
（Ａ）成分、（Ｂ）成分、（Ｃ）成分の配合比率は特に限定されず、目的にあわせ任意の割合で使用できる。最も好ましくは（Ａ）成分と（Ｃ）成分を合計したイソシアネート当量と（Ｂ）成分のアミン当量の比率が１：０．４〜１：３．０の範囲内に入る事であり、６０〜１００℃において１０分以内に硬化するという速硬化性および硬化物における硬度の維持に優れる。 The blending ratio of the component (A), the component (B), and the component (C) is not particularly limited, and can be used in any ratio according to the purpose. Most preferably, the ratio of the isocyanate equivalent of the sum of components (A) and (C) and the amine equivalent of component (B) falls within the range of 1: 0.4 to 1: 3.0, It is excellent in fast curability of curing within 10 minutes at 100 ° C. and maintaining hardness in the cured product.
本発明の組成物には、さらに（Ｄ）成分として１分子内に１以上のエポキシ基および／または化１の様なチイラン基を有する化合物を添加してもよい。（以下、１分子内に１以上のエポキシ基またはチイラン基を有する化合物をそれぞれエポキシ化合物またはチイラン化合物と呼ぶ。）好ましくは、（Ａ）成分のプレポリマーと分離することなく混合できると共に、室温にて液状の化合物である。単独で用いてもよく、２種以上を混合して用いることもできる。 To the composition of the present invention, a compound having one or more epoxy groups and / or thiirane groups such as Chemical Formula 1 in one molecule may be added as component (D). (Hereinafter, compounds having one or more epoxy groups or thiirane groups in one molecule are referred to as epoxy compounds or thiirane compounds, respectively.) It is a liquid compound. They may be used alone or in combination of two or more.
前記エポキシ基を有する化合物の具体例としては、ビスフェノールＡとエピクロルヒドリンから誘導されるジグリシジルエーテル、及びその誘導体、ビスフェノールＦとエピクロルヒドリンから誘導されるジグリシジルエーテル、及びその誘導体等の所謂エピ−ビス型液状エポキシ樹脂、脂肪族・芳香族アルコールとエピクロルヒドリンから誘導されるグリシジルエーテル、多塩基酸とエピクロルヒドリンから誘導されるグリシジルエステル、及びその誘導体、水添ビスフェノールＡとエピクロルヒドリンから誘導されるグリシジルエーテル、３，４−エポキシ−６−メチルシクロヘキシルメチル−３，４−エポキシ−６−メチルシクロヘキサンカルボキシレート、ビニルシクロヘキセンオキサイド、ビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）アジペート等の脂肪族環状エポキシ、及びその誘導体、５，５’−ジメチルヒダントイン型エポキシ樹脂、トリグリシジルイソシアネート、イソブチレンから誘導される置換型エポキシ、γ−グリシドキシプロピルトリメトキシシランなどの分子内にアルコキシシリル基を含む化合物、２，２−ビス（４−（２，３−エピチオプロポキシ）フェニル）プロパン、ビス（４−（２，３−エピチオプロポキシ）フェニル）メタン、１，６−ジ（２，３−エピチオプロポキシ）ナフタレン、１，１，１−トリス−（４−（２，３−エピチオプロポキシ）フェニル）エタン、２，２−ビス（４−（２，３−エピチオプロポキシ）シクロヘキシル）プロパン、ビス（４−（２，３−エピチオプロポキシ）シクロヘキシル）メタン、１，１，１−トリス−（４−（２，３−エピチオプロポキシ）シクロヘキシル）エタン、１，５−ペンタンジオールの２，３−エピチオシクロヘキシル）エーテル、１，６−ヘキサンジオールのジ（３，４−エピチオオクチル）エーテル等が挙げられるがこれらに限定されるものではない。市販されているこれらの製品としては例えばジャパンエポキシレジン株式会社製のＪＥＲ８２８、１００１、８０１、８０６、８０７、１５２、６０４、６３０、８７１、ＹＸ８０００、ＹＸ８０３４、ＹＸ４０００、カージュラＥ１０Ｐ、ＹＬ７０００、ＹＬ７００７、大日本インキ工業株式会社製のエピクロン８３０、８３５ＬＶ、ＨＰ４０３２Ｄ、７０３、７２０、７２６、ＨＰ８２０、旭電化工業株式会社製のＥＰ４１００、ＥＰ４０００、ＥＰ４０８０、ＥＰ４０８５、ＥＰ４０８８、ＥＰＵ６、ＥＰＲ４０２３、ＥＰＲ１３０９、ＥＰ４９−２０、ナガセケムテックス株式会社製デナコールＥＸ４１１、ＥＸ３１４、ＥＸ２０１、ＥＸ２１２、ＥＸ２５２、ＥＸ１１１、ＥＸ１４６、ＥＸ７２１、デナレックスＦＣＡ−０６１Ｌ、ＦＣＡ−０６１Ｍ、信越化学工業株式会社製ＫＢＭ４０３、ＫＢＥ４０２等が挙げられるがこれらに限定されるものではない。 Specific examples of the compound having an epoxy group include diglycidyl ether derived from bisphenol A and epichlorohydrin, and derivatives thereof, diglycidyl ether derived from bisphenol F and epichlorohydrin, and derivatives thereof, so-called epi-bis type. Liquid epoxy resin, glycidyl ether derived from aliphatic / aromatic alcohol and epichlorohydrin, glycidyl ester derived from polybasic acid and epichlorohydrin, and derivatives thereof, glycidyl ether derived from hydrogenated bisphenol A and epichlorohydrin, 3, 4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, vinylcyclohexene oxide, bis (3,4-epoxy-6-methylsilane) Aliphatic cyclic epoxy such as (rohexylmethyl) adipate, and derivatives thereof, 5,5′-dimethylhydantoin type epoxy resin, triglycidyl isocyanate, substituted epoxy derived from isobutylene, γ-glycidoxypropyltrimethoxysilane, etc. A compound containing an alkoxysilyl group in the molecule, 2,2-bis (4- (2,3-epithiopropoxy) phenyl) propane, bis (4- (2,3-epithiopropoxy) phenyl) methane, , 6-di (2,3-epithiopropoxy) naphthalene, 1,1,1-tris- (4- (2,3-epithiopropoxy) phenyl) ethane, 2,2-bis (4- (2, 3-epithiopropoxy) cyclohexyl) propane, bis (4- (2,3-epithiopropoxy) cyclohexyl) methane, 1 , 1,1-tris- (4- (2,3-epithiopropoxy) cyclohexyl) ethane, 1,5-pentanediol 2,3-epithiocyclohexyl) ether, 1,6-hexanediol di (3 , 4-epithiooctyl) ether and the like, but are not limited thereto. Examples of these commercially available products include JER828, 1001, 801, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, Cardura E10P, YL7000, YL7007, Dainippon, manufactured by Japan Epoxy Resin Co., Ltd. Epiklone 830, 835LV, HP4032D, 703, 720, 726, HP820, manufactured by Ink Industries Co., Ltd., EP4100, EP4000, EP4080, EP4085, EP4088, EPU6, EPR4023, EPR1309, EP49-20, Nagase Chem, manufactured by Asahi Denka Kogyo Co., Ltd. Denacor EX411, EX314, EX201, EX212, EX252, EX111, EX146, EX721, manufactured by Tex Co., Ltd., Denalex FCA-061L FCA-061M, but manufactured by Shin-Etsu Chemical Co. KBM403, KBE402, etc. it is not limited thereto.
前記チイラン基を有する化合物の具体例としては、２，２−ビス（４−（２，３−エピチオプロポキシ）フェニル）プロパン、ビス（４−（２，３−エピチオプロポキシ）フェニル）メタン、１，６−ジ（２，３−エピチオプロポキシ）ナフタレン、１，１，１−トリス−（４−（２，３−エピチオプロポキシ）フェニル）エタン、２，２−ビス（４−（２，３−エピチオプロポキシ）シクロヘキシル）プロパン、ビス（４−（２，３−エピチオプロポキシ）シクロヘキシル）メタン、１，１，１−トリス−（４−（２，３−エピチオプロポキシ）シクロヘキシル）エタン、１，５−ペンタンジオールの２，３−エピチオシクロヘキシル）エーテル、１，６−ヘキサンジオールのジ（３，４−エピチオオクチル）エーテル等が挙げられるが、これらに限定されるものではない。 Specific examples of the compound having a thiirane group include 2,2-bis (4- (2,3-epithiopropoxy) phenyl) propane, bis (4- (2,3-epithiopropoxy) phenyl) methane, 1,6-di (2,3-epithiopropoxy) naphthalene, 1,1,1-tris- (4- (2,3-epithiopropoxy) phenyl) ethane, 2,2-bis (4- (2 , 3-epithiopropoxy) cyclohexyl) propane, bis (4- (2,3-epithiopropoxy) cyclohexyl) methane, 1,1,1-tris- (4- (2,3-epithiopropoxy) cyclohexyl) Ethane, 1,5-pentanediol 2,3-epithiocyclohexyl) ether, 1,6-hexanediol di (3,4-epithiooctyl) ether, and the like. The present invention is not limited to these.
（Ｄ）成分を添加することで粘度の低減や、接着力、耐久性などの特性が向上する。エポキシ化合物の配合割合は特に限定されず目的に応じ任意の割合で添加できるが、（Ａ）成分と（Ｃ）成分の合計１００質量部に対して、前記（Ｄ）成分を０．１〜１００重量部の範囲で添加すると、硬化物の特性である柔軟性を損なわずに粘度の低減や接着力、耐久性の向上を図ることができる。 By adding the component (D), properties such as viscosity reduction, adhesive strength and durability are improved. Although the compounding ratio of an epoxy compound is not specifically limited, It can add in arbitrary ratios according to the objective, However The said (D) component is 0.1-100 with respect to a total of 100 mass parts of (A) component and (C) component. When added in the range of parts by weight, the viscosity can be reduced, the adhesive force and the durability can be improved without impairing the flexibility that is a characteristic of the cured product.
本発明の組成物には、本発明の特性を損なわない範囲において、有機錫系触媒、ビスマス系触媒、チタン系触媒、アミン類等の湿気重合触媒、ジシアンアミド、アミン−エポキシアダクト、尿素型アダクト、固形イミダゾール等のエポキシ潜在性触媒、リン酸エステル、ホウ酸エステル等の保存性向上剤、顔料、染料などの着色剤、炭酸カルシウム、タルク、シリカ、アルミナ、水酸化アルミニウム、水酸化マグネシウム、カーボン等の無機充填剤およびその表面を有機酸やカップリング剤で表面処理された無機充填剤、難燃剤、アクリルゴムやシリコンゴム等の有機充填剤、可塑剤、分子中にアクリル基等の反応性官能基を含む反応性可塑剤、酸化防止剤、紫外線吸収剤、消泡剤、カップリング剤、脱水剤、レベリング剤、レオロジーコントロール剤等の添加剤を適量配合しても良い。これらの添加により、より柔軟性、樹脂強度、接着強さ、難燃性、熱伝導性、作業性等に優れた組成物およびその硬化物が得られる。 In the composition of the present invention, an organic tin catalyst, a bismuth catalyst, a titanium catalyst, a moisture polymerization catalyst such as amines, dicyanamide, an amine-epoxy adduct, a urea type adduct, as long as the characteristics of the present invention are not impaired. Epoxy latent catalyst such as solid imidazole, preservability improver such as phosphate ester and borate ester, colorant such as pigment and dye, calcium carbonate, talc, silica, alumina, aluminum hydroxide, magnesium hydroxide, carbon, etc. Inorganic fillers and inorganic fillers whose surfaces are treated with organic acids and coupling agents, flame retardants, organic fillers such as acrylic rubber and silicon rubber, plasticizers, reactive functionalities such as acrylic groups in the molecule Reactive plasticizers containing groups, antioxidants, UV absorbers, antifoaming agents, coupling agents, dehydrating agents, leveling agents, rheology components An additive such as a roll material may be appropriate amount. By these additions, a composition excellent in flexibility, resin strength, adhesive strength, flame retardancy, thermal conductivity, workability, and the like and a cured product thereof can be obtained.
本発明の構成成分を混合する順番は特に限定されないが、（Ａ）成分と（Ｂ）成分を最初に混合した後に、その他の成分を混合することが組成物の保存性を高めるうえで好ましい。 The order in which the constituent components of the present invention are mixed is not particularly limited, but it is preferable to mix other components after first mixing the component (A) and the component (B) in order to improve the storage stability of the composition.
本発明の組成物は加熱により速やかに硬化させることができるが、加熱をしなくとも空気中の湿分により硬化させることも可能である。このことは加熱ムラなどで加熱硬化が不充分な部位もその後の室内放置により湿気により硬化できることを意味し、結果的に接着剤の信頼性をより高めることができる。 The composition of the present invention can be cured rapidly by heating, but can be cured by moisture in the air without heating. This means that a part that is not sufficiently heated and cured due to uneven heating can be cured by moisture when left indoors, and as a result, the reliability of the adhesive can be further improved.
次に実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to these Examples.
［プレポリマー１］
加熱温度調節装置を備えた容量３リットルのプラネタリー撹拌装置に、（ａ−１）成分：水素添加ヒマシ油系ポリオール（ＵＲＩＣ１８１５Ｕ 伊藤製油株式会社製）８００．０ｇと（ａ−２）成分：ジフェニルメタン−４，４’−ジイソシアネート（コスモネートＰＨ 三井化学ポリウレタン株式会社製）１６１．０ｇを投入する。窒素雰囲気下４０℃にて１時間、６０℃にて５時間撹拌反応させ、粘度１４２０００ｍＰａ・ｓ（２５℃）の（Ａ）成分であるプレポリマー１を得た。
[Prepolymer 1]
In a planetary stirrer with a capacity of 3 liters equipped with a heating temperature controller, (0.0) component (a-1): hydrogenated castor oil-based polyol (URIC1815U made by Ito Oil Co., Ltd.) and (a-2) component: diphenylmethane Charge 161.0 g of -4,4'-diisocyanate (Cosmonate PH, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.). The mixture was reacted under stirring in a nitrogen atmosphere at 40 ° C. for 1 hour and at 60 ° C. for 5 hours to obtain a prepolymer 1 as component (A) having a viscosity of 142,000 mPa · s (25 ° C.).
［プレポリマー２］
加熱温度調節装置を備えた容量３リットルのプラネタリー撹拌装置に、（ａ−１）成分：水素添加ヒマシ油系ポリオール（ＵＲＩＣ１８１５Ｕ 伊藤製油株式会社製）８００．０ｇと（ａ−２）成分：トリレンジイソシアネート（コスモネートＴ１００ 三井化学ポリウレタン株式会社製）１１５．０ｇを投入する。窒素雰囲気下４０℃にて１時間、６０℃にて５時間撹拌反応させ、粘度３８０００ｍＰａ・ｓ（２５℃）の（Ａ）成分であるプレポリマー２を得た。
[Prepolymer 2]
To a planetary stirrer having a capacity of 3 liters equipped with a heating temperature controller, 800.0 g of component (a-1): hydrogenated castor oil-based polyol (URIC1815U made by Ito Oil Co., Ltd.) and component (a-2): tri 115.0 g of range isocyanate (Cosmonate T100, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) is charged. The mixture was reacted under stirring in a nitrogen atmosphere at 40 ° C. for 1 hour and at 60 ° C. for 5 hours to obtain a prepolymer 2 as component (A) having a viscosity of 38000 mPa · s (25 ° C.).
［プレポリマー３］
加熱温度調節装置を備えた容量３Ｌのプラネタリー撹拌装置に、（ａ−１）成分：水素添加ヒマシ油系ポリオール（ＵＲＩＣ１８１５Ｕ 伊藤製油株式会社製）８００．０ｇと（ａ−２）成分：トリレンジイソシアネート（コスモネートＴ８０ 三井化学ポリウレタン株式会社製）１００．０ｇを投入する。窒素雰囲気下４０℃にて１時間、６０℃にて５時間撹拌反応させ、粘度６００００ｍＰａ・ｓ（２５℃）の（Ａ）成分であるプレポリマー３を得た。
[Prepolymer 3]
To a planetary stirrer with a capacity of 3 L equipped with a heating temperature control device, (0.0-1) component (a-1): hydrogenated castor oil-based polyol (URIC1815U made by Ito Oil Co., Ltd.) and (a-2) component: tolylene Add 100.0 g of isocyanate (Cosmonate T80, Mitsui Chemicals Polyurethane Co., Ltd.). The mixture was reacted under stirring in a nitrogen atmosphere at 40 ° C. for 1 hour and at 60 ° C. for 5 hours to obtain a prepolymer 3 as component (A) having a viscosity of 60000 mPa · s (25 ° C.).
［プレポリマー４］
加熱温度調節装置を備えた容量３Ｌのプラネタリー撹拌装置に、（ａ−１）成分：水素添加ヒマシ油系ポリオール（ＵＲＩＣ１８１５Ｕ 伊藤製油株式会社製）８００．０ｇと（ａ−２）成分：ヘキサメチレンジイソシアネート（タケネート７００ 三井化学ポリウレタン株式会社製）８１．０ｇと錫系触媒（ネオスタンＵ−１００ 日東化成株式会社製）０．４ｇを投入し、窒素雰囲気下４０℃にて１時間、６０℃にて５時間撹拌反応させ、粘度３５０００ｍＰａ・ｓ（２５℃）の（Ａ）成分であるプレポリマー４を得た。
[Prepolymer 4]
To a planetary stirrer with a capacity of 3 L equipped with a heating temperature controller, (0.0) component (a-1): hydrogenated castor oil-based polyol (URIC1815U made by Ito Oil Co., Ltd.) and (a-2) component: hexamethylene 81.0 g of diisocyanate (Takenate 700, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) and 0.4 g of tin-based catalyst (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) were added, and the nitrogen atmosphere was 40 ° C for 1 hour at 60 ° C. The prepolymer 4 which is (A) component with a viscosity of 35000 mPa * s (25 degreeC) was obtained by making it react by stirring for 5 hours.
［プレポリマー５］（比較例）
加熱温度調節装置を備えた容量３Ｌのプラネタリー撹拌装置に、ポリエーテルジオール（Ｐ３０００ 株式会社ＡＤＥＫＡ製）８００．０ｇと（ａ−２）成分：トリレンジイソシアネート（コスモネートＴ１００ 三井化学ポリウレタン株式会社製）９４．０ｇを投入し、窒素雰囲気下４０℃にて１時間、６０℃にて５時間撹拌反応させ、粘度５６００ｍＰａ・ｓ（２５℃）のプレポリマー５を得た。
[Prepolymer 5] (Comparative Example)
In a planetary stirrer with a capacity of 3 L equipped with a heating temperature controller, 800.0 g of polyether diol (P3000 manufactured by ADEKA Corporation) and (a-2) component: Tolylene diisocyanate (Cosmonate T100, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 94.0 g was charged, and the mixture was reacted under stirring in a nitrogen atmosphere at 40 ° C. for 1 hour and at 60 ° C. for 5 hours to obtain a prepolymer 5 having a viscosity of 5600 mPa · s (25 ° C.).
［プレポリマー６］（比較例）
加熱温度調節装置を備えた容量３Ｌのプラネタリー撹拌装置に、ヒマシ油系ポリオール（ＵＲＩＣ Ｈ−５６ 伊藤製油株式会社製）６００．０ｇと（ａ−２）成分：トリレンジイソシアネート（コスモネートＴ１００ 三井化学ポリウレタン株式会社製）１４８．０ｇを投入し、窒素雰囲気下４０℃にて１時間、６０℃にて５時間撹拌反応させ、粘度７３００ｍＰａ・ｓ（２５℃）のプレポリマー６を得た。
[Prepolymer 6] (Comparative Example)
To a planetary stirrer having a capacity of 3 L equipped with a heating temperature controller, castor oil-based polyol (URIC H-56, manufactured by Ito Oil Co., Ltd.) 600.0 g and (a-2) component: tolylene diisocyanate (Cosmonate T100 Mitsui) (Chemical Polyurethane Co., Ltd.) 148.0 g was added, and the mixture was reacted with stirring at 40 ° C. for 1 hour and at 60 ° C. for 5 hours in a nitrogen atmosphere to obtain a prepolymer 6 having a viscosity of 7300 mPa · s (25 ° C.).
［ポリアミン粉１］
結晶塊状態の１，１０−デカンジアミン（融点６２℃）を破砕造粒整粒機で粗粉砕後、ジェットミルで粉砕することにより平均粒径５μｍ、最大粒径１７μｍのアミン微粉体であるポリアミン粉１を得た。粒径の測定にはレーザー回折・散乱式粒度分布測定器（セイシン企業製 ＬＭＳ−３０）を用いた。
[Polyamine powder 1]
1,10-decanediamine (melting point: 62 ° C.) in the crystal lump state is coarsely pulverized with a crushing and granulating granulator and then pulverized with a jet mill to form an amine fine powder having an average particle size of 5 μm and a maximum particle size of 17 μm Powder 1 was obtained. For the measurement of the particle size, a laser diffraction / scattering type particle size distribution measuring device (LMS-30 manufactured by Seishin Enterprise) was used.
［ポリアミン粉２］
結晶塊状態の１，１２−ドデカンジアミン（融点７１℃）を破砕造粒整粒機で粉砕後、篩いで分級し、最大粒径７０μｍのアミン微粉体であるポリアミン粉２を得た。
[Polyamine powder 2]
Crystallized 1,12-dodecanediamine (melting point 71 ° C.) was pulverized with a crushing granulator and classified with a sieve to obtain polyamine powder 2 which is an amine fine powder having a maximum particle size of 70 μm.
［実施例１〜２２］
実施例１〜２２の組成物を調製するために下記成分を準備した。
（Ａ）成分：プレポリマー
・プレポリマー１
・プレポリマー２
・プレポリマー３
・プレポリマー４
（Ｂ）成分：ポリアミン粉
・ポリアミン粉１
・ポリアミン粉２
・１，３−ビス（ヒドラジノカルボノエチル）−５−イソプロピルヒダントイン（アミキュアＶＤＨ−Ｊ 味の素ファインケミカル株式会社）
（Ｃ）成分：イソシアネート化合物
・トリレンジイソシアネート（Ｔ−８０ 三井化学ポリウレタン株式会社）
・ｐ−トルエンスルホニルイソシアネート（東京化成工業株式会社）
・γ−イソシアネートプロピルトリエトキシシラン（Ａ−１３１０ モメンティブパフォーマンスマテリアルジャパン合同会社）
・ポリイソシアネート（ＴＬＡ−１００ 旭化成ケミカルズ株式会社）
（Ｄ）成分：エポキシ化合物
・ビスフェノールＦ型エポキシ樹脂（ＪＥＲ８０７ ジャパンエポキシレジン株式会社）
・水素化ビスフェノールＡ型エポキシ樹脂（ＹＸ８０００ ジャパンエポキシレジン株式会社）
・長鎖脂肪族系エポキシ樹脂（デナレックスＦＣＡ−０６１Ｌ ナガセケムテックス株式会社）
（Ｄ）成分：チイラン化合物
・エピスルフィド樹脂（ＹＬ７００７ ジャパンエポキシレジン株式会社）
その他：添加剤
・３−グリシドキシプロピルトリメトキシシラン（ＫＢＭ−４０３ 信越化学工業株式会社）
・炭酸カルシウム粉（ソフトン１８００ 備北粉化工業株式会社）
・アルミナ粉（Ａ−４３Ｍ 昭和電工株式会社）
・可塑剤（ＧＲ−３０１ 伊藤製油株式会社）
[Examples 1 to 22]
The following ingredients were prepared to prepare the compositions of Examples 1-22.
Component (A): Prepolymer / Prepolymer 1
・ Prepolymer 2
・ Prepolymer 3
・ Prepolymer 4
(B) component: Polyamine powder / polyamine powder 1
・ Polyamine powder 2
1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin (Amicure VDH-J Ajinomoto Fine Chemical Co., Ltd.)
Component (C): Isocyanate compound / tolylene diisocyanate (T-80 Mitsui Chemicals Polyurethanes)
・ P-Toluenesulfonyl isocyanate (Tokyo Chemical Industry Co., Ltd.)
・ Γ-Isocyanatopropyltriethoxysilane (A-1310 Momentive Performance Material Japan GK)
・ Polyisocyanate (TLA-100 Asahi Kasei Chemicals Corporation)
Component (D): epoxy compound / bisphenol F type epoxy resin (JER807 Japan Epoxy Resin Co., Ltd.)
・ Hydrogenated bisphenol A epoxy resin (YX8000 Japan Epoxy Resin Co., Ltd.)
・ Long chain aliphatic epoxy resin (Denalex FCA-061L Nagase ChemteX Corporation)
Component (D): thiirane compound / episulfide resin (YL7007 Japan Epoxy Resin Co., Ltd.)
Others: Additive-3-glycidoxypropyltrimethoxysilane (KBM-403 Shin-Etsu Chemical Co., Ltd.)
・ Calcium carbonate powder (Softon 1800 Bihoku Powder Chemical Co., Ltd.)
・ Alumina powder (A-43M Showa Denko KK)
・ Plasticizer (GR-301 Ito Oil Co., Ltd.)
［比較例１〜２］
比較例１〜２の組成物を調製するために下記成分を準備した。
（Ａ’）成分：（Ａ）成分には入らないプレポリマー
・プレポリマー５
・プレポリマー６
（Ｂ）成分：ポリアミン粉
・ポリアミン粉１
（Ｃ）成分：イソシアネート化合物
・トリレンジイソシアネート（Ｔ−８０ 三井化学ポリウレタン株式会社）
（Ｄ）成分１：エポキシ化合物
・ビスフェノールＦ型エポキシ樹脂（ＪＥＲ８０７ ジャパンエポキシレジン株式会社）
その他：添加剤
・３−グリシドキシプロピルトリメトキシシラン（ＫＢＭ−４０３ 信越化学工業株式会社）
・炭酸カルシウム粉（ソフトン１８００ 備北粉化工業株式会社）
[Comparative Examples 1-2]
In order to prepare the compositions of Comparative Examples 1 and 2, the following components were prepared.
Component (A ′): Prepolymer prepolymer 5 not included in component (A)
・ Prepolymer 6
(B) component: Polyamine powder / polyamine powder 1
Component (C): Isocyanate compound / tolylene diisocyanate (T-80 Mitsui Chemicals Polyurethanes)
(D) Component 1: Epoxy compound / bisphenol F type epoxy resin (JER807 Japan Epoxy Resin Co., Ltd.)
Others: Additive-3-glycidoxypropyltrimethoxysilane (KBM-403 Shin-Etsu Chemical Co., Ltd.)
・ Calcium carbonate powder (Softon 1800 Bihoku Powder Chemical Co., Ltd.)
実施例１〜２２及び比較例１〜２の製造方法は次の通りである。前記（Ａ）成分又は（Ａ’）成分と（Ｂ）成分を秤量して、撹拌機により３０分間撹拌する。（Ｃ）成分、（Ｄ）成分、その他の成分を秤量して撹拌機に添加した後、さらに３０分間撹拌する。詳細な調製量は表１に従い、数値は全て質量部で表記する。撹拌においては真空脱泡しながら撹拌することが好ましい。 The manufacturing method of Examples 1-22 and Comparative Examples 1-2 is as follows. The component (A) or the component (A ′) and the component (B) are weighed and stirred with a stirrer for 30 minutes. (C) Component, (D) component, and other components are weighed and added to a stirrer, and then stirred for another 30 minutes. Detailed preparation amounts follow Table 1, and all numerical values are expressed in parts by mass. In stirring, it is preferable to stir while vacuum degassing.
実施例１〜２２、比較例１〜２の硬化性樹脂組成物に対して以下の試験を実施した。反応性、保存性、硬度の結果を表２に示す。 The following test was implemented with respect to the curable resin composition of Examples 1-22 and Comparative Examples 1-2. Table 2 shows the results of reactivity, storage stability and hardness.
＜反応性の確認＞
カバーガラスの上に１０ｍｍ×１０ｍｍのマスキングをして組成物をスキージして、マスキングを除くと塗膜厚０．３ｍｍの組成物が形成される。８０℃に設定したホットプレートに該カバーガラスを乗せる。組成物が硬化またはゴム状となり流動しなくなるまでの時間を１０秒毎に観察し「ゲルタイム」（秒）とする。ただし、実施例３のみは１５０℃にて確認を行う。
<Confirmation of reactivity>
Masking 10 mm × 10 mm on the cover glass to squeeze the composition, and removing the mask forms a composition with a coating thickness of 0.3 mm. The cover glass is placed on a hot plate set at 80 ° C. The time until the composition becomes hardened or rubbery and does not flow is observed every 10 seconds to be “gel time” (seconds). However, only Example 3 confirms at 150 degreeC.
＜保存性の確認＞
容量２０ｍｌのガラス瓶に各組成物を入れて蓋を閉めた状態で、２５℃に設定した室内に静置する。組成物がゲル化して流動しなくなるまでの日数を１０日毎に観察し「保存安定性」（日）とする。最長で４０日保存性を確認し、４０日以上保存性を確保した組成物には「４０日以上」と表記する。
<Confirmation of storage stability>
Each composition is placed in a glass bottle with a capacity of 20 ml, and the lid is closed, and then left in a room set at 25 ° C. The number of days until the composition gels and no longer flows is observed every 10 days to be “storage stability” (days). The longest 40-day storage stability is confirmed, and “40 days or more” is described for a composition that has secured the storage stability for 40 days or more.
＜硬度の測定＞
組成物を厚み２ｍｍになるように離型処理されたＰＥＴフィルムで挟みこんだ状態で、８０℃にて１０分加熱してシート状の硬化物を作成した。該シート状硬化物を直径２０ｍｍの円盤に打ち抜き、この円盤を気泡が入らないように３枚分重ねる。３枚を１つのテストピースとしてＡ硬度デュロメーターを用いて「硬度」（単位無し）を測定した。詳細についてはＪＩＳＫ６２５３に従う。
<Measurement of hardness>
In a state where the composition was sandwiched between PET films that had been release-treated so as to have a thickness of 2 mm, it was heated at 80 ° C. for 10 minutes to prepare a sheet-like cured product. The sheet-like cured product is punched into a disk having a diameter of 20 mm, and this disk is stacked for three sheets so that no air bubbles enter. “Hardness” (no unit) was measured by using an A hardness durometer with three pieces as one test piece. The details follow JISK6253.
実施例１９を用いて、以下の硬化条件を変えた時の「硬度」を測定した。すべての測定は２５℃にて１０分放置してすぐに測定を行う。以下の結果から加熱硬化単独、加熱硬化と湿気硬化の併用、湿気硬化単独のいずれの条件においても良好なゴム状硬化物を形成することがわかる。
６０℃にて１０分：５５
８０℃にて１０分：６０（前記の硬度測定）
６０℃にて１０分＋２５℃×５５％ＲＨにて３日：６０
８０℃にて３０分：６０
８０℃にて３０分＋２５℃×５５％ＲＨにて３日：６０
２５℃×５５％ＲＨにて７日：６０
Using Example 19, the “hardness” was measured when the following curing conditions were changed. All measurements are taken immediately at 25 ° C. for 10 minutes. From the following results, it can be seen that a favorable rubber-like cured product is formed under any conditions of heat curing alone, combined use of heat curing and moisture curing, and moisture curing alone.
10 minutes at 60 ° C .: 55
10 minutes at 80 ° C .: 60 (the above hardness measurement)
10 days at 60 ° C. + 25 ° C. × 55% RH for 3 days: 60
30 minutes at 80 ° C .: 60
30 days at 80 ° C. + 3 days at 25 ° C. × 55% RH: 60
7 days at 25 ° C. × 55% RH: 60
＜引張せん断接着強さの測定＞
２５ｍｍ×１００ｍｍ×１．６ｍｍの鉄（ＳＰＣＣ）の試験片を使用する。組成物を一方の試験片に塗布して均一に延ばした後、幅方向に２５ｍｍ、長さ方向に１０ｍｍで面一で重ね合わせて、もう一方の試験片を貼り合わせる。治具で固定した状態で８０℃にて１０分加熱してテストピースを作成した。室温に戻った後、接着した試験片を引張り試験器により引張り速度５０ｍｍ／ｍｉｎにて測定し「引張せん断接着強さ」（ＭＰａ）とする。詳細についてはＪＩＳＫ６８５０に従う。
<Measurement of tensile shear bond strength>
A test piece of 25 mm × 100 mm × 1.6 mm iron (SPCC) is used. The composition is applied to one test piece and uniformly spread, and then the other test piece is bonded together by superimposing 25 mm in the width direction and 10 mm in the length direction. A test piece was prepared by heating at 80 ° C. for 10 minutes with the jig fixed. After returning to room temperature, the bonded test piece is measured with a tensile tester at a pulling speed of 50 mm / min to obtain “tensile shear bond strength” (MPa). For details, follow JISK6850.
実施例２０を用いて、鉄以外の材質からなる試験片を用いて引張せん断接着強さを測定した。材質の詳細と併せて、測定結果を表３に示す。この結果から分かる通り、一般的に難接着な材質についても破壊モードが凝集破壊なので、接着剤として有用な接着力を有していることが分かる。 Using Example 20, the tensile shear bond strength was measured using a test piece made of a material other than iron. The measurement results are shown in Table 3 together with details of the materials. As can be seen from these results, it can be seen that even a difficult-to-adhere material has cohesive failure, and therefore has a useful adhesive force as an adhesive.
＜信頼性試験＞
実施例１、実施例１２〜１９、実施例２２、比較例１〜２の各組成物の硬化物に対して、耐熱試験又は耐湿試験を実施した。試験項目は上述の硬度と引張せん断接着強さの２種類の試験を行った。耐熱試験は１３０℃に設定した恒温炉を使用し、耐湿試験は８５℃×８５％ＲＨに設定した恒温恒湿炉を使用し、硬化物を投入してから１４日後に試験を実施する。試験を行う際は、硬化物やテストピースが室温に戻ってから試験を行う。耐熱試験の結果を表４に、耐湿試験の結果を表５にまとめた。表中の「ＮＧ」とは硬化物が脆くなり崩壊してしまうため、測定ができなくなった状態を表す。
<Reliability test>
A heat resistance test or a moisture resistance test was performed on the cured products of the compositions of Example 1, Examples 12 to 19, Example 22, and Comparative Examples 1 and 2. The test items were two kinds of tests, the above-mentioned hardness and tensile shear bond strength. The heat resistance test uses a constant temperature furnace set at 130 ° C., and the humidity resistance test uses a constant temperature and humidity furnace set at 85 ° C. × 85% RH, and the test is carried out 14 days after the cured product is charged. When performing the test, the test is performed after the cured product or test piece has returned to room temperature. The results of the heat resistance test are summarized in Table 4, and the results of the moisture resistance test are summarized in Table 5. “NG” in the table represents a state where the measurement cannot be performed because the cured product becomes brittle and collapses.
表２の実施例１〜２２と比較例１〜２のゲルタイムを比較すると同じ時間で硬化していることから反応性が同じレベルであり、同表の保存安定性を比較すると水素添加ヒマシ油の骨格を有する実施例１〜２２ではアミン粉が表面処理されていなくても保存性が向上している。信頼性試験の耐熱試験と耐湿試験において、比較例１〜２は試験後に硬化物の劣化により測定が出来ない状態まで劣化しているが、実施例１〜２２では測定が可能であると共に初期値とあまり変わらない値を示している。このことから、信頼性試験に於いても本発明の硬化性樹脂組成物が有効である。 When the gel times of Examples 1 to 22 and Comparative Examples 1 and 2 in Table 2 are compared, the reactivity is the same because they are cured in the same time, and the storage stability of the table is compared with that of hydrogenated castor oil. In Examples 1 to 22 having a skeleton, the storage stability is improved even if the amine powder is not surface-treated. In the heat resistance test and the moisture resistance test of the reliability test, Comparative Examples 1 and 2 have deteriorated to a state where they cannot be measured due to deterioration of the cured product after the test, but in Examples 1 to 22, the measurement is possible and the initial value The value is not so different. Therefore, the curable resin composition of the present invention is effective in the reliability test.
本発明は、加熱および／または湿気により短時間で硬化し、広い温度範囲での弾性および耐熱性、耐湿性に優れた硬化型樹脂組成物を与える一液組成物に関するものであり、電気電子分野、輸送機器分野、一般接着等広い分野で接着剤、シール剤、コーティング剤、注型剤等に広く応用が可能なものである。 The present invention relates to a one-component composition that cures in a short time by heating and / or moisture and gives a curable resin composition having excellent elasticity, heat resistance, and moisture resistance in a wide temperature range. It can be widely applied to adhesives, sealants, coating agents, casting agents, etc. in a wide range of fields such as transportation equipment and general adhesion.
Claims (5)
（Ａ）成分：（ａ−１）成分と（ａ−２）成分を反応させて得られる末端にイソシアネート基を有するプレポリマー
（ａ−１）成分：水素添加ヒマシ油系ポリオール
（ａ−２）成分：１分子内に２以上のイソシアネート基を有する化合物
（Ｂ）成分：１分子内に２以上の一級アミン基および／または二級アミン基を有する化合物の粉体 A curable resin composition comprising a component (A) and a component (B).
(A) Component: Prepolymer having an isocyanate group at the terminal obtained by reacting (a-1) component with (a-2) component (a-1) Component: Hydrogenated castor oil-based polyol (a-2) Component: Compound (B) having two or more isocyanate groups in one molecule Component: Powder of a compound having two or more primary amine groups and / or secondary amine groups in one molecule
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| JP2012201813A (en) * | 2011-03-25 | 2012-10-22 | Dainichiseika Color & Chem Mfg Co Ltd | Single component adhesive composition and assembly containing the composition as adhesive layer |
| JP2016014079A (en) * | 2014-06-30 | 2016-01-28 | 横浜ゴム株式会社 | Heat-curable composition |
| WO2016076193A1 (en) * | 2014-11-13 | 2016-05-19 | 横浜ゴム株式会社 | Curable resin composition |
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