CN102143987B - Heat-cured epoxy resin composition - Google Patents
Heat-cured epoxy resin composition Download PDFInfo
- Publication number
- CN102143987B CN102143987B CN2009801344808A CN200980134480A CN102143987B CN 102143987 B CN102143987 B CN 102143987B CN 2009801344808 A CN2009801344808 A CN 2009801344808A CN 200980134480 A CN200980134480 A CN 200980134480A CN 102143987 B CN102143987 B CN 102143987B
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- China
- Prior art keywords
- compound
- formula
- represented
- epoxy
- aromatic polyamine
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 48
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 159
- 125000003118 aryl group Chemical group 0.000 claims abstract description 84
- 229920000768 polyamine Polymers 0.000 claims abstract description 67
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 239000003094 microcapsule Substances 0.000 claims description 55
- 239000004593 Epoxy Substances 0.000 claims description 51
- 229920005989 resin Polymers 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 48
- -1 aromatic hydrocarbyl Chemical group 0.000 claims description 47
- 238000001879 gelation Methods 0.000 claims description 31
- 125000001118 alkylidene group Chemical group 0.000 claims description 20
- 229920005992 thermoplastic resin Polymers 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 3
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 claims description 3
- ZLSQGKSGBJSCCT-UHFFFAOYSA-N 2-(9h-fluoren-1-yl)aniline Chemical class NC1=CC=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 ZLSQGKSGBJSCCT-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 89
- 239000007788 liquid Substances 0.000 description 31
- 238000005538 encapsulation Methods 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000011257 shell material Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 11
- 230000007704 transition Effects 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 239000013034 phenoxy resin Substances 0.000 description 8
- 229920006287 phenoxy resin Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- 239000011354 acetal resin Substances 0.000 description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000006837 decompression Effects 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 239000011115 styrene butadiene Substances 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 5
- 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 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 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
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- ZBCATMYQYDCTIZ-UHFFFAOYSA-N 4-methylcatechol Chemical compound CC1=CC=C(O)C(O)=C1 ZBCATMYQYDCTIZ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- GMKSMTJXIGEYLX-UHFFFAOYSA-N n,n'-bis(2-ethyl-6-methylphenyl)methanediamine Chemical compound CCC1=CC=CC(C)=C1NCNC1=C(C)C=CC=C1CC GMKSMTJXIGEYLX-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003553 thiiranes Chemical group 0.000 description 2
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 2
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- 125000006839 xylylene group Chemical group 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- FQCJGOFQLJELIV-UHFFFAOYSA-N 1-(azetidin-1-yl)prop-2-en-1-one Chemical compound C=CC(=O)N1CCC1 FQCJGOFQLJELIV-UHFFFAOYSA-N 0.000 description 1
- KAJBSGLXSREIHP-UHFFFAOYSA-N 2,2-bis[(2-sulfanylacetyl)oxymethyl]butyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(CC)(COC(=O)CS)COC(=O)CS KAJBSGLXSREIHP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HWRRQRKPNKYPBW-UHFFFAOYSA-N 2,4-dimethylcyclohexan-1-amine Chemical compound CC1CCC(N)C(C)C1 HWRRQRKPNKYPBW-UHFFFAOYSA-N 0.000 description 1
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- NTYQWXQLHWROSQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2,2,2-tris(sulfanyl)acetic acid Chemical compound OC(=O)C(S)(S)S.CCC(CO)(CO)CO NTYQWXQLHWROSQ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
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- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
Provided is a heat-cured epoxy resin composition with excellent curing properties. The heat-cured epoxy resin composition contains an epoxy resin (A), an aromatic polyamine compound (B), and a compound represented by formula (I), and is characterized in that the gelling time is no more than 3 min at 150 C. In the formula, R1 and R2 represent a hydrogen atom and an alkyl group, respectively.
Description
Technical field
The present invention relates to heat-curable epoxy resin composition.
Background technology
The composition that aromatic diamine compound is used as epoxy curing agent can obtain the high cured article of second-order transition temperature.
The applicant disclosed a kind of fine properties and 2 fast liquid type curable resin compositions of the curing speed below the room temperature that contain the 1st liquid of Resins, epoxy at patent documentation 1 in the past.
In addition, also disclose the composition epoxy resin (with reference to patent documentation 2) that contains curable epoxy resin, hardener for epoxy resin and three (4-aminomethyl phenyl) phosphine triphenylborane.
In addition, when triphenylphosphine is used with respect to the phenolic resinoid as epoxy curing agent, can shorten the set time of composition as can be known.
Patent documentation 1: the spy opens the 2007-326906 communique
Patent documentation 2: the spy opens the 2006-290946 communique
Summary of the invention
Yet, when in Resins, epoxy, using aromatic diamine compound as solidifying agent, be present in condition following set time of the elongated shortcoming of 80～250 ℃ of solidification values.
In addition, the application's inventor finds: for the phenolic resinoid as epoxy curing agent, can't shorten set time when using triphenylphosphine as curing catalyst.
And, the application's inventor also finds: for the phenolic resinoid as epoxy curing agent, the situation of the composition epoxy resin of triphenylphosphine triphenylborane or three (4-aminomethyl phenyl) the phosphine triphenylborane of using as curing catalyst when triphenylphosphine is used with respect to the phenolic resinoid as epoxy curing agent is identical, and understand elongated set time (gelation time).
Therefore, the object of the present invention is to provide the good composition epoxy resin of a kind of solidified nature.
This case contriver has carried out conscientiously research in order to solve above-mentioned problem, found that: to the aromatic diamine compound as epoxy curing agent, when using the compound that following formula I represents as curing catalyst, can form the composition that set time is short and solidified nature is good, finish the present invention thus.
(in the formula, R
1, R
2Represent hydrogen atom or alkyl respectively.）
Namely, the invention provides a kind of heat-curable epoxy resin compound, the compound that this heat-curable epoxy resin composition contains Resins, epoxy (A), aromatic polyamine compound (B) and represented by following formula I is characterized in that: be in 3 minutes at gelation time under 150 ℃ the temperature.
(in the formula, R
1, R
2Represent hydrogen atom or alkyl respectively.）
Heat-curable epoxy resin composition solidified nature of the present invention is good.
Embodiment
Below, the present invention is described in detail.
Heat-curable epoxy resin composition of the present invention, this heat-curable epoxy resin composition contains the compound that Resins, epoxy (A), aromatic polyamine compound (B) and following formula I are represented, it is characterized in that: be in 3 minutes at gelation time under 150 ℃ the temperature.
(in the formula, R
1, R
2Represent hydrogen atom or alkyl respectively.）
Below, heat-curable epoxy resin composition of the present invention is called " present composition ".
Below Resins, epoxy (A) is described.
For the Resins, epoxy (A) that composition of the present invention contains, as long as have the compound of plural epoxy group(ing), just there is no particular limitation.For example, can enumerate known Resins, epoxy in the past.Specifically, for example bisphenol A type epoxy resin, dicyclopentadiene-type epoxy resin, diaminodiphenyl-methane type Resins, epoxy, amino-benzene phenol-type epoxy resin, naphthalene type Resins, epoxy, phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, hydrogenation biphenyl type epoxy resin.
Resins, epoxy (A) may be used singly or in combination of two or more.
Below aromatic polyamine compound (B) is described.
The aromatic polyamine compound (B) that the present composition contains is for there being compound amino more than two at bonding on the aromatic hydrocarbyl.
In the present invention, aromatic polyamine compound (B) uses as solidifying agent.Aromatic polyamine compound (B) can react with Resins, epoxy (A).
When composition of the present invention contained aromatic series Neither thiirane compound (C), aromatic polyamine compound (B) can react with Resins, epoxy (A) and aromatic series Neither thiirane compound (C).
When composition of the present invention contains aromatic series Neither thiirane compound (C), aromatic series Neither thiirane compound (C) preferential reaction in aromatic polyamine compound (B) and the present composition and generate the NH base.The NH base that generates can react with Resins, epoxy (A).The amino that aromatic polyamine compound (B) has sometimes also with Resins, epoxy (A) direct reaction.
There is no particular limitation to aromatic hydrocarbyl.Aromatic hydrocarbyl can have substituting group.As substituting group, for example can enumerate alkyl, alkoxyl group.Aromatic hydrocarbyl can have the heteroatoms as Sauerstoffatom, nitrogen-atoms, sulphur atom etc.
As aromatic hydrocarbyl, for example can enumerate the group of being represented by following formula.
In the formula, R
2For being selected from least a in the group of being formed by alkylidene group, aromatic hydrocarbyl, fluorenyl, ether and sulfenyl.
As alkylidene group, for example can enumerate methylene radical, ethylidene.
R
2For being selected from least two kinds in the group of being formed by alkylidene group, aromatic hydrocarbyl, fluorenyl, ether and sulfenyl.
Consider that for the aspect that solidified nature is better optimization aromatic polyamine compounds (B) is aromatic diamine.Aromatic diamine compound is the compound that bonding has two amino on aromatic hydrocarbyl.
As aromatic polyamine compound (B), for example can enumerate the compound of being represented by formula II.Two amino bondeds are on phenyl ring in formula II.
[in the formula II, R
3, R
4Be respectively alkyl, R
5For being selected from least a in the group of being made up of alkylidene group, aromatic hydrocarbyl, fluorenyl, ether and sulfenyl, m, n are respectively 0～4 integer.]
Substituting group as the aromatic polyamine compound of being represented by formula II can have R
3, R
4
Can enumerate the alkyl of carbonatoms 1～6 as alkyl.For example, can enumerate methyl, ethyl, propyl group.Consider preferable methyl, ethyl for package stability, the better aspect of rapidly-curable.
Can enumerate the alkylidene group of carbonatoms 1～6 as alkylidene group.For example, can enumerate methylene radical and ethylidene.
Consider that for package stability, the better aspect of rapidly-curable preferred m, n are respectively 0～2 integer.
Consider that for package stability, the better aspect of rapidly-curable preferred amino is configured in R
5Contraposition.
For aromatic hydrocarbyl, as long as it is two valencys, there is no particular limitation.Aromatic hydrocarbyl can have the substituting group as methyl etc.
If aromatic hydrocarbyl and alkylidene group are made up, then there is no particular limitation to the combination of aromatic hydrocarbons and alkylidene group.For example, can enumerate the alkylidene group with aromatic hydrocarbyl.Specifically, for example, can enumerate following situation: the situation when two alkylidene groups carry out bonding by aromatic hydrocarbons; The situation that aromatic hydrocarbons is arranged as the side chain bonding of alkylidene group; Behind aromatic hydrocarbyl and the alkylidene group bonding, aromatic hydrocarbyl and alkylidene group respectively with the situation of bonding mutually of two phenyl ring shown in the formula II.As aromatic hydrocarbons, for example can enumerate phenyl ring, naphthalene.Aromatic hydrocarbons can have the substituting group as methyl etc.
As aromatic polyamine compound (B), for example, can enumerate compound, the methylene-bis (2-ethyl-6-monomethylaniline) of following formula (4) expression.
In the formula, R
2For being selected from by alkylidene group, aromatic hydrocarbyl, fluorenyl, ether
At least a in the group of forming with sulfenyl.
Aspect better for solidified nature and that package stability is better considers that optimization aromatic polyamine compounds (B) is compound, the methylene-bis (2-ethyl-6-monomethylaniline) by formula (4) expression.
Wherein, consider for the aspect that solidified nature is better that preferred R2 is alkylidene group, carboxyl, fluorenyl, more preferably methylene radical, carbonyl, fluorenyl.
In addition, when the present composition contains aromatic series Neither thiirane compound (C), consider preferred R for the aspect that solidified nature is better
2Be alkylidene group, carbonyl, fluorenyl, more preferably methylene radical, carbonyl.
Aromatic polyamine compound (B) can use separately, also can be used in combination.
There is no particular limitation to its manufacturing for aromatic polyamine compound (B).(B) can use commercially available product as the aromatic polyamine compound.
The aspect that second-order transition temperature (glass transition point) better for solidified nature and cured article is high is considered, the epoxy group(ing) that has with respect to Resins, epoxy (A), the equivalents of the active hydrogen that optimization aromatic polyamine compounds (B) has is 0.5～2.5 equivalent, more preferably 0.7～2.0 equivalent.
In addition, in aromatic polyamine compound (B), comprise amino as the group that contains active hydrogen.Each nitrogen-atoms has two active hydrogens in the amino.
Below the represented compound of formula I is described.
In the present composition, the compound that formula I is represented promotes auxiliary agent (when the present composition further contains aromatic series Neither thiirane compound (C), promoting auxiliary agent as solidifying) to use as curing catalyst or curing.
Compound that the present composition contains, that formula I is represented has following structure.
In the formula, R
1, R
2Represent hydrogen atom or alkyl respectively.
R
1Expression hydrogen atom, alkyl.R
2Expression hydrogen atom, alkyl.
R
1, R
2Can be identical also can be inequality.A plurality of R
1Can be identical also can be inequality.A plurality of R
2Can be identical also can be inequality.
Aspect better for solidified nature and that second-order transition temperature is high considers that the carbonatoms of preferred alkyl is 1～6, more preferably 1～3.As alkyl, specifically, for example can enumerate methyl, ethyl, propyl group.
As the compound that formula I is represented, for example can enumerate the compound of formula (1) expression, the compound of formula (2) expression.
In the formula, Ph represents phenyl or phenylene.Wherein, Ph is phenylene among the Me-Ph-of formula (2).
In the present composition, and aspect that glass transformation temperature high better for solidified nature consider, as the compound that formula I is represented, and the compound of the compound of preferred formula (1) expression and/or formula (2) expression.
Below the compound of formula (1) expression, the compound of formula (2) expression are described.
In the present composition, the compound of the compound of formula (1) expression or formula (2) expression promotes auxiliary agent (when also containing aromatic series Neither thiirane compound (C) in the present composition, promoting auxiliary agent as solidifying) to use as curing catalyst or curing.
The compound name of formula (1) expression is called triphenylphosphine triphenyl-boron acid esters, is referred to as " TPP-S " in present specification sometimes.
The compound name of formula (2) expression is called three p-methylphenyl phosphine triphenyl-boron acid esters, is referred to as " TPTP-S " in present specification sometimes.In the formula (2), the methyl enterprising line unit in any position in ortho position, a position, contraposition respectively closes.
There is no particular limitation to its manufacturing for the compound that formula I is represented.
There is no particular limitation to its manufacturing for the compound of formula (1) expression.The compound of formula (1) expression can use commercially available product.The compound of formula (2) expression also can use commercially available product equally.
The compound that formula I is represented may be used singly or in combination of two or more.
The aspect that glass transformation temperature better for solidified nature and cured article is high considers that with respect to the Resins, epoxy (A) of 100 mass parts, the compound amount that formula I is represented is preferably 1～30 mass parts, more preferably 3～10 mass parts.
In the present invention, the aspect that glass transformation temperature better for solidified nature and cured article is high is considered, the epoxy group(ing) that has with respect to Resins, epoxy (A), the equivalents of the active hydrogen that aromatic polyamine compound (B) has is 0.5～2.5 equivalent, with respect to the Resins, epoxy (A) of 100 mass parts, the compound amount that formula I is represented is preferably 1～30 mass parts.
Below microcapsule are described.
In the present composition, in the compound that above-mentioned formula I is represented and the above-mentioned aromatic polyamine compound any one or both all are included in the composition in the mode of the microcapsule that wrapped in the thermoplastic resin, therefore can form 1 better liquid type composition of package stability when keeping rapidly-curable.
Microcapsule of the present invention have compound that above-mentioned formula I represents and any one or both in the above-mentioned aromatic polyamine compound as nuclear, and have thermoplastic resin as shell.
Considered by the aspect of micro encapsulation that easily compound or the state of aromatic polyamine compound under 25～70 ℃ temperature that preferred formula I is represented are solid (perhaps fusing point is above 70 ℃) during for the manufacturing microcapsule.Consider compound, aromatic diamine that preferred microcapsule nuclear is represented for formula I for the aspect of carrying out micro encapsulation easily.
When if the compound that formula I is represented and aromatic polyamine compound all are included in composition in the mode of the microcapsule that wrapped in the thermoplastic resin, the present composition can contain the microcapsule that microcapsule that compound that formula I represents wrapped in the thermoplastic resin and aromatic polyamine compound are wrapped in the thermoplastic resin.In addition, in microcapsule also can in be surrounded by compound and the aromatic polyamine compound that formula I is represented.
There is no particular limitation for the thermoplastic resin that uses as shell.For example, can enumerate urethane resin; The styrene butadiene elastomerics; Polyvinyl acetal resin; Phenoxy resin; Plexiglass; Polyvinyl alcohol; (methyl) acrylic monomer, for example, carbonatomss such as acrylate, itaconic ester, crotonate are part or all monomer that is all replaced by allyl group etc. of the alkyl hydrogen atom of 1～8 alkyl ester or this alkyl ester; The polymkeric substance that obtains from following monomer: the simple function monomer of vinylbenzene, alpha-methyl styrene, vinyl cyanide, methacrylonitrile, vinyl acetate etc.; And the polyfunctional monomer of ethylene glycol (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, Vinylstyrene, dihydroxyphenyl propane two (methyl) acrylate, methylene-bis (methyl) acrylamide etc.
Thermoplastic resin may be used singly or in combination of two or more.
Wherein, better for package stability and rapidly-curable, make film and physical strength is good and the aspect that can keep the second-order transition temperature of resulting cured article considers that thermoplastic resin is preferably selected from least a resin in the group of being made up of urethane resin, styrene butadiene elastomerics, polyvinyl acetal resin, polyvinyl alcohol and phenoxy resin.
For urethane resin, as long as it is the compound with amino-formate bond, there is no particular limitation.For example, can enumerate the compound that compound that compound that compound that the reaction by polyvalent isocyanate and polynary amine obtains, the reaction by polyvalent isocyanate and water obtain, the reaction by polyvalent isocyanate and polyvalent alcohol obtain, the reaction by polyvalent isocyanate, polynary amine and polyvalent alcohol obtain.
Employed polyvalent isocyanate class during for the manufacturing urethane resin gets final product so long as intramolecularly has the compound of two above isocyanate group.Specifically, for example, can enumerate m-phenylene diisocyanate, right-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,4-disocyanate, ditan-4,4 '-vulcabond, 3,3 '-dimethoxy-4 ', 4 '-biphenyl diisocyanate, 3,3 '-dimethyl diphenylmethane-4,4 '-vulcabond, 4,4 '-dimethyl diphenylmethane-2,2 ', 5,5 '-aromatic poly-isocyanate of tetraisocyanate etc.; Have xylylene-1, bonding has the polymeric polyisocyanate of isocyanate group on the alkylidene group of aromatic hydrocarbonss such as aromatic hydrocarbyl such as 4-vulcabond; Trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-vulcabond, butene-1, the aliphatic polymeric isocyanate of 2-vulcabond, Methionin isocyanic ester etc.; Cyclohexylene-1, cyclohexylidene-1, the ester ring type polymeric polyisocyanate of 4-vulcabond etc.; The affixture of affixture, hexamethylene diisocyanate and the TriMethylolPropane(TMP) of the affixture of the affixture of the affixture of the affixture of hexamethylene diisocyanate and hexanetriol, 2,4 toluene diisocyanate and pyrocatechol, tolylene diisocyanate and hexanetriol, tolylene diisocyanate and TriMethylolPropane(TMP), xylylene vulcabond and TriMethylolPropane(TMP).
Wherein, better and make film and the good aspect of physical strength is considered for package stability and rapidly-curable, preferred tolylene diisocyanate, 4,4 '-aromatic poly-isocyanate of diphenylmethanediisocyanate, right-phenylene diisocyanate, xylylene vulcabond etc.
The polyvalent isocyanate class may be used singly or in combination of two or more.
Employed polynary amine during for the manufacturing urethane resin has compound amino more than two as long as it is intramolecularly.Specifically, for example, can enumerate diethylenetriamine, Triethylenetetramine (TETA), tetren, 1,6-hexamethylene-diamine, 1,8-eight methylene diamine, 1, aliphatic polyamines such as 12-ten dimethylene diamines; At the aromatic polyamine with O-Phenylene Diamine, mphenylenediamine, Ursol D etc.; Bonding has amino polyamines on the alkylidene group with aromatic hydrocarbyls such as o-Xylol diamines, m-xylene diamine, o-Xylol diamines; Menthane diamines, two (4-amino-3-methyl cyclohexyl) methane, isophorone diamine, 1, ester ring type polyamines such as 3-cyclohexanediamine; Volution acetals diamines.
The polyamines class may be used singly or in combination of two or more.
Employed polyvalent alcohol when using urethane resin, can for aliphatics, aromatic series or alicyclic in any.For example, can enumerate pyrocatechol, Resorcinol, 1,2-dihydroxyl-4-methylbenzene, 1,3-dihydroxyl-5-methylbenzene, 3,4-dihydroxyl-1-methylbenzene, 3,5-dihydroxyl-1-methylbenzene, 2,4-dihydroxy ethyl benzene, 1,3-naphthalene glycol, 1,5-naphthalene glycol, 2,7-naphthalene glycol, 2,3-naphthalene glycol, o, o '-xenol, p, p '-xenol, dihydroxyphenyl propane, two (2-hydroxyphenyl) methane, xylyl alcohol, ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,1,1-TriMethylolPropane(TMP), hexanetriol, tetramethylolmethane, glycerine, sorb (sugar) alcohol etc.
Polyvalent alcohol may be used singly or in combination of two or more.
There is no particular limitation for the styrene butadiene elastomerics.For example, can use known elastomerics in the past.
Consider that for package stability, the better aspect of rapidly-curable the elastomeric weight-average molecular weight of styrene butadiene is preferably 12,000～50,000.
Among the present invention, weight-average molecular weight is by being the weight-average molecular weight that the gel permeation chromatograph (GPC) of solvent is converted into polystyrene with the tetrahydrofuran (THF).
There is no particular limitation for polyvinyl acetal resin.For example, can enumerate vinyl-formal resin, polyvinyl butyral resin.
Consider that the weight-average molecular weight of polyvinyl acetal resin is preferably 10,000～60,000 for package stability, the better aspect of rapidly-curable.
There is no particular limitation for polyvinyl alcohol.For example can enumerate known polyvinyl alcohol in the past.Consider that the weight-average molecular weight of polyvinyl alcohol is preferably 10,000～150,000 for package stability, the better aspect of rapidly-curable.
There is no particular limitation for phenoxy resin.For example, its be selected from dihydroxyphenyl propane and/or Bisphenol F, molecular weight is the high molecular expoxy resin more than 10,000.
Manufacturing for microcapsule has no particular limits.For example, can enumerate known manufacture method in the past.
Microcapsule can use separately maybe and can be used in combination.
Wherein, consider the microcapsule of the compound of preferred enwraped type (I) expression for package stability, the better aspect of rapidly-curable.
In addition, better and make film and the better aspect of physical strength is considered for package stability and rapidly-curable, preferably contain at least a microcapsule that are selected from the group of being formed by urethane resin, styrene butadiene elastomerics, polyvinyl acetal resin, polyvinyl alcohol resin and phenoxy resin as shell material.
Among the present invention, composition comprises when containing the microcapsule of the compound that formula I represents as nuclear, and the aromatic polyamine compound can be by micro encapsulation, perhaps also can be not by micro encapsulation.
In addition, composition comprises when containing the microcapsule of aromatic polyamine compound as nuclear, and the compound that formula I is represented can be by micro encapsulation, perhaps also can be not by micro encapsulation.
The thermoplastic resin of microcapsule is better as the second-order transition temperature of resulting cured articles such as Resins, epoxy and package stability and rapidly-curable for keeping, make film and the better aspect of physical strength considers that preferred thermoplastic resin is 1～20 mass parts of whole composition.
Consider that for package stability, the better aspect of rapidly-curable the median size of microcapsule (diameter) is preferably 0.1～50(unit: micron).Median size of the present invention utilizes particle size distribution measurement device SALD-7100(Shimadzu Scisakusho Ltd to make) measure.
Better and make film and the good aspect of physical strength considers that the thickness of microcapsule mesochite is preferably 0.01～10(unit for package stability and rapidly-curable: micron).Thickness of the shell of the present invention utilizes particle size distribution measurement device SALD-7100(Shimano Inc to make manufacturing) measure.
Composition of the present invention can also comprise aromatic series Neither thiirane compound (C).
The aromatic series Neither thiirane compound (C) that the present composition can contain is the aromatic hydrocarbon compound with thiiranes group and aromatic hydrocarbyl.
Aromatic series Neither thiirane compound (C) can be used as curing catalyst and uses among the present invention.In addition, aromatic series Neither thiirane compound of the present invention (C) can be used by instead of part aromatic polyamine compound (B).
Aromatic series Neither thiirane compound (C) generates the SH base with aromatic polyamine compound (B) reaction.The SH base that generates can react with Resins, epoxy (A).
There is no particular limitation for aromatic hydrocarbyl that aromatic series Neither thiirane compound (C) has.For example, can enumerate phenyl, naphthyl.Aromatic hydrocarbyl can have substituting group.As substituting group, for example can enumerate alkyl, alkoxyl group, cycloalkyl, aryl.Aromatic hydrocarbyl can have as heteroatomss such as Sauerstoffatom, nitrogen-atoms, sulphur atoms.
In the aromatic series Neither thiirane compound (C), thiiranes group and aromatic hydrocarbyl carry out bonding by organic radical.
Organic radical is can have as heteroatomic alkyl such as Sauerstoffatom, nitrogen-atoms, sulphur atoms.There is no particular limitation to alkyl.
As organic radical, for example can enumerate-O-CH
2-,-O-CH
2-CH=CH-,-O-CO-CH
2-.
Amount for aromatic series Neither thiirane compound (C), consider for the aspect that solidified nature is better, the epoxy group(ing) that has with respect to described Resins, epoxy (A), the equivalents of the SH base that is generated by aromatic series Neither thiirane compound (C) is preferably 0.3～1.0, and more preferably 0.4～0.7.
In the present composition, except Resins, epoxy (A), aromatic polyamine compound (B), compound that formula I is represented, the aromatic series Neither thiirane compound (C) that can use as required, can also contain additive as required.
In the present composition, except the compound of the compound of Resins, epoxy (A), aromatic polyamine compound (B), aromatic series Neither thiirane compound (C) and formula (1) expression and/or formula (2) expression, can also contain additive as required.
As additive, for example, can enumerate aromatic polyamine compound (B) solidifying agent, weighting agent (filler), reactive diluent, softening agent, thixotropy imparting agent, pigment, dyestuff, antiaging agent, antioxidant, antistatic agent, fire retardant, tackifier, dispersion agent, solvent in addition.
As heat-curable epoxy resin composition of the present invention, for example, can enumerate 1 liquid type heat-curable epoxy resin composition, 2 liquid type heat-curable epoxy resin compositions.Among the present invention, sometimes " 1 liquid type heat-curable epoxy resin composition " is recited as " 1 liquid type ", " 2 liquid type heat-curable epoxy resin composition " is recited as " 2 liquid type ".
There is no particular limitation to its manufacture method for the present composition.For example, under decompression or nitrogen environment, compound and additive that the abundant mixing Resins, epoxy of whipping appts (A), aromatic polyamine compound (B), formula I such as employing mixing and blending machine are represented, so that its even dispersion can produce the present composition as 1 liquid type composition thus.
In addition, for example, under decompression or nitrogen environment, can adopt the compound of the compound of the abundant mixing Resins, epoxy of whipping appts (A) such as mixing and blending machine, aromatic polyamine compound (B), formula (1) expression and/or formula (2) expression and operable additive as required, so that its even dispersion produces the present composition as 1 liquid type composition thus.
In the present composition, even be wrapped under the situation of microcapsule in the compound that formula I is represented and/or the solidifying agent quilt, also there is no particular limitation to its manufacturing.When the compound of microcapsule enwraped type (I) expression, for example, under decompression or nitrogen environment, microcapsule, the solidifying agent of the compound of the fully mixed Resins, epoxy of whipping appts such as employing mixing and blending machine, enwraped type (I) expression and the additive that can use as required can produce the present composition as 1 liquid type composition thus.In addition, when wrapping solidifying agent in the microcapsule, for example, under decompression or nitrogen environment, adopt the fully mixed Resins, epoxy of whipping appts, the compound that formula I is represented, the microcapsule of interior bag solidifying agent and the additives that can use as required such as mixing and blending machine, can produce the present composition as 1 liquid type composition thus.
In the present composition, when being wrapped in microcapsule in compound that formula I is represented and/or the solidifying agent, consider for the aspect that package stability is better, with respect to initial stage viscosity, the viscosity rate of rise is below 10% after placing 24 hours under 25 ℃ of conditions, thereby preferred.Viscosity is the value that adopts E type viscometer VISCONIC EHD type (Toki Sangyo Co., Ltd.'s manufacturing) to measure under 25 ℃ temperature.
Be wrapped under the situation of microcapsule fine properties and can be under room temperature (20～30 ℃) preserving for a long time in the compound that formula I is represented in the present composition and/or the solidifying agent.
When the present composition was 1 liquid type, on-the-spot operation was good.
When the present composition was 2 liquid types, there is no particular limitation to its manufacturing.For example, can produce comprise the 1st liquid (host) that contains Resins, epoxy (A) and contain the compound that aromatic polyamine compound (B), formula I represent the 2nd liquid (solidifying agent), as the present composition of 2 liquid type compositions.Additive can add in the 1st liquid and/or the 2nd liquid.Under decompression or nitrogen environment, whipping apptss such as employing mixing and blending machine carry out fully mixing, so that its even dispersion can produce the 1st liquid and the 2nd liquid respectively thus.
In addition, for example, can produce comprise the 1st liquid (host) that contains Resins, epoxy (A) and contain the compound of aromatic polyamine compound (B), formula (1) expression and/or the 2nd liquid (solidifying agent) of the compound of formula (2) expression, as the present composition of 2 liquid type compositions.Additive can add in the 1st liquid and/or the 2nd liquid.Under decompression or nitrogen environment, whipping apptss such as employing mixing and blending machine carry out fully mixing, so that its even dispersion can produce the 1st liquid and the 2nd liquid respectively thus.
When the present composition is 2 liquid types, fine properties, thereby preferred.
Among the present invention, under 150 ℃ temperature, the gelation time of heat-curable epoxy resin composition (gelation time) is in 3 minutes (180 seconds).Be preferably in 60 seconds at the gelation time under 150 ℃ the temperature, in more preferably 50 seconds.
Gelation time among the present invention (gelation time) can be measured by JIS C2161:1997 standard method or peace field formula gelation time tester.
The present composition for example can be used for binding agent, coating, civil construction, electric, conveyor, medical treatment, packing, fiber, Leisure Sport.
As the adherend that can be suitable for the present composition, for example, can enumerate metal, glass, plastics, mortar, cement, rubber, timber, skin, cloth, paper etc.
There is no particular limitation for composition of the present invention being paid method to adherend.For example, can enumerate known method in the past.
The aspect that second-order transition temperature better for solidified nature, cured article is high considers that the temperature the when present composition is cured is preferably 100～250 ℃, more preferably 120～200 ℃.
Embodiment
Below, be specifically described by the present invention of embodiment.Yet the present invention is not limited to these embodiment.
1. estimate
For the composition epoxy resin that obtains by following manner, the method shown in utilization is following is estimated gelation time, second-order transition temperature.Its result is illustrated in the 1st table, the 2nd table.
(1) gelation time
During the evaluation of being cured property, utilize peace field formula gelation time tester (doing manufacturing, No.153 gelation time tester by Co., Ltd.'s smart mechanism in peace field), under 150 ℃ temperature, measure gelation time.
Peace field formula gelation time tester is following apparatus: in the developmental tube internal rotation rotor that adds test portion, if the required fixed torque of gelation is had an effect, then rotor falls and makes timer to stop by magnetic shaft coupling mechanism in oil bath.
(2) second-order transition temperature
To in 150 ℃ baking oven, carry out 1 hour curing by the composition epoxy resin that following manner obtains, then under the condition of distortion 0.01%, frequency 10Hz, 5 ℃/min of heat-up rate, cured article is carried out the measurement of dynamic viscous-elastic behaviour (Dynamic Mechanical Analysis), and in the temperature province of room temperature to 200 ℃, force stretching vibration to store Young's modulus (G ') to measure.
2. the manufacturing of composition epoxy resin
Composition shown in following the 1st table, the 2nd table is mixed according to the amount (mass parts) shown in this table, produce composition epoxy resin thus.
[table 1]
[table 2]
The details of each composition is as follows in the 1st table and the 2nd table.
Resins, epoxy (A): EP4100E(is made by ADEKA company), bisphenol A type epoxy resin, epoxy equivalent (weight) be 188g/mol
Aromatic polyamine compound (B) 1: the compound that following formula is represented, made by Tokyo HuaCheng Industry Co., Ltd
Aromatic polyamine compound (B) 3: two (aminophenyl) fluorenes that following formula is represented, made by JFE KCC
Aromatic polyamine compound (B) 4: the methylene-bis that following formula is represented (2-ethyl-6-monomethylaniline), (commodity are called カ ヤ Ha one De MED, are made by IHARA chemical industry Co., Ltd.)
Compound 1 shown in the formula I: the compound of following formula (1) expression, made by Hokko Chemical Industry Co., Ltd.
Compound 2 shown in the formula I: the compound of following formula (2) expression, made by Hokko Chemical Industry Co., Ltd.
TPP: make, promote auxiliary agent to use as solidifying by Tokyo HuaCheng Industry Co., Ltd
Fatty amine: the compound that following formula is represented, commodity DMP-30 by name, Tokyo HuaCheng Industry Co., Ltd make
Amine latent curing agent: PN23J(is made by aginomoto Fine-Techno Co., Ltd.)
Novolac resin solidifying agent: MEH-8000H(is by bright and change into Co., Ltd. and make)
Aralkyl phenolic resin curative: MEH-7800S(is by bright and change into Co., Ltd. and make)
Anhydride curing agent: リ カ シ ッ De MT-500(is made by New Japan Chem Co., Ltd)
From the result shown in the 1st table, the 2nd table as can be known, do not contain in the comparative example I-1 of the compound that formula I represents, gelation time surpasses 3 minutes and solidified nature is bad, second-order transition temperature is low under 150 ℃ temperature.Do not contain in the comparative example I-5 of the compound that formula I represents, under 150 ℃ temperature gelation time surpass 3 minutes and solidified nature bad.In addition, do not contain the compound that formula I represents and contain in the comparative example I-2～4 of other curing catalysts (TPP, fatty amine, amine latent curing agent), gelation time surpasses 3 minutes and solidified nature is bad, second-order transition temperature is low under 150 ℃ temperature.Do not contain the compound that formula I represents and contain in the comparative example I-6～8 of other curing catalysts (TPP, fatty amine, amine latent curing agent), under 150 ℃ temperature gelation time surpass 3 minutes and solidified nature bad.To using as the phenolic resinoid of epoxy curing agent in the comparative example I-9 of triphenylphosphine, the gelation time under 150 ℃ of temperature surpass 3 minutes and solidified nature bad.And, comprise comparative example I-compound that 10～11(formula I is represented and the combination of phenolic resinoid of the phenolic resinoid solidifying agent that contains the compound that formula I represents), contain the comparative example I-12 of acid anhydride type curing agent, itself and comparative example I-9 are same, the gelation time under 150 ℃ of temperature surpass 3 minutes and solidified nature bad.
With respect to this, in embodiment I-1～13, the gelation time under 150 ℃ of temperature be 120 seconds with interior, solidified nature is good and the second-order transition temperature height of resulting cured article.In detail, in embodiment I-1～13, no matter whether contain aromatic polyamine, can under 120～200 ℃ condition, be cured, and set time is short.That is, heat-curable epoxy resin composition of the present invention with contain Resins, epoxy and composition epoxy resin aromatic polyamine, in the past is compared, curability at low temperatures is good.
3. estimate
The composition that obtains by following manner is estimated gelation time, viscosity, viscosity rate of rise by the following method.Its result is illustrated in the 3rd table～the 7 table.
(1) gelation time (rapidly-curable)
The solidified nature evaluation is according to JIS C2161:1997 regulation, measures gelation time under 150 ℃ of temperature at hot-plate.Specifically, place the composition epoxy resin that 0.1g obtains by following manner at hot plate, and stir with 60 ± 5 times/minute speed, and will be made as gelation time (gelation time) from the time (integral body can't stir the degree that maybe can't adhere to needle point) that begins to estimate the composition gel.
(2) viscosity
Under 25 ℃ condition, use E type viscometer VISCONIC EHD type (being made by Toki Sangyo Co., Ltd.) to measure initial stage viscosity.
In addition, under 25 ℃ condition, will in thermostatic bath, preserve 24 hours by the composition that following manner obtains, measure composition viscosity (viscosity after the preservation) by the mode identical with measuring initial stage viscosity then.
(3) viscosity rate of rise (package stability)
Viscosity number after resulting initial stage viscosity and the preservation is updated to following formula to calculate the viscosity rate of rise.
Viscosity rate of rise (%)=(viscosity after the preservation-initial stage viscosity)/initial stage viscosity * 100
As the judgement criteria of viscosity rate of rise, if be in 10%, then can be used as 1 liquid type heat-curable epoxy resin composition and use.
4. the micro encapsulation (producing the compound of representing with formula I is the microcapsule of nuclear) of the compound represented of formula I
The micro encapsulation utilization is undertaken by spray-drying process big and the spraying drying GS310 that science Co., Ltd. makes.
(1) microcapsule TPP-S(10g, the fusing point that thickness is equivalent to examine heavy 10 mass parts be 205 ℃, by Hokko Chemical Industry Co., Ltd. make, following identical.) (perhaps TPTP-S:10g, fusing point be 171 ℃, by Hokko Chemical Industry Co., Ltd. make, following identical.) with solvent: the curing catalyst solution 50g, the solvent that are suspended in ethyl acetate (40g): after the thermoplastic resin solution's (thermoplastic resin that contains 1g in the solvent) who is dissolved in ethyl acetate (9g) mixes, utilize above-mentioned spray drying unit to carry out spraying drying and obtain powder (thickness is equivalent to the microcapsule of 10 mass parts).
(2) thickness is equivalent to examine the microcapsule TPP-S(10g of heavy 20 mass parts) (perhaps TPTP-S:10g) and solvent: the curing catalyst solution 50g, the solvent that are suspended in ethyl acetate (40g): after the thermoplastic resin solution's (thermoplastic resin that contains 2g in the solvent) who is dissolved in ethyl acetate (18g) mixes, utilize above-mentioned spray drying unit to carry out spraying drying and obtain powder (thickness is equivalent to the microcapsule of 20 mass parts).
（1）TPP-S@MC1
The shell agent: urethane resin Desmocoll500(is made by Bayer Co., below identical.) mode of 10 mass parts that is equivalent to nuclear (TPP-S) according to its thickness carries out micro encapsulation.With resulting microcapsule as TPP-S@MC1.The median size of TPP-S@MC1 is 10 μ m.
（2）TPP-S@MC2
The shell agent: urethane resin Desmocoll500 carries out micro encapsulation according to the mode that its thickness is equivalent to 20 mass parts of nuclear (TPP-S).With resulting microcapsule as TPP-S@MC2.The median size of TPP-S@MC2 is 11 μ m.
（3）TPP-S@MC3
The shell agent: styrene butadiene elastomerics タ Off プ レ Application 912(is by Asahi Kasei Corporation's manufacturing, segmented copolymer, following identical.) mode of 10 mass parts that is equivalent to nuclear (TPP-S) according to its thickness carries out micro encapsulation.With resulting microcapsule as TPP-S@MC3.The median size of TPP-S@MC3 is 10 μ m.
（4）TPP-S@MC4
The shell agent: polyvinyl acetal resin KS10(by Sekisui Chemical Co., Ltd make, weight-average molecular weight is 56,000, hydroxyl 18mol%, acetalizing degree 80mol%, following identical.) mode of 10 mass parts that is equivalent to nuclear (TPP-S) according to its thickness carries out micro encapsulation.With resulting microcapsule as TPP-S@MC4.The median size of TPP-S@MC4 is 10 μ m.
（5）TPP-S@MC5
The shell agent: phenoxy resin YP-50(is 60,000～80,000, following identical by Toto Kasei KK's manufacturing, weight-average molecular weight.) mode of 10 mass parts that is equivalent to nuclear (TPP-S) according to its thickness carries out micro encapsulation.With resulting microcapsule as TPP-S@MC5.The median size of TPP-S@MC5 is 10 μ m.
（6）TPP-S@MC6
The shell agent: polyvinyl alcohol (trade(brand)name NH-18, made by Japanese synthetic chemistry Co., Ltd.) carries out micro encapsulation according to the mode that its thickness is equivalent to 10 mass parts of nuclear (TPP-S).With resulting microcapsule as TPP-S@MC6.The median size of TPP-S@MC6 is 10 μ m.
（7）TPTP-S@MC1
The shell agent: phenoxy resin YP-50 carries out micro encapsulation according to the mode that its thickness is equivalent to 10 mass parts of nuclear (TPTP-S).With resulting microcapsule as TPTP-S@MC1.The median size of TPTP-S@MC1 is 10 μ m.
5, the micro encapsulation of solidifying agent (producing the microcapsule of solidifying agent as nuclear)
(1) solidifying agent (1) @MC1
The shell agent: urethane resin Desmocoll500 according to its thickness be equivalent to nuclear [solidifying agent (1): the compound that following formula is represented, 89 ℃ of fusing points, by Tokyo HuaCheng Industry Co., Ltd make, following identical.] the mode of 10 mass parts carry out micro encapsulation.With resulting microcapsule as solidifying agent (1) @MC1.(median size of 1) @MC1 is 10 μ m to solidifying agent.
(2) solidifying agent (1) @MC2
The shell agent: urethane resin Desmocoll500 carries out micro encapsulation according to the mode that its thickness is equivalent to 20 mass parts of nuclear [solidifying agent (1)].With resulting microcapsule as solidifying agent (1) @MC2.(median size of 1) @MC2 is 10 μ m to solidifying agent.
(3) solidifying agent (1) @MC3
The shell agent: styrene butadiene elastomerics タ Off プ レ Application 912 carries out micro encapsulation according to the mode that its thickness is equivalent to 10 mass parts of nuclear [solidifying agent (1)].With resulting microcapsule as solidifying agent (1) @MC3.(median size of 1) @MC3 is 10 μ m to solidifying agent.
(4) solidifying agent (1) @MC4
The shell agent: polyvinyl acetal resin carries out micro encapsulation according to the mode that its thickness is equivalent to 10 mass parts of nuclear [solidifying agent (1)].With resulting microcapsule as solidifying agent (1) @MC4.(median size of 1) @MC4 is 10 μ m to solidifying agent.
(5) solidifying agent (1) @MC5
The shell agent: phenoxy resin YP-50 carries out micro encapsulation according to the mode that its thickness is equivalent to 10 mass parts of nuclear [solidifying agent (1)].With resulting microcapsule as solidifying agent (1) @MC5.(median size of 1) @MC5 is 10 μ m to solidifying agent.
(6) solidifying agent (2) @MC1
The shell agent: phenoxy resin YP-50 carries out micro encapsulation according to the mode that its thickness is equivalent to 10 mass parts of nuclear [solidifying agent (2): two (aminophenyl, fusing point are 237 ℃) fluorenes that following formula is represented, made by JFE KCC].With resulting microcapsule as solidifying agent (2) @MC1.(median size of 2) @MC1 is 10 μ m to solidifying agent.
6. the manufacturing of composition
Composition shown in the 3rd table～the 7 table is used according to the amount (mass parts) shown in this table, and utilize in the decompression stirrer and mix these compositions, produce composition thus.
In the 3rd table, the 4th table, the 6th table, has " eq " numerical value in the unit as curing dose and is the equivalents (active hydrogen/epoxy group(ing)) with respect to the active hydrogen of the solidifying agent of epoxy group(ing).
In the 3rd table, the 4th table, for the microcapsule of the compound of enwraped type (I) expression, its expression is as the amount (mass parts) of microcapsule.
In the 5th table, for the microcapsule of interior bag solidifying agent, its expression is as the amount (mass parts) of microcapsule.
[table 3]
[table 4]
[table 5]
Wherein, the curing dose of the 5th table is represented the amount as microcapsule.
In addition, with respect to the epoxy group(ing) of Resins, epoxy, the active hydrogen amount of the solidifying agent of bag is 1.0 equivalents in the microcapsule.
[table 6]
[table 7]
Each composition shown in the 3rd table～the 7 table is as follows.
Resins, epoxy: same with the 1st epiphase
Solidifying agent (1): identical with aromatic polyamine compound (B) 1 of the 1st table
Solidifying agent (2): identical with aromatic polyamine compound (B) 3 of the 1st table
Solidifying agent (3): the TMTG that following formula is represented: the trimethylolpropane tris mercaptoacetate, chemical society makes by forming sediment
Solidifying agent (4): the hydrosulphonyl silane condenses that following formula is represented (Z6362H, by Toray Dow company make)
N is 6～8 in the formula.
Solidifying agent (5): trade(brand)name PN, phenolic varnish (being made by Nippon Kayaku K. K)
Solidifying agent (6): trade(brand)name XYLOK-4L, xylyl alcohol/phenolic condensation compound (being made by Mitsui Chemicals, Inc)
Solidifying agent (7): the methylene-bis that following formula is represented (2-ethyl-6-monomethylaniline) (commodity are called カ ヤ Ha one De MED, are made by IHARA chemical industry Co., Ltd.)
[changing 19]
TPP-S@MC1～TPP-S@MC6, TPTP-S@MC1: the microcapsule of compound that make by the way, enwraped type (I) expression
Solidifying agent (1) @MC1～solidifying agent (1) @MC5, solidifying agent (2) @MC1: microcapsule that make, interior bag solidifying agent by the way
TPP-S: the compound of representing with the formula I of the 1st table 1 is identical
TPTP-S: the compound of representing with the formula I of the 1st table 2 is identical
Novolac resin solidifying agent: same with the 2nd epiphase
Aralkyl phenolic resin curative: same with the 2nd epiphase
Anhydride curing agent: same with the 2nd epiphase
TPP: same with the 2nd epiphase
Fatty amine: same with the 2nd epiphase
Amine latent curing agent: same with the 2nd epiphase
From the 3rd table to the result shown in the 7th table as can be known, the aromatic polyamine that comprises compound that Resins, epoxy, formula I represent, represents as the formula II of solidifying agent, wherein the compound represented of formula I and solidifying agent are not wrapped in the embodiment IV-1～6 of thermoplastic resin in having, and rapidly-curable is good.Yet, not containing aromatic polyamine that formula II represents and replaced by the condenses that contains resol or resol in the comparative example III-5,6 of the aromatic polyamine that formula II represents, rapidly-curable is poor.
In addition, rapidly-curable is poor in the comparative example IV-1～8 that does not contain the compound that formula I represents.Containing resol as solidifying agent and containing the comparative example IV-9 of TPP as curing catalyst, do not contain the aromatic polyamine that formula II represents as solidifying agent but contain the resol that replaces it and contain as curing catalyst in the comparative example IV-10～12 of TPP-S, rapidly-curable is poor.
With respect to this, in embodiment II-1～15, embodiment III-1～12, the viscosity rate of rise is 10% with interior and fine properties the time, can keep good rapidly-curable.
Claims (10)
1. a heat-curable epoxy resin composition is characterized in that, the compound that contains Resins, epoxy (A), aromatic polyamine compound (B) and represented by following formula I, and wherein, gelation time is being in 3 minutes under 150 ℃ the temperature,
The compound of described aromatic polyamine compound (B) for being represented by following formula II,
With respect to the epoxy group(ing) that described Resins, epoxy (A) has, the equivalents of the active hydrogen that described aromatic polyamine compound (B) has is 0.7～2.0 equivalent,
With respect to the described Resins, epoxy (A) of 100 mass parts, the compound amount of being represented by described formula I is 3～10 mass parts,
In the formula, R
1, R
2Represent hydrogen atom or alkyl respectively,
In the formula II, R
3, R
4Be respectively alkyl, R
5For being selected from least a in the group of being made up of alkylidene group, aromatic hydrocarbyl, fluorenyl, ether and sulfenyl, m, n are respectively 0～4 integer.
2. heat-curable epoxy resin composition as claimed in claim 1 is characterized in that, the compound of representing as described formula I contains the compound of following formula (1) expression and/or the compound of following formula (2) expression,
In the formula, Ph represents phenyl or phenylene.
3. heat-curable epoxy resin composition as claimed in claim 1 or 2, it is characterized in that any in the compound that described formula I is represented and the described aromatic polyamine compound (B) or both are contained in the interior mode that is wrapped in the microcapsule of thermoplastic resin.
4. a heat-curable epoxy resin composition is characterized in that, the compound that contains Resins, epoxy (A), aromatic polyamine compound (B) and represented by following formula I, and wherein, gelation time is being in 3 minutes under 150 ℃ the temperature,
Described aromatic polyamine compound (B) is for to be selected from the group of being made up of following formula (a), formula (b) and formula (c) and can to have substituent at least a aromatic diamine compound,
With respect to the epoxy group(ing) that described Resins, epoxy (A) has, the equivalents of the active hydrogen that described aromatic polyamine compound (B) has is 0.7～2.0 equivalent,
With respect to the described Resins, epoxy (A) of 100 mass parts, the compound amount of being represented by described formula I is 3～10 mass parts,
In the formula I, R
1, R
2Represent hydrogen atom or alkyl respectively;
In the formula (b), R
2For being selected from least a in the group of being formed by alkylidene group, aromatic hydrocarbyl, fluorenyl, ether and sulfenyl.
5. heat-curable epoxy resin composition as claimed in claim 4 is characterized in that, the compound of representing as described formula I contains the compound of following formula (1) expression and/or the compound of following formula (2) expression,
In the formula, Ph represents phenyl or phenylene.
6. as claim 4 or 5 described heat-curable epoxy resin compositions, it is characterized in that, the compound that described aromatic polyamine compound (B) is represented for following formula II,
In the formula II, R
3, R
4Be respectively alkyl, R
5For being selected from least a in the group of being made up of alkylidene group, aromatic hydrocarbyl, fluorenyl, ether and sulfenyl, m, n are respectively 0～4 integer.
7. as claim 4 or 5 described heat-curable epoxy resin compositions, it is characterized in that any in the compound that described formula I is represented and the described aromatic polyamine compound (B) or both are contained in the interior mode that is wrapped in the microcapsule of thermoplastic resin.
8. a heat-curable epoxy resin composition is characterized in that, the compound that contains Resins, epoxy (A), aromatic polyamine compound (B) and represented by following formula I, and wherein, gelation time is being in 3 minutes under 150 ℃ the temperature,
Described aromatic polyamine compound (B) is 4,4 '-diaminodiphenyl-methane, methylene-bis (2-ethyl-6-methyl) aniline or two (aminophenyl) fluorenes,
With respect to the epoxy group(ing) that described Resins, epoxy (A) has, the equivalents of the active hydrogen that described aromatic polyamine compound (B) has is 0.7～2.0 equivalent,
With respect to the described Resins, epoxy (A) of 100 mass parts, the compound amount of being represented by described formula I is 3～10 mass parts,
In the formula, R
1, R
2Represent hydrogen atom or alkyl respectively.
9. heat-curable epoxy resin composition as claimed in claim 8 is characterized in that, the compound of representing as described formula I contains the compound of following formula (1) expression and/or the compound of following formula (2) expression,
In the formula, Ph represents phenyl or phenylene.
10. heat-curable epoxy resin composition as claimed in claim 8 or 9, it is characterized in that any in the compound that described formula I is represented and the described aromatic polyamine compound (B) or both are contained in the interior mode that is wrapped in the microcapsule of thermoplastic resin.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
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| JP2008-228312 | 2008-09-05 | ||
| JP2008228312 | 2008-09-05 | ||
| JP2008267327 | 2008-10-16 | ||
| JP2008-267327 | 2008-10-16 | ||
| JP2008286992 | 2008-11-07 | ||
| JP2008-286992 | 2008-11-07 | ||
| JP2009117615 | 2009-05-14 | ||
| JP2009-117615 | 2009-05-14 | ||
| JP2009126401 | 2009-05-26 | ||
| JP2009-126401 | 2009-05-26 | ||
| PCT/JP2009/004417 WO2010026777A1 (en) | 2008-09-05 | 2009-09-07 | Heat-cured epoxy resin composition |
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| Publication Number | Publication Date |
|---|---|
| CN102143987A CN102143987A (en) | 2011-08-03 |
| CN102143987B true CN102143987B (en) | 2013-08-21 |
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| JP (1) | JP4737345B2 (en) |
| KR (1) | KR101245132B1 (en) |
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| JP5485830B2 (en) * | 2010-08-20 | 2014-05-07 | 積水化学工業株式会社 | Epoxy resin curing microcapsules |
| CN102423673A (en) * | 2011-07-28 | 2012-04-25 | 西北工业大学 | Latent microcapsule curing agent initiating thermosetting epoxy resin curing at medium temperature and preparation method of adhesive thereof |
| JP6989486B2 (en) * | 2016-02-25 | 2022-01-05 | 昭和電工マテリアルズ株式会社 | Epoxy resin molding material, molded product, molded molded product, and manufacturing method of molded cured product |
| JP6943010B2 (en) * | 2017-05-10 | 2021-09-29 | 信越化学工業株式会社 | Semiconductor device |
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| CN1370802A (en) * | 2001-02-15 | 2002-09-25 | 日立化成工业株式会社 | Resin composition and its use and production process thereof |
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| JPH07133339A (en) * | 1993-06-18 | 1995-05-23 | Nippon Kayaku Co Ltd | Microcapsuled phosphorus cure accelerator, epoxy resin composition containing same, and its cured item |
| JPH093164A (en) * | 1995-06-15 | 1997-01-07 | Nitto Denko Corp | Micro-capsule type hardener or hardening accelerator and epoxy resin composition containing the same |
| JP2006290946A (en) * | 2005-04-07 | 2006-10-26 | Hokko Chem Ind Co Ltd | Curing promoter for epoxy resin, and epoxy resin composition |
| JP5044414B2 (en) | 2005-11-30 | 2012-10-10 | パナソニック株式会社 | Halogen-free epoxy resin composition, coverlay film, bonding sheet, prepreg, laminate for printed wiring board |
| WO2008136096A1 (en) * | 2007-04-24 | 2008-11-13 | Panasonic Electric Works Co., Ltd. | Halogen-free epoxy resin composition, coverlay film, bonding sheet, prepreg and printed wiring board laminate |
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| CN1370802A (en) * | 2001-02-15 | 2002-09-25 | 日立化成工业株式会社 | Resin composition and its use and production process thereof |
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| Title |
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| JP特开平9-3164A 1997.01.07 |
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| Publication number | Publication date |
|---|---|
| KR20110055656A (en) | 2011-05-25 |
| CN102143987A (en) | 2011-08-03 |
| WO2010026777A1 (en) | 2010-03-11 |
| KR101245132B1 (en) | 2013-03-25 |
| JPWO2010026777A1 (en) | 2012-02-02 |
| JP4737345B2 (en) | 2011-07-27 |
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