JP2024024961A - Curing agent for epoxy resin and epoxy resin composition - Google Patents
Curing agent for epoxy resin and epoxy resin composition Download PDFInfo
- Publication number
- JP2024024961A JP2024024961A JP2022127976A JP2022127976A JP2024024961A JP 2024024961 A JP2024024961 A JP 2024024961A JP 2022127976 A JP2022127976 A JP 2022127976A JP 2022127976 A JP2022127976 A JP 2022127976A JP 2024024961 A JP2024024961 A JP 2024024961A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- carboxylic acid
- curing agent
- acid
- composition according
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 130
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 130
- 239000000203 mixture Substances 0.000 title claims abstract description 84
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 29
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000003566 sealing material Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- 239000011810 insulating material Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- SWHSXWLSBBYLGM-UHFFFAOYSA-N 2-[(2-carboxyphenoxy)methoxy]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1OCOC1=CC=CC=C1C(O)=O SWHSXWLSBBYLGM-UHFFFAOYSA-N 0.000 claims description 3
- UYDGECQHZQNTQS-UHFFFAOYSA-N 2-amino-4,6-dimethylpyridine-3-carboxamide Chemical compound CC1=CC(C)=C(C(N)=O)C(N)=N1 UYDGECQHZQNTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZJWUEJOPKFYFQD-UHFFFAOYSA-N 2-hydroxy-3-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1O ZJWUEJOPKFYFQD-UHFFFAOYSA-N 0.000 claims description 3
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000000696 magnetic material Substances 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- WHSXTWFYRGOBGO-UHFFFAOYSA-N o-cresotic acid Natural products CC1=CC=CC(C(O)=O)=C1O WHSXTWFYRGOBGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000000565 sealant Substances 0.000 claims description 3
- 238000013016 damping Methods 0.000 claims description 2
- 239000004848 polyfunctional curative Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims 1
- -1 carboxylic acid compound Chemical class 0.000 abstract description 25
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 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 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000000411 transmission spectrum Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- GRGBENNNGZARRZ-UHFFFAOYSA-N dodecanedihydrazide Chemical compound NNC(=O)CCCCCCCCCCC(=O)NN GRGBENNNGZARRZ-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Chemical group 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- RXFZJKXZSLVQJV-UHFFFAOYSA-N icosa-8,12-dienedihydrazide Chemical compound NNC(=O)CCCCCCC=CCCC=CCCCCCCC(=O)NN RXFZJKXZSLVQJV-UHFFFAOYSA-N 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- ZSQNWXGSUBTAJV-UHFFFAOYSA-N C(=O)(NC)NC.C(=O)(NC)NC.C1(=CC=CC=C1)C Chemical compound C(=O)(NC)NC.C(=O)(NC)NC.C1(=CC=CC=C1)C ZSQNWXGSUBTAJV-UHFFFAOYSA-N 0.000 description 1
- PUNIDMUCDALJAS-UHFFFAOYSA-N C(C1=CC=C(C=C1)N(C(=O)NC)C)C1=CC=C(C=C1)N(C(=O)NC)C Chemical compound C(C1=CC=C(C=C1)N(C(=O)NC)C)C1=CC=C(C=C1)N(C(=O)NC)C PUNIDMUCDALJAS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- GRNNGULEILSPIG-UHFFFAOYSA-N [[tert-butyl(cyclohexyl)carbamoyl]-[(dimethylamino)methyl]amino]methylcarbamic acid Chemical compound CN(C)CN(C(=O)N(C(C)(C)C)C1CCCCC1)CNC(=O)O GRNNGULEILSPIG-UHFFFAOYSA-N 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004643 cyanate ester Chemical class 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-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
-
- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4035—Hydrazines; Hydrazides
-
- 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
- C08G59/62—Alcohols or phenols
- C08G59/625—Hydroxyacids
- C08G59/626—Lactones
-
- 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
- C08G59/62—Alcohols or phenols
- C08G59/625—Hydroxyacids
- C08G59/628—Phenolcarboxylic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C08G2150/00—Compositions for coatings
-
- 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
- C08G2170/00—Compositions for adhesives
-
- 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
- C08G2190/00—Compositions for sealing or packing joints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
本発明は、エポキシ樹脂用硬化剤およびエポキシ樹脂組成物に関する。 The present invention relates to a curing agent for epoxy resins and an epoxy resin composition.
ジヒドラジド化合物はエポキシ樹脂の硬化剤として使用した場合、透明性の高い硬化物が得られる特徴があり、透明性が必要な電子デバイスなどのエポキシ樹脂封止材や接着剤の硬化剤として有用である。しかしながら、ジヒドラジド化合物を使用したエポキシ樹脂組成物は硬化性、特に低温での硬化性が不十分であるという問題がある。 When dihydrazide compounds are used as curing agents for epoxy resins, they have the characteristic of producing highly transparent cured products, making them useful as curing agents for epoxy resin encapsulants and adhesives for electronic devices that require transparency. . However, epoxy resin compositions using dihydrazide compounds have a problem in that their curability, particularly at low temperatures, is insufficient.
特許文献1には、ジヒドラジド化合物と二塩基酸を組合せて使用することで、エポキシ樹脂組成物の硬化性を改善する技術が開示されている。しかしながら、特許文献1のエポキシ樹脂組成物の硬化性は必ずしも十分なものとはいえず、更なる硬化性の改善が求められている。 Patent Document 1 discloses a technique for improving the curability of an epoxy resin composition by using a combination of a dihydrazide compound and a dibasic acid. However, the curability of the epoxy resin composition of Patent Document 1 is not necessarily sufficient, and further improvement in curability is desired.
本発明の課題は、硬化性に優れるエポキシ樹脂組成物をもたらす、ジヒドラジド化合物を含むエポキシ樹脂用硬化剤を提供することである。 An object of the present invention is to provide a curing agent for epoxy resin containing a dihydrazide compound, which provides an epoxy resin composition with excellent curability.
本発明者らは、上記課題を解決すべく鋭意検討した結果、ジヒドラジド化合物と、特定の構造を有するカルボン酸化合物とを組み合わせることによって、エポキシ樹脂組成物の硬化性を向上できることを見出し、本発明を完成するに至った。すなわち、本発明は以下の態様を含むものである。 As a result of intensive studies to solve the above problems, the present inventors discovered that the curability of an epoxy resin composition can be improved by combining a dihydrazide compound and a carboxylic acid compound having a specific structure, and the present invention I was able to complete it. That is, the present invention includes the following aspects.
〔1〕
(A)ジヒドラジド化合物と、
(B)芳香族カルボン酸又は脂肪族カルボン酸と、
を含む、硬化剤組成物であって、
前記芳香族カルボン酸が、1個のカルボキシ基と0~2個のヒドロキシ基とを有する芳香環を1個又は2個含み、
前記脂肪族カルボン酸が、1個のカルボキシ基と1個のヒドロキシ基とを含む、直鎖又は分岐鎖の飽和脂肪族カルボン酸である、
硬化剤組成物。
〔2〕(B)成分として前記芳香族カルボン酸を含み、前記芳香族カルボン酸が、300℃以下の融点を有する、前記〔1〕に記載の硬化剤組成物。
〔3〕前記芳香族カルボン酸が、ベンゼン環又はナフタレン環構造を有する、前記〔2〕に記載の硬化剤組成物。
〔4〕前記芳香族カルボン酸が、サリチル酸、メチレンジサリチル酸、2-ヒドロキシ-1-ナフトエ酸、3-メチルサリチル酸、2,5-ジヒドロキシ安息香酸、3-フェニルサリチル酸、安息香酸及びこれらの組み合わせからなる群から選択される、前記〔3〕に記載の硬化剤組成物。
〔5〕(B)成分として前記脂肪族カルボン酸を含み、前記脂肪族カルボン酸の炭素数が、2個又は3個である、前記〔1〕に記載の硬化剤組成物。
〔6〕前記脂肪族カルボン酸が、乳酸である、前記〔5〕に記載の硬化剤組成物。
〔7〕前記ジヒドラジド化合物が、250℃以下の融点を有する、前記〔1〕~〔6〕に記載の硬化剤組成物。
〔8〕前記〔1〕~〔7〕のいずれか1項に記載の硬化剤組成物と、(C)エポキシ樹脂とを含有する、エポキシ樹脂組成物。
〔9〕前記〔8〕に記載のエポキシ樹脂組成物を含むエポキシ樹脂材料であって、接着剤、接合剤、導電材、磁性材、熱伝導材、絶縁材、封止材、コーティング材、制振・防振材、防音材、充填材及び塗料からなる群から選択される、エポキシ樹脂材料。
〔10〕接着剤又は封止材である、前記〔9〕に記載のエポキシ樹脂材料。
〔11〕前記〔8〕に記載のエポキシ樹脂組成物を硬化させてなる、硬化物。
〔12〕前記〔11〕に記載の硬化物を含む、電子デバイス。
[1]
(A) a dihydrazide compound;
(B) aromatic carboxylic acid or aliphatic carboxylic acid;
A curing agent composition comprising:
The aromatic carboxylic acid contains one or two aromatic rings having one carboxy group and 0 to 2 hydroxy groups,
The aliphatic carboxylic acid is a linear or branched saturated aliphatic carboxylic acid containing one carboxy group and one hydroxy group,
Hardener composition.
[2] The curing agent composition according to [1] above, which contains the aromatic carboxylic acid as the component (B), and the aromatic carboxylic acid has a melting point of 300°C or less.
[3] The curing agent composition according to [2] above, wherein the aromatic carboxylic acid has a benzene ring or naphthalene ring structure.
[4] The aromatic carboxylic acid is selected from salicylic acid, methylenedisalicylic acid, 2-hydroxy-1-naphthoic acid, 3-methylsalicylic acid, 2,5-dihydroxybenzoic acid, 3-phenylsalicylic acid, benzoic acid, and combinations thereof. The curing agent composition according to [3] above, which is selected from the group consisting of:
[5] The curing agent composition according to [1] above, which contains the aliphatic carboxylic acid as the component (B), and the aliphatic carboxylic acid has 2 or 3 carbon atoms.
[6] The curing agent composition according to [5] above, wherein the aliphatic carboxylic acid is lactic acid.
[7] The curing agent composition according to [1] to [6] above, wherein the dihydrazide compound has a melting point of 250°C or less.
[8] An epoxy resin composition containing the curing agent composition according to any one of [1] to [7] above and (C) an epoxy resin.
[9] An epoxy resin material containing the epoxy resin composition according to [8] above, which may be an adhesive, a bonding agent, a conductive material, a magnetic material, a heat conductive material, an insulating material, a sealing material, a coating material, a control material, etc. Epoxy resin material selected from the group consisting of vibration/vibration isolating materials, sound insulating materials, fillers and paints.
[10] The epoxy resin material according to [9] above, which is an adhesive or a sealant.
[11] A cured product obtained by curing the epoxy resin composition described in [8] above.
[12] An electronic device comprising the cured product according to [11] above.
本発明により、硬化性に優れるエポキシ樹脂組成物をもたらす、ジヒドラジド化合物を含むエポキシ樹脂用硬化剤を提供することができる。 According to the present invention, it is possible to provide an epoxy resin curing agent containing a dihydrazide compound, which provides an epoxy resin composition with excellent curability.
本発明は、(A)ジヒドラジド化合物と、(B)芳香族カルボン酸又は脂肪族カルボン酸と、を含む、硬化剤組成物であって、前記芳香族カルボン酸が、1個のカルボキシ基と0~2個のヒドロキシ基とを有する芳香環を1個又は2個含み、前記脂肪族カルボン酸が、1個のカルボキシ基と1個のヒドロキシ基とを含む、直鎖又は分岐鎖の飽和脂肪族カルボン酸である、硬化剤組成物に関する。 The present invention provides a curing agent composition comprising (A) a dihydrazide compound and (B) an aromatic carboxylic acid or an aliphatic carboxylic acid, wherein the aromatic carboxylic acid has one carboxy group and 0 A linear or branched saturated aliphatic acid containing one or two aromatic rings having ~2 hydroxy groups, and the aliphatic carboxylic acid containing one carboxy group and one hydroxy group. The present invention relates to curing agent compositions that are carboxylic acids.
本発明では、硬化剤としてジヒドラジド化合物を使用することによって、透明性の高い硬化物を得ることができる。ジヒドラジド化合物は、特に限定されないが、エポキシ樹脂組成物の硬化性の観点から、融点が250℃以下のものが好ましく、硬化物の透明性の観点からは、185℃以下のものがより好ましく、170℃以下のものがさらにより好ましい。ジヒドラジド化合物の融点の下限値は特に制限されず、例えば、60℃、80℃、又は100℃であってもよい。 In the present invention, a highly transparent cured product can be obtained by using a dihydrazide compound as a curing agent. The dihydrazide compound is not particularly limited, but from the viewpoint of curability of the epoxy resin composition, those with a melting point of 250°C or lower are preferable, and those with a melting point of 185°C or lower are more preferable from the viewpoint of transparency of the cured product, and 170°C or lower. ℃ or less is even more preferred. The lower limit of the melting point of the dihydrazide compound is not particularly limited, and may be, for example, 60°C, 80°C, or 100°C.
ジヒドラジド化合物は粒子状のものが好ましい。粒子状のジヒドラジド化合物の粒子径は、エポキシ樹脂への溶解性や反応性を高める観点からメジアン径が100μm以下のものが好ましく、エポキシ樹脂組成物の粘性を下げる、あるいはエポキシ樹脂への分散性を高めるためにはメジアン径が0.1μm以上のものが好ましく、1~50μmであることがより好ましく、1~20μmであることが更により好ましい。粒子径がこの範囲外にあるもの、あるいは粒子同士が密着して凝集物を形成している場合は、エポキシ樹脂と混合する過程で3本ロールミルやプラネタリーミキサーなどで粒子を潰して、あるいは分散させて、メジアン径を上記範囲内とすることが好ましい。メジアン径は、レーザー回折散乱式粒度分布測定(JIS Z 8825)により粒度分布を体積基準で作成したときの該粒度分布から求めることができる。レーザー回折散乱式粒径分布測定装置としては、堀場製作所社製「LA-500」、島津製作所社製「SALD-2200」等を使用することができる 。 The dihydrazide compound is preferably in particulate form. The particle size of the particulate dihydrazide compound is preferably one with a median diameter of 100 μm or less from the viewpoint of increasing solubility and reactivity in the epoxy resin, and it is preferable to reduce the viscosity of the epoxy resin composition or improve the dispersibility in the epoxy resin. In order to increase the diameter, the median diameter is preferably 0.1 μm or more, more preferably 1 to 50 μm, and even more preferably 1 to 20 μm. If the particle size is outside this range, or if the particles stick together to form aggregates, crush or disperse the particles with a three-roll mill or planetary mixer during the mixing process with the epoxy resin. It is preferable that the median diameter be within the above range. The median diameter can be determined from the particle size distribution created on a volume basis by laser diffraction scattering particle size distribution measurement (JIS Z 8825). As the laser diffraction scattering particle size distribution measuring device, "LA-500" manufactured by Horiba, "SALD-2200" manufactured by Shimadzu Corporation, etc. can be used.
好ましいジヒドラジド化合物としては、例えば、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、7,11-オクタデカジエン-1,18-ジカルボヒドラジド、アジピン酸ジヒドラジド、ドデカン二酸ジヒドラジド、イソフタル酸ジヒドラジド等を挙げることができる。ジヒドラジド化合物は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Preferred dihydrazide compounds include, for example, 1,3-bis(hydrazinocarbonoethyl)-5-isopropylhydantoin, 7,11-octadecadiene-1,18-dicarbohydrazide, adipic dihydrazide, and dodecanedioic acid dihydrazide. , isophthalic acid dihydrazide, and the like. The dihydrazide compounds may be used alone or in combination of two or more.
硬化剤組成物を100質量%とした場合、ジヒドラジド化合物は、好ましくは80~99質量%、より好ましくは85~98.5質量%、更に好ましくは90~98質量%の量で、硬化剤組成物に含まれる。ジヒドラジド化合物の量が上記範囲内であれば、エポキシ樹脂と混合してエポキシ樹脂組成物とした場合に、組成物のポットライフが良好であり、また硬化反応が均一となる傾向となるので好ましい。 When the curing agent composition is 100% by mass, the dihydrazide compound is added in an amount of preferably 80 to 99% by mass, more preferably 85 to 98.5% by mass, even more preferably 90 to 98% by mass. included in things. If the amount of the dihydrazide compound is within the above range, it is preferable because when mixed with an epoxy resin to form an epoxy resin composition, the pot life of the composition is good and the curing reaction tends to be uniform.
本発明の硬化剤組成物は、特定の構造を有する芳香族カルボン酸又は脂肪族カルボン酸を含む。芳香族カルボン酸又は脂肪族カルボン酸は、ジヒドラジド化合物によるエポキシ樹脂組成物の硬化を促進する機能を有する。 The curing agent composition of the present invention contains an aromatic carboxylic acid or an aliphatic carboxylic acid having a specific structure. The aromatic carboxylic acid or the aliphatic carboxylic acid has a function of accelerating the curing of the epoxy resin composition by the dihydrazide compound.
芳香族カルボン酸は、1個のカルボキシ基と0~2個のヒドロキシ基とを有する芳香環を1個又は2個含む。カルボキシ基、ヒドロキシ基及び芳香環の数が上記範囲内であれば、ジヒドラジド化合物の反応をより促進することが可能である。芳香族カルボン酸は、エポキシ樹脂組成物の硬化性の観点から、融点が300℃以下であることが好ましく、硬化物の透明性の観点から、250℃以下であることがより好ましく、220℃以下であることがさらにより好ましい。芳香族カルボン酸の融点の下限値には特に制限はないが、例えば、80℃以上、100℃以上、または120℃以上であってもよい。 Aromatic carboxylic acids contain one or two aromatic rings having one carboxy group and 0 to 2 hydroxy groups. If the number of carboxyl groups, hydroxyl groups, and aromatic rings is within the above range, it is possible to further accelerate the reaction of the dihydrazide compound. From the viewpoint of curability of the epoxy resin composition, the aromatic carboxylic acid preferably has a melting point of 300°C or lower, and from the viewpoint of transparency of the cured product, the melting point is preferably 250°C or lower, and 220°C or lower. Even more preferably. The lower limit of the melting point of the aromatic carboxylic acid is not particularly limited, but may be, for example, 80°C or higher, 100°C or higher, or 120°C or higher.
芳香族カルボン酸としては、例えば、ベンゼン環を有する化合物の他、ビフェニルやベンゾフェノンのような複数のベンゼン環が結合している芳香族多環化合物、ナフタレン環、アントラセン、フェナントレンのような縮合環化合物、ピリジン、フラン、インドールのように炭素の他、窒素、酸素などの複数の元素で環構造が構成される複素芳香族化合物等が挙げられる。エポキシ樹脂への溶解性の観点から、一分子中の環数が3以下のものが好ましい。好ましい芳香族カルボン酸としては、例えば、サリチル酸、メチレンジサリチル酸、2-ヒドロキシ-1-ナフトエ酸、3-メチルサリチル酸、2,5-ジヒドロキシ安息香酸、3-フェニルサリチル酸、安息香酸等を挙げることができる。芳香族カルボン酸は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Examples of aromatic carboxylic acids include compounds having a benzene ring, aromatic polycyclic compounds in which multiple benzene rings are bonded such as biphenyl and benzophenone, and fused ring compounds such as naphthalene rings, anthracene, and phenanthrene. Examples include heteroaromatic compounds such as pyridine, furan, and indole, in which the ring structure is composed of multiple elements such as carbon, nitrogen, and oxygen. From the viewpoint of solubility in the epoxy resin, the number of rings in one molecule is preferably 3 or less. Preferred aromatic carboxylic acids include, for example, salicylic acid, methylenedisalicylic acid, 2-hydroxy-1-naphthoic acid, 3-methylsalicylic acid, 2,5-dihydroxybenzoic acid, 3-phenylsalicylic acid, benzoic acid, and the like. can. Aromatic carboxylic acids may be used alone or in combination of two or more.
脂肪族カルボン酸は、1個のカルボキシ基と1個のヒドロキシ基とを含む、直鎖又は分岐鎖の飽和脂肪族カルボン酸である。脂肪族カルボン酸の炭素数は、エポキシ樹脂への溶解性の観点から、2個又は3個であることが好ましい。本明細書において、脂肪族カルボン酸の炭素数とは、化合物全体に含まれる炭素のうち、カルボキシ基を構成する炭素を除いた残りの炭素の数をいう。 Aliphatic carboxylic acids are linear or branched saturated aliphatic carboxylic acids containing one carboxy group and one hydroxy group. The number of carbon atoms in the aliphatic carboxylic acid is preferably 2 or 3 from the viewpoint of solubility in the epoxy resin. As used herein, the number of carbon atoms in an aliphatic carboxylic acid refers to the number of carbon atoms remaining after excluding carbons constituting a carboxy group among the carbon atoms contained in the entire compound.
好ましい脂肪族カルボン酸としては、例えば、乳酸を挙げることができる。 Preferred aliphatic carboxylic acids include, for example, lactic acid.
硬化剤組成物を100質量%とした場合、芳香族カルボン酸又は脂肪族カルボン酸は、好ましくは1~20質量%、より好ましくは1.5~15質量%、更に好ましくは2~10質量%の量で、硬化剤組成物に含まれる。芳香族カルボン酸又は脂肪族カルボン酸の量が上記範囲内であれば、ジヒドラジド化合物によるエポキシ樹脂の硬化を十分に促進できる。 When the curing agent composition is 100% by mass, the aromatic carboxylic acid or aliphatic carboxylic acid is preferably 1 to 20% by mass, more preferably 1.5 to 15% by mass, and even more preferably 2 to 10% by mass. is included in the curing agent composition in an amount of If the amount of aromatic carboxylic acid or aliphatic carboxylic acid is within the above range, curing of the epoxy resin by the dihydrazide compound can be sufficiently promoted.
本発明における芳香族カルボン酸や脂肪族カルボン酸は、エポキシ樹脂組成物の硬化促進の観点から、アミノ基、ホルミル基、カルボニル基、チオール基、スルホン酸基、ハロゲン等の、カルボキシ基及びヒドロキシ基以外の官能基を含まないことが好ましい。 Aromatic carboxylic acids and aliphatic carboxylic acids in the present invention include carboxy groups and hydroxy groups such as amino groups, formyl groups, carbonyl groups, thiol groups, sulfonic acid groups, and halogens, from the viewpoint of accelerating curing of the epoxy resin composition. It is preferable not to contain any other functional groups.
硬化剤組成物は、本発明の効果を損なわない範囲で、任意に、水分やジヒドラジド化合物合成時の未反応物等を含んでもよい。 The curing agent composition may optionally contain water, unreacted substances during synthesis of the dihydrazide compound, etc., within a range that does not impair the effects of the present invention.
硬化剤組成物の製造方法に特に制限は無く、ジヒドラジド化合物と、芳香族カルボン酸又は脂肪族カルボン酸と、任意に他の成分とを混合することによって得ることができる。 There are no particular restrictions on the method for producing the curing agent composition, and it can be obtained by mixing a dihydrazide compound, an aromatic carboxylic acid or an aliphatic carboxylic acid, and optionally other components.
本発明はまた、硬化剤組成物と、(C)エポキシ樹脂とを含有する、エポキシ樹脂組成物に関する。 The present invention also relates to an epoxy resin composition containing a curing agent composition and (C) an epoxy resin.
エポキシ樹脂組成物に含有されるエポキシ樹脂としては、従来公知のエポキシ樹脂を特に制限なく使用できる。エポキシ樹脂は、用途や硬化物の所望の性質に応じて適宜選択でき、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。エポキシ樹脂は液状であっても、固形状であってもよい。また液状樹脂と固形状樹脂の混合物を用いてもよい。ここで、「液状」および「固形状」とは、常温(25℃)でのエポキシ樹脂の状態を指す。 As the epoxy resin contained in the epoxy resin composition, conventionally known epoxy resins can be used without particular limitation. Epoxy resins can be appropriately selected depending on the intended use and desired properties of the cured product, and may be used alone or in combination of two or more. The epoxy resin may be in liquid or solid form. Alternatively, a mixture of liquid resin and solid resin may be used. Here, "liquid" and "solid" refer to the state of the epoxy resin at room temperature (25° C.).
液状エポキシ樹脂としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールAF型エポキシ樹脂、ナフタレン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、エステル骨格を有する脂環式エポキシ樹脂、及びブタジエン構造を有するエポキシ樹脂が好ましい。液状エポキシ樹脂の具体例としては、DIC社製の「HP4032」、「HP4032D」、「HP4032SS」(ナフタレン型エポキシ樹脂)、三菱化学社製の「828US」、「jER828EL」(ビスフェノールA型エポキシ樹脂)、「jER807」(ビスフェノールF型エポキシ樹脂)、「jER152」(フェノールノボラック型エポキシ樹脂)、「YL7760」(ビスフェノールAF型エポキシ樹脂)、新日鉄住金化学社製の「ZX1059」(ビスフェノールA型エポキシ樹脂とビスフェノールF型エポキシ樹脂の混合品)、ナガセケムテックス社製の「EX-721」(グリシジルエステル型エポキシ樹脂)、ダイセル社製の「セロキサイド2021P」(エステル骨格を有する脂環式エポキシ樹脂)、「PB-3600」(ブタジエン構造を有するエポキシ樹脂)が挙げられる。 Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolak type epoxy resin, and alicyclic epoxy resin having an ester skeleton. , and epoxy resins having a butadiene structure are preferred. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "828US", "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. , "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (bisphenol A type epoxy resin) mixture of bisphenol F type epoxy resin), Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin), Daicel's "Celoxide 2021P" (alicyclic epoxy resin with an ester skeleton), " PB-3600 (an epoxy resin with a butadiene structure).
固体状エポキシ樹脂としては、ナフタレン型4官能エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノール型エポキシ樹脂、ナフトール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、アントラセン型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂が好ましい。固体状エポキシ樹脂の具体例としては、DIC社製の「HP4032H」(ナフタレン型エポキシ樹脂)、「HP-4700」、「HP-4710」(ナフタレン型4官能エポキシ樹脂)、「N-690」(クレゾールノボラック型エポキシ樹脂)、「N-695」(クレゾールノボラック型エポキシ樹脂)、「HP-7200」(ジシクロペンタジエン型エポキシ樹脂)、「HP-7200HH」、「EXA7311」、「EXA7311-G3」、「EXA7311-G4」、「EXA7311-G4S」、「HP6000」(ナフチレンエーテル型エポキシ樹脂)、日本化薬社製の「EPPN-502H」(トリスフェノール型エポキシ樹脂)、「NC7000L」(ナフトールノボラック型エポキシ樹脂)、「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(ビフェニル型エポキシ樹脂)、新日鉄住金化学社製の「ESN475V」(ナフトール型エポキシ樹脂)、「ESN485」(ナフトールノボラック型エポキシ樹脂)、三菱化学社製の「YX4000H」、「YL6121」(ビフェニル型エポキシ樹脂)、「YX4000HK」(ビキシレノール型エポキシ樹脂)、「YX8800」(アントラセン型エポキシ樹脂)、大阪ガスケミカル社製の「PG-100」、「CG-500」、三菱化学社製の「YL7800」(フルオレン型エポキシ樹脂)、三菱化学社製の「jER1010」(固体状ビスフェノールA型エポキシ樹脂)、「jER1031S」(テトラフェニルエタン型エポキシ樹脂)等が挙げられる。 Solid epoxy resins include naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferred. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" (manufactured by DIC). Cresol novolak type epoxy resin), “N-695” (cresol novolac type epoxy resin), “HP-7200” (dicyclopentadiene type epoxy resin), “HP-7200HH”, “EXA7311”, “EXA7311-G3”, "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac type) epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin) Resin), Mitsubishi Chemical's "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), Osaka Gas Chemical's " PG-100'', ``CG-500'', Mitsubishi Chemical's ``YL7800'' (fluorene type epoxy resin), Mitsubishi Chemical's ``jER1010'' (solid bisphenol A type epoxy resin), ``jER1031S'' (tetraphenyl ethane type epoxy resin), etc.
エポキシ樹脂は、硬化剤組成物との均一混合のしやすさや接着性の観点から、使用するエポキシ樹脂全体の少なくとも10質量%以上が液状であるのが好ましく、少なくとも30質量%以上が液状であるのがより好ましく、少なくとも50質量%以上が液状であるのがさらに好ましく、少なくとも80質量%以上が液状であるのが特に好ましい。 From the viewpoint of ease of uniform mixing with the curing agent composition and adhesive properties, it is preferable that at least 10% by mass or more of the entire epoxy resin used is liquid, and at least 30% by mass or more is liquid. More preferably, at least 50% by mass or more is liquid, and particularly preferably at least 80% by mass or more is liquid.
エポキシ樹脂のエポキシ当量は、例えば、50~1000g/eq、好ましくは100~500g/eq、より好ましくは150~300g/eqである。ここで、エポキシ当量とは、1当量のエポキシ基あたりのエポキシ樹脂の質量であり、JIS K7236(2009)に準拠して測定することができる。 The epoxy equivalent of the epoxy resin is, for example, 50 to 1000 g/eq, preferably 100 to 500 g/eq, more preferably 150 to 300 g/eq. Here, the epoxy equivalent is the mass of the epoxy resin per equivalent of epoxy group, and can be measured in accordance with JIS K7236 (2009).
エポキシ樹脂組成物中のエポキシ樹脂の含有量は特に制限されないが、50~95質量%であるのが好ましく、60~90質量%であるのがより好ましく、65~85質量%であるのが更に好ましい。 The content of the epoxy resin in the epoxy resin composition is not particularly limited, but is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 65 to 85% by mass. preferable.
エポキシ樹脂と硬化剤組成物は、(C)エポキシ樹脂のエポキシ当量1に対し、(A)ジヒドラジド化合物と(B)芳香族カルボン酸又は脂肪族カルボン酸との合計の当量が、好ましくは0.8~1.2、より好ましくは0.9~1.1となる量で配合する。配合量が上記範囲内であれば、エポキシ樹脂の未反応物の残留を抑制することができる。 In the epoxy resin and curing agent composition, the total equivalent of (A) dihydrazide compound and (B) aromatic carboxylic acid or aliphatic carboxylic acid is preferably 0.1 to 1 epoxy equivalent of (C) epoxy resin. It is blended in an amount of 8 to 1.2, more preferably 0.9 to 1.1. If the blending amount is within the above range, it is possible to suppress the remaining unreacted substances of the epoxy resin.
エポキシ樹脂組成物は、さらに、(A)成分以外の硬化剤、(B)成分以外の硬化促進剤、熱硬化性樹脂、熱可塑性樹脂、無機充填材、有機充填材、増粘剤、消泡剤、レベリング剤、密着性付与剤、着色剤、有機溶剤および水からなる群から選択される1以上を含有することができる。 The epoxy resin composition further includes a curing agent other than component (A), a curing accelerator other than component (B), a thermosetting resin, a thermoplastic resin, an inorganic filler, an organic filler, a thickener, and an antifoaming agent. The composition may contain one or more selected from the group consisting of an agent, a leveling agent, an adhesion-imparting agent, a coloring agent, an organic solvent, and water.
硬化剤としては、本発明の(A)成分以外のエポキシ樹脂硬化剤を意味し、潜在性硬化剤であることが好ましく、例えば、ウレア化合物、アミン系化合物、チオール化合物、酸無水物化合物、グアニジン化合物、ヒドラジド化合物、フェノール化合物、ナフトール化合物、活性エステル化合物、ベンゾオキサジン化合物、シアネートエステル化合物、及びカルボジイミド化合物などが挙げられる。 The curing agent refers to an epoxy resin curing agent other than component (A) of the present invention, and is preferably a latent curing agent, such as a urea compound, an amine compound, a thiol compound, an acid anhydride compound, or a guanidine compound. compounds, hydrazide compounds, phenol compounds, naphthol compounds, active ester compounds, benzoxazine compounds, cyanate ester compounds, and carbodiimide compounds.
ウレア化合物は、ウレア基を有するものでエポキシ樹脂と反応し得る化合物であれば特に制限はないが、好ましくは芳香族ジメチルウレア又は脂肪族ジメチルウレアが挙げられる。好ましい芳香族ジメチルウレアとしては、例えば、N,N-ジメチル-N’-フェニルウレア、N,N-ジメチル-N’-(3,4-ジクロロフェニル)ウレア、4,4’-メチレンビス(フェニルジメチルウレア)、トルエンビスジメチルウレア等を挙げることができる。好ましい脂肪族ジメチルウレアとしては、ジメチルアミノカルボキシルアミノメチルトリメチルシクロヘキシルジメチルウレア等を挙げることができる。 The urea compound is not particularly limited as long as it has a urea group and can react with the epoxy resin, but aromatic dimethylurea or aliphatic dimethylurea are preferred. Preferred aromatic dimethylureas include, for example, N,N-dimethyl-N'-phenylurea, N,N-dimethyl-N'-(3,4-dichlorophenyl)urea, and 4,4'-methylenebis(phenyldimethylurea). ), toluene bisdimethylurea, and the like. Preferred aliphatic dimethylureas include dimethylaminocarboxylaminomethyltrimethylcyclohexyldimethylurea and the like.
アミン系化合物は、イミダゾール化合物、イミダゾールと酸性化合物の塩、アミン化合物、アミン化合物と酸性化合物の塩、及びアミンアダクト化合物からなる群から選ばれる少なくとも一つであることが好ましい。 The amine compound is preferably at least one selected from the group consisting of imidazole compounds, salts of imidazole and acidic compounds, amine compounds, salts of amine compounds and acidic compounds, and amine adduct compounds.
エポキシ樹脂組成物の調製は、特別の困難はなく、従来公知の方法に準じて行うことができる。例えば、硬化剤組成物の各成分、エポキシ樹脂、及び任意に他の成分を混合して、エポキシ樹脂組成物を調製することができる。混合手段には、従来公知の混合手段を特に制限なく使用することができる。例えば、市販の公転自転撹拌機を用いて撹拌してもよい。 Preparation of the epoxy resin composition is not particularly difficult and can be carried out according to conventionally known methods. For example, an epoxy resin composition can be prepared by mixing each component of the curing agent composition, the epoxy resin, and optionally other components. As the mixing means, conventionally known mixing means can be used without particular limitation. For example, a commercially available revolving and rotating stirrer may be used for stirring.
本発明の硬化剤組成物を使用することで、硬化性に優れるエポキシ樹脂組成物を得ることができる。エポキシ樹脂組成物の硬化性は、例えば、ホットプレート式ゲル化試験機(GT-D:日新化学社製)を用い、特定の温度(例えば、100~150℃の間の温度)に加熱したホットプレート上に約0.5gの樹脂組成物を直径25mmの範囲内となるように乗せ、先端幅約5mmのスパチュラで混ぜながら1秒間に1回転となるように攪拌し、ホットプレート上面から30mmの高さにスパチュラで持ち上げて糸を引かなくなるまでの時間(ゲルタイム)により評価することができる。ゲルタイムが短いほど硬化性が高く、特に100℃でのゲルタイムが短いほど、低温硬化性に優れている。 By using the curing agent composition of the present invention, an epoxy resin composition with excellent curability can be obtained. The curability of the epoxy resin composition can be determined by heating it to a specific temperature (for example, a temperature between 100 and 150°C) using a hot plate gelling tester (GT-D: manufactured by Nissin Chemical Co., Ltd.). Place about 0.5 g of the resin composition on a hot plate so that it is within a diameter of 25 mm, stir it with a spatula with a tip width of about 5 mm at a rate of 1 revolution per second, and keep it at a distance of 30 mm from the top of the hot plate. The gel time can be evaluated by the time it takes for the gel to stop pulling when the gel is lifted with a spatula to a height of . The shorter the gel time, the higher the curability, and especially the shorter the gel time at 100°C, the better the low-temperature curability.
エポキシ樹脂組成物は、例えば、建築、土木、自動車、船舶、宇宙航空、産業機械、ロボット、通信、電気電子、半導体、ディスプレイ等の各分野におけるエポキシ樹脂材料等として用いることができる。より具体的には、接着剤、接合剤、導電材、磁性材、熱伝導材、絶縁材、封止材、コーティング材、制振・防振材、防音材、充填材及び塗料、等として用いることができる。 The epoxy resin composition can be used, for example, as an epoxy resin material in various fields such as architecture, civil engineering, automobiles, ships, aerospace, industrial machinery, robots, communications, electrical and electronics, semiconductors, and displays. More specifically, it is used as adhesives, bonding agents, conductive materials, magnetic materials, thermal conductive materials, insulating materials, sealing materials, coating materials, damping/vibration-proofing materials, soundproofing materials, fillers, paints, etc. be able to.
本発明は、また、エポキシ樹脂組成物を含む接着剤に関する。ここで接着剤は、好ましくは、電子部品の接着剤の分野で使用できる接着剤である。上記接着剤は、本発明のエポキシ樹脂組成物以外に、任意にA成分及びB成分以外のエポキシ樹脂用硬化剤、硬化促進剤、難燃剤、保存安定性向上剤、充填剤、希釈剤、溶剤、顔料、可撓性付与剤、カップリング剤、酸化防止剤、沈降防止剤、分散剤等の各種添加剤を含んでいてもよい。 The present invention also relates to adhesives comprising epoxy resin compositions. The adhesive here is preferably an adhesive that can be used in the field of adhesives for electronic components. In addition to the epoxy resin composition of the present invention, the adhesive may optionally contain a curing agent for epoxy resin other than components A and B, a curing accelerator, a flame retardant, a storage stability improver, a filler, a diluent, and a solvent. , pigments, flexibility-imparting agents, coupling agents, antioxidants, antisettling agents, dispersants, and other various additives.
本発明は、また、エポキシ樹脂組成物を含む封止材に関する。ここで封止材とは、フリップチップ実装時のアンダーフィル剤、チップオンボード用封止剤などの封止用材料である。上記封止材は、本発明のエポキシ樹脂組成物以外に、任意にA成分及びB成分以外のエポキシ樹脂用硬化剤、硬化促進剤、難燃剤、保存安定性向上剤、充填剤、希釈剤、溶剤、顔料、可撓性付与剤、カップリング剤、酸化防止剤、沈降防止剤、分散剤等の各種添加剤を含んでいてもよい。 The present invention also relates to an encapsulant containing an epoxy resin composition. Here, the sealing material is a sealing material such as an underfill agent for flip-chip mounting and a chip-on-board sealant. In addition to the epoxy resin composition of the present invention, the above-mentioned sealing material may optionally include a curing agent for epoxy resin other than component A and component B, a curing accelerator, a flame retardant, a storage stability improver, a filler, a diluent, It may contain various additives such as a solvent, a pigment, a flexibility imparting agent, a coupling agent, an antioxidant, an antisettling agent, and a dispersant.
本発明は、また、上記のエポキシ樹脂組成物を硬化させて得られる硬化物及び当該硬化物を含有する電子デバイスに関する。電子デバイスとしては、例えば、LED、半導体、レーザー、太陽電池、有機ELデバイス等が挙げられる。 The present invention also relates to a cured product obtained by curing the above-mentioned epoxy resin composition and an electronic device containing the cured product. Examples of electronic devices include LEDs, semiconductors, lasers, solar cells, organic EL devices, and the like.
エポキシ樹脂組成物の硬化は、特別の困難はなく、従来公知の方法に準じて行うことができる。例えば、得られたエポキシ樹脂組成物を加熱することで硬化することができる。加熱は、例えば、60~150℃、好ましくは70~130℃、より好ましくは80~120℃の温度で、例えば1~120分、好ましくは3~100分、より好ましくは5~80分の時間行うことが適当である。 Curing of the epoxy resin composition is not particularly difficult and can be carried out according to conventionally known methods. For example, the obtained epoxy resin composition can be cured by heating. Heating is performed at a temperature of, for example, 60 to 150°C, preferably 70 to 130°C, more preferably 80 to 120°C, for example, for 1 to 120 minutes, preferably 3 to 100 minutes, more preferably 5 to 80 minutes. It is appropriate to do so.
本発明のエポキシ樹脂組成物の硬化物は、高い透明性を有する。硬化物の透明性は、例えば、特定の硬化条件で得られた硬化物について、φ80mm積分球(型名SRS-99-010、反射率99%)を装着したファイバ式分光光度計(MCPD-7700、形式311C、大塚電子社製、外部光源ユニット:ハロゲンランプMC-2564(24V、150W仕様))を使用し、硬化物の光透過率スペクトルを測定し、得られた光透過率スペクトルから、硬化物の400nmの全光線透過率を算出することで評価することができる。全光線透過率が高いほど、透明性に優れている。 The cured product of the epoxy resin composition of the present invention has high transparency. For example, the transparency of a cured product can be measured using a fiber spectrophotometer (MCPD-7700) equipped with a φ80 mm integrating sphere (model name SRS-99-010, reflectance 99%) for a cured product obtained under specific curing conditions. , type 311C, manufactured by Otsuka Electronics, external light source unit: halogen lamp MC-2564 (24V, 150W specifications)) was used to measure the light transmittance spectrum of the cured product, and from the obtained light transmittance spectrum, the cured It can be evaluated by calculating the total light transmittance of the object at 400 nm. The higher the total light transmittance, the better the transparency.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
[エポキシ樹脂組成物の調製]
エポキシ樹脂(jER828EL、三菱化学社製、エポキシ当量190)100質量部に、ジヒドラジド化合物と、本発明の芳香族カルボン酸(実施例1~7、9~12)、本発明の脂肪族カルボン酸(実施例8)又は比較物質(比較例2~9)とを、表1~3に示される組成となるように添加し、公転自転撹拌機(株式会社シンキー製ARE-250「あわとり錬太郎」)で2分間撹拌して樹脂組成物を得た。比較例1及び10~13については、エポキシ樹脂にジヒドラジド化合物のみを添加して攪拌した。使用したジヒドラジド化合物は、以下のとおりである。
[Preparation of epoxy resin composition]
A dihydrazide compound, an aromatic carboxylic acid of the present invention (Examples 1 to 7, 9 to 12), an aliphatic carboxylic acid of the present invention ( Example 8) or comparative substances (Comparative Examples 2 to 9) were added to give the compositions shown in Tables 1 to 3, and a revolving stirrer (ARE-250 "Awatori Rentaro" manufactured by Shinky Co., Ltd.) was used. ) for 2 minutes to obtain a resin composition. In Comparative Examples 1 and 10 to 13, only the dihydrazide compound was added to the epoxy resin and stirred. The dihydrazide compounds used are as follows.
VDH-J: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(味の素ファインテクノ社製、メジアン径2μm)
UDH-J:7,11-オクタデカジエン-1,18-ジカルボヒドラジド(味の素ファインテクノ社製、メジアン径2μm)
ADH:アジピン酸ジヒドラジド(日本ファインケム社製、メジアン径13μm)
N-12:ドデカン二酸ジヒドラジド(日本ファインケム社製、メジアン径9μm)
IDH:イソフタル酸ジヒドラジド(日本ファインケム社製)
VDH-J: 1,3-bis(hydrazinocarbonoethyl)-5-isopropylhydantoin (manufactured by Ajinomoto Fine Techno, Inc., median diameter 2 μm)
UDH-J: 7,11-octadecadiene-1,18-dicarbohydrazide (manufactured by Ajinomoto Fine Techno Co., Ltd., median diameter 2 μm)
ADH: Adipic acid dihydrazide (manufactured by Nippon Finechem Co., Ltd., median diameter 13 μm)
N-12: Dodecanedioic acid dihydrazide (manufactured by Nippon Finechem Co., Ltd., median diameter 9 μm)
IDH: Isophthalic acid dihydrazide (manufactured by Nippon Finechem Co., Ltd.)
[ゲルタイムの測定]
ホットプレート式ゲル化試験機(GT-D:日新化学社製)を用い、ジヒドラジド化合物としてVDH-Jを含む組成物については100℃、VDH-J以外を含む組成物については130℃、140℃又は150℃に加熱したホットプレート上に約0.5gの樹脂組成物を直径25mmの範囲内となるように乗せ、先端幅約5mmのスパチュラで混ぜながら1秒間に1回転となるように攪拌し、ホットプレート上面から30mmの高さにスパチュラで持ち上げて糸を引かなくなるまでの時間をゲルタイムとした。結果を表1~3に示す。
[Measurement of gel time]
Using a hot plate gelation tester (GT-D: manufactured by Nissin Kagaku Co., Ltd.), the compositions containing VDH-J as a dihydrazide compound were tested at 100°C, and the compositions containing other than VDH-J were tested at 130°C and 140°C. Place about 0.5 g of the resin composition on a hot plate heated to 150 °C or 150 °C so that it is within a diameter of 25 mm, and stir with a spatula with a tip width of about 5 mm to make one rotation per second. Then, the gel time was defined as the time until the string was no longer pulled when lifted with a spatula to a height of 30 mm from the top of the hot plate. The results are shown in Tables 1 to 3.
[硬化物の透明性の測定]
各エポキシ樹脂組成物を直径3cmの底面が平滑な缶の容器に気泡が入らないように2ml投入し、容器の底面全面が樹脂配合物で満たされるようにスパチュラを用いて樹脂配合物を広げ、熱風循環式オーブンで、ジヒドラジド化合物としてVDH-Jを含む組成物については100℃、VDH-J以外を含む組成物については130℃、140℃又は150℃で30分加熱し、硬化したものについて、硬化物に傷がつかないように缶の容器からはがして硬化物を得た。φ80mm積分球(型名SRS-99-010、反射率99%)を装着したファイバ式分光光度計(MCPD-7700、形式311C、大塚電子社製、外部光源ユニット:ハロゲンランプMC-2564(24V、150W仕様))を使用して、硬化物の光透過率スペクトルを測定した。得られた光透過率スペクトルから、硬化物の400nmの全光線透過率を算出した。結果を表1~3に示す。
[Measurement of transparency of cured product]
Pour 2 ml of each epoxy resin composition into a 3 cm diameter can with a smooth bottom, taking care not to introduce air bubbles, and use a spatula to spread the resin mixture so that the entire bottom of the container is filled with the resin mixture. For those cured by heating in a hot air circulation oven at 100 °C for compositions containing VDH-J as a dihydrazide compound, and 130 °C, 140 °C or 150 °C for compositions containing other than VDH-J for 30 minutes, The cured product was obtained by peeling it off from the can container so as not to damage the cured product. Fiber spectrophotometer (MCPD-7700, type 311C, manufactured by Otsuka Electronics Co., Ltd.) equipped with a φ80 mm integrating sphere (model name SRS-99-010, reflectance 99%), external light source unit: halogen lamp MC-2564 (24 V, The light transmittance spectrum of the cured product was measured using a 150W specification). The total light transmittance of the cured product at 400 nm was calculated from the obtained light transmittance spectrum. The results are shown in Tables 1 to 3.
ジヒドラジド化合物としてVDH-Jを含む実施例1~8と比較例1~9とを比較すると、本発明のカルボン酸化合物を含む実施例1~8では、本発明のカルボン酸化合物及び比較物質を含まない比較例1や、同程度の量の比較物質を含む比較例2~9よりも、ゲルタイムが短かった。また、VDH-J以外のジヒドラジド化合物を含む実施例9~12と比較例10~13についても、同じジヒドラジド化合物を含むもの同士で比較すると、本発明のカルボン酸化合物を含む実施例9~12では、本発明のカルボン酸化合物及び比較物質を含まない比較例10~13よりも、ゲルタイムが短かった。 Comparing Examples 1 to 8 containing VDH-J as the dihydrazide compound and Comparative Examples 1 to 9, it is found that Examples 1 to 8 containing the carboxylic acid compound of the present invention contain the carboxylic acid compound of the present invention and the comparative substance. The gel time was shorter than that of Comparative Example 1, which did not contain the substance, and Comparative Examples 2 to 9, which contained the same amount of the comparative substance. Furthermore, when comparing Examples 9 to 12 and Comparative Examples 10 to 13 containing dihydrazide compounds other than VDH-J, it was found that Examples 9 to 12 containing the carboxylic acid compound of the present invention The gel time was shorter than that of Comparative Examples 10 to 13, which did not contain the carboxylic acid compound of the present invention and the comparative substance.
硬化物の透明性の測定において、比較例1~13ではいずれも硬化性が不十分なため、測定のための硬化物が得られなかったのに対し、実施例1~12ではいずれも硬化物が得られた。硬化物が得られた実施例1~12について、透過率を求めたところ、使用したジヒドラジド化合物の融点が低いものほど透明性が高い傾向が見られ、特にVDH-Jを含む組成物からは透明性の高い硬化物が得られた。 In measuring the transparency of the cured products, all of Comparative Examples 1 to 13 had insufficient curability and no cured products could be obtained for measurement, whereas in Examples 1 to 12, the cured products were all was gotten. When the transmittance was determined for Examples 1 to 12 in which cured products were obtained, it was found that the lower the melting point of the dihydrazide compound used, the higher the transparency. A cured product with high properties was obtained.
本発明の硬化剤組成物を使用したエポキシ樹脂組成物は、接着剤や封止材に好適に用いることができ、その硬化物は、電子デバイスとして使用することができる。 Epoxy resin compositions using the curing agent composition of the present invention can be suitably used for adhesives and sealants, and cured products thereof can be used as electronic devices.
Claims (12)
(B)芳香族カルボン酸又は脂肪族カルボン酸と、
を含む、硬化剤組成物であって、
前記芳香族カルボン酸が、1個のカルボキシ基と0~2個のヒドロキシ基とを有する芳香環を1個又は2個含み、
前記脂肪族カルボン酸が、1個のカルボキシ基と1個のヒドロキシ基とを含む、直鎖又は分岐鎖の飽和脂肪族カルボン酸である、
硬化剤組成物。 (A) a dihydrazide compound;
(B) aromatic carboxylic acid or aliphatic carboxylic acid;
A curing agent composition comprising:
The aromatic carboxylic acid contains one or two aromatic rings having one carboxy group and 0 to 2 hydroxy groups,
The aliphatic carboxylic acid is a linear or branched saturated aliphatic carboxylic acid containing one carboxy group and one hydroxy group,
Hardener composition.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2022127976A JP2024024961A (en) | 2022-08-10 | 2022-08-10 | Curing agent for epoxy resin and epoxy resin composition |
CN202310953513.3A CN117586479A (en) | 2022-08-10 | 2023-07-31 | Curing agent for epoxy resin and epoxy resin composition |
TW112129338A TW202411288A (en) | 2022-08-10 | 2023-08-04 | Curing agent for epoxy resin and epoxy resin composition combining a dihydrazide compound with a carboxylic acid compound having a specific structure to form an epoxy resin composition with excellent curability |
KR1020230103645A KR20240021722A (en) | 2022-08-10 | 2023-08-08 | Curing agent for epoxy resin and epoxy resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2022127976A JP2024024961A (en) | 2022-08-10 | 2022-08-10 | Curing agent for epoxy resin and epoxy resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2024024961A true JP2024024961A (en) | 2024-02-26 |
Family
ID=89915530
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2022127976A Pending JP2024024961A (en) | 2022-08-10 | 2022-08-10 | Curing agent for epoxy resin and epoxy resin composition |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP2024024961A (en) |
KR (1) | KR20240021722A (en) |
CN (1) | CN117586479A (en) |
TW (1) | TW202411288A (en) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0657741B2 (en) | 1986-09-25 | 1994-08-03 | 味の素株式会社 | One-part epoxy resin composition |
-
2022
- 2022-08-10 JP JP2022127976A patent/JP2024024961A/en active Pending
-
2023
- 2023-07-31 CN CN202310953513.3A patent/CN117586479A/en active Pending
- 2023-08-04 TW TW112129338A patent/TW202411288A/en unknown
- 2023-08-08 KR KR1020230103645A patent/KR20240021722A/en unknown
Also Published As
Publication number | Publication date |
---|---|
CN117586479A (en) | 2024-02-23 |
KR20240021722A (en) | 2024-02-19 |
TW202411288A (en) | 2024-03-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4587323B2 (en) | Use of urea-derivatives as accelerators for epoxy resins | |
TWI608028B (en) | Curable resin compositions | |
TWI650370B (en) | Soft epoxy resin composition | |
JPH075708B2 (en) | Masterbatch type hardener for one-part epoxy resin | |
TWI554539B (en) | Curable resin compositions | |
TW201730233A (en) | Epoxy resin composition | |
CN108250899A (en) | A kind of air drying type room temperature-cured aqueous epoxy water-repellent paint and its preparation method and application | |
JP3007026B2 (en) | Heat-curable epoxy resin composition | |
JP6555042B2 (en) | Granular resin composition | |
JP2024024961A (en) | Curing agent for epoxy resin and epoxy resin composition | |
JP2019038960A (en) | Polycarbodiimide compound and thermosetting resin composition | |
JP2004115729A (en) | One-pack type epoxy resin composition | |
JP2019143085A (en) | Thermosetting epoxy resin composition, adhesive, epoxy resin cured product, salt, and curing agent | |
JPS61190521A (en) | Epoxy resin composition | |
JP2015101633A (en) | Epoxy resin composition | |
JP5258205B2 (en) | Two-component curable resin composition | |
JP2014173008A (en) | Curable resin composition | |
JP2013001875A (en) | Masterbatch type hardener composition, one-part epoxy resin composition and molded article using the same, and method for producing the masterbatch type hardener composition | |
CN106189974A (en) | A kind of preparation technology of the good conducting resinl of LED caking property | |
JPH0627183B2 (en) | Liquid epoxy resin composition | |
JPWO2018159564A1 (en) | Resin composition | |
JP2016108429A (en) | Microcapsule-type amine-based curing agent, curable resin composition, fine chemical and composition | |
JPH10101773A (en) | One-pack epoxy resin composition | |
JP2019199511A (en) | Method for producing epoxy resin composition | |
JP6039895B2 (en) | Curing agent, microcapsule type curing agent, masterbatch type curing agent composition, one-part epoxy resin composition and processed product |