CN112552487A - Epoxy resin curing agent, epoxy resin composition, and cured product thereof - Google Patents
Epoxy resin curing agent, epoxy resin composition, and cured product thereof Download PDFInfo
- Publication number
- CN112552487A CN112552487A CN202010928102.5A CN202010928102A CN112552487A CN 112552487 A CN112552487 A CN 112552487A CN 202010928102 A CN202010928102 A CN 202010928102A CN 112552487 A CN112552487 A CN 112552487A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- group
- compound
- curing agent
- resin curing
- 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
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 164
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 164
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 70
- -1 imidazole compound Chemical class 0.000 claims abstract description 46
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 230000009257 reactivity Effects 0.000 claims description 24
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 20
- 150000002894 organic compounds Chemical class 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000000524 functional group Chemical group 0.000 claims description 13
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 238000001723 curing Methods 0.000 description 59
- 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 12
- 239000002904 solvent Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910000679 solder Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 239000002981 blocking agent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 4
- 230000006324 decarbonylation Effects 0.000 description 4
- 238000006606 decarbonylation reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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
- YMKWWHFRGALXLE-UHFFFAOYSA-N 4-methyl-1-phenyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound C1CC(C)=CP1(=O)C1=CC=CC=C1 YMKWWHFRGALXLE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$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
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
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- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000008096 xylene Substances 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
- C08G59/56—Amines together with other curing agents
-
- 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
- C08G59/4028—Isocyanates; Thioisocyanates
-
- 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
- C08G59/4042—Imines; Imides
-
- 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
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides an epoxy resin curing agent, an epoxy resin composition containing the epoxy resin curing agent and a cured product of the epoxy resin composition. The present invention relates to an epoxy resin curing agent containing a predetermined polycarbodiimide compound and a predetermined imidazole compound, an epoxy resin composition containing the curing agent and an epoxy resin, and a cured product thereof.
Description
Technical Field
The present invention relates to an epoxy resin curing agent containing a polycarbodiimide compound, an epoxy resin composition containing the epoxy resin curing agent, and a cured product thereof.
Background
Epoxy resins are thermosetting resins having excellent electrical insulating properties, and are used for various electronic component applications such as electronic substrate materials and semiconductor element sealing materials, for example, by utilizing their properties. In the epoxy resin used for such applications, various properties such as heat resistance, dimensional stability, and handling property are further improved.
For example, patent document 1 describes that an epoxy resin composition having excellent storage stability and excellent handling properties and moldability can be obtained by adding a polycarbodiimide compound derived from a predetermined diphenylmethane diisocyanate (MDI) to an epoxy resin.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2019-38960
Disclosure of Invention
However, when an epoxy resin composition to which the MDI-derived polycarbodiimide compound described in patent document 1 is added is cured, the reactivity of the polycarbodiimide compound is not necessarily high. Therefore, in the cured product of the epoxy resin composition, an unreacted polycarbodiimide compound remains, and the effect of improving the dimensional stability and heat resistance of the epoxy resin during heating may not be sufficiently obtained.
Therefore, it is required to improve the reactivity of the polycarbodiimide compound added to the epoxy resin with respect to the epoxy resin.
The present invention has been made to solve the above problems, and an object of the present invention is to provide an epoxy resin curing agent which is an epoxy resin curing agent containing a polycarbodiimide compound and can improve the reactivity of the polycarbodiimide compound with an epoxy resin and further improve the dimensional stability and heat resistance of the epoxy resin cured product when heated, and an epoxy resin composition containing the epoxy resin curing agent, and a cured product thereof.
The present invention has been accomplished based on the finding that the reactivity of a polycarbodiimide compound to an epoxy resin can be improved by adding the polycarbodiimide compound to the epoxy resin together with a predetermined imidazole compound.
Namely, the present invention provides the following [1] to [9 ].
[1] An epoxy resin curing agent comprising a polycarbodiimide compound represented by the following formula (1) and an imidazole compound represented by the following formula (2).
R1-X1-R3-(N＝C＝N-R3)n-X2-R2 (1)
(in the formula (1), R1And R2Each independently is a residue obtained by removing 1 functional group reactive with an isocyanate group from an organic compound having the functional group.
R3Is a 2-valent residue obtained by removing 2 isocyanate groups from 1 molecule of each diisocyanate compound of the following (i) or (ii).
(i) Diisocyanate compound comprising 2,4 '-diphenylmethane diisocyanate and 4, 4' -diphenylmethane diisocyanate in a molar ratio of 30/70 to 70/30
(ii) Dicyclohexylmethane-4, 4' -diisocyanate
X1And X2Each independently is a bond formed by the reaction of the functional group of the organic compound with the isocyanate group of the diisocyanate compound.
n represents a number of 2 to 30. )
[ chemical formula 1]
(in the formula (2), R11Is a hydrogen atom, a methyl group or a benzyl group.
R12Is hydrogen atom, alkyl group with 1-18 carbon atoms or phenyl group.
R13Is a hydrogen atom or a methyl group. )
[2] The curing agent for epoxy resin according to the above [1], wherein the imidazole compound is contained in an amount of 0.5 to 10 parts by mass per 100 parts by mass of the polycarbodiimide compound.
[3] The curing agent for epoxy resin according to the above [1] or [2], wherein the organic compound is at least one selected from the group consisting of monoisocyanates, monoalcohols, monoamines, monocarboxylic acids and carboxylic anhydrides.
[4]According to the above [1]～[3]The epoxy resin curing agent according to any one of the above formulas (2), wherein R is11Is a hydrogen atom or a methyl group, R12Is methyl or ethyl, R13Is a hydrogen atom or a methyl group.
[5] The curing agent for epoxy resin according to any one of the above [1] to [4], wherein the imidazole compound is at least one selected from the group consisting of 2-methylimidazole, 1, 2-dimethylimidazole and 2-ethyl-4-methylimidazole.
[6] An epoxy resin composition comprising the epoxy resin curing agent according to any one of the above [1] to [5] and an epoxy resin.
[7] The epoxy resin composition according to the above [6], wherein the content of the epoxy resin curing agent is such that the carbodiimide group of the polycarbodiimide compound is in the range of 0.1 to 2.0 mol based on 1 mol of the epoxy group of the epoxy resin.
[8] A cured product obtained by curing the epoxy resin composition according to [6] or [7 ].
[9] An electronic component material comprising the cured product according to [8 ].
According to the present invention, an epoxy resin curing agent containing a polycarbodiimide compound, which has high reactivity with an epoxy resin, can be obtained.
Further, according to the epoxy resin composition containing the epoxy resin curing agent, a cured product excellent in dimensional stability and heat resistance when heated can be provided, and the cured product can be suitably used as an electronic component material.
Detailed Description
The epoxy resin curing agent of the present invention, an epoxy resin composition containing the epoxy resin curing agent, and a cured product thereof will be described in detail below.
[ curing agent for epoxy resin ]
The epoxy resin curing agent of the present invention contains a predetermined polycarbodiimide compound (a) and a predetermined imidazole compound (B).
By using a predetermined polycarbodiimide compound (A) and a predetermined imidazole compound (B) in combination, the reactivity of the polycarbodiimide compound (A) to an epoxy resin can be improved.
The reactivity of the polycarbodiimide compound (a) with respect to the epoxy resin can be confirmed by using, as an index, the amount of carbodiimide group of the polycarbodiimide compound (a) added to the epoxy resin, which decreases before and after the curing reaction of the epoxy resin. Specifically, as described in the examples below, the wavenumber of the carbodiimide group-derived material, which can be determined based on infrared absorption (IR) spectroscopy, is 2150cm-1The reaction rate was determined by the peak height of the absorbance at the left and right sides.
When the reaction rate is 70% or more, preferably 75% or more, more preferably 80% or more, and further preferably 90% or more, the reactivity of the polycarbodiimide compound (a) to the epoxy resin can be said to be high.
< polycarbodiimide Compound (A) >)
The polycarbodiimide compound (a) in the epoxy resin curing agent of the present invention is a compound represented by the following formula (1).
R1-X1-R3-(N＝C＝N-R3)n-X2-R2 (1)
(R1And R2)
R in the formula (1)1And R2Each independently is a residue obtained by removing 1 functional group reactive with an isocyanate group from an organic compound having the functional group. The organic compound is a blocking agent for blocking a terminal isocyanate group in the compound represented by the formula (1). The R is1And said R2May be the same as or different from each other.
Examples of the functional group having reactivity with an isocyanate group include a hydroxyl group, an amino group, an isocyanate group, a carboxyl group, and a carboxylic anhydride. When the functional group is a hydroxyl group, the functional group is formed by the reaction with an isocyanate groupA urethane bond. In addition, the functional group forms a urea bond when it is an amino group, a carbodiimide bond when it is an isocyanate group, an amide bond when it is a carboxyl group, and an imide bond when it is a carboxylic anhydride. The bond formed by the reaction of these functional groups with an isocyanate group corresponds to X in the formula (1)1And X2。
Examples of the organic compound include monoisocyanates, monoalcohols, monoamines, monocarboxylic acids, and carboxylic anhydrides. The organic compound may be a single one of these organic compounds, or 2 or more.
When the organic compound is a monoisocyanate, a carbodiimide bond (carbodiimide group) is formed by a reaction with the terminal isocyanate group, whereby the content of the carbodiimide group in the polycarbodiimide compound (a) can be increased.
Examples of the monoisocyanate include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, 2, 6-diisopropylphenyl isocyanate, and the like. Wherein R is selected from the group consisting of3In view of reactivity of the diisocyanate compound of the source compound (b), cyclohexyl isocyanate, phenyl isocyanate and tolyl isocyanate are preferable, and cyclohexyl isocyanate and phenyl isocyanate are more preferable.
Examples of the monohydric alcohol include methanol, ethanol, 1-propanol, cyclohexanol, 2-ethylhexanol, (poly) ethylene glycol monomethyl ether, (poly) propylene glycol monomethyl ether, phenol, cresol, naphthol, and the like.
Examples of the monoamine include butylamine, pentylamine, cyclohexylamine, diethylamine, dipropylamine, dibutylamine, and dicyclohexylamine.
Examples of the monocarboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, cyclohexanecarboxylic acid, adamantaneacetic acid, benzoic acid, and phenylacetic acid.
Examples of the carboxylic anhydride include phthalic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, and benzoic anhydride.
(R3)
R in the formula (1)3Is a 2-valent residue obtained by removing 2 isocyanate groups from 1 molecule of each diisocyanate compound (B) of the following (i) or (ii). A plurality of R in the formula (1)3May be the same as or different from each other.
(i) Diisocyanate compound (MDI) comprising 2,4 '-diphenylmethane diisocyanate (2, 4' -MDI) and 4,4 '-diphenylmethane diisocyanate (4, 4' -MDI) in a molar ratio of 30/70 to 70/30
(ii) Dicyclohexylmethane-4, 4' -diisocyanate (HMDI)
The 2,4 '-MDI and the 4, 4' -MDI in (i) are isomers having different bonding positions of isocyanate groups bonded to 2 benzene rings, respectively. 2 isocyanate groups of 2,4 '-MDI are located closer to 4, 4' -MDI, and it is considered that the crystallinity is likely to be lowered by steric hindrance in polycarbodiimidization.
In the (i), the molar ratio of 2,4 '-MDI to 4, 4' -MDI is 30/70 to 70/30, preferably 40/60 to 65/35, and more preferably 50/50 to 60/40, from the viewpoint of reactivity of the polycarbodiimide compound (A) obtained by polymerizing the diisocyanate compound with an epoxy resin.
When the molar ratio of 2,4 '-MDI to 4, 4' -MDI is less than 30/70, the crystallinity of the polycarbodiimide compound obtained by polymerization thereof tends to be high, and the reactivity of the polycarbodiimide compound with the epoxy resin tends to be high, but the solubility in an organic solvent is low, and the handling is difficult.
On the other hand, when the molar ratio exceeds 70/30, the steric hindrance becomes large, and thus the reactivity of the polycarbodiimide compound with respect to the epoxy resin tends to be low.
The HMDI of (ii) is a compound in which 2 benzene rings of 4, 4' -MDI are replaced with cyclohexane rings, and is an alicyclic diisocyanate compound also called hydrogenated MDI. HMDI has a structure similar to 4, 4' -MDI, and can improve the reactivity of the polycarbodiimide compound (a) obtained by polymerizing the diisocyanate compound with an epoxy resin.
(X1And X2)
X in the formula (1)1And X2Each independently represents the group represented by the organic compound and R3A bond formed by reaction of an isocyanate group of a diisocyanate compound of the source compound (1). As described above, X1And X2Are bonds corresponding to organic compounds and may be the same as or different from each other.
From the viewpoint of increasing the reaction point of the polycarbodiimide compound with the epoxy resin and improving the crosslinking density of the epoxy resin, X is1And X2The bond (b) is preferably a carbodiimide bond.
(n)
In the formula (1), n represents by as R3The number of carbodiimide groups generated by polymerization (decarbonylation condensation reaction) between the diisocyanate compounds of the source compound of (1), and represents an average value of polycarbodiimide compounds obtained by polymerization.
From the viewpoint of reactivity, handling, etc., of the polycarbodiimide compound (A) to the epoxy resin, the n is a number of 2 to 30, preferably 3 to 25, more preferably 4 to 20.
When n is less than 2, the reaction point of the polycarbodiimide compound with the epoxy resin decreases, and it is difficult to increase the crosslinking density of the epoxy resin.
On the other hand, when n exceeds 30, the polycarbodiimide compound is easily gelled, and the workability in applying the epoxy resin curing agent to an epoxy resin is poor.
The content of the polycarbodiimide compound (a) in the epoxy resin curing agent is preferably 85 mass% or more, more preferably 90 mass% or more, and still more preferably 95 mass% or more, out of 100 mass% of the epoxy resin curing agent, from the viewpoint of efficiently obtaining a cured product of an epoxy resin having desired dimensional stability, heat resistance, and the like by adding the polycarbodiimide compound (a).
< preparation of polycarbodiimide Compound (A) >
The method for producing the polycarbodiimide compound (a) is not particularly limited, and a known method can be used. For example, the following synthesis methods (a) to (c) can be mentioned.
(a) Will be said R3The diisocyanate compound of the source compound (a) and the organic compound (a blocking agent) are mixed, and a carbodiimidization reaction and a blocking reaction are carried out in the presence of a catalyst
(b) A method in which the diisocyanate compound is subjected to carbodiimidization in the presence of a catalyst to obtain an isocyanate-terminated polycarbodiimide, and then the organic compound (blocking agent) is added to carry out a blocking reaction
(c) A method of reacting the diisocyanate compound with the organic compound, adding a catalyst, and carrying out a carbodiimidization reaction and a blocking reaction
Among these synthesis methods, the method (a) is preferable from the viewpoint of ease of controlling the number of n.
(Carbodiimidization reaction)
The carbodiimidization reaction is preferably, for example, polymerization (decarbonylation condensation reaction) of the diisocyanate compound in the presence of a carbodiimidization catalyst.
Examples of the carbodiimidization catalyst include phospholene oxides such as 1-phenyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof. Among them, 3-methyl-1-phenyl-2-phosphole-1-oxide is preferable from the viewpoint of reactivity, availability, and the like.
The carbodiimidization catalyst is used in an amount of preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the diisocyanate compound.
The decarbonylation condensation reaction of the diisocyanate compound may be carried out in a solvent or without a solvent. Examples of the solvent to be used include alicyclic ethers such as tetrahydrofuran, 1, 3-dioxane and dioxolane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, perchloroethylene, trichloroethane, and dichloroethane; cyclohexanone, and the like. These solvents may be used alone or in combination of 2 or more.
When the reaction is carried out in a solvent, the concentration of the diisocyanate compound is preferably 5 to 55% by mass, more preferably 5 to 20% by mass, from the viewpoint of homogenization of the reaction system.
The reaction temperature of the decarbonylation condensation reaction can be appropriately set according to an appropriate reaction acceleration, a polymerization degree of a carbodiimide group, and the like. It is usually preferably from 40 to 250 ℃, more preferably from 50 to 230 ℃, and still more preferably from 60 to 200 ℃. When the reaction is carried out in a solvent, a temperature in the range of 40 ℃ to the boiling point of the solvent is preferred.
The reaction time is appropriately set depending on the reaction temperature, the degree of polymerization of the carbodiimide group, and the like. It is usually preferably from 0.5 to 100 hours, more preferably from 1 to 80 hours, and still more preferably from 2 to 60 hours.
The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or a rare gas.
(end capping reaction)
The blocking reaction is a reaction of the terminal isocyanate group after the polymerization of the diisocyanate compound and the organic compound (blocking agent). For example, in the method (a) described above, the terminal-blocking reaction can be carried out together with the carbodiimidization reaction of the diisocyanate compound by heating the diisocyanate compound and the organic compound (blocking agent) in the presence of a carbodiimidization catalyst.
The reaction temperature of the end-capping reaction is appropriately set within a range in which side reactions can be suppressed and the reaction can be promoted. It is usually preferably from 40 to 250 ℃, more preferably from 80 to 220 ℃, and still more preferably from 100 ℃ to 200 ℃.
The reaction time is appropriately set within a range in which the reaction temperature and side reactions can be suppressed. It is usually preferably from 0.1 to 20 hours, more preferably from 0.5 to 10 hours, and still more preferably from 1 to 3 hours. The time for the blocking reaction in the method (a) is within the time required for the carbodiimidization reaction.
< imidazole Compound (B) >
The epoxy resin curing agent of the present invention contains an imidazole compound (B) represented by the following formula (2). By using the imidazole compound (B) in combination, the reactivity of the polycarbodiimide compound (A) to an epoxy resin can be improved, and as a result, the dimensional stability and heat resistance of a cured product of the epoxy resin can be improved.
[ chemical formula 2]
R in the formula (2)11Is a hydrogen atom, a methyl group or a benzyl group, preferably a hydrogen atom or a methyl group.
R12Is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a phenyl group, preferably a methyl group or an ethyl group.
R13Is a hydrogen atom or a methyl group.
Some imidazole compounds used as epoxy resin curing agents do not exhibit sufficient activity in the curing reaction of epoxy resins unless they are in a high temperature range of 140 ℃. On the other hand, the imidazole compound (B) of the present invention exhibits sufficient activity in the curing reaction of the epoxy resin in a relatively low temperature region of less than 140 ℃, and such an imidazole compound can effectively improve the reactivity of the polycarbodiimide compound (A) to the epoxy resin.
Thus, as the imidazole compound showing sufficient activity in the curing reaction of the epoxy resin even in a relatively low temperature region of less than 140 ℃, preferably 70 to 130 ℃, R in the formula (2) is more preferable11Is a hydrogen atom or a methyl group, R12Is methyl or ethyl, R13Is a hydrogen atom or a methyl group.
Specific examples of such imidazole compounds include 2-methylimidazole, 1, 2-dimethylimidazole, and 2-ethyl-4-methylimidazole. These imidazole compounds may be used alone or in combination of 2 or more.
From the viewpoint of effectively improving the reactivity of the polycarbodiimide compound (a) to the epoxy resin, the content of the imidazole compound (B) in the epoxy resin curing agent is preferably 0.5 to 10 parts by mass, more preferably 1.0 to 5.0 parts by mass, and still more preferably 1.5 to 3.0 parts by mass, relative to 100 parts by mass of the polycarbodiimide compound (a).
The epoxy resin curing agent may contain, in addition to the polycarbodiimide compound (a) and the imidazole compound (B), known additives and solvents suitable for use in epoxy resin curing agents, such as an antioxidant, a flame retardant, an ultraviolet absorber, and a colorant. However, from the viewpoint of not hindering the effect of improving the reactivity of the polycarbodiimide compound (a) with respect to the epoxy resin, the total content of the polycarbodiimide compound (a) and the imidazole compound (B) in 100% by mass of the epoxy resin curing agent is preferably 85 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
[ epoxy resin composition ]
The epoxy resin composition of the present invention comprises the epoxy resin curing agent and an epoxy resin.
< epoxy resin >
The epoxy resin is not particularly limited as long as it has 2 or more epoxy groups in 1 molecule, and a known epoxy resin can be used. Examples thereof include bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, cyclopentadiene type epoxy resins, and the like. Among them, from the viewpoint of production efficiency of a cured product of an epoxy resin, it is preferable to use an epoxy resin that is liquid at room temperature or a solid epoxy resin dissolved in a solvent. The epoxy resin may be used alone or in combination of 2 or more.
In the epoxy resin composition, the carbodiimide group of the polycarbodiimide compound (a) in the epoxy resin curing agent is preferably in an amount of 0.1 to 2.0 moles, more preferably 0.2 to 1.5 moles, and even more preferably 0.3 to 1.0 mole, based on 1 mole of the epoxy group of the epoxy resin, from the viewpoint of efficiently obtaining a cured product of the epoxy resin having desired dimensional stability, heat resistance, and the like.
When the carbodiimide group is 0.1 mol or more, a sufficient effect of improving dimensional stability, heat resistance and the like of a cured product of the epoxy resin composition when heated can be obtained. In addition, from the viewpoint of enhancing the effect by adding the epoxy resin curing agent, a sufficient amount is obtained when the carbodiimide group is 2.0 mol or less.
From the viewpoints of ease of production of the epoxy resin composition, performance required for use, and the like, the epoxy resin composition may contain, as necessary, known additives and solvents suitable for epoxy resins, such as a filler, a release agent, a colorant, a flame retardant, and an antifoaming agent, within a range not impairing the effects of the present invention. These additives and solvents may be derived from the epoxy resin curing agent or may be added during the preparation of the epoxy resin composition.
The epoxy resin composition can be obtained by mixing the epoxy resin and the epoxy resin curing agent. In this case, the polycarbodiimide compound (a) and the imidazole compound (B) in the epoxy resin curing agent may be added separately, or may be added as components that are mixed and integrated in advance.
[ cured product of epoxy resin (composition) ]
The epoxy resin composition is cured by a known curing method for an epoxy resin, whereby a cured product of the epoxy resin (composition) can be obtained.
The curing conditions for curing the epoxy resin are appropriately set depending on the type and use of the epoxy resin. Generally, it can be cured at a curing temperature of 100 ℃ and 220 ℃ for a curing time of 0.1 to 5.0 hours.
The epoxy resin is cured by various molding methods such as casting, laminating, compression molding, transfer molding, and filament winding. The molded article may be made of a composite material containing glass fibers, carbon fibers, and the like.
The cured product has excellent dimensional stability during heating. In addition, even when a solder heat resistance, particularly a lead-free solder having a melting point higher than that of a general solder (e.g., 288 ℃), is applied, excellent solder heat resistance is exhibited.
Therefore, the cured product is suitable for use as an electronic substrate material, a sealing material for a semiconductor element, and other various electronic component materials.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.
[ Compounds to be used ]
The following epoxy resin curing agents, epoxy resin compositions, and polycarbodiimide compounds, imidazole compounds, and epoxy resins used in the preparation of cured products thereof in the following examples and comparative examples are shown.
< polycarbodiimide Compound >
Polycarbodiimide compounds (a1) and (a2) synthesized as follows were used.
(Synthesis of polycarbodiimide Compound (A1) (derived from MDI))
100 parts by weight of a mixture (MILLIONATE (registered trademark) NM, manufactured by Tosoh corporation) of 2,4 '-MDI and 4, 4' -MDI (molar ratio 54/46), 6.3 parts by weight of phenyl isocyanate, and 0.6 part by weight of 3-methyl-1-phenyl-2-phospholene-1-oxide as a carbodiimidization catalyst were charged into a reaction vessel equipped with a reflux tube and a stirrer, and stirred at 100 ℃ for 2 hours under a nitrogen stream. The wave number was confirmed to be 2270cm by IR spectroscopy (measuring apparatus: Fourier transform infrared spectrophotometer "FTIR-8200 PC", manufactured by Shimadzu corporation, the same shall apply hereinafter)-1The absorption peaks due to the left and right isocyanate groups were almost disappeared to obtain polycarbodiimide compound (a1) (wherein n in formula (1) is 16). The polycarbodiimide compound (A1) was pulverized into a powder by a pulverizer.
(Synthesis of polycarbodiimide Compound (A2) (from HMDI))
100 parts by mass of HMDI, 6.4 parts by mass of cyclohexyl isocyanate and 1.1 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide as carbodiimidization catalyst were charged into a reaction vessel equipped with a reflux tube and a stirrer, and stirred at 100 ℃ for 56 hours under a nitrogen stream. The wave number was confirmed to be 2270cm by IR spectroscopy-1The absorption peaks due to the left and right isocyanate groups were almost disappeared to obtain polycarbodiimide compound (a2) (wherein n in formula (1) is 16). The polycarbodiimide compound (A2) was pulverized into a powder by a pulverizer.
< imidazole Compounds >
1.2 DMZ: 1, 2-dimethylimidazole; "Curezol (registered trademark, the same applies hereinafter)" 1.2DMZ ", manufactured by four national chemical industry Co., Ltd
2E4 MZ: 2-ethyl-4-methylimidazole; "Curezol 2E4 MZ", manufactured by Sizhou Kasei Kogyo
2 MZ-H: 2-methylimidazole; "Curezol 2 MZ-H", manufactured by four national chemical industries, Ltd
2 PHZ-PW: 2-phenyl-4, 5-dihydroxymethylimidazole; "Curezol 2 PHZ-PW", manufactured by four national chemical industries, Ltd
TBZ: 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole; "Curezol TBZ", manufactured by Sination chemical industries Co., Ltd
< epoxy resin >
N-690: "Epiclon (registered trademark) N-690", available from DIC corporation, epoxy equivalent 214, cresol novolak type
HP-7200: epiclon (registered trademark) HP-7200, epoxy equivalent 259 manufactured by DIC corporation, dicyclopentadiene type
(example 1)
An epoxy resin composition obtained by adding an epoxy resin curing agent (1) to 100 parts by mass of epoxy resin N-690 was hot-pressed by a Mini test press (manufactured by Toyo Seiki Seisaku-Sho Ltd., a pressure of 3.0MPa) under curing conditions of a curing temperature of 200 ℃ and a curing time of 2 hours to obtain a sheet-like cured product having a thickness of 1mm, wherein the epoxy resin curing agent (1) was prepared by blending 83 parts by mass of a polycarbodiimide compound (A1) and 1.8 parts by mass of 1.2 DMZ.
(examples 2 to 8 and comparative examples 1 to 5)
Epoxy resin compositions in which the epoxy resin curing agent and the epoxy resin were set to the types and blending amounts shown in the following table 1 were subjected to a curing reaction under the same curing conditions as in example 1 to obtain respective cured products.
[ measurement evaluation ]
The following measurement evaluations were made for each cured product of the epoxy resin compositions prepared in the above examples and comparative examples. The results of these measurements are shown in table 1 below.
< reaction Rate >
For the epoxy resin composition, the wave number from the benzene ring was 1500cm as measured by IR spectroscopy-1The wave number of the carbodiimide group was determined at 2150cm based on the peak height of the absorbance at the left and right sides-1The ratio of the peak height of the absorbance to the peak height was defined as the pre-reaction peak intensity ratio P1. Further, the peak heights use the baseline corrected values.
Similarly, the peak height ratio of a cured product obtained by curing the epoxy resin composition was also determined and used as the peak intensity ratio P after the reaction2。
Then, from the pre-reaction peak intensity ratio P1And the peak intensity ratio P after the reaction2The reaction rate X [% by the following formula (3)]。
X[％]＝[1-P2/P1]×100 (3)
The reaction rate X represents the reactivity of the carbodiimide group in the epoxy resin curing agent with respect to the epoxy resin, and a larger numerical value indicates a higher reactivity of the carbodiimide group.
< coefficient of mean linear expansion >
A test piece 5mm square was cut out from a cured product of a sheet-like epoxy resin composition having a thickness of 1 mm.
The temperature of the test piece was increased at 10 ℃/min by a thermomechanical analyzer ("TMA 6100", manufactured by hitachi High-tech Science), and the change in the length of the test piece in the thickness direction was measured in a temperature range of 30 to 300 ℃ to determine the glass transition temperature (Tg) and the average linear expansion coefficient. The average linear expansion coefficient in a temperature range of 30 ℃ or more and glass transition temperature (Tg) or less is represented by α 1, and the average linear expansion coefficient in a temperature range of Tg or more and 300 ℃ or less is represented by α 2.
In comparative examples 1 to 3, 2 peaks considered to be Tg were detected, and the peak temperature on the low temperature side was used as Tg for the reference in obtaining the average linear expansion coefficient. When the epoxy resin and the polycarbodiimide compound (A) were not sufficiently reacted and a large amount of unreacted polycarbodiimide compound remained, 2 peaks were detected.
The average linear expansion coefficient varies depending on the type of the epoxy resin, but the smaller the value, the smaller the volume change due to heat, and it can be said that the cured product has excellent dimensional stability against temperature change. That is, in the case where the types of epoxy resins are the same, it can be said that the smaller the value of the average linear expansion coefficient, the more excellent the effect of improving the dimensional stability during heating by adding the epoxy resin curing agent is provided.
< solder Heat resistance >
A5 cm square sample was cut out of a cured product of a sheet-like epoxy resin composition having a thickness of 1 mm. Further, as a sample for evaluation of solder heat resistance, a cured product obtained by hot pressing in a state of being sandwiched by copper foils having a thickness of 35 μm was used.
The sample was immersed in a solder bath (lead-free solder) at 288 ℃, and the heat resistance time was measured as the time (maximum 60 seconds) until visible swelling appeared on the appearance.
When the heat resistance time exceeds 50 seconds, the solder heat resistance is determined to be good.
[ Table 1]
TABLE 1
As is clear from the measurement and evaluation results shown in table 1, according to the epoxy resin composition using the epoxy resin curing agent of the present invention, a cured product having high reactivity of a carbodiimide group in the epoxy resin curing agent with respect to an epoxy resin, excellent dimensional stability during heating, and excellent soldering heat resistance can be obtained.
Claims (9)
1. An epoxy resin curing agent comprising a polycarbodiimide compound represented by the following formula (1) and an imidazole compound represented by the following formula (2),
R1-X1-R3-(N＝C＝N-R3)n-X2-R2 (1)
in the formula (1), R1And R2Each independently is a residue obtained by removing 1 functional group having reactivity with an isocyanate group from an organic compound having the functional group;
R3a 2-valent residue obtained by removing 2 isocyanate groups from 1 molecule of each diisocyanate compound of the following (i) or (ii);
(i) diisocyanate compound comprising 2,4 '-diphenylmethane diisocyanate and 4, 4' -diphenylmethane diisocyanate in a molar ratio of 30/70 to 70/30
(ii) Dicyclohexylmethane-4, 4' -diisocyanate
X1And X2Each independently is a bond formed by the reaction of the functional group of the organic compound with the isocyanate group of the diisocyanate compound;
n represents a number of 2 to 30;
[ chemical formula 1]
In the formula (2), R11Is a hydrogen atom, a methyl group or a benzyl group;
R12is hydrogenAn alkyl group or a phenyl group having 1 to 18 carbon atoms;
R13is a hydrogen atom or a methyl group.
2. The epoxy resin curing agent according to claim 1, wherein the imidazole compound is contained in an amount of 0.5 to 10 parts by mass based on 100 parts by mass of the polycarbodiimide compound.
3. The epoxy resin curing agent according to claim 1 or 2, wherein the organic compound is one or more selected from the group consisting of monoisocyanates, monoalcohols, monoamines, monocarboxylic acids, and carboxylic anhydrides.
4. The epoxy resin curing agent according to any one of claims 1 to 3, wherein in the formula (2), R is11Is a hydrogen atom or a methyl group, R12Is methyl or ethyl, R13Is a hydrogen atom or a methyl group.
5. The epoxy resin curing agent according to any one of claims 1 to 4, wherein the imidazole compound is one or more selected from the group consisting of 2-methylimidazole, 1, 2-dimethylimidazole and 2-ethyl-4-methylimidazole.
6. An epoxy resin composition comprising the epoxy resin curing agent according to any one of claims 1 to 5 and an epoxy resin.
7. The epoxy resin composition according to claim 6, wherein the content of the epoxy resin curing agent is such that the carbodiimide group of the polycarbodiimide compound is 0.1 to 2.0 mol based on 1 mol of the epoxy group of the epoxy resin.
8. A cured product obtained by curing the epoxy resin composition according to claim 6 or 7.
9. An electronic component material comprising the cured product according to claim 8.
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| JP2019174722A JP2021050287A (en) | 2019-09-25 | 2019-09-25 | Curing agent for epoxy resin, epoxy resin composition and cured product thereof |
| JP2019-174722 | 2019-09-25 |
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| CN113390818A (en) * | 2021-06-11 | 2021-09-14 | 哈尔滨电机厂有限责任公司 | Method for measuring epoxy group and carboxyl group contents of VPI (vacuum pressure impregnation) resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123043A (en) * | 1999-10-26 | 2001-05-08 | Matsushita Electric Works Ltd | Epoxy resin composition, prepreg, resin attached metal foil and laminate |
| JP2005290215A (en) * | 2004-03-31 | 2005-10-20 | Tdk Corp | Epoxy resin composition, coil body and inductor |
| JP2008081727A (en) * | 2006-08-28 | 2008-04-10 | Matsushita Electric Works Ltd | Substrate-containing adhesive sheet for flexible printed wiring board and method for manufacturing the same, multilayer flexible printed wiring board, and flex rigid printed wiring board |
| CN107428914A (en) * | 2015-04-06 | 2017-12-01 | 日清纺化学株式会社 | Composition epoxy resin |
| WO2019044719A1 (en) * | 2017-08-28 | 2019-03-07 | 日清紡ケミカル株式会社 | Polycarbodiimide compound and thermosetting resin composition |
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| JP2015229763A (en) * | 2014-06-06 | 2015-12-21 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, metal-clad laminate sheet, printed wiring board |
| JP6849269B2 (en) * | 2015-04-06 | 2021-03-24 | 日清紡ケミカル株式会社 | Modified polycarbodiimide compound, curing agent and thermosetting resin composition |
| KR102508097B1 (en) * | 2017-03-10 | 2023-03-10 | 세키스이가가쿠 고교가부시키가이샤 | Resin materials, laminated films and multi-layer printed wiring boards |
-
2019
- 2019-09-25 JP JP2019174722A patent/JP2021050287A/en active Pending
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2020
- 2020-09-07 CN CN202010928102.5A patent/CN112552487A/en active Pending
- 2020-09-08 KR KR1020200114734A patent/KR20210036261A/en unknown
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123043A (en) * | 1999-10-26 | 2001-05-08 | Matsushita Electric Works Ltd | Epoxy resin composition, prepreg, resin attached metal foil and laminate |
| JP2005290215A (en) * | 2004-03-31 | 2005-10-20 | Tdk Corp | Epoxy resin composition, coil body and inductor |
| JP2008081727A (en) * | 2006-08-28 | 2008-04-10 | Matsushita Electric Works Ltd | Substrate-containing adhesive sheet for flexible printed wiring board and method for manufacturing the same, multilayer flexible printed wiring board, and flex rigid printed wiring board |
| CN107428914A (en) * | 2015-04-06 | 2017-12-01 | 日清纺化学株式会社 | Composition epoxy resin |
| WO2019044719A1 (en) * | 2017-08-28 | 2019-03-07 | 日清紡ケミカル株式会社 | Polycarbodiimide compound and thermosetting resin composition |
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| KR20210036261A (en) | 2021-04-02 |
| TW202116852A (en) | 2021-05-01 |
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