WO2022202610A1 - エポキシ樹脂組成物、エポキシ樹脂硬化物 - Google Patents
エポキシ樹脂組成物、エポキシ樹脂硬化物 Download PDFInfo
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- WO2022202610A1 WO2022202610A1 PCT/JP2022/012297 JP2022012297W WO2022202610A1 WO 2022202610 A1 WO2022202610 A1 WO 2022202610A1 JP 2022012297 W JP2022012297 W JP 2022012297W WO 2022202610 A1 WO2022202610 A1 WO 2022202610A1
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- Prior art keywords
- epoxy resin
- resin composition
- compound
- formula
- mass
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 126
- 239000000203 mixture Substances 0.000 title claims abstract description 61
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
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- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- -1 carboxylic acid compounds Chemical class 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
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- 230000008646 thermal stress Effects 0.000 abstract description 6
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
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- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- PGGYWYZJYRRNPJ-UHFFFAOYSA-N cyclohexanone;n,n-dimethylformamide Chemical compound CN(C)C=O.O=C1CCCCC1 PGGYWYZJYRRNPJ-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
-
- 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
Definitions
- the present invention relates to epoxy resin compositions and epoxy resin cured products.
- Epoxy resin has excellent moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, etc., and has been used in fields such as molding materials, adhesive materials, electronic parts, and ink materials. Epoxy resins are also used as sealing materials for electronic components such as semiconductor devices.
- cured epoxy resins used as sealing materials are required not to crack or peel off due to stress such as thermal expansion or thermal contraction.
- stress such as thermal expansion or thermal contraction.
- Patent Document 1 it has been studied to add various additives to the epoxy resin.
- the present invention has been made in view of such circumstances, and provides an epoxy resin composition capable of suppressing cracks and peeling due to thermal stress while suppressing the deterioration of the inherent mechanical and thermal properties of epoxy resins. It provides
- an epoxy resin (A) 100 parts by mass of an epoxy resin (A), 5 to 90 parts by mass of a compound (B) represented by the following formula (1), and 10 to 90 parts by mass of a curing agent (C) are included.
- An epoxy resin composition is provided.
- the epoxy resin composition of one embodiment of the present invention contains an epoxy resin (A), a compound (B), and a curing agent (C).
- Epoxy resin (A) means a compound other than compound (B) having multiple epoxy groups (preferably multiple glycidyl groups).
- the number of epoxy groups in one molecule of the epoxy resin (A) is, for example, 2, 3 or 4, preferably 2 or 3, more preferably 2.
- the epoxy equivalent of the epoxy resin (A) is, for example, 120 to 400 (g/eq). eq) and may be in a range between any two of the values exemplified herein. Epoxy equivalent can be measured according to JIS K 7236:2009.
- the epoxy resin (A) is preferably liquid at 25°C from the viewpoint of handling.
- the weight average molecular weight (Mw) of the epoxy resin (A) is, for example, 240 to 600, specifically, for example, 240, 280, 320, 360, 400, 440, 480, 520, 560, 600, It may be in a range between any two of the numerical values exemplified here. Mw can be measured by a gel permeation chromatography (GPC) method.
- the epoxy resin (A) preferably does not have a reactive functional group selected from an amino group, a carboxyl group, a phenolic hydroxyl group, and a thiol group, and is not a carboxylic acid anhydride. Since such a reactive functional group has high reactivity with the epoxy group, it reacts with the epoxy group contained in the compound (B) to form a bond between the epoxy resin (A) and the compound (B). This is because the mechanical properties and thermophysical properties inherent in the epoxy resin tend to deteriorate.
- the epoxy resin (A) and the compound (B) are bonded via the curing agent (C), and the epoxy resin (A) and the compound (B) are It is preferred not to react directly.
- the epoxy resin (A) and the compound (B) may not cure. preferable.
- the epoxy resin (A) preferably does not have an addition reaction site (hereinafter referred to as "DA reaction addition site") formed by a Diels-Alder reaction from a conjugated diene structure and a dienophile structure. This is because such an addition reaction portion tends to deteriorate the mechanical properties and thermophysical properties inherent in the epoxy resin.
- DA reaction addition site an addition reaction site formed by a Diels-Alder reaction from a conjugated diene structure and a dienophile structure.
- Examples of the epoxy resin (A) include bifunctional or crystalline epoxy resins such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin; Novolac epoxy resins such as epoxy resins, phenol novolak epoxy resins, and naphthol novolak epoxy resins; Aralkyl-type epoxy resins; trifunctional epoxy resins such as triphenolmethane-type epoxy resins and alkyl-modified triphenolmethane-type epoxy resins are preferred. Particularly preferred are cresol novolac type epoxy resins and biphenylene skeleton-containing phenol aralkyl type epoxy resins.
- Examples of commercially available epoxy resins (A) are as follows. ⁇ Biphenyl type epoxy resin: YX4000 (Mitsubishi Chemical) ⁇ Bisphenol A type epoxy resin: jER-828 (Mitsubishi Chemical) ⁇ Bisphenol F type epoxy resin: EPICLON 830 (DIC) ⁇ Cresol novolac type epoxy resin: EPICLON N-680 (DIC) ⁇ Biphenylene skeleton-containing phenol aralkyl type epoxy resin: NC3000 (Nippon Kayaku)
- Compound (B) is a compound represented by the following formula (1).
- Compound (B) comprises a DA reaction adduct.
- the DA addition reaction part dissociates when the cured epoxy resin is exposed to high temperatures, thereby relieving the stress of the cured epoxy resin and suppressing the occurrence of cracks and peeling in the cured epoxy resin. .
- the content of the compound (B) with respect to 100 parts by mass of the epoxy resin (A) is 5 to 90 parts by mass, preferably 5 to 80 parts by mass, more preferably 5 to 60 parts by mass. If the content of the compound (B) is too small, the stress relaxation effect will not be sufficiently exhibited. If the content of the compound (B) is too large, the mechanical properties and thermophysical properties tend to deteriorate significantly. Specifically, this content is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 parts by mass. , within a range between any two of the numerical values exemplified herein.
- R 1 is * 2 —(CH 2 ) a —X—(CH 2 ) b —* 1 or * 2 —Ar 1 —(CH 2 ) a —X—(CH 2 ) b ⁇ * 1
- * 1 is the bond with the epoxy group
- * 2 is the bond with the other group
- X is a group represented by -O-, -S-, -NR 2 - or -COO-
- R 2 is -CH 3 , -C 2 H 5 or -(CH 2 ) a - a group represented by CH(O) CH2
- Ar 1 is an unsubstituted phenyl group or a phenyl group substituted with 1 to 4 (eg, 1,2,3,4) methyl or ethyl groups
- a is an integer of 0 to 5 (eg, 0, 1, 2, 3, 4, 5)
- b is an integer of 1 to 5 (eg, 1, 2, 3, 4, 5)
- Y is a
- R 3 is —(CH 2 ) d —, —[(CH 2 ) d —O] e —(CH 2 ) d —, —Ar 2 —, or —Ar 3 —R 4 -Ar 3 -
- d is an integer of 1 to 8 (eg, 1,2,3,4,5,6,7,8)
- e is an integer of 1 to 3 (eg, 1,2,3)
- Ar 2 and Ar 3 are each an unsubstituted phenyl group, a phenyl group substituted with 1 to 4 (eg, 1,2,3,4) methyl or ethyl groups, an unsubstituted biphenyl group, or a biphenyl group substituted with 1 to 8 (e.g., 1,2,3,4,5,6,7,8) methyl or ethyl groups
- R 4 is -(CH 2 ) f -, -O-, -S-, -SO-, -SO 2 -
- Y in formula (1) is preferably a group represented by formula (2).
- the compound (B) has two DA reaction addition sites, so that the stress relaxation effect is remarkable.
- R 3 in formula (2) is preferably -Ar 3 -R 4 -Ar 3 -.
- the compound (B) can be obtained, for example, by subjecting a conjugated diene compound represented by formula (3) and a dienophile compound represented by formula (4) or (5) to Diels-Alder reaction.
- the compound (B) preferably has a dissociation initiation temperature of 80 to 190°C.
- the dissociation initiation temperature is the temperature at which dissociation of the DA addition reaction portion of compound (B) is initiated, and can be measured by the method described in "3. Evaluation of epoxy resin composition" below. If the dissociation starting temperature is too low, the mechanical properties and thermophysical properties tend to deteriorate. Hard to be effective.
- the dissociation start temperature is, for example, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190° C. may be within the range.
- Compound (B) does not have a reactive functional group selected from an amino group, a carboxyl group, a phenolic hydroxyl group, and a thiol group, and is not a carboxylic acid anhydride, so that compound (B) is an epoxy resin (A). does not react with the epoxy groups of
- the curing agent (C) is a compound capable of reacting with a plurality of epoxy groups and linking compounds having epoxy groups.
- the curing agent (C) preferably has a plurality of reactive functional groups selected from amino groups, carboxyl groups, phenolic hydroxyl groups and thiol groups, or is a carboxylic acid anhydride.
- the epoxy resin composition is cured by the curing agent (C) connecting the epoxy resins (A) to each other, the compounds (B) to each other, or the epoxy resin (A) and the compound (B) to each other to increase the molecular weight. It becomes an epoxy resin hardened product.
- the content of the curing agent (C) with respect to 100 parts by mass of the epoxy resin (A) is 10 to 90 parts by mass, preferably 20 to 85 parts by mass, more preferably 30 to 80 parts by mass. If the curing agent (C) is too little or too much, the mechanical properties and thermophysical properties of the epoxy resin cured product tend to deteriorate.
- This content is specifically, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 parts by mass, here may be within a range between any two of the numerical values exemplified in .
- the total epoxy equivalent weight of the epoxy resin (A) and the compound (B) and the curing agent It is preferable that the curing agent (C) is contained in the composition so that the functional group equivalent weight of (C) is close to that of the curing agent (C).
- the value of ⁇ functional group equivalent of curing agent (C) ⁇ / ⁇ total value of epoxy equivalents of epoxy resin (A) and compound (B) ⁇ is, for example, 0.8 to 1.2, specifically For example, 0.8, 0.9, 1.0, 1.1, 1.2, and may be in the range between any two of the numerical values exemplified herein.
- the epoxy resin cured product obtained by curing the epoxy resin composition in which the epoxy resin (A), the compound (B) and the curing agent (C) are blended in the above ratio has the mechanical and thermophysical properties inherent in the epoxy resin. Cracks and peeling due to thermal stress are suppressed while suppressing the deterioration of
- the curing agent (C) is preferably at least one selected from amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and polyvalent carboxylic acid compounds.
- amine curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylylenediamine (MXDA); diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), diaminodiphenyl One or more selected from the group consisting of aromatic polyamines such as sulfone (DDS); and polyamine compounds such as dicyandiamide (DICY) and organic acid dihydralazide. Aliphatic polyamines are particularly preferred as amine-based curing agents.
- amine curing agents examples include as follows. ⁇ Aliphatic polyamine: jER Cure ST12 (Mitsubishi Chemical), ADEKA Hardener EH-6019 (ADEKA)
- phenolic curing agent examples include phenolic novolac resins, cresol novolak resins and other phenols, cresols, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene.
- Novolak resins obtained by condensation or co-condensation of phenols such as phenols and formaldehyde or ketones in the presence of an acidic catalyst; One or more selected from the group consisting of aralkyl resins; phenol aralkyl resins such as phenol aralkyl resins having a biphenylene skeleton; and phenol resins having a trisphenylmethane skeleton.
- the phenolic curing agent preferably contains one or more resins selected from the group consisting of biphenylaralkyl-type phenolic resins and triphenylmethane-type phenolic resins.
- cresol novolak resins and phenol aralkyl resins having a biphenylene skeleton are particularly preferred.
- phenolic curing agents examples include as follows. ⁇ Cresol novolak type: PHENOLITETD-2131 (DIC) ⁇ Biphenyl aralkyl type: KAYAHARDGPH-65 (Nippon Kayaku)
- Acid anhydride curing agents include, for example, hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), alicyclic acid anhydrides such as maleic anhydride; trimellitic anhydride (TMA), pyroanhydride
- HHPA hexahydrophthalic anhydride
- MTHPA methyltetrahydrophthalic anhydride
- TMA trimellitic anhydride
- pyroanhydride One or more selected from the group consisting of aromatic acid anhydrides such as mellitic acid (PMDA), benzophenonetetracarboxylic acid (BTDA), and phthalic anhydride can be used.
- polycarboxylic acid compounds include phthalic acid, hydroxyisophthalic acid, succinic acid, sebacic acid, maleic acid, dodecenylsuccinic acid, chlorendic acid, pyromellitic acid, trimellitic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid. , tetrahydrophthalic acid, methyltetrahydrophthalic acid, and methylnadic acid.
- the epoxy resin composition of the present invention may contain a curing catalyst. By containing a curing catalyst, the epoxy resin composition can shorten the curing time.
- the content of the curing catalyst with respect to 100 parts by mass of the epoxy resin (A) is 0.1 to 5 parts by mass, preferably 0.3 to 4.5 parts by mass, more preferably 0.5 to 4.0 parts by mass. .
- this content is, for example, 0.1, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 , 4.5, and 5.0 parts by mass, and may be within a range between any two of the numerical values exemplified herein.
- Curing catalysts include, for example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or salts thereof; 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or salts thereof tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol and N,N-dimethylcyclohexylamine; and phosphines such as triphenylphosphine and tris(dimethoxy)phosphine.
- DBU 1,8-diazabicyclo[5.4.0]undecene-7
- DBN 1,5-diazabicyclo[4.3.0]nonene-5
- tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol and N,N-dimethylcyclohexylamine
- phosphines such as triphen
- the epoxy resin composition of the present invention may optionally contain ultraviolet absorbers, antioxidants, antiseptics, rust inhibitors, pigments, tackifiers, surface lubricants, brighteners, water repellents, and photosensitizers. , Organic / inorganic fibers, plasticizers, conductive fillers, inorganic fillers, flame retardants, antistatic agents, foam stabilizers, release agents, colorants and foaming agents. good.
- An additive may be used individually by 1 type, and may use 2 or more types.
- the content of the additive with respect to 100 parts by mass of the epoxy resin (A) is, for example, 0 to 50 parts by mass, more preferably 0 to 20 parts by mass. Specifically, this content is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 parts by mass, and ranges between any two of the numerical values illustrated here may be within
- the epoxy resin composition of the present invention may contain a solvent.
- solvents include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane and cyclooctane.
- Ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, 1,2-dichloroethane , halogenated hydrocarbons such as chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; N,N-dimethylformamide, N, amides such as N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; and sulfoxides such as
- the content of the solvent in the epoxy resin composition of the present invention is usually 70% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less.
- a cured epoxy resin product can be formed by curing the epoxy resin composition of the present invention.
- the epoxy resin composition can be cured by heating or light irradiation, for example.
- the heating temperature (curing temperature) during curing is usually 20 to 300°C, preferably 40 to 250°C, more preferably 60 to 200°C.
- the curing temperature is, for example, 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 250, 260, 280, 300 ° C. Numerical values exemplified here may be in the range between any two of
- the heating time (curing time) for curing is usually 10 to 1440 minutes, preferably 30 to 900 minutes, more preferably 60 to 480 minutes.
- the heating can also be performed in multiple stages.
- light such as ultraviolet light, visible light, and infrared light can be used, and ultraviolet light is preferred.
- the exposure dose is preferably 1 to 10000 mJ/cm 2 , more preferably 10 to 3000 mJ/cm 2 .
- light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, chemical lamps, black light fluorescent lamps, and electrodeless UV lamps.
- the curing reaction can be carried out by coating the epoxy resin composition of the present invention on a substrate, or by injecting it into a mold.
- the shape of the cured product of the present invention is not particularly limited, and examples thereof include plate-like, sheet-like and film-like shapes.
- Their thickness is, for example, usually 0.01 to 1000 mm, preferably 0.1 to 100 mm, more preferably 0.1 to 5 mm.
- the epoxy resin composition may be of a one-component type or a two-component type.
- the first component contains the epoxy resin (A) and the compound (B)
- the second component contains the curing agent (C).
- the curing agent (C) since the curing agent (C) does not react with the epoxy resin (A) or the compound (B) during storage, the storage stability is improved.
- the curing agent (C) can be reacted with the epoxy resin (A) and the compound (B) by mixing the first liquid and the second liquid.
- the epoxy resin composition of the present invention it is possible to form an epoxy resin cured product that suppresses cracks and peeling due to thermal stress while suppressing the deterioration of the mechanical and thermal properties inherent in the epoxy resin.
- the epoxy resin composition of the present invention has the above properties, it can be used for applications such as electronic materials, binders, paints, and adhesives.
- substrate substrates for electronic members such as semiconductor packages, build-up films, solder resist inks, underfill materials, solid sealing materials for packages, binders for paving, binders for carbon fiber reinforced plastics (CFRP), Cationic electrodeposition coating agents, heavy-duty anti-corrosion coatings, powder coatings, infrastructure repair/reinforcing adhesives, general household/industrial adhesives.
- CFRP carbon fiber reinforced plastics
- Production example 4 18.9 g (0.10 mol) of 4-hydroxyphenylmaleimide, 3.22 g (0.01 mol) of tetrabutylammonium bromide, 40% by mass of water were placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. 80 g of an aqueous sodium oxide solution and 80 g of toluene were charged, the temperature was raised to 60° C. while introducing nitrogen gas, 46.3 g (0.50 mol) of epichlorohydrin was added dropwise, and the mixture was stirred for 2 hours.
- Production example 6 50.0 g (0.24 mol) of 9-(hydroxymethyl)anthracene, 7.74 g (0.024 mol) of tetrabutylammonium bromide, 40 masses were placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. % sodium hydroxide aqueous solution and 200 g of toluene were charged, the temperature was raised to 60° C. while introducing nitrogen gas, 111.1 g (1.2 mol) of epichlorohydrin was added dropwise, and the mixture was stirred for 2 hours.
- epoxy resin composition 2-1 100 parts by mass of epoxy resin (A) (jER-828, manufactured by Mitsubishi Chemical) and 10 parts by mass of compound (B1) were placed in a container and left in an environment of 80° C. for 1 hour. Then, using a glass rod, jER-828 and compound (B1) were mixed and allowed to stand until the temperature of the mixture reached 25°C. After that, a mixture of jER-828 and compound (B1) and 52 parts by mass of curing agent (C) (ST-12: manufactured by DIC) were mixed in a mixer (ARE-310: manufactured by Thinky) for 2 minutes to form an epoxy resin composition. got stuff
- Example 2-9 Comparative Examples 1-3, Reference Examples 1-3 Epoxy resin compositions of Examples 2 to 9, Comparative Examples 1 to 3, and Reference Examples 1 to 3 were obtained in the same manner as in Example 1, except that the composition was changed to those shown in Tables 1 and 2.
- the curing agent (C) was heated at 80° C. for 30 minutes before being charged into the mixer.
- jER-828 bisphenol A type epoxy resin
- Mitsubishi Chemical EPICLON830 bisphenol F type epoxy resin
- DIC ST12 aliphatic polyamine curing agent (jER Cure ST12)
- Mitsubishi Chemical TD-2131 cresol novolac type curing agent ( PHENOLITETD-2131); PPh 3 manufactured by DIC: triphenylphosphine
- the examples had higher glass transition temperatures than the comparative examples, and had values close to those of the reference examples that did not contain the compound (B).
- the tensile elastic modulus, the maximum tensile stress, the shear adhesive strength and the storage elastic modulus were also equivalent to those of the reference example.
- the examples were superior to the reference examples in the results of the thermal cycle test. From the above, it was found that according to the examples of the present invention, cracks and peeling due to thermal stress can be suppressed while suppressing the deterioration of the mechanical properties and thermophysical properties inherent in the epoxy resin.
- the details of the evaluation are as follows. [Glass transition temperature/dissociation start temperature]
- the epoxy resin composition to be evaluated was poured into a mold treated with a fluorine-based mold release agent, heated at 80° C. for 3 hours, and further heat-cured at 120° C. for 3 hours to prepare a dumbbell test piece.
- the test piece is sealed in a simple sealed pan, and a differential scanning calorimeter (DSC) is used to measure the heat change by raising the temperature from 30 ° C. to 200 ° C. at a rate of 10 ° C./min under a nitrogen stream.
- a graph was drawn between calorific value and temperature, and the characteristic inflection observed at this time was taken as the glass transition.
- the glass transition temperature the value obtained by the midpoint method from the DSC curve was used.
- the dissociation start temperature the value of the extrapolated start temperature of the endothermic peak appearing at a temperature higher than the glass transition temperature was used.
- the epoxy resin composition to be evaluated was poured into a mold treated with a fluorine-based mold release agent, heated at 80° C. for 3 hours, and further heat-cured at 120° C. for 3 hours to prepare a dumbbell test piece.
- the tensile modulus and maximum tensile stress of the obtained test piece were measured according to JIS-K7161 under the following conditions. ⁇ Sample size: Dumbbell size 1BA ⁇ Test speed: 1.0 mm/min ⁇ Measurement environment: Temperature 25°C ⁇ Number of measurements: Measured 3 times and calculated from the average value
- the obtained test piece is left in an environment of 25°C for 24 hours, and a thermal shock device TSA-71L-A (manufactured by Espec) is used to perform a thermal cycle of -40°C x 30 minutes and 200°C x 30 minutes as one cycle. was repeated 150 times, and the presence or absence of peeling of the test piece was visually confirmed. The test was performed three times for the same curable composition, and the numbers in the table indicate the number of times peeling occurred.
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Abstract
Description
本発明の一実施形態のエポキシ樹脂組成物は、エポキシ樹脂(A)と、化合物(B)と、硬化剤(C)を含有する。
エポキシ樹脂(A)は、複数のエポキシ基(好ましくは複数のグリシジル基)を有する、化合物(B)以外の化合物を意味する。エポキシ樹脂(A)の1分子中のエポキシ基の数は、例えば、2、3、4であり、2又は3が好ましく、2がさらに好ましい。エポキシ樹脂(A)のエポキシ当量は、例えば120~400(g/eq)であり、具体的には例えば、120、140、160、180、200、220、240、260、280、300(g/eq)であり、ここで例示した数値の何れか2つの間の範囲内であってもよい。エポキシ当量は、JIS K 7236:2009に従って測定することができる。
・ビフェニル型エポキシ樹脂:YX4000(三菱ケミカル)
・ビスフェノールA型エポキシ樹脂:jER-828(三菱ケミカル)
・ビスフェノールF型エポキシ樹脂:EPICLON 830(DIC)
・クレゾールノボラック型エポキシ樹脂:EPICLON N-680(DIC)
・ビフェニレン骨格含有フェノールアラルキル型エポキシ樹脂:NC3000(日本化薬)
化合物(B)は、下記式(1)で示される化合物である。化合物(B)は、DA反応付加部を備える。DA付加反応部は、エポキシ樹脂硬化物が高温にさらされたときに解離することによって、エポキシ樹脂硬化物の応力が緩和されて、エポキシ樹脂硬化物にクラックや剥がれが発生することが抑制される。
Xは、-O-、-S-、-NR2-、又は-COO-で表される基であり、R2は、-CH3、-C2H5、又は-(CH2)a-CH(O)CH2で表される基あり、
Ar1は、未置換のフェニル基、又は1~4(例:1,2,3,4)個のメチル基又はエチル基で置換されたフェニル基であり、
aは、0~5(例:0,1,2,3,4,5)の整数、bは、1~5(例:1,2,3,4,5)の整数であり、
Yは、直接結合又は式(2)で表される基であり、式(2)中の*3及び*4は、それぞれ、R1及びNとの結合部である。)
dは、1~8(例:1,2,3,4,5,6,7,8)の整数、eは、1~3(例:1,2,3)の整数であり、
Ar2及びAr3は、それぞれ、未置換のフェニル基、1~4(例:1,2,3,4)個のメチル基又はエチル基で置換されたフェニル基、未置換のビフェニル基、又は1~8(例:1,2,3,4,5,6,7,8)個のメチル基又はエチル基で置換されたビフェニル基であり、
R4は、-(CH2)f-、-O-、-S-、-SO-、-SO2-、-CO-、又は-[(CH2)f-O]g-(CH2)f-で表される基であり、
fは、1~8(例:1,2,3,4,5,6,7,8)の整数、gは、1~3(例:1,2,3)の整数である。)
硬化剤(C)は、複数のエポキシ基と反応して、エポキシ基を有する化合物同士を連結可能な化合物である。硬化剤(C)は、アミノ基、カルボキシ基、フェノール性水酸基、及びチオール基から選択される反応性官能基を複数有するか、又はカルボン酸無水物であることが好ましい。硬化剤(C)によって、エポキシ樹脂(A)同士、化合物(B)同士、又はエポキシ樹脂(A)と化合物(B)が互いに連結されて高分子量化することによって、エポキシ樹脂組成物が硬化して、エポキシ樹脂硬化物となる。
アミン系硬化剤としては、たとえば、ジエチレントリアミン(DETA)、トリエチレンテトラミン(TETA)、メタキシリレンジアミン(MXDA)などの脂肪族ポリアミン;ジアミノジフェニルメタン(DDM)、m-フェニレンジアミン(MPDA)、ジアミノジフェニルスルホン(DDS)などの芳香族ポリアミン;ジシアンジアミド(DICY)や有機酸ジヒドララジドなどのポリアミン化合物からなる群から選択される1種または2種以上が挙げられる。アミン系硬化剤としては、脂肪族ポリアミンが特に好ましい。
・脂肪族ポリアミン:jERキュアST12(三菱ケミカル)、アデカハードナーEH-6019(ADEKA)
フェノール系硬化剤としては、たとえば、フェノールノボラック樹脂、クレゾールノボラック樹脂をはじめとするフェノール、クレゾール、レゾルシン、カテコール、ビスフェノールA、ビスフェノールF、フェニルフェノール、アミノフェノール、α-ナフトール、β-ナフトール、ジヒドロキシナフタレン等のフェノール類とホルムアルデヒドやケトン類とを酸性触媒下で縮合または共縮合させて得られるノボラック樹脂;上述のフェノール類とジメトキシパラキシレンまたはビス(メトキシメチル)ビフェニルから合成されるフェニレン骨格を有するフェノールアラルキル樹脂;ビフェニレン骨格を有するフェノールアラルキル樹脂などのフェノールアラルキル樹脂;トリスフェニルメタン骨格を有するフェノール樹脂からなる群から選択される1種または2種以上が挙げられる。フェノール系硬化剤は、好ましくはビフェニルアラルキル型フェノール樹脂およびトリフェニルメタン型フェノール樹脂からなる群から選択される1または2以上の樹脂を含む。
・クレゾールノボラック型:PHENOLITETD-2131(DIC)
・ビフェニルアラルキル型:KAYAHARDGPH-65(日本化薬)
酸無水物系硬化剤としては、たとえば、ヘキサヒドロ無水フタル酸(HHPA)、メチルテトラヒドロ無水フタル酸(MTHPA)や無水マレイン酸などの脂環族酸無水物;無水トリメリット酸(TMA)、無水ピロメリット酸(PMDA)、ベンゾフェノンテトラカルボン酸(BTDA)、無水フタル酸などの芳香族酸無水物からなる群から選択される1種または2種以上が挙げられる。
多価カルボン酸化合物としては、例えば、フタル酸、ヒドロキシイソフタル酸、コハク酸、セバシン酸、マレイン酸、ドデセニルコハク酸、クロレンデック酸、ピロメリット酸、トリメリット酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、メチルナジック酸が挙げられる。
本発明のエポキシ樹脂組成物は、硬化触媒を含有してもよい。硬化触媒を含有することで、エポキシ樹脂組成物が硬化時間を短縮することができる。
エポキシ樹脂(A)100質量部に対する硬化触媒の含有量は、0.1~5質量部であり、0.3~4.5質量部が好ましく、0.5~4.0質量部がさらに好ましい。この含有量は、具体的には例えば、0.1、0.3、0.5、1.0、1.5、2.0、2.5、3.0、3.5、4.0、4.5、5.0質量部であり、ここで例示した数値の何れか2つの間の範囲内であってもよい。
本発明のエポキシ樹脂組成物は、必要に応じて、紫外線吸収剤、酸化防止剤、防腐剤、防錆剤、顔料、粘着付与剤、表面潤滑剤、光沢剤、撥水剤、感光剤、有機・無機繊維、可塑剤、導電性フィラー、無機フィラー、難燃剤、帯電防止剤、整泡剤、離型剤、着色剤および発泡剤から選ばれる少なくとも1種の添加剤を含有してもよい。添加剤は1種単独で用いてもよく、2種以上を用いてもよい。エポキシ樹脂(A)100質量部に対する添加剤の含有量は、例えば0~50質量部であり、0~20質量部がさらに好ましい。この含有量は、具体的には例えば、0、5、10、15、20、25、30、35、40、45、50質量部であり、ここで例示した数値の何れか2つの間の範囲内であってもよい。
本発明のエポキシ樹脂組成物は、溶媒を含有してもよい。溶媒としては、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素;n-ペンタン、n-ヘキサン、n-ヘプタン、n-オクタン等の脂肪族炭化水素;シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン等の脂環式炭化水素;ジエチルエーテル、ジイソプロピルエーテル、1,2-ジメトキシエタン、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソール、フェニルエチルエーテル、ジフェニルエーテル等のエーテル;クロロホルム、四塩化炭素、1,2-ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素;酢酸エチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル等のエステル;アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン;N,N-ジメチルホルムアミド、N,N-ジメチルアセタミド、N-メチルピロリドン等のアミド;アセトニトリル、ベンゾニトリル等のニトリル;ジメチルスルホキシド、スルホラン等のスルホキシドが挙げられる。溶媒は1種単独で用いてもよく、2種以上を用いてもよい。
本発明のエポキシ樹脂組成物を硬化させることによってエポキシ樹脂硬化物を形成することができる。エポキシ樹脂組成物は、一例では、加熱又は光照射によって硬化させることができる。
1-1.製造例1
撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に3,3'-ジメチル-5,5'-ジエチル-4,4'-ジフェニルメタンビスマレイミド(BMI-5100:大和化成工業製) 66.4g(0.15mol)、フルフリルグリシジルエーテル 92.5g(0.60mol)を仕込み、窒素ガスを導入しながら80℃まで昇温し、その後2時間攪拌した。室温まで冷却後、酢酸エチル:ヘキサン=3:1の混合溶媒で希釈した後、シリカゲルクロマトグラフィーで精製を行い、式(6)で表される化合物(B1)を得た。
3,3'-ジメチル-5,5'-ジエチル-4,4'-ジフェニルメタンビスマレイミド0.15molの代わりに、m-フェニレンビスマレイミド(BMI-3000:大和化成工業製)40.2g(0.15mol)を使用したこと以外は、製造例1と同様の方法で、式(7)で表される化合物(B2)を得た。
3,3'-ジメチル-5,5'-ジエチル-4,4'-ジフェニルメタンビスマレイミド0.15molの代わりに、1,2-ビス(マレイミド)エタン33.0g(0.15mol)を使用したこと以外は、製造例1と同様の方法で、式(8)で表される化合物(B3)を得た。
撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に4-ヒドロキシフェニルマレイミド18.9g(0.10mol)、テトラブチルアンモニウムブロミド3.22g(0.01mol)、40質量%水酸化ナトリウム水溶液80g、トルエン80gを仕込み、窒素ガスを導入しながら60℃まで昇温し、エピクロロヒドリン46.3g(0.50mol)を滴下後、2時間攪拌した。反応終了後、水層を分離し、有機層をイオン交換水で3回洗浄し、硫酸マグネシウムで乾燥後、濃縮した。ついで撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に濃縮残渣、フルフリルグリシジルエーテル30.8g(0.20mol)を仕込み、窒素ガスを導入しながら80℃まで昇温し、その後2時間攪拌した。室温まで冷却後、酢酸エチル:ヘキサン=3:1の混合溶媒で希釈した後、シリカゲルクロマトグラフィーで精製を行い、式(9)で表される化合物(B4)を得た。
フルフリルグリシジルエーテル0.60molの代わりにフルフリルアルコール58.9g(0.60mol)を使用したこと以外は、製造例1と同様の方法で、式(10)で表される比較化合物1を得た。
撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に9-(ヒドロキシメチル)アントラセン50.0g(0.24mol)、テトラブチルアンモニウムブロミド7.74g(0.024mol)、40質量%水酸化ナトリウム水溶液200g、トルエン200gを仕込み、窒素ガスを導入しながら60℃まで昇温し、エピクロロヒドリン111.1g(1.2mol)を滴下後、2時間攪拌した。反応終了後、水層を分離し、有機層をイオン交換水で3回洗浄し、硫酸マグネシウムで乾燥後、濃縮した。ついで撹拌機、還流冷却器、温度計および窒素道入管を備えた反応装置に濃縮残渣、3,3'-ジメチル-5,5'-ジエチル-4,4'-ジフェニルメタンビスマレイミド(BMI-5100:大和化成工業製)26.6g(0.06mol)を仕込み、窒素ガスを導入しながら180℃まで昇温し、その後2時間攪拌した。室温まで冷却後、酢酸エチルで希釈した後、シリカゲルクロマトグラフィーで精製を行い、式(11)で表される比較化合物2を得た。
2-1.実施例1
エポキシ樹脂(A)(jER-828:三菱ケミカル製)100質量部、化合物(B1)10質量部を容器に入れ、80℃環境下で1時間放置した。その後、ガラス棒を用い、jER-828と化合物(B1)を混合し、混合物の温度が25℃になるまで放置した。その後、jER-828と化合物(B1)の混合物と、硬化剤(C)(ST-12:DIC製)52質量部とをミキサー(ARE-310:シンキー製)で2分間混合し、エポキシ樹脂組成物を得た。
表1~表2に記載の配合組成に変更した以外は実施例1と同様の方法によって、実施例2~9、比較例1~3、参考例1~3のエポキシ樹脂組成物を得た。
なお、実施例5、参考例2については、硬化剤(C)をミキサーに投入する前に80℃で30分間加熱した。
jER-828:ビスフェノールA型エポキシ樹脂;三菱ケミカル製
EPICLON830:ビスフェノールF型エポキシ樹脂;DIC製
ST12:脂肪族ポリアミン系硬化剤(jERキュアST12);三菱ケミカル製
TD-2131:クレゾールノボラック型硬化剤(PHENOLITETD-2131);DIC製
PPh3:トリフェニルホスフィン
実施例・比較例・参考例のエポキシ樹脂組成物について、各種評価を実施した。その結果を表1~表2に示す。
[ガラス転移温度・解離開始温度]
評価対象のエポキシ樹脂組成物をフッ素系離型剤で処理した成形型に流し込み、80℃で3時間加熱した後、さらに120℃3時間加熱硬化し、ダンベル試験片を作製した。
評価対象のエポキシ樹脂組成物をフッ素系離型剤で処理した成形型に流し込み、80℃で3時間加熱した後、さらに120℃3時間加熱硬化し、ダンベル試験片を作製した。
・試料サイズ:ダンベル寸法1BA
・試験速度:1.0mm/min
・測定環境:温度25℃
・測定回数:3回測定し、平均値から算出
幅25mm×長さ100mm×厚さ1.0mmのSUS板に、評価対象のエポキシ樹脂組成物を塗布し、硬化性組成物が塗布されたSUS板を得た。その後、別の幅25mm×長さ100mm×厚さ1.0mmのSUS板を貼り付け面積が25mm×12.5mm、硬化物の厚さが0.20mmとなるように、前記エポキシ樹脂組成物が塗布されたSUS板の硬化性組成物が塗布された側に貼り合わせ、クリップで固定した。その後、80℃で3時間加熱後、さらに120℃で3時間加熱し試験片を得た。得られた試験片について、万能引張試験機にてせん断接着力をJIS K 6850:1999に従い測定した(引っ張り速度2.0mm/min.、試験環境温度25℃)。
評価対象のエポキシ樹脂組成物をフッ素系離型剤で処理した成形型に流し込み、80℃で3時間加熱した後、さらに120℃3時間加熱硬化し、長さ5.0cm、幅1.0cm、厚さ1.0mmの試験片を作製した。得られた試験片について、動的粘弾性測定装置RSA3(TAInstruments製)を用いて、貯蔵弾性率を下記の条件で測定した。なお、表に記載の貯蔵弾性率の値は、200℃における貯蔵弾性率の値である。
・昇温速度5℃/min
・周波数1.0Hz
・測定温度範囲:30~300℃
幅25mm×長さ100mm×厚さ1.0mmのSUS板に、評価対象のエポキシ樹脂組成物を塗布し、硬化性組成物が塗布されたSUS板を得た。その後、別の幅25mm×長さ100mm×厚さ1.0mmのSUS板を貼り付け面積が25mm×12.5mm、硬化物の厚さが0.20mmとなるように前記エポキシ樹脂組成物が塗布されたSUS板の硬化性組成物が塗布された側に貼り合わせ、クリップで固定した。その後、80℃で3時間加熱後、さらに120℃で3時間加熱し試験片を得た。得られた試験片を25℃環境下に24時間放置し、冷熱衝撃装置TSA-71L-A(エスペック製)を用い、-40℃×30分、200℃×30分を1サイクルとする冷熱サイクルを150回繰り返した後の試験片の剥がれの有無を目視で確認した。試験は同一硬化性組成物につき3回実施し、表中の数値は剥がれが生じた回数を示す。
Claims (6)
- エポキシ樹脂(A)100質量部と、
下記式(1)で示される化合物(B)を5~90質量部と、
硬化剤(C)10~90質量部と、
を含むエポキシ樹脂組成物。
Xは、-O-、-S-、-NR2-、又は-COO-で表される基であり、R2は、-CH3、-C2H5、又は-(CH2)a-CH(O)CH2で表される基あり、
Ar1は、未置換のフェニル基、又は1~4個のメチル基又はエチル基で置換されたフェニル基であり、
aは、0~5の整数、bは、1~5の整数であり、
Yは、直接結合又は式(2)で表される基であり、式(2)中の*3及び*4は、それぞれ、R1及びNとの結合部である。)
dは、1~8の整数、eは、1~3の整数であり、
Ar2及びAr3は、それぞれ、未置換のフェニル基、1~4個のメチル基又はエチル基で置換されたフェニル基、未置換のビフェニル基、又は1~8個のメチル基又はエチル基で置換されたビフェニル基であり、
R4は、-(CH2)f-、-O-、-S-、-SO-、-SO2-、-CO-、又は-[(CH2)f-O]g-(CH2)f-で表される基であり、
fは、1~8の整数、gは、1~3の整数である。) - 請求項1に記載のエポキシ樹脂組成物であって、
前記式(1)中のYは、式(2)で表される基である、エポキシ樹脂組成物。 - 請求項2に記載のエポキシ樹脂組成物であって、
前記式(2)のR3は、-Ar3-R4-Ar3-である、エポキシ樹脂組成物。 - 請求項1~請求項3の何れか1つに記載のエポキシ樹脂組成物であって、
前記硬化剤が、アミン系硬化剤、フェノール系硬化剤、酸無水物系硬化剤、多価カルボン酸化合物から選ばれる少なくとも1つである、エポキシ樹脂組成物。 - 請求項1~請求項4の何れか1つに記載のエポキシ樹脂組成物であって、
前記エポキシ樹脂(A)100質量部に対して、前記化合物(B)を5~80質量部含む、エポキシ樹脂組成物。 - 請求項1~請求項5の何れか1つに記載のエポキシ樹脂組成物を硬化させて得られるエポキシ樹脂硬化物。
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CN116120348A (zh) * | 2023-02-20 | 2023-05-16 | 深圳先进技术研究院 | 自合成的da结构环氧树脂、底部填充胶及其制备方法 |
WO2024053402A1 (ja) * | 2022-09-06 | 2024-03-14 | Dic株式会社 | グリシジル基含有化合物、硬化性樹脂組成物、硬化物及び積層体 |
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CN104194038A (zh) * | 2014-08-29 | 2014-12-10 | 浙江大学 | 一种环氧树脂组合物及其湿法超声降解方法和应用 |
CN105694790A (zh) * | 2016-02-29 | 2016-06-22 | 中国工程物理研究院材料研究所 | 一种可快速拆解的环氧胶粘剂及其制备和拆解方法 |
CN108219111A (zh) * | 2018-01-03 | 2018-06-29 | 中国工程物理研究院化工材料研究所 | 一种温和条件下自修复、可再加工和可循环利用的热固性材料及其处理方法 |
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CN104194038A (zh) * | 2014-08-29 | 2014-12-10 | 浙江大学 | 一种环氧树脂组合物及其湿法超声降解方法和应用 |
CN105694790A (zh) * | 2016-02-29 | 2016-06-22 | 中国工程物理研究院材料研究所 | 一种可快速拆解的环氧胶粘剂及其制备和拆解方法 |
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CN116120348A (zh) * | 2023-02-20 | 2023-05-16 | 深圳先进技术研究院 | 自合成的da结构环氧树脂、底部填充胶及其制备方法 |
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