WO2023149493A1 - エポキシ樹脂、エポキシ樹脂組成物およびエポキシ樹脂硬化物 - Google Patents

エポキシ樹脂、エポキシ樹脂組成物およびエポキシ樹脂硬化物 Download PDF

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WO2023149493A1
WO2023149493A1 PCT/JP2023/003303 JP2023003303W WO2023149493A1 WO 2023149493 A1 WO2023149493 A1 WO 2023149493A1 JP 2023003303 W JP2023003303 W JP 2023003303W WO 2023149493 A1 WO2023149493 A1 WO 2023149493A1
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epoxy resin
resin composition
epoxy
present
cured product
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PCT/JP2023/003303
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English (en)
French (fr)
Japanese (ja)
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昌己 大村
浩一郎 大神
ニランジャン クマール スレスタ
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日鉄ケミカル＆マテリアル株式会社
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Priority to KR1020247025596A priority Critical patent/KR20240140085A/ko
Priority to JP2023578610A priority patent/JPWO2023149493A1/ja
Publication of WO2023149493A1 publication Critical patent/WO2023149493A1/ja

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    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • 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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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

Definitions

  • the present invention relates to epoxy resins, epoxy resin compositions, and cured epoxy resins. More specifically, the present invention relates to an epoxy resin, an epoxy resin composition, and a cured epoxy resin, which are useful as insulating materials for electric and electronic parts such as semiconductor encapsulation, laminates, and heat dissipation substrates, and have good handleability as solids at room temperature. , epoxy resins and epoxy resin compositions having low viscosity during molding and excellent solvent solubility, and epoxy resin cured products having excellent heat resistance, thermal decomposition stability, and thermal conductivity obtained by curing them.
  • Epoxy resins have been used in a wide range of industrial applications, but the required performance has become more sophisticated in recent years.
  • the electric/electronics field and the power electronics field where electronic circuits are becoming more dense and higher in frequency, the amount of heat generated from electronic circuits is increasing. It's becoming Conventionally, this heat dissipation has been covered by the thermal conductivity of the filler, but in order to achieve higher integration, it has become necessary to improve the thermal conductivity of the matrix epoxy resin itself.
  • an epoxy resin composition excellent in high thermal conductivity one using an epoxy resin having a mesogenic structure is known. It discloses an epoxy resin composition as a component, which is excellent in stability and strength at high temperatures and can be used in a wide range of fields such as adhesion, casting, sealing, molding and lamination. Further, Patent Document 2 discloses an epoxy compound having two mesogenic structures linked by a bent chain in its molecule. Furthermore, Patent Document 3 discloses a resin composition containing an epoxy compound having a mesogenic group.
  • epoxy resins with such a mesogenic structure have a high melting point, and when mixed, the high-melting-point component is difficult to dissolve and remains undissolved, resulting in reduced curability and heat resistance.
  • a high temperature was required to uniformly mix such an epoxy resin with a curing agent. At high temperatures, the curing reaction of the epoxy resin proceeds rapidly and the gelling time is shortened. If a third component with good solubility is added to make up for this drawback, the melting point of the resin is lowered to facilitate uniform mixing, but the resulting cured product has a problem of reduced thermal conductivity.
  • Patent Document 4 discloses an epoxy resin obtained by epoxidizing a mixture of hydroquinone and 4,4'-dihydroxybiphenyl
  • Patent Document 5 discloses 4,4'-dihydroxy Epoxy resins are disclosed which are epoxidized mixtures of diphenylmethane and 4,4'-dihydroxybiphenyl.
  • Patent Document 6 discloses an epoxy resin composition having a diphenyl ether structure, but the curing agent is limited, and general-purpose curing agents such as phenol novolak are insufficient in thermal conductivity and heat resistance. .
  • an object of the present invention is to solve the above problems, and to provide excellent handleability as a solid at normal temperature, which is useful as an insulating material for electric and electronic parts such as highly reliable semiconductor encapsulation, laminates, and heat dissipation substrates.
  • An object of the present invention is to provide an epoxy resin having low viscosity during molding and excellent solvent solubility, an epoxy resin composition using the same, and a cured product obtained therefrom having excellent high thermal conductivity.
  • the present invention is an epoxy resin characterized by being represented by the following general formula (1).
  • X is independently a direct bond, an oxygen atom, a sulfur atom, -SO 2 -, -CO-, -COO-, -CONH-, -CH 2 - or -C(CH 3 ) 2 -
  • A independently represents a benzonitrile structure or -(CH 2 )m-, having both structures in at least one molecule, n represents a number from 2 to 15, and m represents a number from 3 to 10.
  • the present invention also relates to an epoxy resin represented by general formula (2). (However, p and q each independently represent a number from 1 to 15, and m represents a number from 3 to 10.)
  • the present invention relates to an epoxy resin composition characterized by comprising the above epoxy resin and a curing agent as essential components, and an epoxy resin cured product characterized by curing the epoxy resin cured product. is.
  • the epoxy resin of the present invention has good melt-kneadability at 100 ° C. or less, has solvent solubility, and is used for lamination, molding, casting, adhesion, etc.
  • Epoxy resin composition and cured product thereof Suitable for This cured product is also excellent in heat resistance, thermal decomposition stability, and thermal conductivity.
  • FIG. 1 is an FD-MS spectrum of the phenolic compound (hydroxy resin) obtained in Example 1.
  • FIG. 1 is a GPC chart of a phenolic compound (hydroxy resin) obtained in Example 1.
  • FIG. 1 is a GPC chart of the epoxy resin obtained in Example 1.
  • the present invention is an epoxy resin represented by general formula (1).
  • X independently represents a direct bond, an oxygen atom, a sulfur atom, --SO 2 --, --CO--, --COO--, --CONH--, --CH 2 -- or --C(CH 3 ) 2 --.
  • A independently represents a benzonitrile structure or —(CH 2 ) m —, and has both the benzonitrile structure and —(CH 2 ) m — in at least one molecule.
  • n represents a number from 2 to 15 and m represents a number from 3 to 10.
  • X is preferably a biphenyl structure that is a direct bond, —SO 2 —, —CO—, —COO— or —CONH—, more preferably a biphenyl structure that is a direct bond, of which 4, A biphenyl structure at the 4'-position is particularly preferred.
  • an oxygen atom, a sulfur atom, —CH 2 —, and —C(CH 3 ) 2 — are preferred from the standpoint of moldability and solvent solubility.
  • the epoxy resin of the formula (1) of the present invention can be a mixture of structures in which X is different, and has high thermal conductivity, moldability, and solvent solubility. can be adjusted.
  • n is the number of repetitions (number average) and indicates a number from 2 to 15. Preferred are mixtures of components with different values of n.
  • n is larger than 15, the reactivity tends to be low, and the heat resistance tends to decrease when unreacted components are generated during curing.
  • a preferred range for n is 2-12, more preferably 2-8.
  • A represents a benzonitrile structure or an alkyl structure represented by -(CH 2 ) m -. As described above, at least one molecule has both the benzonitrile structure and the alkyl structure represented by —(CH 2 ) m —. That is, as A is also "independently", the epoxy resin of the formula (1) of the present invention can be a mixture of structures in which A is different, and has high thermal conductivity, moldability, and solvent solubility. It is possible to adjust gender.
  • the ratio of the benzonitrile structure and the alkyl structure is preferably 50 mol% or less, more preferably 10 mol% to 40 mol%, more preferably 20 mol% to 40 mol%, based on the mass of the raw material compound.
  • the alkyl structure is more than 50 mol %, the thermal conductivity and heat resistance of the cured product tend to decrease, and when the alkyl structure is not included, the crystallinity tends to increase and solvent solubility tends to decrease.
  • m is the number of repetitions and indicates a number from 3 to 10. More preferably, it is a number of 4-8. If it is less than 3, the flexibility tends to be low and the effect of alleviating crystallinity tends to be low. If it is greater than 10, the thermal conductivity and heat resistance of the cured product tend to be greatly reduced.
  • an epoxy resin represented by the following formula (2) can be preferably exemplified. (However, p and q each independently represent a number from 1 to 15, and m represents a number from 3 to 10.)
  • p and q are the number of repetitions (number average) and indicate numbers from 1 to 15.
  • a preferred range for p is 1-10, more preferably 1-7.
  • a preferred range for q is 1-7, more preferably 1-3.
  • the epoxy equivalent of the epoxy resin of the present invention is 200-280 g/eq. is preferred. If it exceeds this range, the reactivity tends to be low, and unreacted components are produced during curing, which tends to reduce heat resistance and reliability. If it is less than this range, it means that the bifunctional epoxy resin component that does not contain a benzonitrile structure or an alkyl structure increases. When the amount of the functional liquid epoxy resin is large, the heat resistance and thermal conductivity of the cured product tend to decrease.
  • X is independently a direct bond, an oxygen atom, a sulfur atom, -SO 2 -, -CO-, -COO-, -CONH-, -CH 2 - or -C(CH 3 ) 2 -
  • Each A independently represents a benzonitrile structure or -(CH 2 ) m -, at least one of which represents -(CH 2 ) m -, and has both structures in at least one molecule.
  • m is each independently, n is 2 to 15, m is 3 to 10.
  • the melting point is preferably 140°C to 300°C, more preferably 150°C to 250°C.
  • the phenolic compound represented by formula (3) is not limited, but examples include 2,4-dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,6-dichlorobenzonitrile, 3,5 - benzonitrile compounds such as dichlorobenzonitrile, 2,4-dibromobenzonitrile, 2,5-dibromobenzonitrile, 2,6-dibromobenzonitrile, 3,5-dibromobenzonitrile, and 1,3-dibromopropane, Dihalogen alkyl compounds such as 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4' -Dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone
  • the method for producing the phenolic compound is not particularly limited, but for example, the method described in WO2021/201046 can be used.
  • the charge ratio (molar ratio) for the reaction at this time for the purpose of achieving both the solvent solubility of the resulting resin and the thermal conductivity of the cured product, the total amount of the benzonitrile compound and the dihalogenalkyl compound is set to X It is preferable to charge the dihydroxy compound having a group at 1 to 4 times the molar amount. More preferably, it is charged in a 2- to 3-fold molar amount.
  • the usage ratio of the benzonitrile compound and the dihalogenalkyl compound is as described above.
  • Epichlorohydrin is used in an excess amount relative to the hydroxyl groups in the phenolic compound, usually 1.5 to 15 mol per 1 mol of hydroxyl groups in the phenolic compound. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and the solvent is distilled off to obtain the desired epoxy. resin can be obtained.
  • a solvent such as toluene or methyl isobutyl ketone
  • the epoxy resin of the present invention can also be synthesized using a mixture of the phenolic compound represented by general formula (3) and other phenolic compounds.
  • the mixing ratio of the phenolic compound represented by general formula (3) is preferably 50 wt % or more.
  • other phenolic compounds are not particularly limited, and are selected from those having two or more hydroxyl groups in one molecule.
  • the purity of this epoxy resin should be less from the viewpoint of improving the reliability of electronic components to which it is applied. Although not particularly limited, it is preferably 1000 ppm or less, more preferably 500 ppm or less.
  • the hydrolyzable chlorine referred to in the present invention refers to the value measured by the following method. That is, after dissolving 0.5 g of the sample in 30 ml of dioxane, 10 ml of 1N-KOH was added and the mixture was boiled and refluxed for 30 minutes, cooled to room temperature, further 100 ml of 80% acetone water was added, and a potential difference was obtained with an aqueous 0.002N- AgNO3 solution. It is a value obtained by titration.
  • epoxy resin composition of the present invention in addition to the epoxy resin of formula (1) used as an essential component, other epoxy resins having two or more epoxy groups in the molecule may be used in combination as epoxy resin components.
  • examples include bisphenol A, bisphenol F, 3,3′,5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, fluorene bisphenol, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,2'-biphenol, resorcin, catechol , t-butyl catechol, t-butyl hydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-
  • the blending ratio of the epoxy resin of formula (1) used in the epoxy resin composition of the present invention is 50 wt% or more, preferably 70 wt% or more, more preferably 90 wt% or more of the total epoxy resin. Furthermore, it is desirable that the total amount of the bifunctional epoxy resin is 90 wt % or more, preferably 95 wt % or more. If the amount is less than this, there is a possibility that the effect of improving physical properties such as thermal conductivity in the cured product may be reduced. This is because the higher the content of the epoxy resin of formula (1) and the higher the content of the bifunctional epoxy resin, the higher the degree of orientation of the molded product.
  • curing agent used in the epoxy resin composition of the present invention all those generally known as curing agents for epoxy resins can be used, including dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines. etc.
  • polyhydric phenols are preferably used as a curing agent in fields such as semiconductor encapsulants that require high electrical insulation. Specific examples of the curing agent are shown below.
  • polyhydric phenols examples include dihydric phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalene diol, or , tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. There are phenols.
  • dihydric phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthalenediol
  • polyhydric phenolic compounds synthesized with condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde and p-xylylene glycol.
  • acid anhydride curing agents examples include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl himic anhydride, dodecynylsuccinic anhydride, nadic anhydride, and trimellitic anhydride.
  • Amine curing agents include aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine and p-xylylenediamine; There are aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine.
  • One or a mixture of two or more of these curing agents can be used in the epoxy resin composition.
  • the blending ratio of the epoxy resin and the curing agent is preferably in the range of 0.8 to 1.5 in terms of the equivalent ratio of the epoxy groups to the functional groups in the curing agent. Outside this range, unreacted epoxy groups or functional groups in the curing agent remain even after curing, which may reduce the reliability of the sealing function.
  • oligomers or polymer compounds such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-cumarone resin, phenoxy resin, etc. may be used as other modifiers. It may be blended as appropriate. The amount added is usually in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the total resin components.
  • Additives such as inorganic fillers, pigments, flame retardants, thixotropic agents, coupling agents, fluidity improvers and the like can be added to the epoxy resin composition of the present invention.
  • inorganic fillers include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, and hydrated alumina.
  • the blending amount is preferably 70% by weight or more, more preferably 80% by weight or more.
  • Pigments include organic or inorganic extender pigments and scaly pigments.
  • examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite-based agents.
  • a curing accelerator can be used in the epoxy resin composition of the present invention as necessary.
  • examples include amines, imidazoles, organic phosphines, Lewis acids, etc. Specific examples include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, tri Tertiary amines such as ethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2- imidazoles such as heptadecyl imidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; tetraphenylphosphonium/tetraphenyl
  • the epoxy resin composition of the present invention may contain a releasing agent such as carnauba wax or OP wax, a coupling agent such as ⁇ -glycidoxypropyltrimethoxysilane, a coloring agent such as carbon black, Flame retardants such as antimony oxide, stress reducing agents such as silicone oil, and lubricants such as calcium stearate can be used.
  • a releasing agent such as carnauba wax or OP wax
  • a coupling agent such as ⁇ -glycidoxypropyltrimethoxysilane
  • a coloring agent such as carbon black
  • Flame retardants such as antimony oxide
  • stress reducing agents such as silicone oil
  • lubricants such as calcium stearate
  • the epoxy resin composition of the present invention is made into a varnish state by dissolving an organic solvent, impregnated with a fibrous material such as a glass cloth, an aramid nonwoven fabric, a polyester nonwoven fabric such as a liquid crystal polymer, etc., and then the solvent is removed to form a prepreg. can do.
  • a laminate can be obtained by coating a sheet-like material such as a copper foil, a stainless steel foil, a polyimide film, a polyester film, or the like.
  • the resin cured product of the present invention By curing the epoxy resin composition of the present invention by heating, the resin cured product of the present invention can be obtained.
  • This cured product can be obtained by molding the epoxy resin composition by a method such as casting, compression molding, or transfer molding.
  • the temperature at this time is usually in the range of 120 to 220°C.
  • GPC Measurement A main body (HLC-8220GPC, manufactured by Tosoh Corporation) equipped with columns (4 TSKgel SuperMultiporeHZ-N, manufactured by Tosoh Corporation) in series was used, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as an eluent at a flow rate of 0.35 mL/min, and a differential refractive index detector was used as a detector. As a measurement sample, 0.1 g of the sample was dissolved in 10 mL of THF and filtered through a microfilter, and 50 ⁇ L of the solution was used. For data processing, GPC-8020 model II version 6.00 manufactured by Tosoh Corporation was used.
  • THF Tetrahydrofuran
  • Tg Glass transition point
  • Thermal conductivity was measured by the unsteady hot wire method using a NETZSCH LFA447 thermal conductivity meter.
  • Example 1 After dissolving 81.8 g of 4,4′-dihydroxybiphenyl, 6.7 g of 1,5-dibromopentane and 500 g of N-methyl-2-pyrrolidone in a 2 L four-necked separable flask, 32.4 g of potassium carbonate was added, The temperature was raised to 120° C. while stirring under a nitrogen stream. After that, 20.2 g of 2,6-dichlorobenzonitrile was added, the temperature was raised to 145° C., and reaction was carried out for 6 hours. After neutralizing the reaction mixture by adding 28.2 g of acetic acid, N-methyl-2-pyrrolidone was distilled off under reduced pressure.
  • Epoxy resin A Epoxy resin A
  • a GPC chart of the obtained epoxy resin A is shown in FIG.
  • Example 2 The reaction was carried out in the same manner as in Example 1 except that the amount of 1,5-dibromopentane used was 13.5 g and the amount of 2,6-dichlorobenzonitrile used was 15.2 g to obtain 77 g of an epoxy resin. (epoxy resin B).
  • the hydroxyl equivalent of the intermediate hydroxy resin was 159 g/eq. , a melting point of 257° C. and an Mn of 370.
  • Example 3 The reaction was carried out in the same manner as in Example 1 except that the amount of 1,5-dibromopentane used was changed to 20.2 g and the amount of 2,6-dichlorobenzonitrile used was changed to 22.7 g to obtain 82 g of an epoxy resin. . (epoxy resin C).
  • the hydroxyl group equivalent of the intermediate hydroxy resin was 226 g/eq. , a melting point of 245° C. and an Mn of 520.
  • Comparative example 1 The reaction was carried out in the same manner as in Example 1 except that 1,5-dibromopentane was not used and the amount of 2,6-dichlorobenzonitrile used was changed to 25.2 g to obtain 74 g of an epoxy resin. (epoxy resin E).
  • the hydroxyl group equivalent of the intermediate hydroxy resin was 220 g/eq. , a melting point of 272° C. and an Mn of 500.
  • Comparative example 2 The reaction was carried out in the same manner as in Example 1 except that 2,6-dichlorobenzonitrile was not used and the amount of 1,5-dibromopentane used was changed to 33.8 g to obtain 45 g of hydroxy resin.
  • the resulting hydroxy resin had a melting point of 300° C. or higher and was insoluble in the solvent, so the epoxidation reaction did not proceed.
  • Examples 5-8 and Comparative Examples 3-5 As epoxy resin components, epoxy resin A obtained in Example 1, epoxy resin B obtained in Example 2, epoxy resin C obtained in Example 3, epoxy resin D obtained in Example 4, and epoxy resin D obtained in Comparative Example 1 were used.
  • Epoxy resin E epoxy resin F (4,4'-dihydroxydiphenyl ether type epoxy resin, epoxy equivalent 163 g / eq.; YSLV-80DE, manufactured by Nippon Steel Chemical & Material) and epoxy resin G (biphenyl type epoxy resin, epoxy equivalent 195 g / eq.; YX-4000H, manufactured by Mitsubishi Chemical), a phenol novolac resin (OH equivalent 105, softening point 83 ° C.; BRG-557, manufactured by Aica Kogyo) as a curing agent, and tritri as a curing accelerator.
  • the epoxy resins obtained in the examples have excellent melt-kneadability and solvent solubility, and the cured products thereof have good thermal stability and thermal conductivity. Suitable.
  • Epoxy resin cured products obtained from the epoxy resin composition of the present invention are suitable for encapsulation of electrical and electronic parts, circuit board materials, and the like.

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PCT/JP2023/003303 2022-02-04 2023-02-02 エポキシ樹脂、エポキシ樹脂組成物およびエポキシ樹脂硬化物 WO2023149493A1 (ja)

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WO2012070590A1 (ja) * 2010-11-24 2012-05-31 Jsr株式会社 樹脂組成物、絶縁膜、膜形成方法および電子部品
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