WO2014065152A1 - Composition de résine époxy, procédé de production d'un produit durci à base de résine époxy, et dispositif semi-conducteur - Google Patents

Composition de résine époxy, procédé de production d'un produit durci à base de résine époxy, et dispositif semi-conducteur Download PDF

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WO2014065152A1
WO2014065152A1 PCT/JP2013/077921 JP2013077921W WO2014065152A1 WO 2014065152 A1 WO2014065152 A1 WO 2014065152A1 JP 2013077921 W JP2013077921 W JP 2013077921W WO 2014065152 A1 WO2014065152 A1 WO 2014065152A1
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epoxy resin
resin composition
temperature
curing
cured product
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PCT/JP2013/077921
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English (en)
Japanese (ja)
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大神　浩一郎
健 廣田
山田　尚史
秀安 朝蔭
梶　正史
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新日鉄住金化学株式会社
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Priority to JP2014543239A priority Critical patent/JPWO2014065152A1/ja
Publication of WO2014065152A1 publication Critical patent/WO2014065152A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—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
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus

Definitions

  • the present invention relates to an epoxy resin composition, a method for producing an epoxy resin cured product, and a semiconductor device. More specifically, an epoxy resin cured product having excellent heat resistance and thermal decomposition stability is obtained, and fluidity during molding is provided.
  • the present invention relates to an epoxy resin composition suitable for power semiconductor sealing, a method for producing a cured epoxy resin, and a semiconductor device.
  • Epoxy resins are used in a wide range of industrial applications.
  • there is an application as a sealing material in a semiconductor device but the required performance in the semiconductor device has become increasingly sophisticated in recent years, and the required power density has become a region that is difficult to reach with conventional Si devices. .
  • SiC power devices can be cited as devices that are expected to have higher power density and are being developed in recent years.
  • the temperature of the chip surface during operation Reaches 250 ° C. Therefore, development of a sealing material that can withstand the temperature and can maintain the physical properties for 1000 hours or more is strongly desired.
  • Patent Document 1 discloses an epoxy resin, an epoxy resin composition, and a cured product having a biphenol-biphenyl aralkyl structure, and shows excellent heat resistance, moisture resistance, and thermal conductivity. Has been. However, even when the epoxy resin disclosed in Patent Document 1 is used as described above, only a cured product having a glass transition temperature of about 200 ° C. is obtained when phenol novolac is used as a curing agent by a normal molding method. Absent. Therefore, the subject that the characteristic of the sealing material for high heat resistant SiC power devices which can endure a high operating temperature of 250 degreeC cannot be satisfied occurred. Moreover, in patent document 1, long-term thermal stability required for the sealing material for SiC power devices is not described.
  • an object of the present invention is to obtain an epoxy resin cured product excellent in high Tg property (heat resistance), weight retention property (thermal decomposition stability) at high temperature and long term, and mechanical strength retention property, and molding.
  • Another object of the present invention is to provide an epoxy resin composition that is excellent in fluidity and suitable for use as a power device sealing material.
  • Another object of the present invention is to provide a method for producing a cured epoxy resin such as a power device encapsulant by using this epoxy resin composition.
  • the present invention is an epoxy resin composition containing an epoxy resin represented by the following general formula (1), a phenolic curing agent, a curing catalyst, and an inorganic filler, and the temperature of the epoxy resin composition is increased.
  • An epoxy resin composition characterized by having an exothermic peak top of 150 ° C. or higher when differential scanning calorimetry is performed at a rate of 10 ° C./min. (However, n represents an average value of 0.2 to 4.0, and G represents a glycidyl group.)
  • the present invention also provides the epoxy resin composition as described above, wherein the curing catalyst is at least one selected from the group consisting of imidazoles, organic phosphines, and amines.
  • this invention is an epoxy resin composition as described above in which a phenol type hardening
  • R represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and l represents a number of 0 or 1.
  • A represents a benzene ring, naphthalene ring or biphenyl ring, k represents a number of 1 to 15, and m and p each represents a number of 1 or 2.
  • the present invention contains an epoxy resin represented by the following general formula (1), a phenolic curing agent, a curing catalyst, and an inorganic filler, and was subjected to differential scanning calorimetry at a temperature rising rate of 10 ° C./min.
  • An epoxy resin composition having an exothermic peak top of 150 ° C. or higher is molded at a molding temperature of 100 ° C. to 200 ° C. and then post-cured at 200 ° C. to 300 ° C. Is the method. (However, n represents an average value of 0.2 to 4.0, and G represents a glycidyl group.)
  • the cured epoxy resin obtained above is suitable for a power semiconductor encapsulant.
  • the present invention is a semiconductor device characterized in that a power semiconductor element is sealed with the cured epoxy resin.
  • the cured epoxy resin obtained using the poxy resin composition of the present invention is excellent in high Tg property, weight retention at high temperature and long term, and mechanical strength retention. Excellent fluidity. Therefore, the epoxy resin composition of this invention can be used conveniently for the use of the sealing material of a power semiconductor.
  • the epoxy resin represented by the general formula (1) which is an essential component of the epoxy resin composition of the present invention, reacts a polyvalent hydroxy resin represented by the following general formula (a) with epichlorohydrin. Can be manufactured. And this polyhydric hydroxy resin can be manufactured by making biphenols and the biphenyl type condensing agent represented by the following general formula (b) react.
  • n represents an average value of 0.2 to 4.0.
  • X represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms.
  • Examples of the biphenols used as the raw material for synthesizing the polyvalent hydroxy resin include dihydroxybiphenyls such as 4,4'-dihydroxybiphenyl and 2,2'-dihydroxybiphenyl. These bifunctional phenolic compounds may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. Examples of the substituent include a methyl group, an ethyl group, an isopropyl group, an allyl group, a tertiary butyl group, an amyl group, a cyclohexyl group, and a phenyl group. These dihydroxybiphenyls may be used alone or in combination of two or more.
  • X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms.
  • Specific examples of the biphenyl condensing agent represented by the general formula (b) include 4,4′-bishydroxymethylbiphenyl, 4,4′-bischloromethylbiphenyl, 4,4′-bisbromomethylbiphenyl, 4,4 Examples include '-bismethoxymethylbiphenyl and 4,4'-bisethoxymethylbiphenyl. From the viewpoint of reactivity, 4,4′-bishydroxymethylbiphenyl and 4,4′-bischloromethylbiphenyl are preferable. From the viewpoint of reducing ionic impurities, 4,4′-bishydroxymethylbiphenyl, 4 4,4'-bismethoxymethylbiphenyl is preferred.
  • the molar ratio in the reaction is such that the biphenyl condensing agent should be 1 mol or less per 1 mol of 4,4′-dihydroxybiphenyl, and generally ranges from 0.1 to 0.7 mol. More preferably, it is in the range of 0.2 to 0.5 mol. If it is less than this, the crystallinity becomes strong, the solubility in epichlorohydrin when synthesizing the epoxy resin is lowered, the melting point of the obtained epoxy resin is increased, and the handleability is lowered. On the other hand, if the amount is larger than this, the crystallinity of the resin is lowered and the softening point and the melt viscosity are increased, which hinders handling workability and moldability.
  • the reaction can be carried out in the absence of a catalyst, but this condensation reaction is usually carried out in the presence of an acidic catalyst.
  • the acidic catalyst can be appropriately selected from known inorganic acids and organic acids.
  • mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, metasulfone
  • organic acids such as acid and trifluorometasulfonic acid
  • Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride, and solid acids.
  • This reaction is carried out at 10 to 250 ° C. for 1 to 20 hours.
  • alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, and aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as a solvent.
  • aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as a solvent.
  • the solvent or water and alcohol produced by the condensation reaction are removed as necessary.
  • the method for producing the epoxy resin of the present invention by the reaction between the polyvalent hydroxy resin represented by the general formula (a) and epichlorohydrin will be described. This reaction can be performed in the same manner as a well-known epoxidation reaction.
  • the polyvalent hydroxy resin represented by the general formula (a) is dissolved in excess epichlorohydrin, it is 50 to 150 ° C., preferably 60 ° C. in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
  • an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
  • a method of reacting in the range of ⁇ 120 ° C. for 1 to 10 hours is mentioned.
  • the amount of epichlorohydrin used in this case is in the range of 0.8 to 2 mol, preferably 0.9 to 1.2 mol, relative to 1 mol of hydroxyl group in the polyvalent hydroxy resin.
  • the target epoxy resin represented by 1) can be obtained.
  • a catalyst such as a quaternary ammonium salt may be used.
  • the purity of the epoxy resin of the present invention is better from the viewpoint of improving the reliability of the applied electronic component.
  • it does not specifically limit, Preferably it is 1000 ppm or less, More preferably, it is 500 ppm or less.
  • the hydrolyzable chlorine as used in the field of this invention means the value measured by the following method. That is, the potential difference the sample 0.5g were dissolved in dioxane 30 ml, 1N-KOH, after the added boiled under reflux for 30 minutes 10 ml, cooled to room temperature, 80% aqueous acetone 100ml was added, with 0.002 N-AgNO 3 aqueous solution This is a value obtained by titration.
  • the epoxy resin composition of this invention contains the epoxy resin of the said General formula (1), a phenol type hardening
  • a curing catalyst having an active site in a high temperature region in the epoxy resin composition for the purpose of promoting curing and improving fluidity during molding.
  • high temperature active catalyst for the purpose of promoting curing and improving fluidity during molding.
  • the content of the curing catalyst is preferably in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.
  • the amount is preferably 0.5 to 3 parts by weight, more preferably 0.5 to 2.5 parts by weight. If it is smaller than this, the curability will be lowered, and conversely if it is larger than this, the fluidity improving effect at the time of molding will not be sufficiently exhibited.
  • the DSC exothermic peak temperature of the epoxy resin composition using the high temperature active catalyst is 150 ° C. or higher, preferably 155 ° C. or higher, more preferably 165 ° C. or higher.
  • This DSC exothermic peak temperature is the maximum exothermic peak (exothermic heat) when differential scanning calorimetry (DSC measurement) is performed on an epoxy resin composition containing a high-temperature active catalyst as a curing catalyst at a temperature rising rate of 10 ° C / min. This is a temperature indicating a peak top.
  • the upper limit of the DSC exothermic peak temperature is substantially 300 ° C. considering that the curing temperature range by post-cure is preferably 200 ° C. to 300 ° C.
  • curing catalyst high temperature active catalyst
  • examples of the curing catalyst include imidazoles, organic phosphines, amines and the like.
  • imidazoles include 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-heptadecylimidazole, and 2,4-diamino-6- [2′-dimethyl.
  • organic phosphines such as diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine include tris- (2,6-dimethoxyphenyl) phosphine, tri-p-tolylphosphine,
  • amines such as tris (p-chlorophenyl) phosphine and tris (p-methoxyphenyl) phosphine include 1,8-dia Bicyclo (5,4,0) phenol novolak salts of undecene-7 can be mentioned. One or two or more of these may be used in combination.
  • the curing conditions by using a high-temperature active catalyst having a specific active temperature region as a curing catalyst, it is possible to suppress a decrease in fluidity. Further, regarding the curing conditions, particularly when the epoxy resin of the present invention is used. In addition, it has been found that the curing conditions at high temperature greatly affect the glass transition temperature.
  • a phenolic curing agent is used as the curing agent.
  • polyhydric phenols are preferably used as curing agents. Below, the specific example of a hardening
  • polyhydric phenols examples include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, hydroquinone, resorcin, catechol, biphenols, naphthalenediols, and tris- (4-hydroxyphenyl).
  • divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, hydroquinone, resorcin, catechol, biphenols, naphthalenediols, and tris- (4-hydroxyphenyl).
  • Trivalent or higher typified by methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, dicyclopentadiene type phenol resin, phenol aralkyl resin, etc. There are phenols.
  • phenols, naphthols, or divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4 ′ -biphenol, 2,2 ′ -biphenol, hydroquinone, resorcin, catechol, naphthalene diols, etc.
  • a preferable phenolic curing agent is preferably an aralkyl type phenol resin represented by the following general formula (2) or (3).
  • R represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
  • l represents a number from 0 to 2.
  • A represents a benzene ring, a naphthalene ring, or a biphenyl ring
  • m and p independently represent a number of 1 or 2.
  • the benzene ring, naphthalene ring or biphenyl ring may have a substituent, and a preferred substituent is an alkyl group having 1 to 3 carbon atoms.
  • k is the number of repetitions and is a number of 1 to 15, and the average is preferably in the range of 1 to 2.
  • the polyvalent hydroxy compound (phenolic curing agent) represented by the general formula (2) can be produced by reacting salicylaldehyde or p-hydroxyaldehyde with a phenolic hydroxyl group-containing compound.
  • phenol o-cresol, m-cresol, p-cresol
  • 2-ethylphenol 4-ethylphenol
  • 2-propylphenol 4-propylphenol
  • 4-neopentylphenol 2-cyclopentylphenol, 2-hexylphenol, 4-hexylphenol and the like.
  • the polyvalent hydroxy compound (phenolic curing agent) represented by the general formula (3) can be produced by reacting a phenolic hydroxyl group-containing compound having a benzene ring or a naphthalene ring with an aromatic crosslinking agent.
  • phenol phenol, hydroquinone, resorcin, catechol, pyrogallol, phloroglucinol, 1-naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7 -Naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, 2,2'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, etc.
  • Aromatic cross-linking agents include those having a benzene skeleton and those having a biphenyl skeleton.
  • a substance having a benzene skeleton may be any of o-form, m-form and p-form, and preferably m-form and p-form.
  • p-xylylene glycol ⁇ , ⁇ '-dimethoxy-p-xylene, ⁇ , ⁇ '-diethoxy-p-xylene, ⁇ , ⁇ '-diisopropyl-p-xylene, ⁇ , ⁇ '-dibutoxy -P-xylene, m-xylylene glycol, ⁇ , ⁇ '-dimethoxy-m-xylene, ⁇ , ⁇ '-diethoxy-m-xylene, ⁇ , ⁇ '-diisopropoxy-m-xylene, ⁇ , ⁇ ' -Dibutoxy-m-xylene and the like.
  • Examples of those having a biphenyl skeleton include 4,4′-dihydroxymethylbiphenyl, 2,4′-dihydroxymethylbiphenyl, 2,2′-dihydroxymethylbiphenyl, 4,4′-dimethoxymethylbiphenyl, 2,4 ′.
  • the total crosslinking agent contains 50 wt% or more of the 4,4′-isomer. If it is less than this, the curing rate as an epoxy resin curing agent will decrease, or the resulting cured product will tend to be brittle.
  • k is a number from 1 to 15.
  • the value of k can be easily prepared by changing the molar ratio between the phenolic hydroxyl group-containing compound and the crosslinking agent when they are reacted. That is, the value of k can be controlled smaller as the phenolic hydroxyl group-containing compound is used in excess relative to the crosslinking agent.
  • the larger the value of k the higher the softening point and viscosity of the obtained resin. Further, the smaller the value of k, the lower the viscosity.
  • the amount of unreacted phenolic hydroxyl group-containing compound at the time of synthesis increases, and the production efficiency of the resin decreases.
  • the molar ratio of the two must be 1 mol or less, preferably 0.1 to 0.9 mol, per mol of the phenolic hydroxyl group-containing compound.
  • the amount is less than 0.1 mol, the amount of unreacted phenolic hydroxyl group-containing compound is increased, which is not industrially preferable.
  • the blending amount of the phenolic curing agent in the epoxy resin composition is blended in consideration of the equivalent balance between the epoxy group in the epoxy resin represented by the general formula (1) and the hydroxyl group of the phenolic curing agent.
  • the equivalent ratio of epoxy resin and curing agent is usually in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0, more preferably in the range of 0.8 to 1.5. It is. If it is larger or smaller than this, the curability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength and the like of the cured product are lowered.
  • curing agent component in addition to the phenolic curing agent.
  • curing agent examples include dicyandiamide, acid anhydrides, aromatic and aliphatic amines, and one or more of these curing agents can be used in combination.
  • the amount of the curing agent other than the phenol-based curing agent is preferably 50 wt% or less of the total curing agent.
  • the compounding amount of the epoxy resin represented by the general formula (1) in the epoxy resin composition is preferably 0.1 wt% to 28 wt%, and preferably 3 wt% to 16 wt%. If the blending amount of the epoxy resin of the general formula (1) is less than 0.1 wt%, the heat resistance and thermal decomposition stability of the cured product is not sufficiently improved. Conversely, if it exceeds 28 wt%, the equivalent balance of epoxy group and hydroxyl group The heat resistance, mechanical strength, etc. of the cured product are reduced.
  • epoxy resin composition other epoxy resins may be blended as an epoxy resin component in addition to the epoxy resin represented by the general formula (1).
  • epoxy resin in this case, all ordinary epoxy resins having two or more epoxy groups in the molecule can be used. Examples include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4 ′ -biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, resorcin, naphthalenediols Trivalent or more epoxides of divalent phenols such as tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, etc.
  • These epoxy resins can be used alone or in combination of two or more.
  • the amount of the epoxy resin represented by the general formula (1) is 5 to 100 wt%, preferably 60 to 100 wt% in the whole epoxy resin.
  • the inorganic filler for example, silica powder such as spherical or crushed fused silica, crystalline silica, alumina powder, glass powder, or mica, talc, calcium carbonate, alumina, hydrated alumina, boron nitride, aluminum nitride, Examples thereof include silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, and magnesium oxide.
  • the blending amount of the inorganic filler in the epoxy resin composition is particularly preferably 70% by weight to 95% by weight, more preferably 80% by weight to 90% by weight, particularly when used for a semiconductor sealing material. .
  • the epoxy resin composition of the present invention further includes a release agent such as carnauba wax and OP wax, a coupling agent such as 4-aminopropylethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane, carbon, if necessary.
  • a colorant such as black, a flame retardant such as antimony trioxide, and a lubricant such as calcium stearate may be blended.
  • an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene coumarone resin, phenoxy resin or the like is used as a modifier. You may mix
  • the epoxy resin composition of the present invention may also contain additives such as pigments, refractory agents, thixotropic agents, coupling agents, fluidity improvers, and antioxidants.
  • pigments there are organic or inorganic extender pigments, scaly pigments, and the like.
  • examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite.
  • the epoxy resin composition of the present invention is made into a varnish in which an organic solvent is dissolved, and then impregnated into a fibrous material such as glass cloth, aramid nonwoven fabric, polyester nonwoven fabric such as liquid crystal polymer, and the like, and then the solvent is removed. It can be. Moreover, it can be set as a laminated body by apply
  • any method may be used for preparing the epoxy resin composition of the present invention as long as various raw materials can be uniformly dispersed and mixed.
  • raw materials of a predetermined blending amount are sufficiently mixed by a mixer or the like. Then, a method of melt-kneading with a mixing roll, an extruder or the like, cooling, and pulverizing can be mentioned.
  • the epoxy resin composition of the present invention and its cured product are particularly suitable for sealing power semiconductor devices.
  • the cured product of the present invention can be obtained by thermally curing the above epoxy resin composition.
  • methods such as transfer molding, press molding, cast molding, injection molding, and extrusion molding are applied, but from the viewpoint of mass productivity. Transfer molding is preferred.
  • the curing method of the epoxy resin composition of the present invention is 100 ° C. to 200 ° C., preferably 120 ° C. to 190 ° C., more preferably 150 to 180 ° C., and then 200 ° C. to 300 ° C., preferably 220 ° C. to 280 ° C. More preferably, it is produced by post-curing at 230 to 270 ° C., and a cured product excellent in terms of Tg, high-temperature long-term weight retention, mechanical strength retention and the like can be obtained.
  • the molding time is preferably 1 to 60 minutes, more preferably 1 to 10 minutes. If the molding time is long, the productivity will be poor, and if it is too short, it will be difficult to release.
  • the post cure time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 8 hours, and particularly preferably 2 hours to 6 hours. When the post-cure time is short, curing does not proceed sufficiently, and sufficient characteristics such as heat resistance and mechanical properties cannot be obtained. Moreover, productivity will fall when it exceeds 10 hours.
  • the curing reaction proceeds even in a high post-cure temperature region where a general epoxy resin composition cannot react, and has a very high Tg, high temperature long-term weight retention, and mechanical strength retention.
  • a cured product having properties and the like can be obtained.
  • Synthesis example 1 In a 1000 ml four-necked flask, 77.5 g of 4,4′-dihydroxybiphenyl, 180.8 g of diethylene glycol dimethyl ether and 52.3 g of 4,4′-bischloromethylbiphenyl were charged, and the temperature was raised to 170 ° C. with stirring in a nitrogen stream. The reaction was allowed to warm for 2 hours. After the reaction, 123 g of diethylene glycol dimethyl ether was recovered, dissolved in 385.4 g of epichlorohydrin and 57.8 g of diethylene glycol dimethyl ether, and 69.4 g of 48% aqueous sodium hydroxide solution was added dropwise at 62 ° C.
  • the peak temperature in this DSC measurement result using the differential scanning calorimeter shown below for this epoxy resin A was 126 degreeC
  • the melt viscosity in 150 degreeC was 0.68 Pa.s.
  • the measuring method of these physical-property values is as having shown below.
  • Example 1 As an epoxy resin component, 102 g of epoxy resin A obtained in Synthesis Example 1, and as a curing agent component, a triphenylmethane type polyvalent hydroxy resin (manufactured by Gunei Chemical Industry Co., Ltd., OH equivalent 97.5, softening point 105 ° C.) 51 g was used. Further, curing catalyst A: 1.6 g of 2-phenyl-4,5-dihydroxymethylimidazole (product name: 2PHZ-PW, manufactured by Shikoku Kasei Co., Ltd.) and spherical silica (product name: FB-8S) as an inorganic filler , Manufactured by Denki Kagaku Kogyo Co., Ltd.).
  • a triphenylmethane type polyvalent hydroxy resin manufactured by Gunei Chemical Industry Co., Ltd., OH equivalent 97.5, softening point 105 ° C.
  • curing catalyst A 1.6 g of 2-phenyl-4,5-dihydroxy
  • Examples 2-7, Comparative Examples 1-4 An epoxy resin composition was prepared by kneading the epoxy resin A obtained in Synthesis Example 1 above, a curing agent, an inorganic filler, a curing accelerator, and other additives in a blending ratio shown in Tables 1 and 2. And the hardened
  • molding was performed using the epoxy resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 4 under the following molding conditions. And after obtaining the hardened
  • the exothermic peak temperature of the epoxy resin composition was determined under the condition of a temperature rising rate of 10 ° C / min using a DSC6200 thermomechanical measuring device manufactured by Seiko Instruments.
  • Tg Glass transition point
  • A Weight retention rate Test piece weight after 1000 hours at 250 ° C. and test piece before heating using a thermostatic chamber with a rotating frame (GPHH-201, manufactured by Tabai Espec Co., Ltd.) The weight retention (wt%) was determined from the difference from the weight.
  • B Bending strength retention rate Using a thermostatic device with a rotating frame (GPHH-201, manufactured by Tabai Espec Co., Ltd.), the bending strength of the test piece after 1000 hours at 250 ° C. and the bending strength of the test piece before heating The bending strength retention rate (%) was determined from the difference. The bending strength was measured at room temperature by the above test method.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention concerne : une composition de résine époxy qui est capable de donner un produit durci ayant une excellente résistance à la chaleur, stabilité à la décomposition thermique et capacité de rétention de sa résistance mécanique, tout en manifestant une excellente fluidité pendant le moulage, et qui se prête à la production de matériaux de scellement pour alimentations électriques ; et un procédé de production d'un produit durci à base de résine époxy. La composition de résine époxy selon l'invention contient une résine époxy représentée par la formule générale (1), un durcisseur phénolique, un catalyseur de durcissage et une charge inorganique, et présente un pic de température exothermique, déterminé par une analyse calorimétrique différentielle par balayage, de 150°C ou plus à une vitesse de chauffage de 10°C/minute. Un procédé de production d'un produit durci à base de résine époxy, la composition de résine époxy étant moulée à une température de 100 à 200°C puis soumise à un post-durcissage à une température de 200 à 300°C est en outre décrit. (Dans la formule, n représente une moyenne de 0,2 à 4,0 ; et G représente un groupe glycidyle).
PCT/JP2013/077921 2012-10-26 2013-10-15 Composition de résine époxy, procédé de production d'un produit durci à base de résine époxy, et dispositif semi-conducteur WO2014065152A1 (fr)

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JP2015117311A (ja) * 2013-12-18 2015-06-25 日東電工株式会社 半導体モジュール用熱伝導性シート
JP2016074805A (ja) * 2014-10-06 2016-05-12 新日鉄住金化学株式会社 半導体封止用樹脂組成物及び半導体装置
JP2016204420A (ja) * 2015-04-15 2016-12-08 京セラ株式会社 封止用エポキシ樹脂成形材料及び電子部品
JP2017019919A (ja) * 2015-07-09 2017-01-26 三菱化学株式会社 エポキシ樹脂、組成物、硬化物及び電気・電子部品
JP2017119768A (ja) * 2015-12-28 2017-07-06 新日鉄住金化学株式会社 多価ヒドロキシ樹脂及びエポキシ樹脂の製造方法
WO2017170703A1 (fr) * 2016-03-30 2017-10-05 新日鉄住金化学株式会社 Résine polyhydroxy, son procédé de production, résine époxy, composition de résine époxy et produit durci de composition de résine époxy
JP2018513236A (ja) * 2015-03-13 2018-05-24 ランクセス ソリューションズ ユーエス インコーポレイテッド リン含有難燃剤を含む積層板および複合体のための難燃性樹脂
JP6350891B1 (ja) * 2016-09-12 2018-07-04 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板
CN110003616A (zh) * 2017-12-12 2019-07-12 日铁化学材料株式会社 环氧树脂组合物及其固化物
KR20200002668A (ko) 2018-06-29 2020-01-08 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 다가 하이드록시 수지의 제조 방법
WO2020090491A1 (fr) * 2018-11-01 2020-05-07 住友ベークライト株式会社 Composition de résine de scellement de dispositif d'alimentation et dispositif d'alimentation
CN111378093A (zh) * 2018-12-28 2020-07-07 日铁化学材料株式会社 环氧树脂及其制造方法、环氧树脂组合物及环氧树脂硬化物
JP6954485B1 (ja) * 2021-02-17 2021-10-27 住友ベークライト株式会社 射出成形用封止樹脂組成物
CN114206976A (zh) * 2019-08-08 2022-03-18 住友电木株式会社 密封树脂组合物和电子部件
KR20240026887A (ko) 2021-06-30 2024-02-29 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 에폭시 수지, 에폭시 수지 조성물, 및 그 경화물

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JP2015117311A (ja) * 2013-12-18 2015-06-25 日東電工株式会社 半導体モジュール用熱伝導性シート
JP2016074805A (ja) * 2014-10-06 2016-05-12 新日鉄住金化学株式会社 半導体封止用樹脂組成物及び半導体装置
JP2018513236A (ja) * 2015-03-13 2018-05-24 ランクセス ソリューションズ ユーエス インコーポレイテッド リン含有難燃剤を含む積層板および複合体のための難燃性樹脂
JP2016204420A (ja) * 2015-04-15 2016-12-08 京セラ株式会社 封止用エポキシ樹脂成形材料及び電子部品
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WO2017170703A1 (fr) * 2016-03-30 2017-10-05 新日鉄住金化学株式会社 Résine polyhydroxy, son procédé de production, résine époxy, composition de résine époxy et produit durci de composition de résine époxy
JPWO2017170703A1 (ja) * 2016-03-30 2019-02-21 日鉄ケミカル＆マテリアル株式会社 多価ヒドロキシ樹脂、その製造方法、エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
US10703855B2 (en) 2016-09-12 2020-07-07 Mitsubishi Gas Chemical Company, Inc. Resin composition, prepreg, metal-foil-clad laminate, resin sheet, and printed circuit board
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JP7255633B2 (ja) 2018-11-01 2023-04-11 住友ベークライト株式会社 パワーデバイス封止用樹脂組成物およびパワーデバイス
WO2020090491A1 (fr) * 2018-11-01 2020-05-07 住友ベークライト株式会社 Composition de résine de scellement de dispositif d'alimentation et dispositif d'alimentation
JP2021119248A (ja) * 2018-11-01 2021-08-12 住友ベークライト株式会社 パワーデバイス封止用樹脂組成物およびパワーデバイス
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