阅读说明：本技术 环氧树脂组合物及其硬化物 (Epoxy resin composition and cured product thereof ) 是由 大村昌己 广田健 于 2019-02-25 设计创作，主要内容包括：本发明提供一种可获得耐漏电起痕性优异、与耐热性的平衡及热分解稳定性也优异的环氧树脂硬化物、并且尤其作为功率半导体密封用途而优选的环氧树脂组合物、环氧树脂硬化物、以及半导体。一种环氧树脂组合物,其将(A)由下述通式(1)所表示的环氧树脂、(B)5％重量减少温度为260℃以上的非芳香族性环氧树脂或非硅酮系橡胶、(C)硬化剂、以及(D)硬化促进剂作为必需成分,所述环氧树脂组合物的特征在于：相对于成分(A)～成分(D)的合计而含有1重量％～50重量％的成分(B)。其中,n表示0～20的数,G表示缩水甘油基。<Image he="203" wi="700" file="DDA0002668564900000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides aAn epoxy resin cured product excellent in tracking resistance, heat resistance, and thermal decomposition stability, and an epoxy resin composition, an epoxy resin cured product, and a semiconductor which are particularly preferable for power semiconductor sealing applications can be obtained. An epoxy resin composition comprising, as essential components, (A) an epoxy resin represented by the following general formula (1), (B) a non-aromatic epoxy resin or non-silicone rubber having a 5% weight loss temperature of 260 ℃ or higher, (C) a curing agent, and (D) a curing accelerator, wherein: the component (B) is contained in an amount of 1 to 50 wt% based on the total amount of the components (A) to (D). Wherein n represents a number of 0to 20, and G represents a glycidyl group.)

1. An epoxy resin composition comprising the following components A to D as essential components:

a is an aromatic epoxy resin represented by the following general formula (1),

B is a modifier selected from the group consisting of a non-aromatic epoxy resin or a non-silicone rubber having a 5% weight loss temperature of 260 ℃ or higher as determined by thermogravimetric/differential thermal analysis at a temperature rise rate of 10 ℃/min under a nitrogen gas flow, and a rubber composition containing the same,

C a curing agent, and

d a hardening accelerator, said epoxy resin composition characterized by: contains 1 to 50 wt% of component B based on the total amount of components A to D,

[ solution 1]

Wherein n represents a number of 0to 20, and G represents a glycidyl group.

2. The epoxy resin composition according to claim 1, wherein the component B is a modifier comprising a bifunctional epoxy resin comprising at least one epoxy resin selected from the group consisting of glycidyl esters of C15-64 divalent aliphatic carboxylic acids and glycidyl ethers of C15-64 divalent aliphatic alcohols.

3. The epoxy resin composition according to claim 1, wherein the component B is a rubber-based modifier comprising a styrene-based rubber or an acrylic rubber.

4. The epoxy resin composition according to claim 2 or 3, wherein the component C is a hardener comprising a phenol resin represented by the following general formula (2),

[ solution 2]

Wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents a number of 0 or 1.

5. A cured epoxy resin obtained by curing the epoxy resin composition according to any one of claims 1 to 4.

6. A semiconductor device obtained by sealing a semiconductor element with the epoxy resin composition according to any one of claims 1 to 4.

Technical Field

The present invention relates to an epoxy resin composition, a cured epoxy resin, and a semiconductor device, and more particularly, to an epoxy resin composition, a cured epoxy resin, and a semiconductor device which can provide a cured epoxy resin having excellent heat resistance and thermal decomposition stability, and which have excellent tracking resistance and are particularly preferable for power semiconductor sealing applications.

Background

Epoxy resins are used industrially in a wide range of applications. As an example thereof, there is an application as an encapsulating material in a semiconductor device, and in recent years, the performance required in the semiconductor device has been advanced, and the required power density is in a range that has been difficult to achieve with the Si device. In such a case, further increase in power density is expected, and in recent years, SiC power devices are cited as devices whose development has been advanced, but in order to achieve increase in power density, the temperature of the chip surface during operation also reaches 200 ℃. Therefore, it is desired to develop a sealing material which can withstand the above temperature and maintain its physical properties for 1000 hours or more.

In particular, in a semiconductor device for vehicle mounting, various sensors and electronic control units for safety control are integrated, and are exposed to heat generation of an engine and a power module or heat generation due to integration for a long time, and thus, a demand for a material that can withstand a high-temperature environment is also increasing.

Further, not only the demand for thermal durability is increasing, but also the demand for insulation performance accompanying the increase in voltage and current is also increasing. In a power semiconductor device used under high voltage such as a vehicle, an electric vehicle, a wind power generator, and a solar power generator, and in a semiconductor package which is being made smaller and thinner, a circuit pitch width and a lead terminal pitch distance are reduced, and a sealing material and a substrate material are required to have tracking resistance of 600V or more in order to secure a space distance and a creepage distance for electrically insulating these components.

As a method for improving tracking resistance, 1) inhibition of thermal/oxidative decomposition (increase in thermal decomposition initiation temperature and inhibition of volatile gas components), 2) improvement of electrical insulation at high temperature (increase in glass transition temperature), 3) inhibition of carbonization (reduction in residual carbon content and blending of inorganic filler), and the like are effective, and various methods have been proposed. For example, there are proposed: a semiconductor device in which a silicone resin is used as a sealing material having high tracking resistance and excellent workability on the surface thereof and sealed (patent document 1); a flame-retardant non-halogen epoxy resin composition which is excellent in tracking resistance, contains 0.1% by weight or less of a halogen and an antimony compound, and is a polycondensate in which at least one of the curing agents is a phenol, a compound having a triazine ring, or an aldehyde (patent document 2); a sealing material for semiconductor chips which comprises an epoxidized cyclic conjugated diene polymer as a resin component and may contain an inorganic filler as a conductive filler (patent document 3). Further, there are proposed: a resin composition for sealing a semiconductor, which is excellent in tracking resistance and contains an alicyclic epoxy resin system having a cyclohexane polyether skeleton without a benzene skeleton, a dicyclopentadiene type phenol resin, and the like (patent document 4); an epoxy resin composition for semiconductor encapsulation, which contains a metal hydroxide as an inorganic filler in an epoxy resin (patent document 5), but has low heat resistance. On the other hand, an epoxy resin composition for sealing a semiconductor, which contains an epoxy resin, a curing agent, an inorganic filler and spherical silicone powder, is disclosed (patent document 6), but the resin composition is not intended to improve tracking resistance. Further, a sealing resin composition containing a silicone rubber powder (patent document 7) is excellent in tracking resistance, but insufficient in heat resistance. In addition, when the low molecular weight component volatilizes, the silicone rubber powder may cause contact failure. Further, an epoxy resin composition, and a cured product having a biphenol-biphenyl aralkyl structure as a structure excellent in heat resistance have been disclosed, but tracking resistance has not been described (patent documents 8 and 9).

Disclosure of Invention

Detailed Description

The present invention will be described in detail below.

The epoxy resin composition of the present invention contains the following components (a) to (D) as essential components. (A) An aromatic epoxy resin represented by the general formula (1), (B) a modifier selected from a non-aromatic epoxy resin or a non-silicone rubber, (C) a curing agent, and (D) a curing accelerator.

The component (a) is an epoxy resin represented by the general formula (1), and is also referred to as a biphenyl aralkyl type epoxy resin because it has a biphenyl structure. Wherein n represents a number of 0to 20, and G represents a glycidyl group. n is a repeating number and represents a number of 0 or more, and the average value (number average) thereof is 1.3 to 20, preferably 1.5 to 15, more preferably 1.7 to 10, and still more preferably 2 to 6. In view of reactivity and fluidity, the content of the component n 0, where n is 0, is preferably 30 area% or less as measured by Gel Permeation Chromatography (GPC). If the amount is more than this, crystallinity becomes strong and handling becomes difficult. In the case of using the laminate by dissolving it in an organic solvent in applications such as laminate applications, the solvent solubility may be less than 15 area%, preferably 10 area% or less. From the viewpoint of improving heat resistance, the content of the n-5 component or more is 15 area% or more, preferably 20 area% or more. The weight average molecular weight (Mw) measured by GPC is preferably 1,000 to 8,000, more preferably 2,000 to 7,000, and still more preferably 2,000 to 5,000.

The epoxy resin can be manufactured by: a polyhydric hydroxyl resin represented by the following general formula (3) is reacted with epichlorohydrin (epichlorohydrin). The polyhydric hydroxyl resin is also called a biphenyl aralkyl type hydroxyl resin because it has a biphenyl structure. Further, the biphenyl aralkyl type hydroxyl resin can be obtained by: biphenols are reacted with a biphenyl condensing agent represented by the following general formula (4).

[ solution 3]

Wherein n represents a number of 0to 20.

[ solution 4]

Wherein X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms.

Examples of diphenols as starting materials for the synthesis of the biphenylaralkyl type hydroxy resins include 4, 4' -dihydroxybiphenyls.

Specific examples of the biphenyl-based condensing agent include: 4, 4 ' -bishydroxymethylbiphenyl, 4 ' -bischloromethylbiphenyl, 4 ' -bisbromomethylbiphenyl, 4 ' -bismethoxymethylbiphenyl, 4 ' -bisethoxymethylbiphenyl. From the viewpoint of reactivity, 4 '-bishydroxymethylbiphenyl and 4, 4' -bischloromethylbiphenyl are preferable, and from the viewpoint of reduction of ionic impurities, 4 '-bishydroxymethylbiphenyl and 4, 4' -bismethoxymethylbiphenyl are preferable.

The molar ratio during the reaction is preferably 1mol or less, usually in the range of 0.1 to 0.7 mol, and more preferably in the range of 0.2 to 0.5 mol, based on 1mol of 4, 4' -dihydroxybiphenyl. If the amount is less than this, crystallinity becomes strong, solubility in epichlorohydrin at the time of synthesizing the epoxy resin is lowered, and the melting point of the obtained epoxy resin becomes high, and handling property is lowered. If the amount is more than this, the crystallinity of the resin decreases, and the softening point and melt viscosity increase, which may hinder the workability and moldability.

In addition, when chloromethyl biphenyl is used as the condensing agent, the reaction can be carried out without a catalyst, but in general, the present condensation reaction is carried out in the presence of an acidic catalyst. The acid catalyst may be suitably selected from well-known inorganic acids and organic acids, and examples thereof include: mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; or organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like; or Lewis acids (Lewis acids) such as zinc chloride, aluminum chloride, ferric chloride and boron trifluoride; or solid acids, etc.

The reaction is carried out at 10-250 ℃ for 1-30 hours. In addition, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether (triglyme), aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene, and the like can be used as the solvent in the reaction. After the reaction is completed, the solvent or water or alcohol produced by the condensation reaction is removed as necessary.

The method for producing a biphenylaralkyl type epoxy resin represented by the general formula (1) by the reaction of a biphenylaralkyl type hydroxy resin with epichlorohydrin will be described. The reaction can be carried out in the same manner as the well-known epoxidation reaction.

For example, the following methods can be cited: the biphenyl aralkyl type hydroxy resin is dissolved in an excess amount of epichlorohydrin, and then reacted in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at 50 to 150 ℃, preferably 60 to 120 ℃ for 1 to 10 hours. The amount of epichlorohydrin used in this case is in the range of 0.8 to 2.0 moles, preferably 0.9 to 1.2 moles, based on 1 mole of hydroxyl groups in the polyhydric hydroxyl resin. After the reaction is completed, the excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, and the inorganic salt is removed by filtration and washing with water, and then the solvent is distilled off, whereby the objective epoxy resin represented by the general formula (1) can be obtained. In the epoxidation reaction, a catalyst such as a quaternary ammonium salt may be used.

From the viewpoint of improving the reliability of electronic parts to be used, the purity of the biphenyl aralkyl type epoxy resin, particularly the amount of hydrolyzable chlorine, is preferably small. Although not particularly limited, the amount is preferably 1000ppm or less, and more preferably 500ppm or less. The hydrolyzable chlorine in the present invention is a value measured by the following method. That is, 0.5g of a sample was dissolved in 30ml of dioxane, 10ml of 1N-KOH was added thereto, boiling reflux was performed for 30 minutes, the mixture was cooled to room temperature, 100ml of 80% acetone water was further added thereto, and 0.002N-AgNO was used₃The aqueous solution was subjected to potentiometric titration.

In the epoxy resin composition of the present invention, in addition to the epoxy resin of the component (a), an epoxy resin as another component may be blended. The epoxy resin as the other component is also referred to as component (F).

The component (F) is preferably an aromatic epoxy resin obtained by epoxidizing a phenolic hydroxyl group.

As the epoxy resin, any of common aromatic epoxy resins having two or more epoxy groups in the molecule can be used. If the example is given, then: epoxides of diphenols such as bisphenol a, bisphenol F, bisphenol S, fluorene bisphenol, 4 '-biphenol, 3', 5, 5 '-tetramethyl-4, 4' -dihydroxybiphenyl, resorcinol, and naphthalenediol; epoxides of three or more tertiary phenols such as tris- (4-hydroxyphenyl) methane, 1, 2, 2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac, and the like; epoxides of co-condensation resins obtained from dicyclopentadiene and phenols; epoxides of co-condensation resins obtained from cresols with formaldehyde and alkoxy-substituted naphthalenes; epoxides of phenol aralkyl resins obtained from phenols and p-xylylene dichloride and the like; epoxides of biphenyl aralkyl type phenol resins obtained from phenols with bischloromethylbiphenyl and the like; and epoxides of naphthol aralkyl resins synthesized from naphthols and p-xylylene dichloride and the like. These epoxy resins may be used singly or in combination of two or more. In the epoxy resin composition of the present invention, the amount of the epoxy resin represented by the general formula (1) may be in the range of 5 to 100 wt%, preferably 60 to 100 wt%, based on the total amount of the epoxy resin.

The component (B) is a non-silicone modifier selected from non-aromatic epoxy resins and non-silicone rubbers, and the modifier has a 5% weight loss temperature of 260 ℃ or higher as determined by TG/DTA measurement under a nitrogen gas flow at a temperature rise rate of 10 ℃/min. The modifier functions as a modifier for improving tracking resistance.

It is considered that when the modifier is blended, the modifier causes phase separation in the resin, thereby suppressing aggregation of a carbonized layer generated during thermal decomposition, and an improvement in tracking resistance can be expected.

By using a modifier having a 5% weight loss temperature of 260 ℃ or higher, the deterioration of mechanical strength can be prevented even when used at a high temperature of 200 ℃ or higher.

The use of a non-silicone modifier as the modifier has the following advantages. The silicone modifier such as silicone rubber has the following problems: there are concerns that a contact failure may occur when a low-molecular component volatilizes, and that a phase separation from an epoxy resin is easily caused, and it is difficult to obtain a uniform composition, but a non-silicone modifier can solve such a problem. In addition, the non-silicone modifier is also advantageous in terms of cost.

The content of the modifier is 1 to 50% by weight, preferably 2 to 30% by weight, based on the total amount of the components (a) to (D).

From another viewpoint, the amount of the epoxy resin composition may be in the range of 1 to 50 parts by weight, preferably 2 to 30 parts by weight, based on 100 parts by weight of the total amount of the resin components in the epoxy resin composition. If the amount is less than this, the effect of suppressing the aggregation of the carbide layer is low, and conversely, if the amount is more than this, the glass transition temperature Tg of the cured product is lowered and the mechanical strength is also lowered.

The modifier is preferably dispersed in a phase-separated state of 10 μm or less or in a particulate form. The particle diameter (median average diameter) is preferably in the range of 0.01 to 10 μm, more preferably 0.05 to 5 μm, and particularly preferably 0.1 to 1 μm.

These modifiers may be those well known in the art, and are not particularly limited. The modifier having excellent thermal stability is preferably a bifunctional epoxy resin containing, as an essential component, at least one epoxy resin selected from the group consisting of glycidyl esters of divalent aliphatic carboxylic acids having 15 to 64 carbon atoms and glycidyl ethers of divalent aliphatic alcohols having 15 to 64 carbon atoms.

Further, rubbers containing a styrene rubber or an acrylic rubber are also excellent as a modifier.

Examples of the divalent aliphatic carboxylic acid having 15 to 64 carbon atoms include: aliphatic dicarboxylic acids such as 2-dodecylsuccinic acid, hexadecanedioic acid, 8-hexadecanedioic acid, 8, 9-diethylhexadecanedioic acid, eicosanedioic acid, 7-vinyltetradecanedioic acid, 1, 16- (6-ethylhexadecane) dicarboxylic acid, 1, 18- (7, 12-octadecadienyl) dicarboxylic acid, and 1, 12- (diethyldodecane) dicarboxylic acid; or dimer acid whose main component is dibasic acid having 36 carbon atoms obtained by intermolecular reaction of two or more unsaturated fatty acids (e.g., linoleic acid and oleic acid), hydrogenated dimer acid obtained by hydrogenating the dimer acid, and the like, are not particularly limited. By esterifying the diglycidyl esters of these divalent aliphatic carboxylic acids by a known epoxidation technique, an epoxy resin of a glycidyl ester of a divalent aliphatic carboxylic acid having 15 to 64 carbon atoms can be obtained.

Examples of the divalent aliphatic alcohol having 15 to 64 carbon atoms include: examples of the aliphatic diol include long-chain aliphatic diols such as 1, 15-pentadecanediol, 1, 16-hexadecanediol, 1, 18-octadecanediol and 1, 19-nonadecane diol, polyethylene glycols such as octaethylene glycol and nonaethylene glycol, polypropylene glycols such as pentapropylene glycol and hexapropylene glycol, ring-containing diols such as 4, 4' - (propane-2, 2-diyl) bis (cyclohexanol), and dimer diols and hydrogenated dimer diols obtained by reducing the carboxyl groups of the dimer acids and hydrogenated dimer acids to hydroxyl groups, and the like, and the dimer diols and the hydrogenated dimer diols are not particularly limited. By etherifying these diglycidyl esters of divalent aliphatic alcohols by a known epoxidation technique, an epoxy resin of glycidyl ethers of divalent aliphatic alcohols having 15 to 64 carbon atoms can be obtained.

As the styrene-based rubber and the acrylic-based rubber, those containing styrene (including substituted styrene) and acrylic (acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, acrylonitrile, etc.) as a component (monomer) of the rubber or a part of the raw material can be used. Further, a non-silicone natural rubber, a diene rubber such as a butadiene rubber, or the like may be used.

Examples of the styrene-based rubber include: acrylonitrile butadiene styrene copolymer (ABS), acrylonitrile chlorinated polyethylene styrene copolymer (ACS), acrylonitrile ethylene propylene rubber styrene copolymer (AES), acrylonitrile styrene acrylate copolymer (ASA), methyl methacrylate acrylonitrile butadiene styrene copolymer (methyl methacrylate-acrylonitrile butadiene styrene copolymer (MABS), methyl methacrylate butadiene styrene copolymer (methyl methacrylate-butadiene styrene copolymer (MBS), styrene butadiene copolymer (styrene-butadiene styrene copolymer (SB)), acrylonitrile styrene copolymer (SAN), styrene butadiene styrene copolymer (MBS), styrene butadiene copolymer (SBs-styrene block copolymer, SBs-styrene copolymer (SBs-styrene block copolymer), SEBS), styrene ethylene propylene styrene block copolymer (SEPS), styrene isoprene styrene block copolymer (SIS), acrylonitrile styrene dimethylsiloxane alkyl acrylate copolymer, and the like. Among them, from the viewpoint of reducing the modulus of elasticity and improving the impact resistance, rubbers obtained by copolymerization of styrene and a monomer having an unsaturated double bond, such as styrene butadiene copolymer (SB), methyl methacrylate butadiene styrene copolymer (MBS), acrylonitrile styrene dimethylsiloxane alkyl acrylate copolymer, are preferable.

As the acrylic rubber, for example, acrylic rubbers obtained by copolymerizing one or more kinds of alkyl (meth) acrylates and one or more kinds of vinyl monomers copolymerizable therewith can be preferably cited, and as the vinyl monomers copolymerizable with the alkyl (meth) acrylates, for example, crosslinkable monomers can be preferably cited: aromatic polyfunctional vinyl monomers such as divinylbenzene and divinyltoluene; di (meth) acrylate or tri (meth) acrylate of polyhydric alcohol such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate; one or more of diallyl compounds or triallyl compounds such as allyl (meth) acrylate, diallyl phthalate, diallyl sebacate, triallyl triazine, triallyl cyanurate, triallyl isocyanurate, and the like may be used alone or in combination.

The component (C) is a curing agent for epoxy resin. As the curing agent, known curing agents for epoxy resins can be used, and in the field where high electrical insulation is required such as semiconductor sealing materials, polyphenols are preferably used as the curing agent. Specific examples of the curing agent are shown below.

Examples of the polyhydric phenols include: diphenols such as bisphenol a, bisphenol F, bisphenol S, fluorene bisphenol, hydroquinone, resorcinol, catechol, biphenol, and naphthalenediol; and further tris-or more-valent phenols represented by tris- (4-hydroxyphenyl) methane, 1, 2, 2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, dicyclopentadiene type phenol resin, phenol aralkyl resin, and the like; further, phenol compounds, naphthols, or bisphenol a, bisphenol F, bisphenol S, fluorene bisphenol, 4 '-biphenol, 2' -biphenol, hydroquinone, resorcinol, catechol, naphthalenediol and other diphenols, and crosslinking agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylenediol dimethyl ether, divinylbenzene, diisopropenylbenzene, dimethoxymethylbiphenyls, divinylbiphenylene, diisopropenylbiphenyls and the like, biphenyl aralkyl type phenol resins obtained from phenols and bischloromethylbiphenyls and the like, naphthol aralkyl resins obtained from phenols and p-xylylene dichlorides and the like.

Among these, preferred phenolic hardeners are aralkyl phenol resins represented by the general formula (2).

In the general formula (2), R is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents a number of 0 or 1.

By using the aralkyl phenol resin or the curing agent containing the aralkyl phenol resin, it is found that the high Tg property of 200 ℃ or higher required for a power device sealing material is maintained in a glass state in a long-term heat resistance test, and long-term thermal stability is exhibited.

The aralkyl type phenol resin represented by the general formula (2) can be produced by: reacting a salicylaldehyde or a p-hydroxyaldehyde with a compound containing a phenolic hydroxyl group.

The amount of the curing agent to be blended may be adjusted in consideration of the equivalent balance between the epoxy group in the epoxy resin and the active hydrogen (hydroxyl group in the case of polyhydric phenol) in the curing agent. The equivalent ratio of the epoxy resin to the curing agent is usually in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0, and more preferably in the range of 0.8 to 1.5. If the amount is larger or smaller than this, the hardenability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength, and the like of the cured product are lowered.

In addition, in the epoxy resin composition, other kinds of curing agents may be blended as the curing agent component in addition to the aromatic hydroxy compound. Examples of hardeners in this case are: dicyandiamide, acid anhydrides, aromatic amines, aliphatic amines, and the like. In the epoxy resin composition of the present invention, one of these curing agents may be used, or two or more of them may be used in combination.

Examples of the acid anhydride hardener include: phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, nadic anhydride (nadic anhydride), trimellitic anhydride, and the like.

Examples of the amines include aromatic amines such as 4, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylpropane, 4 ' -diaminodiphenylsulfone, m-phenylenediamine and p-xylylenediamine, and aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine.

The component (D) is a hardening accelerator for the epoxy resin composition. The hardening accelerator may be one well known in the art of epoxy resins, and is not particularly limited. Examples thereof include amines, imidazoles, organophosphines, Lewis acids, and the like.

Specifically, there are: tertiary amines such as 1, 8-diazabicyclo (5.4.0) undecene-7 (1, 8-diazabicyclo (5.4.0) undecene-7, DBU), triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; tetra-substituted phosphonium tetra-substituted borates such as tetraphenylphosphonium-tetraphenylborate, tetraphenylphosphonium-ethyltriphenylborate and tetrabutylphosphonium-tetrabutylborate, and tetraphenylboronium salts such as 2-ethyl-4-methylimidazole-tetraphenylborate and N-methylmorpholine-tetraphenylborate. The amount of the epoxy resin is usually in the range of 0.2 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

Oligomers or high molecular compounds such as polyesters, polyamides, polyimides, polyethers, polyurethanes, petroleum resins, indene-benzofuran resins, phenoxy resins, and the like may be suitably blended as other modifiers in the epoxy resin composition of the present invention. The amount of the epoxy resin is usually in the range of 2 to 30 parts by weight based on 100 parts by weight of the epoxy resin.

The epoxy resin composition of the present invention may contain additives such as inorganic fillers, pigments, flame retardants, thixotropy imparting agents, coupling agents, and fluidity improving agents. Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like, and the amount of the inorganic filler to be used for a semiconductor sealing material is preferably 70% by weight or more, more preferably 80% by weight or more.

Examples of the pigment include organic or inorganic extender pigments and flake pigments. As the thixotropy imparting agent, there may be mentioned: castor oil series, aliphatic amide wax, oxidized polyethylene wax, organic bentonite (bentonite) series, and the like.

Further, in the resin composition of the present invention, as required, there can be used: release agents such as carnauba wax (carnauba wax) and OP wax; coupling agents such as gamma-glycidoxypropyltrimethoxysilane; a colorant such as carbon black; flame retardants such as antimony trioxide; lubricants such as calcium stearate.

The epoxy resin composition of the present invention can be prepared into a prepreg by dissolving a part or the whole of the composition in an organic solvent to prepare a varnish state, impregnating the varnish in a fibrous material such as a glass cloth, an aromatic polyamide nonwoven fabric, or a polyester nonwoven fabric of a liquid crystal polymer, and removing the solvent. When the solvent-insoluble component such as an inorganic filler is contained, it is not necessary to dissolve the component, and it is desirable to form a suspension and to form a uniform solution. Further, the laminate can be prepared by coating a sheet-like material such as a copper foil, a stainless steel foil, a polyimide film, or a polyester film.

When the epoxy resin composition of the present invention is heat-cured, a cured epoxy resin product having excellent low moisture absorption, high heat resistance, adhesion, flame retardancy, and the like can be obtained. The cured product can be obtained by molding the epoxy resin composition by a method such as injection molding, compression molding, or transfer molding. The temperature in this case is usually in the range of 120 ℃ to 220 ℃. The epoxy resin composition of the present invention is particularly excellent for use as a sealing material. Further, the semiconductor device of the present invention can be obtained by sealing a semiconductor element with the epoxy resin composition.