JP2008094970A - Epoxy resin molding material for sealing and electronic component device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding material for sealing, which has good moldability in terms of flow property, curability, etc., and reduces warpage deformation even when used on a batch-molded, single-side sealed package, and an electronic component device equipped with an element sealed with the same. <P>SOLUTION: The epoxy resin molding material for sealing contains (A) a silicon-containing polymer having bonds (a) and (b) (wherein R<SP>1</SP>is chosen from (non)substituted monovalent 1-12C hydrocarbon groups, provided that all R<SP>1</SP>s in the silicon-containing polymer may be identical to or different from each other; and X is a monovalent organic group containing an epoxy group), has a functional group chosen from R<SP>1</SP>, a hydroxy group and an alkoxy group at its terminal and has an epoxy equivalent of 500-1,700, (B) an adduct of a tertiary phosphine compound and a quinone compound, (C) an epoxy resin and (D) a hardener. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an epoxy resin molding material for sealing and an electronic component device.

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin molding materials have been widely used. This is because epoxy resins are balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts.

  In recent years, along with the high density mounting of electronic component devices on printed wiring boards, electronic component devices are mainly used in surface mount type packages rather than conventional pin insertion type packages. Surface-mount ICs, LSIs, etc. are thin and small packages in order to increase the mounting density and reduce the mounting height, and the volume occupied by the device package increases, resulting in a very thick package. It has become thinner.

  In addition, in order to cope with further reduction in size and weight, CSP (Quad Flat Package), SOP (Small Outline Package), and other forms of packages are easy to cope with higher pin count and CSP capable of higher density mounting. It is shifting to an area mounting package such as BGA (Ball Grid Array) including (Chip Size Package). In recent years, these packages have been developed with new structures such as face-down type, stacked type, flip chip type, and wafer level type in order to realize high speed and multiple functions. Many have a single-side sealed package form in which only one side on the element mounting surface side is sealed with a sealing material such as an epoxy resin molding material, and then solder balls are formed on the back surface to join the circuit board. ing. In addition, as substrates used for single-sided sealed packages, glass substrate epoxy resin substrates, hard circuit substrates such as glass substrate bismaleimide / triazine resin substrates, and flexible circuit substrates such as polyimide resin film substrates are mainly used. Is done. Furthermore, instead of the conventional one-chip / one-cavity sealing method, the resin-sealing process for producing a single-side-sealed package has been developed as a batch mold type sealing method that seals multiple chips in one cavity. As a result, production efficiency is improved and costs are reduced.

  The single-side sealed package has a single-side sealed shape as the electronic component device. Therefore, when it is cooled from the molding temperature to room temperature or due to the difference in physical properties between the substrate and the molding material, the heat in the reflow process Due to the history, there is a problem that warp deformation tends to occur starting from the central part of the electronic component device. Along with this warp deformation, there is a difference in height between a plurality of solder balls arranged on the same surface of the element mounting substrate, and when a test such as a package D / C operation inspection process is performed in such a state, Problems such as failure to perform sufficient inspection due to hindered connector connection may occur. Further, when the electronic component device is surface-mounted on a mounting substrate, a part of the solder ball may not be completely connected to the corresponding wiring layer, and the reliability of the connection portion may be reduced.

  Therefore, as a technique for reducing the warpage deformation amount, a method of increasing the Tg of the cured epoxy resin molding material by increasing the crosslink density by using a polyfunctional resin for the epoxy resin and the phenol resin is disclosed. (For example, refer to Patent Document 1). On the other hand, using a crystalline epoxy resin and a polyfunctional phenol resin to reduce the viscosity of the epoxy resin molding material for sealing, and filling the filler with a high filling material achieves both low expansion coefficient and high Tg of the cured product. And a method for improving the reflow crack resistance is disclosed (for example, see Patent Documents 2 and 3).

Japanese Patent Laid-Open No. 11-35803 Japanese Patent Laid-Open No. 11-100100 JP-A-11-163224

  However, since the melt viscosity of the resin is high only by the method described in Patent Document 1, it is difficult to ensure sufficient fluidity in the molding material, and when the fluidity is ensured by lowering the amount of filler. Has a problem of causing a decrease in reflow crack resistance accompanying an increase in water absorption of the cured product. Further, even in the methods described in Patent Documents 2 and 3, the improvement in fluidity is not satisfactory, and when such an epoxy resin molding material for sealing is used in a batch mold type electronic component device, it is not yet satisfactory. There is a problem that causes filling

  The present invention has been made in view of such a situation, and has an excellent moldability such as fluidity and curability, and an epoxy for sealing that can reduce the amount of warpage deformation even when used in a single-sided sealed package of a batch mold type. An object of the present invention is to provide an electronic component device including a resin molding material and an element sealed thereby.

  As a result of intensive studies in order to solve the above problems, the present inventors can achieve the above object by using an epoxy resin molding material for sealing containing a silicon-containing polymer having a specific bond and epoxy equivalent. As a result, the present invention has been completed.

The present invention relates to the following.
<1> (A) A silicon-containing polymer having the following bonds (a) and (b), having a terminal selected from R ¹ , a hydroxyl group and an alkoxy group, and an epoxy equivalent of 500 to 1700. (B) An epoxy resin molding material for sealing containing an addition reaction product of a third phosphine compound and a quinone compound, (C) an epoxy resin, and (D) a curing agent.

（ここで、Ｒ^１は炭素数１〜１２の置換または非置換の１価の炭化水素基から選ばれ、ケイ素含有重合物中の全Ｒ^１はすべてが同一でも異なっていてもよい。Ｘはエポキシ基を含む１価の有機基を示す。）

(Here, R ¹ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ¹ in the silicon-containing polymer may be the same or different. X is Indicates a monovalent organic group containing an epoxy group.)

<2> (A) The epoxy resin molding material for sealing according to <1>, wherein the silicon-containing polymer further has a bond (c).

（ここで、Ｒ^１は炭素数１〜１２の置換または非置換の１価の炭化水素基から選ばれ、ケイ素含有重合物中の全Ｒ^１はすべてが同一でも異なっていてもよい。）

(Here, R ¹ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ¹ in the silicon-containing polymer may be all the same or different.)

<3> (A) The epoxy resin molding material for sealing according to <1> or <2>, wherein the softening point of the silicon-containing polymer is 40 ° C. or higher and 120 ° C. or lower.
<4> (A) The epoxy for sealing according to any one of <1> to <3>, wherein R ¹ in the silicon-containing polymer is at least ^one of a substituted or unsubstituted phenyl group and a methyl group. Resin molding material.
<5> (A) In the above <1> to <4>, the ratio of the substituted or unsubstituted phenyl group having 1 to 12 carbon atoms in all R ¹ in the silicon-containing polymer is 60 mol% to 100 mol%. The epoxy resin molding material for sealing according to any one of the above.
<6> The component according to any one of <1> to <5>, wherein the component (B) is an addition reaction product of a third phosphine compound represented by the following formula (I) and a quinone compound represented by the following formula (II): Epoxy resin molding material for sealing.

（ここで、式（Ｉ）中のＲ^１〜Ｒ^３は、置換又は非置換の炭素数１〜１２のアルキル基もしくは置換又は非置換の炭素数６〜１２のアリール基を示し、全て同一でも異なっていてもよい。また、式（ＩＩ）中のＲ^４〜Ｒ^６は水素原子または炭素数１〜１２の炭化水素基を示し、全て同一でも異なっていてもよく、Ｒ^４とＲ^５が結合して環状構造となっていてもよい。）

(Wherein R ^{1 to} R ³ in formula (I) represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, In the formula (II), R ^{4 to} R ⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be all the same or different, and R ⁴ and R ⁵ may be different from each other. It may be bonded to form a ring structure.)

<7> The epoxy resin molding material for sealing according to <6>, wherein the component (B) contains an addition reaction product of tributylphosphine and 1,4-benzoquinone.
<8> The epoxy resin molding material for sealing according to <6>, wherein the component (B) contains an addition reaction product of triphenylphosphine and 1,4-benzoquinone.
<9> Furthermore, (E) the epoxy resin for sealing according to any one of <1> to <8>, wherein the inorganic filler is contained in an amount of 70% by mass to 95% by mass with respect to the epoxy resin molding material for sealing. Molding material.
<10> An electronic component device including an element sealed with the sealing epoxy resin molding material according to any one of <1> to <9>.

  Since the epoxy resin molding material for sealing according to the present invention has a small substrate warp, if it is used to seal an electronic component such as a single-side sealed package of a batch mold type, the connection reliability during mounting is good. Products can be obtained, and their industrial value is great.

The silicon-containing polymer (A) used in the present invention has the following bonds (a) and (b), the terminal is a functional group selected from R ¹ , a hydroxyl group and an alkoxy group, and an epoxy equivalent is 500 Although there will be no restriction | limiting in particular if it is-1700, For example, branched polysiloxane etc. are mentioned as such a polymer.

（ここで、Ｒ^１は炭素数１〜１２の置換または非置換の１価の炭化水素基から選ばれ、ケイ素含有重合物中の全Ｒ^１はすべてが同一でも異なっていてもよい。Ｘはエポキシ基を含む１価の有機基を示す。）

(Here, R ¹ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ¹ in the silicon-containing polymer may be the same or different. X is Indicates a monovalent organic group containing an epoxy group.)

R ¹ in the general formulas (a) and (b) is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group. , Alkyl groups such as 2-ethylhexyl group, alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group, benzyl group And an aralkyl group such as a phenethyl group. Among them, a methyl group or a phenyl group is preferable.

  X in the general formula (b) is 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxy Propyl group, 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group and the like, among which 3-glycidoxypropyl group is mentioned. preferable.

Moreover, the terminal of (A) silicon-containing polymer needs to be any of the aforementioned R ¹ , hydroxyl group and alkoxy group from the viewpoint of storage stability of the polymer. In this case, examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Furthermore, the epoxy equivalent of (A) silicon-containing polymer needs to be in the range of 500 to 1700, and is preferably 800 to 1700 from the viewpoint of curability. On the other hand, if it is smaller than 500, the fluidity of the sealing epoxy resin molding material tends to be lowered, and if it is larger than 1700, the amount of change in warpage tends to increase, so that molding failure tends to occur.

  (A) The silicon-containing polymer is further preferable from the viewpoint of coexistence of fluidity and low warpage of the epoxy resin molding material for sealing obtained to have the following bond (c).

（ここで、Ｒ^１はケイ素含有重合物中の全Ｒ^１に対して炭素数１〜１２の置換又は非置換の１価の炭化水素基から選ばれ、ケイ素含有重合物中の全Ｒ^１はすべてが同一でも異なっていてもよい。）

(Here, R ¹ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms with respect to all R ¹ in the silicon-containing polymer, and all R ¹ in the silicon-containing polymer is All may be the same or different.)

R ¹ in the general formula (c) is methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl. Alkyl groups such as vinyl groups, vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups and other alkenyl groups, phenyl groups, tolyl groups, xylyl groups, naphthyl groups, biphenyl groups and other aryl groups, benzyl groups, phenethyl groups, etc. And a methyl group or a phenyl group is preferable.

  The softening point of such (A) silicon-containing polymer is preferably set to 40 ° C to 120 ° C, and more preferably set to 50 ° C to 100 ° C. When the temperature is lower than 40 ° C, the mechanical strength of the cured epoxy resin molding material obtained tends to decrease. When the temperature is higher than 120 ° C, the (A) silicon-containing polymer contained in the sealing epoxy resin molding material Dispersibility tends to decrease. (A) As a method for adjusting the softening point of the silicon-containing polymer, (A) the molecular weight of the silicon-containing polymer, the structural bond units (for example, (a) to (c) content ratio, etc.), and the organic bonded to the silicon atom Although it is possible by setting the kind of group, from the viewpoint of the dispersibility of the (A) silicon-containing polymer in the epoxy resin molding material for sealing and the fluidity of the resulting epoxy resin molding material for sealing ( A) It is preferable to adjust the softening point by setting the content of the aryl group in the silicon-containing polymer. Examples of the aryl group in this case include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group, and a phenyl group is more preferable. (A) Desirable by setting content of phenyl group in monovalent organic group bonded to silicon atom in silicon-containing polymer to 60 mol% to 99 mol%, preferably 70 mol% to 85 mol% A silicon-containing polymer having a softening point of (A) can be obtained.

  (A) The mass average molecular weight (Mw) of the silicon-containing polymer is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve, preferably 1000 to 30000, more preferably 2000. To 20000, more preferably 3000 to 10000. Also. (A) The silicon-containing polymer is preferably a random copolymer.

  Such (A) silicon-containing polymer can be obtained by the production method shown below, but is commercially available as trade name AY42-119 manufactured by Toray Dow Corning Silicone Co., Ltd.

  (A) The manufacturing method of a silicon containing polymer can be manufactured by a well-known method without a restriction | limiting in particular. For example, organochlorosilane, organoalkoxysilane, siloxane, or an organic solvent that can dissolve the raw materials and reaction products thereof, which can form the above units (a) to (c) by hydrolysis condensation reaction, and It can be obtained by mixing all the hydrolyzable groups of the raw material in a mixed solution with a hydrolyzable amount of water and subjecting it to a hydrolytic condensation reaction. At this time, in order to reduce the amount of chlorine contained as an impurity in the sealing epoxy resin molding material, it is preferable to use organoalkoxysilane and / or siloxane as a raw material. In this case, it is preferable to add an acid, a base, or an organometallic compound as a catalyst for promoting the reaction.

  (A) The organoalkoxysilane and / or siloxane used as a raw material for the silicon-containing polymer are methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane. , Phenyltrimethoxysilane, phenyltoethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, phenylvinyldimethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylvinyldiethoxysilane, phenylvinyldiethoxy Silane, diphenyldiethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxy Propyl (phenyl) dimethoxysilane, 3-glycidoxypropyl (phenyl) diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) ) Diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, and their hydrolysis condensates. It is done.

  (A) 0.2 mass%-1.5 mass% of the whole epoxy resin molding material for sealing is preferable, and 0.3 mass%-1.3 mass% are more preferable. When the amount is less than 0.2% by mass, the effect of adding the (A) silicon-containing polymer is not observed, and when the amount is more than 1.5% by mass, the hot-time hardness of the resulting epoxy resin molding material for sealing tends to decrease. .

  The (B) curing accelerator used in the present invention is not particularly limited as long as it acts as a curing accelerator for the epoxy resin molding material for sealing as an addition reaction product of the third phosphine compound and the quinone compound. However, an addition reaction product of a phosphine compound represented by the following general formula (I) and a quinone compound represented by the following general formula (II) is preferable from the viewpoint of fluidity.

（ここで、式（Ｉ）中のＲ^１〜Ｒ^３は、置換又は非置換の炭素数１〜１２のアルキル基もしくは置換又は非置換の炭素数６〜１２のアリール基を示し、全て同一でも異なっていてもよい。また、式（ＩＩ）中のＲ^４〜Ｒ^６は水素原子または炭素数１〜１２の炭化水素基を示し、全て同一でも異なっていてもよく、Ｒ^４とＲ^５が結合して環状構造となっていてもよい。）

(Wherein R ^{1 to} R ³ in formula (I) represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, In the formula (II), R ^{4 to} R ⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be all the same or different, and R ⁴ and R ⁵ may be different from each other. It may be bonded to form a ring structure.)

R ^{1 to} R ³ in the above general formula (I) represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. There is no restriction | limiting in particular as a C1-C12 alkyl group of, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group Chain alkyl groups such as octyl group, decyl group and dodecyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group, aryl group substituted alkyl such as benzyl group and phenethyl group Group, alkoxy group-substituted alkyl group such as methoxy group-substituted alkyl group, ethoxy group-substituted alkyl group, butoxy group-substituted alkyl group, dimethyl group Amino group, an amino group-substituted alkyl group such as a diethylamino group, a hydroxyl group-substituted alkyl group.

  Examples of the substituted or unsubstituted aryl group having 1 to 12 carbon atoms include unsubstituted aryl groups such as phenyl group and naphthyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, and t-butylphenyl group. Alkyl group-substituted aryl groups such as dimethylnaphthyl group, alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group and methoxynaphthyl group, amino such as dimethylamino group and diethylamino group Examples include a group-substituted aryl group and a hydroxyl group-substituted aryl group.

  Examples of the phosphine compound represented by the general formula (I) include triphenylphosphine, diphenyl-p-tolylphosphine, tri-p-tolylphosphine, diphenyl-p-methoxyphenylphosphine, tri-p-methoxyphenylphosphine, tricyclohexyl. Phosphine, dicyclohexylphenylphosphine, dicyclohexyl-p-tolylphosphine, cyclohexyldiphenylphosphine, cyclohexyldi-p-tolylphosphine, tributylphosphine, dibutylphenylphosphine, dibutyl-p-tolylphosphine, butyldiphenylphosphine, butyldi-p-tolylphosphine, Trioctylphosphine, dioctylphenylphosphine, dioctyl-p-tolylphosphine, octyldiphenylphosphine, o Chiruji -p- tolylphosphine, and the like, triphenylphosphine or tributylphosphine is preferred from the viewpoint of inter alia curing fluidity properties.

R ^{4 to} R ⁶ in the general formula (II) represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, but the hydrocarbon group having 1 to 12 carbon atoms is not particularly limited. Or an unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms. Etc.

  Examples of the substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and a pentyl group. , Alkyl groups such as hexyl group, octyl group, decyl group, dodecyl group, allyl group, methoxy group, ethoxy group, propoxyl group, n-butoxy group, alkoxy group such as t-butoxy group, dimethylamino group, diethylamino group Alkylamino groups such as methylthio group, ethylthio group, butylthio group, dodecylthio group and other alkylthio groups, amino group substituted alkyl groups, alkoxy substituted alkyl groups, hydroxyl group substituted alkyl groups, substituted alkyl groups such as aryl group substituted alkyl groups, amino Substituents such as group-substituted alkoxy groups, hydroxyl group-substituted alkoxy groups, aryl group-substituted alkoxy groups, etc. Such as alkoxy groups.

  Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms include, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, and an aryl group. Examples thereof include those substituted with a group, a hydroxyl group, an amino group, halogen and the like.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms include an aryl group such as a phenyl group and a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, and a t-butylphenyl group. Alkyl group substituted aryl groups, alkoxy groups substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group, aryloxy groups such as phenoxy group, crezoxy group, phenylthio group, tolylthio group, diphenylamino group And those substituted with an amino group, halogen or the like.

In addition, the quinone compound represented by the general formula (II) may have a cyclic structure by bonding R ⁴ and R ⁵ . The polycyclic quinone compound having a cyclic structure by bonding R ⁴ and R ⁵ used in the present invention is not particularly limited, and examples thereof include the following general groups in which a substituted tetramethylene group, tetramethine group and the like are bonded. And polycyclic quinone compounds represented by formulas (VII) to (IX).

  Examples of the quinone compound represented by the general formula (II) include 1,4-benzoquinone, 2,3-dimethoxy-1,4benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, and methoxy-1,4-benzoquinone. 2,3-dimethyl-1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone, methyl-1,4-benzoquinone, 2,5-di-t-butyl-1,4-benzoquinone, t -Butyl-1,4-benzoquinone, phenyl-1,4-benzoquinone and the like can be mentioned, among which 1,4-benzoquinone is preferable from the viewpoint of fluidity and curability.

  Examples of the structure of the addition reaction product of the phosphine compound represented by the general formula (I) and the quinone compound represented by the general formula (II) include compounds represented by the following general formula (X).

（ここで、Ｒ^１〜Ｒ^３は、置換又は非置換の炭素数１〜１２のアルキル基もしくは置換又は非置換の炭素数６〜１２のアリール基を示し、全て同一でも異なっていてもよい。Ｒ^４〜Ｒ^６は水素原子又は炭素数１〜１２の炭化水素基を示し、全て同一でも、異なっていてもよく、Ｒ^４とＲ^５が結合して環状構造となっていてもよい。）

(Here, R ^{1 to} R ³ represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and may all be the same or different. R ^{4 to} R ^{6 each} represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may all be the same or different, and R ⁴ and R ⁵ may be bonded to form a cyclic structure.

Examples of the addition reaction product of the third phosphine compound and the quinone compound represented by the general formula (X) include addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone, tricyclohexylphosphine, 1,4-benzoquinone, Addition reaction product, addition reaction product of tricyclohexylphosphine and methyl-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and 2,3-dimethyl-1,4-benzoquinone, tricyclohexylphosphine and 2,5 -Addition reaction product of dimethyl-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and methoxy-1,4-benzoquinone, addition reaction of tricyclohexylphosphine and 2,3-dimethoxy-1,4-benzoquinone , Tricyclohexylphosphine and 2,5-dimeth Addition reaction product of cis-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and methyl-1,4-benzoquinone, cyclohexyldiphenylphosphine and 2 , 3-Dimethyl-1,4-benzoquinone addition reaction product, cyclohexyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone addition reaction product, cyclohexyldiphenylphosphine and methoxy-1,4-benzoquinone Addition reaction product, addition reaction product of cyclohexyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, cyclohexyldi-p -Birds Addition reaction product of phosphine and 1,4-benzoquinone, addition reaction product of cyclohexyldi-p-tolylphosphine and methyl-1,4-benzoquinone, cyclohexyldi-p-tolylphosphine and 2,3-dimethyl-1, Addition reaction product with 4-benzoquinone, addition reaction product of cyclohexyldi-p-tolylphosphine and 2,5-dimethyl-1,4-benzoquinone, cyclohexyldi-p-tolylphosphine and methoxy-1,4-benzoquinone Addition reaction product of cyclohexyldi-p-tolylphosphine and 2,3-dimethoxy-1,4-benzoquinone, cyclohexyldi-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone Addition reaction product of dicyclohexylphenylphosphine with 1,4-benzoquinone Product, addition reaction product of dicyclohexylphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, dicyclohexylphenylphosphine and 2,5-dimethyl- Addition reaction product of 1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, dicyclohexyl Addition reaction product of phenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, dicyclohexyl-p-tolylphosphine and 1,4-benzoquinone Addition reaction product, addition reaction product of dicyclohexyl-p-tolylphosphine and methyl-1,4-benzoquinone, addition reaction product of dicyclohexyl-p-tolylphosphine and 2,3-dimethyl-1,4-benzoquinone, dicyclohexyl- Addition reaction product of p-tolylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of dicyclohexyl-p-tolylphosphine and methoxy-1,4-benzoquinone, dicyclohexyl-p-tolylphosphine and 2 , 3-dimethoxy-1,4-benzoquinone addition reaction, dicyclohexyl-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone addition reaction, dicyclohexyl-p-tolylphosphine and 1,4 -Addition reaction product with benzoquinone, tributylphosphine and 1,4 Addition reaction product of benzoquinone, addition reaction product of tributylphosphine and methyl-1,4-benzoquinone, addition reaction product of tributylphosphine and 2,3-dimethyl-1,4-benzoquinone, tributylphosphine and 2,5- Addition reaction product of dimethyl-1,4-benzoquinone, addition reaction product of tributylphosphine and methoxy-1,4-benzoquinone, addition reaction product of tributylphosphine and 2,3-dimethoxy-1,4-benzoquinone, tributyl Addition reaction product of phosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of dibutylphenylphosphine and methyl-1,4-benzoquinone, dibutylphenylphosphine and 2,3-dimethyl-1,4- Addition reaction product with benzoquinone, dibutylphenylphosphine and 2,5-dimethyl Addition reaction product of ru-1,4-benzoquinone, addition reaction product of dibutylphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of dibutylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone Addition reaction product of dibutylphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of dibutyl-p-tolylphosphine and methyl-1,4-benzoquinone, dibutyl-p-tolylphosphine and 2 , 3-Dimethyl-1,4-benzoquinone addition reaction product, dibutyl-p-tolylphosphine and 2,5-dimethyl-1,4-benzoquinone addition reaction product, dibutyl-p-tolylphosphine and methoxy-1 , 4-Benzoquinone addition reaction product, dibutyl-p-tolylphosphine and 2,3-dimethoxy-1,4 Addition reaction product of benzoquinone, addition reaction product of dibutyl-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and 1,4-benzoquinone, butyldiphenylphosphine and Addition reaction product of methyl-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, butyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone Addition reaction product of butyldiphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, butyldiphenylphosphine and 2,5 -Addition reaction product with dimethoxy-1,4-benzoquinone, butyl -Addition reaction product of p-tolylphosphine and 1,4-benzoquinone, addition reaction product of butyldi-p-tolylphosphine and methyl-1,4-benzoquinone, butyldi-p-tolylphosphine and 2,3-dimethyl- 1,4-benzoquinone addition reaction product, butyldi-p-tolylphosphine and 2,5-dimethyl-1,4-benzoquinone addition reaction product, butyldi-p-tolylphosphine and methoxy-1,4-benzoquinone Addition reaction product of butyldi-p-tolylphosphine with 2,3-dimethoxy-1,4-benzoquinone, addition of butyldi-p-tolylphosphine with 2,5-dimethoxy-1,4-benzoquinone Reaction product, addition reaction product of trioctylphosphine and 1,4-benzoquinone, trioctylphosphine and methyl-1,4-ben Addition reaction product of zoquinone, addition reaction product of trioctylphosphine and 2,3-dimethyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and 2,5-dimethyl-1,4-benzoquinone, tri Addition reaction product of octylphosphine and methoxy-1,4-benzoquinone, addition reaction product of trioctylphosphine and 2,3-dimethoxy-1,4-benzoquinone, trioctylphosphine and 2,5-dimethoxy-1,4 -Addition reaction product of benzoquinone, addition reaction product of dioctylphenylphosphine and 1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and methyl-1,4-benzoquinone, dioctylphenylphosphine and 2,3-dimethyl- Addition reaction product with 1,4-benzoquinone, dioctylphenylphosphine and 2 Addition reaction product of 5-dimethyl-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and methoxy-1,4-benzoquinone, addition of dioctylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone Reaction product, addition reaction product of dioctylphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of dioctyl-p-tolylphosphine and 1,4-benzoquinone, dioctyl-p-tolylphosphine and methyl -1,4-benzoquinone addition reaction product, dioctyl-p-tolylphosphine and 2,3-dimethyl-1,4-benzoquinone addition reaction product, dioctyl-p-tolylphosphine and 2,5-dimethyl-1 , 4-Benzoquinone addition reaction product, dioctyl-p-tolylphosphine and methoxy Addition reaction product of 1,4-benzoquinone, addition reaction product of dioctyl-p-tolylphosphine and 2,3-dimethoxy-1,4-benzoquinone, dioctyl-p-tolylphosphine and 2,5-dimethoxy-1, Addition reaction product of 4-benzoquinone, addition reaction product of octyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and methyl-1,4-benzoquinone, octyldiphenylphosphine and 2,3-dimethyl Addition reaction product of -1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and methoxy-1,4-benzoquinone, Octyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoyl Non-addition reaction product, octyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone addition reaction product, octyldi-p-tolylphosphine and 1,4-benzoquinone addition reaction product, octyldi-p- Addition reaction product of tolylphosphine and methyl-1,4-benzoquinone, addition reaction product of octyldi-p-tolylphosphine and 2,3-dimethyl-1,4-benzoquinone, octyldi-p-tolylphosphine and 2,5 -Addition reaction product with dimethyl-1,4-benzoquinone, addition reaction product with octyldi-p-tolylphosphine and methoxy-1,4-benzoquinone, octyldi-p-tolylphosphine and 2,3-dimethoxy-1,4 An addition reaction product with benzoquinone, octyldi-p-tolylphosphine and 2,5-dimethoxy-1,4-ben Addition reaction product of quinone, addition reaction product of triphenylphosphine and 1,4-benzoquinone, addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone, triphenylphosphine and 2,3-dimethyl-1 , 4-benzoquinone addition reaction product, triphenylphosphine and 2,5-dimethyl-1,4-benzoquinone addition reaction product, triphenylphosphine and methoxy-1,4-benzoquinone addition reaction product, triphenyl Addition reaction product of phosphine and 2,3-dimethoxy-1,4-benzoquinone, addition reaction product of triphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, diphenyl-p-tolylphosphine and 1,4 -Addition reaction product with benzoquinone, diphenyl-p-tolylphosphine and methyl-1,4-benzoyl Reaction product of diphenyl-p-tolylphosphine and 2,3-dimethyl-1,4-benzoquinone, diphenyl-p-tolylphosphine and 2,5-dimethyl-1,4-benzoquinone Addition reaction product of diphenyl-p-tolylphosphine and methoxy-1,4-benzoquinone, addition reaction product of diphenyl-p-tolylphosphine and 2,3-dimethoxy-1,4-benzoquinone, diphenyl -Addition reaction product of p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of tri-p-tolylphosphine and 1,4-benzoquinone, tri-p-tolylphosphine and methyl- Addition reaction product of 1,4-benzoquinone, addition reaction of tri-p-tolylphosphine and 2,3-dimethyl-1,4-benzoquinone Reaction product, addition reaction product of tri-p-tolylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of tri-p-tolylphosphine and methoxy-1,4-benzoquinone, tri-p- Addition reaction product of tolylphosphine and 2,3-dimethoxy-1,4-benzoquinone, addition reaction product of tri-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone, tri-p-methoxyphenyl Addition reaction product of phosphine and 1,4-benzoquinone, addition reaction product of tri-p-methoxyphenylphosphine and methyl-1,4-benzoquinone, tri-p-methoxyphenylphosphine and 2,3-dimethyl-1, Addition reaction product with 4-benzoquinone, addition reaction of tri-p-methoxyphenylphosphine with 2,5-dimethyl-1,4-benzoquinone Addition reaction product of tri-p-methoxyphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of tri-p-methoxyphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, tri-p -Reaction product of methoxyphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of diphenyl-p-methoxyphenylphosphine and 1,4-benzoquinone, diphenyl-p-methoxyphenylphosphine and methyl -1,4-benzoquinone addition reaction product, diphenyl-p-methoxyphenylphosphine and 2,3-dimethyl-1,4-benzoquinone addition reaction product, diphenyl-p-methoxyphenylphosphine and 2,5-dimethyl -1,4-Benzoquinone addition reaction product, diphenyl-p-methoxyphenyl Addition reaction product of nylphosphine and methoxy-1,4-benzoquinone, addition reaction product of diphenyl-p-methoxyphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, diphenyl-p-methoxyphenylphosphine and 2 , 5-dimethoxy-1,4-benzoquinone addition reaction product, triphenylphosphine and t-butyl-1,4-benzoquinone addition reaction product, tricyclohexylphosphine and t-butyl-1,4-benzoquinone Addition reaction product, addition reaction product of tributylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and t-butyl-1,4-benzoquinone, dicyclohexylphenylphosphine and t-butyl-1 , 4-benzoquinone addition reaction product, dibutylphenylphosphine and Addition reaction product of t-butyl-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and t-butyl-1,4-benzoquinone, addition of cyclohexyldiphenylphosphine and t-butyl-1,4-benzoquinone Reaction product, addition reaction product of butyldiphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and t-butyl-1,4-benzoquinone, dicyclohexyl-p-tolylphosphine and t- Addition reaction product of butyl-1,4-benzoquinone, addition reaction product of dibutyl-p-tolylphosphine and t-butyl-1,4-benzoquinone, dioctyl-p-tolylphosphine and t-butyl-1,4- Addition reaction product with benzoquinone, cyclohexyldi-p-tolylphosphine and t-butyl- , 4-benzoquinone addition reaction product, butyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone addition reaction product, octyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone Addition reaction product, addition reaction product of triphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of diphenyl-p-tolylphosphine and t-butyl-1,4-benzoquinone, diphenyl-p-methoxy Addition reaction product of phenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of tri-p-tolylphosphine and t-butyl-1,4-benzoquinone, tri-p-methoxyphenylphosphine and t- Addition reaction product with butyl-1,4-benzoquinone, triphenylphosphine and 2,5-di-t-butyl-1,4-ben Addition reaction product of quinone, addition reaction product of tricyclohexylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, tributylphosphine and 2,5-di-t-butyl-1,4-benzoquinone Addition reaction product of trioctylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, dicyclohexylphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone Addition reaction product of dibutylphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, dioctylphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone Addition reaction product of cyclohexyldiphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, butyldiphenylphosphine Addition reaction product of sphin and 2,5-di-t-butyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, dicyclohexyl- Addition reaction product of p-tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, dibutyl-p-tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone Addition reaction product, addition reaction product of dioctyl-p-tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, cyclohexyl di-p-tolylphosphine and 2,5-di-t-butyl- 1,4-benzoquinone addition reaction product, butyldi-p-tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone addition reaction product, octyldi-p-tolylphosphine And 2,5-di-t-butyl-1,4-benzoquinone addition reaction product, triphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone addition reaction product, diphenyl- Addition reaction product of p-tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, diphenyl-p-methoxyphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone Addition reaction product of tri-p-tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, tri-p-methoxyphenylphosphine and 2,5-di-t-butyl -1,4-benzoquinone addition reaction product, triphenylphosphine and phenyl-1,4-benzoquinone addition reaction product, tricyclohexylphosphine and phenyl-1,4-benzoquinone Addition reaction product, addition reaction product of tributylphosphine and phenyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and phenyl-1,4-benzoquinone, dicyclohexylphenylphosphine and phenyl-1,4-benzoquinone Addition reaction product, addition reaction product of dibutylphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and phenyl-1,4-benzoquinone, cyclohexyldiphenylphosphine and phenyl-1,4-benzoquinone Addition reaction product of butyldiphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and phenyl-1,4-benzoquinone, dicyclohexyl-p-tolylphosphine and phenyl-1 , 4-benzoquinone addition reaction product, dibutyl-p-tolylphosphine and phenyl-1,4-benzoquinone addition reaction product, dioctyl-p-tolylphosphine and phenyl-1,4-benzoquinone addition reaction product, Addition reaction product of cyclohexyldi-p-tolylphosphine and phenyl-1,4-benzoquinone, addition reaction product of butyldi-p-tolylphosphine and phenyl-1,4-benzoquinone, octyldi-p-tolylphosphine and phenyl- 1,4-benzoquinone addition reaction product, triphenylphosphine and phenyl-1,4-benzoquinone addition reaction product, diphenyl-p-tolylphosphine and phenyl-1,4-benzoquinone addition reaction product, diphenyl- Addition of p-methoxyphenylphosphine and phenyl-1,4-benzoquinone Reactants, addition reaction products of tri -p- tolyl phosphine and phenyl-1,4-benzoquinone, an addition reaction products of the avian -p- methoxyphenyl phosphine and phenyl-1,4-benzoquinone and the like.

  Among these, from the viewpoint of the reactivity between the phosphine compound and the quinone compound, addition reaction product of triphenylphosphine and 1,4-benzoquinone, addition reaction of diphenyl-p-tolylphosphine and 1,4-benzoquinone. , Addition reaction product of diphenyl-p-methoxyphenylphosphine and 1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone Addition reaction product of tricyclohexylphosphine and 1,4-benzoquinone, addition reaction product of trioctylphosphine and 1,4-benzoquinone, addition reaction product of tributylphosphine and 1,4-benzoquinone, trioctylphosphine and 1 , 4-Benzoquinone addition reaction product Addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of diphenyl-p-tolylphosphine and methyl-1,4-benzoquinone, diphenyl-p-methoxyphenylphosphine and methyl-1,4 -Addition reaction product of benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and methyl-1,4-benzoquinone, tricyclohexylphosphine and methyl-1, Addition reaction product of 4-benzoquinone, addition reaction product of trioctylphosphine and methyl-1,4-benzoquinone, addition reaction product of tributylphosphine and methyl-1,4-benzoquinone, and trioctylphosphine and methyl-1, Addition with 4-benzoquinone Applied Physics is preferable. Further, from the viewpoint of fluidity and curability, an addition reaction product of triphenylphosphine and 1,4-benzoquinone and an addition reaction product of tributylphosphine and 1,4-benzoquinone are more preferable.

(B) Although there is no restriction | limiting in particular as a manufacturing method of the addition reaction product of a 3rd phosphine compound and a quinone compound, For example, the phosphine compound and quinone compound which are used as a raw material are addition-reacted in the organic solvent in which both melt | dissolve. The method of isolation is mentioned. Specifically, a solution obtained by dissolving 41.6 g (1 mol) of triphenylphosphine in 120 g of acetone and a solution of 17.6 g (1 mol) of 1,4-benzoquinone in 80 g of acetone are used at room temperature to 80 ° C. And the yellow-brown crystals deposited after standing for 2 to 5 hours are collected by filtration. As a solvent at this time, a mixed solvent of acetone and toluene may be used instead of acetone. Also,
(D) It can also be produced by a method of addition reaction in a phenol resin used as a curing agent. In this case, the compounding component of the epoxy resin composition is dissolved in the phenol resin as it is without isolating the addition reaction product. Can be used as

  (B) Although there is no restriction | limiting in particular in the compounding quantity of the addition reaction material of a tertiary phosphine compound and a quinone compound, in order to exhibit the performance, 30 mass% or more is preferable with respect to all the hardening accelerators, and 50 mass% or more Is more preferable, and 60% by mass or more is more preferable.

  (B) When only the addition reaction product of a tertiary phosphine compound and a quinone compound is used as a curing accelerator, the blending amount is 0.2 to 10 mass with respect to the total amount of (C) epoxy resin and (D) curing agent. % Is preferred. If it is less than 0.2% by mass, the curability effect tends to be insufficient, and if it exceeds 10% by mass, the fluidity tends to decrease.

  The epoxy resin molding material for sealing of the present invention only needs to contain an addition reaction product of (B) a third phosphine compound and a quinone compound, and is otherwise generally used for epoxy resin molding materials for sealing. A curing accelerator can be used in combination. Examples of the curing accelerator used in combination include 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, 5,6-dibutylamino-1. , 8-diazabicyclo [5.4.0] undecene-7 and the like, derivatives thereof, and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2, Quinones such as 3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone Benzyldimethylamine, a compound with intramolecular polarization formed by adding a compound having a π bond, such as a compound, diazophenylmethane, or a phenol resin Tertiary amines such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole And the like, trialkylphosphine such as tributylphosphine, dialkylarylphosphine such as dimethylphenylphosphine, alkyldiarylphosphine such as methyldiphenylphosphine, trisphosphine, tris (4-methylphenyl) phosphine (Alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl-alkoxyphenyl) phosphine, tris (dialkylphenyl) ) Phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, diphenylphosphine, diphenyl (p- Tolyl) phosphine and other organic phosphines, derivatives thereof, phosphorus compounds having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, diazophenylmethane, and phenol resin, tetraphenylphosphonium tetraphenylborate , Triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, etc. Ron salts and derivatives thereof, and the like complexes of organic phosphines and organic boron compound. These curing accelerators may be used alone or in combination of two or more.

  The epoxy resin (C) used in the present invention contains two or more epoxy groups in one molecule and is not particularly limited. For example, a phenol novolak type epoxy resin, an orthocresol novolak type epoxy resin, a triphenylmethane skeleton is used. Phenols such as epoxy resin, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, etc. and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde Epoxidized novolak resin obtained by condensation or cocondensation with a compound having an aldehyde group such as benzaldehyde and salicylaldehyde under an acidic catalyst, alkyl substitution, aromatic ring substitution Glycidyl ester obtained by reaction of polychlorobasic acid such as diglycidyl ether such as substituted or unsubstituted bisphenol A, bisphenol F, bisphenol S, biphenol, stilbene type epoxy resin, hydroquinone type epoxy resin, phthalic acid, dimer acid and epichlorohydrin Type epoxy resin, diaminodiphenylmethane, isocyanuric acid and other polyamines obtained by reaction of epichlorohydrin, glycidylamine type epoxy resin, epoxidized product of dicyclopentadiene and phenols co-condensation resin, epoxy resin having naphthalene ring, phenols And / or aralkyls such as phenol / aralkyl resins and naphthol / aralkyl resins synthesized from naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Epoxy product of phenol resin, trimethylolpropane type epoxy resin, terpene modified epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, alicyclic epoxy resin, epoxy containing sulfur atom Resin etc. are mentioned, These 1 type may be used independently or may be used in combination of 2 or more type.

  Among them, from the viewpoint of compatibility between fluidity and low warpage, biphenyl type epoxy resin that is diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted biphenol and bisphenol F-type epoxy resin that is diglycidyl ether of bisphenol F It is preferable to contain 1 type (s) or 2 or more types.

  Examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (III).

（ここで、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０又は１〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and all may be the same or different. N is 0 or 1 to 1. Indicates an integer of 3.)

The biphenyl type epoxy resin represented by the general formula (III) can be obtained by reacting a biphenol compound with epichlorohydrin by a known method. As R < ¹ > -R < ⁸ > in general formula (III), it is C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, t-butyl group etc., for example. C1-C10 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned, Especially, a hydrogen atom or a methyl group is preferable. Examples of such an epoxy resin include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5 ′. -Epoxy resin mainly composed of tetramethylbiphenyl, epoxy resin obtained by reacting epichlorohydrin with 4,4'-biphenol or 4,4 '-(3,3', 5,5'-tetramethyl) biphenol Etc. Among these, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable. Such an epoxy resin is commercially available as a trade name YX-4000 manufactured by Japan Epoxy Resin Co., Ltd. The blending amount of the biphenyl type epoxy resin is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 50% by weight or more based on the total amount of the epoxy resin (C) in order to exhibit its performance. preferable.

  Examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (IV).

（ここで、Ｒ^１〜Ｒ^８は水素原子及び炭素数１〜１０の置換又は非置換の一価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。ｎは０又は１〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and all may be the same or different. N is 0 or 1 to 1. Indicates an integer of 3.)

The bisphenol F type epoxy resin represented by the general formula (IV) is obtained by reacting a bisphenol compound with epichlorohydrin by a known method. As R < ¹ > -R < ⁸ > in general formula (IV), it is C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, t-butyl group etc., for example. C1-C10 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned, Especially, a hydrogen atom or a methyl group is preferable. Examples of such an epoxy resin include an epoxy resin mainly composed of 4,4′-methylenebis (2,6-dimethylphenol) diglycidyl ether, and 4,4′-methylenebis (2,3,6-trimethyl). Phenolic) diglycidyl ether as the main component, 4,4′-methylenebisphenol diglycidyl ether as the main component, 4,4′-methylene bis (2,6- An epoxy resin mainly composed of diglycidyl ether of (dimethylphenol) is preferred. Such an epoxy resin is commercially available as a trade name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. The blending amount of the bisphenol F-type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more based on the total amount of the (C) epoxy resin in order to exhibit its performance. Further preferred.

  These biphenyl type epoxy resins and bisphenol F type epoxy resins may be used alone or in combination of two or more, but the blending amount when using two or more in combination is as follows: In order to exhibit the performance, (C) the total amount of the epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more.

  The (D) curing agent used in the present invention is generally used for an epoxy resin molding material for sealing and is not particularly limited. For example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F Acid catalysts for phenols such as phenylphenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde Phenol synthesized from novolak-type phenolic resin, phenols and / or naphthols, and dimethoxyparaxylene or bis (methoxymethyl) biphenyl obtained by condensation or cocondensation under Aralkyl resins such as aralkyl resins, naphthol / aralkyl resins, paraxylylene and / or metaxylylene modified phenol resins, melamine modified phenol resins, terpene modified phenol resins, dicyclopentadiene modified phenol resins, cyclopentadiene modified phenol resins, polycyclic aromatic rings Examples thereof include modified phenolic resin fats, and these may be used alone or in combination of two or more.

  Among these, from the viewpoint of flame retardancy, a phenol / aralkyl resin represented by the following general formula (V) and a naphthol / aralkyl resin represented by the following general formula (VI) are preferable.

（ここで、Ｘは芳香環を含む基を示し、ｎは０又は１〜１０の整数を示す。）

(Here, X represents a group containing an aromatic ring, and n represents 0 or an integer of 1 to 10.)

（ここで、Ｘは芳香環を含む基を示し、ｎは０又は１〜１０の整数を示す。）

(Here, X represents a group containing an aromatic ring, and n represents 0 or an integer of 1 to 10.)

  X in the general formulas (V) to (VI) represents an aromatic ring-containing group, for example, an arylene group such as a phenylene group, a biphenylene group or a naphthylene group, an alkyl group-substituted arylene group such as a tolylene group or a xylylene group, or an alkoxyl group. Examples thereof include aralkyl groups such as group-substituted arylene groups, benzyl groups, and phenethyl groups, and aralkyl group-substituted arylene groups. Among them, substituted or unsubstituted phenylene groups and biphenylene groups are preferable from the viewpoint of flame retardancy, and biphenylene groups Is more preferable. N in the general formulas (V) to (VI) represents 0 or an integer of 1 to 10, and is preferably 6 or less on average.

  As the phenol / aralkyl resin represented by the general formula (V), a phenol resin in which X is a substituted or unsubstituted phenylene group or biphenylene group is preferable. For example, the phenol / aralkyl resin represented by the following general formulas (XI) and (XII) A phenol resin etc. are mentioned.

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

  As the phenol / aralkyl resin represented by the general formula (XI), a trade name XLC manufactured by Mitsui Chemicals, Inc. may be mentioned as a commercially available product, and as a phenol / aralkyl resin represented by the general formula (XII), A trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd. may be mentioned.

  The naphthol / aralkyl resin represented by the general formula (VI) is preferably a naphthol / aralkyl resin in which X is a substituted or unsubstituted phenylene group or biphenylene group. For example, in the following general formulas (XIII) to (XVI): And naphthol / aralkyl resins shown.

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

  Among the naphthol / aralkyl resins represented by the general formulas (XIII) to (XVI), naphthol / aralkyl resins represented by the general formulas (XIII) and (XV) are used from the viewpoint of compatibility between moldability and flame retardancy. preferable. As a naphthol / aralkyl resin represented by the general formula (XIII), a commercial product, trade name SN-475 manufactured by Nippon Steel Chemical Co., Ltd. may be mentioned. As the naphthol / aralkyl resin represented by the general formula (XV), As a commercial item, Nippon Steel Chemical Co., Ltd. product name SN-170 is mentioned.

  The phenol / aralkyl resin represented by the general formula (V) and the naphthol / aralkyl resin represented by the general formula (VI) are preferably partially mixed with acenaphthylene from the viewpoint of flame retardancy. . Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Further, it can be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins. Examples of a method for obtaining a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, and anionic polymerization. In the polymerization, a conventionally known catalyst can be used, but it can also be carried out only by heat without using a catalyst. At this time, the polymerization temperature is preferably 80 to 160 ° C, more preferably 90 to 150 ° C. 60-150 degreeC is preferable and, as for the softening point of the polymer of the polymer of acenaphthylene obtained or acenaphthylene and another aromatic olefin, 70-130 degreeC is more preferable. When the temperature is lower than 60 ° C., the moldability tends to decrease due to oozing during molding, and when the temperature is higher than 150 ° C., the compatibility with the resin tends to decrease. Examples of other aromatic olefins to be copolymerized with acenaphthylene include styrene, α-methylstyrene, indene, benzothiophene, benzofuran, vinylnaphthalene, vinylbiphenyl, and alkyl-substituted products thereof. In addition to the above-mentioned aromatic olefins, aliphatic olefins can be used in combination as long as the effects of the present invention are not hindered. Examples of the aliphatic olefin include (meth) acrylic acid and esters thereof, maleic anhydride, itaconic anhydride, fumaric acid and esters thereof. The amount of these aliphatic olefins used is preferably 20% by mass or less, more preferably 9% by mass or less, based on the total amount of the polymerization monomers.

  (D) As a method of premixing part or all of the curing agent with acenaphthylene, (D) a method of finely pulverizing the curing agent and acenaphthylene, respectively, and mixing them with a mixer or the like in a solid state, dissolving both components A method of removing the solvent after uniformly dissolving in the solvent, (D) a method of melting and mixing both at a temperature equal to or higher than the softening point of the curing agent and / or acenaphthylene, etc. Therefore, a melt mixing method with less contamination of impurities is preferable. The melt mixing is not limited as long as the temperature is equal to or higher than the softening point of (D) the curing agent and / or acenaphthylene, but is preferably 100 to 250 ° C, more preferably 120 to 200 ° C. Moreover, although melt mixing will not have a restriction | limiting in mixing time if both are mixed uniformly, 1 to 20 hours are preferable and 2 to 15 hours are more preferable. When (D) the curing agent and acenaphthylene are premixed, the acenaphthylene may be polymerized or reacted with the (D) curing agent during mixing.

  In the epoxy resin molding material for sealing of the present invention, it is preferable that 50% by mass or more of the above-mentioned preliminary mixture (acenaphthylene-modified curing agent) is contained in the (D) curing agent from the viewpoint of improving flame retardancy. 5-40 mass% is preferable and, as for the quantity of the polymer of the aromatic olefin containing acenaphthylene and / or acenaphthylene contained in an acenaphthylene modified hardening | curing agent, 8-25 mass% is more preferable. When the amount is less than 5% by mass, the effect of improving the flame retardancy tends to be lowered, and when the amount is more than 40% by mass, the moldability tends to be lowered. The content of the acenaphthylene structure contained in the epoxy resin molding material for sealing of the present invention is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass from the viewpoints of flame retardancy and moldability. preferable. If the amount is less than 0.1% by mass, the effect of improving the flame retardancy tends to be lowered, and if it is more than 5% by mass, the moldability tends to be lowered.

  (C) The equivalent ratio of epoxy resin to (D) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (number of hydroxyl groups in the curing agent / number of epoxy groups in the epoxy resin) is: Although there is no restriction | limiting in particular, In order to suppress each unreacted part small, it is preferable to set to the range of 0.5-2, and 0.6-1.3 are more preferable. In order to obtain an epoxy resin molding material for sealing having excellent moldability, it is more preferably set in the range of 0.8 to 1.2.

  It is preferable that (E) an inorganic filler is further blended in the sealing epoxy resin molding material of the present invention. (E) The inorganic filler is blended into the molding material for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate , Calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc., or beads spheroidized from these, A glass fiber etc. are mentioned, These may be used independently or may be used in combination of 2 or more type. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoint of fluidity and mold wear during molding.

  (E) The blending amount of the inorganic filler is preferably 70 to 95% by mass with respect to the sealing epoxy resin molding material from the viewpoint of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction and strength improvement. 85-95 mass% is more preferable from a viewpoint of hygroscopicity and a linear expansion coefficient reduction, and 90-94 mass% is still more preferable. If it is less than 70% by mass, the effect of improving flame retardancy and reflow resistance tends to be reduced, and if it exceeds 95% by mass, the fluidity tends to be insufficient.

  In the sealing epoxy resin molding material of the present invention, an ion trapping agent can be further blended as necessary from the viewpoint of improving the moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC. The ion trapping agent is not particularly limited, and conventionally known ones can be used. Examples thereof include hydrotalcites and hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. These may be used alone or in combination of two or more. Of these, hydrotalcite represented by the following composition formula (XVII) is preferable.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XVII)
(0 <X ≦ 0.5, m is a positive number)
The compounding amount of the ion trapping agent is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but from the viewpoint of fluidity and bending strength, 0.1 to 30 mass with respect to (C) epoxy resin. % Is preferable, 0.5 to 10% by mass is more preferable, and 1 to 5% by mass is more preferable.

  In addition, the epoxy resin molding material for sealing of the present invention includes an epoxy silane, a mercapto silane, an amino silane, an alkyl silane, a ureido silane, and a vinyl silane as necessary in order to improve the adhesion between the resin component and the inorganic filler. Various known coupling agents such as various silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added. Examples of these include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (Aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxy Silane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ Silane coupling agents such as mercaptopropylmethyldimethoxysilane, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxy Acetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl Phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate And titanate-based coupling agents, and the like. These may be used alone or in combination of two or more.

  The blending amount of the coupling agent is preferably 0.05 to 5% by mass and more preferably 0.1 to 2.5% by mass with respect to (E) the inorganic filler. If it is less than 0.05% by mass, the effect of improving the adhesiveness with various package components tends to decrease, and if it exceeds 5% by mass, molding defects such as voids tend to occur.

  A flame retardant can be blended with the epoxy resin molding material for sealing of the present invention as necessary. Conventionally known brominated epoxy resins and antimony trioxide can be used as the flame retardant, and conventionally known non-halogen and non-antimony flame retardants can be used. For example, red phosphorus coated with a thermosetting resin such as red phosphorus, phenol resin, phosphorous ester, phosphorus compound such as triphenylphosphine oxide, melamine, melamine derivative, melamine modified phenolic resin, compound having triazine ring, Nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, metal complex compounds such as dicyclopentadienyl iron, zinc oxide, zinc stannate, zinc borate, and zinc molybdate Zinc compounds, metal oxides such as iron oxide and molybdenum oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, composite metal hydroxides represented by the following composition formula (XVIII), and the like can be given.

p (M ¹ aOb) · q (M ² cOd) · r (M ³ cOd) · mH ₂ O (XVIII)
(Here, M ¹ , M ² and M ³ represent different metal elements, a, b, c, d, p, q and m are positive numbers, and r is 0 or a positive number.)

M ¹ , M ² and M ^{3 in the} composition formula (XVIII) are not particularly limited as long as they are different metal elements, but from the viewpoint of flame retardancy, M ¹ is a metal element of the third period, group IIA Preferably selected from metal elements belonging to the alkaline earth metal elements, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA, and M ² is selected from transition metal elements of groups IIIB to IIB, More preferably, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is selected from iron, cobalt, nickel, copper and zinc. From the viewpoint of fluidity, it is preferable that M ¹ is magnesium, M ² is zinc or nickel, and r = 0. The molar ratio of p, q and r is not particularly limited, but preferably r = 0 and p / q is 1/99 to 1/1. In addition, the classification of metal elements is a long-period type periodic rate table in which the typical element is the A subgroup and the transition element is the B subgroup (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987) (Reduced plate 30th printing). The above flame retardants may be used alone or in combination of two or more.

  Furthermore, the epoxy resin molding material for sealing of the present invention includes, as other additives, higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylene, release agents such as polyethylene oxide, carbon black, etc. If necessary, a color relieving agent, a silicone oil, a stress relaxation agent such as rubber powder, and the like can be blended.

  The epoxy resin molding material for sealing of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. However, as a general method, a raw material having a predetermined blending amount is mixed with a mixer or the like. A method of cooling and pulverizing after mixing sufficiently, melt-kneading with a mixing roll, an extruder or the like can be mentioned. It is easy to use if it is tableted with dimensions and mass that match the molding conditions.

  As an electronic component device provided with an element sealed with an epoxy resin molding material for sealing obtained in the present invention, a semiconductor chip is mounted on a support member such as a lead frame, a wired tape carrier, a wiring board, glass, or a silicon wafer. An electronic component device equipped with active elements such as transistors, diodes and thyristors, and passive elements such as capacitors, resistors and coils, and encapsulated with the epoxy resin molding material for sealing of the present invention Etc. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, a terminal portion of a device such as a bonding pad and a lead portion are connected by wire bonding or a bump, and then the sealing epoxy resin of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Out Package), which is sealed by molding using a molding material. General resin-sealed type I such as lead package, TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc. A semiconductor chip connected to a tape carrier with a bump is sealed with a tape carrier package (TCP) sealed with an epoxy resin molding material of the present invention, wiring formed on a wiring board or glass, wire bonding, flip chip bonding COB (Chip) in which active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc., which are connected by solder, etc., are sealed with the sealing epoxy resin molding material of the present invention On Board) After mounting the semiconductor chip on the interposer board on which the module, hybrid IC, multi-chip module, and motherboard connection terminals are formed, and connecting the wiring formed on the semiconductor chip and the interposer board by bump or wire bonding, One-side sealed packages such as BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package) in which the semiconductor chip mounting side is sealed with the epoxy resin molding material for sealing of the present invention can be mentioned. Among these, the single-side sealed package provided with the element sealed with the sealing epoxy resin molding material obtained in the present invention has a feature that the amount of warpage is small. Furthermore, the epoxy resin molding material for sealing of the present invention can also be used effectively for printed circuit boards.

  As a method for sealing an element using the epoxy resin molding material for sealing of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.

  EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.

Examples 1-8, Comparative Examples 1-8
The following components are blended in parts by mass shown in Tables 1 and 2, respectively, and roll kneading is carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. For sealing Examples 1 to 8 and Comparative Examples 1 to 8 An epoxy resin molding material was produced.

  As an epoxy resin, an epoxy equivalent of 187 and a melting point of 109 ° C. biphenyl type epoxy resin (Epoxy Resin, trade name Epicoat YX-4000 manufactured by Japan Epoxy Resin Co., Ltd.), an epoxy equivalent of 188 and a melting point of 75 ° C. bisphenol F type epoxy resin (epoxy) Resin 2, Nippon Steel Chemical Co., Ltd. trade name YSLV-80XY) was used.

  A phenol aralkyl resin (trade name: Millex XLC-3L, manufactured by Mitsui Chemicals, Inc.) having a hydroxyl group equivalent of 176 and a softening point of 70 ° C. was used as a curing agent.

  An addition reaction product of triphenylphosphine and 1,4-benzoquinone was used as a curing accelerator.

As a silicon-containing polymer, polysiloxane having an epoxy equivalent of 600 to 1780 (silicon-containing polymer 1-a to 1-e, developed by Toray Dow Corning Silicone Co., Ltd.), epoxy group-containing silicone powder (silicon-containing polymer 2) , Toray Dow Corning Silicone Co., Ltd. trade name DC4-7051) Silicone oil (silicon-containing polymer 3, Toray Dow Corning Silicone Co., Ltd. trade name, epoxy equivalent 2900, viscosity 2850 mm ² / s (25 ° C.) BY16-876) was used.

Spherical fused silica having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² / g as an inorganic filler; γ-glycidoxypropyltrimethoxysilane (trade name A-187 manufactured by Nihon Unicar Co., Ltd.) as a coupling agent used.

  As other additives, carnauba wax (manufactured by Clariant) and carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation) were used.

  The produced epoxy resin molding materials for sealing of Examples and Comparative Examples were evaluated by the following tests. The results are shown in Tables 3 and 4.

The epoxy resin molding material for sealing was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 180 ° C. for 5 hours.
(1) Spiral flow (fluidity index)
Using a spiral flow measurement mold according to EMMI-1-66, the sealing epoxy resin molding material was molded under the above conditions, and the flow distance (cm) was determined.
(2) Disc flow (liquidity index)
Weighing using a flat plate mold for measuring disk flow having an upper mold of 200 mm (W) × 200 mm (D) × 25 mm (H) and a lower mold of 200 mm (W) × 200 mm (D) × 15 mm (H) 5 g of the sample (sealing epoxy resin molding material) placed on the center of the lower mold heated to 180 ° C. After 5 seconds, the upper mold heated to 180 ° C. is closed, and the load is 78 N and the curing time is 90 seconds. The major axis (mm) and the minor axis (mm) of the molded product were measured with a caliper, and the average value (mm) was defined as a disc flow.
(3) Hardness during heating The sealing epoxy resin molding material was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and was measured immediately after molding using a Shore D type hardness meter.
(4) Warpage amount 40 mm by using an epoxy resin molding material for sealing on a glass substrate epoxy resin substrate (trade name MCL-E-679, manufactured by Hitachi Chemical Co., Ltd.) having a substrate size of 60 mm × 90 mm × 0.4 mm. One side sealing in a range of × 70 mm × 0.6 mm, the obtained molded product is subjected to post-curing and cooled to room temperature (25 ° C.), and the warping amount <warping amount (initial)> and after 260 ° C. IR reflow The amount of warpage <warpage amount (after heating)> after cooling to room temperature (25 ° C.) was evaluated. The amount of warpage is measured by measuring the displacement in the height direction using a variable temperature three-dimensional shape measuring instrument (Tetec Co., Ltd.) in the long side direction of the sealing range, and changing the difference between the maximum and minimum values. Evaluated as a quantity.

The epoxy equivalent was measured as follows. Calibration curve: Samples (several types) with known epoxy (%) were measured with a Fourier transform type near-infrared spectroscopic analyzer, respectively, and the absorbance in the 6300 to 6000 ⁻¹ region was determined as the absorption of the epoxy group, respectively. A calibration curve is prepared and measured by multiplication: A blank test is performed with a Fourier transform type near-infrared spectroscopic analyzer without filling the sample. Next, the sample is filled and the absorbance in the 6300 to 6000 ⁻¹ region is determined. The epoxy (%) is quantified from the obtained absorbance. The epoxy equivalent was determined by the formula (epoxy equivalent = 4300 / epoxy (%)).

(A) Comparative Examples 1 and 2 not containing a silicon-containing polymer in the present invention, Comparative Examples 3 and 5 using an epoxy group-containing silicone powder, Comparative Example 4 using a silicone oil having a viscosity of 2850 mm ² / s (25 ° C.) 6, the initial warpage amount and the warpage change amount are large. In Comparative Examples 7 and 8 using polysiloxane and having an epoxy equivalent of 1780, the initial warpage amount is small but the warpage change amount is large. Similarly, all of Examples 1 to 8 in which the epoxy equivalent of polysiloxane is 600 to 1650 are excellent in fluidity shown by spiral flow and disk flow, and further, the initial amount of warpage and the amount of change in warpage are small. In particular, in Examples 2 to 4 and 6 to 8 having an epoxy equivalent of 1200 to 1650, not only the fluidity and the initial amount of warpage and the amount of change in warpage are excellent, but also the balance of curability indicated by the hardness upon heating is excellent.

Claims (10)

(A) a silicon-containing polymer having the following bonds (a) and (b), a terminal having a functional group selected from R ¹ , a hydroxyl group and an alkoxy group, and having an epoxy equivalent of 500 to 1700, (B An epoxy resin molding material for sealing containing an addition reaction product of a third phosphine compound and a quinone compound, (C) an epoxy resin, and (D) a curing agent.

(Here, R ¹ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ¹ in the silicon-containing polymer may be the same or different. X is Indicates a monovalent organic group containing an epoxy group.) (A) The epoxy resin molding material for sealing according to claim 1, wherein the silicon-containing polymer further has a bond (c).

(Here, R ¹ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ¹ in the silicon-containing polymer may be all the same or different.)   (A) The epoxy resin molding material for sealing of Claim 1 or Claim 2 whose softening point of a silicon containing polymer is 40 degreeC or more and 120 degrees C or less. (A) The epoxy resin molding material for sealing according to any one of claims 1 to 3, wherein R ¹ in the silicon-containing polymer is at least ^one of a substituted or unsubstituted phenyl group and a methyl group. (A) The ratio of a substituted or unsubstituted phenyl group having 1 to 12 carbon atoms in all R ¹ in the silicon-containing polymer is 60 mol% to 100 mol%. Epoxy resin molding material for fastening. The component (B) is an addition reaction product of a third phosphine compound represented by the following formula (I) and a quinone compound represented by the following formula (II): The epoxy resin for sealing according to any one of claims 1 to 5 Molding material.

(Wherein R ^{1 to} R ³ in formula (I) represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, In the formula (II), R ^{4 to} R ⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be all the same or different, and R ⁴ and R ⁵ may be different from each other. It may be bonded to form a ring structure.)   The epoxy resin molding material for sealing according to claim 6, wherein the component (B) contains an addition reaction product of tributylphosphine and 1,4-benzoquinone.   The epoxy resin molding material for sealing according to claim 6, wherein the component (B) contains an addition reaction product of triphenylphosphine and 1,4-benzoquinone.   Furthermore, the epoxy resin molding material for sealing in any one of Claims 1-8 which contains (E) inorganic filler 70 mass%-95 mass% with respect to the epoxy resin molding material for sealing.   The electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing in any one of Claims 1-9.