JP2003171441A - Epoxy resin composition for sealing use and electronic component device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing use containing neither halogen nor antimony and good in flame retardancy while retaining its moldability, reflow resistance, moisture resistance and reliability including property retention even after left to stand at high temperatures. <P>SOLUTION: This epoxy resin composition essentially comprises an epoxy resin, a curing agent, a curing promoter, an inorganic filler and a compound metal hydroxide; wherein the curing promoter comprises an adduct or mixture of a phosphine compound of the general formula (I) (wherein, Rs are the same or different and selected from H, 1-12C hydrocarbon group and 1-12C alkoxy group) and a quinone compound, or an adduct or mixture of a phosphine compound with at least one alkyl group bound to the phosphorus atom and a quinone compound. The other objective electronic component device mounted with element(s) sealed with the epoxy resin composition is provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition, particularly an epoxy resin composition for encapsulation which is non-halogen, non-antimony and flame retardant and is suitable for encapsulation of VLSI, and an encapsulation composition. The present invention relates to an electronic component device having a stopped element.

[0002]

2. Description of the Related Art Conventionally, resin encapsulation has been the mainstream in the field of element encapsulation of electronic component devices such as transistors and ICs from the viewpoints of productivity and cost. Resin compositions are widely used. The reason for this is that the epoxy resin is well balanced in various characteristics such as electric characteristics, moisture resistance, heat resistance, mechanical characteristics, and adhesiveness with insert products. The flame retardancy of these epoxy resin compositions for encapsulation has been mainly carried out by a combination of a brominated resin such as diglycidyl ether of tetrabromobisphenol A and antimony oxide. In recent years, the dioxin problem originated from the viewpoint of environmental protection, and halogenated resins such as decabrom and antimony compounds are being regulated. Non-halogenated (non-brominated) and non-antimony compounds are also used for epoxy resin compositions for encapsulation. There is a demand for conversion. Further, it is known that the bromine compound has an adverse effect on the high temperature storage property of the plastic encapsulation IC, and from this viewpoint, it is desired to reduce the amount of the brominating resin.

Therefore, as a method for achieving flame retardancy without using a brominated resin or antimony oxide, a method using red phosphorus (JP-A-9-227765) or a method using a phosphoric acid ester compound (JP-A-HEI) No. 9-235449), a method using a phosphazene compound (JP-A-8-2).
25714), a method using a metal hydroxide (JP-A-9-241483), a method using a metal hydroxide and a metal oxide in combination (JP-A-9-100337),
A method using a cyclopentadienyl compound such as ferrocene (JP-A-11-269349), a method using an organometallic compound such as copper acetylacetonate (Hiroshi Kato,
Attempts have been made to use functional materials, halogens such as 11 (6), 34 (1991)) and flame retardants other than antimony, and methods for increasing the proportion of filler (Japanese Patent Laid-Open No. 7-82343).

[0004]

However, when red phosphorus is used in the epoxy resin composition for encapsulation, there is a problem of deterioration of moisture resistance, and when a phosphoric acid ester compound or a phosphazene compound is used, moldability due to plasticization is caused. Of metal hydroxide and metal oxide, the problem of release property and fluidity decrease when metal hydroxide or metal oxide is used, and the problem of fluidity decrease when the proportion of filler is increased. There are each. When an organometallic compound such as acetylacetonato copper is used,
There is a problem that the curing reaction is hindered and the moldability is lowered. As described above, none of these halogen-free and antimony-based flame retardants has been able to achieve the same moldability and reliability as the encapsulating epoxy resin composition in which the brominated resin and antimony oxide are used in combination. The present invention has been made in view of such circumstances, and is particularly halogen-free and antimony required from the viewpoint of environmental friendliness, and is suitable for VLSI sealing such as moldability, reflow resistance, moisture resistance, and high temperature storage characteristics. It is an object of the present invention to provide an epoxy resin composition for encapsulation which has good flame retardancy without lowering reliability, and an electronic component device provided with an element encapsulated by this resin composition.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to solve the above-mentioned problems, as a result, an epoxy resin for encapsulation containing a specific phosphorus-based curing accelerator and a composite metal hydroxide. It has been found that the composition can achieve the above-mentioned object, and the present invention has been completed.

That is, the epoxy resin composition for encapsulation of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler and (E) a composite metal hydroxide. An epoxy resin composition for encapsulation, wherein the curing accelerator (C) includes an adduct of a phosphine compound represented by the following general formula (I) and a quinone compound. .

[Chemical 5] (In the general formula (I), R is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, all of which are the same. But it may be different.)

Further, the epoxy resin composition for encapsulation of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler and (E) a composite metal hydroxide. Is an essential component, and (C) a curing accelerator is the above general formula (I).
The gist of the invention is to include a phosphine compound represented by

Further, the encapsulating epoxy resin composition of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler and (E) a composite metal hydroxide. An epoxy resin composition for encapsulation containing a product as an essential component,
(C) The curing accelerator contains an adduct of a phosphine compound in which at least one alkyl group is bound to a phosphorus atom and a quinone compound, or (C) At least one alkyl group is bound to a phosphorus atom as the curing accelerator. The gist of the present invention is to include the phosphine compound described above and further include a quinone compound. Particularly, as the phosphine compound in which at least one alkyl group is bonded to the phosphorus atom, the phosphine compound represented by the following general formula (II) is preferable.

[Chemical 6] (Here, R ¹ in the general formula (II) represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, R ² and R ³ is a hydrogen atom or a substituted or unsubstituted C 1-12 Represents a hydrocarbon group, and they may all be the same or different.)

In particular, in the encapsulating epoxy resin composition of the present invention, the (E) composite metal hydroxide is preferably a compound represented by the following composition formula (III).

Embedded image m (M ¹ _a O _b ) .n (M ² _c O _d ) .h (H ₂ O) (III) (wherein M ¹ and M ² represent different metal elements,
a, b, c, d, m, n and h represent positive numbers. )

Further, in order to prevent M ¹ and M ² in the composition formula (III) from being the same, M ¹ is a metal element of the third period, an alkaline earth metal element of the IIA group, IVB group, IIB group and VIII group. , IB
Selected from the group consisting of metal elements belonging to Group IIIA, Group IIIA and Group IVA,
It is preferred that M ² is selected from the group IIIB-IIB transition metal elements. Here, the M ¹ is magnesium, calcium,
Preferably, it is selected from aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and the M ² is selected from iron, cobalt, nickel, copper and zinc. M ¹ is magnesium and M ² is zinc or nickel,
Molar ratio m / n of M ¹ _a O _b and M ² _c O _{d in} the composition formula (III)
Is more preferably 99/1 to 50/50.

The (A) epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a sulfur atom-containing epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin and a triphenylmethane type epoxy resin. And (B) the curing agent contains at least one of biphenyl type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin and novolac type phenol resin. It is preferable.

Furthermore, the gist of the present invention is an electronic component device provided with an element sealed with any of the above sealing epoxy resin compositions.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION First, the essential components of the epoxy resin composition for sealing of the present invention will be described. The (A) epoxy resin used in the present invention is generally used in epoxy resin compositions for sealing and is not particularly limited.
For example, phenols such as phenol novolac type epoxy resin, ortho-cresol novolac type epoxy resin, epoxy resin having a triphenylmethane skeleton, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol A, and / or α and the like. -Epoxy novolak resin obtained by condensing or co-condensing naphthols such as naphthol, β-naphthol, and dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde under an acidic catalyst. Novolac type epoxy resin; diglycidyl ether of bisphenol A, bisphenol F, bisphenol S (bisphenol type epoxy resin ); Diglycidyl ether (biphenyl type epoxy resin) such as alkyl-substituted or unsubstituted biphenol; Stilbene type epoxy resin; Hydroquinone type epoxy resin; Glycidyl ester obtained by reaction of polybasic acid such as phthalic acid and dimer acid with epichlorohydrin Type epoxy resin; diaminodiphenylmethane,
Glycidylamine type epoxy resin obtained by reacting polyamine such as isocyanuric acid with epichlorohydrin;
Epoxidized products of co-condensation resin of dicyclopentadiene and phenols (dicyclopentadiene type epoxy resin);
Epoxy resin having naphthalene ring (naphthalene type epoxy resin); epoxidized aralkyl type phenol resin such as phenol / aralkyl resin and naphthol / aralkyl resin; trimethylolpropane type epoxy resin;
A terpene-modified epoxy resin; a linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; an alicyclic epoxy resin; a sulfur atom-containing epoxy resin; and a triphenylmethane type epoxy resin. These may be used alone or in combination of two or more.

Of these, a biphenyl type epoxy resin, a stilbene type epoxy resin and a sulfur atom-containing epoxy resin are preferable from the viewpoint of reflow resistance, a novolac type epoxy resin is preferable from the viewpoint of curability, and a low hygroscopicity is preferable. Is preferably a dicyclopentadiene type epoxy resin, and from the viewpoint of heat resistance and low warpage, a naphthalene type epoxy resin and a triphenylmethane type epoxy resin are preferable. From the biphenyl type epoxy resin, the stilbene type epoxy resin, the sulfur atom-containing epoxy resin, the novolac type epoxy resin, the dicyclopentadiene type epoxy resin, the naphthalene type epoxy resin and the triphenylmethane type epoxy resin, which are preferable seven types of epoxy resins, Any one kind may be used alone or two or more kinds may be used in combination, but the compounding amount thereof is preferably 50% by weight or more in total with respect to the total amount of the epoxy resin, 60
It is more preferably at least 80% by weight, still more preferably at least 80% by weight.

The biphenyl type epoxy resin includes, for example, an epoxy resin represented by the following general formula (IV), and the stilbene type epoxy resin includes, for example, an epoxy resin represented by the following general formula (V), and sulfur. As the atom-containing epoxy resin, for example, the following general formula (V
Examples thereof include epoxy resins represented by I).

[Chemical 8] (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 to 3 Indicates an integer.)

[Chemical 9] (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 to 3 Indicates an integer.)

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

The biphenyl type epoxy resin represented by the above general formula (IV) is, for example, 4,4'-bis (2,3-epoxypropoxy) biphenyl or 4,4 '.
′ -Bis (2,3-epoxypropoxy) -3,3 ′,
Epoxy resin containing 5,5'-tetramethylbiphenyl as a main component, epichlorohydrin and 4,4'-biphenol or 4,4 '-(3,3', 5,5'-tetramethyl) biphenol are reacted. The epoxy resin etc. which are obtained are mentioned. Among them, an epoxy resin containing 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl as a main component is preferable.

The stilbene type epoxy resin represented by the above general formula (V) can be obtained by reacting stilbene phenols as raw materials with epichlorohydrin in the presence of a basic substance. Examples of the stilbene-based phenols as the raw material include 3-t-butyl-4,4 '.
-Dihydroxy-3 ', 5,5'-trimethylstilbene, 3-t-butyl-4,4'-dihydroxy-3',
5 ', 6-trimethylstilbene, 4,4'-dihydroxy-3,3', 5,5'-tetramethylstilbene,
4,4'-dihydroxy-3,3'-di-t-butyl-
5,5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene and the like can be mentioned, among which 3-t-butyl-4,
4'-dihydroxy-3 ', 5,5'-trimethylstilbene, and 4,4'-dihydroxy-3,3', 5
5'-Tetramethylstilbene is preferred. These stilbene type phenols may be used alone or in combination of two or more kinds.

Among the sulfur atom-containing epoxy resins represented by the above general formula (VI), R ^{1 to} R ⁸ are hydrogen atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted carbon atom. An epoxy resin selected from the alkoxy groups of the formulas 1 to 10 is preferable, and an epoxy resin in which R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms and R ¹ , R ³ , R ⁶ and R ⁸ are alkyl groups is preferable. More preferred is an epoxy resin in which R ² , R ⁴ , R ^5, and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are methyl groups, and R ³ and R ⁶ are t-butyl groups. As such a compound, YSLV-120TE (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) and the like are commercially available.

These three kinds of epoxy resins may be used alone or in combination of two or more kinds, but the mixing amount thereof is based on the total amount of the epoxy resin in order to exert its performance. The total amount is preferably 20% by weight or more, more preferably 30% by weight or more, and 50% by weight
It is more preferable to set the above.

Examples of the novolac type epoxy resin include epoxy resins represented by the following general formula (VII).

[Chemical 11] (Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 10.) Represented by the above general formula (VII). The novolac type epoxy resin is easily obtained by reacting novolac type phenol resin with epichlorohydrin. Among them, R in the general formula (VII) is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or another alkyl group having 1 to 10 carbon atoms, a methoxy group, an ethoxy group, a propoxy group. 1 to 1 carbon atoms such as butoxy group
An alkoxyl group of 0 is preferable, and a hydrogen atom or a methyl group is more preferable. n is preferably an integer of 0 to 3. Among the novolac type epoxy resins represented by the general formula (VII), orthocresol novolac type epoxy resins are preferable. When using novolac type epoxy resin,
The blending amount thereof is preferably 20% by weight or more based on the total amount of the epoxy resin in order to exert its performance.
It is more preferably 0% by weight or more.

Examples of the dicyclopentadiene type epoxy resin include epoxy resins represented by the following general formula (VIII).

[Chemical 12] (Here, R ¹ and R ² are independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is Represents an integer of 0 to 6.) Examples of R ¹ in the above formula (VIII) include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t-butyl group, Vinyl group,
Alkenyl groups such as allyl groups and butenyl groups, halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups, and other substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms. However, an alkyl group such as a methyl group and an ethyl group and a hydrogen atom are preferable, and a methyl group and a hydrogen atom are more preferable. Examples of R ² include hydrogen atom, methyl group, ethyl group, propyl group, butyl group,
Alkyl group such as isopropyl group, t-butyl group, alkenyl group such as vinyl group, allyl group, butenyl group, halogenated alkyl group, amino group-substituted alkyl group, mercapto group-substituted alkyl group and the like having 1 to 10 carbon atoms Or, it may be an unsubstituted monovalent hydrocarbon group, and among them, a hydrogen atom is preferable. When a dicyclopentadiene type epoxy resin is used, its content is preferably 20% by weight or more, and more preferably 30% by weight or more based on the total amount of the epoxy resin in order to exert its performance.

The naphthalene type epoxy resin includes, for example, an epoxy resin represented by the following general formula (IX), and the triphenylmethane type epoxy resin includes, for example, an epoxy resin represented by the following general formula (X). .

[Chemical 13] (Here, R ^{1 to} R ³ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and all may be the same or different. P is 1 or 0. so,
h and m are each an integer of 0 to 11, and (h + m)
Is an integer from 1 to 11 and (h + p) is an integer from 1 to 12. i is an integer of 0 to 3, j is an integer of 0 to 2, and k is an integer of 0 to 4. ) The naphthalene-type epoxy resin represented by the general formula (IX) includes a random copolymer randomly containing h constituent units and m constituent units, an alternating copolymer containing them alternately, and a copolymer containing them regularly. Examples thereof include polymers and block copolymers contained in a block form, and any one of these may be used alone or in combination of two or more.

[Chemical 14] (Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10.)

These two kinds of epoxy resins may be used alone or in combination of two kinds, but the compounding amount thereof is adjusted to the total amount of the epoxy resin in order to exert its performance. It is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 50% by weight or more.

The curing agent (B) used in the present invention is generally used in epoxy resin compositions for encapsulation and is not particularly limited. For example, phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, benzaldehyde, salicylaldehyde, etc. Novolac type phenolic resin obtained by condensation or co-condensation with a compound having an aldehyde group under an acidic catalyst; phenol aralkyl synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Resins, aralkyl-type phenolic resins such as naphthol and aralkyl resins;
Dicyclopentadiene type phenolic resins such as dicyclopentadiene type phenol novolac resins and naphthol novolac resins, which are synthesized by copolymerization of phenols and / or naphthols and dicyclopentadiene; terpene modified phenolic resins; biphenyl type phenolic resins; Examples thereof include phenylmethane type phenol resin. These may be used alone or in combination of two or more.

Of these, a biphenyl type phenol resin is preferable from the viewpoint of flame retardancy, and an aralkyl type phenol resin is preferable from the viewpoint of reflow resistance and curability.
Dicyclopentadiene type phenolic resin is preferable from the viewpoint of low hygroscopicity, heat resistance, triphenylmethane type phenolic resin is preferable from the viewpoint of low expansion coefficient and low warpage, and novolac type phenolic resin is preferable from the viewpoint of curability. Preferably, it contains at least one of these phenolic resins.

Examples of the biphenyl type phenol resin include a phenol resin represented by the following general formula (XI).

[Chemical 15] R in the above formula (XI)¹~ R⁹Are all the same or different
Also, hydrogen atom, methyl group, ethyl group, propyl group,
Carbon number 1 such as butyl, isopropyl, and isobutyl groups
-10 alkyl group, methoxy group, ethoxy group, propoxy group
Alkoxy having 1 to 10 carbon atoms such as xy group and butoxy group
6 to 6 carbon atoms such as groups, phenyl groups, tolyl groups, xylyl groups, etc.
10 aryl groups, benzyl groups, phenethyl groups, etc.
Selected from aralkyl groups having 6 to 10 carbon atoms, among which
A hydrogen atom and a methyl group are preferred. n is an integer from 0 to 10
Show. Biphenyl-type pheno represented by the above general formula (XI)
Examples of the resin include R ¹~ R⁹Are all hydrogen atoms
Compounds and the like, among them, from the viewpoint of melt viscosity,
Mixture of condensate containing 50% by weight or more of condensate in which n is 1 or more
The thing is preferable. Such compounds include MEH-7
851 (Meiwa Kasei Co., Ltd. product name) entered as a commercial product
It is possible. Use biphenyl type phenolic resin
In that case, the amount of the curing agent is set in order to exert its performance.
It is preferably 30% by weight or more based on the total amount, and 5
0 wt% or more is more preferable, and 60 wt% or more is further
preferable.

The aralkyl type phenol resin includes, for example, phenol / aralkyl resin, naphthol / aralkyl resin, and the like. Phenol / aralkyl resin represented by the following general formula (XII) is preferable, and general formula (XII)
A phenol / aralkyl resin in which R is a hydrogen atom and the average value of n is 0 to 8 is more preferable. Specific examples include p-xylylene type phenol / aralkyl resin, m
Examples include xylylene type phenol and aralkyl resin. When these aralkyl type phenol resins are used, the compounding amount thereof is preferably 30% by weight or more with respect to the total amount of the curing agent in order to exert its performance,
It is more preferably at least wt%.

[Chemical 16] (Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.)

Examples of the dicyclopentadiene type phenol resin include phenol resins represented by the following general formula (XIII).

[Chemical 17] (Here, R ¹ and R ² are independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is Indicates an integer of 0 to 6.) When using a dicyclopentadiene type phenol resin,
The blending amount thereof is preferably 30% by weight or more and more preferably 50% by weight or more based on the total amount of the curing agent in order to exert its performance.

Examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (XIV).

[Chemical 18] (Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.) When using a triphenylmethane type phenol resin In order to exert its performance, its content is preferably 30% by weight or more, and 50% by weight based on the total amount of the curing agent.
The above is more preferable.

Examples of the novolac type phenolic resin include phenol novolac resin, cresol novolac resin, naphthol novolac resin, and the like, of which phenol novolac resin is preferable. When the novolac type phenol resin is used, its content is preferably 30% by weight or more, and more preferably 50% by weight or more based on the total amount of the curing agent in order to exert its performance.

The above-mentioned biphenyl type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin and novolac type phenol resin may be used alone or in combination of two or more kinds. Although they may be used together, the total amount thereof is preferably 60% by weight or more, more preferably 80% by weight or more, based on the total amount of the curing agent.

Equivalent ratio of (A) epoxy resin to (B) curing agent, ie, ratio of number of hydroxyl groups in curing agent to number of epoxy groups in epoxy resin (number of hydroxyl groups in curing agent / number of epoxy groups in epoxy resin) ) Is not particularly limited, but is preferably set in the range of 0.5 to 2 and more preferably 0.6 to 1.3 in order to suppress the unreacted content of each. In order to obtain an epoxy resin composition for encapsulation which is excellent in moldability and reflow resistance, the range is more preferably set to 0.8 to 1.2.

The encapsulating epoxy resin composition of the present invention contains (C) a curing accelerator containing an adduct of a phosphine compound represented by the following general formula (I) and a quinone compound, or (C) A phosphine compound represented by the general formula (I) as a curing accelerator, and a quinone compound, or (C) a phosphine compound having a phosphorus atom bonded to at least one alkyl group and a quinone compound as a curing accelerator. Or (C) a phosphine compound having at least one alkyl group bonded to a phosphorus atom as a curing accelerator, and a quinone compound. As the phosphine compound having at least one alkyl group bonded to the phosphorus atom, a phosphine compound represented by the following general formula (II) is preferable. In addition,
In the present invention, the adduct is not particularly limited, and examples thereof include an addition reaction product and a compound produced by the intermolecular force of two compounds having different π electron densities.

[Chemical 19]

[Chemical 20]

R in the general formula (I) is selected from a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms, all of which may be the same or different. The hydrocarbon group and the alkoxy group may be substituted. R is preferably independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. From the viewpoint of releasability, R is 1
One or more are preferably alkyl groups or alkoxyl groups, and more preferably all are alkyl groups or alkoxyl groups.

Examples of the phosphine compound represented by the general formula (I) include triphenylphosphine and diphenyl-p-.
Tolylphosphine, diphenyl (p-methoxyphenyl) phosphine, di-p-tolylphenylphosphine, bis- (p-methoxyphenyl) phenylphosphine, tri-p-tolylphosphine, tri-o-tolylphosphine, tri-m-tolyl Phosphine, tris- (p-ethylphenyl) phosphine, tris- (pn-butylphenyl) phosphine, tris- (p-methoxyphenyl)
Examples thereof include phosphine, tris- (o-methoxyphenyl) phosphine and tris- (m-methoxyphenyl) phosphine. Among them, phenyldi-p-tolylphosphine, phenylbis- (p-methoxyphenyl) phosphine, tri-p- Tolylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tris- (p
-Ethylphenyl) phosphine, tris- (pn-butylphenyl) phosphine, tris- (p-methoxyphenyl) phosphine, etc. have two or more para-positions of electron-donating substituents such as alkyl groups and alkoxy groups. Phenylbis- (p-alkylphenyl) phosphine, phenylbis- (p-alkoxyphenyl) phosphine, tris- (p-alkylphenyl) phosphine, tris- (o-alkylphenyl) introduced at the meta, ortho ortho position Phosphine, tris- (m-alkylphenyl) phosphine, tris- (p-alkoxyphenyl) phosphine and the like are preferable because they have excellent curability. The phosphine compound represented by the general formula (I) may be appropriately selected from one kind or two or more kinds, and is used in the form of an adduct with a quinone compound or together with a quinone compound, and is used as a quinone compound in terms of fluidity. Is preferred.

Further, R in the general formula (II)¹Has 1 to 1 carbon atoms
12 alkyl groups, R²And R ³Is a hydrogen atom or
Indicates a hydrocarbon group having 1 to 12 carbon atoms, all of which are the same
It may be one or different. The alkyl group and carbonization
The hydrogen group may be substituted. R¹, R²And R³But,
Each independently selected from an alkyl group having 1 to 12 carbon atoms
It is preferable that R be R¹~ R³Out of
One or more is cyclohexyl, butyl or octyl
It is preferably a group.

Examples of the phosphine compound represented by the general formula (II) include trialkylphosphines such as tributylphosphine, tricyclohexylphosphine and trioctylphosphine, aryldialkylphosphines such as phenyldibutylphosphine and phenyldicyclohexylphosphine, diphenylbutylphosphine and diphenyl. Examples thereof include diaryldialkylphosphines such as cyclohexylphosphine. Of these, trialkylphosphines such as tributylphosphine, tricyclohexylphosphine, and trioctylphosphine are preferable from the viewpoint of curability, and aryldialkylphosphines such as diphenylbutylphosphine and diphenylcyclohexylphosphine are preferable from the viewpoint of reflow resistance. General formula (II)
The phosphine compound represented by may be appropriately selected from one kind or two or more kinds, and in the form of an adduct with a quinone compound,
Alternatively, it is used together with a quinone compound, and an adduct with a quinone compound is preferable from the viewpoint of fluidity.

Examples of the quinone compound contained in the encapsulating epoxy resin composition in the form of an adduct with a phosphine compound or together with the phosphine compound include benzoquinone, naphthoquinone and anthraquinone.
Among them, 1,4-benzoquinone, methyl-1,4-benzoquinone, methoxy-1,4-benzoquinone, t-butyl-1,4-benzoquinone, phenyl-1,4-benzoquinone, 2,3-dimethyl-1,4 -Benzoquinone, 2,
5-dimethyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, 2,5-dimethoxy-
1,4-benzoquinone, 2,5-di-t-butyl-1,
4-benzoquinone, 1,4-naphthoquinone, 9,10-
P-quinones such as anthraquinone are preferred. Among them, 1,4-benzoquinone and methyl-p-benzoquinone are more preferable because they have excellent reactivity with the phosphine compound. The quinone compound may also be used alone or in combination of two or more.

The adduct of the phosphine compound represented by the general formula (I) and the quinone compound is not particularly limited,
From the viewpoint of curability, an adduct of tris- (p-methoxyphenyl) phosphine and 1,4-benzoquinone, tris- (p-methoxyphenyl) phosphine and methyl-
1,4-benzoquinone adduct, tris- (p-methoxyphenyl) phosphine and t-butyl-1,4-benzoquinone adduct, tri-p-tolylphosphine and 1,
Addition product of 4-benzoquinone, addition product of tri-p-tolylphosphine and methyl-1,4-benzoquinone, tri-
Addition product of p-tolylphosphine and t-butyl-1,4-benzoquinone, addition product of tri-o-tolylphosphine and 1,4-benzoquinone, tri-o-tolylphosphine and methyl-1,4-benzoquinone With adduct, tri-o-tolylphosphine with t-butyl-1,4-benzoquinone, tri-m-tolylphosphine with 1,4-benzoquinone, tri-m-tolylphosphine Methyl-
Reaction of 1,4-benzoquinone with 1,4-benzoquinone, addition of tri-m-tolylphosphine with t-butyl-1,4-benzoquinone, reaction of bis- (p-methoxyphenyl) phenylphosphine with 1,4-benzoquinone , Bis- (p-methoxyphenyl) phenylphosphine and methyl-1,4
A reaction product with benzoquinone, a reaction product with bis- (p-methoxyphenyl) phenylphosphine and t-butyl-1,4-benzoquinone, a reaction product with di-p-tolylphenylphosphine and 1,4-benzoquinone, Reaction product of di-p-tolylphenylphosphine and methyl-1,4-benzoquinone, di-p-tolylphenylphosphine and t-butyl-
An adduct of a phosphine compound and a quinone compound having two or more aryl groups having an electron-donating substituent introduced into a phenyl group such as a reaction product with 1,4-benzoquinone is preferable. From the viewpoint of reflow resistance, diphenyl (p
-Methoxyphenyl) phosphine and 1,4-benzoquinone adduct, diphenyl (p-methoxyphenyl) phosphine and methyl-1,4-benzoquinone adduct,
Diphenyl (p-methoxyphenyl) phosphine and t-
Butyl-1,4-benzoquinone adduct, diphenyl
Addition product of -p-tolylphosphine and 1,4-benzoquinone, diphenyl-p-tolylphosphine and methyl-1,4
An adduct of benzoquinone, an adduct of diphenyl-p-tolylphosphine and t-butyl-1,4-benzoquinone, an adduct of triphenylphosphine and 1,4-benzoquinone, triphenylphosphine and methyl-1, 4-
Adduct with benzoquinone, triphenylphosphine and t
An addition reaction product of a phosphine compound and a quinone compound which does not have two or more aryl groups having an electron-donating substituent introduced therein, such as an adduct with -butyl-1,4-benzoquinone, is preferable.

The adduct of the phosphine compound represented by the general formula (II) and the quinone compound is not particularly limited,
From the viewpoint of curability, an adduct of tricyclohexylphosphine and 1,4-benzoquinone, an adduct of tricyclohexylphosphine and methyl-1,4-benzoquinone, tricyclohexylphosphine and t-butyl-1,
4-benzoquinone adduct, tributylphosphine and 1,4-benzoquinone adduct, tributylphosphine and methyl-1,4-benzoquinone adduct, tributylphosphine and t-butyl-1,4-benzoquinone Addition product, addition product of trioctylphosphine and 1,4-benzoquinone, trioctylphosphine and methyl-
An adduct of a trialkylphosphine with a quinone compound such as an adduct of 1,4-benzoquinone or an adduct of trioctylphosphine with t-butyl-1,4-benzoquinone is preferable. Further, from the viewpoint of reflow resistance, an adduct of cyclohexyldiphenylphosphine and 1,4-benzoquinone, an adduct of cyclohexyldiphenylphosphine and methyl-1,4-benzoquinone, cyclohexyldiphenylphosphine and t-butyl-1, Adduct with 4-benzoquinone, butyldiphenylphosphine and 1,4
-Addition product of benzoquinone, addition product of butyldiphenylphosphine and methyl-1,4-benzoquinone, addition product of butyldiphenylphosphine and t-butyl-1,4-benzoquinone, dicyclohexylphenylphosphine and 1,4-benzoquinone With dicyclohexylphenylphosphine and methyl-1,4-benzoquinone with dicyclohexylphenylphosphine and t-
Addition product of butyl-1,4-benzoquinone, addition product of dibutylphenylphosphine and 1,4-benzoquinone,
Addition product of dibutylphenylphosphine and methyl-1,4-benzoquinone, dibutylphenylphosphine and t-
Preferred is an adduct of an alkyldiarylphosphine such as an adduct with butyl-1,4-benzoquinone or an adduct of a dialkylarylphosphine with a quinone compound. Among them, an adduct of cyclohexyldiphenylphosphine and 1,4-benzoquinone, butyldiphenylphosphine And 1,4
More preferred are adducts of alkyldiphenylphosphine with 1,4-benzoquinone, such as adducts with benzoquinone and adducts of octyldiphenylphosphine with 1,4-benzoquinone.

Method for producing adduct of phosphine compound represented by general formula (I) and quinone compound and general formula (II)
The method for producing an adduct of a phosphine compound and a quinone compound represented by is not particularly limited, but for example, the phosphine compound and the quinone compound used as raw materials are subjected to an addition reaction in an organic solvent in which both are dissolved and isolated. And a method of performing an addition reaction in the curing agent of the component (B). In the latter method, it is used as a blending component of the epoxy resin composition in a state of being directly dissolved in the curing agent without isolation. You can The adduct of the phosphine compound represented by the general formula (I) and the quinone compound may be used alone or in combination of two or more. Further, the adduct of the phosphine compound represented by the general formula (II) and the quinone compound may be used alone or in combination of two or more kinds. When the phosphine compound and the quinone compound are used at the same time, the molar ratio is 1/1
The range of 1 / 1.5 is preferable.

The curing accelerator (C) may be, for example, a phosphorus compound, a tertiary amine compound,
A curing accelerator such as an imidazole compound may be included. In this case, in order to obtain the effect of the present invention, the content thereof is preferably 95% by weight or less with respect to the total amount of the curing accelerator.

The amount of the (C) curing accelerator compounded is not particularly limited as long as the curing acceleration effect is achieved, but 0.005 to 2 with respect to the encapsulating epoxy resin composition.
Weight% is preferable, and 0.01 to 0.5 weight% is more preferable. If it is less than 0.005% by weight, the curability in a short time tends to be inferior, and if it exceeds 2% by weight, the curing rate tends to be too fast, and it tends to be difficult to obtain a good molded product.

The inorganic filler (D) used in the present invention is added to the composition for the purposes of hygroscopicity, reduction of linear expansion coefficient, improvement of thermal conductivity and improvement of strength, and examples thereof include fused silica and crystals. Powders of 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., Alternatively, beads, glass fibers, and the like obtained by making them spherical may be used, and these may be used alone or in combination of two or more kinds. Of these, fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoint of fluidity during molding and wear of the mold. From the viewpoint of flame retardancy, moldability, hygroscopicity, reduction of linear expansion coefficient and improvement of strength, the content of the inorganic filler (D) is preferably 60% by weight or more, and 70% by weight or more with respect to the epoxy resin composition for sealing. -95% by weight is more preferable, and 75-
92% by weight is more preferred. If it is less than 60% by weight, the flame retardancy and reflow resistance tend to decrease, and 95% by weight.
If it exceeds, liquidity tends to be insufficient.

The (E) composite metal hydroxide used in the present invention acts as a flame retardant and is not particularly limited as long as the effects of the present invention can be obtained, but the compound represented by the following composition formula (III) is preferable.

Embedded image m (M ¹ _a O _b ) .n (M ² _c O _d ) .h (H ₂ O) (III) (wherein M ¹ and M ² represent different metal elements,
a, b, c, d, m, n and h represent positive numbers. )

There is no particular limitation on M ¹ and M ² in the above composition formula (III) as long as they are different metal elements, but from the viewpoint of flame retardancy, M ¹ and M ² should not be the same. ¹ is the third period metal element, Group IIA alkaline earth metal element, IV
It is preferable that M ² is selected from the group B, IIB, VIII, IB, IIIA, and IVA group metal elements, M ² is selected from the IIIB to IIB group transition metal elements, and M ¹ is magnesium or calcium. Aluminum, tin, titanium, iron,
More preferably, it is selected from cobalt, nickel, copper and zinc, and M ² is selected from iron, cobalt, nickel, copper and zinc. Further, from the viewpoint of fluidity, M ¹ is preferably magnesium and M ² is zinc or nickel, more preferably M ¹ is magnesium and M ² is zinc. The molar ratio m / n of M ¹ _a O _b and M ² _c O _d is not particularly limited as long as the effect of the present invention can be obtained, but m / n is 99.
It is preferably / 1 to 50/50. In addition, the metal element shall include what is called a metalloid element,
Refers to all elements except non-metallic elements. The metal elements are classified into a long-period type periodic table with a typical element being the A group and a transition element being the B group (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987, a reduced version) The 30th printing).

The shape of the (E) composite metal hydroxide is not particularly limited, but from the viewpoint of fluidity, a polyhedral shape having an appropriate thickness is preferable to a flat plate shape. The complex metal hydroxide is more likely to obtain polyhedral crystals than the metal hydroxide. The compounding amount of the (E) composite metal hydroxide is not particularly limited, but is 0.5 to 20 relative to the encapsulating epoxy resin composition.
Weight% is preferable, 0.7-15 weight% is more preferable, 1.4-12 weight% is still more preferable. If it is less than 0.5% by weight, flame retardancy tends to be insufficient, and if it exceeds 20% by weight, fluidity and reflow resistance tend to be lowered.

The epoxy resin composition for encapsulation of the present invention includes
In addition to the above essential components, the following components can be included. In addition to the (E) composite metal hydroxide, a conventionally known non-halogen or non-antimony flame retardant can be blended as necessary. For example, red phosphorus, phosphorus-containing compounds such as phosphates, melamine, melamine derivatives, melamine-modified phenolic resins, compounds having a triazine ring,
Nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron, etc. Compounds containing the above metal element are listed, and one kind thereof may be used alone or two or more kinds may be used in combination.

The epoxy resin composition for encapsulation of the present invention comprises
From the viewpoint of improving the moisture resistance and the high-temperature storage property of semiconductor elements such as ICs, an ion trap agent can be further added if necessary. The ion trap agent is not particularly limited, and conventionally known ones can be used,
Examples thereof include hydrotalcites and hydrous 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 (XV) is preferable.

Embedded image Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XV) (0 <X ≦ 0.5, m is a positive number) Compounding of an ion trap agent The amount is not particularly limited as long as it is a sufficient amount to capture anions such as halogen ions, but from the viewpoint of moldability, moisture resistance and high-temperature storage characteristics, it is 0.1 to 30 wt% relative to (A) epoxy resin. % Is preferable, and 0.
5 to 10% by weight is more preferable, and 1 to 5% by weight is further preferable.

In addition, in the encapsulating epoxy resin composition of the present invention, epoxy silane, mercapto silane, amino silane, alkyl silane, and ureide are added, if necessary, in order to enhance the adhesiveness between the resin component and the inorganic filler. Silane,
Known coupling agents such as various silane compounds such as vinylsilane, titanium compounds, aluminum chelates, aluminum / zirconium compounds and the like can be added. The amount of the coupling agent blended is preferably 0.05 to 5% by weight, more preferably 0.1 to 2.5% by weight, based on the inorganic filler as the component (D). 0.05
If it is less than 5% by weight, the adhesiveness to the frame tends to decrease, and if it exceeds 5% by weight, the moldability of the package tends to decrease.

Examples of the above coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri. Methoxysilane, 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 , Methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ
-Chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane, isopropyltriisostearoyl 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) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri (dioctyl phosphate) Titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dio Chill phosphite) titanate coupling agents such as titanates and the like, may be used in combination of two or more even with these alone.

Further, in the encapsulating epoxy resin composition of the present invention, as other additives, a releasing agent such as higher fatty acid, higher fatty acid metal salt, ester wax, polyolefin wax, polyethylene or oxidized polyethylene, A coloring agent such as carbon black, a stress relieving agent such as silicone oil or silicone rubber powder, and the like can be blended as necessary.

The encapsulating epoxy resin composition of the present invention can be prepared by any method as long as it can uniformly disperse and mix various raw materials, but as a general method, a predetermined amount of the raw materials is mixed. Examples include a method of sufficiently mixing with a mixer or the like, melting and kneading with a mixing roll, an extruder or the like, and then cooling and pulverizing. It is easy to use if it is made into a tablet with dimensions and weight that match the molding conditions.

The electronic component device of the present invention comprising an element sealed with the sealing epoxy resin composition obtained in the present invention includes a lead frame, a pre-wired tape carrier,
Elements such as semiconductor chips, transistors, diodes, active elements such as thyristors, passive elements such as capacitors, resistors, and coils are mounted on a supporting member such as a wiring board, glass, and a silicon wafer, and necessary parts are mounted according to the present invention. Examples include electronic component devices and the like, which are sealed with a sealing epoxy resin composition.
A low-pressure transfer molding method is the most general method for sealing an element using the epoxy resin composition for sealing of the present invention, but an injection molding method, a compression molding method or the like may be used.

In the electronic component device of the present invention, specifically, a semiconductor element is fixed on a lead frame, the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding or bump, and then the present invention is applied. DIP (Dual Inline Package), PLCC (Pla) formed by transfer molding or the like using the epoxy resin composition for sealing of
stic Leaded Chip Carrier), QFP (Quad Flat Pack)
age), SOP (SmallOutline Package), SOJ (Sma
ll Outline J-lead package), TSOP (Thin Small)
Outline Package), TQFP (Thin Quad Flat Packag)
General resin-encapsulated ICs such as e); TCP (Tape Carrier Packag) in which a semiconductor chip connected to a tape carrier by bumps is encapsulated with the encapsulating epoxy resin composition of the present invention.
e); Active elements such as semiconductor chips, transistors, diodes, thyristors, etc. that are connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. and / or passive elements such as capacitors, resistors, coils, etc. A COB (Chip On Board) module in which an element is encapsulated with the encapsulating epoxy resin composition of the present invention; a hybrid IC; a multi-chip module; an element is formed on the surface of an organic substrate on which terminals for connecting wiring boards are formed on the back surface. A BGA (Ball Grid) in which the device is mounted and the element and the wiring formed on the organic substrate are connected by bumps or wire bonding, and then the element is encapsulated with the encapsulating epoxy resin composition of the present invention.
Array); CSP (Chip Size Package) and the like. Further, the epoxy resin composition for encapsulation of the present invention can be effectively used for printed circuit boards.

[0056]

The present invention will now be described with reference to examples, but the scope of the present invention is not limited to these examples. (Examples 1 to 6 and Comparative Examples 1 to 6) Epoxy equivalent 192 as an epoxy resin, biphenyl type epoxy resin having a melting point of 105 ° C. (epoxy resin 1: Yuka Shell Epoxy Co., Ltd. trade name Epicoat YX-4000H), epoxy equivalent 210, a stilbene type epoxy resin having a softening point of 130 ° C. (epoxy resin 2: ES manufactured by Sumitomo Chemical Co., Ltd.
LV-210), an epoxy equivalent of 195, and an o-cresol novolac type epoxy resin having a softening point of 65 ° C. (epoxy resin 3: manufactured by Sumitomo Chemical Co., Ltd., trade name ESCN-19).
0), an epoxy equivalent of 244, and a sulfur atom-containing epoxy resin having a melting point of 118 ° C. (epoxy resin 4: trade name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd.) were prepared. Phenol aralkyl resin having a hydroxyl equivalent of 172 and a softening point of 70 ° C. as a curing agent (curing agent 1: Mitsui Chemicals, Inc., trade name Milex XL-225), hydroxyl equivalent of 199, and a softening point of 8
A biphenyl type phenolic resin (curing agent 2: MEH-7851, manufactured by Meiwa Kasei Co., Ltd.) at 0 ° C. was prepared.

As a curing accelerator, an adduct of tri-p-tolylphosphine and 1,4-benzoquinone (curing accelerator 1), a mixture of tri-p-tolylphosphine and 1,4-benzoquinone (curing accelerator 2) , Tri-p-tolylphosphine / 1,4-benzoquinone molar ratio 1 / 1.2),
Prepare an adduct of triphenylphosphine and 1,4-benzoquinone (curing accelerator 3), triphenylphosphine (curing accelerator 4), an adduct of tributylphosphine and 1,4-benzoquinone (curing accelerator 5) did.

As an inorganic filler, the average particle size is 17.5 μm.
m spherical silica having a specific surface area of 3.8 m ² / g was prepared. M ¹ in the above composition formula (III) as a composite metal hydroxide
Is magnesium, M ² is zinc, m is 7, n is 3, h is 10, and all of a, b, c and d are 1 magnesium hydroxide / zinc solid solution (trade name of Tateho Chemical Industry Co., Ltd.) Echo mug Z10) was prepared. Other flame retardants include red phosphorus (Nova Excel 140 manufactured by Rin Chemical Industry Co., Ltd.), antimony trioxide and epoxy equivalent 37
5, bisphenol A type brominated epoxy resin having a softening point of 80 ° C and a bromine content of 48% by weight (trade name ESB-400T manufactured by Sumitomo Chemical Co., Ltd.), and an epoxy silane coupling agent (Shin-Etsu Chemical Co., Ltd.) as other additives. Product name KBM403), carnauba wax (manufactured by Clariant Co., Ltd.) and carbon black (Mitsubishi Chemical Co., Ltd. product name MA-100) were prepared. These were blended in the respective parts by weight shown in Table 1, and roll kneading was carried out under the conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes.
The epoxy resin compositions for sealing of Nos. 6 to 6 were produced.

[0059]

[Table 1]

The produced epoxy resin compositions for encapsulation of Examples and Comparative Examples were evaluated by the following tests. The results are shown in Table 2. The epoxy resin composition for encapsulation was molded by a transfer molding machine under the 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) Flame-retardant Using a mold for molding a test piece having a thickness of 1/16 inch,
The epoxy resin composition for encapsulation was molded under the above conditions, post-cured, and flame retardancy was evaluated according to the UL-94 test method. (2) Spiral flow Using a mold for spiral flow measurement according to EMMI-1-66, the epoxy resin composition for encapsulation was molded under the above conditions, and the flow distance was determined. (3) 50 mm diameter of the epoxy resin composition for hot hardness encapsulation under the above conditions
It was molded into a disk having a thickness of 3 mm, and immediately after molding, the molded product in the mold was measured with a Shore D hardness meter. (4) Shear releasability A 50 mm long × 35 mm wide × 0.4 mm thick chrome-plated stainless steel plate is inserted, and a mold for molding a disc with a diameter of 20 mm is used on the epoxy resin composition for sealing. The product was molded under the above conditions, and immediately after the molding, the stainless steel plate was pulled out and the maximum drawing force was recorded. This is repeated 10 times for the same stainless steel plate from the second time to 10 times.
The average value of the pulling forces up to the second time was obtained and evaluated. (5) Molding an 80-pin flat package (QFP) having an external dimension of 20 mm × 14 mm × 2 mm on which a silicone chip having a reflow resistance of 8 mm × 10 mm × 0.4 mm is mounted, using an epoxy resin composition for encapsulation under the above conditions. , Post-cured and made, 8
Humidify under conditions of 5 ° C and 85% RH for 240
Reflow treatment was performed under conditions of 10 ° C. for 10 seconds, the presence or absence of cracks was observed, and the number of cracked packages was evaluated with respect to the number of test packages (5). (6) Moisture resistance External dimensions of 20 mm x 14 m mounted with a 6 mm x 6 mm x 0.4 mm test silicone chip in which aluminum wiring with a line width of 10 μm and a thickness of 1 μm is formed on an oxide film with a thickness of 5 μm
mx 2.7 mm 80-pin flat package (QF
P) is molded and post-cured using the epoxy resin composition for encapsulation under the above conditions, pre-treated, humidified, and examined for disconnection defects due to aluminum wiring corrosion every predetermined time, and tested. The number of defective packages to the number of packages (10) was evaluated. The pretreatment was performed at 85 ° C., 85% RH for 72 hours after humidifying the flat package, then at 215 ° C. for 90 minutes.
A vapor phase reflow process for 2 seconds was performed. The subsequent humidification was performed under the conditions of 0.2 MPa and 121 ° C. (7) High temperature storage characteristics 42 mm alloy lead with a partial silver plating of a 5 mm x 9 mm x 0.4 mm test silicone chip in which an aluminum wiring having a line width of 10 μm and a thickness of 1 μm is formed on an oxide film having a thickness of 5 μm. A 16-pin DIP (Dual Inline Package) in which a chip bonding pad and inner lead are connected by Au wire at 200 ° C is mounted on a frame by using a silver paste on a frame with epoxy resin for sealing. The composition was molded under the above conditions and post-cured to be prepared, stored in a high temperature bath at 200 ° C., taken out at predetermined intervals and subjected to a continuity test, and the number of test packages (1
The high temperature storage characteristics were evaluated by the number of poorly conductive packages with respect to 0).

[0061]

[Table 2]

Comparative Examples 1, 5 and 6 containing the phosphine compound but not the quinone compound are inferior in fluidity and reflow resistance. Comparative Examples 2 to 4 containing no (E) composite metal hydroxide in the present invention are inferior in any of flame retardancy, moisture resistance and high temperature storage property, and do not satisfy the object of the present invention.
In particular, Comparative Example 4 using a brominated epoxy resin and an antimony compound is extremely inferior in high temperature storage property. On the other hand, Examples 1 to 6 containing both the adduct of the phosphine compound and the quinone compound of the present invention, or both the phosphine compound and the quinone compound, and further containing all the components (A) to (E).
Shows that the reflow resistance, moisture resistance and high temperature storage characteristics are not deteriorated, and the UL-94 test shows V-
A value of 0 is achieved, indicating good flame retardancy. In particular, R of the general formula (I)
In Examples 1 and 2 using a phosphine compound in which is an alkyl group and Example 4 using an adduct of the phosphine compound represented by the general formula (II) and a quinone compound, shear releasability is also good. .

[0063]

Industrial Applicability The encapsulating epoxy resin composition according to the present invention can achieve flame retardancy with non-halogen and non-antimony as shown in Examples, and can be used for encapsulating electronic parts such as IC and LSI. For example, it is possible to obtain a product having good moldability and good reliability such as reflow resistance, moisture resistance and high-temperature storage property, and its industrial value is great.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ryoichi Ikezawa             48 Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd.             Company Research Institute (72) Inventor Takayuki Akimoto             48 Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd.             Company Research Institute (72) Inventor Mitsuo Katayose             48 Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd.             Company Research Institute F-term (reference) 4J002 CC042 CC062 CC272 CD021                       CD031 CD051 CD061 CD111                       DE069 DE079 DE098 DE099                       DE109 DE119 DE138 DE139                       DE148 DF018 DJ008 DJ018                       DK008 EE057 EW016 FD018                       FD139 FD142 FD156 FD157                       GQ01 GQ05                 4J036 AA01 AB07 AD07 AD08 AF01                       AF05 AF06 AF07 AF08 AF09                       AJ08 DA01 DA05 DB28 DD07                       FA01 FA02 FA03 FA04 FA05                       FA06 FB07 FB08 JA07 KA01                 4M109 AA01 CA21 EB04 EB07 EC20

Claims (12)

[Claims] 1. An epoxy resin (A), a curing agent (B),
(C) a curing accelerator, (D) an inorganic filler, and (E) a composite metal hydroxide as essential components, and (C) a curing accelerator comprises a phosphine compound represented by the following general formula (I) and a quinone compound. An epoxy resin composition for encapsulation, which comprises an additive. [Chemical 1] (R in the general formula (I) is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, all of which are the same. It may be different.) 2. An epoxy resin (A), a curing agent (B),
(C) a curing accelerator, (D) an inorganic filler and (E) a composite metal hydroxide as essential components, the (C) curing accelerator contains a phosphine compound represented by the general formula (I), and further a quinone compound. An epoxy resin composition for encapsulation, comprising: [Chemical 2] (R in the general formula (I) is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, all of which are the same. It may be different.) 3. An epoxy resin (A), a curing agent (B),
(C) a curing accelerator, (D) an inorganic filler, and (E) a composite metal hydroxide as essential components, and the (C) curing accelerator is a phosphine compound in which at least one alkyl group is bonded to a phosphorus atom, and a quinone. An epoxy resin composition for encapsulation, which contains an adduct with a compound or (C) contains a phosphine compound having at least one alkyl group bonded to a phosphorus atom as a curing accelerator, and further contains a quinone compound. . 4. The encapsulating epoxy resin composition according to claim 3, wherein the phosphine compound in which at least one alkyl group is bonded to a phosphorus atom is an adduct of the phosphine compound represented by the general formula (II) and a quinone compound. object. [Chemical 3] (R ¹ in the general formula (II) is a substituted or unsubstituted C ¹ to C ¹
12 represents an alkyl group, R ² and R ³ represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms,
All may be the same or different. ) 5. The epoxy resin composition for encapsulation according to claim 1, wherein (E) the composite metal hydroxide is a compound represented by the following composition formula (III). Embedded image m (M ¹ _a O _b ) · n (M ² _c O _d ) · h (H ₂ O) (III) (wherein M ¹ and M ² represent different metal elements,
a, b, c, d, m, n and h represent positive numbers. ) 6. M ¹ in the composition formula (III) is a metal element of the third period, an alkaline earth metal element of IIA group, IVB group, IIB.
The encapsulating epoxy resin composition according to claim 5, wherein M ² is selected from the group III, VIII, IB, IIIA, and IVA group metal elements, and M ² is selected from the IIIB to IIB group transition metal elements. 7. M ¹ in the composition formula (III) is magnesium,
The epoxy resin composition for encapsulation according to claim 6, which is selected from calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is selected from iron, cobalt, nickel, copper and zinc. 8. The encapsulating epoxy resin composition according to claim 7, wherein M ¹ in the composition formula (III) is magnesium and M ² is zinc or nickel. 9. M ¹ _a O _b and M ² _c O _{d in the} composition formula (III).
The molar ratio m / n of is 99/1 to 50/50.
The epoxy resin composition for encapsulation according to any one of to 8. 10. The (A) epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a sulfur atom-containing epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin and a triphenylmethane type epoxy resin. At least one of
The epoxy resin composition for encapsulation according to claim 1, which contains a seed. 11. The (B) curing agent contains at least one of a biphenyl type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin and a novolac type phenol resin. 10. The epoxy resin composition for encapsulation according to any one of 10. 12. An electronic component device comprising an element encapsulated with the epoxy resin composition for encapsulation according to claim 1.