JP2003321533A - Epoxy resin molding material for sealing and electronic part apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin material for sealing not containing a halogen and antimony, having good flame retardance without lowering reliability of moldability, reflow resistance, moisture resistance and high-temperature leaving characteristics, etc., and an electronic part apparatus equipped with an element sealed thereby. <P>SOLUTION: The epoxy resin molding material comprises (A) an epoxy resin, (B) a curing agent and (C) a complex metal hydroxide as essential components and has ≥80 mm circular plate flow. The electronic part apparatus is equipped with the element sealed by the epoxy resin molding material for sealing. <P>COPYRIGHT: (C)2004,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 molding material for encapsulation, particularly a halogen-free, non-antimony and flame-retardant epoxy resin molding material for encapsulation which is required from the viewpoint of environmental friendliness. VL that requires moldability
The present invention relates to a molding material suitable for SI sealing and an electronic component device provided with an element sealed with this molding material.

[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 viewpoint of productivity and cost, and epoxy resin molding materials have been 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 encapsulating epoxy resin molding materials is mainly achieved by combining antimony oxide with a brominated resin such as diglycidyl ether of tetrabromobisphenol A. In recent years, the dioxin problem originated from the viewpoint of environmental protection, and the amount of halogenated resins such as decabrom and antimony compounds are being regulated, and epoxy resin molding materials for encapsulation are also non-halogenated (non-bromine) and non-brominated. There is a demand for antimony.
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 of achieving flame retardancy without using brominated resin or antimony oxide, a method using red phosphorus (Japanese Patent Laid-Open No. 9-22
7765), a method using a phosphoric acid ester compound (JP-A-9-235449), a method using a phosphazene compound (JP-A-8-225714), and a method using a metal hydroxide (JP-A-9-241483). JP-A-9-300337), a method of using a metal hydroxide and a metal oxide in combination (JP-A-9-100337), a cyclopentadienyl compound such as ferrocene (JP-A-11-269349), and acetylacetonate copper (Kato). Generous, functional material, 1
1 (6), 34 (1991)) and the like, methods using a flame retardant other than halogen and antimony, such as a method using an organometallic compound, and a method of increasing the proportion of the filler (JP-A-7-8).
No. 2343) has been tried.

[0003]

However, when red phosphorus is used as the epoxy resin molding material for encapsulation, there is a problem of reduced moisture resistance, and when a phosphoric acid ester compound or a phosphazene compound is used, moldability due to plasticization is caused. Of metal and hydroxide resistance, when metal hydroxide is used, fluidity and mold releasability are deteriorated, when metal oxide is used, and when the proportion of filler is increased. There are problems of reduced liquidity. Further, when an organometallic compound such as acetylacetonato copper is used, there is a problem that the curing reaction is hindered and moldability is lowered. As described above, in these non-halogen and non-antimony flame retardants, in any case, it is possible to obtain the same moldability, reliability and safety as the encapsulating epoxy resin molding material using the brominated resin and antimony oxide in combination. Not in. The present invention has been made in view of such circumstances, and is a halogen-free and antimony-free encapsulating epoxy having good flame retardancy without lowering reliability such as moldability, reflow resistance, moisture resistance, and high temperature storage characteristics. It is intended to provide an electronic component device including a resin material and an element sealed by the resin material.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors achieved the above object by using an epoxy resin molding compound for encapsulation containing a composite metal hydroxide. The inventors have discovered what is possible and have completed the present invention. That is, the present application relates to the following inventions. (1) An epoxy resin molding material for encapsulation, which comprises (A) an epoxy resin, (B) a curing agent, and (C) a composite metal hydroxide as essential components and has a disc flow of 80 mm or more. (2) The epoxy resin molding material for sealing according to (1) above, which further contains (D) an inorganic filler. (3) The epoxy resin molding material for encapsulation according to the above (1) or (2), wherein the composite metal hydroxide (C) is a compound represented by the following composition formula (I). p (M ¹ aOb) · q (M ² cOd) · r (M ³ cOd) · mH ₂ O (I) (wherein M ¹ , M ² and M ³ represent different metal elements, and a, b , c, d, p, q and m are positive numbers, r is 0 or indicate a positive number.) (4) M ¹ such M ¹ and M ² in formula (I) is not the same Selected from metal elements belonging to the third period, group IIA alkaline earth metal elements, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA, and M ² is IIIB to II
The encapsulating epoxy resin molding material according to (3) above, which is selected from Group B transition metal elements. (5) M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc so that M ¹ and M ² in the composition formula (I) are not the same, and M ² is The epoxy resin molding material for sealing according to (4) above, which is selected from iron, cobalt, nickel, copper and zinc. (6) The epoxy resin molding material for sealing according to the above (5), wherein M ¹ in the composition formula (I) is magnesium and M ² is zinc or nickel. (7) In the composition formula (I), when r = 0, the molar ratio p of p and q is p.
(3) to (6), wherein / q is 99/1 to 50/50.
The epoxy resin molding material for sealing according to any one of 1. (8) The epoxy resin molding material for encapsulation according to any one of the above (1) to (7), further containing (E) a silane coupling agent having a secondary amino group. (9) The epoxy resin molding material for encapsulation according to the above (8), wherein the silane coupling agent having a secondary amino group (E) contains a compound represented by the following general formula (II).

[Chemical 3] (Here, R ¹ is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to ² carbon atoms, R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, and R
³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to 3. (10) The epoxy resin molding material for encapsulation according to any one of (1) to (9) above, which further contains a phosphoric acid ester (F). (11) The epoxy resin molding material for encapsulation according to the above (10), wherein the phosphoric acid ester (F) contains a compound represented by the following general formula (III).

[Chemical 4] (Here, 8 Rs in the formula represent an alkyl group having 1 to 4 carbon atoms, and all may be the same or different. Ar represents an aromatic ring.) (12) (A) Epoxy resin Biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin,
(1) containing at least one kind of naphthalene type epoxy resin and triphenylmethane type epoxy resin
The epoxy resin molding material for sealing according to any one of (11). (13) (B) curing agent is a biphenyl type phenol resin,
The encapsulating epoxy resin molding according to any one of (1) to (12) above, which contains at least one of an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin and a novolac type phenol resin. material. And (14) An electronic component device including an element sealed with the epoxy resin molding material for sealing according to any one of (1) to (13) above.

The present invention also relates to the following inventions. (15) The composite metal hydroxide (C) has the following composition formula (Ia).
The epoxy resin molding material for encapsulation according to (1) or (2) above, which is a compound represented by: m (M ¹ aOb) · n (M ² cOd) · l (H ₂ O) (Ia) (where M ¹ and M ² represent different metal elements,
a, b, c, d, m, n and l represent positive numbers. (16) An electronic component device comprising an element sealed with the sealing epoxy resin molding material according to (15).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Used in the Present Invention
Epoxy resin is generally used as a sealing epoxy resin molding material and is not particularly limited, and examples thereof include phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, and epoxy resin having a triphenylmethane skeleton. And phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and /
Or a novolak resin obtained by condensing or co-condensing naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene with a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde under an acidic catalyst. Epoxidized, bisphenol A,
Diglycidyl ethers such as bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenols, stilbene-type epoxy resins, hydroquinone-type epoxy resins, polybasic acids such as phthalic acid and dimer acid, and glycidyl ester-type epoxies obtained by the reaction of epichlorohydrin Resin, glycidylamine type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane, isocyanuric acid, and epichlorohydrin, epoxidized product of co-condensation resin of dicyclopentadiene and phenols, epoxy resin having naphthalene ring, phenol / aralkyl resin , Epoxidized aralkyl type phenol resin such as naphthol / aralkyl resin, trimethylol propane type epoxy resin, terpene modified epoxy resin, olefin bond with pervine Examples thereof include linear aliphatic epoxy resins, alicyclic epoxy resins, and sulfur atom-containing epoxy resins obtained by oxidation with peracids such as these, and these may be used alone or in combination of two or more kinds. . Among them, biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin and sulfur atom-containing epoxy resin are preferable from the viewpoint of reflow resistance, and novolac type epoxy resin is preferable from the viewpoint of curability, and low hygroscopicity. From the viewpoint of, dicyclopentadiene type epoxy resin is preferable, from the viewpoint of heat resistance and low warpage, naphthalene type epoxy resin and triphenylmethane type epoxy resin are preferable, and at least one of these epoxy resins is contained. It is preferable.

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

[Chemical 5] (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 6] (Here, R ^{1 to} R ⁸ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and 6 to 6 carbon atoms.
It is selected from an aryl group having 10 and an aralkyl group having 6 to 10 carbon atoms, all of which may be the same or different. n shows the integer of 0-3. )

[Chemical 7] (Here, R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms, and all may be the same or different. N is 0 to 10). Indicates an integer.)

[Chemical 8] (Where R¹~ R⁸Is a hydrogen atom, a substituted or unsubstituted carbon
Alkyl group of number 1 to 10 and substituted or unsubstituted carbon number 1
Selected from 10 to 10 alkoxy groups, all the same or different
You may n shows the integer of 0-3. ) Biphenyl type epoxy resin represented by the above general formula (IV)
Is, for example, 4,4'-bis (2,3-epoxy)
Cipropoxy) biphenyl or 4,4'-bis (2,3
-Epoxypropoxy) -3,3 ', 5,5'-tetra
Epoxy resin based on methylbiphenyl
Lorhydrin and 4,4'-biphenol or 4,4'-
With (3,3 ', 5,5'-tetramethyl) biphenol
An epoxy resin and the like obtained by reacting Na
Even 4,4'-bis (2,3-epoxypropoxy)
Mainly composed of -3,3 ', 5,5'-tetramethylbiphenyl
The epoxy resin used as the component is preferable. In the above general formula (V)
The bisphenol F type epoxy resin shown is as follows:
For example, R¹, R³, R⁶And R⁸Is a methyl group and R²,
R^Four, R^FiveAnd R⁷Is a hydrogen atom, and n = 0 is the main component
YSLV-80XY (product of Nippon Steel Chemical Co., Ltd.
Name) is commercially available. The above general formula (VI)
The stilbene type epoxy resin represented by
Bases of tilbene phenols and epichlorohydrin
It can be obtained by reacting in the presence of a volatile substance. This raw material
Examples of the stilbene-based phenols are
-T-butyl-4,4'-dihydroxy-3 ', 5,
5'-trimethylstilbene, 3-t-butyl-4,
4'-dihydroxy-3 ', 5', 6-trimethylstyro
Ruben, 4,4'-dihydroxy-3,3 ', 5,5'
-Tetramethylstilbene, 4,4'-dihydroxy-
3,3'-di-t-butyl-5,5'-dimethylstill
Ben, 4,4'-dihydroxy-3,3'-di-t-bu
Tyl-6,6'-dimethylstilbene and the like,
Even 3-t-butyl-4,4'-dihydroxy-
3 ', 5,5'-trimethylstilbene, and 4,4'
-Dihydroxy-3,3 ', 5,5'-tetramethyls
Tilbene is preferred. These stilbene-type phenols
These may be used alone or in combination of two or more.
Yes. Sulfur atom-containing epoxy represented by the above general formula (VII)
Among resin, R², R ³, R⁶And R⁷Is a hydrogen atom
And R¹, R^Four, R^FiveAnd R⁸An epoxy in which is an alkyl group
Resin is preferred, R², R³, R⁶And R⁷Is a hydrogen atom,
R¹And R⁸Is a t-butyl group, and R^FourAnd R^FiveIs a methyl group
Some epoxy resins are more preferred. With such compounds
Then, YSLV-120TE (made by Nippon Steel Chemical Co., Ltd.)
It is available for sale. These epoxy resins Yes
Even if one type is used alone or two or more types are used in combination
However, the blending amount is in order to exert its performance.
20% by weight or more in total with respect to the total amount of epoxy resin
Is preferable, more preferably 30% by weight or more, and 5
It is more preferable that the content be 0 wt% or more.

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

[Chemical 9] (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 general formula (VIII). The novolac type epoxy resin is easily obtained by reacting novolac type phenol resin with epichlorohydrin. Among them, R in the general formula (VIII) is a C 1-10 alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a methoxy group, an ethoxy group or 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 (VIII), 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 (IX).

[Chemical 10] (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 It represents an integer of 0 to 6.) As R ¹ in the above formula (IX), for example, a hydrogen atom,
Alkyl group such as methyl group, ethyl group, propyl group, butyl group, 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 Examples thereof include a substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms such as a substituted alkyl group, and among them, 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. preferable. Examples of R ² 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, a vinyl group,
Alkyl groups such as allyl group and butenyl group, halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups and other substituted or unsubstituted monovalent hydrocarbon groups having 1 to 5 carbon atoms. However, 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 (X), and the triphenylmethane type epoxy resin includes, for example, an epoxy resin represented by the following general formula (XI). .

[Chemical 11] (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,
l and m are each an integer of 0 to 11, and (l + m)
Is an integer from 1 to 11 and (l + 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. ) As the naphthalene type epoxy resin represented by the general formula (X), a random copolymer randomly containing 1 constitutional unit and m constitutional units, an alternating copolymer containing alternately,
Examples thereof include a regularly-containing copolymer and a block-containing block copolymer, and any one of these may be used alone, or two or more thereof may be used in combination.

[Chemical 12] (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.) One of these epoxy resins is used. May be used alone or in combination with each other, but the compounding amount thereof is preferably 20% by weight or more in total with respect to the total amount of the epoxy resin in order to exert its performance, and 30% by weight is preferable. The above is more preferable, and 50% by weight or more is further preferable.

Any one of the above-mentioned biphenyl type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and triphenylmethane type epoxy resin may be used. May be used alone or in combination of two or more kinds, but the compounding amount thereof is preferably 50% by weight or more, more preferably 60% by weight or more, more preferably 80% by weight in total with respect to the total amount of the epoxy resin.
It is more preferably at least wt%.

The curing agent (B) used in the present invention is generally used in epoxy resin molding materials for sealing and is not particularly limited. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol. F, phenylphenol, phenol such as aminophenol and / or α-naphthol,
Novolac phenolic resins, phenols and / or naphthols obtained by condensing or co-condensing naphthols such as β-naphthol and dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde, benzaldehyde and salicylaldehyde under an acidic catalyst. Aralkyl-type phenol resin such as phenol / aralkyl resin, naphthol / aralkyl resin, etc., which are synthesized from bis (methoxymethyl) biphenyl and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, dichloro, which is synthesized by copolymerization from phenols and / or naphthols and cyclopentadiene. Pentadiene-type phenol novolac resins, dichloropentadiene-type phenolic resins such as naphthol novolac resins, terpene-modified phenolic resins, etc. It may be used in combination on. Among them, the biphenyl type phenol resin is preferable from the viewpoint of flame retardancy, the aralkyl type phenol resin is preferable from the viewpoint of reflow resistance and curability, and the dicyclopentadiene type phenol resin is preferable from the viewpoint of low hygroscopicity, From the viewpoint of heat resistance, low expansion coefficient and low warpage, triphenylmethane type phenol resin is preferable, from the viewpoint of curability, novolac type phenol resin is preferable, and at least one of these phenol resins is contained. Is preferred.

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

[Chemical 13] All of R ^{1 to} R ⁹ in the above formula (IX) may be the same or different, and a hydrogen atom, a methyl group, an ethyl group, a propyl group,
Carbon number 1 such as butyl, isopropyl, and isobutyl groups
-10 alkyl group, methoxy group, ethoxy group, propoxy group, butoxy group, etc., alkoxy group having 1 to 10 carbon atoms, phenyl group, tolyl group, xylyl group, etc., having 6 to 10 carbon atoms
It is selected from an aryl group having 10 carbon atoms and an aralkyl group having 6 to 10 carbon atoms such as a benzyl group and a phenethyl group, and among them, a hydrogen atom and a methyl group are preferable. n shows the integer of 0-10. Examples of the biphenyl type phenol resin represented by the general formula (XII) include compounds in which R ^{1 to} R ⁹ are all hydrogen atoms, and among them, from the viewpoint of melt viscosity, a condensate in which n is 1 or more is used. A mixture of condensates containing 50% by weight or more is preferred. Such compounds include MEH
-7851 (trade name, manufactured by Meiwa Kasei Co., Ltd.) is commercially available. When a biphenyl type phenol resin is used, its content is preferably 30% by weight or more, more preferably 50% by weight or more, and more preferably 60% by weight or more based on the total amount of the curing agent in order to exert its performance. More preferable.

Examples of the aralkyl type phenol resin include phenol / aralkyl resin, naphthol / aralkyl resin and the like, and the phenol / aralkyl resin represented by the following general formula (XIII) is preferable, and the general formula (XIII) is preferable.
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 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 0 to 10.)

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

[Chemical 15] (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 (XV).

[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 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 biphenyl type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin and novolak 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.

The equivalent ratio of (A) epoxy resin to (B) 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 (the number of hydroxyl groups in the curing agent / the number of epoxy groups in the 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 molding material for sealing which is excellent in moldability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.

(C) Composite metal used in the present invention
Hydroxide acts as a flame retardant, and the effect of the present invention
There is no particular limitation so long as the following composition formula (I) is obtained.
Compounds are preferred.       p (M¹aOb) ・ q (M²cOd) ・ r (M³cOd) / mH₂O (I) (Where M¹, M²And M³Are different metal elements
, A, b, c, d, p, q and m are positive numbers, r is 0 or
Indicates a positive number. ) Among them, compounds in which r in the composition formula (I) is 0,
That is, the compound represented by the following composition formula (Ia) is
Is preferred. m (M¹aOb) ・ n (M²cOd) ・ l (H₂O) (Ia) (Where M¹And M²Are different metal elements,
a, b, c, d, m, n and l represent positive numbers. ) M in the above composition formulas (I) and (Ia)¹And M²Are each other
There is no particular limitation as long as it is a different metal element,
From the point, M¹And M²So that they are not the same ¹Is the third
Periodic metal elements, Group IIA alkaline earth metal elements, IVB
Belong to Group III, Group IIB, Group VIII, Group IB, Group IIIA and Group IVA
Selected from metallic elements to²Is IIIB-IIB group transition gold
It is preferable to be selected from the group elements, M¹Is magnesiu
Aluminum, calcium, aluminum, tin, titanium, iron,
Selected from Baltic, Nickel, Copper and Zinc, M²Is iron,
It may be selected from cobalt, nickel, copper and zinc.
More preferable. From a liquidity point of view, M¹Is magnesiu
M, M²Is preferably zinc or nickel, and M¹
Is magnesium and M²Is more preferably zinc
Yes. The molar ratio of p, q and r in the above composition formula (I) is the present invention.
There is no particular limitation as long as the effect of
And the molar ratio p / q of q is 99/1 to 50/50
Is preferred. That is, m and m in the above composition formula (Ia)
The molar ratio m / n of n is 99/1 to 50/50.
preferable. For the classification of metallic elements, the typical elements are
Group of long-period periodicity table with group B and transition elements
Source: Kyoritsu Shuppan Co., Ltd. “Chemical Dictionary 4” 1987
It was conducted based on the February 15, 15th printing press plate). Compound money
Commercial products of the genus hydroxide include, for example, Tateho Chemical Co., Ltd.
You can get the product name Echo Mag Z-10 manufactured by Shikisha.
Wear.

The shape of the composite metal hydroxide (C) 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 (C) composite metal hydroxide is not particularly limited, but is 0.5 to 2 with respect to the epoxy resin molding material for sealing.
0% by weight is preferable, 0.7 to 15% by weight is more preferable, and 1.4 to 12% by weight is further preferable. If it is less than 0.5% by weight, flame retardancy tends to be insufficient, and if it exceeds 20% by weight, fluidity such as disc flow and reflow resistance tend to be deteriorated.

The inorganic filler (D) used in the present invention is added to the molding material for 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., Or beads such as spheres, glass fibers, and the like,
These may be used alone or in combination of two or more. Among them, fused silica is preferable from the viewpoint of linear expansion coefficient reduction, and alumina is preferable from the viewpoint of high thermal conductivity,
The shape of the filler is preferably spherical from the viewpoint of fluidity at the time of molding and mold wear resistance. (D) The inorganic filler content is flame retardant,
From the viewpoint of moldability, hygroscopicity, reduction of linear expansion coefficient and improvement of strength, 70 to 95% by weight is preferable, and 75 to 92% by weight is more preferable, with respect to the epoxy resin molding material for sealing. 7
If it is less than 0% by weight, flame retardancy and reflow resistance tend to be lowered, and if it exceeds 95% by weight, fluidity tends to be insufficient.

In the encapsulating epoxy resin molding material of the present invention, a curing accelerator (G) can be used, if necessary, in order to accelerate the reaction between the epoxy resin (A) and the curing agent (B). The curing accelerator (G) is generally used in epoxy resin molding materials for sealing and is not particularly limited, but, for example, 1,8-diaza-bicyclo (5,4,4).
0) undecene-7,1,5-diaza-bicyclo (4,
3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 and other cycloamidine compounds, and these compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,
4-naphthoquinone, 2,3-dimethylbenzoquinone,
2,6-dimethylbenzoquinone, 2,3-dimethoxy-
Add quinone compounds such as 5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane and phenol resin. Compounds having intramolecular polarization, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tertiary amines such as tris (dimethylaminomethyl) phenol and derivatives thereof, 2-methylimidazole, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole and other imidazoles and derivatives thereof, phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine And a phosphorus compound having an intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, and a phenol resin to these phosphine compounds, tetraphenylphosphonium tetraphenylborate, triphenylphosphine Tetraphenylboron, 2-ethyl-4-methylimidazole tetraphenylborate, tetraphenylboron salts such as N-methylmorpholine tetraphenylborate and derivatives thereof, and the like can be mentioned. Even if these are used alone, two or more kinds are combined. You may use it. Among them, from the viewpoint of curability and fluidity, a phosphine compound and an adduct of a phosphine compound and a quinone compound are preferable, and a third phosphine compound such as triphenylphosphine and an adduct of a triphenylphosphine and a quinone compound are more preferable. preferable. When a third phosphine compound is used, it is preferable to further contain a quinone compound. Further, from the viewpoint of storage stability, an adduct of a cycloamidine compound and a phenol resin is preferable, and a phenol novolac resin salt of diazabicycloundecene is more preferable.

The compounding amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.005 to 2% by weight with respect to the epoxy resin molding material for sealing. , 0.01 to 0.5% by 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 encapsulating epoxy resin molding material of the present invention may further contain (H) an ion trap agent, if necessary, from the viewpoint of improving the moisture resistance and high temperature storage characteristics of semiconductor elements such as ICs. it can. The (H) ion trap agent is not particularly limited, and conventionally known ones can be used. For example, hydrotalcites and
Magnesium, aluminum, titanium, zirconium,
Examples include hydrous oxides of elements selected from bismuth,
These may be used alone or in combination of two or more. Of these, hydrotalcite represented by the following composition formula (XVI) is preferable. Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XVI) (0 <X ≦ 0.5, m is a positive number) (H) Compounding amount of ion trapping agent Is not particularly limited as long as it is a sufficient amount to capture anions such as halogen ions, but from the viewpoint of fluidity and bending strength, 0.1 to 30% by weight is preferable with respect to the epoxy resin (A), and 0.1. 5-1
0% by weight is more preferable, and 1 to 5% by weight is further preferable.

The encapsulating epoxy resin molding material of the present invention may contain epoxy silane, mercapto silane, amino silane, alkyl silane and ureide, 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. Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycine. Sidoxypropyltrimethoxysilane, 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 -A silane coupling agent such as mercaptopropylmethyldimethoxysilane, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri N- aminoethyl - aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyl-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, Examples of titanate coupling agents such as isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, etc. can be used alone or in combination of two or more. Good. Among them, a silane coupling agent having a secondary amino group is preferable, and an aminosilane coupling agent represented by the following general formula (II) is particularly preferable, from the viewpoint of obtaining fluidity and particularly good disc flow.

[Chemical 17] (Here, R ¹ is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to ² carbon atoms, R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, and R
³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to 3. ) Examples of the aminosilane coupling agent represented by the general formula (II) include γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, and γ.
-Anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilino Methyltriethoxysilane,
γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p-methoxyphenyl) -γ
-Aminopropyltrimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropyltriethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl)- γ-aminopropylmethyldiethoxysilane, N
-(P-methoxyphenyl) -γ-aminopropylethyldiethoxysilane, N- (p-methoxyphenyl)-
γ-aminopropylethyldimethoxysilane and the like can be mentioned. Particularly preferred is γ-anilinopropyltrimethoxysilane.

The compounding amount of the above coupling agent 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).
If it is less than 0.05% by weight, the adhesiveness to the frame tends to decrease, the disc flow decreases, the wire flow,
Molding defects such as voids are likely to occur. If it exceeds 5% by weight, the moldability of the package tends to decrease.

The encapsulating epoxy resin molding material of the present invention may optionally contain a conventionally known non-halogen or non-antimony flame retardant for the purpose of further improving flame retardancy. For example, inorganic compounds such as red phosphorus and zinc oxide, and phosphorus compounds such as red phosphorus and phosphoric acid ester coated with a thermosetting resin such as phenol resin, melamine, melamine derivatives, melamine-modified phenol 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, aluminum hydroxide, magnesium hydroxide, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, molybdic acid Examples thereof include compounds containing a metal element such as zinc and dicyclopentadienyl iron. These may be used alone or in combination of two or more. Of these, phosphoric acid esters are preferable from the viewpoint of fluidity and obtaining a particularly good disc flow. The phosphoric acid ester is not particularly limited as long as it is an ester compound of phosphoric acid and an alcohol compound or a phenol compound, for example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, Examples thereof include xylenyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, and condensed aromatic phosphate ester. Among them, the aromatic condensed phosphoric acid ester represented by the following general formula (III) is preferable from the viewpoint of hydrolysis resistance.

[Chemical 18] Examples of the phosphoric acid ester of the above formula (III) include phosphoric acid esters represented by the following structural formulas (XVII) to (XXI).

[Chemical 19] The addition amount of these phosphoric acid esters is 0.2 to 3.0% by weight in terms of phosphorus atom with respect to all the other compounding ingredients except the filler.
It is preferably within the range. If the amount is less than 0.2% by weight, the flow of the disc is reduced, and wire defects, voids and other molding defects are likely to occur. Further, since it has a flame retardant effect, when it is also used as a flame retardant, the flame retardant effect tends to be low. If it exceeds 3.0% by weight, moldability,
There is a case where the moisture resistance is lowered, or these phosphates are exuded during molding, which impairs the appearance.

Further, in the encapsulating epoxy resin molding material 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 polyethylene oxide,
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 epoxy resin molding material for sealing of the present invention is
From the viewpoint of suppressing the occurrence of molding defects such as wire flow and voids, it is necessary that the disc flow be 80 mm or more. Here, the disc flow is an index showing fluidity under a load of 78 N, and 5 g of the epoxy resin molding material for sealing is applied at a mold temperature of 180 ° C., a load of 78 N, and a curing time of 9
The average value of the measured values of the major axis and the minor axis of the molded product molded under the condition of 0 seconds. By using a sealing epoxy resin molding material having a disc flow of 80 mm or more, it is possible to reduce the occurrence of molding defects such as wire flow and voids even in a thin semiconductor device having a long wire and a narrow pad pitch. Become. In the present invention, the disc flow is 80 mm or more by adjusting the combination and blending amount of the components used as (A) epoxy resin, (B) curing agent, (C) complex metal hydroxide and other additives. It is possible to obtain an epoxy resin molding material for sealing which is
It is more preferable to contain (E) a silane coupling agent having a secondary amino group and / or (F) a phosphoric acid ester so that the disc flow is 80 mm or more.

The epoxy resin molding material for sealing of the present invention is
As long as various raw materials can be uniformly dispersed and mixed, it can be prepared by any method, but as a general method,
A method may be mentioned in which a predetermined amount of raw materials are sufficiently mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder or the like, and then cooled and pulverized. 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 provided with the element encapsulated by the encapsulating epoxy resin molding material obtained in the present invention can be used as a supporting member such as a lead frame, a wired tape carrier, a wiring board, glass, and a silicon wafer. , Semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors, elements such as passive elements such as coils are mounted, and necessary parts are sealed with the epoxy resin molding material for sealing of the present invention, Examples include electronic component devices.
As such an electronic component device, for example, after fixing a semiconductor element on a lead frame and connecting the terminal portion of the element such as a bonding pad and the lead portion by wire bonding or bump, the sealing epoxy resin of the present invention is used. DI formed by transfer molding using a molding material
P (Dual Inline Package), PLCC (Plastic Leade)
d Chip Carrier), QFP (Quad Flat Package), S
OP (Small Outline Package), SOJ (Small Outli
ne J-lead package), TSOP (Thin Small Outline)
Package), TQFP (Thin Quad Flat Package), and other general resin-sealed ICs, TCP (Tape Carrier) in which a semiconductor chip connected to a tape carrier by bumps is encapsulated with the encapsulating epoxy resin molding material of the present invention. Package), 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 and coils. A device is formed on the surface of a COB (Chip On Board) module, a hybrid IC, a multi-chip module in which an element is encapsulated with the encapsulating epoxy resin molding material of the present invention, and an organic substrate on which terminals for connecting wiring boards are formed on the back surface. Equipped with,
BGA (Ball Grid Ar) in which the element and the wiring formed on the organic substrate are connected by bumps or wire bonding and then the element is encapsulated by the encapsulating epoxy resin molding material of the present invention.
ray), CSP (Chip Size Package), and the like. Further, the epoxy resin molding material for sealing of the present invention can be effectively used for printed circuit boards.

As a method of encapsulating an element using the encapsulating epoxy resin molding material of the present invention, the low pressure transfer molding method is the most general method.
A compression molding method or the like may be used.

[0034]

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 11 and Comparative Examples 1 to 6 As an epoxy resin, epoxy equivalent 196, melting point 106
C. Biphenyl type epoxy resin (Japan Epoxy Resin Co., Ltd. trade name Epicoat YX-4000H), epoxy equivalent 186, melting point 75 ° C. bisphenol F type epoxy resin (Nippon Steel Chemical Co., Ltd. trade name YSLV-8)
0XY), epoxy equivalent 210, melting point 120 ° C. stilbene type epoxy resin (trade name E manufactured by Sumitomo Chemical Co., Ltd.
SLV-210), epoxy equivalent 245, melting point 110 ° C.
Sulfur atom-containing epoxy resin (trade name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd.) and epoxy equivalent 195,
O-cresol novolac type epoxy resin having a softening point of 65 ° C. (trade name ESCN-19 manufactured by Sumitomo Chemical Co., Ltd.)
0), a phenol / aralkyl resin having a softening point of 70 ° C. and a hydroxyl equivalent of 175 as a curing agent (trade name Milex XL-225 manufactured by Mitsui Chemicals, Inc.), a biphenyl type phenol resin having a softening point of 80 ° C. and a hydroxyl equivalent of 199 (Meiwa Kasei Corporation Company name MEH-7851), softening point 80 ° C., phenolic novolac resin with a hydroxyl equivalent of 106 (Meiwa Kasei Co., Ltd. product name H-1), triphenylphosphine and p-benzoquinone adduct as a curing accelerator (curing) Accelerator), γ-anilinopropyltrimethoxysilane (anilinosilane) as a coupling agent, γ-glycidoxypropyltrimethoxysilane (epoxysilane), an aromatic condensed phosphoric acid ester as a phosphoric acid ester (manufactured by Daihachi Chemical Co., Ltd. Name PX-200), triphenyl phosphate,
As a flame retardant, Tateho Chemical Co., Ltd. composite metal hydroxide Echomag Z-10, antimony trioxide and epoxy equivalent 375,
Bisphenol A with a softening point of 80 ° C and a bromine content of 48% by weight
Type brominated epoxy resin (Sumitomo Chemical Co., Ltd. trade name ESB-400T), average particle size 1 as an inorganic filler
Table 1 shows spherical fused silica having 7.5 μm and a specific surface area of 3.8 m ² / g, carnauba wax (manufactured by Clariant) and carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Co., Ltd.) as other additives. Parts were mixed in parts by weight, and roll kneading was carried out under the conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes to prepare epoxy resin molding materials for encapsulation of Examples 1 to 11 and Comparative Examples 1 to 6.

[0036]

[Table 1]

The encapsulating epoxy resin molding materials of Examples and Comparative Examples produced were evaluated by the following tests. The results are shown in Table 2. The epoxy resin molding material for sealing 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) Spiral flow Using a mold for spiral flow measurement according to EMMI-1-66, the epoxy resin molding material for sealing is molded by a transfer molding machine at a mold temperature of 180 ° C and a molding pressure of 6.9M.
Molded under the conditions of Pa and curing time of 90 seconds, flow distance (c
m) was calculated. (2) Disc flow 200 mm (W) x 200 mm (D) x 25 mm (H)
Upper mold and 200mm (W) × 200mm (D) × 15m
A sample (epoxy resin molding material for sealing) precisely weighed using a flat plate mold for disc flow measurement having a lower mold of m (H) 5
g on the center of the lower mold heated to 180 ° C, and after 5 seconds,
The upper mold heated to 180 ° C. is closed, compression molding is performed under the conditions of a load of 78 N and a curing time of 90 seconds, and the major axis (mm) and the minor axis (mm) of the molded product are measured with a caliper, and the average value (m
m) is the disc flow. (3) 50 mm diameter of the epoxy resin molding material for hot hardness sealing under the above conditions
C. A disk having a thickness of 3 mm was molded and measured immediately after molding using a Shore D hardness meter. (4) Flame-retardant Using a mold for molding a test piece having a thickness of 1/16 inch,
Mold the epoxy resin molding material for encapsulation under the above conditions and
Post-curing was performed at 0 ° C for 5 hours, and flame retardancy was evaluated according to the UL-94 test method.

[0038]

[Table 2]

Fabrication of Semiconductor Device (LQFP) Next, a semiconductor device was fabricated using the fabricated epoxy resin molding materials of Examples and Comparative Examples. The sealing with the epoxy resin molding material for sealing is performed by using a transfer molding machine at a mold temperature of 180 ° C. and a molding pressure of 6.9 MP.
a, molding was performed under the condition that the curing time was 90 seconds, and then post-curing was performed at 180 ° C. for 5 hours. Using the encapsulating epoxy resin molding materials of Examples and Comparative Examples, 10 mm × 10 mm
× 0.4 mm (area 100 mm ² ), pad pitch 80
Equipped with a test silicon chip of μm, diameter 18μ
m, wire bonding with a maximum length of 3 mm of a gold wire, outer shape 20 mm × 20 mm, thickness of encapsulant on top of semiconductor chip 0.5 mm, thickness of encapsulant on back of semiconductor chip 0. 5 mm, total thickness of semiconductor device 1.5
mm semiconductor device of Examples 1 to 14 (100-pin LQF
P) was prepared.

Next, using the semiconductor device manufactured as described above, the amount of wire deformation and the amount of void generation were measured as follows. The results are shown in Table 3. (5) Amount of wire deformation (index of wire flow) Soft X-ray measuring device (PRO-TEST 100 manufactured by Softex)
Type), the amount of wire deformation was obtained by performing a transparent observation of the semiconductor device under the conditions of a voltage of 100 kV and a current of 1.5 mA, and the wire flow was evaluated. As shown in FIG. 1, the observation is performed in a direction perpendicular to the frame surface, and the shortest wire bonding distance L (the linear distance connecting the terminal portion 3 of the semiconductor chip 1 and the lead 4) and the maximum displacement amount X of the wire 2 are measured. Then, X / L × 100 was defined as the wire deformation amount (%). (6) Void generation amount The semiconductor device is subjected to perspective observation in the same manner as in (5) above,
The presence / absence of voids having a diameter of 0.1 mm or more was observed and evaluated by the number of voided semiconductor devices / the number of test semiconductor devices.

[0041]

[Table 3]

Next, using the epoxy resin molding materials for encapsulation prepared in Examples and Comparative Examples, semiconductor devices were prepared as follows and various reliability tests were conducted. The results are shown in Table 4. (7) Reflow resistance A 80-pin flat package with external dimensions of 20 mm × 14 mm × 2 mm, which is mounted with a silicone chip of 8 mm × 10 mm × 0.4 mm, is molded under the above conditions using a sealing epoxy resin molding material, and post-cured. Manufactured at 85 ℃, 8
Humidify under the condition of 5% RH at a predetermined time every 240 ° C for 10
Reflow treatment was performed under the condition of seconds, and 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). (8) Moisture resistance 6 mm with aluminum wiring having a line width of 10 μm and a thickness of 1 μm
80 with external dimensions of 19 mm x 14 mm x 2.7 mm mounted with a test silicone chip of x 6 mm x 0.4 mm
A pin-flat package is molded by using an epoxy resin molding material for encapsulation under the above conditions, and post-cured to make it.After pre-treatment, humidification is performed and a disconnection defect due to aluminum wiring corrosion is checked every predetermined time, The number of defective packages to the number of test packages (10) was evaluated. The pretreatment is 85 ° C,
After humidifying the flat package under the conditions of 85% RH and 72 hours, vapor phase reflow treatment was performed at 215 ° C. for 90 seconds. Humidification after that is 0.2 MPa, 121 ℃
It went on condition of. (9) High-temperature storage property A test package manufactured in the same manner as in (8) above was used for 200
The sample was stored in a high temperature tank at a temperature of ℃, taken out at a predetermined time, and subjected to a continuity test.

[0043]

[Table 4]

Comparative Example 5 containing no (C) composite metal hydroxide in the present invention has low flame retardancy and does not achieve UL-94 V-0. Further, Comparative Example 4 using only the phosphoric acid ester is inferior in moisture resistance, and Comparative Example 6 using the brominated epoxy resin and the antimony compound is inferior in high temperature storage property. (C) Although the composite metal hydroxide is included, Comparative Examples 1 to 4 which do not satisfy the requirement that the disc flow is 80 mm or more have large wire deformation amounts and void generation amounts. On the other hand, Examples 1 to 11 which include all the components (A) to (C) of the present invention and have a disc flow of 80 mm or more are non-halogen and non-antimony and achieve UL-94 V-0. It exhibits flame retardancy, less wire deformation and void generation, and has good reliability such as reflow resistance, moisture resistance, and high temperature storage property.

[0045]

The encapsulating epoxy resin molding material of the present invention can achieve flame retardancy with non-halogen and antimony as shown in the examples, and by using this, electronic parts such as IC and LSI are encapsulated. If so, the moldability is good, the reliability such as reflow resistance, moisture resistance and high temperature storage property is good, and its industrial value is great.

[Brief description of drawings]

FIG. 1 is a diagram showing a method of measuring a wire deformation amount.

[Explanation of symbols]

1: Semiconductor chip 2: Wire 3: Terminal part (bonding pad) 4: Terminal part of wiring board

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshihiro Takahashi             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) 4J036 AA02 AB01 AC01 AC05 AD08                       AD10 AD15 AD20 AD21 AF01                       AF05 AF06 AF15 AF27 AG04                       AG06 AG07 AH04 AJ05 AJ08                       AJ17 AJ19 DA01 DA02 DA04                       DC03 DC11 DC12 DC40 DC41                       DC46 DD07 DD09 FA03 FA12                       FA13 FB07 JA07                 4M109 AA01 CA21 EB07

Claims (14)

[Claims] 1. An epoxy resin (A), a curing agent (B),
(C) An epoxy resin molding material for encapsulation, which contains a composite metal hydroxide as an essential component and has a disc flow of 80 mm or more. 2. The epoxy resin molding material for sealing according to claim 1, further comprising (D) an inorganic filler. 3. The epoxy resin molding material for encapsulation according to claim 1, wherein (C) the composite metal hydroxide is a compound represented by the following composition formula (I). p (M ¹ aOb) · q (M ² cOd) · r (M ³ cOd) · mH ₂ O (I) (wherein M ¹ , M ² and M ³ represent different metal elements, and a, b , C, d, p, q and m are positive numbers, and r is 0 or a positive number.) 4. M ¹ and M ² are the M ¹ so as not the same metal element of the third period in the composition formula (I), IIA group alkaline earth metal elements, IVB Group, IIB group, VIII group , IB, II
Selected from metal elements belonging to Group IA and Group IVA, where M ² is II
The encapsulating epoxy resin molding material according to claim 3, which is selected from the group IB to IIB transition metal elements. 5. M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc so that M ¹ and M ² in the composition formula (I) are not the same. ^The epoxy resin molding material for sealing according to claim 4, wherein ² is selected from iron, cobalt, nickel, copper and zinc. 6. The encapsulating epoxy resin molding material according to claim 5, wherein M ¹ in the composition formula (I) is magnesium and M ² is zinc or nickel. 7. The composition formula (I), wherein r = 0 and the molar ratio p / q of p and q is 99/1 to 50/50.
The epoxy resin molding material for sealing according to any one of 6 above. 8. The encapsulating epoxy resin molding material according to claim 1, further comprising (E) a silane coupling agent having a secondary amino group. 9. The encapsulating epoxy resin molding material according to claim 8, wherein (E) the silane coupling agent having a secondary amino group contains a compound represented by the following general formula (II). [Chemical 1] (Here, R ¹ is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to ² carbon atoms, R ² is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, and R
³ represents a methyl group or an ethyl group, n represents an integer of 1 to 6, and m represents an integer of 1 to 3. ) 10. The epoxy resin molding material for encapsulation according to claim 1, further comprising (F) a phosphoric acid ester. 11. The encapsulating epoxy resin molding material according to claim 10, wherein the phosphoric acid ester (F) contains a compound represented by the following general formula (III). [Chemical 2] (Here, 8 R's in the formula represent an alkyl group having 1 to 4 carbon atoms and may be the same or different. Ar represents an aromatic ring.) 12. The (A) epoxy resin is a biphenyl type epoxy resin, a bisphenol F 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 The epoxy resin molding material for encapsulation according to claim 1, containing at least one triphenylmethane type epoxy resin. 13. 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. 13. The epoxy resin molding material for sealing according to any one of 12. 14. An electronic component device comprising an element encapsulated with the epoxy resin molding material for encapsulation according to any one of claims 1 to 13.