JP2003012772A - Epoxy resin molding material for sealing and electronic part device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin molding material for sealing, free from a halogen and antimony, and having good flame retardancy without reducing the reliability such as moldability, resistance to solder-reflow, moisture resistance and characteristics after being left at high temperatures, and further to provide an electronic part device having an element sealed with the molding material. SOLUTION: The epoxy resin molding material for sealing comprises (A) an epoxy resin and (B) a curing agent as essential components, and is regulated so that the curing agent (B) may contain a phenol resin represented by formula (I) (wherein, R<1> , R<2> and R<3> are each selected from hydrogen atom, a substituted or unsabstituted 1-10C hydrocarbon group and a substituted or unssabstituted 1-10C alkoxy group, and are same or different; and (m) and (n) are each an integer of 0-10).

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. The present invention relates to a molding material suitable for required VLSI 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. There is a problem of deterioration of fluidity and deterioration of moisture resistance, and a problem of deterioration of fluidity when a metal hydroxide or metal oxide is used or when a proportion of a filler is increased. Further, when an organometallic compound is used, there is a problem that the curing reaction is obstructed 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 molding material 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 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 material for encapsulation containing a specific curing agent. The present invention was found and the present invention was completed.

That is, according to the present invention, (1) an epoxy resin (A) and a curing agent (B) are essential components, and the curing agent (B) contains a phenol resin represented by the following general formula (I) for sealing. Epoxy resin molding material,

[Chemical 3] (Here, R ¹ , R ² and R ³ are selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, all of which are They may be the same or different. M and n represent an integer of 1 to 10.) (2) The (A) epoxy resin contains the epoxy resin represented by the following general formula (II). Epoxy resin molding material for sealing,

[Chemical 4] (Here, R ¹ , R ² and R ³ are selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, all of which are They may be the same or different. M and n represent an integer of 1 to 10.) (3) (A) The epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a sulfur atom-containing epoxy resin, a novolac type epoxy resin. 1 or 2 selected from dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and triphenylmethane type epoxy resin
The epoxy resin molding material for encapsulation according to the above (1) or (2), containing at least one kind, (4) The above (1) to (C) further containing a curing accelerator.
(5) (C) an addition product of a phosphine compound and a quinone compound and / or a phenol novolac resin salt of diazabicycloundecene, wherein the epoxy resin molding material for encapsulation according to any one of (3). The epoxy resin molding material for encapsulation according to (4) above, which further comprises (6) (C) the curing accelerator contains a third phosphine compound, and further comprises a quinone compound according to (4) or (5) above. Epoxy resin molding material for sealing, (7) The above (1) to (D) further containing an inorganic filler.
An epoxy resin molding material for encapsulation according to any one of (6), and (8) an element encapsulated with the epoxy resin molding material for encapsulation according to any of (1) to (7) above. Electronic component device.

[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, diaminodiphenylmethane, isocyanuric acid, and other polyamines, glycidylamine type epoxy resins obtained by reaction of epichlorohydrin, epoxidized products of co-condensed resins of dicyclopentadiene and phenols, epoxy resins having naphthalene ring, phenols and / or
Alternatively, a phenol / aralkyl resin synthesized from naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, an epoxide of an aralkyl type phenol resin such as a naphthol / aralkyl resin, a trimethylolpropane type epoxy resin, a terpene modified epoxy resin, an olefin Examples thereof include linear aliphatic epoxy resins, alicyclic epoxy resins, and sulfur atom-containing epoxy resins obtained by oxidizing the bond with a peracid such as peracetic acid. Even if one of these is used alone, two or more kinds are used. You may use in combination. Among them, from the viewpoint of flame retardancy, an aralkyl type epoxy resin which is an epoxidized product of an aralkyl type phenol resin such as phenol / aralkyl resin and naphthol / aralkyl resin is preferable, and an epoxy resin represented by the following general formula (II) is more preferable. Preferably, R ¹ and R ^{2 in} the general formula (II) are
And R ³ is more preferably a hydrogen atom.

[Chemical 5] Here, R ¹ , R ² and R ³ are selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, all of which are the same. But it can be different. m and n show the integer of 1-10. (R ² ) ₄ represents 4 R ² , and (R ³ ) ₄ represents 4 R ³ . As R ^{1 to} R ³ in the general formula (II),
For example, hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group, alkyl group such as isobutyl group, alkenyl group such as vinyl group, allyl group, butenyl group, phenyl group, tolyl group, xylyl group, etc. Aralkyl group such as aryl group, benzyl group, phenethyl group, amino group-substituted alkyl group, mercapto group-substituted alkyl group, alkenyl group-substituted alkyl group, alkyl group-substituted aryl group, alkyl group-substituted aralkyl group, etc. A substituted or unsubstituted alkoxyl group having 1 to 10 carbon atoms, such as a hydrocarbon group, a methoxy group, an ethoxy group, a propoxy group and a butoxy group, an alkyl group-substituted alkoxyl group, an amino group-substituted alkoxyl group and the like. Group, among them, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is Ri preferred. In the formula (m + n +
1) R ¹ , (8 × m) R ² , (4 × n) R ³
Are all the same or different, and R
¹ , R ² and R may be the same or different. The epoxy resin represented by the general formula (II) is a copolymer of repeating units represented by () m and () n,
A random copolymer in which these repeating units are randomly bonded, a copolymer in which they are alternately bonded, or a block copolymer may be used, but from the viewpoint of flame retardancy, it is random. Copolymers or alternating copolymers are preferred. The copolymerization ratio m / n is not particularly limited, but the weight ratio is preferably 10 to 0.1, more preferably 5 to 0.5. If the weight ratio m / n is less than 0.1, the flame retardancy tends to decrease, and if it exceeds 10, the moldability tends to decrease. The compounding amount of the aralkyl type epoxy resin is preferably 50% by weight or more, more preferably 60% by weight or more, and further preferably 80% by weight or more with respect to the total amount of the (A) epoxy resin in order to exert its performance. preferable.

From the viewpoint of reflow resistance, biphenyl type epoxy resin, stilbene type epoxy resin and sulfur atom-containing epoxy resin are preferable, from the viewpoint of curability, novolac type epoxy resin is preferable, and from the viewpoint of low hygroscopicity. A dicyclopentadiene type epoxy resin is preferable, a naphthalene type epoxy resin and a triphenylmethane type epoxy resin are preferable from the viewpoint of heat resistance and low warpage, and one or more kinds selected from these epoxy resins are contained. Is preferred.

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

[Chemical 6] (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 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] (Here, R ^{1 to} R ⁸ are a hydrogen atom, a substituted or unsubstituted C 1-10 alkyl group, and a substituted or unsubstituted C 1
Selected from alkoxy groups of 10 to 10, all of which may be the same or different. n shows the integer of 0-3. )

The biphenyl type epoxy resin represented by the general formula (III) is, for example, 4,4'-bis (2,3-epoxypropoxy) biphenyl or 4,4'-bis (2,3-epoxypropoxy) biphenyl.
4'-bis (2,3-epoxypropoxy) -3,
Epoxy resin containing 3 ', 5,5'-tetramethylbiphenyl as a main component, epichlorohydrin and 4,4'-biphenol or 4,4'-(3,3 ', 5,5'-tetramethyl) biphenol Examples thereof include epoxy resins obtained by the reaction. Among them, 4,4'-bis (2,3
-Epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl-based epoxy resin is preferred. The stilbene type epoxy resin represented by the above general formula (IV) can be obtained by reacting the raw material stilbene phenols 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 general formula (V), R ¹ , R ⁴ , R ⁵ and R ⁸ are hydrogen atoms and R ² , R ³ , R ⁶ and R ⁷ are alkyl groups. Epoxy resins are preferred, R ¹ , R ⁴ , R ⁵ and R ⁸
Is more preferably a hydrogen atom, R ² and R ⁷ are methyl groups, and R ³ and R ⁶ are t-butyl groups. As such a compound, YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd.) and the like are commercially available. These biphenyl type epoxy resins, stilbene type epoxy resins, and sulfur atom-containing epoxy resins may be used alone or in combination of two or more kinds, but the blending amount shows the performance. Therefore, the total amount of the epoxy resin (A) is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 50% by weight or more.

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

[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 (VI). The novolac type epoxy resin is obtained by reacting a novolac type phenol resin with epichlorohydrin. R in the general formula (VI) is an alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, methoxy group, ethoxy group, propoxy group, butoxy group, etc. Is preferably an alkoxyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a methyl group. n is preferably an integer of 0 to 3. Among the novolac type epoxy resins represented by the general formula (VI), orthocresol novolac type epoxy resins are preferable. When using a novolac type epoxy resin, the compounding amount is
In order to exert its performance, it is preferably 20% by weight or more, and 30% by weight based on the total amount of (A) epoxy resin.
The above is more preferable.

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

[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 (VII), 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 the 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 (A) in order to exert its performance.

The naphthalene type epoxy resin includes, for example, an epoxy resin represented by the following general formula (VIII), and the triphenylmethane type epoxy resin includes, for example, an epoxy resin represented by the following general formula (IX). . Examples of the naphthalene-type epoxy resin represented by the following general formula (VIII) include a random copolymer containing 1 constitutional unit and m constitutional units at random, an alternating copolymer containing alternating constitutional units, and a copolymerization containing regularly. Examples thereof include a block copolymer and a block copolymer containing a block. Any one of these may be used alone, or two or more thereof may be used in combination. The triphenylmethane type epoxy resin represented by the following general formula (IX) is not particularly limited, but salicylaldehyde type epoxy resin is preferable.

[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. )

[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.) These naphthalene type epoxy resins and triphenyl The methane type epoxy resin may be used alone or in combination of two types, but the compounding amount thereof is 20 in total with respect to the total amount of the (A) epoxy resin in order to exert its performance. It is preferably not less than 30% by weight, more preferably not less than 30% by weight, still more preferably not less than 50% by weight.

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 can be used. May be used alone or in combination of two or more, but the compounding amount thereof is preferably 20% by weight or more in total with respect to the total amount of the epoxy resin (A), and more preferably 40% by weight or more. It is preferably 50% by weight or more, and further preferably.

The (B) curing agent used in the present invention is required to contain a phenol resin represented by the following general formula (I). Above all, from the viewpoint of flame retardancy,
It is preferable that R ¹ , R ² and R ^{3 in the following} general formula (I) are hydrogen atoms.

[Chemical 13] Here, R ¹ , R ² and R ³ are each a hydrogen atom or a carbon number of 1 to
10 represents a substituted or unsubstituted hydrocarbon group or an alkoxy group, which may be the same or different. m and n are 1 to 1
Indicates an integer of 0. (R ² ) ₄ represents four R ² ,
(R ³ ) ₄ represents 4 R ³ . R in the general formula (I)
Examples of ^{1 to} R ³ 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 an isobutyl group, an alkenyl group such as a vinyl group, an allyl group and a butenyl group, a phenyl group, Aryl groups such as tolyl and xylyl groups, aralkyl groups such as benzyl and phenethyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups, alkenyl group-substituted alkyl groups, alkyl group-substituted aryl groups, alkyl group-substituted aralkyl groups, etc. A substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, an alkoxyl group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an alkyl group-substituted alkoxyl group, an amino group-substituted alkoxyl group, or the like. Carbon number 1
The alkoxy group of 10 is mentioned, Especially, a hydrogen atom or a methyl group is preferable and a hydrogen atom is more preferable. In the formula, (m + n + 1) R ¹ , (8 × m) R ² , (4 ×
n) R ^{3 s} may all be the same or different, and R ¹ , R ² and R may be the same or different. The phenol resin represented by the above general formula (I) is
Although it is a copolymer of repeating units represented by () m and () n, whether it is a random copolymer in which these repeating units are randomly bonded or a copolymer in which they are alternately bonded, Although it may be a block copolymer, a random copolymer or an alternating copolymer is preferable from the viewpoint of flame retardancy. The copolymerization ratio m / n is not particularly limited, but the weight ratio is preferably 10 to 0.1, more preferably 5 to 0.5. If the weight ratio m / n is less than 0.1, the flame retardancy tends to decrease, and if it exceeds 10, the moldability tends to decrease. The compounding amount of the phenol resin represented by the general formula (I) is preferably 50% by weight or more, more preferably 60% by weight or more, and more preferably 80% by weight based on the total amount of the curing agent (B) in order to exert its performance. It is more preferably at least wt%.

In addition to the phenol resin represented by the above general formula (I), conventionally known curing agents may be used in combination with the epoxy resin molding material for encapsulation and the electronic component device of the present invention. For example, phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, and formaldehyde, benzaldehyde, salicylaldehyde, etc. Novolak-type phenol resin obtained by condensation or co-condensation with a compound having an aldehyde group under acidic catalyst, phenol / aralkyl resin synthesized from phenols and / or naphthols and dimethoxyparaxylene, naphthol / aralkyl resin, etc. Aralkyl-type phenolic resin, diclopentadiene-type phenol novolac resin synthesized by copolymerization from phenols and / or naphthols and cyclopentadiene, Examples thereof include dichloropentadiene type phenolic resins such as futol novolac resins and terpene-modified phenolic resins. These may be used alone or in combination of two or more. Among them, aralkyl type phenolic resin is preferable from the viewpoint of reflow resistance and curability, dicyclopentadiene type phenolic resin is preferable from the viewpoint of low hygroscopicity, and heat resistance, low expansion coefficient and low warpage are preferable. A triphenylmethane type phenol resin is preferable, and a novolac type phenol resin is preferable from the viewpoint of curability.

Examples of the aralkyl type phenol resin include a phenol / aralkyl resin and a naphthol / aralkyl resin, and a phenol / aralkyl resin represented by the following general formula (X) is preferable, and a general formula (X) 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.

[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.) As the dicyclopentadiene type phenol resin, For example, a phenol resin represented by the following general formula (XI) may be mentioned.

[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 An integer of 0 to 6 is shown.) Examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (XII). The triphenylmethane type phenolic resin represented by the following general formula (XII) is not particularly limited, and examples thereof include salicylaldehyde type phenolic resin, o-hydroxybenzaldehyde type phenolic resin, m-hydroxybenzaldehyde type phenolic resin and the like. , One of these may be used alone, or two or more thereof may be used in combination. Among them, salicylaldehyde type phenol resin is preferable.

[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.) Examples of the novolac type phenol resin include phenol. Examples thereof include novolac resin, cresol novolac resin, and naphthol novolac resin. Of these, phenol novolac resin is preferable.

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.

The encapsulating epoxy resin molding material of the present invention may optionally contain (C) a curing accelerator. The (C) curing accelerator is generally used in epoxy resin molding materials for encapsulation and is not particularly limited. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7,1 , 5-diaza-bicyclo (4,3,0)
Cycloamidine compounds such as nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 and maleic anhydride, 1,4
-Benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-
1,4-benzoquinone, 2,3-dimethoxy-1,4-
Benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, compounds having π bond such as diazophenylmethane and phenol resin, and compounds having intramolecular polarization, benzyldimethylamine, triethanolamine, dimethylaminoethanol , Tertiary amines such as tris (dimethylaminomethyl) phenol and their derivatives, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and their derivatives, tributylphosphine, methyl Phosphine compounds such as diphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine, and these phosphine compounds with maleic anhydride and the above quinone compound. , A phosphorus compound having an intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane or phenol resin, tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetra Examples thereof include tetraphenylboron salts such as phenylborate and N-methylmorpholine tetraphenylborate, and derivatives thereof. These may be used alone or in combination of two or more. 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 novolak resin salt of diazabicycloundecene is more preferable.

The amount of the (C) curing accelerator compounded is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.005 to 2% by weight based on the epoxy resin molding material for sealing. , 0.01 to 0.5% by weight is more preferable. 0.
If it is less than 005% by weight, the curability in a short time tends to be poor, 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 sealing epoxy resin molding material of the present invention may optionally contain (D) an inorganic filler. (D) The inorganic filler is hygroscopic, has a reduced linear expansion coefficient,
It is added to a molding material for improving thermal conductivity and strength, and examples thereof include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate,
Potassium titanate, silicon carbide, silicon nitride, aluminum nitride,
Examples include powders of boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc., or beads obtained by sphering these, glass fibers, and the like, and two or more of them may be used alone. You may use in combination. 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 amount of the inorganic filler (D) is preferably 70 to 95% by weight with respect to the epoxy resin molding material for sealing. 75-92% by weight
Is more preferable. If it is less than 70% by weight, the flame retardancy and reflow resistance tend to decrease, and if it exceeds 95% by weight, the fluidity tends to be insufficient.

From the viewpoint of improving the moisture resistance and the high-temperature storage property of semiconductor elements such as ICs, the encapsulating epoxy resin molding material of the present invention may further contain an ion trap agent, if necessary. The ion trap agent is not particularly limited, and conventionally known ones can be used, and examples thereof include hydrotalcites, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. , These one
The seeds may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following composition formula (XIII) is preferable.

Embedded image Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XIII) (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,
From the viewpoint of fluidity and bending strength, 0.1 to 30% by weight is preferable, 0.5 to 10% by weight is more preferable, and 1 to 5% by weight is further preferable with respect to the epoxy resin (A).

Further, in the epoxy resin molding material for sealing 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. These are exemplified by 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.
The seeds may be used alone or in combination of two or more.

The content of the coupling agent is preferably 0.05 to 5% by weight, more preferably 0.1 to 2.5% by weight, based on the inorganic filler (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.

The sealing epoxy resin molding material of the present invention may contain a conventionally known non-halogen or non-antimony flame retardant, if necessary. For example, red phosphorus,
Aluminum hydroxide, magnesium hydroxide, inorganic substances such as zinc oxide and / or red phosphorus coated with a thermosetting resin such as a phenol resin, phosphorus compounds such as phosphate ester,
Melamine, melamine derivatives, melamine modified phenolic resins, compounds with triazine ring, cyanuric acid derivatives,
Examples thereof include nitrogen-containing compounds such as isocyanuric acid derivatives, phosphorus- and nitrogen-containing compounds such as cyclophosphazene, aluminum hydroxide, magnesium hydroxide and complex metal hydroxides represented by the following composition formula (XIV).

Embedded image p (M ¹ aOb) · q (M ² cOd) · r (M ³ cOd) · mH ₂ O (XIV) (wherein M ¹ , M ² and M ³ represent different metal elements from each other. , A, b, c, d, p, q and m are positive numbers and r is 0 or a positive number.) In the above composition formula (XIV), M ¹ , M ² and M ³ are different metals from each other. The element is not particularly limited as long as it is an element, but from the viewpoint of flame retardancy, M ¹ is a metal element of the third period, an IIA group alkaline earth metal element, a IVB group, a IIB group, a VIII group, a IB group, and IIIA. Selected from the group consisting of metal elements belonging to the group IVA and MVA, M ² is IIIB
It is preferably selected from the group IIB transition metal elements, and M
¹ is magnesium, calcium, aluminum, tin,
More preferably, it is selected from titanium, iron, cobalt, nickel, copper and zinc, and M ² is selected from iron, cobalt, nickel, copper and zinc. From a liquidity point of view, M ¹
Is magnesium, M ² is zinc or nickel, and r = 0 is preferable. The molar ratio of p, q and r is not particularly limited, but preferably r = 0 and p / q is 1/99 to 1/1. In addition, the classification of metal elements is a periodic table of a long period type in which a typical element is a subgroup A and a transition element is a subgroup B (Source: Kyoritsu Shuppan Co., Ltd. “Chemical Dictionary 4” February 15, 1987) The printing plate No. 30). ) In addition, compounds containing a metal element such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron are listed.
The seeds may be used alone or in combination of two or more.

Further, in the epoxy resin molding material for encapsulation 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 and 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
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, a glass, a silicon wafer and the like. , 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 semiconductor chip is mounted on a COB (Chip On Board) module in which elements are encapsulated with the encapsulating epoxy resin molding material of the present invention, a hybrid IC, a multi-chip module, an interposer substrate on which terminals for connecting to a mother board are formed, and bumps are formed. Or formed on the semiconductor chip and interposer substrate by wire bonding After connecting the wires, BGA sealing the semiconductor chip mounting side with an epoxy resin molding material for sealing of the present invention (Ball Grid Arra
y), CSP (Chip Size Package), MCP (Multi Ch
ip Package) and so on. Further, the epoxy resin molding material for sealing of the present invention can be effectively used for printed circuit boards.

The low-pressure transfer molding method is the most general method for sealing an element using the epoxy resin molding material for sealing of the present invention.
A compression molding method or the like may be used.

[0029]

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 9 As an epoxy resin, an aralkyl type epoxy resin represented by the following general formula (XV), an epoxy resin 1 having a weight ratio m / n of 5 and an epoxy equivalent of 273: 1 An epoxy resin 2 having a weight ratio m / n of 1 and an epoxy equivalent of 260, and an epoxy resin 3 having a weight ratio m / n of 0.1 and an epoxy equivalent of 243, an epoxy equivalent 280, and a biphenylene having a softening point of 60 ° C. Group-containing aralkyl type epoxy resin 4
(Nippon Kayaku Co., Ltd. NC-3000), epoxy equivalent 196, melting point 106 ° C. biphenyl type epoxy resin 5
(Yukaka Shell Epoxy Co., Ltd. product name Epicoat YX
-4000H), an epoxy equivalent of 245, a sulfur atom-containing epoxy resin 6 having a melting point of 110 ° C. (product name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd.), or an epoxy equivalent of 19
5, o-cresol novolac type epoxy resin 7 having a softening point of 65 ° C. (trade name ESCN-1 manufactured by Sumitomo Chemical Co., Ltd.)
90), a aralkyl-type phenol resin represented by the following general formula (XVI) as a curing agent, a phenol resin 1 having a weight ratio m / n of 5 and a hydroxyl equivalent of 195, a weight ratio m / n
Of 1 and a hydroxyl equivalent of 187, and a phenol resin 3 having a weight ratio m / n of 0.1 and a hydroxyl equivalent of 177, a hydroxyl equivalent of 199, and an aralkyl type containing a biphenylene group having a softening point of 80 ° C. Phenolic resin 4
(Meiwa Kasei Co., Ltd., trade name MEH-7851), hydroxyl equivalent 175, softening point 70 ° C. phenol aralkyl resin (phenol resin 5, Mitsui Chemicals, Inc. trade name Milex XL-225), or hydroxyl equivalent 106, softening. Phenol novolac resin (phenol resin 6, trade name H-1 manufactured by Meiwa Kasei Co., Ltd.) at a temperature of 80 ° C., an addition product of triphenylphosphine and 1,4-benzoquinone as a curing accelerator (curing accelerator 1), or 1 , 8-diaza-bicyclo (5,4,0) undecene-7 phenol novolac resin salt (curing accelerator 2), spherical filler with an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g as an inorganic filler Silica, red phosphorus coated with aluminum hydroxide and phenolic resin as a flame retardant (trade name NOVA EXCEL manufactured by Rin Kagaku Kogyo Co., Ltd. 140), or bisphenol A type brominated epoxy resin (Sumitomo Chemical Co., Ltd. trade name ESB-400T) having antimony trioxide and epoxy equivalent 375, softening point 80 ° C., and bromine content 48% by weight, and γ as a coupling agent. -Glycidoxypropyltrimethoxysilane (epoxysilane), carnauba wax (manufactured by Clariant Co.) and carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Co., Ltd.) as other additives in the weights shown in Table 1 and Table 2, respectively. Blended in parts, kneading temperature 80
Roll kneading was performed under conditions of a temperature of 10 minutes 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 9.

[Chemical 19]

[Chemical 20]

[0031]

[Table 1]

[0032]

[Table 2]

The encapsulating epoxy resin molding materials of Examples and Comparative Examples produced were evaluated by the following tests. The results are shown in Tables 3 and 4. The epoxy resin molding material for sealing is molded by a transfer molding machine at a mold temperature of 18
It was carried out under conditions of 0 ° C., molding pressure of 6.9 MPa and 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 molding material for sealing was molded under the above conditions, post-cured, and evaluated for flame retardancy according to the UL-94 test method. (2) Spiral flow (index of fluidity) Using a mold for spiral flow measurement according to EMMI-1-66, the epoxy resin molding material for sealing is molded under the above conditions, and the flow distance (cm) is determined. It was (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) Storage stability Epoxy resin molding material for encapsulation at 30 ° C, humidity 40% RH
The sample was stored in the above environment for a predetermined time, the spiral flow (flow distance) was measured in the same manner as in (2) above, and the storage time at which the flow distance before storage was 90% was obtained. (5) Reflow resistance A 80-pin flat package with external dimensions of 20 mm × 14 mm × 2 mm mounted with a silicone chip of 8 mm × 10 mm × 0.4 mm is molded under the above conditions using an epoxy resin molding material for sealing, 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). (6) Moisture resistance 6 mm with wire width 10 μm and thickness 1 μm aluminum wiring
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, post-cured to make it, and after pretreatment, moisturized and checked for disconnection defects due to aluminum wiring corrosion 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. (7) High-temperature storage property A test package manufactured in the same manner as in (7) 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.

[0034]

[Table 3]

[0035]

[Table 4]

None of the comparative examples of the present invention containing the phenolic resin represented by the general formula (I) satisfy the characteristics of the present invention. That is, Comparative Examples 1 to 3, 6 and 8 were inferior in flame retardancy and did not achieve V-0 in UL-94. Further, Comparative Example 4 using the red phosphorus flame retardant is inferior in moisture resistance. Comparative Examples 5, 7 and 9 using the brominated flame retardant and antimony trioxide are inferior in high temperature storage property. On the other hand, in Examples 1 to 11, UL-94 achieved V-0, and the fluidity, the hardness at the time of heat, the reflow resistance,
Both moisture resistance and high-temperature storage properties are good without deterioration.

[0037]

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. By doing so, 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    F-term (reference) 4J036 AA01 AA05 AB02 AC08 AD20                       AE05 AF06 AF07 AF08 AF26                       AF27 AG07 AH10 AH18 AJ07                       AJ08 DA01 DA02 DB17 DB28                       DC05 DC40 DC46 DD07 DD09                       FA04 FA05 FA08 FA13 FB08                       GA28 HA12 JA07 KA06                 4M109 AA01 CA21 EA02 EA03 EA04                       EB03 EB04 EB07 EC20

Claims (8)

[Claims] 1. An epoxy resin molding material for encapsulation, comprising (A) an epoxy resin and (B) a curing agent as essential components, and (B) a curing agent containing a phenol resin represented by the following general formula (I). [Chemical 1] (Here, R ¹ , R ² and R ³ are selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, all of which are They may be the same or different. M and n are integers of 1 to 10.) 2. The epoxy resin molding material for encapsulation according to claim 1, wherein the epoxy resin (A) contains an epoxy resin represented by the following general formula (II). [Chemical 2] (Here, R ¹ , R ² and R ³ are selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, all of which are They may be the same or different. M and n are integers of 1 to 10.) 3. 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. The epoxy resin molding material for encapsulation according to claim 1 or 2, containing one or more selected from the group consisting of: 4. The epoxy resin molding material for sealing according to claim 1, further comprising (C) a curing accelerator. 5. The curing accelerator (C) contains an adduct of a phosphine compound and a quinone compound and / or a phenol novolac resin salt of diazabicycloundecene.
The epoxy resin molding material for sealing according to the above. 6. The epoxy resin molding material for encapsulation according to claim 4, wherein the curing accelerator (C) contains a third phosphine compound and further contains a quinone compound. 7. The encapsulating epoxy resin molding material according to claim 1, further comprising (D) an inorganic filler. 8. An electronic component device comprising an element encapsulated with the epoxy resin molding material for encapsulation according to claim 1.