JP2003292583A - Epoxy resin molding material and electronic part device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding material slightly causing chip shifts, voids and wire sweeps in a thin surface mounting type package and having excellent reflow resistance and an electronic part device having an element sealed with the epoxy resin molding material. <P>SOLUTION: The epoxy resin molding material consists essentially of (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator and (D) an inorganic filler. The curing agent (B) contains a phenol resin represented by general formula (I) (wherein, R denotes a hydrogen atom, a substituted or an unsubstituted 1-6C alkyl group; m denotes 0 or an integer of 1-2; and n denotes 0 or an integer of 1-10). The amount of the component of the phenol resin in which n is ≥1 is ≤11 wt.%. The content of a polyfunctional phenol resin containing ≥3 phenolic hydroxy groups on the average in one molecule is <10 wt.% in the total amount of the curing agent (B). <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 which is excellent in fluidity and has a small amount of wire shift in the occurrence of chip shift in a thin surface mounting type package, and an excellent reflow resistance, and the epoxy resin molding material. The present invention relates to an electronic component device including an element sealed with a material.

[0002]

2. Description of the Related Art Conventionally, epoxy resin molding materials have been widely used in the field of encapsulating electronic parts such as transistors and ICs. 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. In particular, the combination of the ortho-cresol novolac type epoxy resin and the phenol novolac curing agent has an excellent balance of these, and has become the mainstream of the base resin of the molding material for sealing. In recent years, along with high-density mounting of electronic components on a printed wiring board, surface mount type packages have become the mainstream of electronic component devices, instead of the conventional pin insertion type. Surface mount type ICs, LSIs, etc. are thin and small packages in order to increase the mounting density and lower the mounting height, and the volume occupied by the element with respect to the package is large, and the thickness of the package is It has become very thin.
Especially TSOP (Thin Small Outline Package), TQF
In a package such as P (Thin Quad Flat Package) with a very thin wall, if the epoxy resin molding material for encapsulation has low fluidity, chip shift occurs during molding, and voids may occur due to these shifts. However, the balance of the thicknesses of the upper and lower epoxy resin molding materials is lost, which causes a reduction in reflow resistance. Further, as the mounting density increases, the number of pins per package increases, so that the gold wire used for connecting the element and the lead inside the package is long and the pitch thereof is narrowing. Therefore, when the fluidity of the epoxy molding material is low, deformation of the gold wire (wire sweep) is caused, which causes a malfunction due to contact between the gold wires and disconnection. Therefore, studies have been made to improve the fluidity of the epoxy resin molding material, but the solution has not been sufficiently solved.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has excellent fluidity, less chip shift, voids and wire sweeps in a thin surface mount type package, and excellent reflow resistance. Another object of the present invention is to provide an epoxy resin molding material and an electronic component device including an element sealed with the epoxy resin molding material.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention can achieve the above object with an epoxy resin molding material containing a curing agent having a specific structure. As a result, they have completed the present invention.

That is, the present invention comprises (1) (A) epoxy resin, (B) curing agent, (C) curing accelerator, and (D) inorganic filler as essential components, and (B) curing agent A polyfunctional phenolic resin represented by the following general formula (I), which contains a phenolic resin in which the component amount of n = 1 or more is 11% by weight or less and which contains an average of 3 or more phenolic hydroxyl groups in one molecule. Of (B) is less than 10% by weight based on the total amount of the curing agent.

[Chemical 6] However, in the general formula (I), R represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and m is 0 or 1
The integer of 2 and n show 0 or the integer of 1-10.

(2) In the epoxy resin molding material described in (1) above, it is preferable that the curing agent (B) contains a dicyclopentadiene type phenol resin represented by the following general formula (II).

[Chemical 7] However, in the general formula (II), R ¹ and R ² are independently selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms,
All m may be the same or different. m is 0 or 1
Shows the integer of -6, n shows the integer of 0 or 1-10.

(3) In the epoxy resin molding material described in (2), the average value of n of the dicyclopentadiene type phenol resin represented by the general formula (II) is 0 or more and 0.5 or more.
It is preferably less than.

(4) In the epoxy resin molding material as described in any of (1) to (3) above, it is preferable that the epoxy resin (A) contains an epoxy resin represented by the following general formula (III).

[Chemical 8] However, in the general formula (III), R represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and all m may be the same or different. m represents 0 or an integer of 1 to 2, and n represents an integer of 0 or 1 to 10.

(5) In the epoxy resin molding material described in any one of (1) to (4) above, it is preferable that the epoxy resin (A) contains an epoxy resin represented by the following general formula (IV).

[Chemical 9] However, in the general formula (IV), R ¹ and R ² are independently selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and all m may be the same or different. m represents 0 or an integer of 1 to 6, and n represents an integer of 0 or 1 to 10.

(6) In the epoxy resin molding material according to any one of (1) to (5), it is preferable that the epoxy resin (A) contains an epoxy resin represented by the following general formula (V).

[Chemical 10] However, in the general formula (V), R ¹ is selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and all may be the same or different. R ² and R ³ represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and m
Represents an integer of 0 or 1 to 4, and n represents an integer of 0 or 1 to 5.

(7) In the epoxy resin molding material according to any one of (1) to (6) above, it is preferable that (A) the epoxy resin contains at least one of a sulfur atom-containing epoxy resin and a biphenyl type epoxy resin. .

The present invention also relates to an electronic component device having an element sealed with the epoxy resin molding material according to any one of the above (1) to (7).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Used in the Present Invention
The epoxy resin is generally used in the epoxy resin composition for sealing and is not particularly limited. For example, phenols such as phenol novolac type epoxy resin, ortho-cresol novolac type epoxy resin, epoxy resin having a triphenylmethane skeleton, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol A, and / or α and the like. -Naphthols such as naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde,
A novolak type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation with a compound having an aldehyde group such as salicylaldehyde under an acidic catalyst; bisphenol A, bisphenol F, bisphenol S
Such as diglycidyl ether of bisphenol (bisphenol type epoxy resin); diglycidyl ether such as alkyl-substituted or unsubstituted biphenol (biphenyl type epoxy resin); stilbene type epoxy resin; hydroquinone type epoxy resin; phthalic acid, dimer acid, etc. Glycidyl ester type epoxy resin obtained by reaction of polybasic acid and epichlorohydrin; glycidyl amine 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 (Dicyclopentadiene type epoxy resin); Epoxy resin having naphthalene ring (naphthalene type epoxy resin); Phenol / aralkyl resin, naphthol / aralkyl resin Epoxidized aralkyl type phenolic resin such as; trimethylolpropane type epoxy resin; terpene modified epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; alicyclic epoxy resin; Examples thereof include sulfur atom-containing epoxy resins. These may be used alone or in combination of two or more. Among them, a novolac type epoxy resin is preferable from the viewpoint of curability, it is preferable to contain a dicyclopentadiene type epoxy resin from the viewpoint of low hygroscopicity, and diglycidyl bisphenol from the viewpoint of reflow resistance and wire sweep. It is preferable to contain an ether (bisphenol type epoxy resin), a sulfur atom-containing epoxy resin or a biphenyl type epoxy resin.

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

[Chemical 11] (Here, R is a hydrogen atom, or a substituted or unsubstituted carbon number 1 to
6 represents an alkyl group, and all m may be the same or different. m represents 0 or an integer of 1 to 2, and n represents an integer of 0 or 1 to 10. The novolac type epoxy resin represented by the general formula (III) can be easily obtained by reacting a novolac type phenol resin with epichlorohydrin. Among them, R in the general formula (III) is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, an alkyl group having 1 to 6 carbon atoms such as a t-butyl group. A hydrogen atom or a methyl group is more preferable, and a methyl group is further preferable. m is preferably 0 or 1, and more preferably 1. n is preferably 0 or an integer of 1 to 5. As a preferable structure of the novolac type epoxy resin represented by the general formula (III), for example, an orthocresol novolac type epoxy resin represented by the following general formula (VI) can be mentioned. When using the novolac type epoxy resin, the compounding amount is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 40% by weight or more based on the total amount of the epoxy resin in order to exert its performance. preferable.

[Chemical 12] (Here, n represents 0 or an integer of 1 to 5.)

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

[Chemical 13] (Here, R ¹ and R ² are independently selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and all m may be the same or different. M is an integer of 0 or 1 to 6. And n is 0 or an integer of 1 to 10.) As R ¹ in the above formula (IV), for example, a hydrogen atom,
C1-C6 such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group
And an alkyl group such as a methyl group or an ethyl group and a hydrogen atom are preferable, and a methyl group and a hydrogen atom are more preferable. Examples of R ² include hydrogen atom, methyl group, ethyl group, propyl group, butyl group,
Examples thereof include an alkyl group having 1 to 6 carbon atoms such as an isopropyl group, an isobutyl group and a t-butyl group, and among them, a hydrogen atom is preferable. m is preferably 0 or 1, and more preferably 0. n is preferably 0 or an integer of 1 to 5. A preferred structure of the dicyclopentadiene type epoxy resin represented by the above general formula (IV) is, for example, the following general formula (VII)
A dicyclopentadiene type epoxy resin represented by When the dicyclopentadiene type epoxy resin is used, the compounding amount thereof is preferably 1 to 30% by weight, more preferably 5 to 20% by weight based on the total amount of the epoxy resin in order to exert its performance.

[Chemical 14] (Here, n represents 0 or 1.)

Examples of the diglycidyl ether of bisphenol (bisphenol type epoxy resin) include epoxy resins represented by the following general formula (V).

[Chemical 15] (Here, R ¹ is a hydrogen atom, a substituted or unsubstituted C 1
Selected from alkyl groups of 6 to 6, all of which may be the same or different. R ² and R ³ represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and m is 0 or 1 to 4
Is shown, and n shows the integer of 0 or 1-5. ) Examples of R ¹ in the general formula (V) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a t-butyl group, and other alkyl groups having 1 to 6 carbon atoms. Of these, 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. R ² and R ³ include, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group and the like having 1 carbon atom.
~ 6 alkyl group, vinyl group, allyl group, alkenyl group such as butenyl group, phenyl group, biphenyl group, aryl group such as 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p -Tolyl group, 2,3-xylyl group, 2,4-xylyl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, alkyl group-substituted aryl group such as mesityl group, halogenated alkyl group, amino group Substituted alkyl groups, mercapto groups Substituted alkyl groups, etc., having 1 to 1 carbon atoms
And 12 substituted or unsubstituted monovalent hydrocarbon groups,
Among them, hydrogen atom, methyl group, ethyl group, phenyl group,
A biphenyl group is preferable, and a methyl group and a phenyl group are more preferable. m is preferably 0, 1 or 2, and more preferably 0. n is preferably 0 or an integer of 1 to 3. A preferred structure of the diglycidyl ether of bisphenol represented by the general formula (V) is, for example, the following general formula (VI
II) and epoxy resins represented by (IX). When the diglycidyl ether of bisphenol is used, the compounding amount is preferably 1 to 30% by weight based on the total amount of the epoxy resin in order to exert its performance, and 5-2.
0% by weight is more preferred.

[Chemical 16] (Here, n represents 0 or an integer of 1 to 3.)

[Chemical 17] (Here, n represents 0 or an integer of 1 to 3.)

Examples of the sulfur atom-containing epoxy resin include epoxy resins represented by the following general formula (X).

[Chemical 18] (Here, R ¹ is a hydrogen atom and a substituted or unsubstituted C ¹ atom.
Selected from alkyl groups of 6 to 6, all of which may be the same or different. m represents an integer of 0 or 1 to 4, and n represents an integer of 0 or 1 to 3. ) R ¹ in the above general formula (X) is, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group or the like having 1 carbon atom.
Alkyl groups of 6 to 6 are mentioned, and among them, a hydrogen atom and a methyl group, an ethyl group, a propyl group and a t-butyl group are preferable, and a hydrogen atom, a methyl group and a t-butyl group are more preferable. m is preferably 0, 1 or 2, and more preferably 2.
n is preferably 0, 1 or 2. A preferable structure of the sulfur atom-containing epoxy resin represented by the general formula (X) is, for example, an epoxy resin represented by the following general formula (XI).

[Chemical 19] (Here, n represents 0, 1, and 2.) When the sulfur atom-containing epoxy resin is used, the compounding amount is
1 to the total amount of epoxy resin to exert its performance
-40% by weight, preferably 10-30% by weight
Is more preferable.

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

[Chemical 20] (Here, R ¹ is a hydrogen atom and a substituted or unsubstituted C ¹ atom.
Selected from alkyl groups of 6 to 6, all of which may be the same or different. m represents an integer of 0 or 1 to 4, and n represents an integer of 0 or 1 to 3. ) R ¹ in the above general formula (XII) is, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group or the like having 1 carbon atom.
Alkyl groups of 6 to 6 are mentioned, among which a hydrogen atom, a methyl group and an ethyl group are preferable, and a hydrogen atom and a methyl group are more preferable. m is preferably 0, 1 or 2, and more preferably 2. n is preferably 0, 1 or 2. A preferred structure of the biphenyl type epoxy resin represented by the general formula (XII) is, for example, an epoxy resin represented by the following general formula (XIII).

[Chemical 21] (Here, n represents 0, 1, and 2.) When a biphenyl type epoxy resin is used, its content should be 1 to 40% by weight based on the total amount of the epoxy resin in order to exert its performance. Is preferred, and 10 to 30% by weight is more preferred.

The above novolac type epoxy resin, dicyclopentadiene type epoxy resin, biphenol diglycidyl ether, sulfur atom-containing epoxy resin, and biphenyl type epoxy resin are blended in an amount of 50% by weight or more based on the total amount of the epoxy resin. Is preferred, 60% by weight or more is more preferred, and 80% by weight or more is even more preferred. Furthermore, when the above-mentioned epoxy resin is used in combination, the ratio is (dicyclopentadiene type epoxy resin, diphenol diglycidyl ether of biphenol, sulfur atom-containing epoxy resin, biphenyl type epoxy resin) total weight / (novolak type epoxy resin) weight. The ratio is preferably 1/5 to 4/1, more preferably 1/4 to 3/1, and 1 /
3 to 2/1 is more preferable. If the total ratio of (dicyclopentadiene type epoxy resin, diglycidyl ether of biphenol, sulfur atom-containing epoxy resin and biphenyl type epoxy resin) becomes too large, the hardness at the time of heating tends to decrease, and the ratio of novolac type epoxy resin If the amount is too large, the reflow resistance tends to decrease.

The curing agent (B) used in the present invention contains at least a phenol resin represented by the following general formula (I), and the amount of the component of n = 1 or more in the general formula (I) is represented by the general formula (I). 11) in the phenolic resin represented by
It is sufficient if the content of the polyfunctional phenol component is not more than 10% by weight and the average of three or more phenolic hydroxyl groups in one molecule is less than 10% by weight based on the total amount of the curing agent (B), and otherwise It is also possible to use in combination with a generally used epoxy resin molding material for sealing.

[Chemical formula 22] (Here, R is a hydrogen atom, or a substituted or unsubstituted carbon number 1 to
6 is an alkyl group, m is 0 or an integer of 1-2, and n is 0 or an integer of 1-10. )

R in the above general formula (I) is, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a t-butyl group having 1 to 6 carbon atoms. Examples thereof include an alkyl group, of which a hydrogen atom, a methyl group and an ethyl group are preferable, and a hydrogen atom and a methyl group are more preferable. m is preferably 0, 1 or 2, and more preferably 0. n is preferably 0, 1 or 2.
A preferred structure of the phenol resin represented by the general formula (I) includes, for example, a phenol resin represented by the following general formula (XIV).

[Chemical formula 23] In the phenol resin represented by the general formula (I), n is 0.
Alternatively, the structure represented by an integer of 1 to 10 is used as a constituent component, but the ratio of the components is n = 1 or more, and the amount is 11% by weight or less of the entire phenol resin represented by the general formula (I), and 10% by weight. % Or less is preferable, and 5% by weight or less is more preferable. When it is more than 11% by weight, the fluidity, the reflow resistance and the wire sweep property tend to be deteriorated.
The amount of the constituent component of n = 1 or more of the phenol resin represented by the general formula (I) can be obtained by a conventionally known method, for example, from the area ratio measured by gel permeation chromatography.

In order to obtain the effects of the present invention, the amount of the component of n = 0 in the phenol resin represented by the general formula (I) is important, and they are represented by the following general formulas (XV) to (XVII). Can have an isomeric structure. The ratio of these isomers is not particularly limited, but the structure represented by the general formula (XVII) is contained in the phenol resin represented by the general formula (I) in an amount of 10 to 60% by weight in the total amount of n = 0 components. %, More preferably 20 to 40% by weight. If it is less than 10% by weight, the softening point of the phenolic resin tends to be low and the workability tends to be low.
When the amount is larger, the softening point of the phenol resin becomes higher and the dispersion in the epoxy resin molding material tends to be insufficient.

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

The curing agent (B) of the present invention which can be used in combination with the phenol resin represented by the general formula (I) is a curing agent which is generally used in epoxy resin compositions for encapsulation and is not particularly limited. Absent. For example, phenol,
Phenols such as cresol, resorcin, catechol, bisphenol A, phenylphenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde. A novolac-type phenol resin obtained by condensation or co-condensation with a compound having a group under an acidic catalyst; a phenol / aralkyl resin synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, Aralkyl-type phenolic resins such as naphthol / aralkyl resins; dicyclosynthesized by copolymerization of phenols and / or naphthols and cyclopentadiene Pentadiene-type phenol resin, dicyclopentadiene-type naphthol resin, terpene-modified phenol resin, biphenyl-type phenol resin, triphenylmethane-type phenol resin, etc. may be used alone or in combination of two or more kinds. Good. Among them, dicyclopentadiene type phenol resin is preferable from the viewpoint of low hygroscopicity.

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

[Chemical 27] (Here, R ¹ and R ² are independently selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and all m may be the same or different. M is an integer of 0 or 1 to 6. And n represents 0 or an integer of 1 to 10.) Examples of R ¹ and R ² in the general formula (II) include, for example,
Examples thereof include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and an alkyl group having 1 to 6 carbon atoms such as a t-butyl group. Among them, a hydrogen atom and a methyl group are preferable, and a hydrogen atom is preferable. Atoms are more preferred.
n may be 0 or an integer of 1 to 10, but the component amount represented by an integer of n = 1 or more is represented by the general formula (II).
30% by weight or less, preferably 20% by weight
The following is more preferable. If it is more than 30% by weight, the fluidity tends to decrease. In addition, when n of each component contained in the dicyclopentadiene type phenol resin represented by the general formula (II) is averaged over the entire dicyclopentadiene type phenol resin represented by the general formula (II), the average of n is 0. It is preferably 0.5 or more and less than 0.5, more preferably 0 to 0.4,
0 to 0.3 is more preferable. Here, when the average of n is 0, it means that the dicyclopentadiene type phenol resin represented by the general formula (II) is composed of only bifunctional components, and when the average of n is 1, the above general Formula (II)
The dicyclopentadiene type phenolic resin represented by can be considered as a trifunctional phenolic resin as a whole. If the average value of n is 0.5 or more, the fluidity tends to decrease.

The softening point of the dicyclopentadiene type phenolic resin represented by the general formula (II) can be used without particular limitation, but in order to mix it uniformly in the epoxy resin molding material of the present invention, The temperature is preferably in the range of 40 ° C to 110 ° C, and more preferably 50 ° C to 90 ° C from the viewpoint of reflow resistance. A preferred structure of the dicyclopentadiene type phenol resin represented by the general formula (II) is, for example, a dicyclopentadiene type phenol resin represented by the following general formula (XVIII).

[Chemical 28] (Here, n represents 0 or an integer of 1 to 10.) When a dicyclopentadiene type phenol resin is used,
The compounding amount thereof is preferably 20 to 80% by weight based on the total amount of the curing agent in order to exert its performance, and 30 to 30% by weight.
70% by weight or more is more preferable, and 40 to 65% by weight is further preferable. If it is less than 20% by weight, the effect of addition is not sufficiently exerted, and if it is more than 80% by weight, the fluidity tends to decrease.

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

The (C) curing accelerator used in the present invention is generally used in epoxy resin molding materials and is not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene is used. Cycloamidine compounds such as -7,1,5-diazabicyclo [4.3.0] nonene-5,5,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7 and compounds thereof 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,
A compound having an intramolecular polarization formed by adding a quinone compound such as 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and a compound having a π bond such as diazophenylmethane and phenol resin, benzyl Tertiary amines such as dimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-
Imidazoles such as 4-methylimidazole and 2-heptadecylimidazole and derivatives thereof, organic phosphines 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, or a phenol resin to these phosphines, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyl Tetra-substituted phosphonium / tetra-substituted borate such as triphenyl borate, tetrabutyl phosphonium tetrabutyl borate, 2-ethyl-4-methyl imidazole / tetraf Niruboreto, N- such tetraphenyl boron salts and derivatives thereof such as methyl morpholine tetraphenylborate and the like, may be used in combination of two or more kinds with these alone. Among them, an adduct of a tertiary phosphine and a quinone compound is preferable from the viewpoint of curability and fluidity, an adduct of a cycloamidine compound and a phenol resin is preferable from the viewpoint of storage stability, and diazabicycloundecene is preferable. The phenol novolac resin salt of is more preferable. The total content of these curing accelerators is preferably 60% by weight or more, more preferably 80% by weight or more, based on the total amount of the curing accelerators.

The third phosphine used in the adduct of the third phosphine and the quinone compound is not particularly limited, and examples thereof include tributylphosphine, tricyclohexylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine,
Triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (t -Butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2,6-dimethylphenyl)
Phosphine, tris (2,4,6-trimethylphenyl)
Examples of the third phosphine having an aryl group such as phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, and tris (4-ethoxyphenyl) phosphine are mentioned. From the viewpoint, triphenylphosphine or tris (4-methylphenyl) phosphine is preferable. Further, the quinone compound used as the adduct of the tertiary phosphine and the quinone compound is not particularly limited, but examples thereof include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like. From the viewpoint of sex, p-benzoquinone is preferable.

The compounding amount of the curing accelerator is not particularly limited as long as the curing promoting effect is achieved,
0.1 to 10 parts by weight is preferable with respect to 100 parts by weight of the total amount of (A) epoxy resin and (B) curing agent, and 0.3 to 5 parts by weight.
More preferably parts by weight. If it is less than 0.1 part by weight, it is difficult to cure it in a short time, and if it exceeds 10 parts by weight, the curing rate tends to be too fast to obtain a good molded product.

The inorganic filler (D) used in the present invention is added to the epoxy resin molding material for the purposes of hygroscopicity, reduction of linear expansion coefficient, improvement of thermal conductivity and improvement of strength, for example, fused silica. Powder of crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc. Examples thereof include a body, beads made of spherical particles, glass fiber, and the like, and one of these may be used alone, or two or more thereof may be used in combination. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, complex metal hydroxides such as complex hydroxide of magnesium and zinc, and the like.
These 1 type may be used individually or may be used in combination of 2 or more type. Of these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The shape of the filler is preferably a sphere or a shape close to a sphere from the viewpoint of fluidity at the time of molding or abrasion of the mold. The blending amount of the inorganic filler (D) is preferably 70% by weight or more, and more than 80% by weight, based on the epoxy resin molding material, from the viewpoints of moldability, hygroscopicity, reduction of linear expansion coefficient and improvement of strength.
It is more preferably less than or equal to wt%. If it is less than 70% by weight, the reflow crack resistance tends to decrease, and if it exceeds 95% by weight, the fluidity tends to be insufficient.

Further, in the epoxy resin molding material of the present invention, in order to enhance the adhesiveness between the resin component and the inorganic filler,
If necessary, various known silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, methacrylsilane, ureidosilane, vinylsilane, titanium compounds, aluminum chelates, aluminum / zirconium compounds, etc. Can be added. These are exemplified by vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxy Silane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ -Mercaptopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxy Silane coupling agents such as propyltriethoxysilane, isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate,
Tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-
Butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl Titanate coupling agents such as isostearoyl diacrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, etc. can be mentioned, and one of these can be used alone. Also 2
You may use it in combination of 2 or more types.

The amount of the coupling agent blended is preferably 0.05 to 5% by weight, and 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 tends to decrease.

The epoxy resin molding material of the present invention may optionally contain a conventionally known flame retardant. For example, aluminum hydroxide, magnesium hydroxide, zinc oxide, zinc stannate, zinc borate, iron oxide, antimony oxide,
Inorganic compounds containing metal elements such as molybdenum oxide and zinc molybdate; phosphorus compounds such as red phosphorus, phosphoric acid esters and phosphine oxides; melamine, melamine derivatives, melamine modified phenolic resins, compounds having triazine ring, cyanuric acid derivatives, Nitrogen-containing compounds such as isocyanuric acid derivatives; phosphorus- and nitrogen-containing compounds such as cyclophosphazenes; flame-retardant halides such as brominated epoxy resins and brominated phenol resins; organometallic compounds such as dicyclopentadienyl iron; Examples thereof include complex metal hydroxides represented by the formula (XIX). These 1 type may be used individually or may be used in combination of 2 or more type. In addition, among the flame retardants shown above, inorganic ones improve dispersibility in epoxy resin molding materials, prevent decomposition due to moisture absorption,
A coating made of an organic material may be applied for the purpose of increasing curability.

Embedded image p (M ¹ _a O _b ) .q (M ² _c O _d ) .r (M ³ _c O _d ) .mH ₂ O (XIX) (wherein M ¹ , M ² and M ³ are A metal element different from each other is shown, and a, b, c, d, p, q and m are positive numbers and r is 0 or a positive number.)

There is no particular limitation on M ¹ , M ² and M ^{3 in the} composition formula (XIX) as long as they are different metal elements, but from the viewpoint of flame retardancy, M ¹ is a metal element of the third period. , Group IIA alkaline earth metal elements, Group IVB, Group IIB, Group VIII, IB
Selected from the group consisting of metal elements belonging to Group IIIA, Group IIIA and Group IVA,
M ² is preferably selected from Group IIIB to IIB transition metal elements, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is iron or cobalt. More preferably, it is selected from nickel, copper, and zinc. From the viewpoint of fluidity, it is preferable that M ¹ is magnesium, M ² is zinc or nickel, and r = 0. The molar ratio of p, q and r is not particularly limited, but when r = 0, p / q is 1/99 to 1 /
It is preferably 1. In addition, the classification of metallic 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”)
It was conducted on the basis of the 30th edition of the reduced edition of February 15, 1987).

If desired, an anion exchanger may be added to the epoxy resin molding material of the present invention for the purpose of improving the moisture resistance of the IC and the high temperature storage property. The anion exchanger is not particularly limited, and conventionally known ones can be used, and examples thereof include hydrotalcites and hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. These may be used alone or in combination of two or more. Of these, hydrotalcite represented by the following formula (XX) is preferable.

Embedded image Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XX) (0 <X ≦ 0.5, m is a positive integer) These anion exchanges The compounding amount of the body is not particularly limited as long as it is an amount sufficient to capture anions such as halogen ions, but is 0.1 to 30% by weight relative to (A) epoxy resin.
Is preferable, and 1 to 5% by weight is more preferable.

The epoxy resin molding material of the present invention may optionally contain an adhesion promoter. In particular, the addition of an adhesion promoter is effective for improving the adhesion between the copper frame and the epoxy resin molding material. The adhesion promoter is not particularly limited and may be a conventionally known one, for example, imidazole, triazole, tetrazole, triazine and derivatives thereof, anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid. ,
Examples thereof include aminophenol, quinoline and the like and derivatives thereof, aliphatic acid amide compounds, dithiocarbamate, thiadiazole derivatives and the like, and these may be used alone or in combination of two or more kinds.

A release agent may be used in the epoxy resin molding material of the present invention, if necessary. As the release agent, it is preferable to use 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight of an oxidized or non-oxidized polyolefin with respect to 100 parts by weight of the (A) epoxy resin. . If it is less than 0.01 part by weight, the releasability tends to be insufficient, and if it exceeds 10 parts by weight, the adhesiveness tends to be lowered. As the oxidized or non-oxidized polyolefin,
Examples include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE and PED series manufactured by Hoechst Co., Ltd. Examples of other release agents include carnauba wax, montanic acid ester, montanic acid, stearic acid and the like, and one of these may be used alone or two or more of them may be used in combination. When these other mold release agents are used in combination with the oxidized or non-oxidized polyolefin, the compounding amount thereof is 0.1 part with respect to 100 parts by weight of the epoxy resin (A). 1 to 10 parts by weight is preferable, and 0.5 to 3 parts by weight is more preferable. In addition, as other additives, a stress relaxation agent such as silicone oil and silicone rubber powder, a carbon black, an organic dye, an organic pigment, a coloring agent such as titanium oxide, red lead, red iron oxide, and the like may be added according to the invention. It can be compounded with an epoxy resin molding material.

The epoxy resin molding material of the present invention can be prepared by any method as long as it can uniformly disperse and mix various components. As a general method, a predetermined amount of components is mixed with a mixer or the like. Examples include a method of sufficiently mixing, melt-kneading with a mixing roll, an extruder or the like, and then cooling and pulverizing. For example, a predetermined amount of the above-mentioned components are uniformly stirred and mixed, and 70 to 1 in advance.
It can be obtained by a method such as kneading with a kneader, roll, extruder or the like heated to 40 ° C., cooling and pulverizing. It is easy to use if it is made into a tablet with dimensions and weight that match the molding conditions.

As an electronic component device provided with an element sealed with the epoxy resin molding material obtained in the present invention, a semiconductor chip is used as a supporting member such as a lead frame, a wired tape carrier, a wiring board, glass and a silicon wafer. , Electronic devices such as transistors, diodes, active elements such as thyristors, capacitors, resistors, passive elements such as coils are mounted, and necessary parts are sealed with the epoxy resin molding material of the present invention. To be As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding or bumps, and then the epoxy resin molding material of the present invention is used. DIP (Dual Inline Pa
ckage), PLCC (Plastic Leaded Chip Carrier),
QFP (Quad Flat Package), SOP (Small Outline)
Package), SOJ (Small Outline J-lead packag
e), TSOP (Thin Small Outline Package), TQ
General resin encapsulation type IC such as FP (Thin Quad Flat Package), TCP in which a semiconductor chip connected to a tape carrier with bumps is encapsulated with the epoxy resin molding material of the present invention.
(Tape Carrier 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 capacitors, resistors, coils COB (Chip On Boar) in which passive elements such as
d) Modules, hybrid ICs, multi-chip modules, after mounting an element on the surface of an organic substrate having terminals for connecting a wiring board on the back side, and connecting the element and the wiring formed on the organic substrate by bumps or wire bonding , B in which an element is sealed with the epoxy resin molding material of the present invention
GA (Ball Grid Array), CSP (Chip Size Packag
e) and the like. Also, the epoxy resin molding material of the present invention can be effectively used for a printed circuit board.

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

[0041]

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 10 and Comparative Examples 1 to 4) As an epoxy resin, epoxy resin 1: orthocresol novolac type epoxy resin (epoxy equivalent 195, softening point 62 ° C, trade name ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.), Epoxy resin 2: dicyclopentadiene-modified phenol novolac type epoxy resin (epoxy equivalent 264, softening point 64 ° C, trade name HP manufactured by Dainippon Ink and Chemicals, Inc.
-7200), epoxy resin 3: bisphenol A type epoxy resin (epoxy equivalent 468, softening point 64 ° C, trade name E-1001 manufactured by Japan Epoxy Resin Co., Ltd.), epoxy resin 4: biphenyl skeleton type epoxy resin (epoxy equivalent 187, Melting point 106 ° C., Japan Epoxy Resin Co., Ltd. product name YX-4000), Epoxy resin 5: Sulfur atom-containing epoxy resin (epoxy equivalent 242, melting point 119 ° C., Nippon Steel Chemical Co., Ltd. product name YSLV-120TE) is prepared. did.

The curing agent is a curing agent 1: a phenol novolac resin represented by the following general formula (XIV), in which the amount of the component of n = 1 or more in the formula is 10% by weight (hydroxyl group equivalent 100, melting point 120 ° C., Honshu Kagaku) (Trade name: bisphenol F) manufactured by Kogyo Co., Ltd., curing agent 2: 1 with an average of phenolic hydroxyl groups in the molecule of 2.
Two dicyclopentadiene type phenolic resins (hydroxyl equivalent 166, softening point 93 ° C, trade name DPP-L manufactured by Nippon Petrochemical Co., Ltd.), curing agent 3: represented by the following general formula (XIV) and n in the formula = 82% by weight of component amount of 1 or more and an average value of n is 4.0 (hydroxyl group equivalent 106, softening point 8
0 ° C, product name Tamanor 75 manufactured by Arakawa Chemical Industry Co., Ltd.
8), curing agent 4: 1 average of phenolic hydroxyl groups in the molecule 3.
Phenol aralkyl resin containing 5 (hydroxyl equivalent 1
76, softening point 70 ° C., trade name Mirex XLC manufactured by Mitsui Chemicals, Inc.) was prepared.

The curing accelerator is an addition reaction product of triphenylphosphine and p-benzoquinone (curing accelerator 1), and the coupling agent is γ-glycidoxypropyltrimethoxysilane (coupling agent: Nippon Unicar Co., Ltd. Brand name A-187 manufactured by the company, spherical fused silica having an average particle size of 25.0 μm and a specific surface area of 3.3 m ² / g as an inorganic filler, and a bisphenol A type brominated epoxy resin (epoxy resin 6: Sumitomo Chemical Co., Ltd.) as a flame retardant. Kogyo Co., Ltd., trade name ESB-400T, epoxy equivalent 375, softening point 80 ° C., bromine content 48% by weight), antimony trioxide, carnauba wax as an additive (Cerarica NODA Co., Ltd.), carbon black (Mitsubishi Chemical) Product name MA-100 manufactured by Co., Ltd. was prepared. These are blended in parts by weight shown in Tables 1 and 2, respectively, and roll kneading is carried out under the conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes.
0 and the epoxy resin molding materials of Comparative Examples 1 to 4 were produced. In Tables 1 and 2, the "polyfunctional component" indicates the weight% of the polyfunctional phenolic resin containing 3 or more phenolic hydroxyl groups in the molecule on average in the total amount of the (B) curing agent.

[Chemical 31]

[0044]

[Table 1]

[0045]

[Table 2]

The prepared epoxy resin molding materials of Examples and Comparative Examples were evaluated by the following tests. The epoxy resin molding material is molded by a transfer molding machine at a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90.
It went under the condition of second. Further, post-curing was performed at 180 ° C. for 5 hours. The evaluation results are shown in Table 2. (1) Spiral flow (index of fluidity) Using a mold for spiral flow measurement according to EMMI-1-66, an epoxy resin molding material was molded under the above conditions, and a flow distance (cm) was obtained. (2) Disc flow (index of fluidity) 200 mm (W) x 200 mm (D) x 25 mm (H)
Upper mold and 200mm (W) × 200mm (D) × 15m
1 g of 5 g of a sample (epoxy resin molding material) weighed using a flat plate mold for disc flow measurement having a lower mold of m (H)
Place on the center of the lower mold heated to 80 ° C, and after 5 seconds,
Close the upper mold heated to 0 ℃, load 78N, curing time 9
Compression molding is performed under the condition of 0 seconds, and the long diameter of the molded product (m
m) and minor axis (mm) are measured, and the average value (mm)
Is the disc flow. (3) Hardness at heat Epoxy resin molding material 50 mm in diameter under the above molding conditions
It was molded into a disk having a thickness of 3 mm and measured immediately after molding using a Shore D type hardness meter. (4) Water absorption rate The disc molded in (3) above was post-cured under the above conditions to obtain 85
The sample was left standing for 168 hours under the condition of ° C / 85% RH, and the weight change before and after standing was measured to evaluate the water absorption. (5) Chip shift amount A 42-alloy lead frame with a LOC (Lead On Chip) structure is mounted with a silicone chip of 8.6 mm × 15.0 mm × 0.28 mm, and the thickness from the upper surface of the lead frame to the upper surface of the package is 0. 0.22 mm, TSOP with a thickness of 0.28 mm from the bottom surface of the chip to the bottom surface of the package
(Thin Small Outline Package) was formed by molding under the above conditions, and the chip shift amount was determined from the fracture surface observation. Regarding chip shift, a shift amount of less than 20 μm was considered good, and a shift amount of 20 μm or more was considered defective. (6) Void generation amount Using the same TSOP as in the above (5), a soft X-ray measuring device (PRO-TEST100 type manufactured by Softec Co., Ltd.) was used for fluoroscopic observation under conditions of a voltage of 100 kV and a current of 1.5 mA, and a diameter of 0. The presence / absence of voids of 1 mm or more was observed, and evaluation was made by the number of voided packages / total number of packages. (7) Wire sweep amount External dimensions 24 × 24 × 1. With a 5.8 × 5.8 × 0.3 mm thick silicone chip mounted on a copper lead frame.
4mm thick 216p QFP package (gold wire: 27μm
A diameter of 4.1 mm and a pad pitch of 80 μm) were molded by using an epoxy resin molding material under the above conditions. The voltage of the obtained package was 100 k using a soft X-ray measuring device (PRO-TEST100 type manufactured by Softec).
Fluorescence observation was performed under the conditions of V and current of 1.5 mA, and the wire sweep amount (flow amount) / (gold wire length) (unit%) was measured and evaluated by the average value of 10 packages. (8) Reflow crack resistance 42 alloy External dimensions 20 × 14 × mounted with a 8 × 10 × 0.4 mm thick silicone chip on an alloy lead frame
A 2.0 mm thick 80 pQFP package was molded under the above conditions using an epoxy resin molding material, and the obtained package was subjected to a moisture absorption treatment at 85 ° C./85% RH for a predetermined time, and then at 245 ° C./15 by an IR reflow device. The presence or absence of cracks was confirmed by performing reflow treatment under the condition of seconds, and evaluation was made by the number of cracked packages / total number of packages.

[0047]

[Table 3]

[0048]

[Table 4]

As can be seen in Tables 3 and 4, Examples 1-10 using the (B) curing agent specified in the present invention.
Has excellent fluidity such as spiral flow and disc flow, good chip shift, no voids, small wire sweep, and excellent reflow resistance. In particular, Examples 2 and 4 to 10 in which the curing agent 2 is used as the curing agent component (B) are excellent in reflow crack resistance. On the other hand, in Comparative Examples 1 to 4 not containing the (B) curing agent defined in the present invention, any one of chip shift, void generation amount, wire sweep, and reflow resistance is compared with the examples. Inferior to

[0050]

By using the epoxy resin molding material of the present invention to seal electronic parts such as ICs and LSIs, chip shifts and voids are less likely to occur even in thin surface mounting type packages such as TSOP. In addition, the wire sweep property and the reflow resistance can be obtained, and a highly reliable electronic component device can be obtained, so that its industrial value is great.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 24, 2002 (2002.6.2)
4)

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

The inorganic filler (D) used in the present invention is added to the epoxy resin molding material for the purposes of hygroscopicity, reduction of linear expansion coefficient, improvement of thermal conductivity and improvement of strength, for example, fused silica. Powder of crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc. Examples thereof include a body, beads made of spherical particles, glass fiber, and the like, and one of these may be used alone, or two or more thereof may be used in combination. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, complex metal hydroxides such as complex hydroxide of magnesium and zinc, and the like.
These 1 type may be used individually or may be used in combination of 2 or more type. Of these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The shape of the filler is preferably a sphere or a shape close to a sphere from the viewpoint of fluidity at the time of molding or abrasion of the mold. The blending amount of the inorganic filler (D) is preferably 70% by weight or more, and more than 80% by weight, based on the epoxy resin molding material, from the viewpoints of moldability, hygroscopicity, reduction of linear expansion coefficient and improvement of strength.
It is more preferably less than or equal to wt%. Riff resistance below 70% by weight
When it exceeds 95% by weight, the fluidity tends to be insufficient.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

[0041]

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 10 and Comparative Examples 1 to 4) As an epoxy resin, epoxy resin 1: orthocresol novolac type epoxy resin (epoxy equivalent 195, softening point 62 ° C, trade name ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.), epoxy resin 2: dicyclopenta diene-type epoxy resin (epoxy equivalent 264, softening point 64 ° C., Dainippon Ink and Chemicals, Inc., trade name HP-7200), the epoxy resin 3: bisphenol A type epoxy resin (epoxy equivalent 468, softening point 64 ° C., product name E-1001 manufactured by Japan Epoxy Resin Co., Ltd., epoxy resin 4: biphenyl skeleton type epoxy resin (epoxy equivalent 187, melting point 106 ° C., product name YX-4000 manufactured by Japan Epoxy Resin Co., Ltd.), epoxy resin 5 : Sulfur atom-containing epoxy resin (epoxy equivalent 242 Melting point 119 ℃, manufactured by Nippon Steel Chemical Co., Ltd. trade name YSLV-120TE) was prepared.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

The prepared epoxy resin molding materials of Examples and Comparative Examples were evaluated by the following tests. The epoxy resin molding material is molded by a transfer molding machine at a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90.
It went under the condition of second. Further, post-curing was performed at 180 ° C. for 5 hours. The evaluation results are shown in Table 2. (1) Spiral flow (index of fluidity) Using a mold for spiral flow measurement according to EMMI-1-66, an epoxy resin molding material was molded under the above conditions, and a flow distance (cm) was obtained. (2) Disc flow (index of fluidity) 200 mm (W) x 200 mm (D) x 25 mm (H)
Upper mold and 200mm (W) × 200mm (D) × 15m
1 g of 5 g of a sample (epoxy resin molding material) weighed using a flat plate mold for disc flow measurement having a lower mold of m (H)
Place on the center of the lower mold heated to 80 ° C, and after 5 seconds,
Close the upper mold heated to 0 ℃, load 78N, curing time 9
Compression molding is performed under the condition of 0 seconds, and the long diameter of the molded product (m
m) and minor axis (mm) are measured, and the average value (mm)
Is the disc flow. (3) Hardness at heat Epoxy resin molding material 50 mm in diameter under the above molding conditions
It was molded into a disk having a thickness of 3 mm and measured immediately after molding using a Shore D type hardness meter. (4) Water absorption rate The disc molded in (3) above was post-cured under the above conditions to obtain 85
The sample was left standing for 168 hours under the condition of ° C / 85% RH, and the weight change before and after standing was measured to evaluate the water absorption. (5) Chip shift amount A 42-alloy lead frame with a LOC (Lead On Chip) structure is mounted with a silicone chip of 8.6 mm × 15.0 mm × 0.28 mm, and the thickness from the upper surface of the lead frame to the upper surface of the package is 0. 0.22 mm, TSOP with a thickness of 0.28 mm from the bottom surface of the chip to the bottom surface of the package
(Thin Small Outline Package) was formed by molding under the above conditions, and the chip shift amount was determined from the fracture surface observation. Regarding chip shift, a shift amount of less than 20 μm was considered good, and a shift amount of 20 μm or more was considered defective. (6) Void generation amount Using the same TSOP as in the above (5), a soft X-ray measuring device (PRO-TEST100 type manufactured by Softec Co., Ltd.) was used for fluoroscopic observation under conditions of a voltage of 100 kV and a current of 1.5 mA, and a diameter of 0. The presence / absence of voids of 1 mm or more was observed, and evaluation was made by the number of voided packages / total number of packages. (7) Wire sweep amount External dimensions 24 × 24 × 1. With a 5.8 × 5.8 × 0.3 mm thick silicone chip mounted on a copper lead frame.
4mm thick 216p QFP package (gold wire: 27μm
A diameter of 4.1 mm and a pad pitch of 80 μm) were molded by using an epoxy resin molding material under the above conditions. The voltage of the obtained package was 100 k using a soft X-ray measuring device (PRO-TEST100 type manufactured by Softec).
Fluorescence observation was performed under the conditions of V and current of 1.5 mA, and the wire sweep amount (flow amount) / (gold wire length) (unit%) was measured and evaluated by the average value of 10 packages. (8) Reflow-resistant 42 alloy Lead frame mounted with a silicon chip of 8 × 10 × 0.4 mm thickness 20 × 14 ×
A 2.0 mm thick 80 pQFP package was molded under the above conditions using an epoxy resin molding material, and the obtained package was subjected to a moisture absorption treatment at 85 ° C./85% RH for a predetermined time, and then at 245 ° C./15 by an IR reflow device. The presence or absence of cracks was confirmed by performing reflow treatment under the condition of seconds, and evaluation was made by the number of cracked packages / total number of packages.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

As can be seen in Tables 3 and 4, Examples 1-10 using the (B) curing agent specified in the present invention.
Has excellent fluidity such as spiral flow and disc flow, good chip shift, no voids, small wire sweep, and excellent reflow resistance. In particular, Examples 2 and 4 to 10 in which the curing agent 2 is also used as the (B) curing agent component are excellent in reflow resistance. On the other hand, in Comparative Examples 1 to 4 not containing the (B) curing agent defined in the present invention, any one of chip shift, void generation amount, wire sweep, and reflow resistance is compared with the examples. Inferior to

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Mitsuo Katayose             48 Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd.             Company Research Institute F term (reference) 4J036 AD08 AD11 AE07 AF06 FA01                       FB06 JA07                 4M109 AA01 EA03 EB02 EB03 EB04                       EB12

Claims (8)

[Claims] 1. An epoxy resin (A), a curing agent (B),
(C) a curing accelerator and (D) an inorganic filler as essential components, and (B) a curing agent is represented by the following general formula (I) and n =
Contain at least 1% by weight of a phenolic resin in an amount of 11% by weight or less, and average 3 phenolic hydroxyl groups in one molecule.
The content of the polyfunctional phenolic resin containing at least one is (B)
An epoxy resin molding material containing less than 10% by weight based on the total amount of the curing agent. [Chemical 1] (Here, R is a hydrogen atom, or a substituted or unsubstituted carbon number 1 to
6 is an alkyl group, m is 0 or an integer of 1-2, and n is 0 or an integer of 1-10. ) 2. The epoxy resin molding material according to claim 1, wherein the curing agent (B) contains a dicyclopentadiene type phenol resin represented by the following general formula (II). [Chemical 2] (Here, R ¹ and R ² are independently selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and all m may be the same or different. M is an integer of 0 or 1 to 6. And n represents 0 or an integer of 1 to 10.) 3. The epoxy resin molding material according to claim 2, wherein the dicyclopentadiene type phenol resin represented by the general formula (II) has an average value of n of 0 or more and less than 0.5. 4. The epoxy resin (A) is represented by the following general formula (II
The epoxy resin molding material according to claim 1, which comprises the epoxy resin represented by I). [Chemical 3] (Here, R is a hydrogen atom, or a substituted or unsubstituted carbon number 1 to
6 represents an alkyl group, and all m may be the same or different. m represents 0 or an integer of 1 to 2, and n represents an integer of 0 or 1 to 10. ) 5. The epoxy resin (A) has the following general formula (I
The epoxy resin molding material according to any one of claims 1 to 4, which contains an epoxy resin represented by V). [Chemical 4] (Here, R ¹ and R ² are independently selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and all m may be the same or different. M is an integer of 0 or 1 to 6. And n represents 0 or an integer of 1 to 10.) 6. The epoxy resin (A) is represented by the following general formula (V):
The epoxy resin molding material according to any one of claims 1 to 5, containing the epoxy resin represented by the formula (1). [Chemical 5] (Here, R ¹ is a hydrogen atom, a substituted or unsubstituted C 1
Selected from alkyl groups of 6 to 6, all of which may be the same or different. R ² and R ³ represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and m is 0 or 1 to 4
Is shown, and n shows the integer of 0 or 1-5. ) 7. The epoxy resin molding material according to claim 1, wherein the epoxy resin (A) contains at least one of a sulfur atom-containing epoxy resin and a biphenyl type epoxy resin. 8. An electronic component device comprising an element sealed with the epoxy resin molding material according to claim 1.