JP2003292732A - Thermosetting resin composition, epoxy resin molding material and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding material in which rapid curing property is compatible with storage stability. <P>SOLUTION: The epoxy resin molding material comprises (A) a compound having two or more epoxy groups in one molecule, (B) a compound having two or more phenolic hydroxy groups in one molecule, (C) an organic phosphine represented by formula (1) (P is phosphorus atom; R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>are each a substituted or unsubstituted aromatic group or an alkyl group), (D) at least one compound selected from boron oxide, boric acid and boric acid esters and (E) an inorganic filler as essential components. The resin molding material is obtained by previously melting and mixing total or a part of the component (B) with the component (C) and the component (D). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting resin composition having good curability and storability and useful in the field of electric and electronic materials, an epoxy resin molding material using the same, and a semiconductor device. .

[0002]

2. Description of the Related Art In recent years, electric / electronic materials, especially semiconductor encapsulation materials, have been required to have a fast curing property for the purpose of improving production efficiency and a preservability for improving the handling property during distribution and storage. Is becoming available. Conventionally, epoxy resins for the electric and electronic materials field include amines, imidazole compounds, nitrogen-containing heterocyclic compounds such as diazabicycloundecene, quaternary ammonium, phosphonium or arsonium compounds as curing accelerators. Various compounds have been used. Amines, especially imidazoles, etc. show excellent curability, but as a semiconductor encapsulating material cause internal wiring corrosion under high temperature and high humidity conditions,
That is, the moisture resistance reliability tends to be low, and there is a problem in use in the field of electric / electronic materials, and the use of phosphorus compounds such as phosphonium compounds is common. These commonly used curing accelerators often exhibit a curing promoting action even at a relatively low temperature such as room temperature. This means that the viscosity of the resin composition during production and storage increases,
This is a cause of deterioration in quality of the resin composition such as deterioration in fluidity and variation in curability.

In order to solve this problem, in recent years, research on so-called latent curing accelerators has been actively conducted, which suppresses changes in viscosity and fluidity at a low temperature over time and causes a curing reaction only by molding and heating during molding. Has been done. As a means for this, research has been conducted to develop latent properties by protecting the active sites of the curing accelerator with ion pairs.
Japanese Patent Publication No. 90 discloses latent curing accelerators having a salt structure of various organic acids and phosphonium ions.
However, this phosphonium salt does not have a specific higher-order molecular structure, and the ion pair is relatively easily affected by the external environment. Therefore, molecules such as low molecular weight epoxy resins and phenol aralkyl resins are likely to move in recent years. The encapsulating material for semiconductors using a phenolic resin curing agent has a problem that storage stability is deteriorated.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a thermosetting resin composition having good curability and storability and useful in the field of electric and electronic materials, an epoxy resin molding material using the same, and a moisture resistance reliability. It is an object to provide an excellent semiconductor device.

[0005]

The present invention provides [1] a compound (A) having two or more epoxy groups in one molecule, and a compound (B) generally having two or more phenolic hydroxyl groups in one molecule. The organic phosphine (C) represented by the formula (1) and at least one compound (D) selected from boron oxide, boric acid, or boric acid ester as an essential component, and all or one of the components (B). Part, (C) component,
A thermosetting resin composition comprising the components (D) pre-melted and mixed, [2] a compound (A) having two or more epoxy groups in one molecule, and a phenolic hydroxyl group in one molecule. A compound (B) having two or more, an organic phosphine (C) represented by the general formula (1), boron oxide, boric acid,
Alternatively, at least one compound (D) selected from borate esters and an inorganic filler (E) are used as essential components,
An epoxy resin molding material, characterized in that all or part of the component (B), the component (C) and the component (D) are melt-mixed in advance,

[0006]

[Chemical 2] (P is a phosphorus atom, R ₁ , R ₂ and R ₃ are substituted or unsubstituted aromatic groups or alkyl groups)

[3] A semiconductor device comprising a semiconductor element encapsulated with the epoxy resin molding material according to the item [2]. By using these, an epoxy resin molding material having good curability and storage stability can be obtained.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (A) having two or more epoxy groups in one molecule used in the present invention is not limited as long as it has two or more epoxy groups in one molecule. Examples thereof include biphenyl-type epoxy resins, novolac-type epoxy resins, naphthalene-type epoxy resins, phenols such as biphenols, phenol resins, epoxy resins obtained by reacting hydroxyl groups such as naphthols with epichlorohydrin, and epoxy compounds. Other examples include epoxy resins such as alicyclic epoxy resins, which are epoxidized by oxidizing olefins with peracid, and those in which dihydroxybenzenes such as hydroquinone are epoxidized with epichlorohydrin.

The compound (B) having two or more phenolic hydroxyl groups in one molecule used in the present invention acts as a curing agent for the compound (A) having two or more epoxy groups in one molecule. Specifically, phenol novolac resins, cresol novolac resins, alkyl-modified novolac resins (including resins in which cycloalkene double bonds are reacted with phenols by Friedel-Crafts type reaction and co-condensed), phenol aralkyl resins, naphthols Examples thereof include a resin in which phenols and a carbonyl group-containing compound are co-condensed with each other, and a compound in which two or more hydrogen atoms bonded to an aromatic ring in one molecule are substituted with hydroxyl groups may be used.

The organic phosphine (C) which acts as a curing accelerator in the present invention is represented by the general formula (1). This organic phosphine (C) is at least one or more selected from all or part of the compound (B) having two or more phenolic hydroxyl groups, organic phosphine (C), boron oxide, boric acid, or boric acid ester. The compound (D) is used by being melt-mixed in advance. By melt-mixing these components, at least one compound (D) selected from boron oxide, boric acid, or boric acid ester reacts with the phenolic hydroxyl group to form boric acid ester. Further, it is considered that the lone electron pair of the phosphorus atom of the organic phosphine flows into the boron atom of the reaction product of the phenolic hydroxyl group generated and is stabilized. The organic phosphine capable of having such a structure is preferably a tri-substituted phosphine having a substituted or unsubstituted aryl group or an alkyl group as a substituent, and specifically, a triaryl-substituted phosphine such as triphenylphosphine and tritolylphosphine, diphenyl. Examples include diarylmonoalkylphosphines such as methylphosphine and trialkyl-substituted phosphines such as tributylphosphine.

The compound (B) having two or more phenolic hydroxyl groups in one molecule used in the present invention, the organic phosphine (C) and at least one compound selected from boron oxide, boric acid, and borate ester ( In the molten mixture of D), the organic phosphine-boron coordination product is formed as described above, but there is no problem if the molar amount of the boron atom is equal to or larger than the phosphorus atom of the organic phosphine.

The compounding amount of the organic phosphine (C) is such that the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule acting as a curing agent. When the total weight of the above is 100 parts by weight, about 0.5 to 20 parts by weight is preferable because of good balance of curability, storability and other properties. The compounding ratio of the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule has two or more epoxy groups in one molecule. 0.5 to 2 mol, preferably 0.8 to 1. mol of the phenolic hydroxyl group of the compound (B) having two or more phenolic hydroxyl groups in one molecule with respect to 1 mol of the epoxy group of the compound (A).
When used so that the molar ratio is about 2, curability, heat resistance,
The electrical characteristics and the like become better.

The type of the inorganic filler (E) used in the present invention is not particularly limited, and those generally used as a sealing material can be used. Examples thereof include fused crushed silica powder, fused spherical silica powder, crystalline silica powder, secondary agglomerated silica powder, alumina, titanium white, aluminum hydroxide, talc, clay and glass fiber, and fused spherical silica powder is particularly preferable. It is preferable that the shape is infinitely spherical, and the filling amount can be increased by mixing particles having different particle sizes.

The blending amount of this inorganic filler (E) is as follows.
200 to 240 per 100 parts by weight of the total amount of the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule.
0 parts by weight is preferred. If it is less than the lower limit value, the reinforcing effect of the inorganic filler may not be sufficiently exhibited, and if it exceeds the upper limit value, the fluidity of the molding material may be lowered, and filling failure may occur during molding, which is not preferable. In particular, when the compounding amount of the inorganic filler is 250 to 1400 parts by weight per 100 parts by weight of the total amount of the components (A) and (B), the moisture absorption rate of the cured material of the molding material is low, and solder cracking occurs. Is more preferable, and the viscosity of the molding material at the time of melting is lowered, so that there is no possibility of causing deformation of the gold wire inside the semiconductor device, which is more preferable. Further, it is preferable that the inorganic filler is sufficiently mixed in advance.

The epoxy resin molding material of the present invention is (A)
In addition to the component (E), if necessary, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, a brominated epoxy resin, an antimony oxide, a flame retardant such as a phosphorus compound, Various additives such as low stress components such as silicone oil and silicone rubber, natural wax, synthetic wax, higher fatty acid or metal salt thereof, mold release agent such as paraffin, antioxidant and the like can be blended. In the range that does not impair the characteristics of the organic phosphine (C) that functions as a curing accelerator in 1,
8-diazabicyclo (5,4,0) undecene-7,2
-There is no problem even if it is used together with a curing accelerator such as methylimidazole.

The epoxy resin molding material of the present invention is (B)
After melt-mixing all or part of the components, the component (C), and the component (D) in advance, the component (A), the component (E), and other additives are mixed at room temperature using a mixer, It is obtained by kneading with a kneader such as a roll or an extruder, cooling and pulverizing. The method in which all or part of the component (B), the component (C), and the component (D) are melt-mixed in advance is performed by the reaction of the component (B) and the component (D) to form a borate ester, and (C). The method is not particularly limited as long as it is a melt mixing method in which the stabilization of the boric acid ester produced by the above reaction of the lone pair of phosphorus atoms of the component is caused by flowing into the boron atom, but, for example, a separator with a stirrer Using a flask, the contents become uniformly transparent under a nitrogen stream and heated and stirred until the production of water or alcohol is completed, then water or alcohol is completely removed by vacuum defoaming, and then the molten product is taken out to a stainless vat. Examples include a method of pulverizing after cooling.

Using the epoxy resin molding material of the present invention,
In order to seal an electronic component such as a semiconductor and manufacture a semiconductor device, it can be cured and molded by a molding method such as a transfer mold, a compression mold or an injection mold. The semiconductor device encapsulated with the cured product of the epoxy resin molding material of the present invention is included in the technical scope of the present invention and exhibits excellent moisture resistance.

[0018]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. [Synthesis of Melt Mixture] Selected from compound (B) having two or more phenolic hydroxyl groups in one molecule, organic phosphine (C) represented by general formula (1), boron oxide, boric acid or boric acid ester. At least one compound (D), which was prepared, was heated and stirred under a nitrogen stream until the contents became uniformly transparent. Hereinafter, this is referred to as (M). After that, the molten mixture is taken out, cooled and pulverized for use.

(Melting and mixing 1) XL in a 500 ml separable flask equipped with a stirrer, manufactured by Mitsui Chemicals, Inc.
C-LL 90 g, triphenylphosphine 10 g
(38 mmol), boron oxide 3 g (43 mmol)
Is charged, heated to 150 ° C., and dissolved by stirring. After the contents become uniform and transparent and water is generated, vacuum degassing is performed.
Completely remove water or alcohol. Then, the molten product is taken out into a stainless steel vat, cooled, and then ground. This is designated as M1. (Melting and mixing 2) XLC-LL 9 manufactured by Mitsui Chemicals, Inc. in a 500 ml separable flask equipped with a stirrer.
0 g, di (diphenylphosphino) ethane 10 g (2
5 mmol) and 4 g (65 mmol) of boric acid are charged, and the mixture is heated to 150 ° C. and dissolved with stirring. After the contents become uniformly transparent and the generation of water is completed, vacuum defoaming is performed to completely remove water or alcohol. Then, the molten product is taken out into a stainless steel vat, cooled, and then ground. This is M
Set to 2. (Melting and mixing 3) XLC-LL 9 manufactured by Mitsui Chemicals, Inc. in a 500 ml separable flask equipped with a stirrer
0 g, diphenylethylphosphine 10 g (47 mmol) and tributyl borate 11 g (48 mmol) were charged, and the mixture was heated to 150 ° C. and dissolved with stirring. After the content becomes uniformly transparent and the butanol production is completed, vacuum defoaming is performed and removed. Then, the molten product is taken out into a stainless steel vat, cooled, and then ground. This is designated as M3. (Melting and mixing 4) In a 500 ml separable flask equipped with a stirrer, 90 g of a phenol novolac resin having a hydroxyl equivalent of 104, a softening point of 95 ° C., 10 g (38 mmol) of triphenylphosphine, 3 g (4) of boron oxide.
(3 mmol), and heated to 150 ° C. to dissolve with stirring. After the contents become uniformly transparent and the generation of water is completed, vacuum defoaming is performed to completely remove water or alcohol.
Then, the molten product is taken out into a stainless steel vat, cooled, and then ground. This is designated as M4. (Melting and mixing 5) XLC-LL 9 manufactured by Mitsui Chemicals, Inc. in a 500 ml separable flask equipped with a stirrer
0 g and 10 g (38 mmol) of triphenylphosphine are charged and heated to 150 ° C. to dissolve with stirring. When the contents become uniform and transparent, no water is generated. afterwards,
The molten product is taken out into a stainless steel vat, cooled, and then ground. This is designated as M5. (Melting and mixing 6) XLC-LL 1 manufactured by Mitsui Chemicals, Inc. in a 500 ml separable flask equipped with a stirrer
00 g and boron oxide 3 g (boron 43 mmol) are charged and heated to 150 ° C. to dissolve with stirring. After the contents become uniformly transparent and the generation of water is completed, vacuum defoaming is performed to completely remove water or alcohol. Then, the molten product is taken out into a stainless steel vat, cooled, and then ground. This is designated as M6.

[Evaluation of Thermosetting Resin Composition] First, a compound (B) having two or more phenolic hydroxyl groups in one molecule, an organic phosphine (C), boron oxide, boric acid or boric acid ester is selected. A molten mixture M of at least one or more compounds (D) and a compound (A) having two or more epoxy groups in one molecule are mixed, and further 11
The mixture was melt-kneaded on a hot plate at 0 ° C. for 2 minutes and then cooled and pulverized to prepare a sample of the composition for evaluation. The evaluation method is
It is as follows. (1) Curing torque Using the composition prepared by the sample preparation method described above, a curast meter (manufactured by Orientec Co., JS
R Curastometer 4PS type) at 175 ° C,
The torque after 45 seconds was determined. The torque in the curast meter is a parameter of curability, and the larger this value, the better the curability. The unit is Nm. (2) Curing exotherm residual rate (evaluation of storability) Using the composition prepared by the above sample preparation method, the initial curing exotherm immediately after preparation and the curing exotherm after storage treatment at 40 ° C for 3 days were measured. , Initial curing heat value (mJ
/ Mg) heat value of curing (mJ / m)
The percentage of g) was calculated. The curing exotherm was measured by differential thermal analysis under the conditions of a temperature rising rate of 10 ° C / min.
The larger this value is, the better the storage stability is.

(Examples 1 to 4 and Comparative Examples 1 to 8) For Examples 1 to 4 and Comparative Examples 1 to 8, samples of the composition were prepared by the above-mentioned method according to the formulation shown in Table 1 and evaluated. did. The evaluation results of the obtained compositions are as shown in Table 1.

[0022]

[Table 1]

As shown in the examples, the thermosetting resin composition of the present invention has good curability and storability, whereas the resin composition of Comparative Example prepared by melt-mixing only triphenylphosphine is preserved. In addition, the resin composition obtained by melt mixing only boron has poor storage stability.

[Evaluation of Epoxy Resin Molding Material] (Example 5) Japan Epoxy Resin Co., Ltd. YX-4000H 29 parts by weight Mitsui Chemicals Co., Ltd. XLC-LL 48 parts by weight Melt mixture M1 26 parts by weight Fused spherical silica (Average particle size 15 μm) 500 parts by weight carbon black 2 parts by weight Brominated bisphenol A type epoxy resin 2 parts by weight Carnauba wax 2 parts by weight are mixed, and the mixture is kneaded at 93 ° C. for 9 minutes using a hot roll and pulverized after cooling. Then, an epoxy resin molding material was obtained. The obtained epoxy resin molding material was evaluated by the following methods. The results are shown in Table 2.

Evaluation method (1) For the spiral flow, a mold for spiral flow measurement conforming to EMMI-I-66 was used, and the mold temperature was 17
It was measured at 5 ° C., injection pressure of 6.9 MPa, and curing time of 2 minutes. Spiral flow is a parameter of liquidity,
The larger the number, the better the fluidity. Unit is c
m. (2) As for the curing torque, a torque after 55 seconds at 175 ° C. was measured using a Curastometer (JSR Curastometer 4PS type manufactured by Orientec Co., Ltd.). The larger this value, the better the curability. The unit is Nm. (3) The residual flow rate was measured by measuring the spiral flow immediately after production and after storage at 30 ° C. for 1 week, and expressed as a percentage of the spiral flow immediately after production after storage. Units%.

(Examples 6 to 10 and Comparative Examples 9 to 16) With respect to Examples 6 to 10 and Comparative Examples 9 to 16, epoxy resin molding materials were prepared and evaluated in the same manner as in Example 5 according to the formulation shown in Table 2. did. The results are shown in Table 2.

[0027]

[Table 2]

The epoxy resin molding materials of Examples 5 to 10 according to the present invention have very good storage stability and curability. On the other hand, the epoxy resin molding materials of Comparative Examples 9 to 16 are curable,
Either the fluidity or the storability is inferior as compared with Examples 5-10.

[0029]

INDUSTRIAL APPLICABILITY The thermosetting resin composition and epoxy resin molding material of the present invention have excellent curability and storability, and a semiconductor device obtained by encapsulating a semiconductor element using the composition is industrially useful. Is.

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Claims (3)

[Claims] 1. A compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, an organic phosphine represented by the general formula (1) ( C) and at least one compound (D) selected from boron oxide, boric acid, or boric acid ester as an essential component, and all or part of the component (B),
A thermosetting resin composition, characterized in that the component (C) and the component (D) are melt-mixed in advance. 2. A compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, an organic phosphine represented by the general formula (1) ( C), at least one compound (D) selected from boron oxide, boric acid, or boric acid ester,
And an inorganic filler (E) as an essential component, and all or a part of the component (B), the component (C), and the component (D) are melt-mixed in advance, and the epoxy resin molding material is characterized. [Chemical 1] (P is a phosphorus atom, R ₁ , R ₂ and R ₃ are substituted or unsubstituted aromatic groups or alkyl groups) 3. A semiconductor device comprising a semiconductor element encapsulated with the epoxy resin molding material according to claim 2.