JPH07268184A - Epoxy resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in water repellency and water resistance without impairing its high adhesivity to various base materials and heat resistance, useful as a sealing material for semiconductor devices, by blending, in a molten state, an epoxy resin and a fluoro(meth)acrylate resin. CONSTITUTION:This composition is obtained by blending, in a molten state, (A) an epoxy resin solid at room temperature, having in one molecule at least two glycidyl groups and (B) a fluoro(meth)acrylate resin virtually incompatible with the component A, produced by polymerizing a feedstock essentially containing a perfluoroal,kyl group-bearing polymerizable monomer of formula I [X is H, Cl, F or methyl; Y is a 1-4C alkylene or of formula II (R is a l-4C alkyl or H; (n) is 1-4); Rf is a 1-15C perfluoroalkyl.] to homogeneously disperse the component Bas fine particles <=30mum in diameter in the component A followed by cooling.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition and a method for producing the same. More specifically, the present invention relates to an epoxy resin composition which is excellent in water repellency and water resistance in addition to high adhesion to various base materials, which is an advantage of epoxy resins, heat resistance, and high mechanical strength, and a method for producing the same. The epoxy resin composition of the present invention is particularly preferably used as a resin composition for sealing a resin-sealed semiconductor device.

[0002]

2. Description of the Related Art A resin polymerized from a (meth) acrylate having a perfluoroalkyl group (hereinafter, sometimes referred to as PFA. Here, (meth) acrylate means acrylate and methacrylate) is excellent. It is known to show water repellency. (For example, "Fluoropolymer Handbook" published by Nikkan Kogyo Shimbun).

Utilizing the characteristics of a resin polymerized from such a (meth) acrylate having a perfluoroalkyl group, Japanese Patent Application Laid-Open No. 48-4528 or Japanese Patent Application Laid-Open No. 50-55630 discloses the characteristics of the resin. Application of resins to paint applications is disclosed. Further, JP-A-4-328151 discloses an epoxy resin composition containing a specific copolymer containing a (meth) acrylate having a perfluoroalkyl group.

[0004]

On the other hand, the water repellency of a polymer made of PFA increases as the carbon number of the perfluoroalkyl group increases, but in that case, a hydrocarbon solvent or epoxy usually used at the same time is used. It is also difficult to dissolve in resins. Therefore, in the above-mentioned conventional combination of the resin and the epoxy resin, the PFA copolymer obtained by copolymerizing PFA and various other monomer components is used by dissolving it in a solvent or an epoxy resin. I've been broken.
However, the epoxy resin composition thus obtained does not always have sufficient performance in terms of high water repellency and water resistance.

[0005]

[Means for Solving the Problems] The present inventors have made full use of the high water repellency and water resistance of a polymer made of PFA,
In addition, in order not to impair the good properties of the epoxy resin by adding a small amount thereof, the polymer composed of the epoxy resin and the PFA does not dissolve in the epoxy resin, and each phase is separated into two phases having independent domains. The structure is preferred. That is, the present invention provides an epoxy resin composition having a structure in which a polymer obtained by polymerizing PFA which is substantially insoluble in the epoxy resin as a main component in an epoxy resin is uniformly dispersed in a fine particle state, and a method for producing the same. It is provided.

The present invention comprises the following inventions. (1) Epoxy resin (A) which has at least two glycidyl groups in one molecule and is solid at room temperature, and a general formula 2 which is substantially insoluble in the epoxy resin.

[0007]

[Chemical 2]

[In the formula, X represents a hydrogen atom, a chlorine atom, a fluorine atom or a methyl group. Y is an alkylene group having 1 to 4 carbon atoms _{- (CH 2) n N (} R) SO 2 - ( wherein,
R is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and n is 1
Represents an integer of 4; ) Represents. Rf represents a perfluoroalkyl group having 1 to 15 carbon atoms. ] The fluorine-containing (meth) acrylate resin (B) obtained by polymerizing a raw material containing a polymerizable monomer containing a perfluoroalkyl group represented by An epoxy resin composition which is solid at room temperature, wherein the (meth) acrylate resin (B) is uniformly dispersed in the epoxy resin (A) as particles having a particle diameter of 30 μm or less.

(2) The epoxy resin composition as described in the above item (1), which contains a dispersion stabilizer (C). (3) An epoxy resin composition for a resin-encapsulated semiconductor device, which comprises the epoxy resin composition according to item 1 or 2 as an essential component. (4) The epoxy resin (A) and the fluorine-containing (meth)
2. The epoxy according to item 1, wherein the acrylate resin (B) is mixed in a molten state, the fluorine-containing (meth) acrylate resin is dispersed in the epoxy resin in the form of fine particles, and then cooled. A method for producing a resin composition. (5) In the presence of the dispersion stabilizer (C), the epoxy resin (A) and the fluorine-containing (meth) acrylate resin (B) are mixed in a molten state to give the fluorine-containing (meth) acrylate resin. 5. The method for producing an epoxy resin composition according to item 4, wherein the epoxy resin composition is dispersed in the form of fine particles and then cooled.

The epoxy resin composition of the present invention comprises, as a continuous phase, a solid epoxy resin at room temperature, and as a dispersed phase fine particles of 30 μm or less of a fluorine-containing (meth) acrylate resin which is not substantially dissolved in the epoxy resin. It is an epoxy resin composition having a structure that is solid at room temperature.
The structure in which the two phases are separated in this way is characterized by being stable for a long period of time. In the two-phase separated structure, the epoxy resin composition is solid at room temperature, and the two-phase separated structure is substantially frozen. The addition of the dispersion stabilizer (C) in the present invention is preferable because it further improves the particle size control of the fine particles comprising the fluorine-containing (meth) acrylate resin (B) and the dispersion stability of the fine particles in the epoxy resin composition. . In addition, in the curing and molding steps of the resin composition, the resin composition usually undergoes a melting process, but the coalescence of the fluorine-containing (meth) acrylate resin fine particles in the process is suppressed, and a uniform dispersion state is obtained. It is also preferable because it has the effect of maintaining it.

The second invention relates to a method for producing an epoxy resin composition having a structure in which the fluorine-containing (meth) acrylate resin fine particles are uniformly and stably dispersed in an epoxy resin system. That is, both the fluorine-containing (meth) acrylate resin (B) polymerized with PFA as a main component which is substantially insoluble in the epoxy resin (A) and the solid epoxy resin at room temperature are melted, Then, the fluorine-containing (meth) acrylate resin (B) is finely dispersed in the epoxy resin (A) by mechanical mixing such as stirring, and then the resin is obtained by cooling. ) A method for producing an epoxy resin composition in which fine particles of an acrylate resin are uniformly dispersed in an epoxy resin.

In the production method, the stability of the particle size or dispersion state of the fine particles of the fluorine-containing (meth) acrylate resin depends on the strength of the shearing force applied, that is, the shear rate, the viscosity of each component, and the cohesive energy of each component. It is determined in a complex manner by the difference of −, and the condition is appropriately selected.

According to the present invention, it is possible to uniformly disperse a fluorine-containing (meth) acrylate resin which is substantially insoluble in an epoxy resin polymerized mainly with PFA at room temperature in a solid epoxy resin. Become.

Next, each component used in the present invention will be described. Epoxy resin (A) solid at room temperature
There is no particular limitation as long as the softening temperature is room temperature or higher, preferably 50 ° C. or higher, but specific examples include the following.

For example, glycidyl ethers derived from dihydric phenols such as bisphenol A, 1,1'-bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, tetramethylbiphenol and naphthalenediol. Compounds; glycidyl ester compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid; triglycidyl isocyanurate and other solid epoxy resins at room temperature.

Further, phenol, o-cresol, m-
Novolac-based epoxy resin derived from novolac resin which is a reaction product of formaldehyde with phenols such as cresol and p-cresol; phloroglysin, tris- (4-hydroxyphenyl) -methane, 1,1,
It is also possible to use a solid epoxy resin at room temperature, such as a glycidyl ether compound derived from a trivalent or higher phenol such as 2,2, -tetrakis (4-hydroxyphenyl).

Further, by using a halogenated epoxy resin in which a part of hydrogen atoms contained in the epoxy resin molecule is replaced by a halogen atom such as bromine, the epoxy resin composition of the present invention imparted with flame retardancy. Can be obtained.

The fluorine-containing (meth) acrylate resin (B) means

[Chemical 3]

[In the formula, X represents a hydrogen atom, a chlorine atom, a fluorine atom or a methyl group. Y is an alkylene group having 1 to 4 carbon atoms _{- (CH 2) n N (} R) SO 2 - ( wherein,
R is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and n is 1
Represents an integer of 4; ) Represents. Rf represents a perfluoroalkyl group having 1 to 15 carbon atoms. ] It refers to a resin obtained by polymerizing a raw material containing a perfluoroalkyl group-containing (meth) acrylate-based polymerizable monomer represented by the following as an essential component.

The perfluoroalkyl group-containing (meth) acrylate-based polymerizable monomer is not particularly limited as long as it is represented by the above general formula, but in order to further increase the water repellency of the obtained resin. , Rf having 6 or more carbon atoms in the perfluoroalkyl group are particularly preferable. Upon polymerization, one kind selected from them or two or more kinds may be mixed and used. Further, other polymerizable monomers may be mixed and used as long as the object of the present invention is not impaired. The perfluoro group-containing (meth) acrylate-based polymerizable monomer represented by the above general formula is, for example,

[0021]

CH ₂ = CH-COO-CH _2- (CF ₂ ) n-CF ₃ CH ₂ = CH-COO-CH ₂ -CH _2- (CF ₂ ) n-CF ₃ CH ₂ = C (CH ₃ ) COO-CH _2- (CF ₂ ) n-CF ₃ CH ₂ = C (CH ₃ ) COO-CH ₂ -CH _2- (CF ₂ ) n-CF ₃ CH ₂ = CH-COO-CH ₂ -CH ₂ -N (CH ₃ ) S0 _2- (CF ₂ ) n-CF ₃ CH ₂ = C (CH ₃ ) COO-CH ₂ -CH ₂ -N (CH ₃ ) S0 _2- (CF ₂ ) n-CF ₃ CH ₂ = CH-COO-CH ₂ -CH ₂ -N (C ₂ H ₅ ) S 0 _2- (CF ₂ ) n-CF ₃ CH ₂ = CH-COO-CH ₂ -CH ₂ -N (C ₃ H ₇ ) S0 _2- (CF ₂ ) n-CF ₃ CH ₂ = CF-COO-CH _2- (CF ₂ ) n-CF ₃ CH ₂ = CF-COO-CH ₂ -CH _2- (CF ₂ ) n-CF ₃ (In the formula, n represents an integer of 2 to 14, more preferably an integer of 5 to 14) and the like, but not limited thereto.

Containing the above-mentioned perfluoroalkyl group (meth)
Polymerization of the acrylate-based polymerizable monomer can be carried out by a conventional radical polymerization method. In this case, solution polymerization, dispersion polymerization, suspension polymerization, emulsion polymerization method can be used.
It is also possible to add the monomer together with a polymerization initiator to an epoxy resin and carry out non-aqueous dispersion polymerization in the presence of a dispersion stabilizer, which is an industrially advantageous method. As the radical polymerization initiator, known compounds can be used, and as the polymerization initiator, various compounds that generate radicals by thermal decomposition, ultraviolet irradiation or the like can be used. Specifically, the following can be exemplified.

Cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, acetyl peroxide,
Organic peroxides such as methyl ethyl ketone peroxide and lauroyl peroxide; azobisisobutyronitrile (hereinafter,
Azo compounds such as AIBN); binary initiators such as hydrogen peroxide-Fe ²⁺ , persulfate-NaHSO ₃ , benzoyl peroxide-dimethylaniline, and the like can also be used.

The molecular weight and molecular weight distribution of the fluorinated (meth) acrylate resin (B) to be polymerized are controlled by appropriately selecting the polymerization conditions and the like by a conventional method. Further, as described above, a perfluoroalkyl group-containing (meth) acrylate-based polymerizable monomer represented by the above general formula and another radical-polymerizable monomer having no fluorine atom are combined to form a copolymer. Doing is also a useful technique. As these copolymerizable components, for example, acrylic monomers are preferable, and specifically, the following can be exemplified.

Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate and isobutyl (meth) acrylate; alkoxy (meth) acrylates such as methoxy (meth) acrylate; cyanoethyl (Meth) acrylate, acrylamide, (meth) acrylic acid, glycidyl (meth) acrylate and the like.

Among them, the fluorine-containing (meth) acrylate resin particles obtained by copolymerizing glycidyl (meth) acrylate increase the affinity with the epoxy resin, and thus the fluorine-containing (meth) acrylate
It improves the interfacial adhesion between the acrylate resin particles and the epoxy resin, and when the epoxy resin is cured, the reaction between the glycidyl group in the fluorine-containing (meth) acrylate resin and the epoxy resin or the epoxy resin curing agent Three-dimensionalization of (meth) acrylate resin occurs,
It is preferable because it has improved mechanical performance and heat resistance.

In the present invention, the fluorine-containing (meth) acrylate resin (B) which is an essential component is required to be substantially insoluble in the epoxy resin (A), and
In order to obtain high performance by adding a small amount of the fluorine-containing (meth) acrylate resin, the composition of the fluorine-containing (meth) acrylate resin (B) is such that the content of the fluorine-containing (meth) acrylate monomer is It is preferably 50% by weight or more, more preferably 70% by weight or more.

In the present invention, the composition ratio of the epoxy resin (A) and the fluorine-containing (meth) acrylate resin (B) is not particularly limited, but from the viewpoint of the stability of the dispersion structure and the economical efficiency of the composition, the epoxy resin The fluorine-containing (meth) acrylate resin (B) is preferably 100 parts by weight or less, and more preferably 30 parts by weight or less with respect to 100 parts by weight of the resin (A).

The dispersion stabilizer used in the present invention will be described. As the dispersion stabilizer, for example, various oligomers or polymers having a perfluoroalkyl group as a hydrophobic group are preferable, but they contribute to the uniform dispersion of the fluorine-containing (meth) acrylate resin or the stability of the dispersed state. This does not apply if it does.

Specific examples of the dispersion stabilizers preferable in the present invention from commercial products include the following. (1) Megafac F-177 (trade name, perfluoroalkyl group-containing oligomer manufactured by Dainippon Ink and Chemicals, Inc.) (2) Florard FC-430 (trade name, fluoroaliphatic polymeric ester manufactured by 3M) ( 3) Unidyne DS-451 (trade name, perfluoroalkyl oligomer manufactured by Daikin Industries, Ltd.) and the like.

The amount of the dispersion stabilizer added is preferably 0.01 to 100 parts by weight of the epoxy resin (A).
The amount is 5.0 parts by weight, more preferably 0.1 to 2.0 parts by weight.

The epoxy resin composition of the present invention is heat-cured by adding an epoxy resin curing agent by a conventional method. These epoxy curing agents are not particularly limited,
For example, the following can be mentioned.

Examples include amine curing agents such as aromatic amines and aliphatic amines; polyphenol compounds such as phenol novolac and cresol novolac; acid anhydrides, dicyandiamide, and hydrazide compounds. Among them, dicyandiamide is preferable because it has excellent latent curability. The ratio of the epoxy resin and the curing agent is such that the active hydrogen of the curing agent is 0.5 to 1.
It is preferable that the amount is 5 mol in view of curability and performance of a cured product.

Further, if necessary, a curing accelerator can be added. Examples of the curing agent accelerator include amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, and 1,8-diazabicycloundecene; 2-ethyl-4-methylimidazole, etc. Imidazole compound, boron trifluoride amine complex, and the like.

Depending on the purpose of use, the epoxy resin composition of the present invention may include talc, mica, calcium carbonate, alumina hydrate, silicon carbide, carbon black, particulates such as silica, whiskers such as silicon carbide and aluminum borate, and the like.
Alternatively, pigments, dyes and the like can be mixed.

[0036]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Reference Example 1 50 g of β- (perfluorooctyl) ethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light ester FA-108) as a perfluoroalkyl group-containing (meth) acrylate-based polymerizable monomer. As a polymerization initiator
BN 0.05g was added and equipped with a condenser for cooling 2
The mixture was placed in a 00 ml separable flask and polymerized at 100 ° C. for 60 minutes while blowing nitrogen into the system. Then 1
The temperature was raised to 20 ° C. and the pressure was reduced to 10 mmHg to remove the residual monomer to obtain a perfluoroalkyl group-containing acrylate polymer.

The polymer obtained was a homogeneous and transparent resin which was solid at room temperature, and the yield thereof was 95% by weight. According to differential calorimetric analysis (DSC), the melting point of this polymer is 81 ° C., and the viscosity at 100 ° C. is 100.
It was 2 poise. This polymer is referred to as PF-1 in the following examples.

Reference Example 2 45 g of β- (perfluorooctyl) ethyl acrylate (same as above) as a perfluoroalkyl group-containing (meth) acrylate-based polymerizable monomer and glycidyl methacrylate (Kyoeisha Co., Ltd.) as a copolymerization component containing no fluorine atom. Kagaku Co., Ltd., trade name: Light Ester G) 5 g is uniformly dissolved, AIBN 0.05 g is added as a polymerization initiator, and the subsequent operation is exactly the same as in Reference Example 1 and glycidyl methacrylate is included in the copolymerization component. An acrylate polymer containing a perfluoroalkyl group was obtained.

The polymer obtained was a cloudy resin which was solid at room temperature, and the yield was 96% by weight. As a result of elemental analysis, it was confirmed that the copolymerization monomer ratio of this polymer was the same as the charged monomer ratio. The viscosity of this polymer at 100 ° C. was 190 poise. This polymer is referred to as PF-2 in the following examples.

Examples 1 to 4 and Comparative Example 1 Using the perfluoroalkyl group-containing acrylate polymers obtained in Reference Examples 1 and 2, the epoxy resin composition of the present invention was evaluated for coating performance. The composition of the epoxy resin composition used for the evaluation is as shown in Table 1.

First, 100 g of a bisphenol A type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumiepoxy ESA011) which is solid at room temperature, and a predetermined amount of the perfluoroalkyl obtained in Reference Example 1 or Reference Example 2 Group-containing acrylate-based polymer and dispersion stabilizer "Florard FC430" manufactured by Sumitomo 3M Limited (FC430
1 g) is charged into a 200 ml separable flask, the epoxy resin and the perfluoroalkyl group-containing acrylate polymer are melted at 150 ° C., and then the mixture is stirred under vacuum at a rotation speed of 500 rpm for 10 minutes. Then, a milky white uniform resin composition was obtained.

As a result of cooling the resin composition and observing it under a microscope, it was found that all systems were resin compositions in which perfluoroalkyl group-containing acrylate polymer fine particles having a particle size of 1 to 5 μm were uniformly dispersed in an epoxy resin. there were. The resin composition, a curing agent, dicyandiamide (sometimes referred to as DICY), and 2-ethyl-4-methylimidazole (sometimes referred to as 2E4MZ) are mixed in a predetermined amount at room temperature, and three-roll mixing is performed at 60 to 70 ° C. Then, an epoxy resin composition containing a curing agent for coating film performance evaluation was obtained.

The epoxy resin composition was placed on a glass substrate preheated to 120 ° C., and a coating film having a thickness of about 50 μm was formed using an applicator. The coating was cured in an oven at 180 ° C for 30 minutes. The coating film obtained was yellowish white and consisted of fluororesin fine particles and epoxy resin.
It was a phase system.

As the evaluation of the coating film performance, a goose-eye test (according to JIS) for evaluating the adhesion of the coating film and a contact angle with water for evaluating the water repellency were measured.
The contact angle was also evaluated for a system whose surface was polished with # 1200 emery paper. The evaluation results are shown in Table 1. From these results, it was found that the epoxy resin composition according to the present invention is a useful material which exhibits extremely good water repellency and which does not impair the adhesiveness to the substrate which is a feature of the epoxy resin.

[0046]

[Table 1] ────────────────────────────────── Example 1 Example 2 Example 3 Example 4 Comparative Example 1 ────────────────────────────────── Resin Composition ESA011 100 100 100 100 100 100 PF-1 10 20 30 − − PF−2 − − − 20 − DICY 3.0 3.0 3.0 3.0 3.0 3.0 2E4MZ 0.5 0.5 0.5 0.5 0.5 0.5 FC430 1.0 1.0 1.0 1.0 1.0 ────────────────────────────────── Evaluation results Contact angle ° (surface ) 110 115 122 122 116 82 Same (# 1200 polished surface) − 131 − 129 93 Goggle eye test − 100 − 100 100 (ke / 100) ────────────── ──────────────────── (units of the resin composition are by weight)

Example 5 Cresol novolac type epoxy resin solid at room temperature (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumiepoxy E)
SCN195X) 100 g, AIBN 0.046 g dissolved β- (perfluorooctyl) ethyl acrylate (same as in Reference Example 1) 45.6 g, and Sumitomo 3M Florad FC4301.0 as a dispersion stabilizer.
g was placed in a 300 ml separable flask equipped with a condenser for cooling, and polymerized under stirring at 120 ° C. for 2 hours. Then, the temperature was raised to 150 ° C. and the volatile components were removed at 10 mmHg. 1.3g of components removed as volatile matter
Met.

Thus, a uniform white resin composition comprising the epoxy resin and the perfluoroalkyl group-containing acrylate polymer was obtained. As a result of analyzing the resin composition, this system was a system in which the perfluoroalkyl group-containing acrylate polymer was uniformly dispersed in the epoxy resin as spherical particles having a particle size of 3 to 5 μm. A part of the resin composition was put into acetone, and a perfluoroalkyl group-containing acrylate polymer which was a non-dissolved component was separated and analyzed. As a result, the melting point was 80.5 ° C and the viscosity at 100 ° C was 8 ° C. It was 1,000 poise. Hereinafter, the resin composition is referred to as INS-1.

Water resistance of the resin composition was evaluated. Table 2 shows the composition (weight basis) of the examined resin composition. This composition was set based on the composition of the resin for the encapsulating material for the epoxy resin-encapsulated semiconductor device, which is required to have improved water resistance. The resin composition was prepared by mixing the respective components in a predetermined ratio and kneading with two rolls.

The resin-encapsulated semiconductor device was prepared by a conventional transfer molding method. The water absorption rate of the resin-encapsulated semiconductor device and solder heat resistance (package crack occurrence rate) as an effect of lowering water absorption were evaluated. Water absorption rate is 8
Evaluation was performed by maintaining at 5 ° C. and 85% humidity for 72 hours. The solder heat resistance was measured by measuring the number of cracked devices after immersing the semiconductor device after absorbing water under the above conditions in a solder bath at 240 ° C. for 30 seconds. The number of tests was 10. In this evaluation, a 52-pin QFP package (with a package thickness of 2.05 mm) was used as the resin-sealed semiconductor device. The evaluation results are shown in Table 2.

From these results, the epoxy resin composition according to the present invention exhibits excellent water resistance (low water absorption rate and excellent solder heat resistance after water absorption), and is a sealing material for resin-sealed semiconductor devices. Have been found to provide useful resin compositions.

Example 6 In Example 5, the component for polymerizing the perfluoroalkyl group-containing acrylate polymer was AIBN 0.076.
A perfluoroalkyl group-containing acrylate polymer was polymerized in an epoxy resin in exactly the same manner as in Example 5 except that 76.0 g of dissolved β- (perfluorooctyl) ethyl acrylate was used. The amount of components removed as volatile matter was 3.7 g. This system was white like the resin composition obtained in Example 5, and as a result of observation, the particle size was 1 to 5
It was a system in which a perfluoroalkyl group-containing acrylate polymer having a spherical shape of μm was uniformly dispersed in an epoxy resin. Hereinafter, the resin composition is referred to as INS-2.

Water resistance of the resin composition was evaluated in the same manner as in Example 5. The composition of the examined resin composition is shown in Table 2. From these results, it was found that the epoxy resin composition according to the present invention exhibits excellent water resistance and provides a resin composition useful as a sealing material for resin-sealed semiconductor devices.

Comparative Example 2 Instead of the resin composition of the present invention, an epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumiepoxy ESCN-19) was used.
Using 5), the same evaluation as in Example 5 was performed as shown in Table 2.

[0055]

[Table 2] ───────────────────────────────── Example 5 Example 6 Comparative Example 2 ──── ───────────────────────────── Resin composition ESCN-195 − − 100.0 INS-1 100.0 − − INS-2 -100.0- Phenol novolac 37.1 30.7 54.3 Triphenylphosphine 1.02 0.85 1.50 Carnauba wax 1.65 1.57 1.85 Silane coupling agent 2.19 2.092 .47 Fused silica 109.7 104.6 123.4 Spherical silica 438.8 412.2 493.8 ─────────────────────────── ─────── Post-curing conditions 180 ℃ × 5 hours ──────────────────── ──────────── Evaluation results Water absorption (wt%) 0.187 0.185 0.223 Solder heat resistance (Package 69 50 100 Rack generation rate%) ─────── ────────────────────────── (Resin composition unit represents parts by weight)

[0056]

The present invention provides an epoxy resin composition which is excellent in water repellency and water resistance without impairing the high adhesion and heat resistance to various base materials, which are advantages of epoxy resins, and a method for producing the same. The epoxy resin composition is particularly useful as a sealing material for resin-sealed semiconductor devices.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location H01L 23/31 (72) Inventor Hiroshi Shiomi 6 Kitahara, Tsukuba, Ibaraki Sumitomo Chemical Co., Ltd.

Claims (5)

[Claims] 1. An epoxy resin (A) which is solid at room temperature and has at least two glycidyl groups in one molecule,
General formula 1 which is substantially insoluble in the epoxy resin [In the formula, X represents a hydrogen atom, a chlorine atom, a fluorine atom or a methyl group. Y is an alkylene group having 1 to 4 carbon atoms _{- (CH 2) n N (} R) SO 2 - ( wherein, R 1 -C
~ 4 alkyl group or hydrogen atom, n represents an integer of 1 to 4. ) Represents. Rf represents a perfluoroalkyl group having 1 to 15 carbon atoms. ] The fluorine-containing (meth) acrylate resin (B) obtained by polymerizing a raw material containing a polymerizable monomer containing a perfluoroalkyl group represented by An epoxy resin composition which is solid at room temperature, wherein the (meth) acrylate resin (B) is uniformly dispersed in the epoxy resin (A) as particles having a particle diameter of 30 μm or less. 2. The epoxy resin composition according to claim 1, which contains a dispersion stabilizer (C). 3. An epoxy resin composition for a resin-sealed semiconductor device, which comprises the epoxy resin composition according to claim 1 or 2 as an essential component. 4. The epoxy resin (A) and the fluorine-containing (meth) acrylate-based resin (B) are mixed in a molten state so that the fluorine-containing (meth) acrylate-based resin is in the form of fine particles in the epoxy resin. The method for producing an epoxy resin composition according to claim 1, wherein the epoxy resin composition is dispersed in, and then cooled. 5. An epoxy resin (A) and a fluorine-containing (meth) acrylate resin (B) in the presence of a dispersion stabilizer (C).
Are mixed in a molten state to disperse the fluorine-containing (meth) acrylate resin in the epoxy resin in the form of fine particles,
The method for producing an epoxy resin composition according to claim 4, wherein the method is followed by cooling.