JPH0885753A - Thermosetting epoxy resin composition - Google Patents

Abstract

PURPOSE: To obtain a thermosetting epoxy resin composition which can give a cured product having a good internal stress relaxation effect, excellent cracking resistance in thermal cycling, and excellent in humidity resistance. CONSTITUTION: This resin composition mainly consists of 100 pts.wt. epoxy resin containing a curing agent and 0.1-50 pts.wt. fine silicone particles prepared by coating 100 pts.wt. fine spherical silicone rubber particles having a mean particle diameter of 0.1-100μm with 1-500 pts.wt. polyorganosilsesquioxane resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting epoxy resin composition, and more particularly to a thermosetting epoxy resin composition suitable for packaging electronic and electric parts.

[0002]

2. Description of the Related Art Various thermosetting resins are used for packaging electronic and electric parts. Among them, epoxy resins are excellent in mechanical properties, electrical properties, heat resistance, adhesiveness, molding processability, etc. Therefore, it is most widely used in large amounts. The package of electronic parts is in the direction of thinning and miniaturization as represented by IC, but the conventional epoxy resin composition has a drawback that the package is easily cracked when subjected to a cooling / heating cycle. . As a method of solving this drawback, a method of mixing fine particles of silicone rubber with an epoxy resin (Japanese Patent Publication Nos. 62-28971, 63-12489, 63-238125, and 64-4614) However, since the silicone rubber fine particles have a strong cohesive property and the dispersibility in the epoxy resin is poor, the internal stress relaxation effect cannot be sufficiently obtained, and in addition, the strength of the base material is reduced. However, there is a problem that the moisture resistance is poor.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in the method of mixing silicone rubber fine particles with an epoxy resin, and since the internal stress relaxation effect is good, cracks are less likely to occur due to cooling and heating cycles. The present invention is intended to provide a thermosetting epoxy resin composition that gives a cured product having excellent moisture resistance, and particularly a thermosetting epoxy resin composition suitable for packaging electronic and electric parts.

[0004]

The thermosetting epoxy resin composition of the present invention has solved the above-mentioned problems, and has the following components (a) and (b) as main components. (A) 100 parts by weight of an epoxy resin containing a curing agent, (b) silicone in which 100 parts by weight of spherical particles of silicone rubber having an average particle size of 0.1 to 100 μm are coated with 1 to 500 parts by weight of a polyorganosilsesquioxane resin. Fine particles 0.1 to 50 parts by weight. The present invention will be described in more detail below.

The epoxy resin used in the present invention is preferably a compound having at least two epoxy groups in one molecule, but the molecular structure and molecular weight are not particularly limited. Examples of such epoxy compounds include 2,
Diglycidyl ether of 2'-bis (4-hydroxyphenyl) propane or its halide, butadiene diepoxide, vinylcyclohexene dioxide, diglycidyl ether of resorcin, 1,4-bis (2,3
-Epoxypropoxy) benzene, 4,4'-bis (2,3-epoxypropoxy) diphenyl ether,
1,4-bis (2,3-epoxypropoxy) cyclohexene, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 1,2-dioxybenzene or resorcinol, polyhydric phenol or polyhydric alcohol and epichlorohydrin Epoxy glycidyl ether or polyglycidyl ester obtained by condensing with, epoxy novolac obtained by condensing novolac type phenol resin (or halogenated novolac type phenol resin) and epichlorohydrin, epoxidized polyolefin epoxidized by the peroxide method , Epoxidized polybutadiene and the like.

The epoxy compound having at least two epoxy groups in one molecule may be appropriately used in combination with a monoepoxy compound. Examples of the monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide and methylglycidyl. Examples thereof include ether, ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, dodecene oxide and the like. Further, the epoxy resin used is not necessarily limited to only one type, and two or more types can be used in combination.

In the present invention, various kinds of conventionally known curing agents for epoxy resins can be used, and examples thereof include diethylenetriamine, triethylenetetramine, diethylaminopropylamine and N-aminoethyl. Piperazine, bis (4-amino-
3-methylcyclohexyl) methane, metaxylyleneamine, menthanediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5)
5) amine compounds such as undecane; epoxy resin-
Modified aliphatic polyamines such as diethylenetriamine adduct, amine-ethylene oxide adduct, cyanoethylated polyamine; bisphenol A, trimethylolallyloxyphenol, low polymerization degree phenol novolac resin, epoxidized or butylated phenol resin or "Super Beckcite" 1001 [ Nippon Reichhold Chemical Co., Ltd.], “Hitanol” 4010 [Hitachi, Ltd.], Scado form L.9 (Netherlands Scado Zwoll), Methylon 75108 (US General Electric) Known as phenolic resin; "Be
ckamine ”P.138 [Nippon Reichhold Chemicals Co., Ltd.]
], "Melan" [Hitachi, Ltd.], "U-Van"
10R Carbon resins known by trade names such as Toyo High Pressure Industrial Co., Ltd .; Amino resins such as melamine resins and aniline resins; Formula HS (C ₂ H ₄ OCH ₂ OC ₂ H ₄ SS) _n C ₂ H ₄ OCH ₂ OC ₂ H ₄ SH (n
= Integer of 1 to 10), a polysulfide resin having at least two mercapto groups in one molecule; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, methylnadic acid,
Examples thereof include organic acids such as dodecyl succinic anhydride and chlorendic anhydride, or anhydrides thereof.

Of the above-mentioned curing agents, the phenolic resin (phenol novolac resin) gives the composition of the present invention good molding workability (transfer molding, injection molding, etc.) and is used for sealing resin of IC, LSI and the like. It provides good moisture resistance when utilized and is desirable because it is non-toxic and relatively inexpensive. The above-mentioned curing agents are not necessarily limited to one type in use, and two or more types may be used in combination depending on the curing performance of the curing agents. The amount of this curing agent used varies depending on the specific type, but it is generally 1 to 100 parts by weight of the epoxy resin.
The amount is 100 parts by weight, preferably 5 to 50 parts by weight.
This is because if the amount of the curing agent used is less than 1 part by weight, it becomes difficult to cure the composition of the present invention satisfactorily.
If it exceeds 100 parts by weight, it will be economically disadvantageous and the epoxy resin will be diluted and it will take a long time to cure,
Furthermore, it is disadvantageous in that the physical properties of the cured product deteriorate.

The silicone fine particles used in the present invention are
The silicone rubber spherical fine particles having an average particle diameter of 0.1 to 100 μm are coated with a polyorganosilsesquioxane resin.
It is advisable to add an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane to an aqueous dispersion of 100 μm silicone rubber spherical fine particles to cause a hydrolysis-condensation reaction of the organotrialkoxysilane. This method is suitable for the present invention. It can be manufactured.

[0010] The silicone rubber spherical fine particles of the general formula in the molecular structure formula _{^{(1) - (R 1 2}} SiO) a - ····· (1) ( here R ¹ is a methyl group, an ethyl group, a propyl Group, alkyl group such as butyl group, aryl group such as phenyl group and tolyl group, alkenyl group such as vinyl group and allyl group, β-
Aralkyl groups such as phenylethyl group and β-phenylpropyl group, monovalent halogenated hydrocarbon groups such as chloromethyl group and 3,3,3-trifluoropropyl group, and further epoxy group, amino group, mercapto group, acryloxy group Group, one or more monovalent group having 1 to 20 carbon atoms selected from reactive group-containing organic groups such as methacryloxy group, 90 mol% or more of which is preferably methyl group When a is less than 5, the characteristics of the linear organopolysiloxane are not sufficiently exhibited, so that the effects of lowering internal stress and improving lubricity cannot be sufficiently obtained, and the maximum value of a is not particularly specified. However, if it is more than 5,000, it becomes difficult to produce silicone rubber spherical fine particles. Therefore, a is a linear organopolysiloxane represented by 5 to 5,000, preferably 10 to 1,000. Of molecules with a down block, it is made of a cured product of spherical having rubber elasticity.

The silicone rubber spherical fine particles may contain silicone oil, organosilane, inorganic powder, organic powder or the like in the particles, but if the average particle diameter of the spherical fine particles is less than 0.1 μm. Since the fluidity of the particles becomes low, the cohesiveness becomes high, and if it exceeds 100 μm, the moldability of the epoxy resin and the properties of the epoxy resin may be impaired. Therefore, the average particle size is 0.1 to 100 μm. However, the preferable range is 1 to 30 μm.

A cross-linking method in the production of the silicone rubber spherical fine particles is a methoxysilyl group (≡SiOCH ₃ ).
Condensation reaction of hydroxysilyl group (≡SiOH) with mercaptosilyl group (≡SiSH) and vinylsilyl group (≡SiCH)
= CH ₂ ) radical reaction with vinylsilyl group (≡SiCH = C
Examples thereof include those obtained by addition reaction of H ₂ ) with ≡SiH group. However, from the viewpoint of reactivity and reaction process, addition reaction is preferable, and therefore, (a) vinyl group-containing organopolysiloxane. It is preferable to use a composition in which (b) the organohydrogenpolysiloxane and (c) are subjected to an addition reaction in the presence of a platinum-based catalyst to cure.

The component (a) is the main component of the organopolysiloxane which gives the silicone rubber spherical fine particles,
It is a component that is cured by the addition reaction with the component (b) due to the catalytic action of the component (c). The component (a) is required to have at least two vinyl groups bonded to a silicon atom in one molecule. The vinyl group may be present at any part of the molecule, but at least at the terminal of the molecule. Preferably. Examples of the organic group bonded to a silicon atom other than the vinyl group include those selected from the monovalent organic groups similar to R ¹ described above, and 90 mol% or more thereof is preferably a methyl group. The molecular structure of this component may be linear or mixed with a small amount of branches, and the molecular weight of this component is not particularly limited.

As the component (a), for example, the following general formula

Embedded image (Where b and c are 0, 1, 2 or 3 and b + c =
3, d is a positive number, e is 0 or a positive number, and 2b + e
≧ 2. ),

Embedded image (Here, f is an integer of 2 or more, g is 0 or a positive integer, and (f + g) is 4 to 8).

[Chemical 3] (Here, h is 1, 2 or 3, i is 0, 1 or 2, and (h + i) = 3, and j, k, and L are positive numbers.) And the like.

Next, the above component (b) is a cross-linking agent of the component (a), and the hydrogen atom bonded to the silicon atom in this component is the vinyl in the component (a) by the catalytic action of the component (c). It cures by addition reaction with groups. Therefore, this component (b) needs to have at least two hydrogen atoms bonded to a silicon atom in one molecule, and the organic group bonded to a silicon atom other than this hydrogen atom is the same as R ¹ described above. It is selected from the monovalent organic groups described in 1., but 90 mol% or more thereof is preferably a methyl group. The molecular structure of the component (b) is not particularly limited and may be linear, branched or cyclic, or a mixture thereof, and the molecular weight is not particularly limited, either. In order to improve the compatibility with the component (a), the viscosity at 25 ° C is preferably 1 to 10,000 cP. In addition, the addition amount of this component is (a)
When the amount of hydrogen atoms bonded to the silicon atom of this component is less than 0.5 per 1 vinyl group in the component, good curability is difficult to obtain, and hydrogen atom exceeds 20. In the case of the amount, the physical properties of the rubber after curing are deteriorated, and therefore the amount may be 0.5 to 20 hydrogen atoms, preferably 0.5 to 5 hydrogen atoms.

Examples of the component (b) include the following general formula

[Chemical 4] (However, m is 0 or 1, n is 2 or 3, and m + n
= 3, p is 0 or a positive number, q is 0 or a positive number, and 2m + q ≧ 2. ),

[Chemical 5] (However, r is an integer of 2 or more, s is 0 or a positive integer, and (r + s) is 4 to 8.),

[Chemical 6] (However, t is 1, 2 or 3, u is 0, 1 or 2, and (t + u) = 3, and v, w, and x are positive integers.) And the like.

The component (c) is a catalyst for addition-reacting a vinyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom, such as platinum-supported carbon or silica, chloroplatinic acid, platinum-olefin complex. , Platinum-alcohol complex, platinum-phosphorus complex, platinum coordination compound and the like. Regarding the amount of this component used, if the amount of platinum atom is less than 1 ppm relative to component (a), the curing will be slow and susceptible to the effects of catalyst poisons, but if it exceeds 100 ppm, it is expected that the curing rate will be particularly improved. However, the range of 1 to 100 ppm is preferable.

The silicone rubber spherical fine particles can be produced by reacting the above-mentioned component (a) with the component (b) in the presence of the component (c) and curing it into spherical fine particles. (A) component, (b) component and (c)
There are a method of curing a mixture of components in high temperature spray drying, a method of curing in an organic solvent, a method of forming an emulsion mixture and then curing. Among these, since it is preferable to use the silicone rubber spherical fine particles as an aqueous dispersion in the production of the silicone fine particles used in the present invention, it is preferable to use a method in which the mixture is made into an emulsion and then cured in the emulsion particles.

In this method, first, the above-mentioned (a)
A predetermined amount of a vinyl group-containing organopolysiloxane as a component and a predetermined amount of an organohydrogenpolysiloxane as a component (b) are mixed to prepare an organopolysiloxane composition, and then water and a surfactant are added to the obtained composition. After addition, this is emulsified using a commercially available homomixer or the like. The surfactant used here is selected from nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester and glycerin fatty acid ester, which have little adverse effect on the curing reaction. It is preferable to select. If the amount of the surfactant added is less than 0.01 parts by weight per 100 parts by weight of the emulsion, fine particles cannot be obtained, and if it is more than 20 parts by weight, the polyorganosilsesquioxane resin in the post-process described below will not be added. Since it becomes difficult to coat it, it is necessary to set it in the range of 0.01 to 20 parts by weight,
The preferred range is 0.05 to 10 parts by weight.

The content of the vinyl group-containing organopolysiloxane as the component (a) and the organohydrogenpolysiloxane as the component (b) in the emulsion is 1 part by weight based on 100 parts by weight of the emulsion. If it is less than the part, it will be disadvantageous efficiently and 80
If the amount exceeds 1 part by weight, it becomes impossible to form an emulsion of independent cured particles, so the range of 1 to 80 parts by weight,
More preferably, it is in the range of 10 to 60 parts by weight. When silicone oil, silane, inorganic powder, organic powder or the like is contained in the silicone rubber spherical fine particles, an organopolysiloxane composed of the components (a) and (b) is used when emulsifying. These may be mixed in the composition.

The emulsion thus prepared is then added with a platinum-based catalyst as the component (c) to cure the organopolysiloxane, to give a silicone rubber cured product dispersion. A well-known reaction control agent may be added to this platinum-based catalyst. If the platinum-based catalyst and reaction control agent are difficult to disperse in water, a surfactant can be used to disperse them in water. You may add it after doing so. By thus curing with a catalyst, an aqueous dispersion of silicone rubber spherical fine particles having an average particle diameter of 0.1 to 100 μm can be obtained.

The silicone fine particles used in the present invention are obtained by coating the silicone rubber spherical fine particles with a polyorganosilsesquioxane resin. The polyorganosilsesquioxane has the following general formula (2) R ² SiO ^2. _3/2 (2) A resinous polymer having a siloxane unit as a constituent unit. In this formula, R ² is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an aryl group such as a phenyl group or a tolyl group, an alkenyl group such as a vinyl group or an allyl group, a β-phenylethyl group, a β group. -Aralkyl group such as phenylpropyl group, chloromethyl group, 3,3,3
A monovalent halogenated hydrocarbon group such as a trifluoropropyl group, an epoxy group, an amino group, a mercapto group,
It is an organic group having 1 to 20 carbon atoms consisting of one or more selected from monovalent organic groups having a reactive group such as an acryloxy group and a methacryloxy group. Incidentally, 50 mol% or more of R ² is preferably a methyl group, and a small amount of R ² ₂ SiO _2/2 unit other than the R ² SiO _3/2 unit described above is not impaired. , R ² ₃ SiO _1/2 unit and SiO ₂ unit may be contained.

The polyorganosilsesquioxane resin may coat the entire surface of the silicone rubber spherical fine particles uniformly or may cover a part of the surface.
If the amount of this polyorganosilsesquioxane resin is less than 1 part by weight based on 100 parts by weight of the silicone rubber spherical fine particles, the fluidity, dispersibility and dispersibility of the obtained silicone fine particles into the epoxy resin will be poor, and 500 parts by weight will be obtained. If the amount is more than 100 parts, the characteristics of the silicone rubber spherical fine particles, that is, the effect of reducing stress, cannot be fully exerted.
It is necessary to adjust the amount by weight, but preferably 5 to 100
It may be part by weight.

Next, in the method for producing the silicone fine particles used in the present invention, as described above, the average particle size is
A method of adding an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane to an aqueous dispersion of silicone rubber spherical fine particles having a particle size of 0.1 to 100 μm to hydrolyze and condense the organotrialkoxysilane is preferable. Since the silicone rubber spherical fine particles are used in the form of being dispersed in water, the aqueous dispersion produced by the above-mentioned method may be used as it is, or may be further diluted with water before use. Good. If the amount of the silicone rubber fine particles in 100 parts by weight of the aqueous dispersion of the silicone rubber spherical fine particles is less than 1 part by weight, the production efficiency of the desired silicone fine particles will be low.
If the amount is more than the weight part, it becomes difficult to coat the polyorganosilsesquioxane resin on the silicone rubber spherical fine particles, and the particles may aggregate or fuse, so that
This is in the range of 1 to 60 parts by weight, preferably 5 to 40 parts by weight.

Further, in order to improve the dispersibility of the silicone rubber spherical fine particles in the aqueous dispersion, and for uniformly coating the surface of the silicone rubber spherical fine particles of the polyorganosilsesquioxane resin described below, the water dispersion is performed. A surfactant may be added to the liquid. The surfactant is not particularly limited, and examples thereof include cationic surfactants such as quaternary ammonium salt and alkylamine salt, amphoteric ion surfactants such as alkylbetaine, polyoxyethylene alkyl ether, Nonionic surfactants such as polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, glycerin fatty acid ester, etc., anionic surfactants such as organic sulfonates, alkyl sulfate ester, etc., and the like. One kind or two or more kinds can be used.

The alkaline substance or alkaline aqueous solution added to the aqueous dispersion of silicone rubber spherical fine particles is used for promoting the hydrolysis and condensation of the organotrialkoxysilane described below. PH of aqueous dispersions after addition of alkaline substances or alkaline aqueous solutions
Is less than 10.0, the hydrolysis and condensation of the organotrialkoxysilane does not proceed sufficiently, and in some cases fusion of the particles with each other may occur, and when the pH is higher than 13.0, the organotrialkoxy group Since the rate of hydrolysis of silane increases, a hydrolysis reaction occurs at a portion other than the surface of the silicone rubber spherical fine particles, and it becomes difficult to efficiently generate the polyorganosilsesquioxane resin on the surface of the silicone rubber spherical fine particles. , PH is 10.0 to 13.
It is preferable that the range is 0, particularly 10.5 to 12.5.

The alkaline substance or alkaline aqueous solution may be any as long as it has a catalytic action for the hydrolysis and condensation reaction of the organotrialkoxysilane, but usually potassium hydroxide, sodium hydroxide, lithium hydroxide. Alkali metal hydroxides such as, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate,
Ammonia or monomethylamine, dimethylamine,
Amines such as monoethylamine, diethylamine and ethylenediamine, and quaternary ammonium hydroxide such as tetramethylammonium hydroxide may be used,
Of these, ammonia is most suitable because it has excellent solubility in water, catalytic activity, and can be easily removed from the silicone fine particles by volatilization. 28% by weight) may be used.

The organotrialkoxysilane is used for forming a polyorganosilsesquioxane resin on the surface of the silicone rubber spherical fine particles by hydrolysis and condensation reaction, and this organotrialkoxysilane is generally used. Formula (3) R ² Si (OR ³ ) ₃ (3) (wherein R ² is the same monovalent organic group as described above, R ³ is a methyl group,
Those represented by C1-6 alkyl groups such as ethyl, propyl, butyl, etc., such as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane , Propyltrimethoxysilane, butyltrimethoxysilane, N- (β-aminoethyl) -γ-
Aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3,3,3-tri Fluoropropyltrimethoxysilane, 3,3,4,4,5,5,6
6,6-Nonafluorohexyltrimethoxysilane, 3,
3,4,4,5,5,6,6,7,7,8,8,9,
9,10,10,10-heptadecafluorodecyltrimethoxysilane and the like can be used alone or in combination of two or more kinds.

The amount of the organotrialkoxysilane added is 100 parts by weight of water in the aqueous dispersion of silicone rubber spherical fine particles.
If the amount is too much with respect to parts by weight, lumps may be generated, so the amount is preferably 20 parts by weight or less. Further, if the stirring is too strong during hydrolysis and condensation, the particles tend to aggregate or fuse together, especially when the amount of the organotrialkoxysilane used is large, so it is preferable to carry out the stirring under as mild a condition as possible. . Generally, a propeller blade, a flat blade, or the like is suitable as the stirring device used. If the reaction temperature is lower than 0 ° C., the liquid will be solidified, and if it is higher than 60 ° C., particles composed only of the generated polyorganosilsesquioxane will be generated, and the particles may aggregate or fuse with each other. The temperature is preferably 0 to 60 ° C, particularly 5 to 20 ° C.

The addition of the alkaline substance or the alkaline aqueous solution for the hydrolysis or condensation reaction may be carried out at the same time as the addition of the organotrialkoxysilane or after the addition of the organotrialkoxysilane. When a large amount is added, it is preferable to add it to the aqueous dispersion of silicone rubber spherical fine particles in advance. The organotrialkoxysilane may be added to the reaction system all at once, but when the amount is large, particles may aggregate or fuse with each other if added in large amounts, so gradually add a small amount over time. It is advisable to add them each. Stirring during the reaction may be continued for a while after completion of addition of the organotrialkoxysilane until the hydrolysis and condensation reactions are completed, but heating is performed to complete the hydrolysis and condensation reactions. Alternatively, if necessary, an acidic substance may be added for neutralization.

After the completion of the reaction, the dispersion is concentrated by a method such as heat dehydration, filtration, centrifugation, decantation, etc., and then washed with water if necessary, and further dried by heating under normal pressure or reduced pressure, in an air stream. If the water content is removed by spray-drying spraying the dispersion liquid onto the product, heat drying using a fluid heat medium, etc., the desired silicone microparticles obtained by coating the silicone rubber spherical microparticles with polyorganosilsesquioxane resin are obtained. However, if the obtained silicone fine particles are slightly agglomerated, a jet mill,
The crushing may be performed by appropriately using a crusher such as a ball mill and a hammer mill.

The amount of the silicone fine particles obtained as described above is 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the epoxy resin containing a curing agent. This is because if the blending amount is too small, the effect of adding the silicone fine particles, that is, the improvement in the durability against heat and cold cycles and the improvement in the moisture resistance is difficult to manifest, and if it exceeds 50 parts by weight, the original properties of the thermosetting epoxy resin are impaired. further,
The thermosetting epoxy resin composition of the present invention, in addition to the above-mentioned epoxy resin, curing agent, each component of the silicone fine particles,
Various additives generally used in the thermosetting epoxy resin composition can be blended as necessary according to the use and purpose. Examples of such additives include fumed silica, fused silica, crystalline silica, inorganic fillers such as alumina, flame retardants such as antimony oxide, halogen compounds and phosphorus compounds, higher fatty acid metal salts, ester waxes, etc. Examples of the internal release agent, silane coupling agent, pigment, dye and the like. The thermosetting epoxy resin composition of the present invention, each component required, roll,
It can be prepared by uniformly kneading using a mixing device such as a kneader.

[0033]

EXAMPLES Next, examples of the present invention will be described. In the examples, “part” means “part by weight” and “%” means “% by weight”. [Production Example 1] Formula

[Chemical 7] 500g of methyl vinyl siloxane with a viscosity of 600cS
And the expression

Embedded image 20 g of methylhydrogenpolysiloxane having a viscosity of 30 cS shown in 1 is charged into a glass beaker having a capacity of 1 liter, and mixed by stirring at 2,000 rpm using a homomixer, and then polyoxyethylene (number of moles added = 9 moles) octylphenyl When 1 g of ether and 150 g of water were added and stirring was continued at 6,000 rpm, phase inversion occurred and thickening was observed, but when 329 g of water was added while stirring at 2,000 rpm, O / W type An emulsion was obtained.

Then, this emulsion was transferred to a glass flask equipped with a stirrer with an anchor type stirring blade, and at room temperature with stirring, 1 g of a toluene solution of a chloroplatinic acid-olefin complex (platinum content: 0.05%) and polyoxyethylene ( A mixture of 1 g of octyl phenyl ether was added and reacted for 12 hours to obtain a dispersion liquid (hereinafter referred to as silicone rubber spherical fine particle water dispersion liquid-1).
The average particle size of the particles in this dispersion was measured using a Coulter counter (manufactured by Coulter Electronics Co.) and was found to be 15 μm.

2,290 g of water in a 3 liter glass flask,
Silicone rubber spherical fine particle water dispersion liquid-1 obtained above
580 g and ammonia water (concentration 28% by weight) 60 g were charged, and the water temperature was set to 10 ° C., and stirring was performed by an anchor type stirring blade under the condition of a blade rotation speed of 200 rpm. The pH of the liquid at this time was 11.2, but 65 g of methyltrimethoxysilane was added dropwise to this liquid over 20 minutes, while maintaining the liquid temperature at 5 to 15 ° C,
After stirring for an hour, the mixture was heated to 55 to 60 ° C. and then stirred for 1 hour, and the obtained liquid was made into a cake of about 30% water using a pressure filter.

Next, the cake-like product was dried in a hot air circulation dryer at a temperature of 105 ° C., and the dried product was crushed with a jet mill. Observation of the obtained fine particles with an optical microscope confirmed that they were spherical fine particles, but for this, they were dispersed in water using a surfactant and the average particle size was measured using a Coulter counter. Done 15
was μm. In addition, the weight analysis of the silicone fine particles revealed that 100 parts by weight of the silicone rubber spherical fine particles were coated with 10 parts by weight of a polyorganosilsesquioxane resin. Further, when the fluidity and dispersibility were examined according to the method described later, the results shown in Table 1 were obtained.
The obtained silicone fine particles are referred to as silicone fine particles-1.

[Production Example 2] Silicon fine particles were prepared in the same manner as in Production Example 1 except that 65 g of methyltrimethoxysilane of Production Example 1 was changed to a mixture of 55 g of methyltrimethoxysilane and 10 g of γ-glycidoxypropyltrimethoxysilane. It was made. Observation of the obtained fine particles with an optical microscope confirmed that they were spherical fine particles, but for this, they were dispersed in water using a surfactant and the average particle size was measured using a Coulter counter. Done 15
was μm. Further, by weight analysis of the silicone fine particles, 100 parts by weight of the silicone rubber spherical fine particles were coated with 11 parts by weight of a polyorganosilsesquioxane resin. When the fluidity and dispersibility were examined, the results shown in Table 1 were obtained. The obtained silicone fine particles are referred to as silicone fine particles-2.

[Production Example 3] 65 g of methyltrimethoxysilane of Production Example 1 was added dropwise over 20 minutes, and 20 g of methyltrimethoxysilane was added over 10 minutes.
Silicone particles were prepared in the same manner as in Production Example 1. Observation of the obtained fine particles with an optical microscope confirmed that they were spherical fine particles, but for this, they were dispersed in water using a surfactant and the average particle size was measured using a Coulter counter. The result was 15 μm. In addition, by weight analysis, 100 parts by weight of the silicone rubber spherical particles were coated with 3 parts by weight of the polyorganosilsesquioxane resin. When the fluidity and dispersibility were examined, the results shown in Table 1 were obtained. The obtained silicone fine particles are referred to as silicone fine particles-3.

[Production Example 4] 2,290 g of water in a 3 liter glass flask, 350 g of the silicone rubber spherical fine particle water dispersion-1 obtained in Production Example 1 and ammonia water (concentration 28
(Wt%) 60g was charged, the water temperature was 10 ° C, and the blade rotation speed was 200r.
Stirring was performed with an anchor type stirring blade under the condition of pm. The pH of the liquid at this time was 11.1, but 300 g of methyltrimethoxysilane was added dropwise to this liquid over 100 minutes, and the liquid temperature was kept between 5 and 15
After keeping the temperature at ℃ and stirring for 4 hours, it was heated to 55 to 60 ℃, and then stirred for 1 hour, and the obtained liquid was made into a cake of about 30% water using a pressure filter. .

Next, this cake-like material was dried in a hot air circulation dryer at a temperature of 105 ° C., and the dried material was crushed with a jet mill. Observation of the obtained fine particles with an optical microscope confirmed that they were spherical fine particles, but for this, they were dispersed in water using a surfactant and the average particle size was measured using a Coulter counter. Done 18
was μm. Further, by weight analysis of the silicone fine particles, 100 parts by weight of the silicone rubber spherical fine particles were covered with 81 parts by weight of a polyorganosilsesquioxane resin. When the fluidity and dispersibility were examined, the results shown in Table 1 were obtained. The obtained silicone fine particles are referred to as silicone fine particles-4.

[Production Example 5] O in Production Example 1 described above
1g of polyoxyethylene (addition number of moles = 9 moles) octyl phenyl ether used when making / W emulsion
Was 5 g to obtain a silicone rubber spherical fine particle aqueous dispersion (hereinafter referred to as silicone rubber spherical fine particle aqueous dispersion-2) in the same manner as in Production Example 1. The average particle size of the particles in this dispersion was determined by Coulter 3μ when measured using a counter
It was m. This silicone rubber spherical fine particle water dispersion-
Silicone particles were prepared in the same manner as in Production Example 1 except that 2 was used instead of the aqueous dispersion of silicone rubber spherical particles-1. Observation of the obtained fine particles with an optical microscope confirmed that they were spherical fine particles, but for this, they were dispersed in water using a surfactant and the average particle size was measured using a Coulter counter. It was 3 μm. In addition, the weight analysis of the silicone fine particles revealed that 100 parts by weight of the silicone rubber spherical fine particles were coated with 10 parts by weight of a polyorganosilsesquioxane resin. When the fluidity and dispersibility were examined, the results shown in Table 1 were obtained. The obtained silicone fine particles are referred to as silicone fine particles-5.

[Example 1] 67.9 parts of epoxy cresol novolac resin (EOCN-102, manufactured by Nippon Kayaku Co., Ltd.) having an epoxy equivalent of 220, 32.1 parts of phenol novolac resin (MP-120, manufactured by Gunei Chemical Co., Ltd.) , Silicone fine particles-1 to 1
0.0 parts, crystalline quartz powder 370.5 parts, carbon black 12
Parts, 1.2 parts carnauba wax, and as a curing accelerator
1.3 parts of C ₁₁ Z azine (trade name, manufactured by Shikoku Kasei Co., Ltd.) was uniformly mixed, further kneaded with two hot rolls at 80 to 95 ° C., and then pulverized to obtain a thermosetting epoxy resin composition. When the composition was tested for the items described below, the results shown in Table 2 were obtained.

[Examples 2 to 7] Thermosetting epoxy resin compositions were obtained in the same manner as in Example 1 except that the composition of Example 1 was changed as shown in Table 2. When the composition was tested for the items described below, the results shown in Table 2 were obtained.

[Production Example 6] The aqueous dispersion of silicone rubber spherical fine particles-1 obtained in Production Example 1 was heated to 90 ° C to destabilize the dispersion of the fine particles, and then water was added using a pressure filter. A cake of about 30% was obtained and further dried in a dryer at a temperature of 105 ° C. to obtain silicone rubber fine particles. When the obtained silicone rubber fine particles were observed with an optical microscope, it was confirmed that they were spherical fine particles.For this, they were dispersed in water using a surfactant and the average particle size was measured using a Coulter counter. It was 15 μm. When the fluidity and dispersibility were examined, the results shown in Table 1 were obtained. The obtained silicone rubber fine particles are referred to as silicone rubber fine particles-1.

[Production Example 7] Silicon fine particles were prepared in the same manner as in Production Example 1 except that 65 g of methyltrimethoxysilane of Production Example 1 was added dropwise over 20 minutes to 3 g of methyltrimethoxysilane at one time. It was made. Observation of the obtained fine particles with an optical microscope confirmed that they were spherical fine particles, but for this, they were dispersed in water using a surfactant and the average particle size was measured using a Coulter counter. The result was 15 μm. Further, by weight analysis of the silicone fine particles, 100 parts by weight of the silicone rubber spherical fine particles were coated with 0.5 part by weight of a polyorganosilsesquioxane resin. When the fluidity and dispersibility were examined, the results shown in Table 1 were obtained. The obtained silicone fine particles are referred to as silicone fine particles-6.

[Production Example 8] 2,360 g of water in a 3 liter glass flask, 80 g of the silicone rubber spherical fine particle water dispersion-1 obtained in Production Example 1 and ammonia water (concentration 28
(Wt%) 60g was charged, the water temperature was 10 ° C, and the blade rotation speed was 200r.
Stirring was performed with an anchor type stirring blade under the condition of pm. The pH of the liquid at this time was 11.3, but 500 g of methyltrimethoxysilane was added dropwise to this liquid over 180 minutes, during which the liquid temperature was adjusted to 5 to 15
After keeping the temperature at ℃ and stirring for 4 hours, it was heated to 55 to 60 ℃, and then stirred for 1 hour, and the obtained liquid was made into a cake of about 30% water using a pressure filter. .

Then, the cake-like product was dried in a hot air circulation dryer at a temperature of 105 ° C., and the dried product was crushed by a jet mill. Observation of the obtained fine particles with an optical microscope confirmed that they were spherical fine particles, but for this, they were dispersed in water using a surfactant and the average particle size was measured using a Coulter counter. Done 20
was μm. The weight analysis of the silicone particles showed that 100 parts by weight of the silicone rubber spherical particles were coated with 600 parts by weight of polyorganosilsesquioxane resin. Therefore, the polyorganosilsesquioxane resin does not cover all the silicone rubber spherical fine particles,
It was thought that particles of only the polyorganosilsesquioxane resin were present. When the fluidity and dispersibility were examined, the results shown in Table 1 were obtained. The obtained silicone fine particles are used as silicone fine particles-7
I call it.

[Comparative Examples 1 to 5] Thermosetting epoxy resin compositions were obtained in the same manner as in Example 1 except that the composition of Example 1 was changed as shown in Table 2. When the composition was tested for the items described below, the results shown in Table 2 were obtained.

The evaluation methods for examining the fluidity and dispersibility of the silicone fine particles obtained in each production example are as follows. (Evaluation of fluidity) Sample 10 was put in the funnel with the inner diameter of the outlet of 4 mm.
g was added, and the funnel was vibrated with an amplitude of 1 mm using a powder characteristic measuring apparatus, Powder Tester PT-E [trade name, manufactured by Hosokawa Micron Co., Ltd.], and the time required for the sample to be completely discharged from the funnel was measured. (Evaluation of dispersibility) Powder characteristic measuring device, powder tester PT
-Using the E type (mentioned above), apply a vibration with an amplitude of 1 mm to the sieve.
The sieving ability with a 00 mesh, 100 mesh and 60 mesh sieve was measured (90 seconds, sample amount 2 g).

Further, test pieces were prepared from the thermosetting epoxy resin compositions obtained in the respective examples and comparative examples under the following conditions, and the following items were tested. (Molding of test piece) Temperature from thermosetting epoxy resin composition
After transfer-molding various test specimens under the conditions of 160 ° C. and a pressure of 70 kg / cm ² , post-curing was performed at 180 ° C. for 4 hours and the test was performed. (Linear expansion coefficient) Measured according to JIS K 6911. (Flexural modulus) Measured by ASTM D-790. (Dispersibility of Silicone Fine Particles in Cured Product) The fracture surface of the molded product was observed with an electron microscope to examine the dispersion state of the silicone fine particles. (Cooling cycle test) 0.35 mm thick silicon wafer
Cut it into a rectangle of 16mm x 4.5mm and cut it into a 14-pin IC frame (42
After being cured (encapsulated) and post-cured, each composition was adhered to the alloy under the above conditions. The obtained test piece was cooled at −55 ° C. for 30 minutes and heated at 150 ° C. for 30 minutes to perform a so-called cooling / heating cycle, and the number of cycles until the defective rate due to crack cracking of the molding resin reached 50% was measured. (Humidity resistance test) A monitor IC, in which an aluminum simulated element was encapsulated with each composition under the above conditions, was subjected to a pressure cooker test, and the number of defects n /
The parameter (50) was measured.

[0051]

[Table 1]

[0052]

[Table 2]

As shown in Table 2, the thermosetting epoxy resin composition of the present invention has a good dispersion of silicone fine particles, and the molded product has a reduced linear expansion coefficient and bending elastic modulus, and thus has a stress relaxation property. It was excellent in heat resistance, was not easily cracked even by a heat cycle, and had excellent moisture resistance.

[0054]

EFFECT OF THE INVENTION Since the silicone fine particles used in the present invention have weaker cohesiveness and excellent dispersibility in the composition as compared with the conventional silicone rubber fine particles, the thermosetting epoxy resin composition of the present invention is In addition, cracks are less likely to occur due to the cooling / heating cycle, and a molded article having excellent moisture resistance is provided, which is extremely suitable for a package.

Claims (2)

[Claims] 1. A thermosetting epoxy resin composition comprising the following components (a) and (b) as main components. (A) 100 parts by weight of an epoxy resin containing a curing agent, (b) silicone in which 100 parts by weight of spherical particles of silicone rubber having an average particle size of 0.1 to 100 μm are coated with 1 to 500 parts by weight of a polyorganosilsesquioxane resin. Fine particles 0.1 to 50 parts by weight. 2. The silicone fine particles have an average particle diameter of 0.1 to
The product obtained by adding an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane to an aqueous dispersion of silicone rubber spherical fine particles of 100 μm, and hydrolyzing and condensing the organotrialkoxysilane. The thermosetting epoxy resin composition of.