JPH09208839A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin compsn. having a high thermal shock resistance and excellent heat resistance and mechanical properties. SOLUTION: This compsn. contains 100 pts.wt. thermosetting resin, 3-30 pts.wt. silanol-reactive organopolysiloxane, a silicon alkoxide in an amt. of 2-25 pts.wt. in terms of solid silica, water in an amt. of 0.1-10mol per mol of the silicon alkoxide, a catalyst for the reaction of the silicon alkoxide in an amt. of up to 0.3mol per mol of the silicon alkoxide, and an org. solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting resin composition comprising a thermosetting resin, an organopolysiloxane having a functional group reactive with a silanol group, a silicon alkoxide, water, a catalyst and an organic solvent. The present invention relates to a method for producing the same and a cured resin, and is useful as a molding material, a heat insulating material, a coating material, a sliding material, a laminated material and the like.

[0002]

2. Description of the Related Art Among organic polymer materials, thermosetting resins are currently used in a wide range of fields including electricity, electronics, automobiles, construction, and civil engineering. Extensive research has been conducted to improve the properties of the resinous resin. However, since thermosetting resins are generally brittle due to their three-dimensional cross-linking properties, it is an important subject to improve their brittleness, that is, impact resistance.

Therefore, conventionally, it has been widely studied to improve the impact resistance by adding a resin having a low glass transition temperature such as a liquid resin or a rubber resin to a thermosetting resin to form a composite, and it is partially put to practical use. It is shared. For example, a method in which natural rubber, acrylonitrile-butadiene rubber (NBR), rubber emulsion or latex, or a thermoplastic resin such as polyethylene terephthalate or polyurethane is externally added to phenol resin or epoxy resin, A method of introducing a long-chain polyethylene bond or urethane bond into the thermosetting resin has been reported (for example,
Thermosetting resin, Vol. 13, No. 3, pages 32-42).

However, even though impact resistance is improved by these methods in which a resin having a low glass transition temperature related to the thermosetting resin is added and mixed, the heat resistance characteristic of the thermosetting resin is improved. In many cases, it decreases or other static mechanical properties such as elastic modulus and bending strength decrease, which is a big problem in practical use.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a thermosetting resin composition having good impact resistance, heat resistance and mechanical properties. is there.

[0006]

[Means for Solving the Problems] The inventors of the present invention are keen to obtain a thermosetting resin having improved mechanical properties such as impact resistance, flexural strength and elastic modulus while maintaining the heat resistance of the thermosetting resin. As a result of research, a resin cured product obtained from a thermosetting resin composition containing a specific organopolysiloxane, a silicon alkoxide, water, and a catalyst in a thermosetting resin solution contains both organopolysiloxane and silica. The present invention has been completed by finding that a resin composite that is contained in a finely dispersed state becomes a homogeneous resin, and that the cured product of the resin solves the above problems and exhibits excellent properties.

That is, the present invention provides (A) thermosetting resin 100.
Parts by weight, (B) 3 to 30 parts by weight of organopolysiloxane having a functional group reactive with a silanol group, (C) 2 to 25 parts by weight of silicon alkoxide as a silica solid content, and (D) water. And the reaction catalyst of silicon alkoxide are 0.1 to 10 molar ratio of silicon alkoxide and 0, respectively.
A thermosetting resin composition containing (E) an organic solvent,

The present invention also provides (A) thermosetting resin 100.
Parts by weight, (B) 3 to 30 parts by weight of an organopolysiloxane having a silanol group-reactive functional group, (C) 2 to 25 parts by weight of a non-aqueous silica sol as a silica solid content, and (E) It is a thermosetting resin composition containing an organic solvent.

Further, the present invention particularly relates to (A) 100 parts by weight of a thermosetting resin, (B) 3 to 30 parts by weight of an organopolysiloxane having a functional group reactive with a silanol group, and (D).
The reaction catalysts of water and silicon alkoxide are 0.1 to 10 mole ratio and 0 to 0.3 mole ratio of silicon alkoxide, and 20 to 300 parts by weight of (E) organic solvent as the first liquid, and (C) silicon alkoxide is added. A thermosetting resin composition, characterized in that it is a two-liquid mixed type having 2 to 25 parts by weight as a silica solid content and 20 to 250 parts by weight of an organic solvent (E) as a second liquid. The thermosetting resin composition is characterized in that the mixing ratio of the second liquid is 1: 1.

The present invention is also a thermosetting resin composition characterized in that the thermosetting resin is a phenol resin which is particularly soluble in organic solvents, and the silicon alkoxide is represented by the formula 1. A thermosetting resin composition comprising tetraalkoxysilane or a low condensation product thereof. (Formula 1) Si (OR) ₄ (In the formula, R represents C _n H _{2n + 1} and n represents an integer of 1 to 8.)

Further, the present invention uses the thermosetting resin composition of the present invention to cause hydrolysis and polycondensation of silicon alkoxide in a solution containing the thermosetting resin and the organopolysiloxane, and at the same time, removing the solvent and heating. And a method for producing a cured resin product obtained by uniformly finely dispersing both organopolysiloxane and silica in a thermosetting resin, and heat-curing the resin composition of the present invention. It includes a cured resin obtained by curing and containing dispersed silica and organopolysiloxane both having a particle diameter of 1 μm or less.

[0012]

As the thermosetting resin used in the present invention, a general thermosetting resin which is reactively cured by heat can be used, and examples thereof include a phenol resin, an epoxy resin, an unsaturated polyester resin and an alkyd. One or a mixture of two or more selected from resins and melamine resins is used as the thermosetting resin. Particularly preferred is a system containing a phenol resin as a main component or containing at least one component.

Further, the thermosetting resin used in the present invention is preferably one having solvent solubility in an organic solvent before the thermosetting, for example, phenol resin such as resole type or high ortho novolac type. A phenol resin having solvent solubility is favorably used.

The organopolysiloxane having a functional group reactive with the silanol group used in the present invention is a dialkyl polysiloxane such as dimethyl polysiloxane,
It is preferable to have a functional group reactive with a silanol group, but a functional group having a strong affinity for a silanol group can be used even if it is not necessarily a functional group reactive with a silanol group. . Examples of the functional group include a carboxyl group, an epoxy group, a carbinol group, and a phenol group.
OH group, silanol group and the like.

Such a functional group is added in the complex formation process.
It reacts with or has a strong interaction with a condensate of silicon alkoxide or a thermosetting resin. The functional group may be contained in either the terminal or the side chain of the organopolysiloxane, and the number of functional groups used is one or more in one molecule. The molecular weight of the organopolysiloxane is not particularly limited, but in general, a molecular weight of 2000 or more is preferable in order to obtain a good composite effect. The amount of the organopolysiloxane contained in the thermosetting resin composition of the present invention is preferably in the range of 3 to 30 parts by weight with respect to 100 parts by weight of the thermosetting resin. If it is less than 3 parts by weight, the effect of adding the organopolysiloxane will be small, and if it is more than 30 parts by weight, the deterioration of physical properties such as heat resistance and elastic modulus will be large.

As the silicon alkoxide in the present invention, a tetraalkoxysilane represented by the formula 1 or a low condensate thereof is used. (Formula 1) Si (OR) ₄ (In the formula, R represents C _n H _{2n + 1} and n represents an integer of 1 to 8.)

The low condensate is one which is soluble in a solvent and preferably has an average molecular weight of 3,000 or less. In addition, a silicon alkoxide represented by Formula 1 may be a monoalkyltrialkoxysilane (SiR (OR) ₃ , wherein R = C _n H _{2n +} , such as monomethyltrimethoxysilane, in which one is substituted with an alkyl group. ₁ , n = 1
Represents an integer from 1 to 8. ) May be mixed and used, or another metal alkoxide such as titanium or aluminum may be mixed and used.

In any case, the main component must be tetraalkoxysilane or a low condensate thereof, and the amount to be mixed is preferably a small amount, for example, 20% or less. The amount of silicon alkoxide contained in the thermosetting resin composition of the present invention is 2 as a solid content of silica after the hydrolysis / polycondensation reaction based on 100 parts by weight of the thermosetting resin.
-25 parts by weight, preferably 2 to 20 parts by weight, and more preferably 4 to 15 parts by weight.

Specifically, when tetramethoxysilane having a silica conversion rate of about 40% is used, it is about 5 to 63 parts by weight, preferably 5 to 50 parts by weight, more preferably 100 parts by weight of the thermosetting resin. 10 to 37.5 parts by weight of the silicon alkoxide will be included in the thermosetting resin composition. If the amount of silica solids is less than 2 parts by weight with respect to 100 parts by weight of the thermosetting resin, the effect of containing silica becomes unclear, and if it is 25 parts by weight or more, cracks are likely to occur during molding of the resin cured product. Problems are more likely to occur.

On the other hand, as the non-aqueous silica sol used in the present invention, a non-aqueous organic solvent such as methanol is used to have a thickness of several tens nm.
A silica sol containing silica having the following sizes dispersed therein is used, and the amount thereof is preferably 2 to 25 parts by weight as silica solid content relative to 100 parts by weight of the thermosetting resin. On the other hand, when an aqueous silica sol containing water as a dispersion medium is used, a homogeneous composite cannot be obtained.

In the present invention, the water contained in the thermosetting resin composition is 0.1% of the silicon alkoxide used.
Amounts of from 10 to 10 molar ratios are preferred. When the amount is less than 0.1 molar ratio, the hydrolysis and polycondensation of silicon alkoxide becomes too insufficient, and when the amount is more than 10 molar ratio, unnecessary water is too much, which adversely affects the preparation of a homogeneous composite. There is.

The catalyst used in the present invention has a function of promoting the hydrolysis / polycondensation reaction of the silicon alkoxide, and for example, an organic or inorganic acid or a base such as ammonia or an alkaline aqueous solution is used. The amount of these catalysts is 0 to 0.
Amounts of 5 molar ratio are preferred and in some cases no catalyst is used.

The organic solvent used in the present invention is
There is no particular limitation as long as it dissolves a system containing a thermosetting resin, an organopolysiloxane, a silicon alkoxide, and water and a catalyst into a homogeneous solution. Examples thereof include methanol, ethanol, tetrahydrofuran, methyl ethyl ketone, N-methylpydrilone, etc., which may be used alone or in combination.

The resin cured product obtained from the thermosetting resin composition in the present invention is homogeneous without macroscopic phase separation, and the contained organopolysiloxane and silica are both in a finely dispersed state. Is a feature.
Specifically, both organopolysiloxane and silica are 1
The size is not more than μm, preferably not more than 0.5 μm. Further, both silica and organopolysiloxane can be controlled to have a size of 0.1 μm or less, and a good resin cured product having transparency can be obtained.

In the thermosetting resin composition of the present invention, when the thermosetting resin composition containing all the components is required for storage stability, etc., these components are divided into two parts and the thermosetting resin composition is divided into two parts. A thermosetting resin composition of a two-liquid mixture type in which a solution consisting of a resin, an organopolysiloxane having a functional group, water, a catalyst and an organic solvent is used as a first liquid and a silicon alkoxide and an organic solvent are used as a second liquid. May be.

Further, in this case, it is also possible to further add a stabilizer for stabilizing the silicon alkoxide to the second liquid. The method of preparing a resin cured product from a thermosetting resin composition is such that the resin cured product is finally homogeneous without macroscopic phase separation, and both the organopolysiloxane and silica are finely dispersed in the thermoset resin. As long as it can be performed, it is not particularly limited, specifically, using the thermosetting resin composition of the present invention, the hydrolysis and polycondensation reaction of the silicon alkoxide in the solution containing the thermosetting resin and the organopolysiloxane. A method is used in which the solvent is removed and heating is performed while the solvent is removed.

According to the present invention, the brittle property of the thermosetting resin is improved, and it is possible to suppress deterioration of the static mechanical properties such as heat resistance, bending strength and elastic modulus due to the improvement. Such an effect is obtained by the constitution of the present invention, that is, by forming a silica obtained by hydrolysis / polycondensation of a silicon alkoxide in a resin cured product and an organopolysiloxane at the same time as a homogeneous composite in a finely dispersed state. However, the effects of the present invention are not sufficient even if any of them is lacking.

More specifically, the thermosetting resin in which fine silica is dispersed is an organopolysiloxane, especially silano-
It is possible to finely disperse an organopolysiloxane having a functional group reactive with a vinyl group. 1 and 2 show typical dispersion morphology examples of organopolysiloxane in a thermosetting resin.

The thermosetting resin composition in the present invention is prepared in combination with a system containing other glass fibers or glass particles, metal fibers or particles thereof, or organic fibers or powders such as cellulose or aramid. Alternatively, it can be used, and it can be an excellent composite material by exhibiting good adhesion with those fillers.

[0030]

The present invention will be further described with reference to examples. The percentages in the examples are on a weight basis unless otherwise specified.

(Example 1 and Comparative Example 1) Phenol resin (Prio-phen J-325, Reson type manufactured by Dainippon Ink and Chemicals, Inc., methanol solvent, resin solid content =
60%) to 167 parts by weight (100 parts by weight as resin content), 6.5 parts by weight of side chain type polyether / epoxy group-terminated polydimethylsiloxane (manufactured by Toray Dow Corning Silicone Co., Ltd., molecular weight: about 20,000), methano -40 parts by weight of the resin was sequentially added dropwise with stirring to prepare a homogeneous mixed solution.

After holding this mixed solution at 50 ° C. for 6 hours while stirring, in Example 1, 14 parts by weight of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.6 parts by weight as a solid silica content), water A homogeneous solution consisting of 6.5 parts by weight of methanol and 60 parts by weight of methanol was mixed dropwise with 60 parts by weight of methanol in Comparative Example 1 to prepare homogeneous mixed solutions.

This solution was kept in a closed container at 30 ° C. for 1 hour, then cast in a clean polystyrene container, and then the solvent was slowly added at 25 ° C. for about 2 days, and then in a hot air dryer at 80 ° C. After casting for 20 hours, it was taken out from the polystyrene plate and kept at 150 ° C. for 50 minutes.

The film obtained in Example 1 was homogeneous and was semitransparent to transparent (light transmittance = 87%). The film obtained in Comparative Example 1 was cloudy and opaque (light transmittance = 53.
%)Met. Here, the light transmittance (%) = exp {(0.
1 / d) · ln (x / 100)} × 100 (where, d is the film thickness (mm), and x is the light transmittance (%) when the film thickness is d))
Was obtained.

In a scanning electron microscope (SEM) measurement of the fracture surface of the sample in Example 1, the dispersion morphology of silica particles and polydimethylsiloxane was not clear and was estimated to be 0.1 μm or less. Was done. Also,
No interfacial peeling between the matrix resin and the dispersed particles was observed in the fracture surface, and the adhesion was good.

In the SEM measurement of Comparative Example 1, 0.5-
It was observed that the side chain type polyether / epoxy group terminated polydimethylsiloxane having a size of 2 μm was dispersed in the phenol resin matrix. Meanwhile, 2500
From the transmission electron microscope (TEM) measurement at 250,000 times, in Example 1, the silica fine particles and the side chain type polyether / epoxy group-terminated polydimethylsiloxane were finely dispersed in the phenol resin matrix at about 0.005 to 0.01 μm. In Comparative Example 1, the side chain type polyether / epoxy group-terminated polydimethylsiloxane was about 0.5 μm.
It was confirmed that the particles were dispersed in a size of m or more.

Examples of the TEM measurement results of Example 1 and Comparative Example 1 are shown in FIGS. 1 and 2, respectively. Measurement of elastic modulus of the obtained thermosetting resin composite (heating rate 2 ° C./min, 1 Hz,
As a result of the tensile mode), in Comparative Example 1, the elastic modulus at 100 ° C. was 3 GPa and the value of the phenol resin alone (3.6 GP).
It is about 17% lower than that of a), while in Example 1, 4G
Despite the fact that Pa and the organopolysiloxane were contained in the same amounts as in Comparative Example 1, an increase of about 11% was observed, and it was confirmed that the decrease in heat resistance was suppressed.

Also, a cast molding (9.5 mm × 1 m)
As a result of an Izod impact test (m × 50 mm), it was confirmed that in Example 1, it was 28.2 kgf · cm / cm ² , which is higher than the value of the resin alone (16.3 kgf · cm / cm ² ). Was done. On the other hand, in Comparative Example 1, 21.1 kgf
The value of cm / cm ² was higher than that of the resin alone, but the result of Example 1 was better.

Example 2 Example 1 except that the low-condensation product of tetramethoxysilane, which had been hydrolyzed and polycondensed to a molecular weight of about 2000, was 12 parts by weight (6.5 parts by weight as solid silica content). A resin cured product was prepared in the same manner as in. The obtained film was semitransparent (light transmittance = 75%). This cast molding (9.5 mm x 1 mm x 5
0mm) Izot impact test result, 25.9k
The value was gf · cm / cm ² , which exceeded the value of the raw material resin alone.

Example 3 and Comparative Example 2 Phenol resin (Phenolite 5510, novolac type manufactured by Dainippon Ink and Chemicals, Inc., containing 10% by weight of hexamine) 10
0 part by weight and 5.3 parts by weight of side chain type polyether / epoxy group-terminated polydimethylsiloxane (manufactured by Toray Dow Corning Silicone Co., Ltd., molecular weight of about 20,000) were dissolved in 130 parts by weight of methanol to prepare a homogeneous mixed solution. Prepared. After holding this mixed solution at 50 ° C. for 6 hours while stirring, in Example 3, 23 parts by weight of tetramethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (9.2 as silica solids).
(Parts by weight), 70 parts by weight of methanol, and 15 parts by weight of water. In Comparative Example 2, 70 parts by weight of methanol was added dropwise with stirring to prepare a homogeneous mixed solution.

The solution was held in a closed container at 30 ° C. for 1 hour, then cast in a clean polystyrene container, and thereafter at 25 ° C.
The solvent was cast slowly over about 2 days at 70 ° C., after which the temperature was gradually raised to 70 ° C. under vacuum, then taken out from the polystyrene plate and pulverized to obtain particles having a particle size of about 1 mm. This was filled in a mold (spacer having a thickness of 2 mm) and press-molded into a size of 10 mm × 2 mm × 50 mm. The molding conditions were 150 ° C. × 45 min and 15 kg / cm ² .

The transparency of the obtained pressed sample was semitransparent (light transmittance = 83%) in Example 3 and transparent (light transmittance = 91%) in Comparative Example 2. As a result of Izod impact strength test of these molded products, it was 1 in Example 3.
A 9.8kgf · cm / cm ^2, exceeds the value of a resin alone and (4.4kgf · cm / cm ²⁾ larger.
In Comparative Example 2, the value was 12.1 kgf · cm / cm ² , which was higher than the value of the resin alone, but the result of Example 3 was better.

(Example 4) Phenol resin (Pryol-
Fen J-325, Reson type manufactured by Dainippon Ink and Chemicals, Inc., methanol solvent, solid content = 60%) to 167 parts by weight (100 parts by weight as resin content), carbinol-terminated polydimethyl 6.6 parts by weight of siloxane (manufactured by Toray Dow Corning Silicone Co., Ltd., molecular weight of about 2400) and 40 parts by weight of methanol were sequentially added dropwise with stirring to prepare a homogeneous mixed solution.

After holding the mixed solution at 50 ° C. for 6 hours with stirring, 14 parts by weight of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.6 parts by weight as silica solid content) and 6.5 parts by weight of water. And 60 parts by weight of methanol were added dropwise to prepare a homogeneous mixed solution. After holding this solution in a closed container at 30 ° C for 1 hour, cast it in a clean polystyrene container and slowly add about 2% of the solvent at 25 ° C.
After casting for 20 days in a hot air dryer at 80 ° C. for 20 days, it was taken out from the polystyrene plate and kept at 150 ° C. for 50 minutes. The obtained film was homogeneous and semitransparent (light transmittance = 86%).

The size of the dispersed silica particles was estimated to be about 0.05 to 0.25 μm by SEM measurement (magnification: 5000 times), and the adhesion to the matrix resin was good without peeling of the interface. Further, the carbinol-terminated polydimethylsiloxane was finely dispersed in the phenol resin matrix containing fine silica particles without agglomeration. I of the obtained cast molded product (9.5 mm × 1 mm × 50 mm)
As a result of a zod impact test, 27.3 kgf · cm /
cm ² and the value of the raw material resin alone (16.3 kgf ·
cm / cm ² ) was greatly exceeded.

Example 5 Phenol resin (Pryol)
Fen J-325, Reson type manufactured by Dainippon Ink and Chemicals, Inc., methanol solvent, resin solid content = 60%) 16
7 parts by weight (100 parts by weight as resin content) of methanol 4
0 part by weight was added to form a solution. Separately, tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 26 parts by weight (silica solid content 10.4 parts by weight) and side chain type polyether / epoxy terminated polydimethylsiloxane (Toray Dow Corning Silicone Co., Ltd.) Company made, molecular weight about 200
00) 10.5 parts by weight, 2.5 parts by weight of water, and 60 parts by weight of 2-propanol were mixed with stirring to form a homogeneous solution, which was kept at 90 ° C. for 45 minutes with stirring.

This mixed solution and 4 parts by weight of water were dropped and mixed into the above-mentioned phenol resin solution while being sold to obtain a homogeneous solution. This solution was kept in a closed container at 30 ° C for 10 minutes, then cast in a clean polystyrene container, and then the solvent was slowly added at 25 ° C for about 2 days, and then in a hot air dryer at 80 ° C for 20 hours. After casting, it was taken out from the polystyrene plate and kept at 150 ° C. for 50 minutes. The obtained film was homogeneous and semi-transparent (light transmittance = 83%). This cast molding (9.5 mm x 1 mm x 50 m
As a result of Izod impact test of m), 21.9 kgf
-Cm / cm ^2, which is the value of the raw material resin alone (16.3
kgf · cm / cm ² ).

Example 6 Bisphenol type epoxy resin (Epiclon 85 manufactured by Dainippon Ink and Chemicals, Inc.)
0) A solution of 100 parts by weight, 20 parts by weight of an aliphatic amine-based curing agent (Dainippon Ink and Chemicals, Inc., Epicron B-053), and 50 parts by weight of a THF solvent was added at 25 ° C. for 4 hours.
I stirred it for 0 hours. Also, tetramethoxysilane 28.
After reacting 5 parts by weight (11.4 parts by weight as silica solid content), 5.3 parts by weight of side chain poly-terepoxy group-terminated dimethylsiloxane and 2 parts by weight of 2-propanol at 90 ° C. for 45 minutes. , 13.5 parts by weight of water was added.

Both solutions were mixed to form a homogeneous solution, which was then cast on a glass plate to cast the solvent. Then at 80 ° C for 1
Heat treatment was performed for 0 hours at 150 ° C. for 3 hours. The obtained film was translucent (light transmittance = 78%) and homogeneous. 150
The elastic modulus at ° C was 65 MPa, which greatly exceeded the composite of epoxy resin and polydimethylsiloxane (30 MPa) and also exceeded the value of the epoxy resin alone (49 MPa). The impact resistance was about twice that of the epoxy resin alone.

Example 7 Instead of the homogeneous solution of tetramethoxysilane, water and methanol in Example 1, methanol silica sol (manufactured by Nissan Chemical Industries, Ltd.,
A cured resin product was prepared in the same manner as in Example 1 except that a homogeneous solution consisting of 27 parts by weight of SiO ₂ solid content = 30% (8.1 parts by weight as silica solid content) and 48 parts by weight of methanol was used. The resulting film is opaque (light transmittance =
56%). This cast molding (9.5 mm x
1mm × 50mm) Izod impact test results,
A 24.8kgf · cm / cm ^2, exceeds the value of the raw material resin alone and ^{(16.3kgf · cm / cm 2)} .

COMPARATIVE EXAMPLE 3 AND COMPARATIVE EXAMPLE 4 In Comparative Example 3, 70 parts by weight of tetramethoxysilane (28 parts by weight as a solid silica content), 30 parts by weight of water, and a side chain type polyether epoxy group were used. 1 terminal polydimethylsiloxane
A resin cured product was prepared in the same manner as in Example 1 except that the amount was 0.5 part by weight. In Comparative Example 4, 20 parts by weight of tetramethoxysilane (8 parts by weight as silica solid content), 12 parts by weight of water, and 30 parts by weight of side chain type polyether epoxy group-terminated polydimethylsiloxane were used. A resin cured product was prepared in the same manner as in Example 1 except that the above was performed.

The obtained resin cured product was transparent in Comparative Example 3 (light transmittance = 94%), but it was broken into small pieces due to many cracks, and a good film could not be obtained. Further, in Comparative Example 4, an opaque film having a light transmittance of 38% was obtained, but the elastic modulus at 100 ° C. was 1 GPa or less, and the mechanical properties were significantly deteriorated.

(Comparative Example 5) Phenol resin (Pryol-
Fen J-325, Reson type manufactured by Dainippon Ink and Chemicals, Inc., methanol solvent, resin solid content = 60%) 16
To 7 parts by weight (100 parts by weight as a resin component), 6.6 parts by weight of side chain type polyether / epoxy group-terminated polydimethylsiloxane (manufactured by Toray Dow Corning Silicone Co., Ltd., molecular weight: about 20,000), methanol 50 By weight, one part by weight was sequentially mixed dropwise with stirring to prepare a homogeneous mixed solution. After maintaining this mixed solution at 50 ° C. for 6 hours with stirring, a homogeneous solution consisting of 50 parts by weight of methanol and 30 parts by weight of an aqueous silica sol solution (manufactured by Nissan Chemical Industries, Ltd., Snowtex UP, silica solid content = 20%). Although the mixture was added dropwise while stirring, precipitation occurred simultaneously with the addition, a homogeneous mixed solution was not obtained, and a homogeneous complex was not obtained from the mixed solution.

Comparative Example 6 The same as Example 1 except that polydimethylsiloxane having no reactive group (manufactured by Toray Dow Corning Silicone Co., Ltd.) was used in place of the side chain type polyether / epoxy group-terminated polydimethylsiloxane. A film was prepared by the method described in 1. The obtained film had many bubbles, and the surface was oily, and a good composite could not be obtained.

FIG. 1 is a resin cured product obtained from a thermosetting resin composition containing a thermosetting phenol resin according to the present invention, tetramethoxysilane (silicon alkoxide) and dimethylpolysiloxane having an epoxy group in the side chain. It is a transmission electron microscope observation photograph (100,000 times) of the product. Silica obtained by hydrolyzing and polycondensing silicon alkoxide is finely dispersed in the phenol resin in a size of about 10 nm, and organopolysiloxane is also finely dispersed.

On the other hand, FIG. 2 shows a resin cured product obtained from a thermosetting resin composition containing no silicone alkoxide in the composition and containing a thermosetting phenol resin and dimethylpolysiloxane having an epoxy group in the side chain. It is a transmission electron microscope observation photograph (25,000 times) of the product. Here, dimethylpolysiloxane is present as large particles of about 0.5 to 1 μm, and its interface is weak enough to easily peel off when an ultrathin section sample for an electron microscope is prepared. The difference is clear.

Further, in the resin cured product obtained by using the same thermosetting resin composition as in the case of FIG. 1 except that dimethyl polysiloxane having no functional group is used, the dimethyl siloxane is phase-separated and the resin cured product is obtained. It was observed that it was free on the surface of H.p.a., and a homogeneous complex was not obtained.

[0058]

INDUSTRIAL APPLICABILITY The present invention improves the brittle property of a thermosetting resin and suppresses the deterioration of the static mechanical properties such as heat resistance, bending strength and elastic modulus associated with the improvement, and excellent resistance It is possible to provide a thermosetting resin composition having impact resistance, heat resistance, and excellent mechanical properties.

[Brief description of drawings]

FIG. 1 is a view showing a transmission electron microscope observation photograph (100,000 times) of a cured resin product of a phenolic resin, a silanol group-reactive functional group-containing organopolysiloxane and silica in Example 1. Is.

FIG. 2 is a view (25,000 times) showing a transmission electron microscope observation photograph of a resin cured product of a phenol resin and a functional group-containing organopolysiloxane in Comparative Example 1.

Claims (8)

[Claims] 1. (A) 100 parts by weight of a thermosetting resin,
(B) 3 to 30 parts by weight of organopolysiloxane having a functional group reactive with a silanol group, and (C) 2 to 25 parts by weight of silicon alkoxide as a silica solid content,
(D) The reaction catalyst of water and silicon alkoxide is used in a molar ratio of 0.1 to 10 and 0 to 0.
A thermosetting resin composition containing 3 mol ratio and (E) an organic solvent. 2. (A) 100 parts by weight of a thermosetting resin,
(B) 3 to 30 parts by weight of organopolysiloxane having a functional group reactive with a silanol group, (C) 2 to 25 parts by weight of non-aqueous silica sol as a silica solid content, and (E) an organic solvent. A thermosetting resin composition containing. 3. A reaction catalyst of (A) 100 parts by weight of a thermosetting resin, (B) 3 to 30 parts by weight of organopolysiloxane having a functional group reactive with a silanol group, and (D) water and a silicon alkoxide. Are used as the first liquid with 0.1 to 10 mole ratio and 0 to 0.3 mole ratio of silicon alkoxide and 20 to 300 parts by weight of (E) organic solvent as the first liquid, and (C) silicon alkoxide as silica solid content of 2 to 25 2 parts by weight and 20 to 250 parts by weight of (E) organic solvent 2
The thermosetting resin composition according to claim 1, which is a liquid mixture type. 4. The thermosetting resin composition according to claim 3, wherein the mixing ratio of the first liquid and the second liquid is 1: 1. 5. The thermosetting resin composition according to claim 1, wherein the thermosetting resin is an organic solvent-soluble phenol resin. 6. The thermosetting resin composition according to claim 1, wherein the silicon alkoxide is tetraalkoxysilane represented by formula 1 or a low condensate thereof. Stuff. (Formula 1) Si (OR) ₄ (In the formula, R represents C _n H _{2n + 1} and n represents an integer of 1 to 8.) 7. A method of using the thermosetting resin composition according to any one of claims 1, 3, 4, 5 and 6 in which a silicon alkoxide is hydrolyzed in a solution containing the thermosetting resin and the organopolysiloxane. A method for producing a cured resin product which is obtained by homogeneously finely dispersing both organopolysiloxane and silica in a thermosetting resin, characterized by being obtained by decomposing / polycondensing, removing a solvent and heating. . 8. A silica obtained by heat-curing the thermosetting resin composition according to claim 1 and having a particle diameter of 1 μm or less and an organopolysiloxane dispersed therein. A resin cured product characterized by being.