JPH05287077A - Epoxy-modified silicone resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent mechanical strengths, good resistance to heat and moisture, and good workability. CONSTITUTION:100 pts.wt. resin component comprising 95-5wt.% epoxidized polyorganosiloxane and 5-95wt.% silicone resin having structural units of the general formula: R<1>SiO1.5 (wherein R<1> is a monovalent, optionally substd. hydrocarbon group) or the general formula: SiO 2.0 and at least one silanol group is compounded with 0.005-50 pts.wt. cure catalyst to give the title compsn.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to an epoxy-modified silicone resin composition, and more particularly to an epoxy-modified silicone resin composition which gives a cured product having excellent mechanical strength, moisture resistance, heat resistance and releasability.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION AND ITS PROBLEMS Conventionally, epoxy resin-modified silicone resin has both excellent mechanical strength and adhesive property of epoxy resin and excellent heat resistance, electrical property and moisture proof property of silicone resin. Since it gives a molded product that also has, it is widely applied as an excellent thermosetting resin in the electric and electronic fields or heat-resistant paint fields. For example, an epoxy-modified silicone resin comprising a hydroxyl group-containing polyorganosiloxane, an epoxy group-containing compound and an aluminum compound (Japanese Patent Publication No. 60-43371, JP-A No. 56-
103224), an epoxy group-containing compound, a silanol group-containing organosilicon compound and a curable composition comprising a boron compound or a titanium compound (see Japanese Patent Publication No. 54-37998), a hydroxyl group- or alkoxy group-containing organic silicon compound. Silicone-modified epoxy resin composition comprising a compound, an epoxy compound and a carboxylic acid or a carboxylic anhydride
50-153063), an epoxy resin-modified silicone resin composition comprising a hydroxyl group- or alkoxy group-containing organosilicon compound, a hydroxyl group- and epoxy group-containing epoxy resin, an aluminum compound and an amine compound (Japanese Patent Publication No. 63-2462).
No. 4), a curable epoxy resin, an epoxy resin-modified silicone resin, and an epoxy-modified polysiloxane.
7059), a curing agent for an epoxy resin comprising an aluminum compound and a hydroxyl group-containing silicon compound (JP-A-57-42).
No. 721) is known. However, in the resins shown in these, when the mixing ratio of the epoxy resin is high, the moisture resistance and heat resistance are insufficient, while when the mixing ratio of the silicone resin is high, the mechanical strength is insufficient, etc. However, there is a demand for improvement of these problems. In addition, these epoxy resin-modified silicone resins are generally used in the state of a solution dissolved in an organic solvent, but in recent years, the influence of the organic solvent on the human body has been exclaimed, and the use of the organic solvent should be minimized from the viewpoint of environmental hygiene. Measures to reduce it are desired. However, the conventional epoxy resin-modified silicone resin gels when the organic solvent is removed, so the organic solvent must be used, and the organic solvent is no longer needed (or the amount used is small). No resin has been provided.

[0003]

SUMMARY OF THE INVENTION The present invention solves these drawbacks, has excellent mechanical strength, and has good moisture resistance and heat resistance,
An object is to provide an epoxy-modified silicone resin composition having good workability.

[0004]

The present inventors have conducted extensive studies in order to achieve the above object, and as a result, by compounding a silanol group-containing silicone resin having a specific structure with an epoxy group-containing polyorganosiloxane, It was found that an epoxy-modified silicone resin having excellent mechanical strength, good moisture resistance and heat resistance can be obtained, and the present invention has been completed. That is, the present invention relates to (A) epoxy group-containing polyorganosiloxane 95-
5 parts by weight and (B) a structural unit represented by the general formula (I) R ¹ SiO _1.5 (I) (wherein R ¹ represents a monovalent substituted or unsubstituted hydrocarbon group), or a general formula ( II) 100 parts by weight of a resin component containing 5 to 95 parts by weight of a silicone resin containing a structural unit represented by SiO _2.0 (II) and containing at least one silanol group, and (C) a curing catalyst 0.005 to 50 parts by weight And an epoxy-modified silicone resin composition.

The component (A) used in the present invention is a polyorganosiloxane containing an epoxy group, and the epoxy group may be contained in the organic group bonded to the silicon atom. Such an epoxy group-containing polyorganosiloxane can be synthesized by adding an epoxy compound containing an alkenyl group to a polyorganohydrogensiloxane by using a catalyst or the like, or a hydrolysis containing an epoxy group. Method of co-hydrolyzing / condensing a polymerizable silane with other hydrolyzable silane, a method of synthesizing a hydroxyl group-containing epoxy compound by condensation polymerization with a silane or siloxane having a hydroxyl group or a hydrolyzable group, etc. Can be obtained by Among these, solvent-free,
Since an epoxy group-containing polyorganosiloxane having good storage stability can be obtained, a method of synthesizing by adding an alkenyl group-containing epoxy compound to polyorganohydrogensiloxane is preferable. Examples of such polyorganohydrogensiloxane include those containing a siloxane unit represented by the general formula (R ² ) _a (H) _b SiO _{((4-ab) / 2)} (III). Here, R ² is a group selected from an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different, and a and b are integers satisfying 0 ≦ a ≦ 3 and 1 ≦ b ≦ 3. And at least one hydrogen atom bonded to a silicon atom is contained in one molecule. As the epoxy compound containing an alkenyl group,

[0006]

[Chemical 1]

[0007] etc. are exemplified. The addition reaction catalyst used here is a catalyst that promotes the addition reaction of a hydrosilyl group and an alkenyl group, such as chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of platinum and an olefin,
Complexes of platinum and ketones, complexes of platinum and vinyl siloxane, platinum supported on alumina, silica, etc., or platinum-based catalysts such as platinum black, tetrakis (triphenylphosphine) palladium, palladium black and tri A palladium-based catalyst such as a mixture with phenylphosphine,
Examples thereof include rhodium-based catalysts such as tetrakis (triphenylphosphine) rhodium and a mixture of rhodium black and triphenylphosphine. The epoxy group-containing polyorganosiloxane which is the component (A) of the present invention can be obtained by subjecting the above polyorganohydrogensiloxane and an alkenyl group-containing epoxy compound to an addition reaction in the presence of an addition reaction catalyst. In this case, it is preferable to carry out the reaction in an inert solvent because the reaction is easily controlled and the raw materials and products are easily handled. After completion of the reaction, the solvent is removed to obtain the epoxy group-containing organopolysiloxane as the component (A). In the case of a method such as co-hydrolysis / polycondensation of an epoxy group-containing silane with another silane, the epoxy group-containing polyorganosiloxane contains a large amount of residual silanol groups and causes gelation when the solvent is removed. It is necessary to handle it in a solution state. Examples of the epoxy group-containing polyorganosiloxane which is the component (A) of the present invention include the following.

[0008]

[Chemical 2]

A linear polyorganosiloxane represented by the formula (IV) and containing at least one epoxy group in one molecule. Here, R ² is as described above, E is an epoxy group-containing group, R ³ is the same or different from each other and is a group selected from R ² or E, and c and d are 0 ≦ c and 0 ≦. d is preferably 0 ≦ c + d ≦ 100, particularly preferably 10 ≦ c + d ≦ 5.
It is an integer that satisfies 0.

[0010]

[Chemical 3]

A cyclic organopolysiloxane represented by the formula (V). Where R ² and E are as described above, and e and f are 1
It is an integer satisfying ≤e, 3≤e + f, preferably 4≤e + f≤6. (R ³ ₃ SiO _0.5 ) _g (R ³ SiO _1.5 ) _h (VI) A branched polyorganosiloxane represented by the formula (VI). Here, R ³ is as described above, and g and h are integers satisfying 1 ≦ g and 1 ≦ h, preferably 5 ≦ g + h ≦ 50. (R ³ ₃ SiO _0.5 ) _i (SiO _2.0 ) _j (VII) (VII) A branched polyorganosiloxane represented by the formula.
Here, R ³ is as described above, and i and j are 1 ≦ i, 1 ≦ j
Preferably, it is an integer satisfying 5 ≦ i + j ≦ 50. the above
In the polyorganosiloxane represented by (IV) to (VII), the various siloxane units may be present as blocks or randomly. Further, at least one epoxy group, preferably two or more epoxy groups are contained in one molecule. The epoxy group-containing polyorganosiloxane synthesized by the above-mentioned addition reaction has a small amount of residual silanol, usually 2% by weight or less. In the present invention, if 0.5% by weight or less is used, a composition having good storage stability is obtained. A product is obtained, which is preferable. In the composition of the present invention, it is preferable to use the epoxy group-containing polyorganosiloxane represented by (IV) as the component (A) because it has good mechanical strength when combined with the component (B). .. Further, R ² in the formulas (IV) to (VII) is preferably a methyl group because it has good compatibility with the component (B) and good characteristics can be obtained. Also
The viscosity of the component (A) is 5 to 10,000 cP, particularly 20 to 1,000 cP, because it is easy to handle when the composition of the present invention is used without solvent and the mechanical strength of the obtained cured product is good. It is preferable to use one. The epoxy equivalent is 50 to 5,000 because good curability and heat resistance can be obtained.
Especially, it is preferable to use the one of 100 to 500.

The component (B) used in the present invention is a branched silicone resin containing a silanol group and is a component which is a feature of the present invention. The component (B) must contain R ¹ SiO _1.5 units or SiO _2.0 units. Where R
¹ represents a monovalent substituted or unsubstituted hydrocarbon group, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group , Alkyl groups such as dodecyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group, aryl groups such as phenyl group and tolyl group, vinyl group, allyl group Alkenyl groups such as, and hydrogen atoms bonded to carbon atoms of these hydrocarbon groups are partially halogen atoms, acryloxy groups, methacryloxy groups, chrysidoxy groups, 3,4-epoxycyclohexyl groups, mercapto groups, etc. Examples are groups substituted with atoms or groups. Of these, an alkyl group having 1 to 4 carbon atoms or a phenyl group is preferable from the viewpoint of easy synthesis or availability. Especially, since the compatibility with the component (A) is improved,
It is preferable that 5 to 60 mol% of all organic groups are phenyl groups, and 10 to 40 mol% is particularly preferable. Such a silicone resin is obtained by adding a hydrolyzable silane such as organotrichlorosilane, organotrialkoxysilane, tetrachlorosilane or tetraalkoxysilane to water, a solvent and, if necessary, other hydrolyzable silanes. It can be obtained by hydrolysis / polycondensation in the presence of a decomposition catalyst. In this case, the amount of residual silanol, the molecular weight, etc. can be adjusted by changing the amount of water used for hydrolysis, the type of catalyst, the reaction temperature, the time, and the like. The component (B) of the present invention preferably has a silanol content of 2.0% by weight or more,
It is preferably 5.0% by weight or more. The molecular weight is preferably 500 to 10,000, and particularly preferably 1,000 to 5,000, since the curability of the composition of the present invention and the mechanical strength of the cured product are excellent.
Is preferred. The component (B) silicone resin may contain other siloxane units in addition to the R ¹ SiO _1.5 unit or the SiO _2.0 unit, but since the effects of the present invention can be favorably obtained,
The R ¹ SiO _1.5 unit or the SiO _2.0 unit is preferably contained in an amount of 10 mol% or more, and particularly preferably 50 mol% or more, of all siloxane units. Examples of such silanol group-containing silicone resin include the following. (R ¹ SiO _1.5 ) _k (R ¹ ₂ SiO _1.0 ) _m (VIII) A silicone resin represented by the formula (VIII). Here, R ¹ is as described above, and k and m are 1 ≦ k, 0 ≦ m, and preferably 5 ≦ k.
It is an integer that satisfies + m ≦ 100. (R ¹ SiO _1.5 ) _n (R ¹ ₃ SiO _0.5 ) _p (IX) A silicone resin represented by the formula (IX). Where n and p are 1 ≦
It is an integer satisfying n 1, 1 ≦ p, preferably 5 ≦ n + p ≦ 100. (SiO _2.0 ) _q (R ¹ ₂ SiO _1.0 ) _r (X) A silicone resin represented by the formula (X). Where q and r are 1 ≦ q
1≤r, preferably an integer satisfying 5≤q + r≤100. ^{_{(SiO 2.0) s (R 1}} 3 SiO 0.5) t (XI) (XI) a silicone resin represented by the formula. Where s and t are 1 ≤ s
1 ≦ t, preferably an integer satisfying 5 ≦ s + t ≦ 100. In the silicone resin represented by the above formulas (VIII) to (XI), various siloxane units may be present as blocks or randomly. In the composition of the present invention, it is easy to control the amount of silanol and the molecular weight in the case of synthesis, and the cured product has good mechanical strength when combined with the component (A). Formula (VIII) or
It is preferable to use the silanol group-containing silicone resin represented by the formula (X), and it is particularly preferable to use the silicone resin represented by the formula (VIII). Further, as described above, the component (B) is obtained by hydrolysis / condensation polymerization of a hydrolyzable silane and is generally handled with a solution of an organic solvent.However, if the component (B) alone is heated and removed, a gel is formed. In general, it is difficult to eliminate the solvent because it causes the formation of solvent. However, when the organic solvent solution of the component (B) is mixed with the component (A), the solvent can be removed without causing gelation and the like, and the solvent can be eliminated. Therefore, as shown in the present invention (A)
From the components and the component (B), a solvent-free composition useful for environmental hygiene can be obtained.

The blending ratio of the component (A) and the component (B) in the present invention is 5 to 95 parts by weight of the component (B) relative to 95 to 5 parts by weight of the component (A). When the silanol group-containing silicone resin of the component (B) is more than 95 parts by weight in the total 100 parts by weight of the component (A) and the component (B), the curability of the obtained epoxy-modified silicone resin composition is lowered. At the same time, the adhesiveness to various base materials deteriorates. If less than 5 parts by weight,
The heat resistance of the obtained epoxy-modified silicone resin composition decreases. Preferably, relative to 80 to 30 parts by weight of the component (A),
20 to 70 parts by weight of component (B) is blended.

The curing catalyst (C) used in the present invention is (A)
It has a catalytic action for the reaction between the epoxy group of the component and the silanol group of the component (B). Examples of such curing catalysts include aluminum compounds and amino compounds. Examples of the aluminum compound include chelate compounds of acetylacetone compounds such as aluminum trialkylacetoacetate and aluminum trisacetylacetonate, and aluminum alcoholate compounds such as aluminum methyl alcoholate, aluminum ethyl alcoholate and aluminum propyl alcoholate. As the amino compound, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ- Amino group-containing silanes such as aminopropylmethyldimethoxysilane, monoethanolamine, diethanolamine, triethanolamine, diethylaminoethanol, n-hexylamine, tripropylamine, ethylenediamine, triethylenediamine, aniline, tetramethylammonium hydroxide or these Examples thereof include organic acid salts. The curing catalyst is
Two or more kinds may be used together. Among these, an aluminum compound is preferable, and an aluminum chelate is particularly preferable, from the viewpoint of curability of the composition, heat resistance of the obtained cured product, safety of the catalyst, and the like. Amino group-containing silanes are also preferable because the cured product has good adhesion to various substrates. The curing catalyst of the component (C) is blended in an amount of 0.005 to 50 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). If it is less than 0.005 parts by weight, sufficient curability cannot be obtained, and if it is more than 50 parts by weight, the heat resistance and weather resistance of the cured product deteriorate. It is preferably 0.01 to 20 parts by weight. More specifically, 0.01 to 2 parts by weight is preferable when an aluminum compound is used, and 0.1 to 20 parts by weight is preferable when an aluminum compound is used.

Further, since aluminum chelate is generally solid at room temperature and is difficult to dissolve in the component (A) or the component (B), it is preferable to dissolve it in an organic solvent or a liquid epoxy resin to blend it, and particularly to use no solvent. It is preferable to use it by dissolving it in a liquid epoxy resin, since the composition of 1) can be obtained.
The epoxy resin is not particularly limited as long as it is liquid, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, partial cresol novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin. Examples thereof include aliphatic epoxy resins such as propylene glycol glycidyl ether and pentaerythritol polyglycidyl ether, and two or more kinds may be used in combination. This liquid epoxy resin has a good heat resistance of the cured product obtained from the composition of the present invention, in order to improve the heat resistance of the component (A) and the component (B) 100 parts by weight, It is preferable that the amount is not more than parts by weight. Further, the epoxy resin for dissolving / dispersing the aluminum chelate of the catalyst may be used in combination with the epoxy group-containing polyorganosiloxane of the component (A).

When the composition of the present invention is a solvent-free composition, the viscosity of the solvent-free composition is lowered without deteriorating the physical properties of the obtained cured product and the workability is improved. Therefore, an alkoxy group-containing silane may be blended. A silanol group-containing alkoxysilane obtained by partial hydrolysis of this silane or a condensate thereof may be a low-viscosity alkoxy group-containing polysiloxane, but a viscosity of 100 cP or less is preferable. Such an alkoxy group-containing silane is preferably added in an amount of 100 parts by weight or less, particularly preferably 50 parts by weight or less, based on 100 parts by weight of the total amount of the components (A) and (B) of the present invention. use.

When the above alkoxy group-containing silane or the like is blended or when an amino group-containing alkoxysilane or the like is used as a catalyst, the reaction between these alkoxy groups and the silanol group of the component (B) is promoted. It is preferable to incorporate a catalyst. Examples of such catalysts include metal salts of carboxylic acids such as dibutyltin dilaurate and titanate esters such as tetrabutyl titanate. Such a catalyst is preferably 0.005 to 10 with respect to 100 parts by weight of the alkoxy group-containing silane or siloxane.
Parts by weight, particularly preferably 0.01 to 2 parts by weight, are used.

By mixing the components (A) to (C) of the present invention, the reaction proceeds even at room temperature. Therefore, it is preferable to mix the component (C) with other components immediately before use. By combining the component (A) and the component (B) of the present invention, a liquid, solvent-free composition is obtained, and this composition is preferable in terms of environmental hygiene.
Therefore, the combination of component (A) and component (B) is used as a solvent-free component, and component (C) is dissolved / dispersed in epoxy resin or in which component (A) is further added, if necessary. It is preferable to use another solvent-free component and mix these components at the time of use.

In the composition of the present invention, if necessary, a small amount of additives such as a plasticizer, a release agent, a flame retardant, an antioxidant, an ultraviolet absorber or a pigment such as titanium dioxide, carbon black or iron oxide is used. You may mix | blend or a dye. Similarly, fumed silica, silica airgel, silica gel and reinforcing silica fillers obtained by treating these with organosilanes, organosiloxanes or organosilazanes, asbestos, crushed fused quartz, aluminum oxide, aluminum silicate, silica. Zirconate, magnesium oxide, zinc oxide, talc, diatomaceous earth, mica, calcium carbonate, clay,
Fillers such as zirconia, glass, sand, graphite, barium sulfate, zinc sulfate, aluminum powder, sawdust, cork, fluorocarbon polymer powder, silicone rubber powder, and silicone resin powder may be blended. Further, an organic solvent may be added if necessary.

[0020]

The epoxy-modified silicone resin composition of the present invention has good curability, good mechanical strength, moisture resistance, heat resistance, weather resistance, and also good peelability and various substrates. A cured product having excellent adhesiveness is provided. Further, the composition of the present invention can be made into a stable liquid composition without a solvent, and can be preferably used in terms of environmental hygiene. The composition of the present invention having such characteristics is useful as a heat-resistant paint, a weather-resistant paint, a back coating agent for various films, or a vehicle thereof. It is also suitably used as a resin for sealing optical semiconductors and electronic parts and a binder thereof. Alternatively, it is also suitably used as a binder of a heat-resistant electrically insulating thin sheet material, a glass cloth for a laminated plate, a glass cloth-mica foil, a mica foil, or the like. Further, it is preferably used as a coil impregnation for transformers and motors or as a moisture-proof coating agent for electric and electronic parts.

[0021]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In addition, the part in an Example represents a weight part and% represents weight%. The viscosity and specific gravity are values at 25 ° C. Synthesis example 1 General formula

[0022]

[Chemical 4]

762 parts (1.0 mol) of polyorganohydrogensiloxane represented by
Stir to dissolve. Aside from this

[0024]

[Chemical 5]

1368 parts (12.0 mol) of the epoxy compound represented by and an isopropanol solution of chloroplatinic acid were converted into platinum and mixed in an amount of 10 ppm with respect to the epoxy compound. This mixed solution was added dropwise to a stirring toluene solution of polysiloxane. After the dropping was completed, the mixture was heated and stirred at 100 ° C. for 6 hours to carry out an addition reaction. Next, add 12
The mixture was kept at 0 ° C. and 20 mmHg for 1 hour to remove toluene, unreacted epoxy compound and other volatile components. This was pressure filtered using Celite, and the viscosity was 320 cP and the specific gravity was 1.09.
6, an epoxy group-containing polyorganosiloxane (A-1) having an epoxy equivalent of 192 was obtained.

Synthesis Example 2 Instead of the polyorganohydrogensiloxane of Synthesis Example 1, a general formula was used.

[0027]

[Chemical 6]

462 parts of polysiloxane represented by
Mol) and an epoxy compound of 684 parts (6.0 mol) were used, and the same procedure as in Synthesis Example 1 was carried out to obtain a viscosity of 120 cP and a specific gravity of 1.
097, an epoxy group-containing organopolysiloxane (A-2) having an epoxy equivalent of 201 was obtained.

Synthesis Example 3 Instead of the polyorganohydrogensiloxane of Synthesis Example 1, a compound of the general formula

[0030]

[Chemical 7]

268 parts (1.0
Mol) and an epoxy compound of 342 parts (3.0 mol) were used, the same procedure as in Synthesis Example 1 was carried out to obtain a viscosity of 25 cP and a specific gravity of 1.06.
8, an epoxy group-containing organopolysiloxane (A-3) having an epoxy equivalent of 248 was obtained.

Synthesis Example 4 Instead of the polyorganohydrogensiloxane of Synthesis Example 1, 522 parts of a branched siloxane represented by the general formula ((CH ₃ ) ₂ (H) SiO _0.5 ) ₆ (SiO _2.0 ) ₂ ( 1.0 mol) and an epoxy compound (912 parts (8.0 mol)) were used, and the same procedure as in Synthesis Example 1 was carried out to obtain an epoxy group-containing organopolysiloxane (A having a viscosity of 200 cP and a specific gravity of 1.122 epoxy equivalent 226).
-4) got.

Synthesis Example 5 Instead of the epoxy compound of Synthesis Example 3

[0034]

[Chemical 8]

372 parts (3.0 parts) of the epoxy compound represented by
Mol), except that the same procedure as in Synthesis Example 3 was carried out, and the viscosity was 13
An epoxy group-containing organopolysiloxane (A-5) having a 3cP, a specific gravity of 1.066 and an epoxy equivalent of 257 was obtained.

Synthesis Example 6 Instead of the polyorganohydrogensiloxane of Synthesis Example 1, a compound of the general formula

[0037]

[Chemical 9]

The same procedure as in Synthesis Example 1 was carried out except that 1412 parts (0.5 mol) of polysiloxane represented by and 2000 parts of toluene were used, and the viscosity was 500 cP, the specific gravity was 1.107, and the epoxy equivalent was 26.
An epoxy group-containing organopolysiloxane (A-6) of 0 was obtained.

Synthesis Example 7 516 parts (4 mol) of dimethyldichlorosilane, 236 parts (1 mol) of γ-glycidoxypropyltrimethoxysilane,
Hexamethyldisiloxane 45.5 parts (0.5 mol) in water 30
It is added dropwise to a mixed solution of 0 parts and about 1000 parts of toluene, stirred, hydrolyzed and polycondensed, and after removing hydrochloric acid and water and dried over anhydrous sodium sulfate, it has an epoxy equivalent of 580 and a silanol group content.
3.2% epoxy group-containing organopolysiloxane (A-7)
To obtain a 50% solution of toluene. When toluene was heated and decompressed from this solution to remove it, gelation occurred.

Synthesis Example 8 A mixture of 224 parts (1.5 mol) of methyltrichlorosilane, 194 parts (1.5 mol) of dimethyldichlorosilane and 423 parts (2.0 mol) of phenyltrichlorosilane was hydrolyzed and polycondensed in the same manner as in Synthesis Example 7. Thus, a 50% toluene solution (B-1) of a silanol group-containing organopolysiloxane having an average molecular weight of 3,500 and a silanol group content of 4.2% was obtained. Attempting to remove toluene from this solution by heating and reducing the pressure caused gelation.

Synthesis Example 9 A mixture of 150 parts (1.0 mol) of methyltrichlorosilane, 129 parts (1.0 mol) of dimethyldichlorosilane, 423 parts (2.0 mol) of phenyltrichlorosilane and 253 parts (1.0 mol) of diphenyldichlorosilane was prepared as a synthesis example. Hydrolysis and polycondensation were carried out in the same manner as in 7 to obtain a 50% toluene solution (B-2) of a silanol group-containing organopolysiloxane having an average molecular weight of 1600 and a silanol group content of 5.0%.

Synthesis Example 10 880 parts (4.0 mol) of methyltriisopropoxysilane,
A mixture of 64.5 parts (0.5 mol) of dimethyldichlorosilane and 106 parts (0.5 mol) of phenyltrichlorosilane was hydrolyzed and polycondensed in the same manner as in Synthesis Example 7, and had a silanol group content of 2000% and a silanol group content of 5.5%. A 50% toluene solution of organopolysiloxane (B-3) was obtained.

Synthesis Example 11 Using 136 parts (1.0 mol) of methyltrimethoxysilane, 23 parts (1.3 mol) of water, 500 parts of toluene and 1.0 part of acetic acid,
Partially hydrolyzed and polycondensed in the same manner as in Synthesis Example 7 to give a viscosity of 10
An alkoxy group-containing organopolysiloxane (C-1) having P, a specific gravity of 1.102 and a methoxy group content of 50% was obtained.

Synthesis Example 12 A mixture of 150 parts (1.0 mol) of methyltrichlorosilane, 212 parts (1.0 mol) of phenyltrichlorosilane and 253 parts (1.0 mol) of diphenyldichlorosilane was prepared as in Synthesis Example 7.
After hydrolysis and polycondensation in the same manner as above, the aqueous phase was removed and the mixture was alkoxylated with 1000 parts of methanol. By removing hydrochloric acid, toluene and other volatile components, viscosity 70 cP, specific gravity 1.132,
An alkoxy group-containing organopolysiloxane (C-2) having a methoxy group content of 15% was obtained.

Example 1 80 parts of A-1 as the component (A) and 240 parts of B-1 as the component (B)
Part was charged into a 500 ml four-necked flask equipped with a distilling pipe, a cooling pipe, a stirrer, a decompressor and a thermometer, and heated.
Toluene of component (B) was removed under reduced pressure and finally 40mmH
g, hold at 90 ℃ for 20 minutes, finish the removal of toluene,
An epoxy-modified silicone resin component (P-1) having a viscosity of 750 cP was obtained. Next, 100 parts of powdered aluminum trisacetylacetonate as a catalyst and bisphenol type epoxy resin (Epicoat 828, Yuka Shell Epoxy Co., Ltd.) 10
90-100 parts of a mixture of 0 parts and 100 parts of component (A) A-2.
Heat-stirred at ℃ to homogenize, curing catalyst component with viscosity 1500cP
I got (Q-1). Epoxy-modified silicone resin component P-1
100 parts and 5 parts of the curing catalyst component Q-1 are mixed,
A resin composition of the present invention was obtained. The obtained resin composition was injected into a plastic mold for a light emitting diode coated with a release agent, and a frame on which a gallium-arsenic-phosphorus (Ga-As-P) -based emission color yellow chip was mounted was cured. After mounting with a tool and heating at 140 ℃ for 8 hours to cure, remove from the jig and separate them one by one.
ED) was created. The light-emitting device was energized under the conditions of 25 mA and 2.2 V for 168 hours, and the residual brightness ratio was determined from the measured values of the brightness before and after energization. As a result, an excellent value of 93% was shown.

Example 2 80 parts of A-2 as the component (A) and 240 parts of B-2 as the component (B)
Parts were used in the same manner as in Example 1 to obtain an epoxy-modified silicone resin component (P-2) having a viscosity of 825 cP.

100 parts of this component P-2 was mixed with 5 parts of the curing catalyst component Q-1 of Example 1 to obtain a resin composition of the present invention. When this composition was evaluated in the same manner as in Example 1, the residual rate of luminance was 90%.

Comparative Example 1 A silicone resin component (P'-1) and a resin composition were obtained in the same manner as in Example 1 except that diphenylsilanediol was used instead of the component (B) in Example 1. .. When this composition was evaluated in the same manner as in Example 1, the residual ratio of luminance was 81%.
Met.

Examples 3 and 4 The respective components were mixed in the compositions shown in Table 1, the solvent was removed in the same manner as in Example 1, and the epoxy-modified silicone resin component (P
-3, P-4) was obtained. Further, the resin composition of the present invention was prepared with the composition shown in Table 2, and the pigment and the like were dispersed with a three-roll mill to obtain a white paint. This paint is coated on a mild steel plate (SPCC-1) using a bar coater to a film thickness of 30 μm and heated at 120 ° C for 20 minutes, 180 ° C for 20 minutes or 250 ° C for 1 minute. Then, the cured state, heat resistance and weather resistance of the obtained coating film were evaluated. The cured state was evaluated from solvent resistance and pencil hardness, and heat resistance was measured using a test piece cured at 250 ° C for 1 minute, and the gloss retention and color difference (Δ) after heating at 200 ° C for 16 hours were used.
E) and the weather resistance was evaluated by using the same test piece with a sunshine weatherometer for 2000 hours from the gloss retention rate and the color difference (ΔE) after the weather resistance test. The results are shown in Table 3.
Shown in.

Comparative Example 2 As a component (A), 200 parts of a 50% toluene solution of A-7, 120 parts of a silanol group-containing siloxane, a terminal silanol group-containing dimethylpolysiloxane having a viscosity of 700 cP, and an alkoxy group-containing polysiloxane were prepared. Epoxy-modified silicone resin component (P'-2) mixed with 20 parts of C-2 without removing solvent
Then, the same procedure as in Example 3 was carried out to obtain a white coating material. This white paint was evaluated in the same manner as in Example 3. The results are shown in Table 3.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

Examples 5 and 6 The respective components were mixed in the compositions shown in Table 4 and the solvent was removed in the same manner as in Example 1 to obtain silicone resin components (P-5, P-6). Further, a curing catalyst component was added in a composition shown in Table 5,
The compositions of Examples 5 and 6 of the present invention were obtained. Using the above composition, a semiconductor device (MOS-L
SI) was encapsulated and heated at 120 ° C. for 1 hour and further at 150 ° C. for 1 hour to cure, to obtain a semiconductor element encapsulated with the composition of the present invention. The reliability was evaluated from the defect occurrence rate after this semiconductor element was left for 1000 hours or 2000 hours under the conditions of a temperature of 80 ° C. and a humidity of 85%. The results are shown in Table 5.

Comparative Example 3 Bisphenol F type epoxy resin (Epicoat 807
Comparative Example 3 was obtained by mixing 100 parts of Heka Shell Epoxy Co., Ltd.), 100 parts of hexahydrophthalic anhydride, and 2 parts of 2-ethylhexanoate of 1,8-diazabicyclo (5,4,0) undecene 7. To obtain an epoxy resin composition (P'-3). Using this composition, a semiconductor element was sealed in the same manner as in Example 5, and the reliability was evaluated. The results are shown in Table 5.

[0056]

[Table 4]

Comparative Example 4 Silicone resin component (P'-4) was obtained by mixing the components in the composition shown in Table 4. Further, a curing catalyst component was blended in a composition shown in Table 5 to obtain a composition of Comparative Example 4. Using this composition, a semiconductor element was sealed in the same manner as in Example 5, and the reliability was evaluated. The results are shown in Table 5.

[0058]

[Table 5]

Example 7 As component (A), 20 parts of A-3, 210 parts of A-6 and 180 parts of B-3 as component (B) were used, and a viscosity of 850 was obtained in the same manner as in Example 1. An epoxy-modified silicone resin component (P-7) of cP was obtained. 20 parts of the curing catalyst component Q-1 was mixed with 100 parts of this component P-7 to obtain a resin composition of the present invention. This composition
A polyester film (Tetoron film, Teijin Ltd.) with a thickness of 38 μm was applied at a coating thickness of 10 μm at 140 ° C.
It was heated for 2 minutes for curing to obtain a release film. This release film has a one-component polyurethane solution (Krisbon 76
67EL, manufactured by Dainippon Ink and Chemicals, Inc. was applied in a coating film thickness of 30 μm, and heated at 120 ° C. for 3 minutes and dried. The peeling force when peeling this urethane film from the peeling film in the direction of 180 ° was measured with a tensile tester at a pulling speed of 30
When measured as cm / min, a value of 8.0 g / 3 cm was shown.

Comparative Example 5 When the resin composition of Comparative Example 2 was used and evaluated in the same manner as in Example 7, the urethane film showed cohesive failure.

Claims (1)

[Claims] 1. (A) 95 to 5 parts by weight of a polyorganosiloxane containing an epoxy group and (B) a general formula (I) R ¹ SiO _1.5 (I) (wherein R ¹ is a monovalent substituted or non-substituted). 5 to 95 parts by weight of a silicone resin containing a structural unit represented by a substituted hydrocarbon group) or a structural unit represented by the general formula (II) SiO _2.0 (II) and containing at least one silanol group. An epoxy-modified silicone resin composition comprising 100 parts by weight of a resin component comprising 0.005 to 50 parts by weight of a curing catalyst (C).