JP3221718B2 - Epoxy-modified silicone resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. 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 and excellent moisture resistance, heat resistance and peelability.

[0002]

BACKGROUND OF THE INVENTION Conventionally, epoxy resin-modified silicone resins have both the excellent mechanical strength and adhesive properties of epoxy resins and the excellent heat resistance, electrical properties and moisture resistance of silicone resins. Since it gives a molded article having both properties, it is widely used as an excellent thermosetting resin in the electric / electronic field or heat-resistant paint field. For example, an epoxy-modified silicone resin comprising a hydroxyl-containing polyorganosiloxane, an epoxy-containing compound and an aluminum compound (Japanese Patent Publication No. 60-43371;
No. 103224), a curable composition comprising an epoxy group-containing compound, a silanol group-containing organosilicon compound and a boron compound or a titanium compound (see Japanese Patent Publication No. 54-37998), an organosilicon containing a hydroxyl group or an alkoxy group. Silicone-modified epoxy resin composition comprising a compound, an epoxy compound and a carboxylic acid or carboxylic anhydride
No. 50-153063), an epoxy resin-modified silicone resin composition comprising an organic silicon compound containing a hydroxyl group or an alkoxy group, an epoxy resin containing a hydroxyl group and an epoxy group, an aluminum compound and an amine compound (JP-B 63-2462).
No. 4), a silicone-epoxy resin composition comprising a curable epoxy resin, an epoxy resin-modified silicone resin, and an epoxy-modified polysiloxane (Japanese Patent Laid-Open No. 1-21).
No. 7059), a curing agent for an epoxy resin comprising an aluminum compound and a hydroxyl group-containing silicon compound (Japanese Patent Laid-Open No. 57-42).
No. 721) is known. However, among the resins described above, when the blending ratio of the epoxy resin is high, the moisture resistance and heat resistance are insufficient, while when the blending ratio of the silicone resin is high, the mechanical strength is insufficient. Therefore, there is a demand for improvement of these problems. In addition, these epoxy resin-modified silicone resins are generally used in the form of a solution dissolved in an organic solvent. In recent years, however, the effects of organic solvents on the human body have been called for, and from the viewpoint of environmental health, the use of organic solvents is minimized. A way to reduce it is 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 not required (or the amount used is small). No resin has been provided.

[0003]

The object of the present invention is to solve such drawbacks, have excellent mechanical strength, and have good moisture resistance and heat resistance.
An object of the present invention is to provide an epoxy-modified silicone resin composition having good workability.

[0004]

The present inventors have conducted intensive studies to achieve the above object, and as a result, by mixing a silanol group-containing silicone resin having a specific structure with an epoxy group-containing polyorganosiloxane, It has been found that an epoxy-modified silicone resin having excellent mechanical strength and good moisture resistance and heat resistance can be obtained, and the present invention has been completed. That is, the present invention provides (A) an epoxy group-containing polyorganosiloxane 95-
5 parts by weight and a structural unit represented by (B) a 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 comprising 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) 0.005 to 50 parts by weight of a curing catalyst. 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 an organic group bonded to a silicon atom. Such polyorganosiloxane containing an epoxy group is synthesized by adding an epoxy compound containing an alkenyl group to a polyorganohydrogensiloxane using a catalyst or the like, or hydrolyzing an epoxy group-containing polyorganosiloxane. Method of synthesizing by synthesizing and co-hydrolyzing / condensing a hydrophilic silane with other hydrolyzable silanes, etc., and synthesizing by synthesizing an epoxy compound containing a hydroxyl group with a silane or siloxane having a hydroxyl group or a hydrolyzable group. Can be obtained by Among these, with no solvent,
Since an epoxy group-containing polyorganosiloxane having good storage stability can be obtained, a method of adding an alkenyl group-containing epoxy compound to polyorganohydrogensiloxane and synthesizing the same is preferable. Examples of such a 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 from each other, and a and b are integers satisfying 0 ≦ a ≦ 3 and 1 ≦ b ≦ 3. Wherein one molecule contains at least one hydrogen atom bonded to a silicon atom. Epoxy compounds containing alkenyl groups include

[0006]

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And the like. The addition reaction catalyst used herein is a catalyst that promotes the addition reaction between 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 or alumina supported on platinum, or platinum-based catalysts such as platinum black, tetrakis (triphenylphosphine) palladium, palladium black and titanium A palladium-based catalyst such as a mixture with phenylphosphine,
Rhodium-based catalysts such as tetrakis (triphenylphosphine) rhodium and a mixture of rhodium black and triphenylphosphine are exemplified. The epoxy group-containing polyorganosiloxane as the component (A) of the present invention can be obtained by subjecting the above-mentioned polyorganohydrogensiloxane and an alkenyl group-containing epoxy compound to an addition reaction in the presence of an addition reaction catalyst. In this case, the reaction is preferably performed in an inert solvent because the reaction is easily controlled and the raw materials and products are easily handled. After the completion of the reaction, the solvent is removed to obtain the epoxy group-containing organopolysiloxane of the component (A). In the case of a method such as co-hydrolysis and polycondensation of an epoxy group-containing silane with another silane, the epoxy group-containing polyorganosiloxane contains many residual silanol groups, and gelation occurs when the solvent is removed. It must be handled in solution. Examples of the epoxy group-containing polyorganosiloxane as the component (A) of the present invention include the following.

[0008]

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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, and is a group selected from R ² or E, and c and d are 0 ≦ c, 0 ≦ d preferably 0 ≦ c + d ≦ 100, particularly preferably 10 ≦ c + d ≦ 5
An integer that satisfies 0.

[0010]

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A cyclic organopolysiloxane represented by the formula (V): Here, 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) (VI) branched polyorganosiloxane of formula. Here, R ³ is as described above, and g and h are integers satisfying 1 ≦ g, 1 ≦ h, preferably 5 ≦ g + h ≦ 50. _{^{(R 3 3 SiO 0.5) i}} (SiO 2.0) j (VII) (VII) branched polyorganosiloxane of 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 polyorganosiloxanes represented by (IV) to (VII), various siloxane units may be present in blocks or randomly. Further, one molecule contains at least one, preferably two or more epoxy groups. The epoxy group-containing polyorganosiloxane synthesized by the above-mentioned addition reaction has a low residual silanol content, usually 2% by weight or less. In the present invention, when the one having 0.5% by weight or less is used, a composition having good storage stability can be obtained. Is preferred. In the composition of the present invention, it is preferable to use an epoxy group-containing polyorganosiloxane represented by (IV) as the component (A) because the composition has good mechanical strength when combined with the component (B). . 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 from 5 to 10,000 cP, especially from 20 to 1,000 cP, because the composition of the present invention is easy to handle when used without a solvent and the mechanical strength of the obtained cured product is good. It is preferred to use one. The epoxy equivalent is 50 to 5,000 since good curability and heat resistance are obtained.
It is particularly preferable to use those having a molecular weight 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 that characterizes the present invention. It is necessary that the component (B) contains R ¹ SiO _1.5 unit or SiO _2.0 unit. 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 , An alkyl group such as dodecyl group, a cycloalkyl group such as cyclopentyl group and cyclohexyl group, an aralkyl group such as 2-phenylethyl group and 2-phenylpropyl group, an aryl group such as phenyl group and tolyl group, a vinyl group, an allyl group Such as alkenyl groups, and hydrogen atoms bonded to carbon atoms of these hydrocarbon groups are partially halogen atoms, acryloxy groups, methacryloxy groups, cricidoxy groups, 3,4-epoxycyclohexyl groups, mercapto groups, etc. Examples include groups substituted with atoms or groups. Among them, an alkyl group having 1 to 4 carbon atoms or a phenyl group is preferable in terms of synthesis or availability. In particular, since the compatibility with the component (A) is improved,
Preferably, 5 to 60 mol% of all organic groups are phenyl groups, particularly preferably 10 to 40 mol%. Such a silicone resin can be obtained, for example, by adding a hydrolyzable silane such as an organotrichlorosilane, an organotrialkoxysilane, a tetrachlorosilane or a tetraalkoxysilane together with other hydrolyzable silanes if necessary, water, a solvent and, if necessary, a hydrolyzable silane. It can be obtained by hydrolysis and condensation polymerization in the presence of a decomposition catalyst. In this case, the amount of residual silanol, the molecular weight, and the like 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, particularly
It is preferably at least 5.0% by weight. Further, the molecular weight is preferably 500 to 10,000, more 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 silicone resin of the component (B) 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,
Preferably, R ¹ SiO _1.5 units or SiO _2.0 units are contained in an amount of at least 10 mol% of all siloxane units, and particularly preferably at least 50 mol%. Examples of such a silanol group-containing silicone resin include the following. _{^{(R 1 SiO 1.5) k (}} R 1 2 SiO 1.0) m (VIII) (VIII) The silicone resin represented by the formula. Here, R ¹ is as described above, and k and m are 1 ≦ k, 0 ≦ m, 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) (IX) a silicone resin represented by the formula. Where n and p are 1 ≦
n is an integer satisfying 1 ≦ p, preferably 5 ≦ n + p ≦ 100. ^{_{(SiO 2.0) q (R 1}} 2 SiO 1.0) r (X) (X) a silicone resin represented by the formula. Where q and r are 1 ≦ q
Is an integer satisfying 1 ≦ r, preferably 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
Is an integer satisfying 1 ≦ t, preferably 5 ≦ s + t ≦ 100. In the silicone resins 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 or molecular weight when synthesizing, and when combined with the component (A), the cured product has good mechanical strength. Formula (VIII) or
It is preferable to use a silanol group-containing silicone resin represented by the formula (X), and it is particularly preferable to use a silicone resin represented by the formula (VIII). As described above, the component (B) is obtained by hydrolysis and polycondensation of a hydrolyzable silane, and is generally handled in a solution of an organic solvent. Therefore, it is usually difficult to eliminate the 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 or the like, and the solvent can be eliminated. Therefore, (A) shown in the present invention
A solvent-free composition that is environmentally useful is obtained from the component and the component (B).

In the present invention, the mixing ratio of the component (A) to the component (B) is from 5 to 95 parts by weight of the component (A) to 5 to 95 parts by weight of the component (B). When the amount of the silanol group-containing silicone resin of the component (B) is more than 95 parts by weight in the total of 100 parts by weight of the components (A) and (B), the curability of the obtained epoxy-modified silicone resin composition decreases. At the same time, the adhesiveness to various substrates deteriorates. If less than 5 parts by weight,
The heat resistance of the resulting epoxy-modified silicone resin composition decreases. Preferably with respect to 80 to 30 parts by weight of the component (A),
(B) The component is blended in an amount of 20 to 70 parts by weight.

The curing catalyst (C) used in the present invention comprises (A)
It has a catalytic action on the reaction between the epoxy group of the component and the silanol group of the component (B). Examples of such a curing catalyst include an aluminum compound and an amino compound. Examples of the aluminum compound include chelate compounds of acetylacetone-based compounds such as aluminum trialkyl acetoacetate and aluminum trisacetylacetonate, and aluminum alcoholate compounds such as aluminum methyl alcoholate, aluminum ethyl alcoholate, and aluminum propyl alcoholate. Examples of the amino compound include γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and N- (β-aminoethyl) -γ- Amino group-containing silanes such as aminopropylmethyldimethoxysilane, monoethanolamine, diethanolamine, triethanolamine, diethylaminoethanol, n-hexylamine, tripropylamine, ethylenediamine, triethylenediamine, aniline, tetramethylammonium hydroxide or a mixture thereof. Organic acid salts and the like are exemplified. The curing catalyst is
Two or more types may be used in combination. Among these, aluminum compounds are preferred, and aluminum chelates are particularly preferred, in view of the curability of the composition, the heat resistance of the resulting cured product, and the safety of the catalyst. 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 used 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 the amount is less than 0.005 parts by weight, sufficient curability cannot be obtained, and if the amount is more than 50 parts by weight, the heat resistance and weather resistance of the cured product decrease. Preferably it is 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 amino compound is used.

Aluminum chelates are generally solid at room temperature and are difficult to dissolve in the components (A) and (B). Therefore, they are preferably dissolved in an organic solvent or a liquid epoxy resin and blended. It is preferable to use the composition after dissolving it in a liquid epoxy resin.
The epoxy resin is not particularly limited as long as it is a liquid, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, partially cresol novolak type epoxy resin, hydrogenated bisphenol A type epoxy resin And aliphatic epoxy resins such as propylene glycol glycidyl ether and pentaerythritol polyglycidyl ether, and two or more kinds thereof may be used in combination. In order for the liquid epoxy resin to have good heat resistance of the cured product obtained from the composition of the present invention, 10 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B) is required. It is preferable that the content be not more than part by weight. The epoxy resin for dissolving and dispersing the aluminum chelate of the catalyst may be used in combination with the epoxy group-containing polyorganosiloxane (A).

In the composition of the present invention, when a solvent-free composition is used, the viscosity of the solvent-free composition is lowered without lowering the physical properties of the cured product obtained, and the workability is improved. For this reason, an alkoxy group-containing silane may be blended. A silanol group-containing alkoxysilane obtained by partially hydrolyzing the silane or a low-viscosity alkoxy group-containing polysiloxane that is a condensate thereof may be used, but a viscosity of 100 cP or less is preferable. Such an alkoxy group-containing silane or the like is preferably blended 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-mentioned 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 preferred to incorporate a catalyst. Examples of such a catalyst include metal salts of carboxylic acids such as dibutyltin dilaurate and titanates such as tetrabutyl titanate. Such a catalyst is preferably used in an amount of 0.005 to 10 parts by weight per 100 parts by weight of the alkoxy-containing silane or siloxane.
Parts by weight, particularly preferably 0.01 to 2 parts by weight.

The reaction proceeds even at room temperature by mixing the components (A) to (C) of the present invention. Therefore, component (C) is preferably mixed with other components immediately before use. By the combination of the component (A) and the component (B) of the present invention, a liquid and solvent-free composition can be obtained, and this composition is preferable for environmental health.
Therefore, a combination of the components (A) and (B) is used as one solvent-free component, and the component (C) is dissolved and dispersed in an epoxy resin or a component to which the component (A) is added, if necessary. It is preferable to use another solvent-free component and mix these components when used.

The composition of the present invention may contain, if necessary, a small amount of additives, for example, a plasticizer, a release agent, a flame retardant, an antioxidant, an ultraviolet absorber, a pigment such as titanium dioxide, carbon black or iron oxide. And a dye. Similarly, fumed silica, silica aerogel, silica gel, and a reinforcing silica filler obtained by treating these with an organic silane, an organic siloxane, or an organic silazane, asbestos, pulverized fused quartz, aluminum oxide, aluminum silicate, silicon silicate, and the like. Zirconium oxide, 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 as needed.

[0020]

Industrial Applicability The epoxy-modified silicone resin composition of the present invention has good curability, good mechanical strength, moisture resistance, heat resistance, weather resistance, good peelability and good adhesion to various substrates. Gives a cured product with excellent adhesion. Furthermore, the composition of the present invention can be a stable liquid composition without a solvent, and can be preferably used for 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 sealing resin for optical semiconductors and electronic components and its binder. Alternatively, it is also suitably used as a binder for heat-resistant electrically insulating thin sheet materials, glass cloth for laminated sheets, glass cloth-mica foil, mica foil and the like. Further, it is also suitably used as a coil impregnation for transformers and motors or as a moisture-proof coating agent for electric / electronic parts.

[0021]

The present invention will be specifically described below with reference to examples and comparative examples. In the examples, parts represent parts by weight, and% represents% by weight. The viscosity and specific gravity show values at 25 ° C. Synthesis Example 1 General Formula

[0022]

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

[0024]

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1368 parts (12.0 mol) of the epoxy compound represented by the formula and an isopropanol solution of chloroplatinic acid were mixed in an amount of 10 ppm with respect to the epoxy compound in terms of platinum. This mixed solution was dropped into a stirring solution of polysiloxane in toluene. After completion of the dropwise addition, heating and stirring were continued at 100 ° C. for 6 hours to carry out an addition reaction. Next, add this reaction solution to 12
The temperature was kept at 0 ° C. and 20 mmHg for 1 hour to remove toluene, unreacted epoxy compounds and other volatile components. This was filtered under pressure using Celite, and had a viscosity of 320 cP and a specific gravity of 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

[0027]

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462 parts (1.0 parts) of the polysiloxane represented by
Mol) and 684 parts (6.0 mol) of the epoxy compound, except that the viscosity was 120 cP and the specific gravity was 1.
Thus, an epoxy group-containing organopolysiloxane (A-2) having an epoxy equivalent of 201 was obtained.

Synthesis Example 3 In place of the polyorganohydrogensiloxane of Synthesis Example 1, a general formula

[0030]

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268 parts (1.0 parts) of the cyclic siloxane represented by
Mol) and 342 parts (3.0 mol) of the epoxy compound, except that the viscosity was 25 cP and the specific gravity was 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 was used. 1.0 mol) and 912 parts (8.0 mol) of an epoxy compound, and the same procedure as in Synthesis Example 1 was carried out. The epoxy group-containing organopolysiloxane (A) having a viscosity of 200 cP and a specific gravity of 1.122 epoxy equivalent 226 was used.
-4) was obtained.

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

[0034]

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372 parts (3.0 parts) of the epoxy compound represented by
Mol) except that it was used.
An epoxy group-containing organopolysiloxane (A-5) having 3cP, a specific gravity of 1.066 and an epoxy equivalent of 257 was obtained.

Synthesis Example 6 In place of the polyorganohydrogensiloxane of Synthesis Example 1, a general formula

[0037]

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The same procedures as in Synthesis Example 1 were carried out except that 1412 parts (0.5 mol) of polysiloxane and 2,000 parts of toluene were used. The viscosity was 500 cP, the specific gravity was 1.107, and the epoxy equivalent was 26.
Thus, an epoxy group-containing organopolysiloxane (A-6) was obtained.

Synthesis Example 7 516 parts (4 mol) of dimethyldichlorosilane, 236 parts (1 mol) of γ-glycidoxypropyltrimethoxysilane,
45.5 parts (0.5 mol) of hexamethyldisiloxane were added to 30 parts of water.
0 parts and a mixture of about 1000 parts of toluene are dropped and stirred to carry out hydrolysis and condensation polymerization.Hydrochloric acid and water are removed, dried over anhydrous sodium sulfate, epoxy equivalent 580, silanol group content.
3.2% epoxy-containing organopolysiloxane (A-7)
Was obtained in a 50% toluene solution. When the toluene was removed from the solution by heating and reducing the pressure, 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 subjected to hydrolysis and condensation polymerization 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. When the toluene was removed from this solution by heating and reducing the pressure, gelation occurred.

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. Hydrolysis and condensation polymerization were carried out in the same manner as in Example 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 to obtain a silanol group having an average molecular weight of 2,000 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,
After partial hydrolysis and polycondensation in the same manner as in Synthesis Example 7, the viscosity was 10 c
Thus, an alkoxy group-containing organopolysiloxane (C-1) having 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 in Synthesis Example 7.
After hydrolysis and polycondensation in the same manner as described above, the aqueous phase was removed and alkoxylation was carried out with 1000 parts of methanol. Hydrochloric acid, toluene and other volatile components are removed to obtain a viscosity of 70 cP, specific gravity of 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)
The part was charged into a 500 ml four-necked flask equipped with a distillation pipe, a cooling pipe, a stirrer, a decompression device, and a thermometer.
The toluene of the component (B) was removed under reduced pressure, and finally 40 mmH
g, after holding at 90 ° C. for 20 minutes, terminating the removal of toluene,
An epoxy-modified silicone resin component (P-1) having a viscosity of 750 cP was obtained. Next, 100 parts of powdery aluminum trisacetylacetonate as a catalyst and a bisphenol type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co.) 10
A mixture of 0 parts and 100 parts of component (A) A-2
Curing catalyst component with a viscosity of 1500 cP by heating and stirring at ℃
(Q-1) was obtained. Epoxy-modified silicone resin component P-1
Is mixed with 100 parts and 5 parts of the curing catalyst component Q-1.
The resin composition of the present invention was obtained. The obtained resin composition is poured into a plastic mold for light-emitting diodes to which a release agent is applied, and a frame on which a gallium-arsenic-phosphorus (Ga-As-P) -based yellow chip is mounted is cured. After being cured by heating at 140 ° C. for 8 hours, it was removed from the jig and separated one by one.
ED). The light-emitting device was energized under the conditions of 25 mA and 2.2 V for 168 hours, and the residual ratio of the luminance was determined from the measured value of the luminance before and after the 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)
In the same manner as in Example 1, an epoxy-modified silicone resin component (P-2) having a viscosity of 825 cP was obtained.

To 100 parts of the component P-2, 5 parts of the curing catalyst component Q-1 of Example 1 were mixed to obtain a resin composition of the present invention. When this composition was evaluated in the same manner as in Example 1, the residual ratio 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). . 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 components were mixed as shown in Table 1 and the solvent was removed in the same manner as in Example 1 to obtain an epoxy-modified silicone resin component (P
-3, P-4). Further, a resin composition of the present invention was prepared with a composition as shown in Table 2, and a pigment or the like was dispersed with three rolls 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 film were evaluated. The cured state was evaluated from the solvent resistance and the pencil hardness. The heat resistance was determined by using a test piece cured at 250 ° C for 1 minute and heating at 200 ° C for 16 hours for gloss retention and color difference (Δ
E), and the weather resistance was evaluated from the gloss retention and the color difference (ΔE) after the weather resistance test was carried out for 2000 hours with a sunshine weatherometer using the same test piece. Table 3 shows the results
Shown in

Comparative Example 2 200 parts of a 50% toluene solution of A-7 as the component (A), 120 parts of dimethylpolysiloxane having a viscosity of 700 cP containing terminal silanol groups and silanol group-containing siloxane, Mix 20 parts of C-2 and remove the solvent without removing the epoxy-modified silicone resin component (P'-2)
And a white paint was obtained in the same manner as in Example 3. This white paint was evaluated in the same manner as in Example 3. Table 3 shows the results.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

Examples 5 and 6 The components were mixed as 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, the curing catalyst component is blended with the 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) and sealed by heating at 120 ° C. for 1 hour and further at 150 ° C. for 1 hour to obtain a semiconductor device sealed with the composition of the present invention. The reliability was evaluated from the rate of occurrence of defects after leaving the semiconductor element for 1000 hours or 2000 hours at a temperature of 80 ° C. and a humidity of 85%. Table 5 shows the results.

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

[0056]

[Table 4]

Comparative Example 4 Each component was mixed with the composition shown in Table 4 to obtain a silicone resin component (P'-4). Further, the curing catalyst component was blended with the 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. Table 5 shows the results.

[0058]

[Table 5]

Example 7 The procedure of Example 1 was repeated, except that 20 parts of A-3, 210 parts of A-6, and 180 parts of B-3 were used as the component (A). An epoxy-modified silicone resin component (P-7) of cP was obtained. 20 parts of the curing catalyst component Q-1 were mixed with 100 parts of the component P-7 to obtain a resin composition of the present invention. This composition
A 10 µm thick film is applied to a 38 µm thick polyester film (Tetron Film, Teijin Limited) at 140 ° C.
And cured for 2 minutes to obtain a release film. A one-pack type polyurethane solution (Chris Bon 76
67EL, manufactured by Dainippon Ink and Chemicals, Inc.) with a coating thickness of 30 μm, and dried by heating at 120 ° C. for 3 minutes. When the urethane film was peeled from the release film in the direction of 180 °, the peeling force was measured using a tensile tester at a pulling speed of 30.
When measured as cm / min, it showed a value of 8.0 g / 3 cm.

Comparative Example 5 The same evaluation as in Example 7 was carried out using the resin composition of Comparative Example 2, and the urethane film was found to undergo cohesive failure.

────────────────────────────────────────────────── ─── Continued on the front page (56) References JP-A-56-103224 (JP, A) JP-A-59-27952 (JP, A) JP-B-60-43371 (JP, B2) (58) Field (Int.Cl. ⁷ , DB name) C08L 83/06 C08G 77/38 C08G 77/14 C08G 77/16

Claims (1)

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