JPH06298897A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide a curable resin composition which has excellent flowability before cured and which after cured is excellent in flexibility, moisture resistance, and thermal impact resistance. CONSTITUTION:The composition comprises 100 pts.wt. curable resin and 0.1-500 pts.wt. epoxidized silicone resin represented by the formula (R<1>SiO3/2)a (R<2> R<3>SiO2/2)b (SiO4/2)c {wherein R<1>, R<2>, and R<3> are the same or different and each represents a monovalent hydrocarbon group or an epoxidized organic group, provided that the amount of the epoxidized organic groups is 0.1-40mol% based on the total amount of all Si-bonded organic groups in the silicone resin; and a is a positive number and b and c each is 0 or a positive number, provided that 0<=b/a<=10 and 0<=c/(a+b+c)<=0.3} and having a glass transition temp. of -90 deg.C to 150 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition, and more specifically, a curable resin composition having excellent fluidity before curing and flexibility, moisture resistance and thermal shock resistance after curing. Resin composition.

[0002]

2. Description of the Related Art Curable resin compositions have electrical properties such as dielectric properties, volume resistivity, dielectric breakdown strength, etc., and mechanical properties such as bending strength, compressive strength, impact strength, etc. Because it is excellent, it is used in all industries.

However, when such a curable resin composition is used as a coating agent, an adhesive, or a resin for encapsulating electric / electronic elements, the resin obtained after curing is rigid and lacks flexibility. Since the curing shrinkage rate is large, a large stress is applied to the adherend and the electric / electronic element, and the resin is cracked or damaged, the electric / electronic element sealed by the resin is broken, or the resin and the adherend are adhered to each other. There is a problem that a gap is generated between the body and the electric / electronic element.

Further, the curable resin composition has a large coefficient of thermal expansion of the resin obtained by curing the curable resin composition as compared with the coefficient of thermal expansion of the electric / electronic element, and therefore the electric / electronic element sealed by the resin is used. When repeatedly subjected to thermal shock, the resin may crack, the electric / electronic element sealed by the resin may be destroyed, and a gap may be created between the resin and the electric / electronic element. -There was a problem that the reliability of the electronic device was reduced.

Therefore, in order to improve the flexibility, moisture resistance and thermal shock resistance of the cured resin, many curable resin compositions comprising a curable resin and an organopolysiloxane have been proposed in the past. As such a curable resin composition, for example, a curable resin composition comprising an epoxy resin, an epoxy group- and methoxy group-containing organopolysiloxane, a curing agent and an inorganic filler (JP-A-56-136816).
(See JP-A-56-145942), a mixture of an epoxy resin and an organopolysiloxane having a silanol group, an epoxy group-containing organopolysiloxane, an inorganic filler, and a curable resin composition (Claim 56-145942).
(See Japanese Patent Publication).

However, in the curable resin compositions proposed in JP-A-56-136816 and JP-A-56-14592, the epoxy group-containing organopolysiloxane is an epoxy group-containing alkoxysilane and another alkoxysilane. Was obtained by co-hydrolyzing the epoxy resin, and a curable resin composition prepared by blending such an epoxy group-containing organopolysiloxane has flexibility and moisture resistance of the resin obtained by curing. And the thermal shock resistance was not sufficient.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have arrived at the present invention as a result of diligent efforts to solve the above problems.

That is, an object of the present invention is to provide a curable resin composition which forms a resin having excellent fluidity before curing and excellent flexibility, moisture resistance and thermal shock resistance after curing. is there.

[0009]

[Means for Solving the Problems and Their Actions] The present invention comprises (A) 100 parts by weight of a curable resin and (B) a general formula: (R ¹ SiO _3/2 ) _a (R ² R ³ SiO _{2 / 2} ) _b (SiO _4/2 ) _c {wherein R ¹ , R ² and R ³ are the same or different monovalent hydrocarbon groups or epoxy-containing organic groups, provided that
The content of the epoxy-containing organic group with respect to all the silicon atom-bonded organic groups in the component (B) is 0.1 to 40 mol%, a is a positive number, b is 0 or a positive number, and c is 0. Or a positive number and b / a is a number from 0 to 10, and c / (a
+ B + c) is a number from 0 to 0.3. } And a curable resin composition comprising 0.1 to 500 parts by weight of an epoxy group-containing silicone resin having a glass transition point at -90 ° C to 150 ° C.

The curable resin composition of the present invention will be described in detail.

The curable resin as the component (A) is the main material of the composition of the present invention, and the kind thereof is not particularly limited. Specific examples of the curable resin as the component (A) include phenol resin, formaldehyde resin, xylene resin, xylene-formaldehyde resin, ketone-formaldehyde resin, furan resin, urea resin, imide resin, melamine resin, alkyd resin, and unsaturated resin. Examples include polyester resins, aniline resins, sulfone-amide resins, silicone resins, epoxy resins, copolymer resins thereof, and mixtures of two or more of these curable resins, preferably epoxy resins, phenol resins, It is a curable resin selected from the group consisting of imide resins and silicone resins. Also,
The curing mechanism of the component (A) is not particularly limited, and specific examples thereof include a thermosetting resin, an ultraviolet curable resin, and a moisture curable resin. The state of the component (A) at room temperature is not particularly limited, and it may be liquid or solid at room temperature.

In the curable resin composition of the present invention, (A)
As components other than the above-described curable resin, for example, a curing agent, a curing accelerator, a filler, a photosensitizer, a metal salt of a higher fatty acid, an ester wax, and a plasticizer can be blended. . Specific examples of the curing agent that can be added to the component (A) include organic acids such as carboxylic acids and sulfonic acids and their anhydrides, organic hydroxy compounds, silanol groups, alkoxy groups, halogeno groups, and other such groups. Compounds, primary or secondary amino compounds are exemplified, and a mixture of two or more of these curing agents can be used. Further, as the curing accelerator that can be added to the component (A), specifically, tertiary amine compounds, organometallic compounds such as aluminum and zirconium, organic phosphorus compounds such as phosphine, heterocyclic amine compounds, boron complex Examples include compounds, organic ammonium salts, organic sulfonium salts, and organic peroxides. Specific examples of the filler that can be added to the component (A) include glass fibers, asbestos, alumina fibers, ceramic fibers containing alumina and silica as components, boron fibers, zirconia fibers, silicon carbide fibers,
Fibrous fillers such as metal fibers, polyester fibers, aramid fibers, nylon fibers, phenol fibers, natural animal and plant fibers; fused silica, precipitated silica, fumed silica, calcined silica, zinc oxide, calcined clay, carbon black,
Powder beads such as glass beads, alumina, talc, calcium carbonate, clay, aluminum hydroxide, barium sulfate, titanium dioxide, aluminum nitride, silicon carbide, magnesium oxide, beryllium oxide, kaolin, mica, zirconia, and the like A mixture of two or more kinds is exemplified.

In the curable resin composition of the present invention, (B)
The epoxy group-containing silicone resin of the component is (A)
It is a component for improving the fluidity of the obtained curable resin composition by adding it to the component, and also for improving the flexibility, moisture resistance and thermal shock resistance of the resin obtained by curing the curable resin composition. . Such component (B) is represented by the general formula: (R ¹ SiO _3/2 ) _a (R ² R ³ SiO _2/2 ) _b (SiO _4/2 ) _c . In the above formula, R ¹ , R ² and R ³ are the same or different monovalent hydrocarbon groups or epoxy-containing organic groups, and specific examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, Alkyl groups such as butyl group, pentyl group, hexyl group, heptyl group; vinyl group, allyl group,
Alkenyl groups such as butenyl group, pentenyl group, hexenyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group, phenethyl group; chloromethyl group, 3-chloropropyl group, 3 ，
Substituted alkyl groups such as 3,3-trifluoropropyl group and nonafluorobutylethyl group are exemplified, and specific examples of the epoxy-containing organic group include 2,3-epoxypropyl group,
3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) An ethyl group and a 3- (3,4-epoxycyclohexyl) propyl group are exemplified. Here, the content of the epoxy-containing organic groups with respect to the total silicon-bonded organic groups in the component (B) needs to be within the range of 0.1 to 40 mol%. This is because when the content of the epoxy-containing organic groups with respect to all the silicon atom-bonded organic groups in the component (B) is less than 0.1 mol%, the resulting cured resin has flexibility, moisture resistance and thermal shock resistance. Decreased, and also 40 mol%
If it exceeds, the mechanical properties of the obtained cured resin will be significantly reduced. Further, since the affinity between the component (A) and the component (B) is extremely high, it is preferable that 30 mol% or more of R ^{1 in} the component (B) is a phenyl group.

In the above formula, a is a positive number indicating the content of trifunctional siloxane units (T units), and b is 0 or a positive number indicating the content of difunctional siloxane units (D units). And c is 0 or a positive number indicating the content of the tetrafunctional siloxane unit (Q unit). Where b / a is 0 to 1
It is a number within the range of 0. This means that the glass transition point of the component (B) whose b / a exceeds 10 is remarkably lowered,
Also, the affinity with the component (A) is lowered. Also,
c / (a + b + c) is a number in the range of 0 to 0.3,
This is because c / (a + b + c) exceeds 0.3
This is because the dispersibility of the component (B) with the component (A) decreases.

The number average molecular weight and the molecular structure of the component (B) are not particularly limited, but the number average molecular weight is 300.
It is preferably in the range of 50,000 to 50,000, and more preferably in the range of 500 to 10,000. The glass transition point of the component (B) needs to be in the range of -90 ° C to 150 ° C. This is because it is difficult to uniformly mix the component (A) with the component (B) whose glass transition point exceeds 150 ° C., and the glass transition point is -9.
This is because the curable resin composition obtained by blending the component (A) with the component (B) at a temperature lower than 0 ° C. has a reduced mechanical property of the resin obtained by curing the curable resin composition.

The component (B) is composed of (I) the following component (i)
One or a mixture of two or more organopolysiloxanes selected from the group consisting of component (iv) [however, only component (ii) is excluded. ] And (i) an organopolysiloxane having a siloxane unit represented by the general formula: R ⁴ SiO _3/2 , (ii) an organopolysiloxane having a siloxane unit represented by a general formula: R ⁵ R ⁶ SiO _2/2 , (iii) an organopolysiloxane having a siloxane unit represented by the general formula: R ⁴ SiO _3/2 and a siloxane unit represented by the general formula: R ⁵ R ⁶ SiO _2/2 , and (iv) a general formula: R ⁴ SiO An organopolysiloxane comprising a siloxane unit represented by _3/2 and a general formula: R ⁵ R ⁶ SiO _2/2 and a siloxane unit represented by a general formula: SiO _4/2 (wherein R ⁴ , R ⁵ and R ⁶ are the same or different monovalent hydrocarbon groups.) (II) General formula: R ⁷ R ⁸ _d Si (OR ⁹ ) _(3-d) (In the formula, R ⁷ contains an epoxy group. an organic group, R ⁸ is a monovalent hydrocarbon group, R ⁹ is Is an alkyl group and d is 0 or 1.) The epoxy group-containing alkoxysilane represented by the formula (2) or its partial hydrolyzate [the amount of the component (II) is equal to that of the epoxy group-containing organic group in the component (II) , (I) component
0.1 to 4 with respect to the total silicon-bonded organic groups of component (II)
The amount is 0 mol%. ] In the presence of water and a basic catalyst to synthesize a silicone resin, and then the concentration of the silicone resin is adjusted with an organic solvent, followed by equilibrating the silicone resin with the basic catalyst. The epoxy group-containing silicone resin prepared by The epoxy group-containing silicone resin as the component (B) can be generally synthesized by subjecting a cohydrolyzate of an epoxy group-containing alkoxysilane and an organoalkoxysilane to a condensation reaction, but is prepared by such a production method. The epoxy group-containing silicone resin does not show a clear glass transition point in the range of -90 ° C to 150 ° C, and an epoxy group-containing silicone resin suitable for the curable resin composition of the present invention cannot be prepared. Is.

In the above-mentioned method for producing the component (B), the component (I) is a main raw material, and one or a mixture of two or more organopolysiloxanes selected from the group consisting of the following (i) to (iv): However, it is an organopolysiloxane or an organopolysiloxane mixture excluding only the component (ii). As such component (I), only component (i), (iii)
Component only, (iv) component only, a mixture consisting of (i) component and (ii) component, a mixture consisting of (i) component and (iii) component, a mixture consisting of (i) component and (iv) component, (i ) Component and (ii) component and (iii)
Examples thereof include a mixture of components, a mixture of components (i), (ii) and (iv), and a mixture of components (i), (ii), (iii) and (iv). Further, in the method for producing the component (B), since the compatibility between the obtained component (B) and the component (A) is particularly excellent, it is preferable that 30 mol% or more of R ⁴ is a phenyl group in the molecule. preferable.

Among the components (I), the organopolysiloxane of the component (i) is an organopolysiloxane composed of siloxane units (hereinafter, T units) represented by the general formula: R ⁴ SiO _3/2 . In the above formula, R ⁴ is a monovalent hydrocarbon group, and specific examples of such a monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group. Alkyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group; aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl group such as benzyl group and phenethyl group; chloro Substituted alkyl groups such as methyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group and nonafluorobutylethyl group are exemplified. Such an organopolysiloxane of component (i) is generally called an organopolysilsesquioxane, and examples thereof include a ladder-shaped organopolysilsesquioxane and a cage-shaped organopolysilsesquioxane.

Among the components (I), the organopolysiloxane as the component (ii) is an organopolysiloxane composed of siloxane units (hereinafter, D units) represented by the general formula: R ⁵ R ⁶ SiO _2/2 . In the above formulas, R ⁵ and R ⁶ is a monovalent hydrocarbon group having same or different, in particular as a monovalent hydrocarbon group for R ⁵ and R ⁶ the same groups as the R ⁴ can be exemplified. Such an organopolysiloxane of component (ii) is generally called a diorganopolysiloxane, and the group at the terminal of its molecular chain is not particularly limited, and examples thereof include a hydroxyl group, an alkoxy group, and a triorganosiloxy group. To be

Among the components (I), the organopolysiloxane as the component (iii) includes a T unit represented by the general formula: R ⁴ SiO _3/2 and a D unit represented by the general formula: R ⁵ R ⁶ SiO _2/2. It is an organopolysiloxane composed of units. In the above formula, R ⁴ , R ⁵ and R ⁶ are the same or different monovalent hydrocarbon groups, and examples thereof include the same groups as described above.
The organopolysiloxane as the component (iii) is generally called a DT type silicone resin.

Among the components (I), the organopolysiloxane as the component (iv) includes a T unit represented by the general formula: R ⁴ SiO _3/2 and a D unit represented by the general formula: R ⁵ R ⁶ SiO _2/2. Unit and general formula: An organopolysiloxane composed of a siloxane unit represented by SiO _4/2 (hereinafter referred to as Q unit). In the above formula, R ⁴ , R ⁵ and R ⁶ are the same or different monovalent hydrocarbon groups, and examples thereof include the same groups as described above. The organopolysiloxane as the component (iv) is generally called a DTQ type silicone resin.

In the above-mentioned method for producing the component (B), the component (II) is a component for introducing an epoxy group-containing organic group into the epoxy group-containing silicone resin of the component (B) and has the general formula: R ⁷ R ^It is an epoxy group-containing alkoxysilane represented by ⁸ _d Si (OR ⁹ ) _(3-d) or a partial hydrolyzate thereof. In the above formula, R ⁷ is an epoxy group-containing organic group, and specific examples of the epoxy group-containing organic group include 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group It is illustrated. Further, in the above formula, R ⁸ is a monovalent hydrocarbon group, and specific examples of the monovalent hydrocarbon group for R ⁸ include the same monovalent hydrocarbon groups as those for R ⁴ . In the above formula, R ⁹ is an alkyl group, and specific examples of the alkyl group of R ⁹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Further, in the above formula, d is 0 or 1,
When d is 0, the component (II) is an epoxy group-containing trialkoxysilane or a partial hydrolysis product thereof, and when d is 1, the component (II) is an epoxy group-containing organodialkoxysilane or a partial hydrolysis product thereof. Is.

Specific examples of the epoxy group-containing organodialkoxysilane (II) include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, and 3-glycid. Xypropyl (methyl) dibutoxysilane, 2- (3,4-
Epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3-epoxypropyl (phenyl) dimethoxy Examples of silane include (I
Specific examples of the epoxy group-containing trialkoxysilane of component I) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3
-Glycidoxypropyltributoxysilane, 2-
Examples are (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2,3-epoxypropyltrimethoxysilane, and 2,3-epoxypropyltriethoxysilane. It

In the method for producing the component (B), the component (I) and the component (II) are reacted in the presence of water and a basic catalyst to synthesize a silicone resin. In this production method, other alkoxysilane or its hydrolyzate can be blended with the component (II), if necessary.
Specific examples of the alkoxysilane other than the component (II) include methyltrimethoxysilane, methyltriethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane , Dimethyldiethoxysilane,
Methylphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,
An example is dimethoxydiethoxysilane.

In the above-mentioned method for producing the component (B), the compounding amount of the component (II) is such that
It is necessary that the amount is 0.1 to 40 mol% with respect to the total silicon atom-bonded organic groups of the components (I) and (II). This is because the epoxy group-containing organic group in the component (II)
When the component (II) is blended in an amount of less than 0.1 mol% with respect to the total silicon atom-bonded organic groups of the component (I) and the component (II), the obtained epoxy group-containing silicone resin is obtained. Since the content of the epoxy group-containing organic group with respect to all the silicon atom-bonded organic groups in the composition is less than 0.1 mol%, the reactivity between the epoxy group-containing silicone resin and the curable resin is significantly reduced, and the curability is improved. This is because the effect of modifying the physical properties of the resin is not sufficient, and the epoxy group-containing organic group in component (II) is 40 moles based on the total silicon-bonded organic groups of component (I) and component (II). When the component (II) is blended in such an amount that the amount exceeds 100%, the content of the epoxy group-containing organic groups with respect to the total silicon atom-bonded organic groups in the obtained epoxy group-containing silicone resin exceeds 40 mol%. , This epoxy group-containing silicone resin When it reacted with a curable resin, because the epoxy group-containing organic group unreacted increases, the heat resistance of the resulting cured resin is reduced which do not participate in the reaction in (II) component.

In the method for producing the component (B), the amount of water to be added is not particularly limited as long as it is sufficient to hydrolyze the silicon atom-bonded alkoxy groups in the component (I). The basic catalyst is a catalyst for reacting the component (I) with the component (II). Specific examples of such a basic catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide and the like. Alkali metal hydroxides; sodium tert-butoxide, potassium t-butoxide, cesium-t-butoxide and other alkali metal alkoxides; sodium silanolate compounds, potassium silanolate compounds, cesium silanolate compounds, etc. The silanol compound of is exemplified, and potassium-based catalysts and cesium-based catalysts are particularly preferable.

In the method of producing the component (B), the basic catalyst may be added as a solid as it is or after being dissolved in a small amount of water or raw polysiloxane. The addition amount of such a basic catalyst is not particularly limited,
10 ppm to 100 relative to the total amount of component (I) and component (II)
It is preferably within the range of 00 ppm, and further 100 p
More preferably, it is in the range of pm to 5000 ppm.

In the above reaction, it is preferable to use an organic solvent in order to prevent the obtained silicone resin from depositing from the reaction system. The organic solvent that can be used should be appropriately selected depending on the type and characteristics of the silicone resin to be obtained. Specific examples of such an organic solvent include aromatic organic solvents such as toluene and xylene; acetone. Examples include ketone-based organic solvents such as methyl isobutyl ketone; aliphatic-based organic solvents such as hexane, heptane, and octane, and aromatic organic solvents are preferable. Further, it is preferable to add this organic solvent, since excess water and free water due to the condensation reaction of the silicone resin can be removed azeotropically from the obtained silicone resin.

In the above reaction, the conditions are not particularly limited, but the reaction temperature is preferably within the range of 80 ° C to 200 ° C, because the hydrolysis reaction, the condensation reaction and the like proceed smoothly. It is preferably in the range of 100 ° C to 150 ° C. When an organic solvent is used, the hydrolysis-condensation reaction can be easily carried out at the reflux temperature by selecting an organic solvent having a boiling point in the range of 80 to 200 ° C.

Next, in the method for producing the above-mentioned component (B), the silicone resin obtained by the above reaction is adjusted in concentration with an organic solvent, and then the silicone resin is allowed to undergo an equilibration reaction with a basic catalyst. . In this equilibration reaction, the organic solvent used may be the one used in the above reaction, or may be newly added. When a new organic solvent is added, examples of the organic solvent that can be added include the organic solvents exemplified above. In this equilibration reaction, the basic catalyst used may be the same as that used in the above reaction, or may be newly added. When a basic catalyst is newly added, examples of the basic catalyst that can be added include the basic catalysts exemplified above.

In the equilibrium reaction, the concentration of the silicone resin is adjusted by an organic solvent, but the concentration is not particularly limited, and in the method for producing the component (B), the desired molecular weight, softening point and -90 ° C to In order to produce an epoxy group-containing silicone resin having a glass transition point at 150 ° C., it is necessary to appropriately select. Further, in this equilibrium reaction, the organic solvent has a preferable effect of preventing the precipitation of the epoxy group-containing silicone resin obtained by the equilibration reaction and suppressing the viscosity of the reaction system to be low.

The conditions for the above equilibration reaction are not particularly limited. The equilibration reaction randomly causes cleavage and recombination of siloxane bonds, and as a result, the obtained epoxy group-containing silicone resin is in an equilibrium state.
In the method for producing the component (B), the reaction temperature is 80 ° C to 80 ° C because the equilibration reaction does not proceed sufficiently when the reaction temperature is low and the silicon atom-bonded organic group is thermally decomposed when the reaction temperature is too high. It is preferably in the range of 200 ° C.,
In particular, it is preferably within the range of 100 ° C to 150 ° C. Further, by selecting an organic solvent having a boiling point in the range of 80 to 200 ° C, the equilibration reaction can be easily carried out at the reflux temperature.

The progress of the equilibration reaction is most preferably traced by withdrawing a small amount of the reaction solution and measuring the characteristics of the epoxy group-containing silicone resin obtained by neutralizing the solution. As the characteristics to be measured, the molecular weight is most preferable, in the case of a liquid epoxy group-containing silicone resin at room temperature, it is preferable to measure its viscosity, and in the case of a solid epoxy group-containing silicone resin at room temperature. It is preferable to measure its glass transition point and softening point. The end point of the equilibration reaction can be determined by the characteristic value of the epoxy group-containing silicone resin.

In the method for producing the component (B), the reaction may be stopped immediately at the end point of the equilibration reaction, and in order to finely adjust the molecular weight of the epoxy group-containing silicone resin, the organic solvent may be increased or decreased to Further, the equilibration reaction can be performed by finely adjusting the concentration of the silicone resin. This is because when the concentration of the silicone resin is lowered by adding an organic solvent, the molecular weight of the obtained epoxy group-containing silicone resin is lowered to reach an equilibrium state, and when the concentration of the silicone resin is increased by removing the organic solvent, it is obtained. The molecular weight of the epoxy group-containing silicone resin increases and eventually reaches an equilibrium state. This operation is preferably performed as a finishing step after the end point of the equilibration reaction. By this operation, the desired molecular weight, softening point and glass transition point of -90 ° C to 150 ° C can be adjusted before taking out the epoxy group-containing silicone resin from the reaction vessel, so that any desired molecular weight, softening point and -9
An epoxy group-containing silicone resin having a glass transition point of 0 ° C to 150 ° C can be produced with good reproducibility.

At the end point of the equilibration reaction, the method of neutralizing the basic catalyst is not particularly limited, but it is preferable to neutralize by adding a weak acid such as carbon dioxide gas or carboxylic acid. The salt produced by neutralization can be easily removed by filtration or washing with water.

In the curable resin composition of the present invention, (B)
The compounding amount of the component is 0.1 with respect to 100 parts by weight of the component (A).
To 500 parts by weight, preferably 0.5 to 1
It is within the range of 00 parts by weight. This is because when the amount of the component (B) is less than 0.1 parts by weight per 100 parts by weight of the component (A), a cured resin having excellent flexibility, moisture resistance and thermal shock resistance can be obtained. This is because the mechanical strength of the cured resin is remarkably lowered when it exceeds 500 parts by weight.

The curable resin composition of the present invention can be obtained by uniformly mixing the component (A) and the component (B). The method for uniformly mixing the component (A) and the component (B) is not particularly limited, and specifically, the mixing method specifically includes the component (A) and the component (B).
Method of directly mixing components and fillers and other components, method of mixing component (A) and component (B), and then mixing filler and other components, mixture of filler and other components of component (A) Then
Examples thereof include a method of mixing the component (B) with this, and a method of mixing the component (B) with a filler and other components and then mixing the component (A). The device for mixing the component (A) and the component (B) is not particularly limited, and when the component (A) and the component (B) are in various forms such as liquid, solid, powder, etc., they are most suitable for them. It is preferable to appropriately select and use an apparatus, and specific examples of such an apparatus include a single-screw or twin-screw continuous mixer, a twin roll, a loss mixer, and a kneader mixer.

Since the curable resin composition of the present invention has excellent fluidity, it can be used by methods such as transfer molding, injection molding, potting, casting, powder coating, dip coating and dropping. Moreover, since the curable resin composition of the present invention can be cured to form a resin having excellent flexibility, moisture resistance and thermal shock resistance, it is used as a sealing resin composition for electric / electronic elements. It can be used for paints, coating agents, adhesives, etc.

[0039]

EXAMPLES The curable resin composition of the present invention will be described in detail with reference to Examples. In the examples, Mn represents a number average molecular weight, Mw represents a weight average molecular weight, Ph represents a phenyl group, and Ep represents a 3-glycidoxypropyl group. Furthermore, the viscosity value in the examples is a value measured at 25 ° C., and various properties of the curable resin composition and the cured resin were measured by the following methods.

○ Spiral flow: Measured by a method according to the EMMI standard. Molding shrinkage rate: Measured by a method according to JIS-K-6911. Thermal expansion coefficient: A cured resin molded into 5 mm × 5 mm × 16 mm was measured using a thermal expansion meter (DL-7000 manufactured by Vacuum Riko Co., Ltd.). The value of the coefficient of thermal expansion is the value from room temperature to the glass transition point. Glass transition point (Tg): Measured by measuring the coefficient of thermal expansion. Bending elastic modulus: Measured by a method according to JIS-K-6911. ○ Water absorption rate: 2 inches x 0.5 inches x 0.2
Cured resin molded into 5 inches has a temperature of 121 ° C and a humidity of 10
It was measured by measuring the weight increase of the cured resin immediately after humidifying for 20 hours at 0%. Burr: A burr length was measured using a groove having a depth of 20 μm.

○ Thermal shock resistance: Chip size 36 mm
^2. Resin-sealed semiconductor device 20 with a package thickness of 2.0 mm
A piece was molded and subjected to a heat cycle test at a cycle of −196 ° C. ← → + 150 ° C. for 1 minute. After 150 cycles, the surface of the sealing resin was observed with a stereoscopic microscope and the molded product with cracks on the surface was observed. The case where the number was 5 or less was marked with ◯, the case where it was within the range of 6 to 10 was marked with Δ, and the case where it was 11 or more was marked with x.

○ Solder heat resistance: Chip size 36 mm
^2. Resin-sealed semiconductor device 20 with a package thickness of 2.0 mm
Individual pieces were molded, left for 72 hours under the conditions of 85 ° C. and 85% RH, and immediately immersed in a solder bath at 240 ° C. for 1 hour, and the sealing resin surface was observed with a stereoscopic microscope. ○, 6 to 10 when the number of molded products with cracks on the surface is 5 or less
When the number is within the range of Δ, Δ when the number is 11 or more, x
And

[0043]

[Reference Example 1] 250 g of water and 400 g of toluene in a reaction vessel
Was thrown in. While adjusting the liquid temperature of this system to 10 ° C, 300 g of phenyltrichlorosilane and toluene 2 were added to this system.
00 g of the mixed solution was added dropwise. After completion of dropping, the mixture was heated under reflux for 6 hours, and then the toluene solution was separated. This toluene solution was repeatedly washed with 300 g of water until the washing liquid became neutral. Thereafter, this toluene solution was heated under reduced pressure to distill off toluene to prepare 177.7 g of a white solid (hereinafter, referred to as sample A).

[0044]

[Reference Example 2] 100 g of water and 400 g of toluene in a reaction vessel
And 140 g of isopropanol were added. While adjusting the liquid temperature of this system to 10 ° C., 336.7 g of phenyltrichlorosilane and 126 g of dimethyldichlorosilane were added to this system.
And a mixed solution of 126 g of toluene was added dropwise. After dropping 1
After heating under reflux for a period of time, the toluene solution was separated. This toluene solution was repeatedly washed with 300 g of water until the washing liquid became neutral to adjust 452 g of a toluene solution of organopolysiloxane having a solid content of 50% by weight (hereinafter, referred to as sample B).

[0045]

[Reference Example 3] 100 g of water and 400 g of toluene in a reaction vessel
And 140 g of isopropanol were added. While adjusting the liquid temperature of this system to 10 ° C, 317.3 g of phenyltrichlorosilane and 38.7 of dimethyldichlorosilane were added to this system.
g, tetrachlorosilane 34.0 g, and toluene 126 g
The mixed solution of was added dropwise. After completion of the dropping, the mixture was heated under reflux for 1 hour, and then the toluene solution was separated. Add 3 parts of this toluene solution
By repeatedly washing with 00 g of water until the washing liquid becomes neutral, 438 g of a toluene solution of organopolysiloxane having a solid content of 50% by weight was prepared (hereinafter, this toluene solution is referred to as sample C).

[0046]

Reference Example 4 51.6 g of sample A, 23.6 g of 3-glycidoxypropyltrimethoxysilane, 159.4 g of toluene and 0.08 g of cesium hydroxide were placed in a reaction vessel. 5.0 g of water of this system was added, and then the produced methanol and water were distilled off while heating the system. After distilling off water, the system was cooled and an additional 5.0 g of water was added to the system. Then, while heating the system, the produced methanol and water were distilled off. This operation was repeated, the distilled water was extracted with ether, and it was confirmed by gas chromatography that no methanol was produced, and heating was terminated. Then, the solid content concentration is 30% by weight.
The temperature was adjusted to 1, and the mixture was heated under reflux again. After sampling every 1 hour and neutralizing the sample, the molecular weight of the sample was measured by gel permeation chromatograph (hereinafter referred to as GPC) to confirm that the molecular weight distribution became constant. The system was cooled from. After cooling, 0.05 g of acetic acid was added to this system for neutralization. Next, the produced salt was filtered, and the filtrate was heated under reduced pressure to obtain 64.7 g of a colorless transparent solid. This colorless transparent solid has a Mn = 23.
00, Mw = 3820, glass transition point = 106 ° C., softening point = 142 ° C., epoxy equivalent = 680, ²⁹ Si−
By nuclear magnetic resonance spectrum analysis (hereinafter referred to as NMR), it was confirmed to be a 3-glycidoxypropyl group-containing silicone resin represented by the following structural formula.

(PhSiO _3/2 ) _0.8 (EpSiO _3/2 ) _0.2

[0048]

Reference Example 5 116.9 g of sample B, 3.7 g of octamethyltetracyclosiloxane, 12.1 g of 3-glycidoxypropyltrimethoxysilane and 1 of toluene were placed in a reaction vessel.
2.1 g and 0.08 g of cesium hydroxide were added. 5.0 g of water of this system was added, and then the produced methanol and water were distilled off while heating the system. After distilling off water, the system was cooled and an additional 5.0 g of water was added to the system. Then, while heating the system, the produced methanol and water were distilled off. This operation was repeated, the distilled water was extracted with ether, and it was confirmed by gas chromatography that no methanol was produced, and heating was terminated. Then, the concentration of the solid content was adjusted to 50% by weight, and the mixture was heated and refluxed again. Sampling every 1 hour, neutralizing the sample, and then measuring the molecular weight by GPC,
After confirming that the molecular weight distribution became constant, the system was cooled. After cooling, 0.05 g of acetic acid was added to this system for neutralization. Then, the produced salt was filtered, and the filtrate was heated under reduced pressure to obtain 67.4 g of a colorless transparent solid. This colorless transparent solid has Mn = 2320 and Mw = 3.
950, glass transition point = 42 ° C., softening point = 65 ° C., epoxy equivalent = 1470, ²⁹ Si-NMR confirmed to be a 3 glycidoxypropyl group-containing silicone resin represented by the following structural formula. .

(PhSiO _3/2 ) _0.66 [(CH ₃ ) ₂ SiO _2/2 ] _0.26 (EpSiO _3/2 ) _0.08

[0050]

Reference Example 6 12.9 g of sample A, 25.9 g of octamethyltetracyclosiloxane, 11.8 g of 3-glycidoxypropyltrimethoxysilane and 4 toluene in a reaction vessel.
7.2 g and cesium hydroxide 0.05 g were added. 5.0 g of water of this system was added, and then the produced methanol and water were distilled off while heating the system. After distilling off water, the system was cooled and an additional 5.0 g of water was added to the system. Then, while heating the system, the produced methanol and water were distilled off. This operation was repeated, the distilled water was extracted with ether, and it was confirmed by gas chromatography that no methanol was produced, and heating was terminated. Then, the concentration of the solid content was adjusted to 50% by weight, and the mixture was heated and refluxed again. Sampling every 1 hour, neutralizing the sample, and then measuring the molecular weight by GPC,
After confirming that the molecular weight distribution became constant, the system was cooled. After cooling, 0.03 g of acetic acid was added to this system for neutralization. Then, the produced salt was filtered, and the filtrate was heated under reduced pressure to obtain 44.8 g of a colorless transparent liquid. This colorless transparent liquid has Mn = 2240 and Mw = 4.
870, glass transition point = -68 ° C., viscosity = 1500 centipoise, epoxy equivalent = 952, ²⁹ Si-NM
By R, it was confirmed to be a 3-glycidoxypropyl group-containing silicone resin represented by the following structural formula.

(PhSiO _3/2 ) _0.2 [(CH ₃ ) ₂ SiO _2/2 ] _0.7 (EpSiO _3/2 ) _0.1

[0052]

Reference Example 7 113.9 g of Sample B, 11.8 g of 3-glycidoxypropyltrimethoxysilane, 8.4 g of toluene and 0.08 g of cesium hydroxide were placed in a reaction vessel.
5.0 g of water of this system was added, and then the produced methanol and water were distilled off while heating the system. After the water is no longer distilled off, cool the system and add 5.0% more water to the system.
g was added. Then, while heating the system, the produced methanol and water were distilled off. This operation was repeated, the distilled water was extracted with ether, and it was confirmed by gas chromatography that no methanol was produced, and heating was terminated. Then, the concentration of the solid content was adjusted to 50% by weight, and the mixture was heated and refluxed again. Sampling every hour,
After neutralizing the sample, its molecular weight was measured by GPC, and after confirming that the molecular weight distribution became constant, this system was cooled. After cooling, 0.05 g of acetic acid was added to this system for neutralization. Next, the produced salt was filtered, and the filtrate was heated under reduced pressure to obtain 63.3 g of a colorless transparent solid. This colorless transparent solid has Mn = 3870 and Mw = 7.
280, glass transition point = 124 ° C., softening point = 158 ° C.,
The epoxy equivalent was 1340, and it was confirmed by ²⁹ Si-NMR that the silicone resin was a 3-glycidoxypropyl group-containing silicone resin represented by the following structural formula.

(PhSiO _3/2 ) _0.68 [(CH ₃ ) ₂ SiO _2/2 ] _0.14 (EpSiO _3/2 ) _0.09

[0054]

[Reference Example 8] In a reaction vessel, 48.4 g of sample A, 8.9 g of octamethyltetracyclosiloxane, 1.1 g of 3-glycidoxypropylmethyldimethoxysilane and 5 toluene.
8.2 g and 0.07 g of cesium hydroxide were added. 5.0 g of water of this system was added, and then the produced methanol and water were distilled off while heating the system. After distilling off water, the system was cooled and an additional 5.0 g of water was added to the system. Then, while the system was heated, the produced methanol and water were distilled off. This operation was repeated, the distilled water was extracted with ether, and it was confirmed by gas chromatography that no methanol was produced, and heating was terminated. Then, adjust the solid content concentration to 50% by weight,
It was heated to reflux again. After sampling every hour and neutralizing the sample, the molecular weight of the sample was measured by GPC, and after confirming that the molecular weight distribution was constant, the system was cooled. After cooling, 0.04 g of acetic acid was added to this system for neutralization. Then, the produced salt was filtered, and the filtrate was heated under reduced pressure to obtain 54.7 g of a colorless transparent solid. This colorless transparent solid has Mn = 2740, Mw = 4
520, glass transition point = 52 ° C., softening point = 80 ° C., epoxy equivalent = 11900, confirmed by ²⁹ Si-NMR to be a 3-glycidoxypropyl group-containing silicone resin represented by the following structural formula. It was

(PhSiO _3/2 ) _0.75 [(CH ₃ ) ₂ SiO _2/2 ] _0.24 (EpSiO _3/2 ) _0.01

[0056]

Reference Example 9 According to the method for producing a silicone resin described in Reference Example 2 of JP-A-56-136816,
An epoxy group-containing silicone resin was prepared. 240.4 g of dimethyldimethoxysilane and 236.3 g of 3-glycidoxypropyltrimethoxysilane were placed in a reaction vessel. The temperature of this system is heated to 60 ° C., and while stirring, water 36
g was gradually added dropwise. After completion of dropping, heat and stir for 4 hours,
Then, this was removed under reduced pressure of 10 mmHg at 60 ° C. to remove methanol and residual water, and a light brown transparent liquid 26
1.9 g was obtained. When this liquid was allowed to stand at room temperature, crystals of tetramethyldisiloxanediol were precipitated. This liquid was confirmed by infrared spectroscopy to be a 3-glycidoxypropyl group-containing silicone resin having a large amount of methoxy groups. The glass transition point of this silicone resin was measured, but it did not show a clear glass transition point.

[0057]

Reference Example 10 100 g of water, 400 g of toluene, 140 g of isopropyl alcohol and 0.07 in a reaction vessel.
g of potassium hydroxide was added, the system was cooled to 10 ° C., and 35.0 g of phenyltrimethoxysilane and 8.1 were added.
octamethyl tetracyclosiloxane and 10.0 g
A mixed solution of 3-glycidoxypropyltrimethoxysilane of was added dropwise. After the dropping is completed, this is heated under reflux for 1 hour,
It was then cooled. After cooling, the toluene layer was taken out, the temperature of this system was heated to 60 ° C., and 36 g of water was gradually added dropwise with stirring. After completion of the dropwise addition, the mixture was heated and stirred for 4 hours, cooled, and then 0.04 g of acetic acid was added to this system, and the produced potassium acetate was filtered. By heating the filtrate under reduced pressure, 38.0 g of a colorless solid 3-glycidoxypropyl group-containing silicone resin was obtained. As a result of infrared spectroscopic analysis, it was confirmed that this silicone resin had a silanol group. Further, this silicone resin did not show a clear glass transition point.

[0058]

Example 1 Phenol novolac resin (softening point 80
C., hydroxyl equivalent 100) 100 parts by weight, 3-3-glycidoxypropyl group-containing silicone resin prepared in Reference Example 2 28.6 parts by weight, fused silica powder 185.7 parts by weight,
Hexamethylenetetramine (11.4 parts by weight), 3-glycidoxypropyltrimethoxysilane (1.0 parts by weight) and carnauba wax (2.9 parts by weight) were uniformly mixed, and the mixture was further kneaded with a heating roll at 90 ° C. and then cooled. Then, the curable resin composition of the present invention was prepared. Then crush it,
Transfer molding was carried out for 3 minutes under the conditions of 175 ° C. and 70 kg / cm ² . Then, the cured resin was post-cured at 150 ° C. for 2 hours. Table 1 shows various properties of the obtained curable resin composition and cured resin.

[0059]

Comparative Example 1 In Example 1, 3 prepared in Reference Example 4
-Curable resin in the same manner as in Example 1 except that a glycidoxypropyl group-containing silicone resin was replaced by 3-glycidoxypropyl group-containing dimethylpolysiloxane for the side chain of the molecular chain represented by the following structural formula. A composition was prepared. This was cured in the same manner as in Example 1. Table 1 shows various properties of the obtained curable resin composition and cured resin.

[0060]

[Chemical 1]

[0061]

Comparative Example 2 In Example 1, 3 prepared in Reference Example 4
A curable resin composition was prepared in the same manner as in Example 1 except that the glycidoxypropyl group-containing silicone resin was not used. This was cured in the same manner as in Example 1. Various properties of the obtained curable resin composition and the cured resin are shown in Table 1.
It was shown to.

[0062]

[Table 1]

[0063]

Example 2 CH ₃ SiO _3/2 unit 40 mol%, C ₆ H
₅ (CH ₃ ) SiO _2/2 unit 10 mol%, C ₆ H ₅ SiO _3/2
Unit 40 consists mole% and _{(C 6 H 5) 2 SiO} 2/2 units 10 mole%, the silicone resin 50 parts by weight of cresol novolak epoxy resins containing silicon-bonded hydroxyl 5 wt% (softening point 80 ° C., epoxy Equivalent 220) 50
100 parts by weight of silicone-epoxy resin, 38.5 parts by weight of 3-glycidoxypropyl group-containing silicone resin prepared in Reference Example 5, fused silica powder 28
4.6 parts by weight, aluminum acetylacetonate 3.
5 parts by weight, 1.0 part by weight of 3-glycidoxypropyltrimethoxysilane and 3.8 parts by weight of carnauba wax were uniformly mixed, and the mixture was further kneaded with a heating roll at 90 ° C. and then cooled to obtain the present invention. The curable resin composition of was prepared.
Then, this was pulverized, and transfer-molded for 2 minutes at 175 ° C. and 70 kg / cm ² . Then, the cured resin was post-cured at 180 ° C. for 12 hours.
Various properties of the obtained curable resin composition and the cured resin are shown in Table 2.

[0064]

Example 3 In Example 2, 3 prepared in Reference Example 5 was used.
A curable resin composition was prepared in the same manner as in Example 2 except that the 3-glycidoxypropyl group-containing silicone resin prepared in Reference Example 6 was used instead of the glycidoxypropyl group-containing silicone resin. This was cured as in Example 2. Various properties of the obtained curable resin composition and the cured resin are shown in Table 2.

[0065]

Example 4 In Example 2, 3 prepared in Reference Example 5
A curable resin composition was prepared in the same manner as in Example 2 except that the 3-glycidoxypropyl group-containing silicone resin prepared in Reference Example 7 was used instead of the glycidoxypropyl group-containing silicone resin. This was cured as in Example 2. Various properties of the obtained curable resin composition and the cured resin are shown in Table 2.

[0066]

Comparative Example 3 In Example 2, 3 prepared in Reference Example 5
Example 2 except that dimethylpolysiloxane having a 3-glycidoxypropyl group and a trimethoxysilylethyl group in the side chain of the molecular chain represented by the following structural formula was used in place of the glycidoxypropyl group-containing silicone resin. A curable resin composition was prepared in the same manner as. Example 2
It was cured in the same manner. Various properties of the obtained curable resin composition and the cured resin are shown in Table 2.

[0067]

[Chemical 2]

[0068]

Comparative Example 4 In Example 2, 3 prepared in Reference Example 5 was used.
A curable resin composition was prepared in the same manner as in Example 2 except that the glycidoxypropyl group-containing silicone resin was not used. This was cured as in Example 2. The properties of the resulting curable resin composition and cured resin are shown in Table 2.
It was shown to.

[0069]

[Table 2]

[0070]

Example 5 100 parts by weight of a bismaleimide-triazine type thermosetting polyimide resin, prepared in Reference Example 8
Glycidoxypropyl group-containing silicone resin 28.6
Parts by weight, 185.7 parts by weight of fused silica powder, 2.9 parts by weight of carnauba wax, 1.0 part by weight of 3-glycidoxypropyltrimethoxysilane and 0.9 part by weight of aluminum benzoate are uniformly mixed, This was further kneaded with a heating roll at 90 ° C. and then cooled to prepare the curable resin composition of the present invention. Then, this is crushed, 220 ℃, 70kg / c
Transfer molding was carried out for 4 minutes under the condition of m ² .
Then, the cured resin was post-cured at 230 ° C. for 3 hours. Table 3 shows various properties of the obtained curable resin composition and the cured resin.

[0071]

Comparative Example 5 In Example 5, 3 prepared in Reference Example 8
A curable resin composition was prepared in the same manner as in Example 5, except that the glycidoxypropyl group-containing silicone resin was not used. This was cured as in Example 5. Table 3 shows various properties of the obtained curable resin composition and the cured resin.
It was shown to.

[0072]

[Table 3]

[0073]

Example 6 75 parts by weight of ortho-cresol novolac epoxy resin (softening point 80 ° C., epoxy equivalent 220), 260 parts by weight of fused silica powder, 1 part by weight of carnauba wax, 35 parts by weight of phenol novolac resin, triphenylphosphine 0 6 parts by weight, 3-prepared in Reference Example 8
10 parts by weight of a glycidoxypropyl group-containing silicone resin and 1.0 part by weight of 3-glycidoxypropyltrimethoxysilane were uniformly mixed, and this was further kneaded with a heating roll at 90 ° C. and then cooled to cure the composition of the present invention. A resin composition was prepared. Then, this is crushed, 150 ℃, 70kg / c
Transfer molding was carried out for 3 minutes under the condition of m ² .
Then, the cured resin was post-cured at 180 ° C. for 4 hours. Table 4 shows various properties of the obtained curable resin composition and cured resin.

[0074]

Example 7 In Example 6, 3 prepared in Reference Example 8
A curable resin composition was prepared in the same manner as in Example 6 except that the 3-glycidoxypropyl group-containing silicone resin prepared in Reference Example 5 was used instead of the glycidoxypropyl group-containing silicone resin. This was cured in the same manner as in Example 6. Table 4 shows various properties of the obtained curable resin composition and cured resin.

[0075]

Comparative Example 6 In Example 6, 3 prepared in Reference Example 8
A curable resin composition was prepared in the same manner as in Example 6 except that the glycidoxypropyl group-containing silicone resin was not used. This was cured in the same manner as in Example 6. Table 4 shows various properties of the obtained curable resin composition and the cured resin.
It was shown to.

[0076]

Comparative Example 7 In Example 6, 3 prepared in Reference Example 8
A curable resin composition was prepared in the same manner as in Example 6 except that the 3-glycidoxypropyl group-containing silicone resin prepared in Reference Example 9 was used instead of the glycidoxypropyl group-containing silicone resin. This was cured in the same manner as in Example 6. Table 4 shows various properties of the obtained curable resin composition and cured resin. The curable resin composition obtained in Comparative Example 7 was more susceptible to mold staining during molding than the curable resin compositions obtained in Examples 6, 7 and 8.

[0077]

Comparative Example 8 In Example 6, 3 prepared in Reference Example 8
A curable resin composition was prepared in the same manner as in Example 6 except that the 3-glycidoxypropyl group-containing silicone resin prepared in Reference Example 10 was used instead of the glycidoxypropyl group-containing silicone resin. This was cured in the same manner as in Example 6. Table 4 shows various properties of the obtained curable resin composition and cured resin.

[0078]

[Table 4]

[0079]

EFFECTS OF THE INVENTION The curable resin composition of the present invention comprises (A) curable resin and (B) epoxy group-containing silicone resin. In particular, the component (B) has a glass transition point of -90 ° C to 150 ° C. Since it has an epoxy group-containing silicone resin that contains T units as essential components, it forms a resin that has excellent fluidity before curing and excellent flexibility, moisture resistance, and thermal shock resistance after curing. It has the feature of being able to.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 14, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

(PhSiO _3/2 ) _0.75 [(CH ₃ ) ₂ SiO _2/2 ] _0.24 [Ep (CH ₃ ) SiO _2/2 ] _0.01

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

[0060]

[Chemical 1]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0076

[Correction method] Change

[Correction content]

[0076]

Comparative Example 7 In Example 6, 3 prepared in Reference Example 8
A curable resin composition was prepared in the same manner as in Example 6 except that the 3-glycidoxypropyl group-containing silicone resin prepared in Reference Example 9 was used instead of the glycidoxypropyl group-containing silicone resin. This was cured in the same manner as in Example 6. Table 4 shows various properties of the obtained curable resin composition and cured resin. In addition, the curable resin composition obtained in Comparative Example 7 was more prone to mold stains during molding than the curable resin compositions obtained in Examples 6 and 7 .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08L 63/00 NKA 8830-4J NKB 8830-4J (72) Inventor Ken Tanaka Chikusaigan, Ichihara, Chiba Prefecture 2-2 Toray Dow Corning Silicone Co., Ltd.

Claims (4)

[Claims] 1. A curable resin (A) 1
00 parts by weight and (B) general formula: (R ¹ SiO _3/2 ) _a (R ² R ³ SiO _2/2 ) _b (SiO _4/2 ) _c (wherein R ¹ , R ² and R ³ are The same or different monovalent hydrocarbon groups or epoxy group-containing organic groups, provided that
The content of the epoxy group-containing organic group with respect to all the silicon atom-bonded organic groups in the component (B) is 0.1 to 40 mol%, and a
Is a positive number, b is 0 or a positive number, c is 0 or a positive number, and b / a is a number from 0 to 10, c /
(A + b + c) is a number from 0 to 0.3. },
And epoxy group-containing silicone resin having a glass transition point at -90 ° C to 150 ° C
A curable resin composition comprising 0.1 to 500 parts by weight. 2. The curable resin composition according to claim 1, wherein the component (A) is a curable resin selected from the group consisting of epoxy resins, phenol resins, imide resins and silicone resins. 3. The curable resin composition according to claim ¹ , wherein 30 mol% or more of R ^{1 in} the component (B) is a phenyl group. 4. An organopolysiloxane in which component (B) is selected from the group consisting of (I) components (i) to (iv) below.
Species or a mixture of two or more kinds (however, only the component (ii) is excluded. ] And (i) an organopolysiloxane having a siloxane unit represented by the general formula: R ⁴ SiO _3/2 , (ii) an organopolysiloxane having a siloxane unit represented by a general formula: R ⁵ R ⁶ SiO _2/2 , (iii) an organopolysiloxane having a siloxane unit represented by the general formula: R ⁴ SiO _3/2 and a siloxane unit represented by the general formula: R ⁵ R ⁶ SiO _2/2 , and (iv) a general formula: R ⁴ SiO An organopolysiloxane comprising a siloxane unit represented by _3/2 and a general formula: R ⁵ R ⁶ SiO _2/2 and a siloxane unit represented by a general formula: SiO _4/2 (wherein R ⁴ , R ⁵ and R ⁶ are the same or different monovalent hydrocarbon groups.) (II) General formula: R ⁷ R ⁸ _d Si (OR ⁹ ) _(3-d) (In the formula, R ⁷ contains an epoxy group. an organic group, R ⁸ is a monovalent hydrocarbon group, R ⁹ is Is an alkyl group and d is 0 or 1.) The epoxy group-containing alkoxysilane represented by the formula (2) or its partial hydrolyzate [the amount of the component (II) is equal to that of the epoxy group-containing organic group in the component (II). (I) component and (I
0.1 to 40 based on the total silicon-bonded organic groups of component I)
The amount is mol%. ] In the presence of water and a basic catalyst to synthesize a silicone resin, and then
The curable resin composition according to claim 1, wherein the curable resin composition is an epoxy group-containing silicone resin obtained by adjusting the concentration of the silicone resin with an organic solvent and then equilibrating the silicone resin with a basic catalyst.