JP2018111783A - Curable silicon resin composition and cure article thereof, and semiconductor device using them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an addition curable type curable silicon resin composition providing a cured article excellent in heat resistant transparency in a UV region and a visible light region, the cured article, and a semiconductor device using them.SOLUTION: There is provided a curable silicon resin composition containing following (A) Component, (B) Component and (C) Component. (A) Component: a silicon resin represented by the following formula [1]. (B) Component: a silicon resin represented by the following formula [2]. (C) Component: a hydrosilylation catalyst. (H-SiMeO)(MeSiO)(SiO)[1] (R-SiMeO)(MeSiO)(SiO)[2]SELECTED DRAWING: Figure 1

Description

  The present invention relates to a curable silicone resin composition that can be suitably used as a raw material for a sealing material of a semiconductor element such as a light-emitting diode, a raw material for an adhesive, a cured product thereof, and a semiconductor device using these.

  As a sealing material of a light emitting device using a semiconductor element such as a light emitting diode (abbreviation: LED), a cured product such as an epoxy resin composition or a silicone resin composition is used. These sealing materials are required to maintain transparency even when exposed to high temperatures for a long period of time, that is, excellent in “heat-resistant transparency”.

  Generally, an epoxy resin composition is excellent in handling properties and has a high hardness of a cured product. And since durability required for sealing for low output white LED is obtained, it is often used as a sealing material for low output white LED.

  However, with the recent increase in brightness and output of LEDs, conventional cured epoxy resin compositions have power semiconductors and high-intensity light-emitting elements (for example, automotive headlights and LCD TV backs). High-intensity LED for light), heat resistance is insufficient for use as a sealing material for short-wavelength semiconductor lasers such as UV-LED or blue laser, and current leakage or yellowing due to high-temperature deterioration may occur. Are known.

  Recently, in order to solve these problems, a cured product of a resin composition based on a silicone resin excellent in heat resistance has been used as an LED encapsulant in place of an epoxy resin. For example, Patent Document 1 reports an addition-curable silicone resin composition that uses an addition reaction (hydrosilylation reaction) between a SiH group and an alkenyl group as a material for sealing and protecting an optical device or a semiconductor device. .

JP 2000-198930 A

  In recent years, there is an increasing demand for UV light in the UV-A and UV-B regions even in devices using a semiconductor as a light source, and a material having high heat-resistant transparency in the UV region has also been demanded. Conventionally, a sealing method using quartz glass as a sealing material has been taken, but from the viewpoint of simplicity of the manufacturing process, sealing with a resin is suitable. That is, a resin composition that gives a cured product excellent in heat-resistant transparency in the UV region to the visible light region is desired.

  The present invention has been made in view of the above circumstances, and used an addition-curable curable silicone resin composition and a cured product that give a cured product having excellent heat-resistant transparency in the UV region to the visible light region, and the same. An object is to provide a semiconductor device.

As a result of intensive studies to achieve the above object, the present inventors have
It came to complete the curable silicone resin composition containing the following (A) component, (B) component, and (C) component at least.
(A) Component: Silicone resin represented by the following formula [1]
(B) component: silicone resin represented by the following formula [2],
Component (C): Hydrosilylation catalyst.
(In the formula [1], Me represents a methyl group, a, b and c are each greater than 0 and less than 1, satisfying a + b + c = 1, (H-SiMe ₂ O _1/2 ), (Me The oxygen atoms in the structural units represented by ₂ SiO _2/2 ) and (SiO _4/2 ) _d each represent an oxygen atom forming a siloxane bond or an oxygen atom forming a silanol group.
In the formula [2], R ¹ represents a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms, Me represents a methyl group, d, e, and f are each greater than 0 and less than 1, d + e + f = 1 and oxygen atoms in structural units represented by (Vi-SiMe ₂ O _1/2 ), (Me ₂ SiO _2/2 ), and (SiO _4/2 ) each form a siloxane bond. Or an oxygen atom forming a silanol group. )

That is, the present invention includes the following invention 1 to invention 21.
[Invention 1]
A curable silicone resin composition comprising at least the following component (A), component (B) and component (C).
(A) Component: Silicone resin represented by the following formula [1]
(B) component: silicone resin represented by the following formula [2],
Component (C): Hydrosilylation catalyst.
(In the formula [1], Me represents a methyl group, a, b and c are each greater than 0 and less than 1, satisfying a + b + c = 1, (H-SiMe ₂ O _1/2 ), (Me The oxygen atoms in the structural units represented by ₂ SiO _2/2 ) and (SiO _4/2 ) each represent an oxygen atom forming a siloxane bond or an oxygen atom forming a silanol group.
In the formula [2], R ¹ represents a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms, Me represents a methyl group, d, e, and f are each greater than 0 and less than 1, d + e + f = 1 and oxygen atoms in structural units represented by (R ¹ -SiMe ₂ O _1/2 ), (Me ₂ SiO _2/2 ) and (SiO _4/2 ) each form a siloxane bond. An oxygen atom forming a silanol group or an oxygen atom forming a silanol group. )
[Invention 2]
The curable silicone resin composition according to Invention 1, wherein R ¹ in Formula [2] is a vinyl group [Invention 3].
The value of a of the component (A) is 0.05 to 0.50, the value of b is 0.10 to 0.95, and the value of c is 0.01 to 0.95. The composition according to 1 or 2.
[Invention 4]
The value of d of component (B) is 0.05 to 0.50, the value of e is 0.10 to 0.95, and the value of f is 0.01 to 0.95. The composition according to any one of 1 to 3.
[Invention 5]
(A) The composition as described in any one of invention 1 thru | or 4 whose mass mean molecular weight of a component is 500-100,000.
[Invention 6]
(B) The composition as described in any one of invention 1 thru | or 5 whose mass mean molecular weights of component are 500-100,000.
[Invention 7]
Any one of Inventions 1 to 6, wherein [number of moles of H—Si group contained in component (A)] / [number of moles of R ¹ —Si group contained in component (B)] is 1 to 4. The composition according to one item.
[Invention 8]
Cure retarder, antioxidant, light stabilizer, adhesion promoter, phosphor, inorganic particles, release agent, resin modifier, colorant, diluent, antibacterial agent, antifungal agent, leveling agent and anti-sagging agent The composition according to any one of Inventions 1 to 7, further comprising at least one selected from the group consisting of:
[Invention 9]
A method for producing a curable silicone resin composition, comprising at least the following steps (1) to (4).
Step (1): A dimethyl dialkoxysilane compound represented by the general formula [3] and a tetraalkoxysilane compound represented by the general formula [4] are hydrolyzed and polycondensed to obtain a hydrolyzed polycondensate. Process.
Step (2): The hydrolysis polycondensate is reacted with a hydrosilane compound represented by the following general formula [5-1], [5-2], or [5-3], and component (A) As a process of obtaining a silicone resin.
Step (3): The hydrolysis polycondensate is reacted with a silane compound represented by the following general formula [8-1], [8-2], or [8-3] to obtain a component (B) As a process of obtaining a silicone resin.
Step (4): A step of blending the obtained component (A) and component (B) with the hydrosilylation catalyst as component (C).
(In General Formula [3], R ² is each independently an alkyl group having 1 to 3 carbon atoms. In General Formula [4], R ³ is each independently an alkyl group having 1 to 3 carbon atoms. In the general formula [5-2], each R ⁴ is independently an alkyl group having 1 to 3 carbon atoms, and in the general formula [8-1], R ⁷ is a monovalent having 2 to 6 carbon atoms. In the general formula [8-2], R ⁸ is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms, and R ⁹ is an alkyl group having 1 to 3 carbon atoms. In general formula [8-3], each R ¹⁰ independently represents a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms.
[Invention 10]
The curable silicone resin composition according to invention 9, wherein the hydrolyzed polycondensate obtained in the step (1) is purified, and the purified hydrolyzed polycondensate is subjected to the step (2) or the step (3). Manufacturing method.
[Invention 11]
The manufacturing method of the manufacturing method of the curable silicone resin composition of the invention 10 which performs a process (2) or a process (3), without refine | purifying the hydrolysis polycondensate obtained at the said process (1).
[Invention 12]
A method for producing a silicone resin, comprising at least the following first step and the following second step.
First step: A step of hydrolyzing and polycondensing a dimethyldialkoxysilane compound represented by the general formula [3] and a tetraalkoxysilane compound represented by the general formula [4] to obtain a hydrolyzed polycondensate. .
(In General Formula [3], R ² is each independently an alkyl group having 1 to 3 carbon atoms. In General Formula [4], R ³ is each independently an alkyl group having 1 to 3 carbon atoms. .)

Second step: A step of reacting the hydrolyzed polycondensate with a hydrosilane compound represented by the formula [5-1], [5-2], or [5-3] to obtain a silicone resin.
(In the general formula [5-2], each R ⁴ is independently an alkyl group having 1 to 3 carbon atoms.)
[Invention 13]
The method for producing a silicone resin according to invention 12, wherein the hydrolyzed polycondensate obtained in the first step is purified, and the purified hydrolyzed polycondensate is subjected to the second step.
[Invention 14]
The manufacturing method of the silicone resin of the invention 12 which performs a 2nd process, without refine | purifying the hydrolysis polycondensate obtained at said 1st process.
[Invention 15]
A method for producing a silicone resin, comprising at least the following first step and the following second step.
First step: A step of hydrolyzing and polycondensing a dimethyldialkoxysilane compound represented by the general formula [3] and a tetraalkoxysilane compound represented by the general formula [4] to obtain a hydrolyzed polycondensate. .
(In General Formula [3], R ² is each independently an alkyl group having 1 to 3 carbon atoms. In General Formula [4], R ³ is each independently an alkyl group having 1 to 3 carbon atoms. .)

Second step: A step of reacting the hydrolyzed polycondensate with a silane compound represented by the general formula [8-1], [8-2], or [8-3] to obtain a silicone resin.
(In General Formula [8-1], R ⁷ is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms. In General Formula [8-2], R ⁸ has 2 to 6 carbon atoms. R ⁹ is a monovalent unsaturated hydrocarbon group, R ⁹ is an alkyl group having 1 to 3 carbon atoms, and in general formula [8-3], each R ¹⁰ is independently a monovalent having 2 to 6 carbon atoms. Of unsaturated hydrocarbon groups.)
[Invention 16]
The method for producing a silicone resin according to claim 15, wherein the hydrolyzed polycondensate obtained in the first step is purified, and the purified hydrolyzed polycondensate is used in the second step.
[Invention 17]
The manufacturing method of the silicone resin of the invention 15 which performs a 2nd process, without refine | purifying the hydrolysis polycondensate obtained at said 1st process.
[Invention 18]
Hardened | cured material formed by hardening | curing the composition as described in any one of invention 1 thru | or 8.
[Invention 19]
A semiconductor device in which at least a semiconductor element is sealed with the cured product according to the invention 18.
[Invention 20]
A semiconductor adhesive comprising the cured product according to Invention 18.
[Invention 21]
A semiconductor device using the optical semiconductor adhesive according to invention 20.

  ADVANTAGE OF THE INVENTION According to this invention, the curable silicone resin composition which gives the hardened | cured material excellent in the heat-resistant transparency in UV region from visible region, its hardened | cured material, and a semiconductor device using these can be provided.

It is a schematic sectional drawing which shows an example of the semiconductor device of this invention. It is a schematic diagram which shows the result of the long-term heat-resistant transparency test of the hardened | cured material of this invention.

  Hereinafter, the present invention will be described in more detail, but the present invention is not limited thereto.

[Curable silicone resin composition]
The curable silicone resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) contains at least the components (A) to (C). Hereinafter, each component contained in the composition of this invention is demonstrated.

<(A) component>
The component (A) is a silicone resin represented by the following formula [1].
(In the above formula [1], a, b and c are each greater than 0 and less than 1, satisfying a + b + c = 1, (H-SiMe ₂ O _1/2 ), (Me ₂ SiO _2/2 ) And oxygen atoms in the structural unit represented by (SiO _4/2 ) _d each represent an oxygen atom forming a siloxane bond or an oxygen atom forming a silanol group.)

  In the formula [1], the value of a, the value of b, and the value of c are in the range of more than 0 and less than 1, respectively, and are not particularly limited as long as a + b + c = 1 is satisfied. The value of a is preferably 0.05 to 0.50, and particularly preferably 0.05 to 0.35. The value of b is preferably 0.10 to 0.95, and particularly preferably 0.45 to 0.90. The value of c is preferably 0.01 to 0.95, and particularly preferably 0.10 to 0.45. If the values of a, b and c are in the above-mentioned ranges, the composition and the cured product of the present invention have good moldability and good mechanical strength.

The value of a, the value of the value and c b measures the ²⁹ Si-NMR spectrum and ¹ H-NMR spectrum of a silicone compound represented by the formula [1] with a nuclear magnetic resonance apparatus, using these Can be calculated.

In the formula [1], the structural unit represented by (Me ₂ SiO _2/2 ) is a structure represented by the following formula [1-2], that is, a structure represented by (Me ₂ SiO _2/2 ). One of the oxygen atoms bonded to the silicon atom in the unit may include a structure in which a silanol group is formed.

The structural unit represented by (Me ₂ SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-1-b], and further includes the following formula [1-2-b ] May include a portion surrounded by a broken line of the structural unit represented by That is, a structural unit having a group represented by Me (methyl group) and having a hydroxy group remaining at the terminal to form a silicon atom and a silanol group is also represented by (Me ₂ SiO _2/2 ). Included in the structural unit. In the structural units represented by the following formulas [1-1-b] and [1-2-b], an oxygen atom in the Si—O—Si bond forms a siloxane bond with an adjacent silicon atom. And shares an oxygen atom with an adjacent structural unit. Therefore, one oxygen atom in the Si—O—Si bond is defined as “O _1/2 ”.

In the formula [1], the structural unit represented by (SiO _4/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-1-c]. -C], [1-3-c], and [1-4-c] may include a portion surrounded by a broken line. That is, the structural unit remaining at the terminal and forming a silicon atom and a silanol group is also included in the structural unit represented by (SiO _4/2 ).

  The viscosity of (A) component will not be specifically limited if it is 100,000 cP (centipoise) or less in 25 degreeC. From the viewpoint of handling workability, it is preferably 20,000 cP or less. The lower limit is not particularly limited, and the lower the viscosity, the lower the viscosity of the resulting composition of the present invention, and the easier the sealing operation of the semiconductor device. The viscosity of component (A) may be greater than 0 cP and less than or equal to 100,000 cP at 25 ° C., preferably greater than 0 cP and less than or equal to 20,000 cP.

  Here, the viscosity of the component (A) can be measured by a rotational viscometer or the like. Specifically, according to JIS Z8803 (2011) "Viscosity measurement method using a cone-plate type rotational viscometer", a rotational viscometer (manufactured by ANTON PAAR, product name: PHYSICA MCR51, measuring range 200 to 1,000,000 cP) and Using a temperature control unit (manufactured by ANTON PAAR, product name: P-PTD200), measurement was performed at a shear rate of 30 [1 / s] at a temperature of 25 ° C., and the value obtained one minute after the start of the measurement Let it be the viscosity of the composition.

  The component (A) contains at least hydrogen atoms (H—Si groups) bonded to silicon atoms, and the number thereof is not particularly limited. It is preferable to contain 2 or more in one molecule. It is particularly preferably 0.50 to 4.0 mmol / g since a good cured product can be obtained.

  The mass average molecular weight of (A) component is not specifically limited. 500-100,000 are preferable, More preferably, it is 800-30,000. If the mass average molecular weight is 500 or more, the cured product of the present invention has good moldability, and if it is 100,000 or less, the composition of the present invention has good resin strength.

  Here, the mass average molecular weight is obtained by measuring with a gel permeation chromatography (abbreviation: GPC) method and converting with a standard polystyrene calibration curve (the same applies hereinafter).

  (A) The quantity of the HO-Si group contained in a component is not specifically limited. 0.1-4.5 mmol / g is preferable and 0.2-2.5 mmol / g is especially preferable. When the content of the HO-Si group exceeds 4.5 mmol / g, bubbles may be observed in the cured product.

<(B) component>
The component (B) is a silicone resin represented by the following formula [2].
(In the formula [2], R ¹ represents a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms, Me represents a methyl group,
d, e and f are each greater than 0 and less than 1, satisfying d + e + f = 1, and (R ¹ −SiMe ₂ O _1/2 ) _, (Me ₂ SiO _2/2 ), (SiO _4/2 ) The oxygen atom in the structural unit represented by each represents an oxygen atom forming a siloxane bond or an oxygen atom forming a silanol group. )

As the monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms for R ¹ in the formula [2], a vinyl group, a propenyl group, an n-butenyl group, an n-pentenyl group, and an n-hexenyl group are preferable. The group is particularly preferred.

  In the formula [2], the value of d, the value of e, and the value of f are each in the range of more than 0 and less than 1, and are not particularly limited as long as d + e + f = 1 is satisfied. The value of d is preferably 0.05 to 0.50, and particularly preferably 0.05 to 0.35. The value of e is preferably 0.10 to 0.95, particularly preferably 0.45 to 0.90. The value of f is preferably 0.01 to 0.95, and particularly preferably 0.10 to 0.45. If the values of d, e, and f are in the above-mentioned ranges, the composition and the cured product of the present invention have good moldability and good mechanical strength.

In addition, the value of d, the value of e, and the value of f measured ²⁹ Si-NMR spectrum and ¹ H-NMR spectrum of the silicone compound shown by Formula [2] using a nuclear magnetic resonance apparatus, and used these. Can be calculated.

In the formula [2], the structural unit represented by (Me ₂ SiO _2/2 ) is synonymous with the structural unit represented by the above formula [1], and the structural unit represented by (SiO _4/2 ). Is synonymous with the structural unit represented by the above formula [1].

  The viscosity of (B) component will not be specifically limited if it is below 100,000 cP (centipoise) in 25 degreeC. From the viewpoint of handling workability, it is preferably 20,000 cP or less. The lower limit is not particularly limited, and the lower the viscosity, the lower the viscosity of the resulting composition of the present invention, and the easier the sealing operation of the semiconductor device. The viscosity of component (B) may be greater than 0 cP and less than or equal to 100,000 cP at 25 ° C., preferably greater than 0 cP and less than or equal to 20,000 cP.

  Here, the viscosity of the component (B) can be measured with a rotational viscometer or the like. Specifically, according to JIS Z8803 (2011) "Viscosity measurement method using a cone-plate type rotational viscometer", a rotational viscometer (manufactured by ANTON PAAR, product name: PHYSICA MCR51, measuring range 200 to 1,000,000 cP) and Using a temperature control unit (manufactured by ANTON PAAR, product name: P-PTD200), measurement was performed at a shear rate of 30 [1 / s] at a temperature of 25 ° C., and the value obtained one minute after the start of the measurement Let it be the viscosity of the composition.

  The component (B) contains at least a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms bonded to a silicon atom, and the number thereof is not particularly limited. It is preferable to contain 2 or more in one molecule. It is particularly preferably 0.50 to 4.0 mmol / g since a good cured product can be obtained.

  The mass average molecular weight of (B) component is not specifically limited. 500-100,000 are preferable, More preferably, it is 800-30,000. If the mass average molecular weight is 500 or more, the cured product of the present invention has good moldability, and if it is 100,000 or less, the composition of the present invention has good resin strength.

  Here, the mass average molecular weight is obtained by measuring with a gel permeation chromatography (abbreviation: GPC) method and converting with a standard polystyrene calibration curve (the same applies hereinafter).

  The amount of the HO—Si group contained in the component (B) is not particularly limited. 0.1-4.5 mmol / g is preferable and 0.2-2.5 mmol / g is especially preferable. When the content of the HO-Si group exceeds 4.5 mmol / g, bubbles may be observed in the cured product.

<(C) component>
The hydrosilylation catalyst as component (C) is for promoting a hydrosilylation reaction (addition curing reaction) between an H—Si group in component (A) and an R ¹ -Si group in component (B) described later. Blended.

  (C) The kind of component will not be specifically limited if the said hydrosilylation reaction is accelerated | stimulated. It is preferable to use at least one selected from the group consisting of platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Especially, since the transparency of a sealing material can be made high, it is especially preferable to use a platinum-type catalyst.

  Examples of the platinum catalyst include platinum powder, complexes of platinum components such as chloroplatinic acid and chloroplatinic acid, alcohols, aldehydes, ketones, platinum-olefin complexes, platinum-alkenylsiloxane complexes, platinum-carbonyl complexes, and the like. It is done. Examples include platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex (cursed catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex, dicarbonyldichloroplatinum and the like. Of these, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex and the like are preferable.

<Other additives>
In addition to the components (A) to (C), other additives may be added to the composition of the present invention.

((D) component: cure retarder)
As other additives, for example, in the composition of the present invention, for the purpose of improving the storage stability and handling workability of the composition, adjusting the hydrosilylation reactivity in the curing process, etc. A curing retarder (hereinafter sometimes referred to as component (D)) may be blended.
Since the composition of the present invention can be made into a cured product at a relatively low temperature, it can be suitably used for application / sealing to a semiconductor member that is vulnerable to heat. On the other hand, depending on the coating / sealing work environment, it may be preferable to blend a curing retarder in order to adjust the curing rate from the viewpoint of storage stability over time and handling workability of the composition of the present invention. .

  The type of component (D) is not particularly limited as long as it is a compound having a curing delay effect with respect to component (C). For example, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, a nitrogen-containing compound, an organic sulfur compound, an organic peroxide, and the like can be given. These compounds may be used alone or in combination.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleic anhydride, maleic esters, and the like. Specifically, as propargyl alcohols, 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, Examples include 1-ethynyl-1-cyclohexanol. Examples of maleate esters include dimethyl maleate.

  Specific examples of the organophosphorus compound include triorganophosphines, diorganophosphines, organophosphines, and triorganophosphites.

  Examples of the nitrogen-containing compound include N, N, N ′, N′-tetrasubstituted alkylene diamines, N, N-disubstituted alkylene diamines, trisubstituted amines, benzotriazole, 2,2′-bipyridine, and the like. It is done. Specifically, N, N, N ′, N′-tetrasubstituted alkylenediamines include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, and the like. Is mentioned. N, N-disubstituted alkylenediamines include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N-dibutyl-1,3-propanediamine, N, N- Examples thereof include dimethyl-1,3-propanediamine and N, N-dibutyl-1,4-butanediamine. Examples of the trisubstituted amine include tributylamine.

  Specific examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, and benzothiazole disulfide.

Specific examples of the organic peroxide include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and tert-butyl perbenzoate.
Among these oxidation retardants, compounds containing aliphatic unsaturated bonds and nitrogen-containing compounds are preferred. Specifically, maleic esters, propargyl alcohols, N, N, N ′, N′-4 Substituted alkyldiamines are preferred, with dimethyl maleate, 2-methyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, and N, N, N ′, N′-tetramethylethylenediamine being particularly preferred.

  Content of (D) component in the composition of this invention is not specifically limited. Usually, the curing retarder may be added in an amount of 20 to 200 equivalents per 1 equivalent of platinum atoms in the component (C) contained in the composition. The degree of the retarding effect of the retarder varies depending on the chemical structure of the retarder. Therefore, it is preferable to adjust the blending amount to an optimal amount depending on the type of the curing retarder used. By adding an optimal amount of the retarder, the composition of the present invention has long-term storage stability at room temperature (particularly refers to an ambient temperature that is not heated or cooled, usually 15 to 30 ° C., the same applies hereinafter). In addition, the heat curability is excellent.

((E) component: adhesion promoter)
In order to improve the adhesiveness, the composition of the present invention is blended with an adhesion-imparting agent (hereinafter sometimes referred to as (E) component) in addition to the components (A) to (C) described above. May be.

 (E) As a kind of component, a silane coupling agent, its hydrolysis polycondensate, etc. are illustrated. Examples of silane coupling agents include epoxy group-containing silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, (meth) acryl group-containing silane coupling agents, isocyanate group-containing silane coupling agents, and isocyanurate group-containing silanes. Examples include known coupling agents, amino group-containing silane coupling agents, mercapto group-containing silane coupling agents, and the like.

  The content of the component (E) in the composition of the present invention is not particularly limited. It is preferable to mix | blend 1-20 mass% with respect to the total mass of (A)-(C) component, and 5-15 mass% is especially preferable.

((F) component: antioxidant)
In order to suppress generation | occurrence | production of coloring of a hardened | cured material, oxidation deterioration, etc., you may add antioxidant (henceforth a (F) component) to the composition of this invention.

 (F) As a kind of component, a phenolic antioxidant, a thioether type acid additive, a phosphorus antioxidant, etc. are mentioned. Of these, phenolic antioxidants and thioether antioxidants are preferred, and thioether antioxidants are particularly preferred. These antioxidants may be used individually by 1 type, and may use 2 or more types together.

  As the phenolic antioxidant, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H , 5H) -trione, 4,4 ′, 4 ′-(1-methylpropanyl-3-ylidene) tris (6-tert-butyl-m-cresol, 6,6′-di-tert-butyl-4, 4'-butylidene-di-m-cresol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethyl Ruethyl} -2,4,8,10-tetraoxaspiro [5.5] undecene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4 Examples include 6-trimethylbenzene.

As the thioether-based antioxidant, 2,2-bis ({[3- (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl = bis [3- (dodecylthio) propionate], di (tridecyl) 3 , 3'-thiodipropionate and the like.
Examples of phosphorus antioxidants include 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecene, 3,9-bis (2,6 -Di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecene, 2,2'-methylenebis (4,6-di-tert- Butylphenyl) -2-ethylhexyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra-C _12-15 -alkyl (propane-2,2-diylbis ( 4,1-phenylene)) bis (phosphite), 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, triiso Sill phosphite, triphenyl phosphite.

  As these antioxidants, commercially available products may be used, or synthesized products may be used. As a commercial item, ADK STAB (manufactured by Adeka): AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330, AO- Examples thereof include 412S, AO-503, PEP-8, PEP-8W, PEP-36, PEP-36A, HP-10, 2112, 2112RG, 1178, 1500, C, 135A, 3010, and TPP.

  The content of the component (F) in the composition of the present invention is not particularly limited as long as it is an effective amount as an antioxidant within a range that does not impair characteristics such as transparency of the cured product of the present invention. You may mix | blend 0.001-2 mass% with respect to the total mass of (A)-(C) component, and it is preferable to mix | blend 0.01-1 mass%. If it is in this range, the antioxidant ability is sufficiently exhibited, so that a cured product excellent in engineering characteristics can be obtained while suppressing the occurrence of coloring, white turbidity, oxidative degradation and the like.

((G) component: light stabilizer)
In order to impart resistance to light degradation caused by light energy such as sunlight and fluorescent light, a light stabilizer (hereinafter sometimes referred to as (G) component) may be added to the composition of the present invention. .

 (G) As a kind of component, a conventionally well-known thing can be used. Especially, the hindered amine stabilizer which capture | acquires the radical produced | generated by photooxidation (photodegradation) is used suitably, and the antioxidant effect can also be improved more by using together with the above-mentioned antioxidant. Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, tetrakis (1,2 , 2,6,6-Pentamethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate Etc. Among these, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is preferable.

  As the component (G), a commercially available product may be used, or a synthesized product may be used. Examples of commercially available products include ADK STAB (manufactured by Adeka): LA-77Y, LA-77G, LA-82, and the like.

  The blending amount of the component (G) in the composition of the present invention is not particularly limited as long as it is in an amount that does not impair the characteristics such as transparency of the cured product of the present invention and is an effective amount as a light stabilizer. (A)-(C) 0.01-5 mass% may be mix | blended with respect to the total mass of a component, and it is preferable to mix | blend 0.05-0.5 mass%.

((H) component: phosphor)
You may mix | blend a fluorescent substance (henceforth a (H) component) with an arbitrary component in the composition of this invention.

 A conventionally well-known thing can be used as a kind of (H) component. For example, yellow, which is widely used for light emitting diodes (LEDs), is made of an oxide phosphor, an oxynitride phosphor, a nitride phosphor, a sulfide phosphor, an oxysulfide phosphor, etc. , Red, green, and blue light emitting phosphors.

Examples of oxide phosphors include yttrium, aluminum and garnet-based YAG green to yellow light-emitting phosphors containing cerium ions, terbium, aluminum and garnet-based TAG yellow light-emitting phosphors containing cerium ions, cerium and the like. Examples include silicate green to yellow light emitting phosphors containing europium ions. Examples of the oxynitride phosphor include silicon, aluminum, oxygen, and nitrogen-based sialon-based red to green light-emitting phosphors including europium ions. Examples of nitride-based phosphors include calcium, strontium, aluminum, silicon, nitrogen-based casoon-based red light-emitting phosphors including europium ions. Examples of sulfides include ZnS-based green color phosphors including copper ions and aluminum ions. Examples of the oxysulfide phosphor include Y ₂ O ₂ S red light-emitting phosphor containing europium ions. These phosphors may be used alone or in a mixture of two or more.

  The blending amount of the component (H) is not particularly limited as long as it is in an amount that does not impair the characteristics such as transparency of the cured product of the present invention and is an effective amount as a phosphor. It is preferable to mix | blend 10-70 mass% with respect to the total mass of (A)-(C) component, and 20-50 mass% is especially preferable.

((I) component: inorganic particles)
The composition of the present invention may be referred to as inorganic particles (hereinafter referred to as component (I)) for the purpose of improving the optical properties, workability, mechanical properties, and physicochemical properties of the cured product. ) May be blended. (I) The kind of component should just be selected according to the objective, may mix | blend single type, and may mix | blend multiple types in combination. In order to improve dispersibility, the inorganic particles may be surface-treated with a surface treatment agent such as a silane coupling agent.

  (I) Component types include silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide and other inorganic oxide particles, silicon nitride, boron nitride, silicon carbide, nitride Examples thereof include nitride particles such as aluminum, carbon compound particles, and diamond particles, but other materials can be selected according to the purpose, and the present invention is not limited thereto.

  The form of component (I) may be any form depending on the purpose, such as powder or slurry. Depending on the required transparency, it is preferable that the composition of the present invention is blended so that the refractive index of the cured product of the present invention is as equal as possible. Moreover, it is preferable to mix | blend with the composition of this invention as aqueous | water-based / solvent type transparent sol.

The average particle diameter of (I) component to mix | blend is not specifically limited, The thing of the average particle diameter according to the objective is used. Usually, it is about 1/10 or less of the particle diameter of the aforementioned phosphor. The particle diameter is a value obtained by measuring the minor axis and major axis of the particle by SEM (scanning electron microscope) observation and calculating (minor axis + major axis) / 2. This operation is performed on the particles in a certain section in the SEM image, and the arithmetic average value of the obtained particle diameters is defined as the average particle diameter of the component (I).
The blending amount of the component (I) is arbitrary as long as the characteristics such as heat-resistant transparency of the cured product of the present invention are not impaired. If the blending amount of component (I) is too small, the desired effect may not be obtained, and if it is too large, it will adversely affect various properties such as heat-resistant transparency, adhesion, transparency, moldability and hardness of the cured product. Sometimes. About (1) -50 mass% may be mix | blended with respect to the total mass of (A)-(C) component, and it is preferable to mix | blend about 5-35 mass%.

  In addition to the components (D) to (I), the composition of the present invention includes a mold release agent, a resin modifier, a colorant, a diluent, as long as the characteristics such as transparency of the cured product are not impaired. You may mix | blend an antibacterial agent, an antifungal agent, a leveling agent, a sagging prevention agent, etc.

<Blending ratio of (A) component, (B) component and (C) component>
The compounding ratio of the component (A) and the component (B) in the composition of the present invention is not particularly limited. Basically, it is blended based on the molar ratio of the H ¹ -Si group contained in the component (A) and the R ¹ -Si group contained in the component (B). Specifically, [number of moles of H—Si group contained in component (A)] / [number of moles of R ¹ —Si group contained in component (B)] = 1-4. Is preferable, and 1 to 3 is particularly preferable. Within this range, the composition of the present invention exhibits good moldability, and the cured product of the present invention has excellent heat-resistant transparency.

  The compounding quantity of (C) component in the composition of this invention is not specifically limited. Based on the total mass of the component (A), the component (B), and the component (C), the amount of the metal atoms in the component (C) is preferably in the range of 0.003 to 30 ppm in mass units. Especially, since the cured | curing material obtained has the tendency to have the outstanding heat-resistant transparency, 0.003-5.0 ppm is more preferable, 0.003-3.0 ppm is further more preferable, 0.003-2.0 ppm is Particularly preferred. If the amount of component (C) is 0.003 to 30 ppm, the hydrosilylation reaction of component (A) and component (B) proceeds smoothly.

  The viscosity of the composition of the present invention is not particularly limited as long as it is 10,000 cP (centipoise) or less at 25 ° C. If it is 10,000 cP or less, it is preferably 7,000 cP or less. The lower limit is not particularly limited, and the lower the viscosity, the easier the sealing operation of the semiconductor device is preferable. Absent. The viscosity of the composition of the present invention may be more than 0 cP and 10,000 cP or less at 25 ° C., preferably more than 0 cP and 7,000 or less.

Here, the viscosity of the composition of the present invention can be measured with a rotational viscometer or the like. Specifically, according to JIS Z8803 (2011) "cone-viscosity measurement method with plate-type rotational viscometer", rotational viscometer (manufactured by ANTON PAAR, product name: PHYSICA MCR51, measurement range 200 to 1,000,000 cP) and Using a temperature control unit (manufactured by ANTON PAAR, product name: P-PTD200), measurement was performed at a shear rate of 30 [1 / s] at a temperature of 25 ° C., and the value obtained one minute after the start of the measurement Let it be the viscosity of the composition.
Since the composition of the present invention is a low-viscosity resin composition, it has good fluidity. In particular, in the sealing operation of a semiconductor device, the resin composition is less likely to be interrupted and air bubbles are entrapped and easy to apply. Therefore, the sealing work can be performed efficiently. Furthermore, the hardened | cured material obtained from the composition of this invention has sufficient durability in the sealing material use of a semiconductor device. For this reason, the composition of this invention is suitable for the sealing material use of a semiconductor device.

  The total content of HO—Si groups in the component (A) and the component (B) in the composition of the present invention is not particularly limited. 0.1-5.0 mmol / g may be sufficient, 0.1-4.5 mmol / g is preferable and 0.2-2.5 mmol / g is especially preferable. If it exists in this range, hardening of a composition will fully advance and a desired hardened | cured material will be easy to be obtained.

<Preparation of curable silicone resin composition>
The composition of this invention can be prepared by mix | blending (A) component, (B) component, and (C) component, and also mix | blending another additive as needed.

  It is preferable that the component (A), the component (B), the component (C), and the additives added as necessary are dispersed substantially uniformly by mixing. The mixing method is not particularly limited, and a conventionally known mixing method can be employed. For example, a mixing method using a mixing device such as a universal kneader or a kneader can be employed.

  Moreover, you may mix (C) component with (A) component and / or (B) component previously. Moreover, in order to store stably for a long time, (B) component and (C) component are preserve | saved in a separate container, for example, the 1st composition containing a part of (A) component and (C) component, The second composition containing the remainder of the component (A) and the component (B) is stored in separate containers and mixed immediately before use to prepare the composition of the present invention for use. Alternatively, the prepared composition may be further degassed under reduced pressure for use.

(Production method of component (A))
The method for producing the component (A) according to the present invention will be described. (A) The manufacturing method of a component consists of two processes, the 1st process: The manufacturing process of hydrolysis polycondensate (it mentions later for details), and the 2nd process: Functional group modification process. The production method (A-1) for purifying the polycondensate and carrying out the second step, and the production method (A-) for carrying out the second step continuously without purifying the hydrolyzed polycondensate after completion of the first step. There are two types of 2). These methods are described below.

First step: The production of the hydrolyzed polycondensate is carried out by using a dimethyl dialkoxysilane compound represented by the following general formula [3] and a tetraalkoxysilane compound represented by the general formula [4]:
Is a step of synthesizing a condensate obtained by hydrolytic polycondensation (hereinafter sometimes referred to as “hydrolyzed polycondensate”),
Second step: The functional group modification step includes a hydrolysis polycondensate,
Hydrosilane compounds represented by general formula [5-1], [5-2], or [5-3]:
Is a step of reacting. This will be described in detail below.

In the general formula [3], R ² represents an alkyl group having 1 to 3 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group and an ethyl group are preferable. Two R ² may be the same type or different types.

Specific examples of the dimethyl dialkoxysilane compound represented by the general formula [3] (hereinafter sometimes referred to as “dimethyl dialkoxysilane [3]”) include, but are not limited to, the following compounds. Is not:
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, and preferred compounds among these include dimethyldimethoxysilane and dimethyldiethoxysilane.

In the general formula [4], R ³ represents an alkyl group having 1 to ³ carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group and an ethyl group are preferable. The four R ³ may be the same type or different types.

Specific examples of the tetraalkoxysilane compound represented by the general formula [4] (hereinafter sometimes referred to as “tetraalkoxysilane [4]”) include, but are not limited to, the following compounds. Not a thing:
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane.

  Among these, preferred compounds include tetramethoxysilane and tetraethoxysilane.

  The combination of dimethyl dialkoxysilane [3] and tetraalkoxysilane [4] is not particularly limited. Dimethyldialkoxysilane [3] and tetraalkoxysilane [4] may each be used alone or in combination. As a preferred combination, at least one dimethyldialkoxysilane [3] is selected from the group consisting of dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, and dimethyldiisopropoxysilane, and tetraalkoxysilane [4 ] Is selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and tetraisopropoxysilane. Among these, as a particularly preferred combination, at least one dimethyldialkoxysilane [3] is selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane, and tetraalkoxysilane [4] is tetramethoxysilane and tetraethoxy. One or more are selected from the group consisting of silanes.

  The starting material of the first step may include an alkoxysilane compound other than the alkoxysilane compound represented by the general formula [3] and the general formula [4], but the alkoxysilane compound contained in the starting material may be dimethyl It preferably contains only dialkoxysilane [3] and tetraalkoxysilane [4].

  The hydrosilane compounds represented by the general formulas [5-1], [5-2], and [5-3] are “dimethylsilanol [5-1]” and “dimethylalkoxysilane compound [5-2]”, respectively. , “1,1,3,3, -tetramethyldisiloxane [5-3]”, and may be expressed as “hydrosilane compound [5]” when referring to them without distinction. .

In the general formula [5-2], R ⁴ represents an alkyl group having 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group and an ethyl group are preferable.

Specific examples of the dimethylalkoxysilane compound [5-2] include, but are not limited to, the following compounds:
Dimethylmethoxysilane, dimethylethoxysilane, dimethyldi n-propoxysilane, dimethylisopropoxysilane.
Among these, preferred compounds include dimethylmethoxysilane and dimethylethoxysilane.

  1st process: The procedure of manufacture of a hydrolysis polycondensate is demonstrated below. First, dimethyldialkoxysilane [3] and tetraalkoxysilane [4] are reacted at room temperature (particularly an atmospheric temperature not heated or cooled, usually about 15 to about 30 ° C., the same applies hereinafter). After a predetermined amount is added, water for hydrolytic polycondensation of each alkoxysilane compound and, if necessary, a reaction solvent are added, and if desired, a catalyst for advancing the condensation reaction is added to form a reaction solution. . The order of charging at this time is not limited to this, and the reaction solution can be prepared by charging in any order. Next, a hydrolysis polycondensate can be obtained by advancing the reaction at a predetermined temperature for a predetermined time while stirring the reaction solution. At this time, in order to prevent the unreacted raw material alkoxysilane compound, water, reaction solvent and / or catalyst in the reaction system from being distilled out of the reaction system, the reaction vessel is preferably equipped with a reflux device. .

  In the production of the hydrolyzed polycondensate, the amount of dimethyl dialkoxysilane [3] and tetraalkoxysilane [4] used is not particularly limited. From the viewpoint of the physical properties of the component (A), dimethyl dialkoxysilane [3]: tetraalkoxysilane [4] is preferably expressed in molar ratio and mixed in a ratio of 98: 2 to 20:80, and 95: 5 to 35: It is particularly preferred to mix at 65. When the molar ratio of dialkoxysilane [3] is less than 20, it may be higher than the desired molecular weight, and when it exceeds 98, the hydrolysis polycondensation reaction is difficult to proceed and may be lower than the desired molecular weight. is there.

  The amount of water used in the production of the hydrolyzed polycondensate is not particularly limited. From the viewpoint of reaction efficiency, the total molar equivalent of alkoxy groups contained in the alkoxysilane compound of the raw material compound, that is, the total molar equivalent of alkoxy groups contained in dimethyldialkoxysilane [3] and tetraalkoxysilane [4] On the other hand, it is preferably 0.5 times or more and 5 times or less. When the amount is less than 0.5 times molar equivalent, the alkoxysilane compound may not be efficiently hydrolyzed, and it is not necessary to add more than 5 times molar equivalent.

  In the production of the hydrolyzed polycondensate, the reaction can be carried out even under solvent-free conditions, but a reaction solvent can also be used. The type of reaction solvent is not particularly limited as long as it does not inhibit the reaction for producing the hydrolyzed polycondensate. Among these, hydrophilic organic solvents such as alcohols are preferable. Specific examples include methanol, ethanol, normal propanol, isopropanol, butanol and the like, but are not limited thereto. The amount of the reaction solvent used is preferably 0.1 to 1000% by mass, particularly preferably 1 to 300% by mass, based on the total amount of the alkoxysilane compound used. In addition, since alcohols generated from the alkoxysilane compound as a reaction raw material in the reaction process function as a reaction solvent, it may not always be necessary to add.

  In the production of the hydrolyzed polycondensate, an acidic catalyst or a basic catalyst can be used as the type of catalyst used. Since an acid catalyst is used in the next step after the synthesis of the hydrolyzed polycondensate, the use of an acidic catalyst is preferred. The kind of acidic catalyst is not particularly limited. For example, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, trifluoromethanesulfonic acid, tosylic acid, trifluoroacetic acid, oxalic acid, citric acid and the like can be mentioned. Among these, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, citric acid, and hydrofluoric acid are preferable, and citric acid and nitric acid are more preferable because the removal of the acid catalyst after the reaction is easy. More preferred is citric acid. Moreover, the kind of basic catalyst is not specifically limited. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, pyridine and the like.

  In the production of the hydrolyzed polycondensate, the amount of the catalyst used is preferably 0.0001 to 5% by mass, particularly preferably 0.0005 to 1% by mass, based on the total amount of the alkoxysilane compound, solvent and water to be used. %.

  In the production of the hydrolyzed polycondensate, the reaction time is usually from about 3 hours to about 15 hours, and the reaction temperature is usually from 0 ° C. to 150 ° C., preferably from 20 ° C. to 110 ° C.

  In the production method (A-1), the hydrolysis polycondensate is purified from the reaction system after the reaction, and then the second step is performed. However, the purification method is not particularly limited. Examples of the purification method include an extraction method. Specifically, after the temperature of the reaction solution after the above reaction is lowered to room temperature, the hydrolyzed polycondensate present in the reaction system is extracted by contacting with a non-aqueous organic solvent as an extraction solvent. Next, the catalyst contained in the solution after extraction is removed. The method for removing the catalyst is not particularly limited. For example, if the catalyst (for example, acetic acid) used is water-soluble, this catalyst can be removed by washing the solution after extraction with water. Next, a desiccant is added to the solution after removing the catalyst to remove water dissolved in the system. Furthermore, the hydrolysis polycondensate can be purified with high purity by removing the desiccant and removing the extraction solvent under reduced pressure. In particular, it is preferable to isolate the hydrolysis polycondensate. At this time, water may be simultaneously removed under reduced pressure in the process of removing the extraction solvent from the solution after removing the catalyst under reduced pressure without using a desiccant.

  A non-aqueous organic solvent can be used as the extraction solvent. The kind of this non-aqueous organic solvent is not specifically limited. For example, aromatic hydrocarbons, esters, ethers and the like can be mentioned. Specific examples include toluene, xylene, ethyl acetate, diethyl ether, isopropyl ether, dibutyl ether, and the like, but are not limited thereto.

  The desiccant is not particularly limited as long as water can be removed from the system and separated from the hydrolysis polycondensate. As such a desiccant, a solid desiccant is preferably used. Specifically, although magnesium sulfate etc. are mentioned, it is not limited to this.

  In the production method (A-2), in the production of the hydrolyzed polycondensate, the second step is performed at the end of the reaction time without purifying the hydrolyzed polycondensate from the reaction system. This method is particularly preferable for the synthesis of dimethyldialkoxysilane [3]: tetraalkoxysilane [4] in the composition range of 60:40 to 35:65, but the ratio is not limited. At the above ratio, if the purification operation is performed in the first step, the hydrolyzed polycondensate gels or solidifies when the solvent is distilled off, resulting in a problem in handling. With this method, the component (A) can be synthesized even with the above composition ratio.

  Second step: The functional group modification step will be described. Specifically, it is a method of producing the component (A) by reacting the hydrolysis polycondensate with the silane compound [5]. This method involves hydrolysis polycondensate (I) and dimethylsilanol [5-1], dimethylmonoalkoxysilane compound [5-2] or tetramethyldisiloxane [5-4], which is a kind of silane compound [5]. ] In the presence of an acid to produce component (A) (hereinafter referred to as a functional group modification method). This method will be specifically described below.

  In the functional group modification step, first, a predetermined amount of the hydrolyzed polycondensate, and optionally a non-aqueous organic solvent and an alcoholic solvent is placed in the reaction vessel to dissolve the hydrolyzed polycondensate. Next, a predetermined amount of silanol compound [5-2], monoalkoxysilane compound [5-3] or tetramethyldisiloxane [5-3] is added to this solution. Further, a catalyst for advancing hydrolysis and dehydration condensation reaction is added to the reaction system, and the reaction system is stirred for 1 to 48 hours at room temperature to allow the reaction to proceed. Then, (A) component can be obtained by terminating reaction.

  In the functional group modification step, the amount of the hydrolyzed polycondensate and dimethylsilanol [5-1], dimethylmonoalkoxysilane compound [5-2] or tetramethyldisiloxane [5-3] used is not particularly limited. From the viewpoint of the physical properties of component (A), SiH in dimethylsilanol [5-1], dimethylmonoalkoxysilane compound [5-2] or tetramethyldisiloxane [5-3] is used per 1 g of the hydrolyzed polycondensate. It is preferable to use it in the range where the group is 0.2 mmol to 10 mmol.

  In the functional group modification step of the production method (A-1), the solvent to be used includes a water-insoluble organic solvent and an alcohol solvent. The type of the water-insoluble organic solvent is not particularly limited as long as the reaction for producing the component (A) is not inhibited. Of these, aromatic hydrocarbons and ethers are preferable. Specific examples include toluene, diethyl ether, tetrahydrofuran, diisopropyl ether, and the like, but are not limited thereto. The amount of the water-insoluble organic solvent used is preferably 50 to 1000% by mass and particularly preferably 100 to 500% by mass with respect to 1 g of the hydrolyzed polycondensate, but is not limited thereto.

  The type of alcohol solvent is not particularly limited as long as the reaction for producing the component (A) is not inhibited. Among these, alcohol having 1 to 4 carbon atoms is preferable. Specific examples include methanol, ethanol, 1-propanol, 2-propanol, butanol and the like, but are not limited thereto. The amount of the alcohol solvent used is preferably 10 to 500% by mass, particularly preferably 50 to 300% by mass, based on 1 g of the hydrolyzed polycondensate, but is not limited thereto.

  In the functional group modification step of the production method (A-2), it is not necessary to newly add a solvent, but the reaction proceeds without any problem even if it is added. Although the kind of solvent to add is not specifically limited unless the reaction for manufacturing (A) component is inhibited, What was described as a solvent used by manufacturing method (A-1) can be illustrated.

  In the functional group modification step of the production method (A-1), the type of the catalyst used is not particularly limited as long as it has an action of promoting the reaction for producing the component (A). Among these, an acid catalyst is preferable. Specific examples include nitric acid, hydrochloric acid, sulfuric acid, citric acid and the like, but are not limited thereto. The amount of the catalyst used is preferably 0.0001 to 10 mmol, particularly preferably 0.005 to 5 mmol%, based on 1 g of the hydrolyzed polycondensate. When a basic catalyst is used in the first step, it is necessary to add more acid catalyst than the molar amount of the basic catalyst used.

  In the functional group modification step of the production method (A-2), if the catalyst used is an acid catalyst in the first step, it is not necessary to add a new catalyst, but in order to accelerate the progress of the reaction An acid catalyst may be added. Although the kind of catalyst to be used is not particularly limited as long as the reaction for producing the component (A) is not inhibited, those described as the catalyst used in the production method (A-1) can be exemplified.

  In the functional group modification step, the method for terminating the reaction is not particularly limited. Usually, the reaction is terminated by adding water (preferably ion-exchanged water) to the reaction system and stirring. After the reaction, it is preferable to purify the component (A) from the reaction system from the viewpoint of handling the component (A). This purification method is not particularly limited. For example, a method of extracting can be mentioned. Specifically, the organic layer is separated from the solution after the above reaction. Next, the organic layer is washed with water (preferably ion-exchanged water), and further a desiccant is added to remove water dissolved in the system. Thereafter, the desiccant is removed from the organic layer and the water-insoluble organic solvent is removed under reduced pressure, whereby the component (A) can be purified with high purity. At this time, water may be simultaneously removed under reduced pressure in the process of removing the non-aqueous organic solvent under reduced pressure without using a desiccant. It is preferable that the component (A) after the purification further removes moisture contained in the component (A) by heating and stirring without solvent and under reduced pressure. Although the heating temperature at this time is not specifically limited, Usually, it is 100-130 degreeC.

(Production method of component (B))
The method for producing the component (B) according to the present invention will be described. (B) The manufacturing method of a component consists of two processes, the 1st process: manufacture of a hydrolysis polycondensate, and the 2nd process: a functional group modification process, and refine | purifies a hydrolysis polycondensate after completion | finish of a 1st process. The manufacturing method (B-1) for performing the second step and the manufacturing method (B-2) for subsequently performing the second step without purifying the hydrolysis polycondensate after the completion of the first step. is there. The method will be described below.

1st process: It is the same process as the 1st process in the manufacturing method of (A) component,
Second step: The functional group modification step includes a hydrolysis polycondensate,
Silane compound represented by general formula [8-1], [8-2], or [8-3]:
Is a step of reacting. This will be described in detail below.

In the general formula [6], R ⁵ represents an alkyl group having 1 to 3 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group and an ethyl group are preferable. Two R ⁵ may be the same type or different types.

Specific examples of the dimethyl dialkoxysilane compound represented by the general formula [6] (hereinafter sometimes referred to as “dimethyl dialkoxysilane [6]”) include, but are not limited to, the following compounds. Is not:
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, and preferred compounds among these include dimethyldimethoxysilane and dimethyldiethoxysilane.

In the general formula [7], R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group and an ethyl group are preferable. The four R ⁶ may be the same type or different types.

Specific examples of the tetraalkoxysilane compound represented by the general formula [7] (hereinafter sometimes referred to as “tetraalkoxysilane [7]”) include, but are not limited to, the following compounds. Not a thing:
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane.

  Among these, preferred compounds include tetramethoxysilane and tetraethoxysilane.

  The combination of dimethyl dialkoxysilane [6] and tetraalkoxysilane [7] is not particularly limited. Dimethyl dialkoxysilane [6] and tetraalkoxysilane [7] may each be used alone or in combination. As a preferred combination, at least one dimethyldialkoxysilane [6] is selected from the group consisting of dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, and dimethyldiisopropoxysilane, and tetraalkoxysilane [7 ] Is selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and tetraisopropoxysilane. Among these, as a particularly preferred combination, dimethyldialkoxysilane [6] is one or more selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane, and tetraalkoxysilane [7] is tetramethoxysilane and tetraethoxy. One or more are selected from the group consisting of silanes.

  The silane compounds represented by the general formulas [8-1], [8-2] and [8-3] are “dimethylvinylsilanol compound [8-1]” and “dimethylvinylalkoxysilane compound [8- 2] ”and“ 1,3-divinyl 1,1,3,3, -tetramethyldisiloxane compound [8-3] ”. When these are collectively referred to without distinction,“ silane compound ” [8] ".

In General Formula [8-1], R ⁷ has the same meaning as R ^1, and is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms. Specific examples include a vinyl group, a propenyl group, an n-butenyl group, an n-pentenyl group, and an n-hexenyl group. Of these, vinyl groups are preferred.

Specific examples of the dimethylvinylsilanol compound [8-1] represented by the general formula [8-1] include, but are not limited to, the following compounds:
Dimethylvinylsilanol, dimethylpropenylsilanol, dimethyl-n-butenylsilanol, dimethyl-n-pentenylsilanol, dimethyl-n-hexenylsilanol As a preferable compound among these, dimethylvinylsilanol is mentioned.

In General Formula [8-2], R ⁸ has the same meaning as R ¹ and is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms. Specific examples include a vinyl group, a propenyl group, an n-butenyl group, an n-pentenyl group, and an n-hexenyl group. Of these, vinyl groups are preferred.

In the general formula [8-2], R ⁹ represents an alkyl group having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group and an ethyl group are preferable.

Specific examples of the dimethylvinylalkoxysilane compound [8-2] represented by the general formula [8-2] include, but are not limited to, the following compounds:
Dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylpropenylmethoxysilane, dimethylpropenylethoxysilane, dimethyl-n-butenylmethoxysilane, dimethyl-n-butenylethoxysilane, dimethyl-n-pentenylmethoxysilane, dimethyl-n- Pentenylethoxysilane, dimethyl-n-hexenylmethoxysilane, dimethyl-n-hexenylethoxysilane.
Among these, preferred compounds include dimethylvinylmethoxysilane and dimethylvinylethoxysilane.

In General Formula [8-3], R ¹⁰ has the same meaning as R ¹ and is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms. Specific examples include a vinyl group, a propenyl group, an n-butenyl group, an n-pentenyl group, and an n-hexenyl group. Of these, vinyl groups are preferred.

  Specific examples of the 1,3-divinyl 1,1,3,3-tetramethyldisiloxane compound [8-3] represented by the general formula [8-3] include the following compounds. It is not limited to: 1,3-divinyl 1,1,3,3-tetramethyldisiloxane, 1,3-dipropenyl 1,1,3,3, -tetramethyldisiloxane, 1,3- Di-n-butenyl 1,1,3,3-tetramethyldisiloxane, 1,3-di-n-pentenyl 1,1,3,3-tetramethyldisiloxane, 1,3-di-n-hexenyl 1, 1,3,3-tetramethyldisiloxane

  Among these, preferred compounds include 1,3-divinyl 1,1,3,3, -tetramethyldisiloxane.

Next, a method for producing the component (B) by reacting the hydrolyzed polycondensate with the silane compound [8] will be described. The component (B) can be produced by applying the method for producing the component (A) from the hydrolysis polycondensate described above. That is, hydrosilane compound [5], dimethylsilanol [5-1], dimethylmonoalkoxysilane compound [5-2], 1,1,3,3-tetramethyldisiloxane [5-3] in the functional group modification step described above. ] Are replaced by the run compound [8], vinylsilanol compound [8-1], monoalkoxyvinylsilane compound [8-2], divinyldisiloxane compound [8-3], respectively, and SiH group, hydrolysis polycondensate [I] ], (a) component, the production method (a-1), respectively producing method (a-2) Si-CH = CH 2 group, hydrolysis polycondensate, (B) component, the production method (B-1) By replacing with the production method (B-2), a method of producing the component (B) from the hydrolyzed polycondensate can be explained.

  As the platinum catalyst which is the component (C) according to the present invention, a commercially available product may be used, or a synthesized catalyst may be used. When using a commercial item, "Platinum (0) -1,1,3,3-tetramethyldisiloxane complex solution" (made by Aldrich) etc. can be illustrated, for example. In the case of using the synthesized one, the component (C) according to the present invention can be synthesized by a conventionally known method.

  As the antioxidant according to the present invention, a commercially available product or a synthesized product may be used. When using a commercial item, for example, Adeka Stub (manufactured by Adeka): AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330, AO-412S, AO-503, PEP-8, PEP-8W, PEP-36, PEP-36A, HP-10, 2112, 2112RG, 1178, 1500, C, 135A, 3010, TPP, etc. Can do.

  As the light stabilizer according to the present invention, a commercially available product may be used, or a synthesized product may be used. In the case of using a commercially available product, for example, ADK STAB (manufactured by Adeka): LA-77Y, LA-77G, and LA-82 can be exemplified.

[2. Cured product of curable silicone resin composition]
A cured product of the curable silicone resin composition of the present invention (hereinafter sometimes referred to as “cured product of the present invention”) is obtained by heating the composition of the present invention.

  The cured product of the present invention can be used as a sealing material for a semiconductor device, and is particularly suitable as a sealing material for an optical semiconductor device and a power semiconductor device. As a sealing material for optical semiconductor devices, it can be suitably used as a sealing material for LED optical members, a sealing material for optical members for semiconductor lasers, etc., among others, as a sealing material for LED optical members. Particularly preferred.

  In general, the light extraction efficiency of a semiconductor device is enhanced by various technologies. However, if the transparency of the sealing material of the semiconductor element is low, the sealing material absorbs light, and this is used. The light extraction efficiency of the semiconductor device is reduced. As a result, it tends to be difficult to obtain a high-brightness semiconductor device product. Furthermore, the energy corresponding to the decrease in light extraction efficiency is changed to heat, which causes thermal deterioration of the semiconductor device, which is not preferable.

  The cured product of the present invention is excellent in heat-resistant transparency in the UV region to the visible light region, particularly in the UV region. Specifically, the cured product of the present invention has a good light transmittance at a wavelength in the range of usually 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm or less. Therefore, it is preferable to use the cured product of the present invention as the above-described sealing material for a semiconductor device having an emission wavelength in this region because a high-luminance semiconductor device can be obtained. In addition, this does not prevent using the hardened | cured material of this invention as a sealing material for the semiconductor device which has light emission wavelength out of said area | region. The light transmittance can be measured by measuring transmittance with an ultraviolet / visible spectrophotometer.

  The method for curing the composition of the present invention is not particularly limited. For example, the composition of the present invention is sealed like an LED by a method such as injection, dripping, casting, casting, extrusion from a container, or by integral molding by transfer molding or injection molding. By combining with an object and usually heating at 45 to 300 ° C., preferably 60 to 200 ° C., the composition can be cured to obtain a cured product, and the object to be sealed can be sealed. If the heating temperature is 45 ° C. or higher, stickiness is hardly observed in the obtained cured product, and if it is 300 ° C. or lower, foaming is hardly observed in the obtained cured product, which is practical. The heating time is not particularly limited. Usually, it is about 0.5 to 12 hours, and preferably about 1 to 10 hours. If the heating time is 0.5 hours or longer, curing proceeds sufficiently, but if accuracy is required, such as for LED sealing, it is preferable to lengthen the curing time.

[3. Encapsulant]
The hardened | cured material of this invention can be used as a sealing material for semiconductor devices, and may be especially called for optical semiconductor devices, for power semiconductor devices, and a chip scale package (CSP) (wafer level package (WLP)). It is suitable as a sealing material. The sealing material made of the cured product of the present invention is excellent in heat-resistant transparency as described above. Moreover, it is excellent in heat resistance, cold resistance, and electrical insulation similarly to the cured | curing material of the conventional addition curable silicone resin composition normally.

[4. Semiconductor device]
The semiconductor device of the present invention is a semiconductor device including at least a semiconductor element, and the semiconductor element is sealed at least by the cured product of the present invention. Other configurations of the semiconductor device of the present invention are not particularly limited, and members other than the semiconductor elements may be provided. Examples of such members include a base substrate, lead-out wiring, wire wiring, control element, insulating substrate, reflecting material, heat sink, conductive member, die bonding material, bonding pad, and the like. Further, in addition to the semiconductor element, a part or all of the member may be sealed with the cured product of the present invention.

  Specific examples of the semiconductor device of the present invention include, but are not limited to, a light emitting diode (LED) device, a semiconductor laser device, and a photocoupler. The semiconductor device of the present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copy machine, a measurement light source for a vehicle, a signal light, an indicator light, a display device, a light source of a planar light emitter, It is suitably used for displays, decorations, various lights and switching elements.

  An example of the semiconductor device of the present invention is shown in FIG. As illustrated in FIG. 1, the semiconductor device 10 includes at least a sealing material 1, a semiconductor element 2, and a bonding wire 3 on a semiconductor substrate 6. The semiconductor substrate 6 has a recess composed of a bottom surface made of the lead frame 5 and an inner peripheral side surface made of the reflector 4.

  The semiconductor element 2 is connected to the lead frame 5 using a die bond material (not shown). A bonding pad (not shown) provided in the semiconductor element 2 and the lead frame 5 are electrically connected by a bonding wire 3. The reflective material 4 has a function of reflecting light from the semiconductor element 2 in a predetermined direction. The sealing material 1 is filled in the region of the concave portion of the semiconductor substrate 6 so as to at least seal the semiconductor element 2. At this time, the sealing material 1 may be filled so as to also seal the bonding wire 3. The sealing material 1 consists of the hardened | cured material of this invention. The phosphor (not shown) may be included in the sealing material 1. The sealing material 1 can protect the semiconductor element 2 from moisture, dust, and the like, and can maintain reliability over a long period of time. Furthermore, since the sealing material 1 also seals the bonding wire 3, it is possible to prevent electrical problems caused by the bonding wire 3 being disconnected, cut, or short-circuited at the same time.

  As described later, the cured product of the present invention can be used as an adhesive for semiconductors. Therefore, it can also be employed as the above-described die bond material.

  In the semiconductor device 10, as the semiconductor element 2 encapsulated by the encapsulant 1 made of the cured product of the present invention, for example, an LED, a semiconductor laser, a photodiode, a phototransistor, a solar cell, a CCD (charge coupled device), and the like. Can be mentioned. The structure shown in FIG. 1 is merely an example of the semiconductor device of the present invention, and the structure of the reflector, the structure of the lead frame, the mounting structure of the semiconductor element, and the like can be modified as appropriate.

  The method for manufacturing the semiconductor device 10 shown in FIG. 1 is not particularly limited. For example, the semiconductor element 2 is die-bonded to the lead frame 5 including the reflective material 4, the semiconductor element 2 and the lead frame 5 are wire-bonded by the bonding wire 3, and then the reflective material provided around the semiconductor element is used. An example is a method in which the composition of the present invention is filled on the inner side (a recess made of a lead frame and a reflective material) and then cured by heating at 50 to 250 ° C. to obtain the sealing material 1.

[5. Adhesive for semiconductor devices]
Since the composition of the present invention has good adhesion, it can be used as an adhesive for semiconductor devices. Specifically, for example, when bonding a semiconductor element and a package, when bonding a semiconductor element and a submount, when bonding package components, when bonding a semiconductor device and an external optical member, etc. The composition of the invention can be used by coating, printing, potting and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.

1. Method for evaluating physical properties of raw materials [determination of composition ratio and determination of HO-Si group]
To 200 mg of the silicone resin, 0.5 mL of deuterated chloroform was added and dissolved, and 10 mg of chromium (III) acetylacetonate complex was added as a relaxation agent. The solution thus prepared was measured by ²⁹ Si-NMR. As shown in Table 1, the detected signals were classified into peaks (a) to (h), and each peak was calculated as a percentage (integration ratio) from the sum of all integrated values. For the ²⁹ Si-NMR measurement of the silicone resin, a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model number: JNM-AL400) having a resonance frequency of 400 MHz was used.

The values of a, b, and c in the above equation [1] were determined by calculating from the following equations:
a = peak (j) area / total peak area sum,
b = (peak (a) area + peak (b) area) / total peak area,
c = (peak (f) area + peak (g) area + peak (h) area + peak (i) area) / total peak area.
The values of d, e, and f in the above equation [2] were determined by calculating from the following equations:
d = sum of peak (k) area / total peak area,
e = (peak (a) area + peak (b) area) / sum of total peak areas,
f = (peak (f) area + peak (g) area + peak (h) area + peak (i) area) / total peak area.

^{In 29} Si-NMR, when peaks of Me—Si group, Ph—Si group, H—Si group, CH ₂ ═CH—Si group (Vi—Si group) or other groups overlap, ¹ H-NMR Me-Si group in, Ph-Si group, H-Si group _was calculated based on the integrated area of the peak of CH 2 = CH-Si group or other group.

The content of HO—Si groups (mmol / g) was determined according to the following formula from the integration ratio calculated by the above method:

[A] = peak (a) integration ratio + 2 × peak (c) integration ratio + peak (d) integration ratio + 3 × peak (f) integration ratio + 2 × peak (g) integration ratio + peak (h) integration ratio,

[B] = peak (a) integration ratio × 83.16 + peak (b) integration ratio × 74.15 + peak (c) integration ratio × 147.2 + peak (d) integration ratio × 138.2 + peak (e) integration ratio X 129.2 + peak (f) integration ratio x 87.92 + peak (g) integration ratio x 78.10 + peak (h) integration ratio x 69.09 + peak (i) integration ratio x 60.08 + peak (j) integration ratio × 67.16 + peak (k) integration ratio × 93.20,

HO—Si group content (mmol / g) = ([A] / [B]) × 1000.

^In the measurement of ²⁹ Si-NMR, when the peak (j) and the peak (k) overlap with the peak (a), the integration ratio of Ph-Si and H-Si by the measurement of ¹ H-NMR, and the Ph-Si And Vi-Si, if there are other peaks, calculate the percentage of the integration ratio of the other peaks, and calculate the ²⁹ Si-NMR peak (c) integration ratio + peak (d) integration ratio + peak (e) integration ratio. Then, the integration ratio of ²⁹ Si-NMR of peak (j) and peak (k) was determined from the integration ratio of ¹ H-NMR, and the integrated value of peak (a), peak (j) and peak (k) overlapped The integration ratio of peak (a) was calculated by subtracting the integration ratio of peak (j) and peak (k). In other cases, when ²⁹ Si-NMR peaks overlapped, calculation was performed based on the integration ratio of ¹ H-NMR in the same manner as described above.

[Quantification of H-Si group and Vi-Si group]
20-30 mg of silicone resin was weighed into a 6 mL sample tube, and 0.8 mL of heavy dichloromethane was added to dissolve the silicone resin. 10 mg of 1,3,5-trioxane (11 mmol) was added to the solution, the sample tube was closed, and the solution was stirred and made uniform to obtain a measurement sample. The sample was measured by ¹ H-NMR, and the proton ratio of 1,3,5-trioxane and the proton ratio of H—Si group or Vi—Si group were calculated, and the H—Si group in the measurement sample or The number of moles of Vi-Si groups was determined. Next, the content of each functional group in 1 g of the measurement sample was calculated according to the following formula:
Number of moles of functional group in silicone resin (mmol) / measurement sample amount (mg) × 1000 = functional group amount in 1 g of measurement sample (mmol / g).

For the ¹ H-NMR measurement of the silicone resin, a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model number: ECA-400) having a resonance frequency of 400 MHz was used. The chemical shift of each functional group in the silicone resin is shown below:
Me-Si: 0.0 to 0.5 ppm (3H),
H-Si: 4.0 to 5.0 ppm (1H),
Vi-Si: 5.5-6.5 ppm (3H).

[Mass average molecular weight (Mw) measurement]
The mass average molecular weight (Mw) of the silicone resin was calculated by creating a calibration curve using polystyrene as a reference material by the gel permeation chromatography (abbreviation: GPC) method under the following conditions:
Device: manufactured by Tosoh Corporation, product name: HLC-8320GPC,
Column: manufactured by Tosoh Corporation, product name: TSK gel Super HZ 2000x4, 3000x2,
Eluent: tetrahydrofuran.

[Refractive index]
The refractive index of the silicone resin was measured using a refractometer (manufactured by Kyoto Electronics Industry Co., Ltd., model: RA-600).

[Viscosity measurement]
The viscosity of the silicone resin is determined according to “Viscosity measurement method using conical plate-type rotational viscometer” in JIS Z8803 (2011) (manufactured by ANTON PAAR, product name: PHYSICA MCR51, measurement range 200 to 1,000,000 cP). And a temperature control unit (manufactured by ANTON PAAR, product name: P-PTD200), measured at a shear rate of 30 [1 / s] at a temperature of 25 ° C., and the value obtained one minute after the start of the measurement was measured according to the present invention. The viscosity of the composition was employed. When the viscosity was less than the measurement range, it was expressed as “<200”.

[transparency]
The transmittance | permeability of resin in the wavelength range of 405 nm, 365 nm, and 300 nm was measured using the ultraviolet visible spectrophotometer (the Shimadzu Corporation make, model number: UV-3150). The measurement cell used was made of quartz, and the cell thickness was 1 cm.

2. Raw Material Synthesis Example and Comparative Synthetic Example [Raw Material Synthesis Example 1-1] Synthesis of Silicone Resin (I)
In a glass reaction vessel having a volume of 2 L equipped with a stirrer made of fluororesin and a Dimroth type reflux vessel, 601.00 g (5.00 mol) of Me ₂ Si (OMe) ₂ , 104.15 g (0.50 mol) of Si ( OEt) ₄ was collected. Subsequently, 216.18 g of water and 28.37 g of citric acid were added to the reaction vessel, and the inside of the reaction vessel was continuously heated at 100 ° C. for 6 hours to carry out hydrolysis and condensation reactions. Thereafter, the reaction solution was returned to room temperature, and only the aqueous layer was removed. 150 mL of toluene and 250 mL of water were added to the reaction vessel in which the organic layer remained, and after performing a liquid separation operation, the aqueous layer was removed. Next, the organic layer was washed three times with 250 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure using an evaporator. Furthermore, the volatile component was distilled off under reduced pressure by short process distillation. Silicone resin (I) was obtained as a colorless viscous liquid.

The yield of the silicone resin (I) is 203.11 g, the mass average molecular weight (Mw) is 1617, and the composition ratio is (Me ₂ SiO _2/2 ) _0.88 (SiO _4/2 ) _0.12 . The HO—Si group content was 1.61 mmol / g.

[Raw Material Synthesis Example 1-2] Synthesis of Silicone Resin (A1)
99.89 g of silicone resin (I), 299.67 g of toluene, 99.89 g of methanol, 17.51 g of 1,1,3,3-tetramethyldisiloxane and 0.42 mL of 70% concentrated nitric acid were added to the flask. In addition, the mixture was stirred at 40 ° C. After 2 hours, the reaction solution was transferred to a separatory funnel, 300 mL of water was added, extraction operation was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After toluene was distilled off from the organic layer by an evaporator, the volatile component was distilled off under reduced pressure at 100 ° C. and 3.0 Pa in a short process distillation apparatus to obtain a silicone resin (A1) as a colorless and transparent viscous liquid.

The yield of the silicone resin (A1) is 86.34 g, the mass average molecular weight (Mw) is 1833, the viscosity is less than 200 cP, and the composition ratio is (H-SiMe ₂ O _1/2 ) _0.11 (Me ₂ SiO _2/2 ) _0.77 (SiO _4/2 ) _0.12 , the H—Si group content is 1.4 mmol / g, and the HO—Si group content is 0.88 mmol / g. Met.

[Raw Material Synthesis Example 1-3] Synthesis of Silicone Resin (B1)
97.72 g of silicone resin (I), 293.16 g of toluene, 97.72 g of methanol, 23.77 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 8.17 mL of 70 % Concentrated nitric acid was added to the flask and stirred at 40 ° C. After 2 hours, the reaction solution was transferred to a separatory funnel, 293 mL of water was added, extraction operation was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After evaporating toluene from the organic layer with an evaporator, 42.3 mg of 200 ppm platinum toluene solution was added, and the volatile components were distilled off under reduced pressure at 100 ° C. and 3.6 Pa in a short process distillation apparatus to obtain a colorless transparent viscous liquid. As a result, a silicone resin (B1) was obtained.

The yield of the silicone resin (B1) is 83.56 g, the mass average molecular weight (Mw) is 1758, the viscosity is less than 200 cP, and the composition ratio is (Vi-SiMe ₂ O _1/2 ) _0.11 (Me ₂ SiO _2/2 ) _0.76 (SiO _4/2 ) _0.13 , the Vi—Si group content is 1.4 mmol / g, and the HO—Si group content is 0.81 mmol / g. Met.

[Raw Material Synthesis Example 2-1] Synthesis of Silicone Resin (II)
In a glass reaction vessel having a volume of 2 L equipped with a stirrer made of fluororesin and a Dimroth type reflux vessel, 721.20 g (6.00 mol) of Me ₂ Si (OMe) ₂ and 312.45 g (1.50 mol) of Si ( OEt) ₄ was collected. Subsequently, 324.27 g of water and 42.55 g of citric acid were added to the reaction vessel, and the inside of the reaction vessel was continuously heated at 100 ° C. for 6 hours to carry out hydrolysis and condensation reactions. Thereafter, the reaction solution was returned to room temperature, and only the aqueous layer was removed. 400 mL of toluene and 300 mL of water were added to the reaction vessel in which the organic layer remained, and after performing a liquid separation operation, the aqueous layer was removed. Next, the organic layer was washed three times with 300 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure using an evaporator. Furthermore, the volatile component was distilled off under reduced pressure by short process distillation. Silicone resin (II) was obtained as a colorless viscous liquid.

The yield of the silicone resin (II) is 215.18 g, the mass average molecular weight (Mw) is 2985, and the composition ratio is (Me ₂ SiO _2/2 ) _0.78 (SiO _4/2 ) _0.22 . The HO—Si group content was 2.21 mmol / g.

[Raw Material Synthesis Example 2-2] Synthesis of Silicone Resin (A2)
100.01 g of silicone resin (II), 300.03 g of toluene, 100.01 g of methanol, 14.84 g of 1,1,3,3-tetramethyldisiloxane and 0.35 mL of 70% concentrated nitric acid in the flask In addition, the mixture was stirred at 40 ° C. After 2 hours, the reaction solution was transferred to a separatory funnel, 300 mL of water was added, extraction operation was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After evaporating toluene from the organic layer by an evaporator, the volatile component was distilled off under reduced pressure at 100 ° C. and 6.4 Pa in a short process distillation apparatus to obtain a silicone resin (A2) as a colorless and transparent viscous liquid.

The yield of the silicone resin (A2) is 85.24 g, the mass average molecular weight (Mw) is 3099, the viscosity is less than 200 cP, and the composition ratio is (H-SiMe ₂ O _1/2 ) _0.09 (Me ₂ SiO _2/2 ) _0.69 (SiO _4/2 ) _0.22 , the H—Si group content is 1.1 mmol / g, and the HO—Si group content is 1.06 mmol / g. Met.

[Raw Material Synthesis Example 2-3] Synthesis of Silicone Resin (B2)
99.99 g of silicone resin (II), 299.97 g of toluene, 99.99 g of methanol, 20.60 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 7.08 mL of 70 % Concentrated nitric acid was added to the flask and stirred at 40 ° C. After 2 hours, the reaction solution was transferred to a separatory funnel, 300 mL of water was added, extraction operation was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After distilling off toluene from the organic layer with an evaporator, 54.8 mg of 200 ppm platinum toluene solution was added, and the volatile components were distilled off under reduced pressure at 100 ° C. and 4.0 Pa in a short process distillation apparatus. As a result, a silicone resin (B2) was obtained.

The yield of the silicone resin (B2) is 75.22 g, the mass average molecular weight (Mw) is 2951, the viscosity is less than 200 cP, and the composition ratio is (Vi-SiMe ₂ O _1/2 ) _0.10 (Me ₂ SiO _2/2 ) _0.67 (SiO _4/2 ) _0.23 , the Vi—Si group content is 1.1 mmol / g, and the HO—Si group content is 0.96 mmol / g. Met.

[Raw Material Synthesis Example 3-1] Synthesis of Silicone Resin (III)
In a glass reaction vessel having a volume of 2 L equipped with a stirrer made of fluororesin and a Dimroth type reflux vessel, 721.20 g (6.00 mol) of Me ₂ Si (OMe) ₂ , 416.60 g (2.00 mol) of Si ( OEt) ₄ was collected. Next, 360.30 g of water and 47.28 g of citric acid were added to the reaction vessel, and the inside of the reaction vessel was continuously heated at 100 ° C. for 6 hours to carry out hydrolysis and condensation reactions. Thereafter, the reaction solution was returned to room temperature, and only the aqueous layer was removed. 400 mL of toluene and 250 mL of water were added to the reaction vessel in which the organic layer remained, and after performing a liquid separation operation, the aqueous layer was removed. Next, the organic layer was washed three times with 250 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure using an evaporator. Furthermore, the volatile component was distilled off under reduced pressure by short process distillation. Silicone resin (III) was obtained as a colorless viscous liquid.

The yield of the silicone resin (III) is 196.17 g, the mass average molecular weight (Mw) is 3763, and the composition ratio is (Me ₂ SiO _2/2 ) _0.74 (SiO _4/2 ) _0.26 . The HO—Si group content was 2.32 mmol / g.

[Raw Material Synthesis Example 3-2] Synthesis of Silicone Resin (A3)
85.05 g of silicone resin (III), 255.15 g of toluene, 85.05 g of methanol, 13.25 g of 1,1,3,3-tetramethyldisiloxane and 0.32 mL of 70% concentrated nitric acid in the flask In addition, the mixture was stirred at 40 ° C. Two hours later, the reaction solution was transferred to a separatory funnel, 255 mL of water was added, extraction operation was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After toluene was distilled off from the organic layer by an evaporator, the volatile component was distilled off under reduced pressure at 100 ° C. and 5.3 Pa in a short process distillation apparatus to obtain a silicone resin (A3) as a colorless transparent viscous liquid.

The yield of the silicone resin (A3) is 67.40 g, the mass average molecular weight (Mw) is 3753, the viscosity is 253 cP, and the composition ratio is (H-SiMe ₂ O _1/2 ) _0.10 (Me ₂ SiO _2/2 ) _0.66 (SiO _4/2 ) _0.24 , the H—Si group content is 1.3 mmol / g, and the HO—Si group content is 0.76 mmol / g. there were.

[Raw Material Synthesis Example 3-3] Synthesis of Silicone Resin (B3)
85.03 g silicone resin (III), 255.09 g toluene, 85.03 g methanol, 18.39 g 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 6.32 mL 70 % Concentrated nitric acid was added to the flask and stirred at 40 ° C. Two hours later, the reaction solution was transferred to a separatory funnel, 255 mL of water was added, extraction operation was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. Toluene was distilled off from the organic layer by an evaporator, 45.0 mg of 200 ppm platinum toluene solution was added, and volatile components were distilled off under reduced pressure at 100 ° C. and 3.5 Pa in a short process distillation apparatus to obtain a colorless transparent viscous liquid. As a result, a silicone resin (B3) was obtained.

The yield of the silicone resin (B3) is 63.47 g, the mass average molecular weight (Mw) is 3787, the viscosity is 382 cP, and the composition ratio is (Vi-SiMe ₂ O _1/2 ) _0.10 (Me ₂ SiO _2/2 ) _0.65 (SiO _4/2 ) _0.25 , Vi—Si group content is 1.3 mmol / g, and HO—Si group content is 0.48 mmol / g. there were.

[Raw Material Synthesis Example 4-1] Synthesis of Silicone Resin (IV)
300.50 g (2.50 mol) Me ₂ Si (OMe) ₂ , 260.38 g (1.25 mol) Si (into a ₂ L glass reaction vessel equipped with a fluororesin stirring blade and a Dimroth type reflux vessel OEt) ₄ was collected. Next, 180.15 g of water and 23.64 g of citric acid were added to the reaction vessel, and the inside of the reaction vessel was continuously heated at 100 ° C. for 2 hours to carry out hydrolysis and condensation reactions. Thereafter, the reaction solution was returned to room temperature, 400 mL of hexane and 200 mL of water were added to the reaction vessel, and after performing a liquid separation operation, the aqueous layer was removed. Next, the organic layer was washed twice with 250 mL of water. Thereafter, the organic layer was washed with 100 mL of toluene and 200 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure using an evaporator. Silicone resin (IV) was obtained as a colorless viscous liquid.

The yield of the silicone resin (IV) is 255.88 g, the mass average molecular weight (Mw) is 3451, and the composition ratio is (Me ₂ SiO _2/2 ) _0.67 (SiO _4/2 ) _0.33 . The HO—Si group content was 3.11 mmol / g.

[Raw Material Synthesis Example 4-2] Synthesis of Silicone Resin (A4)
104.40 g of silicone resin (IV), 313.19 g of toluene, 104.40 g of methanol, 21.80 g of 1,1,3,3-tetramethyldisiloxane and 0.52 mL of 70% concentrated nitric acid in the flask In addition, the mixture was stirred at 40 ° C. After 2 hours, the reaction solution was transferred to a separatory funnel, 313 mL of water was added, extraction operation was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After evaporating toluene from the organic layer with an evaporator, the volatile component was distilled off under reduced pressure at 100 ° C. and 3.6 Pa in a short process distillation apparatus to obtain a silicone resin (A4) as a colorless transparent viscous liquid.

The yield of the silicone resin (A4) is 66.47 g, the mass average molecular weight (Mw) is 4230, the viscosity is 567 cP, and the composition ratio is (H-SiMe ₂ O _1/2 ) _0.13 (Me ₂ SiO _2/2 ) _0.54 (SiO _4/2 ) _0.33 , the H—Si group content is 2.0 mmol / g, and the HO—Si group content is 0.74 mmol / g. there were.

[Raw Material Synthesis Example 4-3] Synthesis of Silicone Resin (B4)
104.69 g of silicone resin (IV), 314.08 g of toluene, 104.69 g of methanol, 30.35 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 10.44 mL of 70 % Concentrated nitric acid was added to the flask and stirred at 40 ° C. Two hours later, the reaction solution was transferred to a separatory funnel, 314 mL of water was added, and extraction was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After distilling off toluene from the organic layer with an evaporator, 64.3 mg of 200 ppm platinum toluene solution was added, and the volatile components were distilled off under reduced pressure at 100 ° C. and 4.1 Pa in a short process distillation apparatus. As a result, a silicone resin (B4) was obtained.

The yield of the silicone resin (B4) is 58.04 g, the mass average molecular weight (Mw) is 4008, the viscosity is 1751 cP, and the composition ratio is (Vi-SiMe ₂ O _1/2 ) _0.15 (Me ₂ SiO _2/2 ) _0.52 (SiO _4/2 ) _0.33 , Vi—Si group content is 1.8 mmol / g, and HO—Si group content is 0.63 mmol / g. there were.

[Raw Material Synthesis Example 5-1] Synthesis of Silicone Resin (V)
In a glass reaction vessel having a volume of 2 L equipped with a stirrer made of fluororesin and a Dimroth type reflux vessel, 601.00 g (5.00 mol) of Me ₂ Si (OMe) ₂ , 520.75 g (2.50 mol) of Si ( OEt) ₄ was collected. Next, 360.30 g of water and 47.28 g of citric acid were added to the reaction vessel, and the inside of the reaction vessel was continuously heated at 100 ° C. for 6 hours to carry out hydrolysis and condensation reactions. Thereafter, the reaction solution was returned to room temperature, and only the aqueous layer was removed. 400 mL of toluene, 400 mL of hexane, and 250 mL of water were added to the reaction vessel in which the organic layer remained, and after performing a liquid separation operation, the aqueous layer was removed. Next, the organic layer was washed three times with 250 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure using an evaporator. Silicone resin (V) was obtained as a colorless viscous liquid.

The yield of the silicone resin (V) is 431.43 g, the mass average molecular weight (Mw) is 6689, and the composition ratio is (Me ₂ SiO _2/2 ) _0.68 (SiO _4/2 ) _0.32 . The HO—Si group content was 2.40 mmol / g.

[Raw Material Synthesis Example 5-2] Synthesis of Silicone Resin (A5)
95.61 g of silicone resin (V), 286.83 g of toluene, 95.61 g of methanol, 15.41 g of 1,1,3,3-tetramethyldisiloxane and 0.37 mL of 70% concentrated nitric acid in the flask In addition, the mixture was stirred at 40 ° C. After 2 hours, the reaction solution was transferred to a separatory funnel, 287 mL of water was added, and after extraction, the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After toluene was distilled off from the organic layer by an evaporator, the volatile component was distilled off under reduced pressure at 100 ° C. and 3.4 Pa in a short process distillation apparatus to obtain a silicone resin (A5) as a colorless transparent viscous liquid.

The yield of the silicone resin (A5) is 52.15 g, the mass average molecular weight (Mw) is 7262, the viscosity is 5526 cP, and the composition ratio is (H-SiMe ₂ O _1/2 ) _0.11 (Me ₂ SiO _2/2 ) _0.58 (SiO _4/2 ) _0.31 , the H—Si group content is 1.5 mmol / g, and the HO—Si group content is 0.60 mmol / g. there were.

[Raw Material Synthesis Example 5-3] Synthesis of Silicone Resin (B5)
95.81 g of silicone resin (V), 287.43 g of toluene, 95.81 g of methanol, 21.43 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 7.37 mL of 70 % Concentrated nitric acid was added to the flask and stirred at 40 ° C. After 2 hours, the reaction solution was transferred to a separatory funnel, 287 mL of water was added, and after extraction, the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After evaporating toluene from the organic layer with an evaporator, 55.7 mg of a 200 ppm platinum toluene solution was added, and the volatile components were distilled off under reduced pressure at 100 ° C. and 2.7 Pa in a short process distillation apparatus to obtain a colorless transparent viscous liquid. As a result, a silicone resin (B5) was obtained.

The yield of the silicone resin (B5) is 49.78 g, the mass average molecular weight (Mw) is 6579, the viscosity is 11000 cP, and the composition ratio is (Vi-SiMe ₂ O _1/2 ) _0.11 (Me ₂ SiO _2/2 ) _0.59 (SiO _4/2 ) _0.30 , Vi—Si group content is 1.3 mmol / g, and HO—Si group content is 0.67 mmol / g. there were.

[Raw Material Synthesis Example 6-1] Synthesis of Silicone Resin (A6)
In a 500 mL glass reaction vessel equipped with a stirrer made of fluororesin and a Dimroth type reflux vessel, 60.10 g (0.50 mol) Me ₂ Si (OMe) ₂ , 104.15 g (0.50 mol) Si ( OEt) ₄ was collected. Next, 54.05 g of water and 0.071 g of citric acid were added to the reaction vessel, and the inside of the reaction vessel was continuously heated at 40 ° C. to perform hydrolysis and condensation reactions. After the reaction for 4 hours, 36.05 g (0.27 mol) of 1,1,3,3-tetramethyldisiloxane and 0.043 mL of 70% concentrated nitric acid were added into the flask while maintaining stirring at 40 ° C. . Twenty hours after the addition of nitric acid, the reaction solution was transferred to a separatory funnel, and 400 mL of ethyl acetate and 200 mL of water were added to perform a liquid separation operation, and then the organic layer was recovered. The operation of washing the organic layer with 200 mL of water was repeated three times. After evaporation of ethyl acetate from the organic layer with an evaporator, the volatile components were distilled off under reduced pressure at 100 ° C. and 3.4 Pa in a short process distillation apparatus. Silicone resin (A6) was obtained as a transparent viscous liquid.

The yield of the silicone resin (A6) is 31.96 g, the mass average molecular weight (Mw) is 3755, the viscosity is 3900 cP, and the composition ratio is (H-SiMe ₂ O _1/2 ) _0.30 (Me ₂ ). SiO _2/2 ) _0.28 (SiO _4/2 ) _0.42 , H—Si group content is 4.3 mmol / g, and HO—Si group content is 1.82 mmol / g. there were.

[Raw Material Synthesis Example 6-2] Synthesis of Silicone Resin (B6)
In a 500 mL glass reaction vessel equipped with a stirrer made of fluororesin and a Dimroth type reflux vessel, 60.10 g (0.50 mol) Me ₂ Si (OMe) ₂ , 104.15 g (0.50 mol) Si ( OEt) ₄ was collected. Next, 54.05 g of water and 0.071 g of citric acid were added to the reaction vessel, and the inside of the reaction vessel was continuously heated at 40 ° C. to perform hydrolysis and condensation reactions. After reacting for 4 hours, while maintaining stirring at 40 ° C., 50.03 g (0.27 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 0.86 mL of 70% concentrated nitric acid Was added to the flask. Twenty hours after the addition of nitric acid, the reaction solution was transferred to a separatory funnel, and 400 mL of ethyl acetate and 200 mL of water were added to perform a liquid separation operation, and then the organic layer was recovered. The operation of washing the organic layer with 200 mL of water was repeated three times. After evaporation of ethyl acetate from the organic layer with an evaporator, the volatile components were distilled off under reduced pressure at 100 ° C. and 3.4 Pa in a short process distillation apparatus. Silicone resin (B6) was obtained as a transparent viscous liquid.

The yield of the silicone resin (B6) is 53.96 g, the mass average molecular weight (Mw) is 3343, the viscosity is 3900 cP, and the composition ratio is (H-SiMe ₂ O _1/2 ) _0.35 (Me ₂ SiO _2/2 ) _0.27 (SiO _4/2 ) _0.38 , Vi—Si group content is 3.9 mmol / g, and HO—Si group content is 1.26 mmol / g. there were.

[Comparative Synthesis Example 1-1] Synthesis of silicone resin (PI)
96.16 g (0.8 mol) of Me ₂ Si (OMe) ₂ and 158.64 g (0.8 mol) of PhSi (into a ₂ L glass reaction vessel equipped with a fluororesin stirring blade and a Dimroth type reflux vessel In addition to OMe) ₃ , another 52.08 g (0.25 mol) of Si (OEt) ₄ was collected. Next, 180.15 g of water and 0.12 g of acetic acid were added to the flask, and the inside of the flask was continuously heated at 100 ° C. for 6 hours to perform hydrolysis and condensation reactions. Thereafter, the reaction solution was returned to room temperature, transferred to a 2 L separatory funnel, 400 mL of toluene and 400 mL of water were added, and after performing a liquid separation operation, the aqueous layer was removed. Next, the organic layer was washed twice with 400 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure using an evaporator to obtain a silicone resin (PI) as a colorless viscous liquid.

The yield of the silicone resin (PI) is 288.82 g, the mass average molecular weight (Mw) is 1200, and the composition ratio is (Me ₂ SiO _2/2 ) _0.36 (PhSiO _3/2 ) _0.48 (SiO _4/2 ) _0.16 , and the content of the HO-Si group was 8.4 mmol / g.

Comparative Synthesis Example 1-2 Synthesis of Silicone Resin (PA1) 179.22 g of silicone resin (PI), 537.66 g of toluene, 179.22 g of methanol, 35.30 g of 1,1,3,3-tetra Methyldisiloxane and 0.84 mL of 70% concentrated nitric acid were added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 540 g of water was added, and an extraction operation was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After evaporating toluene from the organic layer with an evaporator, vacuum distillation was performed by heating at 150 ° C. for 1 hour, and then vacuum distillation by heating at 170 ° C. for 1 hour was performed twice to obtain a colorless transparent viscous liquid. A silicone resin (PA1) was obtained.

The yield of the silicone resin (PA1) is 159.76 g, the mass average molecular weight (Mw) is 2400, the viscosity is less than 200 cP, and the composition ratio is (H-SiMe ₂ O _1/2 ) _0.23 (Me ₂ SiO _2/2 ) _0.14 (PhSiO _3/2 ) _0.52 (SiO _4/2 ) _0.11 and the content of H—Si group is 2.1 mmol / g, and HO—Si group The content of was 3.2 mmol / g.

Comparative Synthesis Example 1-3 Synthesis of Silicone Resin (PB1) 89.61 g Silicone Resin (PI), 268.83 g Toluene, 89.61 g Methanol, 24.56 g 1,3-Divinyl-1,1 3,3-tetramethyldisiloxane and 24.50 mL of 70% concentrated nitric acid were added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 270 g of water was added, and an extraction operation was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After evaporating toluene from the organic layer with an evaporator, vacuum distillation was performed by heating at 150 ° C. for 1 hour, and then vacuum distillation by heating at 170 ° C. for 1 hour was performed twice to obtain a colorless transparent viscous liquid. A silicone resin (PB1) was obtained.

The yield of the silicone resin (PB1) is 92.52 g, the mass average molecular weight (Mw) is 1700, the viscosity is less than 11000 cP, and the composition ratio is (Vi-SiMe ₂ O _1/2 ) _0.22 (Me ₂ SiO _2/2 ) _0.21 (PhSiO _3/2 ) _0.44 (SiO _4/2 ) _0.13 , Vi—Si group content is 2.0 mmol / g, and HO—Si group The content of was 2.1 mmol / g.

[Comparative Synthesis Example 2-1] Synthesis of Silicone Resin (PII)
961.6 g (8.0 mol) Me ₂ Si (OMe) ₂ , 1586.4 g (8.0 mol) PhSi (in a 10 L glass reaction vessel equipped with a fluororesin stirring blade and a Dimroth type reflux vessel) OMe) ₃ was collected. Subsequently, 1440 g of water and 0.96 g of acetic acid were added to the reaction vessel, and the inside of the reaction vessel was continuously heated at 75 ° C. for 6 hours to perform hydrolysis and condensation reactions. Thereafter, the reaction solution was returned to room temperature, and only the aqueous layer was removed. To the reaction vessel in which the organic layer remained, 3520 g of toluene and 1440 g of water were added, and after performing a liquid separation operation, the aqueous layer was removed. Next, the organic layer was washed four times with 1440 g of water. Thereafter, the organic layer was collected, and toluene was distilled off under reduced pressure with an evaporator to obtain a silicone resin (PII) as a colorless viscous liquid.

The yield of the silicone resin (PII) is 1388.0 g, the mass average molecular weight (Mw) is 900, and the composition ratio is (Me ₂ SiO _2/2 ) _0.49 (PhSiO _3/2 ) _0.51 . The HO—Si group content was 7.2 mmol / g.

Comparative Synthesis Example 2-2 Synthesis of Silicone Resin (PA2) 39.70 g of Silicone Resin (PII), 119.00 g of Toluene, 39.70 g of Methanol, 8.30 g of 1,1,3,3-Tetra Methyldisiloxane and 0.20 mL of 70% concentrated nitric acid were added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 119 g of water was added, and extraction operation was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After evaporating toluene from the organic layer with an evaporator, vacuum distillation was performed by heating at 150 ° C. for 1 hour, and then vacuum distillation by heating at 170 ° C. for 1 hour was performed twice to obtain a colorless transparent viscous liquid. A silicone resin (PA2) was obtained.

The yield of the silicone resin (PA2) is 42.50, the mass average molecular weight (Mw) is 1900, the viscosity is 200 cP, and the composition ratio is (H-SiMe ₂ O _1/2 ) _0.27 (Me ₂ ). SiO _2/2 ) _0.31 (PhSiO _3/2 ) _0.42 , the H—Si group content is 2.8 mmol / g, and the HO—Si group content is 2.0 mmol / g. there were.

Comparative Synthesis Example 2-3 Synthesis of Silicone Resin (PB2) 19.90 g of silicone resin (PII), 59.70 g of toluene, 19.90 g of methanol, 5.76 g of 1,3-divinyl-1,1 , 3,3-tetramethyldisiloxane and 1.98 mL of 70% concentrated nitric acid were added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 59.70 g of water was added and extraction was performed, and then the organic layer was recovered. The organic layer was washed by repeating the same operation four times. After evaporating toluene from the organic layer with an evaporator, vacuum distillation was performed by heating at 150 ° C. for 1 hour, and then vacuum distillation by heating at 170 ° C. for 1 hour was performed twice to obtain a colorless transparent viscous liquid. A silicone resin (PB2) was obtained.

The yield of the silicone resin (PB2) is 20.6 g, the mass average molecular weight (Mw) is 1800, the viscosity is 350 cP, and the composition ratio is (Vi-SiMe ₂ O _1/2 ) _0.23 (Me ₂ SiO _2/2 ) _0.32 (PhSiO _3/2 ) _0.45 , Vi—Si group content is 2.3 mmol / g, and HO—Si group content is 2.1 mmol / g. there were.

  Synthesized silicone resins (A1), (B1), (A2), (B2), (A3), (B3), (A4), (B4), (A5), (B5), (A6), (B6) ), (PA1), (PB1), (PA2), (PB2), composition ratio and physical properties (content of HO-Si group, content of H-Si group or Vi-Si group, mass average molecular weight) , Viscosity, refractive index, transparency) are shown in Table 2. Vi in Table 2 represents a vinyl group (CH2 = CH-group).

  As shown in Table 2, the silicone resins (A1) to (A6) and the silicone resins (B1) to (B6) obtained in the raw material synthesis examples are all silicone resins (PA1) obtained in the comparative synthesis examples. , (PA2), (PB1) and (PB2) also showed high transparency.

3. Preparation of curable silicone resin composition In Examples 1-2 and Comparative Examples 1-3 described later,
One type selected from the group consisting of silicone resins (A1), (A2), (A3), (A4), (A5), (A6), (PA1) and (PA2) is the component (A),
One type selected from the group consisting of silicone resins (B1), (B2), (B3), (B4), (B5), (B6), (PB1) and (PB2) is the component (B),
The (A) component of (A1) to (A5) and the (B) component of (B1) to (B5) were blended so that the mass of the (A) component: the mass of the (B) component = 1: 1. . About (A6) and (B6), it mix | blended so that it might become the mass of (A6) component: mass of (B6) component = 1.5: 1. Furthermore, it mixed with the platinum catalyst as (C) component, and prepared the compositions 1-6.

  On the other hand, the (A) component of (PA1) and (PA2) and the (B) component of (PB1) and (PB2) are set so that the mass of the (A) component: the mass of the (B) component = 2: 1. Furthermore, it mix | blended and mixed with the platinum catalyst as (C) component, and the composition 6 and the composition 7 were prepared.

Here, as the platinum catalyst, a platinum-divinyltetramethyldisiloxane complex was used so that the content of platinum atoms was 0.03 ppm in mass units with respect to the total amount of the composition.
Each composition of the prepared compositions 1-8 is shown in Table 3.

4). Method for evaluating physical properties of composition and cured product thereof Viscosity of prepared composition, HO-Si group content, physical properties of cured product obtained from the composition (hardness, adhesion, transparency, coefficient of linear thermal expansion, adhesion Strength), appearance at the time of curing, and punching moldability were measured as follows.

[Viscosity of composition]
The viscosity of the prepared composition was determined according to “Viscosity measurement method using a cone-plate type rotational viscometer” in JIS Z8803 (2011) (product name: PHYSICA MCR51, manufactured by ANTON PAAR, measurement range: 200 to 1,000, 000 cP) and a temperature control unit (manufactured by ANTON PAAR, product name: P-PTD200), measured at a shear rate of 30 [1 / s] at a temperature of 25 ° C., and the value obtained 1 minute after the start of the measurement Adopted. In the case of a low-viscosity liquid less than the measurement range, “<200” was indicated.

[HO-Si group content of composition]
The HO—Si group content of the prepared composition was calculated from the following formula [8]:
[HO-Si group content of composition] = {(HO-Si group content of component (A)) × 2 + (HO-Si group content of component (B)) / 2/2 [8]

[Hardness of cured product]
The prepared composition was poured into a mold (90 mm × 90 mm × 2 mm), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to prepare a plate-like cured product having a thickness of 2 mm. A test piece having a thickness of 6 mm or more was produced by stacking the cured products. The hardness of Shore A or Shore D of this test piece is determined according to JIS K 7215 “Plastic Durometer Hardness Test Method” using a durometer (manufactured by Tekok Co., Ltd., model: GS-719R, GS-720R). It was measured by. Example 6 is not described because it was not measured.

[Transparency of cured product]
The prepared composition was poured into a mold (90 mm × 90 mm × 2 mm), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to prepare a plate-like cured product having a thickness of 2 mm. Using a UV-visible spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-3150), the transmittance of the plate-like cured product in the 405 nm, 365 nm, and 300 nm wavelength regions was measured. Furthermore, visual observation was also performed and it was determined that the coloring was observed as “x”, and the coloring was not observed as “◯”.

[Heat resistant transparency of cured products]
The prepared composition was poured into a mold (90 mm × 90 mm × 2 mm), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to prepare a plate-like cured product having a thickness of 2 mm. The plate-like cured product was heated at 200 ° C. for 100 hours, and then the transmittance in a wavelength region of 405 nm, 365 nm, and 300 nm was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-3150). . Furthermore, visual observation was also performed and it was determined that the coloring was observed as “x”, and the coloring was not observed as “◯”. Example 6 is not described because it was not measured.

[Linear thermal expansion coefficient of cured product]
0.7 g of the prepared composition is added to a fluororesin tube (inner diameter: 5.8 mmφ, height: 1.8 mm), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to obtain a cured product. Was made. Using ThermoPlusTMA8310 (manufactured by Rigaku Corporation), the cured product was heated in air from 25 ° C. to 200 ° C. at a temperature rising rate of 5 ° C./min, and the linear thermal expansion coefficient was measured. This measurement was performed twice, and the second measured value was adopted. Example 6 is not described because it was not measured.

[Hardened adhesive strength]
A mixture of the prepared composition and zirconia balls having a diameter of 50 μm is placed between a glass chip (5.0 mm × 5.0 mm × 1.1 mm) and a glass substrate (50 mm × 50 mm × 3.0 mm). In the sandwiched state, it was heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to be cured. The adhesive strength (adhesive strength) of the prepared sample was measured with a bond tester (manufactured by Daisy Japan Co., Ltd., model: Dage4000Plus). When the strength of the cured product was weak and the cured product was destroyed at the time of measurement and an adhesive strength value could not be obtained, it was indicated as “cohesive failure”. Example 6 is not described because it was not measured.

[Appearance of cured product]
1 g of the prepared composition was spread on a glass mold (22 mmφ), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to prepare a cured product having a thickness of 22 mmφ and 2 mm. Three test bodies were prepared, and the appearance of the test bodies was visually confirmed. In all the test bodies, a state in which generation of bubbles and cracks in the cured product was not observed was defined as “good”. In other cases, it was determined as “bad”.

[Punching formability test]
The prepared composition was poured into a mold (90 mm × 90 mm × 2 mm), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to produce a plate-like cured product. This plate-like cured product was punched into a dumbbell shape No. 8 according to JIS K 6251. What was punched and formed without cracking or resin chipping when the cured product was punched was evaluated as “good”. In other cases, it was determined as “bad”.

[Long-term heat-resistant transparency test of cured products]
The prepared composition was poured into a mold (9 mm × 9 mm × 2 mm), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to prepare a plate-like cured product having a thickness of 2 mm. After heating this plate-shaped cured product at 200 ° C. for 100 hours, 200 hours, 500 hours, and 1000 hours, using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-3150) at a wavelength of 365 nm The transmittance was measured. Measurements were made on the cured product obtained from the composition 5 (Example 5) and the cured product obtained from the composition 7 (Comparative Example 1).

5. Examples and Comparative Examples [Examples 1-6, Comparative Examples 1-2]
Using the prepared compositions 1 to 6, the above-described physical property evaluation tests were performed (Examples 1 to 6). Similarly, the above-described physical property evaluation test was performed using the prepared Composition 7 and Composition 8 (Comparative Example 1 and Comparative Example 2). These results are shown in Table 3, Table 4, and FIG. In addition, "-" in a table | surface shows unmeasured.

  As shown in Table 3, the compositions 1 to 6 prepared in Examples 1 to 6 were higher in transparency and higher than the compositions 7 and 8 prepared in Comparative Examples 1 and 2. It has heat-resistant transparency. Furthermore, the obtained cured product shows a good appearance and punchability. Further, the compositions 1 to 5 prepared in Examples 1 to 5 have the same or higher Shore hardness and adhesive strength as compared with the compositions 7 and 8 prepared in Comparative Examples 1 and 2. Have physical properties.

  Moreover, as shown in Table 4, the composition 5 prepared in Example 5 has higher transparency when exposed to a high temperature for a long time as compared with the composition 7 prepared in Comparative Example 1.

  From the above, it is shown that the compositions 1 to 6 prepared in Examples 1 to 6 within the scope of the present invention have extremely high transparency and heat-resistant transparency and good physical properties in other physical properties. It was done.

DESCRIPTION OF SYMBOLS 1 ... Sealing material, 2 ... Semiconductor element, 3 ... Bonding wire, 4 ... Reflective material, 5 ... Lead frame, 6 ... Semiconductor substrate, 10 ... Semiconductor device.

Claims (21)

A curable silicone resin composition comprising at least the following component (A), component (B) and component (C).
(A) Component: Silicone resin represented by the following formula [1]
(B) component: silicone resin represented by the following formula [2],
Component (C): Hydrosilylation catalyst.
(In the formula [1], Me represents a methyl group, a, b and c are each greater than 0 and less than 1, satisfying a + b + c = 1, (H-SiMe ₂ O _1/2 ), (Me The oxygen atoms in the structural units represented by ₂ SiO _2/2 ) and (SiO _4/2 ) each represent an oxygen atom forming a siloxane bond or an oxygen atom forming a silanol group.
In the formula [2], R ¹ represents a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms, Me represents a methyl group, d, e, and f are each greater than 0 and less than 1, d + e + f = 1 and oxygen atoms in structural units represented by (R ¹ -SiMe ₂ O _1/2 ), (Me ₂ SiO _2/2 ) and (SiO _4/2 ) each form a siloxane bond. An oxygen atom forming a silanol group or an oxygen atom forming a silanol group. ) The curable silicone resin composition according to claim 1, wherein R ¹ in formula [2] is a vinyl group. The value of a of component (A) is 0.05 to 0.50, the value of b is 0.10 to 0.95, and the value of c is 0.01 to 0.95. Item 3. The composition according to Item 1 or 2. The value of d of component (B) is 0.05 to 0.50, the value of e is 0.10 to 0.95, and the value of f is 0.01 to 0.95. Item 4. The composition according to any one of Items 1 to 3. (A) The composition as described in any one of Claims 1 thru | or 4 whose mass average molecular weights of a component are 500-100,000. (B) The composition as described in any one of Claims 1 thru | or 5 whose mass mean molecular weights of a component are 500-100,000. [Mole number of H—Si group contained in component (A)] / [mole number of R ¹ —Si group contained in component (B)] is 1 to 4. A composition according to claim 1.   Cure retarder, antioxidant, light stabilizer, adhesion promoter, phosphor, inorganic particles, release agent, resin modifier, colorant, diluent, antibacterial agent, antifungal agent, leveling agent and anti-sagging agent The composition according to any one of claims 1 to 7, further comprising at least one selected from the group consisting of: A method for producing a curable silicone resin composition, comprising at least the following steps (1) to (4).
Step (1): A dimethyl dialkoxysilane compound represented by the general formula [3] and a tetraalkoxysilane compound represented by the general formula [4] are hydrolyzed and polycondensed to obtain a hydrolyzed polycondensate. Process.
Step (2): The hydrolysis polycondensate is reacted with a hydrosilane compound represented by the following general formula [5-1], [5-2], or [5-3], and component (A) As a process of obtaining a silicone resin.
Step (3): The hydrolysis polycondensate is reacted with a silane compound represented by the following general formula [8-1], [8-2], or [8-3] to obtain a component (B) As a process of obtaining a silicone resin.
Step (4): A step of blending the obtained component (A) and component (B) with the hydrosilylation catalyst as component (C).
(In General Formula [3], R ² is each independently an alkyl group having 1 to 3 carbon atoms. In General Formula [4], R ³ is each independently an alkyl group having 1 to 3 carbon atoms. In the general formula [5-2], each R ⁴ is independently an alkyl group having 1 to 3 carbon atoms, and in the general formula [8-1], R ⁷ is a monovalent having 2 to 6 carbon atoms. In the general formula [8-2], R ⁸ is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms, and R ⁹ is an alkyl group having 1 to 3 carbon atoms. In general formula [8-3], each R ¹⁰ independently represents a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms. The curable silicone resin according to claim 9, wherein the hydrolyzed polycondensate obtained in the step (1) is purified, and the purified hydrolyzed polycondensate is used in the step (2) or the step (3). A method for producing the composition. The manufacturing method of the manufacturing method of the curable silicone resin composition of Claim 10 which performs a process (2) or a process (3), without refine | purifying the hydrolysis polycondensate obtained at the said process (1). A method for producing a silicone resin, comprising at least the following first step and the following second step.
First step: A step of hydrolyzing and polycondensing a dimethyldialkoxysilane compound represented by the general formula [3] and a tetraalkoxysilane compound represented by the general formula [4] to obtain a hydrolyzed polycondensate. .
(In General Formula [3], R ² is each independently an alkyl group having 1 to 3 carbon atoms. In General Formula [4], R ³ is each independently an alkyl group having 1 to 3 carbon atoms. .)

Second step: A step of reacting the hydrolyzed polycondensate with a hydrosilane compound represented by the formula [5-1], [5-2], or [5-3] to obtain a silicone resin.
(In the general formula [5-2], each R ⁴ is independently an alkyl group having 1 to 3 carbon atoms.) The method for producing a silicone resin according to claim 12, wherein the hydrolyzed polycondensate obtained in the first step is purified, and the purified hydrolyzed polycondensate is used in the second step. The manufacturing method of the silicone resin of Claim 12 which performs a 2nd process, without refine | purifying the hydrolysis polycondensate obtained at said 1st process. A method for producing a silicone resin, comprising at least the following first step and the following second step.
First step: A step of hydrolyzing and polycondensing a dimethyldialkoxysilane compound represented by the general formula [3] and a tetraalkoxysilane compound represented by the general formula [4] to obtain a hydrolyzed polycondensate. .
(In General Formula [3], R ² is each independently an alkyl group having 1 to 3 carbon atoms. In General Formula [4], R ³ is each independently an alkyl group having 1 to 3 carbon atoms. .)

Second step: A step of reacting the hydrolyzed polycondensate with a silane compound represented by the general formula [8-1], [8-2], or [8-3] to obtain a silicone resin.
(In General Formula [8-1], R ⁷ is a monovalent unsaturated hydrocarbon group having 2 to 6 carbon atoms. In General Formula [8-2], R ⁸ has 2 to 6 carbon atoms. R ⁹ is a monovalent unsaturated hydrocarbon group, R ⁹ is an alkyl group having 1 to 3 carbon atoms, and in general formula [8-3], each R ¹⁰ is independently a monovalent having 2 to 6 carbon atoms. Of unsaturated hydrocarbon groups.) The method for producing a silicone resin according to claim 15, wherein the hydrolyzed polycondensate obtained in the first step is purified, and the purified hydrolyzed polycondensate is subjected to the second step. The manufacturing method of the silicone resin of Claim 15 which performs a 2nd process, without refine | purifying the hydrolysis polycondensate obtained at said 1st process.   Hardened | cured material formed by hardening | curing the composition as described in any one of Claims 1 thru | or 8.   The semiconductor device by which the semiconductor element was at least sealed with the hardened | cured material of Claim 18.   The adhesive for semiconductors which consists of a hardened | cured material of Claim 18.   A semiconductor device using the adhesive for optical semiconductors according to claim 20.