WO2016013421A1 - Curable silicone resin composition, cured object obtained therefrom, and optical semiconductor device formed using same - Google Patents

Abstract

This curable silicone resin composition is characterized by comprising component (A), which is a silicone resin containing hydrogen atoms each bonded to a silicon atom (SiH groups), component (B), which is a silicone resin containing vinyl groups each bonded to a silicon atom (Si-CH=CH₂ groups), and component (C), which is a platinum catalyst. The composition is further characterized in that the total content of silanol groups (Si-OH groups) in components (A) and (B) is 0.5-5.0 mmol/g and the content of platinum atoms in component (C) is 0.003-3.0 mass ppm of the sum of components (A), (B), and (C). A cured object obtained by heating the composition is suitable for use as the encapsulating material of an optical semiconductor device.

Description

Curable silicone resin composition, cured product thereof, and optical semiconductor device using the same

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

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

In general, the epoxy resin composition has excellent handling properties because of the high hardness of the cured product. For example, in a low output white LED sealing application, the required durability can be obtained. Many are used.

However, with the recent increase in brightness and output of LEDs, the cured products of conventional transparent epoxy resin compositions have power semiconductors and high-intensity light emitting elements (for example, the backlights of automobile headlights and LCD TVs). It is known that heat resistance is insufficient for use as a sealing material for short-wavelength semiconductor lasers such as high-intensity LEDs for light or blue lasers, and current leakage or yellowing due to high-temperature deterioration occurs. .

Recently, in order to solve these problems, a cured product of a resin composition based on a silicone resin having excellent heat resistance has been used as an LED sealing material 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 protecting and sealing an optical device or a semiconductor device. .

JP 2000-198930 A

Many addition-curable silicone resin compositions contain a platinum-based metal catalyst, particularly a platinum catalyst, as a curing catalyst. However, a silicone resin composition containing a platinum catalyst may turn yellow when exposed to a high temperature for a long time. As a result, a cured product of a silicone resin composition containing a platinum catalyst has a problem that transparency is impaired when exposed to a high temperature for a long time. With the recent development of high-brightness LEDs, a silicone resin that solves such problems and has sufficient transparency even when exposed to high temperatures for a long period of time, that is, a silicone resin that provides a cured product excellent in heat-resistant transparency Development of compositions is desired.

The present invention has been made in view of the above circumstances, and provides an addition-curable curable silicone resin composition that provides a cured product having excellent heat-resistant transparency, a cured product thereof, and an optical semiconductor device using these. With the goal.

（式中、Ｒ¹は炭素数１～３のアルキル基であり、２つのＲ¹は同じまたは互いに異なる種類であってもよく、Ｒ²は炭素数１～３のアルキル基であり、２つのＲ²は同じまたは互いに異なる種類であってもよく、Ｒ³は炭素数１～３のアルキル基または炭素数６～１０の芳香族炭化水素基であり、ａ、ｂおよびｃはそれぞれ０超、１未満の数であり、ｄは０以上、１未満の数であり、ａ＋ｂ＋ｃ＋ｄ＝１を満たし、(ＳｉＲ² ₂Ｏ_2/2)、(Ｒ³ＳｉＯ_3/2)および(ＳｉＯ_4/2)で表される構造単位における酸素原子はそれぞれ、シロキサン結合を形成している酸素原子、またはシラノール基を形成している酸素原子を示す。）

（式中、Ｒ⁴は炭素数１～３のアルキル基であり、２つのＲ⁴は同じまたは互いに異なる種類であってもよく、Ｒ⁵は炭素数１～３のアルキル基であり、２つのＲ⁵は同じまたは互いに異なる種類であってもよく、Ｒ⁶は炭素数１～３のアルキル基または炭素数６～１０の芳香族炭化水素基であり、ｅ、ｆおよびｇはそれぞれ０超、１未満の数であり、ｈは０以上、１未満の数であり、ｅ＋ｆ＋ｇ＋ｈ＝１を満たし、(ＳｉＲ⁵ ₂Ｏ_2/2)、(Ｒ⁶ＳｉＯ_3/2)および(ＳｉＯ_4/2)で表される構造単位における酸素原子はそれぞれ、シロキサン結合を形成している酸素原子、またはシラノール基を形成している酸素原子を示す。） As a result of intensive studies to achieve the above object, the present inventors have
(A) component: a silicone resin represented by the following formula [1] and containing a hydrogen atom (SiH group) bonded to a silicon atom;
Component (B): it is represented by the following formula [2], a silicone resin containing a vinyl group bonded to a silicon atom (Si-CH = CH ₂ groups), and component (C): wherein at least a platinum catalyst, (A The total content of silanol groups (Si—OH groups) in component (B) and component (B) is 0.5 to 5.0 mmol / g, and the content of platinum atoms in component (C) is (A) It has been found that the above-mentioned problem can be achieved by using a curable silicone resin composition having a mass unit of 0.003 to 3.0 ppm with respect to the total mass of the component, the component (B) and the component (C), It came to complete the addition-curable type curable silicone resin composition excellent in heat-resistant transparency.

(Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, two R ^{1 s} may be the same or different, and R ² is an alkyl group having 1 to 3 carbon atoms, R ² may be the same or different from each other, R ³ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a, b and c are each greater than 0, It is a number less than 1, d is a number greater than or equal to 0 and less than 1, satisfies a + b + c + d = 1, (SiR ² ₂ O _2/2 ), (R ³ SiO _3/2 ) and (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.)

(Wherein R ⁴ is an alkyl group having 1 to 3 carbon atoms, two R ⁴ may be the same or different from each other, and R ⁵ is an alkyl group having 1 to 3 carbon atoms, R ⁵ may be the same or different from each other, R ⁶ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and e, f and g are each greater than 0, Is a number less than 1, h is a number greater than or equal to 0 and less than 1, satisfies e + f + g + h = 1, (SiR ⁵ ₂ O _2/2 ), (R ⁶ SiO _3/2 ) and (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.)

That is, the present invention includes the following invention 1 to invention 15.

（式中、Ｒ¹は炭素数１～３のアルキル基であり、２つのＲ¹は同じまたは互いに異なる種類であってもよく、Ｒ²は炭素数１～３のアルキル基であり、２つのＲ²は同じまたは互いに異なる種類であってもよく、Ｒ³は炭素数１～３のアルキル基または炭素数６～１０の芳香族炭化水素基であり、ａ、ｂおよびｃはそれぞれ０超、１未満の数であり、ｄは０以上、１未満の数であり、ａ＋ｂ＋ｃ＋ｄ＝１を満たし、(ＳｉＲ² ₂Ｏ_2/2)、(Ｒ³ＳｉＯ_3/2)および(ＳｉＯ_4/2)で表される構造単位における酸素原子はそれぞれ、シロキサン結合を形成している酸素原子、またはシラノール基を形成している酸素原子を示す。）

（式中、Ｒ⁴は炭素数１～３のアルキル基であり、２つのＲ⁴は同じまたは互いに異なる種類であってもよく、Ｒ⁵は炭素数１～３のアルキル基であり、２つのＲ⁵は同じまたは互いに異なる種類であってもよく、Ｒ⁶は炭素数１～３のアルキル基または炭素数６～１０の芳香族炭化水素基であり、ｅ、ｆおよびｇは、それぞれ０超、１未満の数であり、ｈは０以上、１未満の数であり、ｅ＋ｆ＋ｇ＋ｈ＝１を満たし、(ＳｉＲ⁵ ₂Ｏ_2/2)、(Ｒ⁶ＳｉＯ_3/2)および(ＳｉＯ_4/2)で表される構造単位における酸素原子はそれぞれ、シロキサン結合を形成している酸素原子、またはシラノール基を形成している酸素原子を示す。） [Invention 1]
(A) component: a silicone resin represented by the following formula [1] and containing a hydrogen atom (SiH group) bonded to a silicon atom;
(B) component: a silicone resin represented by the following formula [2] and containing a vinyl group (Si—CH═CH ₂ group) bonded to a silicon atom, and (C) component: at least a platinum catalyst, The total content of silanol groups (Si—OH groups) in component (B) and component (B) is 0.5 to 5.0 mmol / g, and the content of platinum atoms in component (C) is (A) A curable silicone resin composition having a mass unit of 0.003 to 3.0 ppm based on the total mass of the component, the component (B), and the component (C).

(Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, two R ^{1 s} may be the same or different, and R ² is an alkyl group having 1 to 3 carbon atoms, R ² may be the same or different from each other, R ³ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a, b and c are each greater than 0, It is a number less than 1, d is a number greater than or equal to 0 and less than 1, satisfies a + b + c + d = 1, (SiR ² ₂ O _2/2 ), (R ³ SiO _3/2 ) and (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.)

(Wherein R ⁴ is an alkyl group having 1 to 3 carbon atoms, two R ⁴ may be the same or different from each other, and R ⁵ is an alkyl group having 1 to 3 carbon atoms, R ⁵ may be the same or different from each other, R ⁶ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and e, f and g are each greater than 0 Is a number less than 1, h is a number greater than or equal to 0 and less than 1, and satisfies e + f + g + h = 1, and (SiR ⁵ ₂ O _2/2 ), (R ⁶ SiO _3/2 ) and (SiO _4/2 ) Represents an oxygen atom forming a siloxane bond or an oxygen atom forming a silanol group.

[Invention 2]
(A) Number of moles of hydrogen atoms bonded to silicon atoms in component: (B) Number of moles of vinyl groups bonded to silicon atoms in component is 0.8: 0.2 to 0.5: 0.5 A curable silicone resin composition according to Invention 1.

[Invention 3]
In the component (A), a, b, c and d are a: b: c: d = 0.10 to 0.40: 0.10 to 0.80: 0.10 to 0.80: 0 to 0 In the component (B), e, f, g and h are e: f: g: h = 0.10 to 0.40: 0.10 to 0.80: 0.10 to 0. The curable silicone resin composition of Invention 1 or 2, which is 80: 0 to 0.70.

[Invention 4]
In the component (A), a, b, c and d are a: b: c: d = 0.20 to 0.40: 0.10 to 0.40: 0.30 to 0.60: 0.10 In the component (B), e, f, g, and h are e: f: g: h = 0.20 to 0.40: 0.10 to 0.40: 0.30 to 0.60: The curable silicone resin composition according to any one of Inventions 1 to 3, which is 0.10 to 0.30.

[Invention 5]
In component (A), d = 0, and a, b, and c are a: b: c = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80 In component (B), h = 0, and e, f, and g are e: f: g = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80. A curable silicone resin composition of invention 1 or 2.

[Invention 6]
The curable silicone resin composition according to any one of Inventions 1 to 5, further comprising a curing retarder.

[Invention 7]
The curable silicone resin composition according to any one of Inventions 1 to 6, further comprising an antioxidant or a light stabilizer.

[Invention 8]
The curable silicone resin composition according to any one of Inventions 1 to 7, further comprising one or more selected from the group consisting of an adhesion-imparting agent, a phosphor and inorganic particles.

[Invention 9]
Curing according to any one of inventions 1 to 8, further comprising at least one selected from the group consisting of a mold release agent, a resin modifier, a colorant, a diluent, an antibacterial agent, an antifungal agent, a leveling agent, and an anti-sagging agent. Silicone resin composition.

[Invention 10]
A cured product obtained by curing the curable silicone resin composition according to any one of Inventions 1 to 9.

[Invention 11]
A sealing material comprising a cured product of the curable silicone resin composition according to any one of inventions 1 to 9.

[Invention 12]
A method for producing a cured product of a curable silicone resin composition, wherein the curable silicone resin composition according to any one of Inventions 1 to 9 is heated and cured at 45 ° C or higher and 300 ° C or lower.

[Invention 13]
An optical semiconductor device in which an optical semiconductor element is at least sealed with a cured product of the curable silicone resin composition according to any one of Inventions 1 to 9.

[Invention 14]
The adhesive for semiconductors which consists of a hardened | cured material of any one of invention 1 thru | or 9 curable silicone resin composition.

[Invention 15]
An optical semiconductor device using the semiconductor adhesive of invention 14.

In the present specification, specific examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The aromatic hydrocarbon group having 6 to 10 carbon atoms may be a substituted or unsubstituted aromatic hydrocarbon group, and some or all of the hydrogen atoms may be substituted with fluorine atoms. Specific examples include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, and a 3,5-di (trifluoromethylphenyl) group.

According to the present invention, it is possible to provide a curable silicone resin composition that gives a cured product excellent in heat-resistant transparency, a cured product thereof, and an optical semiconductor device using these.

It is a schematic sectional drawing which shows an example of the optical semiconductor device of this invention. FIG. 2 is a graph showing the relationship between the shear viscosity and the temperature of compositions prepared in Examples and Comparative Examples (Composition 1-1 to Composition 1-5, Comparative Composition 1-1). FIG. 4 is a graph showing the relationship between the shear viscosity and the temperature of compositions prepared in Examples and Comparative Examples (Composition 4-1 to Composition 4-3, Comparative Composition 4-1). FIG. 3 is a graph showing the relationship between shear viscosity and time of compositions prepared in Examples (Composition 1-1, Composition 1-6 to Composition 1-9).

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

[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 a predetermined amount of the components (A) to (C), and the composition is heated. The cured product thus obtained is suitably used as a sealing material for optical semiconductor devices. Hereinafter, each component contained in the composition of this invention is demonstrated.

上記式［１］は平均組成式を表す。式［１］中、Ｒ¹は炭素数１～３のアルキル基であり、２つのＲ¹は同じまたは互いに異なる種類であってもよい。Ｒ²は炭素数１～３のアルキル基であり、２つのＲ²は同じまたは互いに異なる種類であってもよい。Ｒ³は炭素数１～３のアルキル基または炭素数６～１０の芳香族炭化水素基である。ａ、ｂおよびｃはそれぞれ０超、１未満の範囲内の数であり、ｄは０以上、１未満の範囲内の数であり、ａ＋ｂ＋ｃ＋ｄ＝１を満たす。(ＳｉＲ² ₂Ｏ_2/2)、(Ｒ³ＳｉＯ_3/2)および(ＳｉＯ_4/2)で表される構造単位における酸素原子はそれぞれ、シロキサン結合を形成している酸素原子、またはシラノール基を形成している酸素原子を示す。 <(A) component>
The component (A) is a silicone resin represented by the following formula [1] and containing a hydrogen atom (SiH group) bonded to a silicon atom. As the component (A), only one type may be used, or two or more types may be used in combination.

The above formula [1] represents an average composition formula. In the formula [1], R ¹ is an alkyl group having 1 to 3 carbon atoms, and two R ¹ may be the same or different from each other. R ² is an alkyl group having 1 to 3 carbon atoms, and the two R ² may be the same or different from each other. R ³ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. a, b and c are numbers in the range of more than 0 and less than 1, respectively, d is a number in the range of 0 to less than 1, and satisfies a + b + c + d = 1. The oxygen atom in the structural unit represented by (SiR ² ₂ O _2/2 ), (R ³ SiO _3/2 ) and (SiO _4/2 ) is an oxygen atom or silanol group forming a siloxane bond, respectively. The oxygen atom which forms is shown.

As the alkyl group having 1 to 3 carbon atoms in R ¹ , a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

As the alkyl group having 1 to 3 carbon atoms in R ² , a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

As the alkyl group having 1 to 3 carbon atoms in R ³ , a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The aromatic hydrocarbon group having 6 to 10 carbon atoms in R ³ is preferably a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or a 3,5-di (trifluoromethylphenyl) group. A phenyl group is particularly preferred.

The combination of R ¹ , R ² and R ³ is not particularly limited. Among them, R ¹ is a methyl group or an ethyl group, R ² is a methyl group or an ethyl group, R ³ is a methyl group, an ethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or 3, It is preferably any one of 5-di (trifluoromethylphenyl) groups, particularly preferably R ¹ is a methyl group, R ² is a methyl group, and R ³ is a phenyl group.

The value of a is in the range of more than 0 and less than 1, and is not particularly limited as long as a + b + c + d = 1 is satisfied. The value of a is preferably 0.05 to 0.40, particularly preferably 0.20 to 0.40. If the value of a is 0.05 or more, the composition of the present invention has good moldability, and if it is 0.40 or less, the cured product of the present invention has good mechanical strength.

The value of b is in the range of more than 0 and less than 1, and is not particularly limited as long as a + b + c + d = 1 is satisfied. The value of b is preferably 0.10 to 0.80, particularly preferably 0.10 to 0.40. If the value of b is 0.10 or more, the composition of the present invention has good moldability, and if it is 0.80 or less, the cured product of the present invention has good mechanical strength.

The value of c is in the range of more than 0 and less than 1, and is not particularly limited as long as a + b + c + d = 1 is satisfied. The value of c is preferably 0.10 to 0.80, particularly preferably 0.30 to 0.60. If the value of c is 0.10 or more, the cured product of the present invention has good mechanical strength, and if it is 0.80 or less, the composition of the present invention has good moldability.

The value of d is in the range of 0 or more and less than 1, and is not particularly limited as long as a + b + c + d = 1 is satisfied. The value of d is preferably 0 to 0.70. Among these, the value of d is particularly preferably 0.10 to 0.30 since the cured product of the present invention exhibits good adhesive strength and good hardness. When the value of d is 0, there is no structural unit of (SiO _4/2 ) in the above formula [1].

The values of a, b, c and d are a: b: c: d = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80: 0 to 0.70. It is particularly preferable that a: b: c: d = 0.20 to 0.40: 0.10 to 0.40: 0.30 to 0.60: 0.10 to 0.30.

When the value of d is 0, the values of a, b and c are a: b: c = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80 Is preferred.

The values of a, b, c and d should be calculated by measuring the ²⁹ Si-NMR spectrum and ¹ H-NMR spectrum of component (A) using a nuclear magnetic resonance apparatus and using these in a complementary combination. Can do.

上記式［１－２］中、Ｒ²は上記式［１］中のＲ²と同義であり、Ｘはヒドロキシ基を表す。 In the above formula [1], the structural unit represented by (SiR ² ₂ O _2/2 ) is a structure represented by the following formula [1-2], that is, represented by (SiR ² ₂ O _2/2 ). The structure unit may include a structure in which one of oxygen atoms bonded to a silicon atom forms a silanol group.

In the formula [1-2], R ² has the same meaning as R ² in the formula [1], X represents a hydroxy group.

上記式［１－ｂ］および［１－２－ｂ］中、Ｒ²は上記式［１］中のＲ²と同義である。上記式［１－２－ｂ］中、Ｘはヒドロキシ基を表す。 The structural unit represented by (SiR ² ₂ O _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-b], and further includes the following formula [1-2-b] The part enclosed with the broken line of the structural unit represented by may be included. That is, a structural unit having a group represented by R ² and having a hydroxy group remaining at the terminal to form a silanol group is also included in the structural unit represented by (SiR ² ₂ O _2/2 ). It is. In the structural units represented by the following formulas [1-b] and [1-2-b], the oxygen atom in the Si—O—Si bond forms a siloxane bond with an adjacent silicon atom, It 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-b] and [1-2-b], R ² has the same meaning as R ² in the formula [1]. In the above formula [1-2-b], X represents a hydroxy group.

上記式［１－３］および式［１－４］中、Ｒ³は上記式［１］中のＲ³と同義であり、Ｘはヒドロキシ基を表す。 The structural unit represented by (R ³ SiO _3/2 ) is a structure represented by the following formula [1-3] or [1-4], that is, a structure represented by (R ³ SiO _3/2 ). A structure in which two of the oxygen atoms bonded to the silicon atom in the unit each form a silanol group, or one of the oxygen atoms bonded to the silicon atom in the structural unit represented by (R ³ SiO _3/2 ) The structure which forms the silanol group may be included.

In the formula [1-3] and the formula [1-4], R ³ has the same meaning as R ³ in the formula [1], X represents a hydroxy group.

上記式［１－ｃ］、［１－３－ｃ］および［１－４－ｃ］中のＲ³は、上記式［１］中のＲ³と同義である。上記式［１－３－ｃ］および［１－４－ｃ］中、Ｘはヒドロキシ基を表す。 The structural unit represented by (R ³ SiO _3/2) includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-c], and further represented by the following formula [1-3-c] or A portion surrounded by a broken line of the structural unit represented by [1-4-c] may be included. That is, a structural unit having a group represented by R ³ and having a hydroxy group remaining at the terminal to form a silanol group is also included in the structural unit represented by (R ³ SiO _3/2 ). .

The formula [1-c], R ³ in [1-3-c] and [1-4-c] has the same meaning as R ³ in the formula [1]. In the above formulas [1-3-c] and [1-4-c], X represents a hydroxy group.

上記式［１－５］、［１－６］および［１－７］中、Ｘはヒドロキシ基を表す。 In the above formula [1], the structural unit represented by (SiO _4/2 ) is a structure represented by the following formula [1-5], [1-6] or [1-7], that is, (SiO _4/2 ) a structure in which three or two oxygen atoms bonded to a silicon atom in the structural unit represented by each form a silanol group, or in a structural unit represented by (SiO _4/2 ) A structure in which one of oxygen atoms bonded to a silicon atom forms a silanol group may be included.

In the above formulas [1-5], [1-6] and [1-7], X represents a hydroxy group.

上記式［１－５－ｄ］、［１－６－ｄ］および［１－７－ｄ］中、Ｘはヒドロキシ基を表す。 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-d], and further includes the following formulas [1-5-d], [1 A portion surrounded by a broken line of the structural unit represented by −6−d] or [1-7-d] may be included. That is, a structural unit in which a hydroxy group remains at the terminal to form a silanol group is also included in the structural unit represented by (SiO _4/2 ).

In the above formulas [1-5-d], [1-6-d] and [1-7-d], X represents a hydroxy group.

The component (A) contains at least hydrogen atoms (SiH groups) bonded to silicon atoms, and the number thereof is not particularly limited. It is preferable to contain 2 or more in one molecule. In order to obtain a good cured product, the content of hydrogen atoms (SiH groups) bonded to silicon atoms in the component (A) is particularly preferably 1.0 mmol / g to 4.0 mmol / g.

The mass average molecular weight of the component (A) is not particularly limited. It is preferably 500 to 10,000, and more preferably 800 to 7,000. If the mass average molecular weight is 500 or more, the cured product of the present invention has good resin strength, and if it is 10,000 or less, the composition of the present invention has good moldability. In particular, when d = 0, the cured product of the present invention has excellent mechanical strength, and therefore, 3,500 to 7,000 is particularly preferable. Here, the mass average molecular weight is a value obtained by measurement by a gel permeation chromatography (abbreviation: GPC) method and conversion by a standard polystyrene calibration curve (the same applies hereinafter).

The viscosity of the component (A) is not particularly limited. From the viewpoint of handling workability, the viscosity at 25 ° C. is preferably 0.001 to 10,000,000 cP (centipoise), more preferably 0.01 to 500,000 cP. If the viscosity is more than 10,000,000 cP, the moldability may be inferior, but it is also possible to treat the temperature by heating. Here, the viscosity of the component (A) can be measured by a rotational viscometer or the like.

The amount of Si—OH group contained in the component (A) is not particularly limited. 0.5 to 4.5 mmol / g is preferable, and 1.0 to 3.5 mmol / g is particularly preferable. If the Si—OH group content exceeds 4.5 mmol / g, bubbles may be observed in the cured product.

上記式［２］は平均組成式を表す。式［２］中、Ｒ⁴は炭素数１～３のアルキル基であり、２つのＲ⁴は同じまたは互いに異なる種類であってもよい。Ｒ⁵は炭素数１～３のアルキル基であり、２つのＲ⁵は同じまたは互いに異なる種類であってもよい。Ｒ⁶は炭素数１～３のアルキル基または炭素数６～１０の芳香族炭化水素基である。ｅ、ｆおよびｇはそれぞれ０超、１未満の範囲内の数であり、ｈは０以上、１未満の範囲内の数であり、ｅ＋ｆ＋ｇ＋ｈ＝１を満たす。 (ＳｉＲ⁵ ₂Ｏ_2/2)、(Ｒ⁶ＳｉＯ_3/2)および(ＳｉＯ_4/2)で表される構造単位における酸素原子はそれぞれ、シロキサン結合を形成している酸素原子、またはシラノール基を形成している酸素原子を示す。 <(B) component>
Component (B) is a silicone resin represented by the following formula [2] and containing a vinyl group (Si—CH═CH ₂ group) bonded to a silicon atom. As the component (B), only one type may be used, or two or more types may be used in combination.

The above formula [2] represents an average composition formula. In the formula [2], R ⁴ is an alkyl group having 1 to 3 carbon atoms, and the two R ⁴ may be the same or different. R ⁵ is an alkyl group having 1 to 3 carbon atoms, and the two R ⁵ may be the same or different. R ⁶ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. Each of e, f, and g is a number in the range of more than 0 and less than 1, h is a number in the range of 0 to less than 1, and satisfies e + f + g + h = 1. The oxygen atoms in the structural units represented by (SiR ⁵ ₂ O _2/2 ), (R ⁶ SiO _3/2 ) and (SiO _4/2 ) are each an oxygen atom forming a siloxane bond or a silanol group The oxygen atom which forms is shown.

As the alkyl group having 1 to 3 carbon atoms in R ⁴ , a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

As the alkyl group having 1 to 3 carbon atoms in R ⁵ , a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

As the alkyl group having 1 to 3 carbon atoms in R ⁶ , a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The aromatic hydrocarbon group having 6 to 10 carbon atoms in R ⁶ is preferably a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or a 3,5-di (trifluoromethylphenyl) group. A phenyl group is particularly preferred.

The combination of R ⁴ , R ⁵ and R ⁶ is not particularly limited. Among them, R ⁴ is a methyl group or an ethyl group, R ⁵ is a methyl group or an ethyl group, R ⁶ is a methyl group, an ethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or 3, It is preferably any one of 5-di (trifluoromethylphenyl) groups, particularly preferably R ⁴ is a methyl group, R ⁵ is a methyl group, and R ⁶ is a methyl group or a phenyl group.

The value of e is in the range of more than 0 and less than 1, and is not particularly limited as long as e + f + g + h = 1 is satisfied. The value of e is preferably 0.05 to 0.40, particularly preferably 0.15 to 0.30. If the value of e is 0.05 or more, the composition of the present invention has good moldability, and if it is 0.40 or less, the cured product of the present invention has good mechanical strength.

The value of f is in the range of more than 0 and less than 1, and is not particularly limited as long as e + f + g + h = 1 is satisfied. The value of f is preferably 0.10 to 0.80, particularly preferably 0.20 to 0.70. If the value of f is 0.10 or more, the composition of the present invention has good moldability, and if it is 0.80 or less, the cured product of the present invention has good mechanical strength.

The value of g is in the range of more than 0 and less than 1, and is not particularly limited as long as e + f + g + h = 1 is satisfied. The value of g is preferably 0.10 to 0.80, particularly preferably 0.20 to 0.70. If the value of g is 0.10 or more, the cured product of the present invention has good mechanical strength, and if it is 0.80 or less, the composition of the present invention has good moldability.

The value of h is in the range of 0 or more and less than 1, and is not particularly limited as long as e + f + g + h = 1 is satisfied. The value of h is preferably 0 to 0.70. Among these, the value of h is particularly preferably 0.10 to 0.30 since the cured product of the present invention exhibits good adhesive strength and good hardness. When the value of h is 0, there is no structural unit of (SiO _4/2 ) in the above formula [2].

The values of e, f, g, and h are e: f: g: h = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80: 0 to 0.70. It is particularly preferred that e: f: g: h = 0.20 to 0.40: 0.10 to 0.40: 0.30 to 0.60: 0.10 to 0.30.

When the value of h is 0, the values of e, f, and g are e: f: g = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80 Is preferred.

The values of e, f, g, and h are calculated by measuring the ²⁹ Si-NMR spectrum and ¹ H-NMR spectrum of component (B) using a nuclear magnetic resonance apparatus, and using these in a complementary combination. Can do.

上記式［２－２］中、Ｒ⁵は上記式［２］中のＲ⁵と同義であり、Ｘはヒドロキシ基を表す。 In the above formula [2], the structural unit represented by (SiR ⁵ ₂ O _2/2 ) is a structure represented by the following formula [2-2], that is, represented by (SiR ⁵ ₂ O _2/2 ). The structure unit may include a structure in which one of oxygen atoms bonded to a silicon atom forms a silanol group.

In the formula [2-2], R ⁵ has the same meaning as R ⁵ in the formula [2], X represents a hydroxy group.

上記式［２－ｂ］および［２－２－ｂ］中、Ｒ⁵は上記式［２］中のＲ⁵と同義である。上記式［２－２－ｂ］中、Ｘはヒドロキシ基を表す。 The structural unit represented by (SiR ⁵ ₂ O _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [2-b], and further includes the following formula [2-2-2-b] The part enclosed with the broken line of the structural unit represented by may be included. That is, a structural unit having a group represented by R ⁵ and having a hydroxy group remaining at the terminal to form a silanol group is also included in the structural unit represented by (SiR ⁵ ₂ O _2/2 ). It is. In the structural units represented by the following formulas [2-b] and [2-2-2-b], the oxygen atom in the Si—O—Si bond forms a siloxane bond with an adjacent silicon atom, It 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 [2-b] and [2-2-b], R ⁵ are the same as R ⁵ in the formula [2]. In the above formula [2-2-2-b], X represents a hydroxy group.

上記式［２－３］および［２－４］中、Ｒ⁶は上記式［２］中のＲ⁶と同義であり、Ｘはヒドロキシ基を表す。 In the above formula [2], the structural unit represented by (R ⁶ SiO _3/2 ) is a structure represented by the following formula [2-3] or [2-4], that is, (R ⁶ SiO _{3 / 2} ) A structure in which _{two of} the oxygen atoms bonded to the silicon atom in the structural unit represented by each form a silanol group, or a silicon atom in the structural unit represented by (R ⁶ SiO _3/2 ) A structure in which one of the bonded oxygen atoms forms a silanol group may be included.

In the formula [2-3] and [2-4], R ⁶ has the same meaning as R ⁶ in the formula [2], X represents a hydroxy group.

上記式［２－ｃ］、［２－３－ｃ］および［２－４－ｃ］中、Ｒ⁶は上記式［２］中のＲ⁶と同義である。上記式［２－３－ｃ］および［２－４－ｃ］中、Ｘはヒドロキシ基を表す。 The structural unit represented by (R ⁶ SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [2-c], and further includes the following formula [2-3-c] or A portion surrounded by a broken line of the structural unit represented by [2-4-c] may be included. That is, a structural unit having a group represented by R ⁶ and having a hydroxy group remaining at the terminal to form a silanol group is also included in the structural unit represented by (R ⁶ SiO _3/2 ). .

The formula [2-c], in [2-3-c] and [2-4-c], R ⁶ has the same meaning as R ⁶ in the formula [2]. In the above formulas [2-3-c] and [2-4-c], X represents a hydroxy group.

上記式［２－５］、［２－６］および［２－７］中、Ｘはヒドロキシ基を表す。 The structural unit represented by (SiO _4/2 ) is represented by the following formula [2-5], [2-6] or [2-7], that is, represented by (SiO _4/2 ). A structure in which three or two oxygen atoms bonded to a silicon atom in a structural unit each form a silanol group, or an oxygen atom bonded to a silicon atom in a structural unit represented by (SiO _4/2 ) One of these may contain a structure in which a silanol group is formed.

In the above formulas [2-5], [2-6] and [2-7], X represents a hydroxy group.

上記式［２－５－ｄ］、［２－６－ｄ］および［２－７－ｄ］中、Ｘはヒドロキシ基を表す。 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 [2-d], and further includes the following formulas [2-5-d], [2 A portion surrounded by a broken line of the structural unit represented by −6−d] or [2-7-d] may be included. That is, a structural unit in which a hydroxy group remains at the terminal to form a silanol group is also included in the structural unit represented by (SiO _4/2 ).

In the above formulas [2-5-d], [2-6-d] and [2-7-d], X represents a hydroxy group.

The component (B) contains at least a vinyl group (Si—CH═CH ₂ group) bonded to a silicon atom, and the number thereof is not particularly limited. It is preferable to contain 2 or more in one molecule. Since a good cured product can be obtained, the content of the vinyl group (Si—CH═CH ₂ group) bonded to the silicon atom in the component (B) is 0.5 mmol / g to 4.0 mmol / g. Particularly preferred.

The mass average molecular weight of the component (B) is not particularly limited. It is preferably 500 to 10,000, and more preferably 800 to 7,000. If the mass average molecular weight is 500 or more, the cured product of the present invention has good resin strength, and if it is 10,000 or less, the composition of the present invention has good moldability. Among these, when h = 0, 3,500 to 7,000 is particularly preferable because the cured product of the present invention has excellent mechanical strength.

(B) The viscosity of a component is not specifically limited. From the viewpoint of handling workability, the viscosity at 25 ° C. is preferably 0.001 to 10,000,000 cP, and more preferably 0.001 to 500,000 cP. If the viscosity is more than 10,000,000 cP, the moldability may be inferior, but it is also possible to treat the temperature by heating. Here, the viscosity of the component (B) can be measured with a rotational viscometer or the like.

The amount of Si—OH group contained in the component (B) is not particularly limited. The content of Si—OH groups is preferably 0.5 to 6.0 mmol / g, particularly preferably 1.0 to 3.5 mmol / g. If the Si—OH group content exceeds 6.0 mmol / g, bubbles may be observed in the cured product.

<(C) component>
The component (C) is blended in order to promote an addition curing reaction between a SiH group in the component (A) and a Si—CH═CH ₂ group in the component (B) described later. (C) A component may be used individually by 1 type, or may use 2 or more types together. (C) The kind of component is not specifically limited. Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex (cursted catalyst), platinum-cyclovinylmethylsiloxane complex, or platinum-octylaldehyde complex Etc. can be illustrated. Of these, platinum-divinyltetramethyldisiloxane complex (cursed catalyst) and platinum-cyclovinylmethylsiloxane complex are preferable.

<Other additives>
In addition to the components (A) to (C) described above, the composition of the present invention aims to improve the storage stability and handling workability of the composition and to adjust the hydrosilylation reactivity during the curing process. As such, a curing retarder 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 heat-sensitive optical semiconductor member. 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 curing retarder is not particularly limited as long as it is a compound having a curing retarding effect on the component (C), and conventionally known compounds can also be used. 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.

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

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

Specific examples of nitrogen-containing compounds include N, N, N ′, N′-tetrasubstituted ethylene compounds such as N, N, N ′, N′-tetramethylethylenediamine and N, N, N ′, N′-tetraethylethylenediamine. Alkylene diamines, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethyl-1,3-propanediamine N, N-dibutyl-1,4-butanediamine, and the like, trisubstituted amines such as tributylamine, benzotriazole, and 2,2′-bipyridine.

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

Specific examples of the organic peroxide include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and tert-butyl perbenzoate. Of these oxidation retarders, compounds containing aliphatic unsaturated bonds and nitrogen-containing compounds are preferred, maleic esters, propargyl alcohols, N, N, N ′, N′-tetrasubstituted alkyldiamines. Dimethyl maleate, 2-methyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, and N, N, N ′, N′-tetramethylethylenediamine are particularly preferred.

The content of the curing retarder in the composition of the present invention is not particularly limited. Usually, a 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, but this is not restrictive. 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 optimum amount of the retarder, the composition of the present invention can be stored for a long period of time at room temperature (especially an ambient temperature not heated or cooled, usually 15 to 30 ° C., the same applies hereinafter). In addition, the heat curability is excellent.

In the composition of the present invention, an adhesion-imparting agent may be blended in addition to the components (A) to (C) described above for the purpose of improving the adhesiveness. Examples of the adhesion-imparting agent include silane coupling agents and hydrolysis condensates thereof. 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 this adhesion-imparting agent in the composition of the present invention is not particularly limited. In the composition of the present invention, it is preferably in the range of 1 to 20% by mass, particularly preferably in the range of 5 to 15% by mass.

Conventionally known antioxidants may be added to the composition of the present invention in order to suppress the occurrence of coloring and oxidative degradation of the cured product. Examples of such antioxidants include phenol-based antioxidants, thioether-based acid additives, and phosphorus-based antioxidants. 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.

Examples of phenolic antioxidants include 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 ester L} -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.

Thioether antioxidants include 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, triisodecyl Sufaito, triphenyl phosphite.

This antioxidant may be a commercially available product or a synthesized product. Commercially available products are 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 blending amount in the case of using this antioxidant is not particularly limited as long as it is within the range that does not impair the characteristics such as transparency of the cured product of the present invention and is an effective amount as an antioxidant. 0.001-2 mass% may be blended with respect to the total mass of the composition of the present invention, and 0.01-1 mass% is preferably blended. If the blending amount is within the above range, the antioxidant ability is sufficiently exhibited, so that a cured product having excellent engineering characteristics can be obtained while suppressing the occurrence of coloring, cloudiness, oxidative degradation, and the like.

Conventionally known light stabilizers may be added to the composition of the present invention in order to impart resistance to light degradation caused by light energy such as sunlight and fluorescent lamps. As this light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidation (photodegradation) is preferably used. By using it together with the above-mentioned antioxidant, the antioxidant effect can be further improved. it can. 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 them, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is preferable.

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

The blending amount in the case of using this light stabilizer 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. It may be blended in an amount of 0.01 to 5% by weight, preferably 0.05 to 0.5% by weight, based on the total weight of the curable silicone resin composition of the present invention.

In the composition of the present invention, a phosphor may be blended as an optional component. The type of the phosphor is not particularly limited. For example, yellow, which is widely used for light emitting diodes (LEDs), such as oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, oxysulfide phosphors, Examples include red, green, and blue light emitting phosphors.

Examples of oxide phosphors include yttrium, aluminum, and garnet-based YAG green to yellow light-emitting phosphors that include cerium ions, terbium, aluminum, and garnet-based TAG-based yellow light-emitting phosphors that include cerium ions. 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 containing 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 amount of the phosphor is not particularly limited. In the composition of the present invention, it is preferably in the range of 10 to 70% by mass, particularly preferably in the range of 20 to 50% by mass.

In the composition of the present invention, inorganic particles may be blended for the purpose of improving optical properties, workability, mechanical properties, and physicochemical properties in the cured product.

The kind of the inorganic particles may be selected according to the purpose, or a single kind may be blended or a plurality of kinds may be blended. In order to improve dispersibility, the inorganic particles may be surface-treated with a surface treatment agent such as a silane coupling agent.

Examples of the inorganic particles include inorganic oxide particles such as silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide, silicon nitride, boron nitride, silicon carbide, and aluminum nitride. Nitride particles such as, carbon compound particles, diamond particles, and the like are exemplified, but other materials can be selected according to the purpose, and are not limited thereto.

The form of the inorganic particles may be any form depending on the purpose, such as powder or slurry. Depending on the required transparency, it is preferable to make the cured product of the present invention have the same refractive index or blend it into the composition of the present invention as an aqueous / solvent transparent sol.

The average particle size of the inorganic particles to be blended is not particularly limited, and those having an average particle size according to the purpose are used. Usually, it is about 1/10 or less of the particle | grains of the fluorescent substance mentioned later. The average particle diameter of the inorganic particles means an arithmetic average value when the major axis is measured by selecting any 20 particles from 50 or more particles by observation with a scanning electron microscope (abbreviation: SEM). .

The blending amount of the inorganic particles 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 blended amount of inorganic particles is too small, the desired effect may not be obtained, and if it is too large, it may adversely affect various properties such as heat-resistant transparency, adhesion, transparency, moldability, and hardness of the cured product. is there. About 1 to 50 mass% may be blended, and about 5 to 35 mass% is preferably blended.

In addition to these, the composition of the present invention has a mold release agent, a resin modifier, a colorant, a diluent, an antibacterial agent, an antifungal agent, and leveling as long as the characteristics such as transparency of the cured product are not impaired. An agent, an anti-sagging agent, and the like may be included.

<Amount 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 SiH group contained in the molecule of the component (A) and the Si—CH═CH ₂ group contained in the molecule of the component (B). Specifically, the number of moles of SiH groups contained in the molecule of component (A): the number of moles of Si—CH═CH ₂ groups contained in the molecule of component (B) is 0.8: 0. A range of 2 to 0.5: 0.5 is preferable. If the ratio of the number of moles of SiH groups to the number of moles of Si—CH═CH ₂ groups is 0.8 or less, the composition of the present invention has good moldability, and if it is 0.5 or more, The cured product of the present invention has good heat transparency.

The blending amount of the component (C) in the composition of the present invention is such that the platinum atom in the component (C) is 0.00 on a mass basis based on the total mass of the component (A), the component (B), and the component (C). The amount is preferably in the range of 003 to 3.0 ppm, more preferably 0.003 to 2.0 ppm. If the amount of component (C) is 0.003 ppm or more, the addition curing reaction of component (A) and component (B) proceeds smoothly, and if it is 3.0 ppm or less, the resulting cured product is excellent. Since it has heat-resistant transparency, discoloration of the cured product due to long-term heating can be suppressed. Even within the above range, the smaller the amount of the component (C), the more the cured product of the present invention tends to have excellent heat-resistant transparency. Therefore, the smaller the amount of the component (C), the better.

The total content of silanol groups (Si—OH groups) in the component (A) and the component (B) in the composition of the present invention may be 0.5 to 5.0 mmol / g, 1.0 to 3.0 mmol / g is preferable, and 1.5 to 3.0 mmol / g is particularly preferable. When it exceeds 5.0 mmol / g, bubbles may be generated in the cured product produced from the composition. Generation | occurrence | production of this bubble becomes one of the causes of the transparency of cured | curing material, and the fall of heat-resistant transparency. Moreover, when exceeding 5.0 mmol / g, there exists a possibility that hardening of the composition may not fully progress, but a desired hardened | cured material may not be obtained.

Among them, in component (A), d = 0 and the mass average molecular weight is 3,500 to 7,000, in component (B), h = 0, and the mass average molecular weight is 3,500 to 7,000. In some cases, the total content of silanol groups (Si—OH groups) in the component (A) and the component (B) may be 1.5 to 5.0 mmol / g, and 1.7 to 3.0 mmol. / G is preferred, and 1.9 to 2.7 mmol / g is particularly preferred because a cured product showing excellent adhesion to packages of various sizes can be obtained.

The content of silanol groups (Si—OH groups) in the component (A) and the component (B) was determined by measuring the ²⁹ Si-NMR spectrum and ¹ H-NMR spectrum for each component using a nuclear magnetic resonance apparatus. Can be calculated using a complementary combination.

The viscosity of the composition of the present invention is not particularly limited. From the viewpoint of handling workability, the viscosity at 25 ° C. is preferably 0.001 to 10,000,000 cP, and more preferably 0.001 to 500,000 cP. If the viscosity is more than 10,000,000 cP, the moldability may be inferior, but it is also possible to treat the temperature by heating. The viscosity of the composition of the present invention can be measured with a rotational viscometer or the like.

<Preparation of curable silicone resin composition>
The composition of this invention can be prepared by mix | blending (A) component, (B) component, (C) component, and 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. For example, a mixing method 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 period of 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 component A) and component (B) is stored in separate containers, mixed immediately before use to obtain the composition of the present invention, and degassed under reduced pressure for use. May be.

一般式［３］中のＲ²は式［１］のＲ²と同義であり、Ｒ⁷は炭素数１～３のアルキル基を表し、２つのＲ⁷は同じまたは互いに異なる種類であってもよい。一般式［４］中のＲ³は上記式［１］のＲ³と同義であり、Ｒ⁸は炭素数１～３のアルキル基を表し、３つのＲ⁸は同じまたは互いに異なる種類であってもよい。一般式［５］中のＲ⁹は炭素数１～３のアルキル基を表し、４つのＲ⁹は同じまたは互いに異なる種類であってもよい。

一般式［９－１］、［９－２］、［９－３］および［９－４］中のＲ¹は、式［１］のＲ¹と同義である。一般式［９－３］中のＲ¹³は炭素数１～３のアルキル基を表す。 (Production method of component (A))
The manufacturing method of (A) component is not specifically limited. For example, hydrolysis polycondensation of a dialkoxysilane compound represented by the following general formula [3], a trialkoxysilane compound represented by the general formula [4] and a tetraalkoxysilane compound represented by the general formula [5] A condensate obtained by the reaction (hereinafter sometimes referred to as “hydrolyzed polycondensate [I]”) and the following general formulas [9-1], [9-2], [9-3] or It can be produced by reacting with a silane compound represented by [9-4].

R ² in the general formula [3] has the same meaning as R ² in the formula [1], R ⁷ represents an alkyl group having 1 to 3 carbon atoms, the two R ⁷ may be the same or different types from each other Good. R ³ in the general formula [4] has the same meaning as R ³ in the formula [1], R ⁸ represents an alkyl group having 1 to 3 carbon atoms, the three R ⁸ are the same or different types from each other Also good. R ⁹ in the general formula [5] represents an alkyl group having 1 to 3 carbon atoms, and the four R ⁹ may be the same or different from each other.

Formula [9-1], [9-2], R ¹ in the [9-3] and [9-4] has the same meaning as R ¹ in the formula [1]. R ¹³ in the general formula [9-3] represents an alkyl group having 1 to 3 carbon atoms.

Hereinafter, the dialkoxysilane compound represented by the general formula [3], the trialkoxysilane compound represented by the general formula [4], and the tetraalkoxysilane compound represented by the general formula [5] are referred to as “dialkoxysilane”, respectively. [3] ”,“ trialkoxysilane [4] ”, and“ tetraalkoxysilane [5] ”. Further, the silane compounds represented by the general formulas [9-1], [9-2], [9-3] and [9-4] are “chlorosilane compound [9-1]”, “silanol compound [ 9-2] ”,“ monoalkoxysilane compound [9-3] ”, and“ disiloxane compound [9-4] ”. When these are collectively referred to without distinction,“ silane compound [9 ] ".

Specific examples of dialkoxysilane [3] include, but are not limited to, the following compounds:
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane.
Among these, preferred compounds include dimethyldimethoxysilane and dimethyldiethoxysilane.

Examples of trialkoxysilane [4] include, but are not limited to, the following compounds:
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxy Silane, 3- (trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane, 3,5- (ditrifluoromethyl) phenyltrimethoxy Silane, 3,5- (ditrifluoromethyl) phenyltriethoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane.
Among these, preferred compounds include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, and 3- (trifluoromethyl) phenyltriethoxysilane. 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane 3,5- (ditrifluoromethyl) phenyltrimethoxysilane, 3,5- (ditrifluoromethyl) phenyltriethoxy Silanes can be mentioned, and particularly preferable compounds include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

Specific examples of the tetraalkoxysilane [5] include, but are not limited to, the following compounds:
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane.
Among these, preferred compounds include tetramethoxysilane and tetraethoxysilane.

The combination of dialkoxysilane [3], trialkoxysilane [4] and tetraalkoxysilane [5] used for the production of component (A) is not particularly limited. The dialkoxysilane [3], trialkoxysilane [4] and tetraalkoxysilane [5] may be used alone or in combination. As a preferred combination, dialkoxysilane [3] is selected from the group consisting of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane and diethyldiethoxysilane, and trialkoxysilane [4] is methyltrimethoxysilane [4]. Methoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, 3- (trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane, 3,5- (di One or more selected from the group consisting of (trifluoromethyl) phenyltrimethoxysilane and 3,5- (ditrifluoromethyl) phenyltriethoxysilane, tetraalkoxysilane [5] is tetramethoxysilane, tetraethoxysilane and tetraisosilane. One or more are selected from the group consisting of propoxysilane. Among these, as a particularly preferable combination, dialkoxysilane [4] is one or more selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane, and trialkoxysilane [5] is methyltrimethoxysilane, methyltrimethoxysilane. One or more are selected from the group consisting of ethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane, and tetraalkoxysilane [6] is selected from the group consisting of tetramethoxysilane and tetraethoxysilane.

Specific examples of the chlorosilane compound [9-1] include, but are not limited to, the following compounds:
Chlorodimethylsilane, chlorodiethylsilane.
Among these, a preferable compound is chlorodimethylsilane.

Specific examples of the silanol compound [9-2] include, but are not limited to, the following compounds:
Dimethylsilanol, diethylsilanol.
Among these, a preferred compound is dimethylsilanol.

Specific examples of the monoalkoxysilane compound [9-3] include, but are not limited to, the following compounds:
Dimethylmethoxysilane, dimethylethoxysilane, diethylmethoxysilane, diethylethoxysilane.
Among these, preferred compounds include dimethylmethoxysilane and dimethylethoxysilane.

Specific examples of the disiloxane compound [9-4] include, but are not limited to, the following compounds:
1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraethyldisiloxane.
Among these, 1,1,3,3-tetramethyldisiloxane is a preferred compound.

An example of the method for producing the hydrolyzed polycondensate [I] is shown below.
First, a predetermined amount of dialkoxysilane [3] and trialkoxysilane [4], and optionally tetraalkoxysilane [5] are placed in a reaction vessel at room temperature, and then each polyalkoxysilane compound is hydrolytically polycondensed. Water, if necessary, a reaction solvent is added, and a catalyst for advancing the condensation reaction is added if necessary to obtain 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, the hydrolysis condensate [I] 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 [I], the amount of dialkoxysilane [3], trialkoxysilane [4] and tetraalkoxysilane [5] used is not particularly limited. From the viewpoint of the physical properties of the component (A), the dialkoxysilane [3]: trialkoxysilane [4] is preferably blended at a molar ratio of 85:15 to 15:85, and 85:15 to 30:70. It is particularly preferable to blend with. When the molar ratio of dialkoxysilane [3] is less than 15, it may be higher than the desired molecular weight, and when it exceeds 85, the hydrolysis polycondensation reaction is difficult to proceed and may be lower than the desired molecular weight. is there. Further, when tetraalkoxysilane [5] is used, the amount is 1 to 80 mol with respect to 100 mol in total of dialkoxysilane [3], trialkoxysilane [4] and tetraalkoxysilane [5]. It is preferably 1 to 60 mol, particularly preferably.

In the production of the hydrolyzed polycondensate [I], the amount of water used 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, alkoxy contained in dialkoxysilane [3], trialkoxysilane [4] and tetraalkoxysilane [5] It is preferably 1.5 times or more and 5 times or less with respect to the total molar equivalent of the group. When the molar equivalent is 1.5 times or more, the alkoxysilane compound is efficiently hydrolyzed, and it is not necessary to add more than 5 molar equivalents.

In the production of the hydrolyzed polycondensate [I], the reaction can be carried out even under solvent-free conditions, but a reaction solvent can also be used. The type of the reaction solvent is not particularly limited as long as it does not inhibit the reaction for producing the hydrolyzed polycondensate [I]. Among these, hydrophilic organic solvents such as alcohols are preferable. Specific examples of the alcohols include methanol, ethanol, normal propanol, isopropanol, and butanol, 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.

As the type of catalyst used in the production of the hydrolyzed polycondensate [I], an acidic catalyst or a basic catalyst can be used. Use of an acidic catalyst is preferred because the molecular weight of the hydrolyzed polycondensate [I] can be easily controlled. 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 and the like can be mentioned. Among these, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, and hydrofluoric acid are preferable, and acetic acid is more preferable because the removal of the acid catalyst after the reaction is easy. 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.

The amount of the catalyst used in the production of the hydrolyzed polycondensate [I] is preferably 0.001 to 5% by mass, particularly preferably 0.005 to 1%, based on the total amount of the alkoxysilane compound, solvent and water used. % By mass.

The reaction time in the production of the hydrolyzed polycondensate [I] is not particularly limited, and may be 3 hours or more and 15 hours or less. Reaction temperature is not specifically limited, 60 degreeC or more and 120 degrees C or less may be sufficient, and 80 degreeC or more and 100 degrees C or less are preferable.

After the reaction, it is preferable to separate and purify the hydrolyzed polycondensate [I] from the reaction system from the viewpoint of handling the hydrolyzed polycondensate [I]. This separation method is not particularly limited. Examples of the separation 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 [I] 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, high purity hydrolysis polycondensate [I] can be separated by removing the desiccant and removing the extraction solvent under reduced pressure. 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.

As the extraction solvent, a non-aqueous organic solvent can be used. The kind of this non-aqueous organic solvent is not specifically limited. Examples thereof include aromatic hydrocarbons and ethers. Specific examples include toluene, 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 hydrolyzed polycondensate [I]. As such a desiccant, a solid desiccant is preferably used. Specifically, although magnesium sulfate etc. are mentioned, it is not limited to this.

The separated and purified hydrolyzed polycondensate [I] may be further subjected to a condensation reaction by heating and stirring in a solvent or under heating without solvent. Thereby, the molecular weight of hydrolysis polycondensate [I] can be increased. When a solvent is used, the hydrolysis polycondensate [I] and the solvent are put into a reaction vessel capable of being heated to reflux to obtain a solution. The solution is heated to reflux and azeotroped with water generated in the system as the condensation proceeds. At this time, tosylic acid or the like may be added to the solution and heated to reflux. The type of the solvent to be used is not particularly limited as long as it can dissolve the hydrolysis condensate [I] and can be heated to reflux. Specific examples include aromatic hydrocarbons such as toluene, xylene, and benzene, ethers such as diethyl ether and diisopropyl ether, and esters such as ethyl acetate. In the absence of a solvent, the hydrolysis polycondensate [I] is charged into a reaction vessel capable of being heated and stirred, heated to 100 ° C. or higher and 150 ° C. or lower and stirred for 6 to 18 hours. At this time, in order to suppress the change in the composition ratio of the hydrolyzed polycondensate [I], it is preferable to provide the reaction vessel with a reflux device (for example, a condenser). After heating and stirring, the content liquid is cooled to room temperature. These series of operations can be repeated, and the number of repetitions is not particularly limited. It is preferably performed 1 to 4 times.

Next, a method for producing the component (A) by reacting the hydrolysis polycondensate [I] with the silane compound [9] will be described. This method is not particularly limited as long as component (A) can be produced. For example, there are two methods, a first method and a second method described later. The first method is to react hydrolysis polycondensate (I) with chlorosilane compound [9-1], which is a kind of silane compound [9], in a water-insoluble organic solvent, and Refers to the method of manufacturing. The second method is a hydrolysis polycondensate (I) and a silanol compound [9-2], a monoalkoxysilane compound [9-3] or a disiloxane compound [9-] which is a kind of silane compound [9]. 4] in the presence of an acid in a mixed solvent of a water-insoluble organic solvent and an alcoholic solvent to produce the component (A). These two methods will be specifically described below.

(First method)
In the first method, first, a predetermined amount of the hydrolyzed polycondensate (I) and a non-aqueous organic solvent are placed in a reaction vessel to dissolve the hydrolyzed polycondensate (I). Next, a predetermined amount of the chlorosilane compound [9-1] is added to the solution while stirring at about 0 to about 10 ° C. The addition method is not particularly limited, but dropping is preferable. After completion of the addition, the reaction is allowed to proceed by stirring for 0.5 to 18 hours while maintaining 0 ° C. to room temperature. Then, (A) component can be obtained by terminating reaction.

In the first method, the amount of the hydrolyzed polycondensate (I) and the chlorosilane compound [9-1] used is not particularly limited. From the viewpoint of the physical properties of the component (A), it is preferable to use 0.2 to 10 mmol of the chlorosilane compound [9-1] with respect to 1 g of the hydrolyzed polycondensate (I).

In the first method, the type of the water-insoluble organic solvent to be used is not particularly limited as long as it is water-insoluble and does not inhibit the reaction for producing the component (A). 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, particularly preferably 300 to 700% by mass, based on 1 g of the hydrolyzed polycondensate (I).

In the first method, the method for terminating the reaction is not particularly limited. Usually, the reaction is terminated by dropping water (preferably ion-exchanged water) into the reaction system. After the reaction, it is preferable that the component (A) is separated from the reaction system and purified from the viewpoint of handling the component (A). This separation and purification method is not particularly limited. For example, a method of extracting can be mentioned. Specifically, the organic layer is separated from the reaction solution after the above reaction, and then the organic layer is washed with an acid and further washed with water. Next, a desiccant is added to the washed organic layer to remove water dissolved in the system. Furthermore, the component (A) can be separated with high purity by removing the desiccant and removing the non-aqueous organic solvent under reduced pressure. 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 separation further removes water contained in the component (A) by heating and stirring without solvent and under reduced pressure. The heating temperature at this time is not particularly limited, but is usually 100 to 130 ° C.

(Second method)
In the second method, first, a hydrolysis polycondensate (I), a non-aqueous organic solvent, and optionally an alcoholic solvent are put in a predetermined amount in a reaction vessel, and the hydrolysis polycondensate (I) is added. Dissolve. Next, a predetermined amount of silanol compound [9-2], monoalkoxysilane compound [9-3] or disiloxane compound [9-4] is added to the solution. Further, a catalyst for proceeding the 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 proceed the reaction. Then, (A) component can be obtained by terminating reaction.

In the second method, the amount of the hydrolyzed polycondensate (I) and the silanol compound [9-2], monoalkoxysilane compound [9-3] or disiloxane compound [9-4] used is not particularly limited. . From the viewpoint of the physical properties of component (A), silanol compound [9-2], monoalkoxysilane compound [9-3] or disiloxane compound [9-4] per 1 g of hydrolyzed polycondensate (I) The SiH group is preferably used in the range of 0.2 mmol to 10 mmol.

In the second method, the type of the water-insoluble organic solvent to be used 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, particularly preferably 100 to 500% by mass, based on 1 g of the hydrolyzed polycondensate (I).

In the second method, the type of alcohol solvent used is not particularly limited as long as the reaction for producing the component (A) is not inhibited. Of these, alcohols having 1 to 4 carbon atoms are preferred. 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 (I).

In the second method, it is preferable to use a mixed solvent of a water-insoluble organic solvent and an alcohol solvent according to the type of catalyst used. When a proton acid catalyst is used, the reactivity can be improved by using this mixed solvent.

In the second method, the type of the catalyst to be used is not particularly limited as long as it has an action of promoting the reaction for producing the component (A). Of these, inorganic acids are preferred. Specific examples include nitric acid, hydrochloric acid, sulfuric 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 (I).

In the second method, 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 separate and purify the component (A) from the reaction system from the viewpoint of handling the component (A). This separation and 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 separated 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 separation further removes water contained in the component (A) by heating and stirring without solvent and under reduced pressure. The heating temperature at this time is not particularly limited, but is usually 100 to 130 ° C.

一般式［６］中のＲ⁵は式［２］のＲ⁵と同義であり、Ｒ¹⁰は炭素数１～３のアルキル基を表し、２つのＲ¹⁰は同じまたは互いに異なる種類であってもよい。一般式［７］中のＲ⁶は式［２］のＲ⁶と同義であり、Ｒ¹¹は炭素数１～３のアルキル基を表し、３つのＲ¹¹は同じまたは互いに異なる種類であってもよい。一般式［８］中のＲ¹²は炭素数１～３のアルキル基を表し、４つのＲ¹²は同じまたは互いに異なる種類であってもよい。

一般式［１０－１］、［１０－２］、［１０－３］および［１０－４］中のＲ⁴は、式［２］のＲ⁴と同義である。一般式［１０－３］中のＲ¹⁴は炭素数１～３のアルキル基を表す。 (Production method of component (B))
The manufacturing method of (B) component is not specifically limited. For example, hydrolysis polycondensation of a dialkoxysilane compound represented by the following general formula [6], a trialkoxysilane compound represented by the general formula [7] and a tetraalkoxysilane compound represented by the general formula [8] A condensate obtained by the reaction (hereinafter sometimes referred to as “hydrolyzed polycondensate [II]”), and a general formula [10-1], [10-2], [10-3] or [10 -4] can be reacted with a vinylsilane compound represented by

The R ⁵ in the general formula [6] has the same meaning as R ⁵ in formula [2], R ¹⁰ represents an alkyl group having 1-3 carbon atoms, two R ¹⁰ may be the same or different types from each other Good. R ⁶ in the general formula [7] has the same meaning as R ⁶ in the formula [2], R ¹¹ represents an alkyl group having 1 to 3 carbon atoms, and three R ¹¹ may be the same or different types from each other Good. R ¹² in the general formula [8] represents an alkyl group having 1 to 3 carbon atoms, and the four R ¹² may be the same or different from each other.

Formula [10-1], [10-2], R ⁴ in the [10-3] and [10-4] has the same meaning as R ⁴ in the formula [2]. R ¹⁴ in the general formula [10-3] represents an alkyl group having 1 to 3 carbon atoms.

Hereinafter, the dialkoxysilane compound represented by the general formula [6], the trialkoxysilane compound represented by the general formula [7], and the tetraalkoxysilane compound represented by the general formula [8] are referred to as “dialkoxysilane”, respectively. [6], “trialkoxysilane [7]”, “tetraalkoxysilane [8]”. The vinylsilane compounds represented by the general formulas [10-1], [10-2], [10-3] and [10-4] are “chlorovinylsilane compound [10-1]” and “vinylsilanol”, respectively. “Compound [10-2]”, “monoalkoxyvinylsilane compound [10-3]”, and “divinyldisiloxane compound [10-4]”. Compound [10] ".

Specific examples of dialkoxysilane [6] include, but are not limited to, the following compounds:
Dimethyldimethoxysilane, dimethyldiethoxysilane, ethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane.
Among these, preferred compounds include dimethyldimethoxysilane and dimethyldiethoxysilane.

Specific examples of trialkoxysilane [7] include, but are not limited to, the following compounds:
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxy Silane, 3- (trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane, 3,5- (ditrifluoromethyl) phenyltrimethoxy Silane, 3,5- (ditrifluoromethyl) phenyltriethoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane.
Among these, preferred compounds include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, and 3- (trifluoromethyl) phenyltriethoxysilane. 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane 3,5- (ditrifluoromethyl) phenyltrimethoxysilane, 3,5- (ditrifluoromethyl) phenyltriethoxy Silanes can be mentioned, and particularly preferable compounds include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

Specific examples of the tetraalkoxysilane [8] include, but are not limited to, the following compounds:
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane.
Among these, preferred compounds include tetramethoxysilane and tetraethoxysilane.

The combination of dialkoxysilane [6], trialkoxysilane [7] and tetraalkoxysilane [8] used for the production of component (B) is not particularly limited. The dialkoxysilane [6], trialkoxysilane [7] and tetraalkoxysilane [8] may be used alone or in combination. As a preferred combination, dialkoxysilane [6] is selected from the group consisting of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane and diethyldiethoxysilane, and trialkoxysilane [7] is methyltrimethoxysilane [7]. Methoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, 3- (trifluoromethyl) phenyltriethoxy Silane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane, 3,5- (ditrifluoromethyl) phenyltrimethoxysilane and , 5- (ditrifluoromethyl) phenyltriethoxysilane is selected from one or more groups, and tetraalkoxysilane [8] is one or more selected from the group consisting of tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane Is done. Among these, as a particularly preferred combination, dialkoxysilane [6] is one or more selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane, and trialkoxysilane [7] is methyltrimethoxysilane, methyltrimethoxysilane. One or more selected from the group consisting of ethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane, and tetraalkoxysilane [8] is selected from the group consisting of tetramethoxysilane and tetraethoxysilane.

Specific examples of the chlorovinylsilane compound [10-1] include, but are not limited to, the following compounds:
Chlorodimethylvinylsilane, chlorodiethylvinylsilane.
Among these, a preferred compound is chlorodimethylvinylsilane.

Specific examples of the vinylsilanol compound [10-2] include, but are not limited to, the following compounds:
Dimethyl vinyl silanol, diethyl vinyl silanol.
Among these, a preferable compound is dimethylvinylsilanol.

Specific examples of the monoalkoxyvinylsilane compound [10-3] include, but are not limited to, the following compounds:
Dimethylmethoxyvinylsilane, dimethylethoxyvinylsilane, diethylmethoxyvinylsilane, diethylethoxyvinylsilane.
Among these, preferred compounds include dimethylmethoxyvinylsilane and dimethylethoxyvinylsilane.

Specific examples of the divinyldisiloxane compound [10-4] include, but are not limited to, the following compounds:
1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraethyl-1,3-divinyldisiloxane.
Among these, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane is a preferred compound.

The hydrolyzed polycondensate [II] can be produced by applying the above-described method for producing the hydrolyzed polycondensate [I]. That is, dialkoxylane [3], trialkoxysilane [4], and tetraalkoxysilane [5] in the method for producing the hydrolysis polycondensate [I] described above are dialkoxysilane [6] and trialkoxysilane [7], respectively. ], Tetraalkoxysilane [8] is substituted, and hydrolyzed polycondensate [I] is replaced with hydrolyzed polycondensate [II], whereby the method for producing hydrolyzed polycondensate [II] can be explained. .

Next, a method for producing the component (B) by reacting the hydrolyzed polycondensate [II] with the vinylsilane compound [10] will be described. The component (B) can be produced by applying the method for producing the component (A) from the hydrolysis polycondensate [I] described above. That is, the silane compound [9], chlorosilane compound [9-1], silanol compound [9-2], monoalkoxysilane compound [9-3], disiloxane in the method for producing the hydrolysis polycondensate [II] described above Compound [9-4] is vinylsilane compound [10], chlorovinylsilane compound [10-1], vinylsilanol compound [10-2], monoalkoxyvinylsilane compound [10-3], divinyldisiloxane compound [10-4], respectively. And the SiH group, the hydrolysis polycondensate [I], and the component (A) are replaced with the Si—CH═CH ₂ group, the hydrolysis polycondensate [II], and the component (B), respectively. A method for producing the component (B) from the polycondensate [II] can be described.

(Method for obtaining component (C))
As the component (C), a commercially available product may be used, or a synthesized product may be used. The component (C) can be synthesized by a conventionally known method.

[Hardened product of curable silicone resin composition]
The cured product of the present invention can be obtained by heating the composition of the present invention.

The cured product of the present invention can be used as a sealing material for semiconductor devices, and is particularly suitable as a sealing material for optical semiconductor devices and power semiconductor devices. 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, optical semiconductor devices have their light extraction efficiency enhanced by various technologies. However, if the transparency of the sealing material of the optical semiconductor element is low, the sealing material absorbs light. The light extraction efficiency of the optical semiconductor device used decreases. As a result, it tends to be difficult to obtain a high-brightness optical semiconductor device product. Furthermore, the energy corresponding to the decrease in light extraction efficiency is changed to heat, which causes thermal deterioration of the optical semiconductor device, which is not preferable.

The cured product of the present invention is excellent in transparency. 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 sealing material in an optical semiconductor device having an emission wavelength in this region because a high-luminance optical 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 optical 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.

Moreover, the cured product of the present invention is excellent in heat-resistant transparency. That is, the cured product of the present invention has a property that the transmittance with respect to light having a predetermined wavelength does not easily fluctuate even when left for a long time under high temperature conditions. Specifically, the cured product of the present invention has a transmittance for light having a wavelength in the region of usually 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm or less before and after being left at 200 ° C. for 100 hours. Has a good retention rate. Therefore, it is preferable to use the cured product of the present invention as an encapsulant for an optical semiconductor device having an emission wavelength in this region because a high-intensity optical semiconductor device can be obtained and heat deterioration hardly occurs. In addition, this does not prevent using the hardened | cured material of this invention as a sealing material for the optical semiconductor device which has light emission wavelength out of said area | region. The variation ratio of the transmittance can be measured by measuring the 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 heating at 45 to 300 ° C., preferably 60 to 200 ° C., the composition can be cured to form 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, but may be 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.

[Encapsulant]
The cured product of the present invention can be used as a sealing material for semiconductor devices, and is particularly suitable as a sealing material for optical semiconductor devices and power semiconductor devices. 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.

[Optical semiconductor device]
The optical semiconductor device of the present invention is an optical semiconductor device including at least an optical semiconductor element, and the optical semiconductor element is sealed at least by the cured product of the present invention. Other configurations of the optical semiconductor device of the present invention are not particularly limited, and members other than the optical semiconductor element 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 optical semiconductor element, a part or all of the members may be sealed with the cured product of the present invention.

Specific examples of the optical 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 optical semiconductor device of the present invention includes, for example, a backlight such as a liquid crystal display, a light source such as illumination, various sensors, a printer and a copier, a measurement light source for a vehicle, a signal light, a display light, a display device, and a light source for a planar light emitter. It is suitably used for displays, decorations, various lights and switching elements.

An example of the optical semiconductor device of the present invention is shown in FIG. As illustrated in FIG. 1, the optical semiconductor device 10 includes at least a sealing material 1, an optical semiconductor element 2, and a bonding wire 3 on an optical semiconductor substrate 6. The optical 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 optical 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 optical 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 optical semiconductor element 2 in a predetermined direction. A sealing material 1 is filled in the region of the concave portion of the optical semiconductor substrate 6 so as to at least seal the optical 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 optical 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.

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

In the optical semiconductor device 10, as the optical semiconductor element 2 sealed with the sealing material 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). Etc. The structure shown in FIG. 1 is only an example of the optical semiconductor device of the present invention, and the structure of the reflector, the structure of the lead frame, the mounting structure of the optical semiconductor element, and the like can be modified as appropriate.

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

[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. Since the composition of the present invention is excellent in heat resistance, it provides a highly reliable optical semiconductor device that can withstand long-term use when used as an adhesive for high-power optical semiconductor devices exposed to high temperatures and ultraviolet light for a long time. can do.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

The physical properties of the silicone resins synthesized in the following synthesis examples and comparative synthesis examples were measured and evaluated according to the following methods.

[Quantification of SiH group and Si—CH═CH ₂ 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. 2.0 μL of dimethyl sulfoxide (0.0282 mmol) was added to the solution with a microsyringe, the sample tube was closed, and the solution was stirred to make it uniform and used as a measurement sample. The sample was measured by ¹ H-NMR, the proton ratio of dimethyl sulfoxide and the proton ratio of H—Si group or CH ₂ ═CH—Si group were calculated, and the H—Si group or CH _{2 in the} measurement sample was calculated. = The number of moles of CH-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 groups in silicone resin (mmol) / measurement sample amount (mg) × 1000 = functional group amount in 1 g of measurement sample (mmol / g).
For 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),
CH ₂ ═CH—Si: 5.5 to 6.5 ppm (3H),
Ph—Si: 7.0 to 8.0 ppm (5H).

[Toluene determination]
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. The sample tube was closed, and the solution was stirred to make the sample uniform. The sample was measured by ¹ H-NMR, the proton ratio of Me group and Ph group in the silicone resin and the proton ratio of Me group in toluene were calculated, and the amount of toluene in the measurement data was determined. The toluene content in the silicone resin was then calculated according to the following formula:
(Molecular weight of toluene (mol / g) × Me (toluene) area / 3) / (((molecular weight of PhSiO _1.5 (mol / g)) × ((Ph area− (Me (toluene) area × 5 / 3)) / 5)) + ((Me ₂ SiO molecular weight (mol / g)) × Me area × 6) + (Toluene molecular weight (mol / g) × Me (toluene) area / 3)) = Toluene content (wt%)
For 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: 0.0 to 0.5 ppm (3H),
Me (toluene): 2.2 to 2.4 ppm (3H),
Ph: 7.0 to 8.0 ppm (5H).

　上記式［１］におけるａ、ｂ、ｃ、ｄの値は以下の式から算出することで決定した：
　ａ＝ピーク（ｉ）面積／全ピーク面積の和、
　ｂ＝（ピーク（ａ）面積＋ピーク（ｂ）面積）／全ピーク面積の和、
　ｃ＝（ピーク（ｃ）面積＋ピーク（ｄ）面積＋ピーク（ｅ）面積）／全ピーク面積の和、
　ｄ＝(ピーク（ｆ）面積＋ピーク（ｇ）面積＋ピーク（ｈ）面積）／全ピーク面積の和。

　上記式［２］におけるｅ、ｆ、ｇ、ｈの値は以下の式から算出することで決定した：
　ｅ＝ピーク（ｊ）面積／全ピーク面積の和、
　ｆ＝（ピーク（ａ）面積＋ピーク（ｂ）面積）／全ピーク面積の和、
　ｇ＝（ピーク（ｃ）面積＋ピーク（ｄ）面積＋ピーク（ｅ）面積）／全ピーク面積の和、
　ｈ＝(ピーク（ｆ）面積＋ピーク（ｇ）面積＋ピーク（ｈ）面積）／全ピーク面積の和。
　²⁹Ｓｉ－ＮＭＲにおいて、Ｍｅ－Ｓｉ基、Ｐｈ－Ｓｉ基、Ｈ－Ｓｉ基、ＣＨ₂＝ＣＨ－Ｓｉ基またはその他の基のピークが重なった場合は、¹Ｈ－ＮＭＲにおけるＭｅ－Ｓｉ基、Ｐｈ－Ｓｉ基、Ｈ－Ｓｉ基、ＣＨ₂＝ＣＨ－Ｓｉ基またはその他の基のピークの積分面積に基づいて算出した。
　比較合成例で合成したシリコーン樹脂（ＤＡ１）および（ＤＢ１）ではさらに、以下の式に基づいてそれぞれ組成比を決定した：
　（Ｈ－ＳｉＯ_3/2）の組成比＝(ピーク（ｋ）面積＋ピーク（ｌ）面積＋ピーク（ｍ）面積）／全ピーク面積の和、
　（ＣＨ₂＝ＣＨＳｉＯ_3/2）の組成比＝(ピーク（ｎ）面積＋ピーク（ｏ）面積＋ピーク（ｐ）面積）／全ピーク面積の和。
　ＨＯ－Ｓｉ基の含有量（ｍｍｏｌ／ｇ）は、上述の方法で算出した積分比から以下の式に従って決定した：
　［Ａ］＝ピーク（ａ）積分比＋２×ピーク（ｃ）積分比＋ピーク（ｄ）積分比＋２×ピーク（ｆ）積分比＋ピーク（ｇ）積分比＋２×ピーク（ｋ）積分比＋ピーク（ｌ）積分比＋２×ピーク（ｎ）積分比＋ピーク（ｏ）積分比、
　［Ｂ］＝ピーク（ａ）積分比×８３．１６＋ピーク（ｂ）積分比×７４．１５＋ピーク（ｃ）積分比×１４７．２＋ピーク（ｄ）積分比×１３８．２＋ピーク（ｅ）積分比×１２９．２＋ピーク（ｆ）積分比×７８．１０＋ピーク（ｇ）積分比×６９．０９＋ピーク（ｈ）積分比×６０．０８＋ピーク（ｉ）積分比×６７．１６＋ピーク（ｊ）積分比×９３．２０＋ピーク（ｋ）積分比×７１．１１＋ピーク（ｌ）積分比×６２．１０＋ピーク（ｍ）積分比×５３．０９＋ピーク（ｎ）積分比×９７．１５＋ピーク（ｏ）積分比×８８．１４＋ピーク（ｐ）積分比×７９．１３、
　ＨＯ－Ｓｉ基の含有量（ｍｍｏｌ／ｇ）＝（［Ａ］／［Ｂ］）×１０００。
　²⁹Ｓｉ－ＮＭＲの測定において、ピーク（ｉ）、およびピーク（ｊ）がピーク（ａ）と重なるときは、¹Ｈ－ＮＭＲの測定によりＰｈ－ＳｉとＨ－Ｓｉの積分比、およびＰｈ－ＳｉとＣＨ＝ＣＨ₂－Ｓｉ、その他のピークがあればその他のピークの積分比の百分率をそれぞれ求め、²⁹Ｓｉ－ＮＭＲのピーク（ｃ）積分比＋ピーク（ｄ）積分比＋ピーク（ｅ）積分比を算出し、¹Ｈ－ＮＭＲの積分比からピーク（ｉ）およびピーク（ｊ）の²⁹Ｓｉ－ＮＭＲの積分比を求め、ピーク（ａ）とピーク（ｉ）およびピーク（ｊ）との重なった積分値から算出したピーク（ｉ）およびピーク（ｊ）の積分比を差引き、ピーク（ａ）の積分値を算出した。その他のケースで²⁹Ｓｉ－ＮＭＲのピークが重なった場合は、上記の方法と同様に¹Ｈ－ＮＭＲの積分比をもとに算出した。 [Quantification 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. The detected signals were classified into peaks (a) to (p) as shown in Table 1, and each peak was calculated as a percentage (integration ratio) from the sum of all integrated values. For ²⁹ Si-NMR measurement of 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, c, and d in the above equation [1] were determined by calculating from the following equations:
a = peak (i) area / total peak area sum,
b = (peak (a) area + peak (b) area) / total peak area,
c = (peak (c) area + peak (d) area + peak (e) area) / total peak area,
d = (peak (f) area + peak (g) area + peak (h) area) / total peak area.

The values of e, f, g, and h in the above equation [2] were determined by calculating from the following equations:
e = sum of peak (j) area / total peak area,
f = (peak (a) area + peak (b) area) / total peak area,
g = (peak (c) area + peak (d) area + peak (e) area) / total peak area,
h = (peak (f) area + peak (g) area + peak (h) area) / total peak area.
^{In 29} Si-NMR, when the peaks of the Me—Si group, Ph—Si group, H—Si group, CH ₂ ═CH—Si group or other groups overlap, the Me—Si group in ¹ H-NMR, The calculation was based on the integrated area of the peak of the Ph—Si group, H—Si group, CH ₂ ═CH—Si group or other group.
In the silicone resins (DA1) and (DB1) synthesized in the comparative synthesis example, the composition ratios were further determined based on the following formulas:
(H—SiO _3/2 ) composition ratio = (peak (k) area + peak (l) area + peak (m) area) / total peak area,
Composition ratio of (CH ₂ = CHSiO _3/2 ) = (peak (n) area + peak (o) area + peak (p) area) / total peak area.
The HO—Si group content (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 + 2 × peak (f) integration ratio + peak (g) integration ratio + 2 × peak (k) integration ratio + peak (L) integration ratio + 2 × peak (n) integration ratio + peak (o) 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 78.10 + peak (g) integration ratio x 69.09 + peak (h) integration ratio x 60.08 + peak (i) integration ratio x 67.16 + peak (j) integration ratio × 93.20 + peak (k) integration ratio × 71.11 + peak (l) integration ratio × 62.10 + peak (m) integration ratio × 53.09 + peak (n) integration ratio × 97.15 + peak (o) integration ratio X 88.14 + peak (p) integration ratio x 79.13,
HO—Si group content (mmol / g) = ([A] / [B]) × 1000.
^{29 In} the measurement of Si-NMR, when peak (i) and peak (j) overlap with peak (a), the integration ratio of Ph-Si and H-Si by the measurement of ¹ H-NMR, and Ph-Si And CH = CH ₂ —Si, and if there are other peaks, the percentages of the integration ratios of the other peaks are obtained, respectively. ²⁹ Si-NMR peak (c) integration ratio + peak (d) integration ratio + peak (e) integration The ratio of ²⁹ Si-NMR of peak (i) and peak (j) was calculated from the integral ratio of ¹ H-NMR, and the overlap of peak (a) with peak (i) and peak (j) The integration value of peak (a) was calculated by subtracting the integration ratio of peak (i) and peak (j) calculated from the integrated value. In other cases, when ²⁹ Si-NMR peaks overlapped, the calculation was performed based on the integration ratio of ¹ H-NMR in the same manner as described above.

[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.
Further, for those having a mass average molecular weight (Mw) exceeding 1500, a calibration curve was prepared using polystyrene as a reference substance by a gel permeation chromatography (abbreviation: GPC) method under the following conditions, and values were calculated:
Device: manufactured by Tosoh Corporation, product name: HLC-8320GPC,
Column: manufactured by Tosoh Corporation, product name: TSK gel Super HZM-Hx2
Eluent: tetrahydrofuran.

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

[Viscosity measurement]
Regarding the viscosity of the silicone resin, a rotational viscometer (Brookfield Engineering Laboratories, Inc., product name: DV-II + PRO) and a temperature control unit (Brookfield Engineering Laboratories, Inc., product name: THERMOSEL) are used, 25 The value at ° C was measured.

[Synthesis Example 1-1]
<Synthesis of silicone resin (I-1)>
In a 2 L three-necked flask equipped with a fluororesin stirring blade and a Dimroth type reflux condenser, 120.2 g (1.0 mol) Me ₂ Si (OMe) ₂ , 198.3 g (1.0 mol) PhSi ( OMe) ₃ was collected. 239.6 g of 2-propanol, 185.0 g of water and 0.12 g of acetic acid are then added into the flask and the flask is continuously warmed at 100 ° C. for 6 hours to allow hydrolysis and A condensation reaction was performed. 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 collected, and toluene was distilled off under reduced pressure using an evaporator to obtain a silicone resin (I-1) as a colorless viscous liquid.
The yield of the silicone resin (I-1) is 160.8 g, the mass average molecular weight (Mw) is 1,000, and the composition ratio is (Me ₂ SiO _2/2 ) _0.43 (PhSiO _3/2 ) _0.57 . The HO—Si group content was 7.8 mmol / g (13 mass%).

[Synthesis Example 1-2]
<Synthesis of silicone resin (A1)>
39.7 g of silicone resin (I-1), 119 g of toluene, 39.7 g of methanol, 8.3 g of 1,1,3,3-tetramethyldisiloxane and 0.20 mL of 70% concentrated nitric acid were added to the flask. In addition, the mixture was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 119 g 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, vacuum distillation (130 ° C., 2 hours) was performed by heating to obtain a silicone resin (A1) as a colorless and transparent viscous liquid.
The yield of the silicone resin (A1) is 42.5 g, the mass average molecular weight (Mw) is 1,900, the viscosity is 200 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.31 (PhSiO _3/2 ) _0.42 (H (Me) ₂ SiO _1/2 ) _0.27 , the H—Si group content is 2.8 mmol / g, and the HO—Si group content is 2.0 mmol / g (3.4 mass%). there were.

[Synthesis Example 1-3]
<Synthesis of silicone resin (B1)>
19.9 g of silicone resin (I-1), 59.7 g of toluene, 19.9 g of methanol, 5.76 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1.98 mL 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 59.7 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 toluene was distilled off from the organic layer by an evaporator, vacuum distillation (130 ° C., 2 hours) was performed by heating to obtain a silicone resin (B1) as a colorless and transparent viscous liquid.
The yield of the silicone resin (B1) is 20.6 g, the mass average molecular weight (Mw) is 1,800, the viscosity is 350 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.32 (PhSiO _3/2 ) _0.45 (CH ₂ = CH (Me) ₂ SiO _1/2 ) _0.23 , the content of CH ₂ = CH-Si group is 2.3 mmol / g, and the content of HO-Si group is 2.1 mmol / g (3 .6 mass%).

[Synthesis Example 2-1]
<Synthesis of silicone resin (I-2)>
Instead of 120.2 g (1.0 mol) Me ₂ Si (OMe) ₂ and 198.3 g (1.0 mol) PhSi (OMe) ₃ , 114.2 g (0.95 mol) Me ₂ Si (OMe) _{2 The same} procedure as in Synthesis Example 1-1 was performed, except that 188.4 g (0.95 mol) of PhSi (OMe) ₃ and 13.0 g (0.063 mol) of Si (OEt) ₄ were used. As a result, a silicone resin (I-2) was obtained as a colorless viscous liquid.
The yield of the silicone resin (I-2) is 163.0 g, the mass average molecular weight (Mw) is 900, and the composition ratio of the product is (Me ₂ SiO _2/2 ) _0.41 (PhSiO _3/2 ) _0.52 ( SiO _4/2 ) _0.06 , and the HO—Si group content was 8.5 mmol / g (14% by mass).

[Synthesis Example 2-2]
<Synthesis of silicone resin (A2)>
55.8 g of silicone resin (I-2), 167.4 g of toluene, 55.8 g of methanol, 12.7 g of 1,1,3,3-tetramethyldisiloxane and 0.30 mL of 70% concentrated nitric acid. It added in the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 167.4 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 toluene was distilled off from the organic layer by an evaporator, vacuum distillation (130 ° C., 2 hours) was performed by heating to obtain a silicone resin (A2) as a colorless and transparent viscous liquid.
The yield of the silicone resin (A2) is 55.1 g, the mass average molecular weight (Mw) is 1,000, the viscosity is 140 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.21 (PhSiO _{3/2 0.45} (SiO _4/2 ) _0.06 (H (Me) ₂ SiO _1/2 ) _0.28 , the H—Si group content is 2.6 mmol / g, and the HO—Si group content is 2. It was 9 mmol / g (4.9 mass%).

[Synthesis Example 2-3]
<Synthesis of silicone resin (B2)>
27.9 g of silicone resin (I-2), 83.7 g of toluene, 27.9 g of methanol, 8.81 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 3.03 mL 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 83.7 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 toluene was distilled off from the organic layer by an evaporator, vacuum distillation by heating (130 ° C., 2 hours) was performed to obtain a silicone resin (B2) as a colorless and transparent viscous liquid.
The yield of the silicone resin (B2) is 29.5 g, the weight average molecular weight (Mw) is 1,100, the viscosity is 200 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.26 (PhSiO _3/2 ) _0.42 (SiO _4/2 ) _0.05 (CH ₂ ═CH (Me) ₂ SiO _1/2 ) 0.27, CH ₂ ═CH—Si group content is 2.7 mmol / g, HO— The Si group content was 1.7 mmol / g (2.9% by mass).

[Synthesis Example 3-1]
<Synthesis of silicone resin (I-3)>
Instead of 120.2 g (1.0 mol) Me ₂ Si (OMe) ₂ and 198.3 g (1.0 mol) PhSi (OMe) ₃ , 108.2 g (0.90 mol) Me ₂ Si (OMe) _{2 The same} procedure as in Synthesis Example 1-1 was performed, except that 178.5 g (0.90 mol) of PhSi (OMe) ₃ and 26.0 g (0.125 mol) of Si (OEt) ₄ were used. As a result, a silicone resin (I-3) was obtained as a colorless and transparent viscous liquid.
The yield of the silicone resin (I-3) is 154.2 g, the mass average molecular weight (Mw) is 900, and the composition ratio is (Me ₂ SiO _2/2 ) _0.35 (PhSiO _3/2 ) _0.56 (SiO _{4 / 2} ) It was _0.10 , and the content of HO—Si groups was 8.5 mmol / g (14% by mass).

[Synthesis Example 3-2]
<Synthesis of silicone resin (A3)>
57.4 g of silicone resin (I-3), 172.2 g of toluene, 57.4 g of methanol, 16.4 g of 1,1,3,3-tetramethyldisiloxane and 0.39 mL of 70% concentrated nitric acid. It added in the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 172.2 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 toluene was distilled off from the organic layer by an evaporator, vacuum distillation by heating (130 ° C., 2 hours) was performed to obtain a silicone resin (A3) as a colorless and transparent viscous liquid.
The yield of the silicone resin (A3) is 58.4 g, the mass average molecular weight (Mw) is 1,100, the viscosity is 180 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.15 (PhSiO _{3/2 0.46} (SiO _4/2 ) _0.07 (H (Me) ₂ SiO _1/2 ) _0.33 , the H—Si group content is 3.2 mmol / g, and the HO—Si group content is 2. It was 7 mmol / g (4.6% by mass).

[Synthesis Example 3-3]
<Synthesis of silicone resin (B3)>
28.7 g of silicone resin (I-3), 86.1 g of toluene, 28.7 g of methanol, 11.4 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 3.92 mL 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 86.1 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. Toluene was distilled off from the organic layer by an evaporator, followed by vacuum distillation (130 ° C., 2 hours) by heating to obtain a silicone resin (B3) as a colorless and transparent viscous liquid.
The yield of the silicone resin (B3) is 32.7 g, the weight average molecular weight (Mw) is 1,300, the viscosity is 230 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.20 (PhSiO _{3/2 0.43} (SiO _4/2 ) _0.07 (CH ₂ ═CH (Me) ₂ SiO _1/2 ) _0.30 , CH ₂ ═CH—Si group content is 2.8 mmol / g, and HO—Si group The content of was 1.7 mmol / g (2.9% by mass).

[Synthesis Example 4-1]
<Synthesis of silicone resin (I-4)>
Instead of 120.2 g (1.0 mol) Me ₂ Si (OMe) ₂ and 198.3 g (1.0 mol) PhSi (OMe) ₃ , 96.2 g (0.80 mol) Me ₂ Si (OMe) _{2 The same} procedure as in Synthesis Example 1-1 was performed, except that 158.6 g (0.80 mol) of PhSi (OMe) ₃ and 52.1 g (0.25 mol) of Si (OEt) ₄ were used. As a result, a silicone resin (I-4) was obtained as a colorless and transparent viscous liquid.
The yield of the silicone resin (I-4) is 143.4 g, the mass average molecular weight (Mw) is 1,100, and the composition ratio is (Me ₂ SiO _2/2 ) _0.34 (PhSiO _3/2 ) _0.51 (SiO _4/2 ) _0.15 , and the HO—Si group content was 7.7 mmol / g (13 mass%).

[Synthesis Example 4-2]
<Synthesis of silicone resin (A4)>
173.7 g of silicone resin (I-4), 521.1 g of toluene, 173.7 g of methanol, 31.4 g of 1,1,3,3-tetramethyldisiloxane and 0.75 mL of 70% concentrated nitric acid. It added in the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 521.1 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 toluene was distilled off from the organic layer by an evaporator, vacuum distillation by heating (130 ° C., 2 hours) was performed to obtain a silicone resin (A4) as a colorless and transparent viscous liquid.
The yield of the silicone resin (A4) is 165.7 g, the mass average molecular weight (Mw) is 1,500, the viscosity is 4,000 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.16 (PhSiO _{3 / 2} ) _0.45 (SiO _4/2 ) _0.15 (H (Me) ₂ SiO _1/2 ) _0.24 , the H—Si group content is 2.2 mmol / g, and the HO—Si group content is It was 3.1 mmol / g (5.3 mass%).

[Synthesis Example 4-3]
<Synthesis of silicone resin (B4)>
91.4 g of silicone resin (I-4), 274.2 g of toluene, 91.4 g of methanol, 23.0 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 7.90 mL 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 274.2 g of water was added to perform extraction, 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, vacuum distillation by heating (130 ° C., 2 hours) was performed to obtain a silicone resin (B4) as a colorless and transparent viscous liquid.
The yield of the silicone resin (B4) is 99.2 g, the weight average molecular weight (Mw) is 1,400, the viscosity is 2,500 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.23 (PhSiO _3/2 ) _0.41 (SiO _4/2 ) _0.13 (CH ₂ ═CH (Me) ₂ SiO _1/2 ) _0.23 , CH ₂ ═CH—Si group content is 2.2 mmol / g, and HO—Si group content is It was 1.9 mmol / g (3.2% by mass).

[Synthesis Example 5-1]
<Synthesis of silicone resin (I-5)>
120.2g instead of PhSi (OMe) ₃ of Me2Si of (1.0mol) (OMe) ₂ and _{198.3g (1.0mol), Me 2 Si} (OMe) 2 in 90.2 g (0.75 mol), The same operation as in Synthesis Example 1-1 was performed, except that 148.7 g (0.75 mol) of PhSi (OMe) ₃ and 65.1 g (0.313 mol) of Si (OEt) ₄ were used. As a result, a silicone resin (I-5) was obtained as a colorless and transparent viscous liquid.
The yield of the silicone resin (I-5) is 137.7 g, the mass average molecular weight (Mw) is 1,300, and the composition ratio is (Me ₂ SiO _2/2 ) _0.28 (PhSiO _3/2 ) _0.53 (SiO _4/2 ) _0.19 , and the HO—Si group content was 7.4 mmol / g (13 mass%).

<Synthesis of silicone resin (A5)>
28.6 g of silicone resin (I-5), 85.8 g of toluene, 28.6 g of methanol, 5.69 g of 1,1,3,3-tetramethyldisiloxane and 0.14 mL of 70% concentrated nitric acid. It added in the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 85.8 g of water was added to perform extraction, 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, vacuum distillation by heating (130 ° C., 2 hours) was performed to obtain a silicone resin (A5) as a colorless and transparent viscous liquid.
The yield of the silicone resin (A5) is 27.5 g, the weight average molecular weight (Mw) is 1,600, the viscosity is 15,000 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.13 (PhSiO _{3 / 2} ) _0.43 (SiO _4/2 ) _0.21 (H (Me) ₂ SiO _1/2 ) _0.23 , the H—Si group content is 2.1 mmol / g, and the HO—Si group content is It was 2.7 mmol / g (4.6% by mass).

<Synthesis of silicone resin (B5)>
14.3 g of silicone resin (I-5), 42.9 g of toluene, 14.3 g of methanol, 3.95 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1.36 mL 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 42.9 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 toluene was distilled off from the organic layer by an evaporator, vacuum distillation by heating (130 ° C., 2 hours) was performed to obtain a silicone resin (B5) as a colorless and transparent viscous liquid.
The yield of the silicone resin (B5) is 15.2 g, the mass average molecular weight (Mw) is 1,500, the viscosity is 23,000 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.18 (PhSiO _{3 / 2} ) _0.40 (SiO _4/2 ) _0.19 (CH ₂ ═CH (Me) ₂ SiO _1/2 ) _0.23 , CH ₂ ═CH—Si group content is 2.3 mmol / g, Si— The OH group content was 1.7 mmol / g (2.9% by mass).

[Synthesis Example 6-1]
<Synthesis of silicone resin (I-6)>
Instead of 120.2 g (1.0 mol) Me ₂ Si (OMe) ₂ and 198.3 g (1.0 mol) PhSi (OMe) ₃ , 84.2 g (0.70 mol) Me ₂ Si (OMe) ₂ The same operation as in Synthesis Example 1-1 was performed, except that 138.8 g (0.70 mol) of PhSi (OMe) ₃ and 78.1 g (0.375 mol) of Si (OEt) ₄ were used. As a result, a silicone resin (I-6) was obtained as a colorless and transparent viscous liquid.
The yield of the silicone resin (I-6) is 140.8 g, the weight average molecular weight (Mw) is 1,500, and the composition ratio is (Me ₂ SiO _2/2 ) _0.29 (PhSiO _3/2 ) 0.44. (SiO _4/2 ) _0.27 , and the HO—Si group content was 6.8 mmol / g (12 mass%).

[Synthesis Example 6-2]
<Synthesis of silicone resin (A6)>
47.9 g of silicone resin (I-6), 143.7 g of toluene, 47.9 g of methanol, 10.9 g of 1,1,3,3-tetramethyldisiloxane and 0.26 mL of 70% concentrated nitric acid. It added in the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 143.7 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 toluene was distilled off from the organic layer by an evaporator, vacuum distillation (130 ° C., 2 hours) was performed by heating to obtain a silicone resin (A6) as a colorless and transparent viscous liquid.
The yield of the silicone resin (A6) is 59.3 g, the weight average molecular weight (Mw) is 1,900, the viscosity is 280,000 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.15 (PhSiO _{3 / 2} ) _0.40 (SiO _4/2 ) _0.22 (H (Me) ₂ SiO _1/2 ) _0.23 , the H—Si group content is 1.6 mmol / g, and the HO—Si group content is It was 2.5 mmol / g (4.3 mass%).

[Synthesis Example 6-3]
<Synthesis of silicone resin (B6)>
23.9 g of silicone resin (I-6), 71.7 g of toluene, 23.9 g of methanol, 7.55 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 2.60 mL 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 71.7 g of water was added to perform an extraction operation, 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, followed by vacuum distillation (130 ° C., 2 hours) by heating to obtain a silicone resin (B6) as a colorless and transparent viscous liquid.
The yield of the silicone resin (B6) is 32.0 g, the mass average molecular weight (Mw) is 1,900, the viscosity is 280,000 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.19 (PhSiO _{3 / 2} ) _0.39 (SiO _4/2 ) _0.21 (CH ₂ ═CH (Me) ₂ SiO _1/2 ) _0.21 , the CH ₂ ═CH—Si group content is 1.9 mmol / g, and HO— The Si group content was 1.6 mmol / g (2.7% by mass).

[Comparative synthesis example]
<Synthesis of silicone resin (DA1)>
Instead of 120.2 g (1.0 mol) Me ₂ Si (OMe) ₂ and 198.3 g (1.0 mol) PhSi (OMe) ₃ , 92.57 g (0.77 mol) Me ₂ Si (OMe) _{2 The same} procedure as in Synthesis Example 1-1 was performed, except that 152.68 g (0.77 mol) of PhSi (OMe) ₃ and 47.05 g (0.385 mol) of HSi (OMe) ₃ were used. As a result, a silicone resin (DA1) was obtained as a colorless and transparent viscous liquid.
The yield of the silicone resin (DA1) is 144.2 g, the mass average molecular weight (Mw) is 1,400, the viscosity is 34,000 cP, and the composition ratio is (Me ₂ SiO _2/2 ) 0.34 ( PhSiO _3/2 ) _0.42 (HSiO _3/2 ) _0.24 , the H—Si group content is 1.5 mmol / g, and the HO—Si group content is 7.2 mmol / g (12% by mass). Met.

<Synthesis of silicone resin (DA2)>
Into a ₂ L three-necked flask equipped with a fluororesin stirring blade and a Dimroth type reflux condenser, 48.1 g (0.40 mol) of Me ₂ Si (OMe) ₂ , 79.3 g (0.40 mol) of PhSi ( OMe) ₃ and 13.4 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane were collected. Next, 106 g of 2-propanol, 79.3 g of water and 0.06 g of acetic acid were added to the flask, and the flask was continuously heated at 100 ° C. for 6 hours to perform hydrolysis and condensation reaction. Went. Thereafter, the reaction solution was returned to room temperature, transferred to a 1 L separatory funnel, 200 mL of toluene and 200 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 200 mL of water. Thereafter, the organic layer was collected, and toluene was distilled off under reduced pressure using an evaporator to obtain a silicone resin (DA2) as a colorless viscous liquid.
The yield of the silicone resin (DA2) is 81.6 g, the mass average molecular weight (Mw) is 650, the viscosity is 300 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.38 (PhSiO _3/2 ) _0.40. (H (Me) ₂ SiO _1/2 ) _0.22 , the H—Si group content is 1.55 mmol / g, and the HO—Si group content is 4.7 mmol / g (8.0% by mass). )Met.

<Synthesis of silicone resin (DB1)>
Instead of 120.2 g (1.0 mol) Me ₂ Si (OMe) ₂ and 198.3 g (1.0 mol) PhSi (OMe) ₃ , 92.57 g (0.77 mol) Me ₂ Si (OMe) ₂ , similar to Synthesis Example 1-1 except that 152.68 g (0.77 mol) of PhSi (OMe) ₃ and 57.07 g (0.385 mol) of CH ₂ ═CH—Si (OMe) ₃ were used. The operation was performed. As a result, a silicone resin (DB1) was obtained as a colorless and transparent viscous liquid.
The yield of the silicone resin (DB1) is 122.3 g, the mass average molecular weight (Mw) is 1,200, the viscosity is 3,700 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.33 (PhSiO _{3 / 2) 0.47 (CH 2 =} CHSiO 3/2) was _0.20, the content of CH ₂ = CH-Si group is 1.7 mmol / g, content of HO-Si groups 10.7 mmol / g ( 18% by mass).

<Synthesis of silicone resin (DB2)>
30.1 g (0.25 mol) of Me ₂ Si (OMe) ₂ , 49.6 g (0.25 mol) of PhSi ( OMe) ₃ and 11.7 g (0.063 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were collected. Then 59.9 g of 2-propanol, 46.3 g of water and 0.03 g of acetic acid are added into the flask and the flask is warmed continuously at 100 ° C. for 6 hours to allow hydrolysis and A condensation reaction was performed. Thereafter, the reaction solution was returned to room temperature, transferred to a 1 L separatory funnel, 100 mL of toluene and 100 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 100 mL of water. Thereafter, the organic layer was collected, and toluene was distilled off under reduced pressure using an evaporator to obtain a silicone resin (DB2) as a colorless viscous liquid.
The yield of the silicone resin (DB2) is 39.8 g, the mass average molecular weight (Mw) is 1,000, the viscosity is 12,000 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.42 (PhSiO _{3 / 2) 0.54 (CH 2 =} CH (Me) 2) is _0.03, the content of CH ₂ = CH-Si group is 0.05 mmol / g, content of HO-Si groups 8.6 mmol / g (15% by mass).

<Synthesis of silicone resin (DB3)>
48.1 g (0.40 mol) Me ₂ Si (OMe) ₂ , 79.3 g (0.40 mol) PhSi (OMe) ₃ and 13.4 g (0.10 mol) 1,1,3,3-tetra Instead of methyldisiloxane, 48.1 g (0.40 mol) Me ₂ Si (OMe) ₂ , 79.3 g (0.40 mol) PhSi (OMe) ₃ and 23.2 g (0.20 mol) dimethylvinyl. Same as <Synthesis of Silicone Resin (DA2)> except that methoxysilane is used and instead of continuously heating at 100 ° C. for 6 hours, continuously heating at 100 ° C. for 15 hours Was performed. As a result, a silicone resin (DB3) was obtained as a colorless viscous liquid.
The yield of the silicone resin (DB3) is 89.3 g, the mass average molecular weight (Mw) is 630, the viscosity is 300 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.37 (PhSiO _3/2 ) _0.47 (CH ₂ = CH (Me) ₂ SiO _1/2 ) _0.16 , CH ₂ = CH-Si group content is 1.30 mmol / g, and HO-Si group content is 6.8 mmol / g. (12% by mass).

Composition ratios and physical property values (HO-Si) in the synthesized silicone resins (A1) to (A6), silicone resins (B1) to (B6), and silicone resins (DA1) to (DA2), (DB1) to (DB3) Table 2 shows the group content, SiH group or Si—CH═CH ₂ group content, mass average molecular weight, viscosity, refractive index, and transparency. In Table 2, Vi represents a vinyl group (CH ₂ ═CH— group).

<Curable silicone resin composition and cured product thereof>
Viscosity of the prepared composition, physical properties of the cured product obtained from the composition (hardness, adhesion, heat resistance, transparency, heat transparency, linear thermal expansion coefficient, 5% weight loss temperature, adhesive strength), curing The starting temperature and the appearance upon curing were measured as follows. The composition used for the measurement was composed of (A) component silicone resin [silicone resins (A1) to (A6), (DA1) to (DA2)] and (B) component silicone resin [silicone resin (B1). To (B6), (DB1) to (DB3)] are blended at a mass ratio of 2: 1 and mixed with the platinum catalyst of component (C) to prepare the compositions of Examples 1 to 6 and Comparative Examples 1 to 3. 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.

[Viscosity of composition]
Regarding the viscosity of the prepared composition, a rotational viscometer (Brookfield Engineering Laboratories, Inc., product name: DV-II + PRO) and a temperature control unit (Brookfield Engineering Laboratories, Inc., product name: THERMOSEL) were used. The value at 25 ° C. was measured at a shear rate of 30 [1 / s].

[Hardness of cured product]
The prepared composition was poured into a mold (25 mmφ), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to produce a cured product having a thickness of 4 to 5 mm. The hardness of Shore A or Shore D of this cured product is determined according to JIS K 7215 “Durometer Hardness Test Method for Plastics” using a durometer (manufactured by TECLOCK, model: GS-719R, GS-720R). It was measured by. In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.

[Adhesion of cured product]
The prepared composition was poured into a 3528 SMD type PPA resin package (3528 surface mount type polyphthalamide resin package) (3.5 mm × 2.8 mm × 0.9 mm), heated in air at 90 ° C. for 1 hour, and further 150 ° C. 16 samples were prepared by heating for 4 hours to obtain a cured product. These specimens were confirmed with an optical microscope, and the cured product peeled from the package was evaluated as “peeling”, and the cured product was evaluated as “adhesion”. Of the 16 samples, the number of samples evaluated as “adherence” was counted as “pass number”. In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.

[Transparency of cured product]
The prepared composition was poured into a mold (22 mmφ), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to produce a cured product having a thickness of 22 mmφ and 2 mm. Using a UV-visible spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-3150), the transmittance of the cured product in the wavelength region of 405 nm and 365 nm was measured. In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.

[Heat resistant transparency of cured products]
The prepared composition was poured into a mold (22 mmφ), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to produce a cured product having a thickness of 22 mmφ and 2 mm. The cured product was heated at 200 ° C. for 100 hours, and then the transmittance in the wavelength range of 405 nm and 365 nm was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-3150). In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.

[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. The linear thermal expansion coefficient of the cured product was measured by heating the cured product from 25 ° C. to 200 ° C. at a temperature increase rate of 5 ° C./min in the air using ThermoPlusTMA8310 (manufactured by Rigaku Corporation). This measurement was performed twice, and the second measured value was adopted. In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.

[5% weight loss temperature (T _d5 )]
The prepared composition was heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to produce a cured product. The cured product was measured using a ThermoPlus TG8120 (manufactured by Rigaku Corporation) as a thermogravimetric / differential thermal measurement apparatus (Thermogravimetric / Differential Thermal Analysis, abbreviated as TG-DTA) at a temperature rising rate of 5 ° C./min. It heated from 25 degreeC to 500 _degreeC, and measured the temperature ( _Td5 ) when a 5% weight loss was carried out. In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.

[Hardened adhesive strength]
A mixture of the prepared composition and zirconia balls having a diameter of 50 μm is mixed with a glass chip (5.0 mm × 5.0 mm × 1.1 mm) and a glass substrate (50 mm × 50 mm × 3.0 mm) or an alumina substrate ( 50 mm × 50 mm × 2.0 mm), and 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). A cured product that was destroyed at the time of measurement and an adhesive strength value could not be obtained was designated as “cohesive failure”. In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.

[Curing start temperature]
After the preparation, the composition was allowed to stand for 10 minutes. A rotational viscometer (Brookfield Engineering Laboratories, Inc., product name: DV-II + PRO) and a temperature control unit (Brookfield Engineering Laboratories, Inc., product name: THERMOSEL) Was used to measure the change in viscosity over time when the temperature was raised from 25 ° C. to 150 ° C. at a rate of 2.09 ° C./min at a shear rate of 30 [1 / s]. The temperature when the viscosity exceeded 30,000 cP was evaluated as the curing start temperature.

[Appearance when cured]
1 g of the prepared composition was thinly spread on a glass mold (22 mmφ). Then, it heated at 90 degreeC in the air for 1 hour, and also heated at 150 degreeC for 4 hours, and produced hardened | cured material. The produced cured product was naturally cooled to 25 ° C. Similarly, three test specimens were produced. Check the appearance of the specimen visually, and in all specimens, it is transparent and no foaming or cracking is observed. “Foamed” was evaluated as “uncured” in any of the test specimens in which the composition did not cure and remained a viscous liquid.

Table 3 shows the evaluation results of the compositions and cured products of Examples 1 to 6 and Comparative Examples 1 to 3.

In Examples 4 to 6 in which the composition ratio of (SiO) _4/2 in the silicone resin of the component (A) or the component (B) is 01 or more, the Shore A hardness exceeds 70 and the Shore D hardness exceeds 10 It was.

In Examples 4 to 6 in which the composition ratio of (SiO) _4/2 in the silicone resin of component (A) or component (B) was 0.1 or more, the adhesive strength exceeded 100N. In Examples 1 to 3, resin destruction (cohesive failure) was observed, and the measured value could not be detected. On the other hand, in Comparative Example 1, the adhesive strength was less than 50N.

Further, in the adhesion test, the cured product was “foamed” in Comparative Example 1, and there was no specimen in which the package was well sealed, whereas in Examples 1 to 6, an intimate specimen was observed. It was. In particular, in Examples 1 to 5, “adhesion” was observed in more than half of the samples, and in all of the 16 samples in Examples 1 and 3 to 5, “adhesion” was observed.

In the transparency test of the cured product, the cured products of Examples 1 to 6 showed high transparency of 88% or more at a wavelength of 365 nm and 90% or more at a wavelength of 405 nm. In contrast, the cured product of Comparative Example 1 had a transmittance of 45% or less. This cause is thought to be due to foaming of the cured product. Further, regarding the transparency (heat-resistant transparency) after the cured product was continuously heated at 200 ° C. for 100 hours, the cured products of Examples 1 to 6 were as high as 88% or more at a wavelength of 405 nm and 79% or more at a wavelength of 365 nm. The transmittance was maintained.

Regarding the heat resistance of the cured products, the cured products of Examples 1 to 6 exhibited T _{d5 of} 285 ° C. or higher, and in particular, the cured products of Examples 3 to 6 exhibited high T _d5 of 395 ° C. or higher.

Regarding the linear thermal expansion coefficient, the cured products of Examples 1 to 6 show less than 300 ppm by volume, in particular, the cured products of Examples 1 and 3 to 6 show less than 250 ppm by volume, and the cured products of Examples 4 to 6 Shows a good linear thermal expansion coefficient of less than 215 ppm by volume. A low linear thermal expansion coefficient indicates that the volume expansion and shrinkage in the heat cycle is small and the mold is difficult to peel off, so that the linear thermal expansion coefficient is preferably low.

The curing start temperature of the compositions of Examples 1 to 6 is as low as 58 to 79 ° C. and has good curability. On the other hand, in Comparative Examples 1 to 3, curing did not start even when the temperature was raised to 150 ° C.

From the above, it was shown that the compositions of Examples 1 to 6 within the scope of the present invention have good curability, and the cured product has high heat-resistant transparency. Also, the adhesion was good. In particular, it was shown that the cured products of Examples 3 to 6 were excellent in heat resistance and Shore hardness. In addition, the cured products of Examples 4 to 6 were shown to have high adhesive strength.

<Evaluation of platinum content and heat-resistant transparency>
Next, the silicone resin (A1) as the component (A) and the silicone resin (B1) as the component (B) are blended at a mass ratio of 2: 1 and mixed with the platinum catalyst as the component (C). 1-1 to Composition 1-5 were prepared. Also, a comparative composition 1-1 was prepared, in which the platinum catalyst of the component (C) was not blended, and the silicone resin (A1) and the silicone resin (B1) were blended at a mass ratio of 2: 1. Here, as the platinum catalyst, a platinum-divinyltetramethyldisiloxane complex was used so that the content of platinum atoms was a predetermined amount in mass units with respect to the total amount of the curable silicone resin composition.

Further, using the silicone resin (A4) instead of the silicone resin (A1) and the silicone resin (B4) instead of the silicone resin (B1), the compositions 4-1 to 4-3 and A comparative composition 4-1 was prepared. Using these compositions and comparative compositions, the physical properties (transparency and heat-resistant transparency) of the cured product, the curing start temperature, and the appearance of the cured product were determined using the above-mentioned [Transparency of cured product], [Curing Evaluation was performed according to the methods described in "Heat Transparency of Products", "Curing Start Temperature", and "Appearance upon Curing". These results are shown in Table 4, FIG. 2 and FIG.

As shown in Table 4, foams and cracks were observed in the cured products of Composition 1-1 to Composition 1-5, Composition 4-1 to Composition 4-3, and Comparative Composition 4-1. The appearance was “good”. In particular, since the appearance was also “good” in the compositions 1-5 and 4-3 in which the platinum atom content was 0.003 mass ppm with respect to the total amount of the composition, (A ) Component and (B) component were shown to have good curability. On the other hand, the comparative composition 1-1 containing no platinum catalyst was “uncured” and a cured product was not obtained. For this reason, various properties of the cured product were not evaluated in Comparative Composition 1-1.

Also, regarding the curing start temperature, the curing start temperature increased as the platinum atom content decreased. The curing start temperature of Composition 1-5 was higher than 150 ° C., but a cured product was obtained without any problem under the curing conditions (heating at 90 ° C. for 1 hour and further heating at 150 ° C. for 4 hours).

The transmittance of all the cured products was in the range of 88 to 91% at a wavelength of 405 nm and in the range of 89 to 91% at a wavelength of 365 nm, indicating high transparency. On the other hand, regarding transparency (heat-resistant transparency) after continuously heating the cured product at 200 ° C. for 100 hours, all cured products maintained high transmittance of 85% or more at a wavelength of 405 nm, but at a wavelength of 365 nm. The transmittance of the cured product of Comparative Composition 4-1 was 70%, and a decrease in transparency was observed. In contrast, the cured products of Composition 1-1 to Composition 1-5 and Composition 4-1 to Composition 4-4 maintained a transparency of 75% or more.

From the above, Composition 1-1 to Composition 1-5 and Composition 4-1 to Composition 4-4 within the scope of the present invention have good curability and high heat transparency. It was shown that.

<Evaluation of curing retarder and heat-resistant transparency>
(A) The silicone resin (A1) as the component and the silicone resin (B1) as the component (B) are blended at a mass ratio of 2: 1, the platinum catalyst of the component (C) is mixed, and various curing delays are further obtained. Compositions 1-6 to 1-9 were prepared by blending the agents. Here, as the platinum catalyst, a platinum-divinyltetramethyldisiloxane complex was used so that the platinum atom content was 2.0 ppm in terms of mass unit with respect to the total mass of the components (A) to (C). . The curing retarder was added in the range of 70 to 80 equivalents with a platinum atom content of 2.0 mass ppm as one equivalent. Specifically, in the preparation of composition 1-6, 118 μg of dimethyl maleate was added as a curing retarder to 1 g of the total composition, and in the preparation of composition 1-7, 3-butyn-2-ol was added. In the preparation of Composition 1-8, 67 μg of 2-methyl was added to 1 g of the total amount of the composition, and 94 μg of 1-ethynyl-1-cyclohexanol was added to 1 g of the total amount of the composition. In addition, 86 μg of tetramethylethylenediamine was added to 1 g of the total amount of the composition.

Using these compositions 1-6 to 1-9 and composition 1-1 as an example of a composition not containing a curing retarder, physical properties of these cured products (transparency and heat-resistant transparency) The appearance of the cured product and the curing start time are evaluated according to the methods described in [Transparency of cured product], [Heat-resistant transparency of cured product], [Appearance at curing], and [Curing start time] below. did. These results are shown in Table 5 and FIG.

[Curing start time]
The viscosity of the composition that was allowed to stand for 10 minutes after preparation was measured using a rotational viscometer (Brookfield Engineering Laboratories, Inc., product name: DV-II + PRO) and a temperature control unit (Brookfield Engineering Laboratories, Inc., product name). THERMEL was measured every 1 minute at 25 ° C. for up to 3 hours at a shear rate of 30 [1 / s]. The time when the viscosity exceeded 30,000 cP from the start of measurement was evaluated as the curing start time.

As shown in Table 5, in the cured products of Composition 1-1 and Composition 1-6 to Composition 1-9, no foaming and cracks were observed, and the appearance was “good”. The curing start time was 26 minutes after the composition 1-1, but more than 2 hours after the composition 1-6 to the composition 1-9 to which the curing retarder was added. It was found that the curability can be controlled by adding. Further, the transmittance of the cured products of the compositions 1-6 to 1-9 is 89% or more at a wavelength of 405 nm and 87% or more at a wavelength of 365 nm, and transparency is not impaired by a curing retarder. It was. Furthermore, the transparency (heat-resistant transparency) after the cured product was continuously heated at 200 ° C. for 100 hours was 85% or more at a wavelength of 405 nm and 74% or more at a wavelength of 365 nm. From this, it was found that the cured products of Composition 1-6 to Composition 1-9 all exhibited almost the same heat-resistant transparency as the cured product of Composition 1-1 to which no curing retarder was added. .

<Evaluation of light stabilizer and antioxidant and heat-resistant transparency>
The silicone resin (A4) as the component (A) and the silicone resin (B4) as the component (B) are blended at a mass ratio of 2: 1, and the platinum catalyst as the component (C) is mixed. Compositions 4-4 to 4-6 were prepared by blending an agent or an antioxidant. Here, as the platinum catalyst, a platinum-divinyltetramethyldisiloxane complex was used so that the content of platinum atoms was 0.2 ppm in mass units with respect to the total mass of the components (A) to (C). . The light stabilizer and the antioxidant were added in the range of 0.05 to 0.2% by mass with respect to the total mass of the components (A) to (C). Specifically, in the preparation of the composition 4-4, 0.5 mg of bis (2,2,6,6-tetramethyl 4-piperidyl) sebacate as a light stabilizer was added to 1 g of the total composition. . In the preparation of the composition 4-5, 1.0 mg of bis (2,2,6,6-tetramethyl 4-piperidyl) sebacate as a light stabilizer was added to 1 g of the whole composition. In the preparation of composition 4-6, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4, was used as an antioxidant. 6- (1H, 3H, 5H) -trione and 2,2-bis ({[3- (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl bis [3- (dodecylthio) propionate] Were added in an amount of 1.5 mg and 0.5 mg, respectively, per 1 g of the total composition.

Using these compositions 4-4 to 4-6 and composition 4-1 as an example of a composition not containing a light stabilizer and an antioxidant, the physical properties (transparency and Heat-resistant transparency) and the appearance of the cured product were evaluated according to the methods described in [Appearance at curing] and [Heat-resistant transparency of cured product containing antioxidant] described below.

[Heat resistant transparency of cured products containing antioxidants]
The prepared composition was heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to prepare a cured product of 22 mmφ and 2 mm thickness. Using a UV-visible spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-3150), the transmittance of the cured product in the wavelength region of 405 nm and 365 nm was measured. The cured product was further heated at 200 ° C., and when it was 100 hours and 200 hours passed, the temperature was once lowered to room temperature. The transmittance of the cured product after the temperature drop was measured in the same manner. From these measurement results, the variation ratio of the transmittance of the cured product after further heating was calculated based on the transmittance of the cured product before further heating.

Table 6 shows the evaluation results of the cured products of Composition 4-1 and Composition 4-4 to Composition 4-6.

As shown in Table 6, in the cured products of Composition 4-1 and Composition 4-4 to Composition 4-6, foaming and cracks were not observed, and the appearance was “good”. In the cured products of all the compositions, the transmittance after 100 hours and 200 hours after further heating at 200 ° C. is the transmittance after 0 hours (the transmittance in the 405 nm and 365 nm wavelength regions of the cured product before further curing). However, the composition 4-4 to 4-6 to which a light stabilizer or an antioxidant was added had a smaller transmittance fluctuation ratio than the composition 4-1. In the composition 4-6 to which the antioxidant was added, the transmittance fluctuation ratio was particularly small. From these results, it was shown that the addition of the light stabilizer or the antioxidant contributes to the improvement of the heat-resistant transparency of the cured product.

[Synthesis Example 7-1]
<High molecular weight of silicone resin (I-1)>
1,000 g of silicone resin in accordance with the silicone resin (I-1) described in Synthesis Example 1-1 was added to a four-necked 2 L flask equipped with a fluororesin stirring blade, Dean Starkle, and Dimroth type refluxing device. Collected. Next, 250 g of toluene was added, and the inside of the flask was continuously heated at 130 ° C. for 24 hours to conduct hydrolysis and condensation reactions. Thereafter, the reaction solution was returned to room temperature to prepare silicone resin (II) containing toluene.
The mass average molecular weight (Mw) of the silicone resin (II) is 5,200, the composition ratio is (Me ₂ SiO _2/2 ) _0.50 (PhSiO _3/2 ) _0.50 , and the content of HO—Si group is 4 0.5 mmol / g (6.7% by mass), and the toluene content was 20.49% by mass.

[Synthesis Example 7-2]
<Synthesis of silicone resin (A7)>
130.00 g of silicone resin (II), 288.91 g of toluene, 103.36 g of methanol, 10.25 g of 1,1,3,3-tetramethyldisiloxane and 0.24 mL of 70% concentrated nitric acid were added to the flask. In addition, the mixture was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 310 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 (A7) was obtained.
The yield of the silicone resin (A7) is 103.23 g, the mass average molecular weight (Mw) is 6,100, the viscosity is 5,100 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.39 (PhSiO _{3 / 2} ) _0.47 (H (Me) ₂ SiO _1/2 ) _0.14 , the H—Si group content is 1.26 mmol / g, and the HO—Si group content is 2.66 mmol / g (4 0.5% by mass).

[Synthesis Example 7-3]
<Synthesis of silicone resin (B7)>
65.00 g of silicone resin (II), 144.45 g of toluene, 51.68 g of methanol, 6.50 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 2.24 mL of 70 % Concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 155 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 (B7) was obtained.
The yield of the silicone resin (B7) is 49.34 g, the weight average molecular weight (Mw) is 4,800, the viscosity is 6,500 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.42 (PhSiO _{3 / 2) 0.49 (CH 2 =} CH (Me) 2 SiO 1/2) _0.9, the content of CH ₂ = CH-Si group is 0.87 mmol / g, content of HO-Si groups 2 It was 0.6 mmol / g (4.3% by mass).

[Synthesis Example 8-1]
<Synthesis of silicone resin (A8)>
130.00 g of silicone resin (II), 288.91 g of toluene, 103.36 g of methanol, 12.49 g of 1,1,3,3-tetramethyldisiloxane and 0.30 mL of 70% concentrated nitric acid in the flask In addition, the mixture was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 310 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 (A8) was obtained.
The yield of the silicone resin (A8) is 107.48 g, the mass average molecular weight (Mw) is 5,600, the viscosity is 2,800 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.40 (PhSiO _{3 / 2} ) _0.48 (H (Me) ₂ SiO _1/2 ) _0.12 , the H—Si group content is 1.40 mmol / g, and the HO—Si group content is 2.1 mmol / g (3 .6 mass%).

[Synthesis Example 8-2]
<Synthesis of silicone resin (B8)>
65.00 g of silicone resin (II), 144.45 g of toluene, 51.68 g of methanol, 8.67 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 2.98 mL of 70 % Concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 155 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 (B8) was obtained.
The yield of the silicone resin (B8) is 51.78 g, the mass average molecular weight (Mw) is 5,300, the viscosity is 5,000 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.39 (PhSiO _3/2 ) _0.44. (CH ₂ ═CH (Me) ₂ SiO _1/2 ) _0.17 , CH ₂ ═CH—Si group content is 1.05 mmol / g, and HO—Si group content is 2.3 mmol / g. (4.0% by mass).

[Synthesis Example 9-1]
<Synthesis of silicone resin (A9)>
130.00 g of silicone resin (II), 288.91 g of toluene, 103.36 g of methanol, 15.62 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 room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 310 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 (A9) was obtained.
The yield of the silicone resin (A9) is 106.52 g, the mass average molecular weight (Mw) is 5,800, the viscosity is 2,100 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.38 (PhSiO _{3 / 2) 0.42 (H (Me} ) 2 SiO 1/2) _0.20, the content of H-Si group is 1.81 mmol / g, content of HO-Si groups 1.7 mmol / g (2 0.9 mass%).

[Synthesis Example 9-2]
<Synthesis of silicone resin (B9)>
65.00 g of silicone resin (II), 144.45 g of toluene, 51.68 g of methanol, 10.84 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 3.73 mL of 70 % Concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 155 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 (B9) was obtained.
The yield of the silicone resin (B9) is 49.16 g, the weight average molecular weight (Mw) is 5,200, the viscosity is 3,900 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.39 (PhSiO _{3 / 2) 0.48 (CH 2 =} CH (Me) 2 SiO 1/2) _0.13, the content of CH ₂ = CH-Si group is 1.17 mmol / g, content of HO-Si groups 2 It was 0.2 mmol / g (3.7 mass%).

[Synthesis Example 10-1]
<Synthesis of silicone resin (A10)>
120.00 g of silicone resin (II), 306.93 g of toluene, 106.34 g of methanol, 24.59 g of 1,1,3,3-tetramethyldisiloxane and 0.59 mL of 70% concentrated nitric acid in the flask In addition, the mixture was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 320 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 (A10) was obtained.
The yield of the silicone resin (A10) is 110.66 g, the mass average molecular weight (Mw) is 5,700, the viscosity is 1,600 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.35 (PhSiO _{3 / 2} ) _0.41 (H (Me) ₂ SiO _1/2 ) _0.24 , the H—Si group content is 2.25 mmol / g, and the HO—Si group content is 1.18 mmol / g (2 0.0 mass%).

[Synthesis Example 10-2]
<Synthesis of silicone resin (B10)>
60.00 g of silicone resin (II), 153.47 g of toluene, 53.17 g of methanol, 17.07 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 5.87 mL of 70 % Concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 160 g 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, 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 (B10) was obtained.
The yield of the silicone resin (B10) is 55.70 g, the mass average molecular weight (Mw) is 4,800, the viscosity is 3,000 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.40 (PhSiO _{3 / 2} ) _0.45 (CH ₂ = CH (Me) ₂ SiO _1/2 ) _0.15 , CH ₂ = CH-Si group content is 1.43 mmol / g, and HO-Si group content is 1 0.9 mmol / g (3.0% by mass).

[Synthesis Example 11-1]
<Synthesis of silicone resin (A11)>
130.00 g of silicone resin (II), 288.91 g of toluene, 103.36 g of methanol, 31.23 g of 1,1,3,3-tetramethyldisiloxane and 0.75 mL of 70% concentrated nitric acid were added to the flask. In addition, the mixture was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 310 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 (A11) was obtained.
The yield of the silicone resin (A11) is 113.15 g, the mass average molecular weight (Mw) is 5,700, the viscosity is 1,000 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.36 (PhSiO _{3 / 2} ) _0.38 (H (Me) ₂ SiO _1/2 ) _0.26 , the H—Si group content is 2.7 mmol / g, and the HO—Si group content is 0.86 mmol / g (1 0.5% by mass).

[Synthesis Example 11-2]
<Synthesis of silicone resin (B11)>
65.00 g of silicone resin (II), 144.45 g of toluene, 51.68 g of methanol, 21.68 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 7.45 mL of 70 % Concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 155 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 (B11) was obtained.
The yield of the silicone resin (B11) is 53.64 g, the mass average molecular weight (Mw) is 5,200, the viscosity is 2,500 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.38 (PhSiO _{3 / 2} ) _0.45 (CH ₂ ═CH (Me) ₂ SiO _1/2 ) _0.17 , CH ₂ ═CH—Si group content is 1.6 mmol / g, and HO—Si group content is 1 It was 0.8 mmol / g (3.0 mass%).

[Synthesis Example 12-1]
<Synthesis of silicone resin (A12)>
39.7 g of silicone resin (I-1), 119 g of toluene, 39.7 g of methanol, 8.3 g of 1,1,3,3-tetramethyldisiloxane and 0.20 mL of 70% concentrated nitric acid were added to the flask. In addition, the mixture was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 119 g 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, 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 (A12) was obtained.
The yield of the silicone resin (A12) is 42.5 g, the weight average molecular weight (Mw) is 1,900, the viscosity is 200 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.31 (PhSiO _3/2 ) _0.42 (H (Me) ₂ SiO _1/2 ) _0.27 , the H—Si group content is 2.8 mmol / g, and the HO—Si group content is 2.0 mmol / g (3.4). Mass%).

[Synthesis Example 12-2]
<Synthesis of silicone resin (B12)>
19.9 g of silicone resin (I-1), 59.7 g of toluene, 19.9 g of methanol, 5.76 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1.98 mL 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, 59.7 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 (B12) was obtained.
The yield of the silicone resin (B12) is 20.6 g, the mass average molecular weight (Mw) is 1,800, the viscosity is 350 cP, and the composition ratio is (Me ₂ SiO _2/2 ) _0.32 (PhSiO _3/2 ) _0.45. (CH ₂ = CH (Me) ₂ SiO _1/2 ) _0.23 , CH ₂ = CH-Si group content is 2.3 mmol / g, and HO-Si group content is 2.1 mmol / g. (3.6% by mass).

Composition ratios and physical properties of the synthesized silicone resins (A7) to (A12) and silicone resins (B7) to (B12) (content of HO—Si group, content of SiH group or Si—CH═CH ₂ group) , Mass average molecular weight, viscosity, refractive index, transparency) are shown in Table 7. In Table 7, Vi represents a vinyl group (CH ₂ ═CH— group).

<Curable silicone resin composition and cured product thereof>
The viscosity of the prepared composition, the physical properties of the cured product obtained from the composition (hardness, adhesion, transparency, linear thermal expansion coefficient, 5% weight loss temperature, adhesive strength), and appearance upon curing are as described above. The measurement was performed according to the measurement methods of Examples 1 to 6 and Comparative Examples 1 to 3. Moreover, about the adhesiveness of hardened | cured material, it measured also about the case where a 6050 SMD type PPA resin package is used instead of a 3528 SMD type PPA resin package, and the measuring method is shown below. The punching moldability of the cured product is shown in the measurement method below. The composition used for the measurement was (A) component silicone resin [silicone resins (A7) to (A12)] and (B) component silicone resins [silicone resins (B7) to (B12)]. The compositions of Examples 7 to 12 were prepared by blending at a mass ratio of 1 and mixing with the platinum catalyst of component (C). 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.

[Adhesion of cured product (6050SMD type PPA resin package)]
The prepared composition was poured into 6050 SMD type PPA (6.0 mm × 5.0 mm × 2.0 mm), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to obtain a cured product 9 A specimen was prepared. These specimens were checked with an optical microscope, and the cured product peeled from the package was evaluated as “peeled”, and the cured product was evaluated as “adherent”. Of the 9 samples, the number of samples evaluated as “adherence” was counted as “pass number”.

[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”.

Table 8 shows the evaluation results of the compositions and cured products of Examples 7 to 12.

As shown in Table 8, the cured products produced in Examples 7 to 12 all have excellent heat-resistant transparency. In the adhesion test, all cured products showed excellent adhesion to the 3528 SMD type PPA resin package substrate. In particular, compared with the cured products of Examples 10 to 12, the cured products of Examples 7 to 9 having a high mass average molecular weight and a high Si—OH group content are larger than the 3528 SMD type PPA resin package. Excellent adhesion to a certain 6050 SMD type PPA resin package was exhibited. Further, in the punchability test, the cured product of Example 12 having a low mass average molecular weight could not be pulled out because of insufficient resin strength, whereas Examples 7 to 7 having a high mass average molecular weight were used. With the cured product of 11, the cured product could be punched without problems.

1 ... Sealing material,
2 ... Optical semiconductor element,
3 ... bonding wire,
4 ... reflecting material,
5 ... Lead frame,
6 ... Optical semiconductor substrate,
10: Optical semiconductor device.

Claims (15)

(A) component: a silicone resin represented by the following formula [1] and containing a hydrogen atom (SiH group) bonded to a silicon atom;
(B) component: a silicone resin represented by the following formula [2] and containing a vinyl group (Si—CH═CH ₂ group) bonded to a silicon atom, and (C) component: at least a platinum catalyst, The total content of silanol groups (Si—OH groups) in component (B) and component (B) is 0.5 to 5.0 mmol / g, and the content of platinum atoms in component (C) is (A) A curable silicone resin composition having a mass unit of 0.003 to 3.0 ppm based on the total mass of the component, the component (B), and the component (C).

(Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, two R ^{1 s} may be the same or different, and R ² is an alkyl group having 1 to 3 carbon atoms, R ² may be the same or different from each other, R ³ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a, b and c are each greater than 0, It is a number less than 1, d is a number greater than or equal to 0 and less than 1, satisfies a + b + c + d = 1, (SiR ² ₂ O _2/2 ), (R ³ SiO _3/2 ) and (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.)

(Wherein R ⁴ is an alkyl group having 1 to 3 carbon atoms, two R ⁴ may be the same or different from each other, and R ⁵ is an alkyl group having 1 to 3 carbon atoms, R ⁵ may be the same or different from each other, R ⁶ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and e, f and g are each greater than 0 Is a number less than 1, h is a number greater than or equal to 0 and less than 1, and satisfies e + f + g + h = 1, and (SiR ⁵ ₂ O _2/2 ), (R ⁶ SiO _3/2 ) and (SiO _4/2 ) Represents an oxygen atom forming a siloxane bond or an oxygen atom forming a silanol group. (A) Number of moles of hydrogen atoms bonded to silicon atoms in component: (B) Number of moles of vinyl groups bonded to silicon atoms in component is 0.8: 0.2 to 0.5: 0.5 The curable silicone resin composition according to claim 1. In the component (A), a, b, c and d are a: b: c: d = 0.10 to 0.40: 0.10 to 0.80: 0.10 to 0.80: 0 to 0 In the component (B), e, f, g and h are e: f: g: h = 0.10 to 0.40: 0.10 to 0.80: 0.10 to 0. 3. The curable silicone resin composition according to claim 1, wherein the curable silicone resin composition is 80: 0 to 0.70. In the component (A), a, b, c and d are a: b: c: d = 0.20 to 0.40: 0.10 to 0.40: 0.30 to 0.60: 0.10 In the component (B), e, f, g, and h are e: f: g: h = 0.20 to 0.40: 0.10 to 0.40: 0.30 to The curable silicone resin composition according to any one of claims 1 to 3, wherein the curable silicone resin composition is 0.60: 0.10 to 0.30. In component (A), d = 0, and a, b, and c are a: b: c = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80 In component (B), h = 0, and e, f, and g are e: f: g = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80. The curable silicone resin composition according to claim 1 or 2, wherein The curable silicone resin composition according to any one of claims 1 to 5, further comprising a curing retarder. The curable silicone resin composition according to any one of claims 1 to 6, further comprising an antioxidant or a light stabilizer. The curable silicone resin composition according to any one of claims 1 to 7, further comprising one or more selected from the group consisting of an adhesion-imparting agent, a phosphor and inorganic particles. 9. The composition according to claim 1, further comprising at least one selected from the group consisting of a mold release agent, a resin modifier, a colorant, a diluent, an antibacterial agent, an antifungal agent, a leveling agent, and an anti-sagging agent. The curable silicone resin composition described in 1. A cured product obtained by curing the curable silicone resin composition according to any one of claims 1 to 9. A sealing material comprising a cured product of the curable silicone resin composition according to any one of claims 1 to 9. A method for producing a cured product of a curable silicone resin composition, wherein the curable silicone resin composition according to any one of claims 1 to 9 is cured by heating at 45 ° C or higher and 300 ° C or lower. An optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable silicone resin composition according to any one of claims 1 to 9. A semiconductor adhesive comprising a cured product of the curable silicone resin composition according to any one of claims 1 to 9. An optical semiconductor device using the semiconductor adhesive according to claim 14.

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