KR101881604B1 - White thermosetting silicone resin composition useful as led reflector and optical semiconductor device using the same - Google Patents

Abstract

(b) 하기 화학식 (2)로 표시되는 실페닐렌 부위를 갖는 유기 규소 화합물,

(B) 백색 안료 3 내지 200 질량부,
(C) (B) 성분 이외의 무기 충전제 300 내지 1000 질량부, 및
(D) 경화 촉매 0.01 내지 10 질량부
를 포함하는 백색 열경화성 실리콘 수지 조성물; 및 광반도체 소자와, 상기 실리콘 수지 조성물의 경화물을 포함하는 리플렉터를 구비하는 광반도체 장치에 관한 것이다.The present invention provides, as the component (A)
(A1) an organosilicon compound having a silphenylene skeleton and a resin-bound organopolysiloxane structure and having a weight average molecular weight of 500 to 20,000 in terms of polystyrene containing a hydroxyl group, or
(A2) a combination of (a) and (b):
(a) an organopolysiloxane represented by the following average composition formula (1) and having a weight average molecular weight in terms of polystyrene of 500 to 20,000,

(b) an organosilicon compound having a silphenylene moiety represented by the following formula (2)

(B) 3 to 200 parts by mass of a white pigment,
(C) 300 to 1000 parts by mass of an inorganic filler other than the component (B), and
(D) Curing catalyst 0.01 to 10 parts by mass
A white thermosetting silicone resin composition; And an optical semiconductor device including the optical semiconductor element and a reflector including a cured product of the silicone resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a white thermosetting silicone resin composition useful as an LED reflector, and a photosemiconductor device using the composition. [0002]

The present invention relates to a white thermosetting silicone resin composition useful as an LED reflector and a photosemiconductor device using the composition.

Optical semiconductor devices such as LEDs (Light Emitting Diodes) have been used as various indicators and light sources such as street displays, automobile lamps, residential lighting, and the like. Among them, white LEDs have been applied to product development rapidly in various fields with the keywords of carbon dioxide reduction and energy saving because of high luminous efficiency.

BACKGROUND ART [0002] Polyphthalamide resin (PPA) is widely used as an optical reflector material which is one of semiconductor devices / devices such as LEDs and electronic equipment / devices. An optical reflector material using PPA exhibits excellent optical characteristics in the long wavelength region. However, as a result of recent advances in optical output and reduction in wavelength of optical semiconductor devices, PPA is used in the vicinity of optical semiconductor devices, which causes severe deterioration such as discoloration and causes a decrease in light output. Therefore, PPA is used as an optical reflector material Inappropriate.

An epoxy resin composition for optical semiconductor encapsulation on a B stage comprising an epoxy resin, a curing agent and a curing accelerator, wherein the composition is composed of a cured body of a resin composition uniformly mixed at a molecular level (Patent Document 1). In this composition, bisphenol A type epoxy resin or bisphenol F type epoxy resin is mainly used as the epoxy resin. Patent Document 1 also discloses that triglycidyl isocyanate and the like can be used, but triglycidyl isocyanate is used in small amounts in bisphenol-type epoxy resins in Examples. According to the studies of the present inventors, there is a problem that the cured product of the epoxy resin composition for semiconductor encapsulation on the B stage is yellowed by being left at a high temperature for a long time.

In addition, the problem of yellowing due to long-term storage at a high temperature even when a triazine derived epoxy resin is used in an epoxy resin composition for sealing a light-emitting element is not sufficiently solved (Patent Documents 2 to 4).

A resin composition for sealing an LED element containing an organopolysiloxane and a condensation catalyst and having excellent ultraviolet ray resistance is known (Patent Literature 5), but the composition is used for applications requiring higher transparency than applications using a white pigment such as a reflector .

The resin composition for an LED reflector using a silicone resin such as an organopolysiloxane is originally characterized by low strength and weakness characteristic of a silicone resin. Providing strength to a silicone resin having excellent heat resistance and weather resistance is a very important problem in resin compositions for LED reflectors.

Recently, a molding package size is becoming larger due to a MAP (Matrix Array Package) method or the like, and the sealing resin may become uncharged. Each of the above compositions is not satisfactory in this regard.

Japanese Patent Application Laid-Open No. 02-189958 Japanese Patent Application Laid-Open No. 2000-196151 Japanese Patent Application Laid-Open No. 2003-224305 Japanese Patent Application Laid-Open No. 2005-306952 Japanese Patent Application Laid-Open No. 2006-77234

Accordingly, it is an object of the present invention to provide a white thermosetting silicone resin composition which has high fluidity, preferably high fluidity, before curing to provide a high-strength cured product, and an optical semiconductor device using the cured product of the composition as a reflector.

As a result of intensive studies, the present inventors have found that the above object can be achieved by the following white thermosetting silicone resin composition and optical semiconductor device, and have completed the present invention.

That is, the present invention firstly,

(A)

(A1) 100 parts by mass of an organosilicon compound having a silphenylene skeleton and a resin-bound organopolysiloxane structure and having a weight average molecular weight of 500 to 20,000 in terms of polystyrene containing a hydroxyl group, or

(A2) 100 parts by mass of the combination of (a) and (b) below:

(a) 70 to 99 parts by mass of a resin-bound organopolysiloxane represented by the following average composition formula (1) and having a weight average molecular weight in terms of polystyrene of 500 to 20,000, and

A, b and c satisfy the following relationships: 0.8? A? 1.5, 0? B? 0.3, 0.001? C? 0.5 and 0.801 a + b + c <2 Lt; / RTI &gt;

(b) 1 to 30 parts by mass of an organosilicon compound having a silphenylene moiety represented by the following formula (2) (provided that the total amount of the components (a) and (b) is 100 parts by mass)

(Wherein R ¹ independently represents an alkoxy group or a hydroxy group, each of R ² and R ³ independently represents a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or a hydroxy group, and each of R ⁴ to R ⁷ Represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms, X independently represents a structural unit represented by the following formula (3) or (4), and X ' 4 '), and n is independently an integer of 0 to 9,

(Wherein each of R ⁸ and R ⁹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group)

Wherein each of R ¹⁰ and R ¹¹ represents a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or a hydroxy group, carbon atoms or other oxygen atoms are bonded to the left binding hand, and carbon Atoms or other silicon atoms are bonded)

(Wherein R &lt; ¹⁰ &gt; and R &lt; ¹¹ &gt; are as defined above)

(B) 3 to 200 parts by mass of a white pigment,

(C) 300 to 1000 parts by mass of an inorganic filler other than the component (B), and

(D) Curing catalyst 0.01 to 10 parts by mass

And a thermosetting silicone resin composition.

The present invention secondly provides an optical semiconductor device comprising a photo semiconductor element and a reflector including a cured product of the composition.

The white thermosetting silicone resin composition of the present invention preferably has high fluidity before curing and hardens to provide a cured product having high strength. The cured product is useful as a reflector, particularly an LED reflector, because it has a high light reflectance. In addition, the composition can be suitably used for forming an optical semiconductor device case such as an LED device case.

Hereinafter, the present invention will be described in more detail. In the present specification, the weight average molecular weight or the weight average molecular weight in terms of polystyrene refers to the weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using, for example, toluene as a developing solvent. Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

[Component (A)] [

1. (A1) Organosilicon compounds having a silphenylene skeleton and a resin-like organopolysiloxane structure

(A1) is an organosilicon compound having a silphenylene skeleton and a resin-bound organopolysiloxane structure (i.e., a branched or three-dimensional network-like organopolysiloxane structure) and having a weight average molecular weight of 500 to 20,000 in terms of polystyrene And contributes to the improvement of the substrate adhesion, heat resistance and mechanical strength of the obtained cured product. The component (A) contains a hydroxyl group and forms a crosslinked structure in the presence of a curing catalyst of the component (D) described later. The component (A1) may be used alone or in combination of two or more.

(A1) is produced by introducing a functional group capable of condensation reaction into an organosilicon compound having a silphenylene moiety (for example, a compound represented by the following formula (5)) to form an alkoxy group or a hydroxy group or a combination thereof (For example, a compound represented by the following formula (8)) and then reacting this with a trifunctional organosilane having an oxygen-containing functional group capable of condensation reaction (Trifunctional organosilane represented by the following formula (6) such as organotrialkoxysilane and organotrihydroxysilane (organosilanetriol)) or a hydrolysis-condensation product thereof (siloxane oligomer) or Can be obtained by a condensation reaction.

(Wherein each of R ⁵¹ to R ⁵⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms)

(Wherein R ⁶⁵ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and each of R ⁶⁶ to R ⁶⁸ represents an alkoxyl group or a hydroxyl group)

Examples of the hydrolytic condensate of a trifunctional organosilane having an oxygen-containing functional group capable of condensation reaction include hydrolysis and condensation products of organotrialkoxysilane such as alkyltrialkoxysilane and alkenyltrialkoxysilane Oligomers) represented by the following formula (7).

Examples of R ⁵¹ to R ⁵⁴ which are monovalent hydrocarbon groups of 1 to 6 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group, cycloalkyl groups such as cyclohexyl group, And aryl groups such as phenyl groups. Among them, the methyl group is preferable in view of the raw material availability and reactivity.

Examples of R ⁶⁵ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group; cycloalkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group and allyl group; And the like. Of these, the methyl group is preferable from the viewpoints of raw material availability and heat resistance.

Examples of the alkoxyl groups R ⁶⁶ to R ⁶⁸ include a methoxy group, an ethoxy group, and an isopropoxy group. Among them, a methoxy group is preferable because it is easy to obtain a raw material.

More specifically, the component (A1) includes, for example, a siloxane oligomer represented by the following formula (7) and a siloxane oligomer having a silphenylene moiety represented by the following formula (8) and containing an alkoxy group or a hydroxy group or a combination thereof Can be obtained by hydrolysis and condensation with an organic silane compound.

(Wherein R ⁷⁹ represents a monovalent hydrocarbon group of 1 to 6 carbon atoms, R ⁷⁰ independently represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms, and n represents a number of 1 to 10)

(Wherein, R ⁸¹ independently represents an alkoxy group or a hydroxy group, R ⁸² and R ⁸³ each independently represent a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or a hydroxyl group, R ⁸⁴ to R ⁸⁷ each Represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; X independently represents a structural unit represented by the following formula (9) or (10); and X ' 10 '), and m is independently an integer of 0 to 9,

(Wherein each of R ¹⁸ and R ¹⁹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group)

(Wherein each of R ²⁰ and R ²¹ represents a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or a hydroxy group, carbon atoms or other oxygen atoms are bonded to the left hand, and carbon Atoms or other silicon atoms are bonded)

(Wherein R &lt; ²⁰ &gt; and R &lt; ²¹ &gt; are as defined above)

Examples of R ⁷⁹ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group and allyl group, And the like. Of these, the methyl group is preferable from the viewpoints of raw material availability and heat resistance.

-OR ⁷⁰ is a hydroxy group or an alkoxy group having 1 to 6 carbon atoms, and examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group and an isopropoxy group. Among them, a methoxy group is preferable because it is easy to obtain a raw material.

Examples of the alkoxy group R ⁸¹ include a methoxy group, an ethoxy group, and an isopropoxy group. Among them, a methoxy group is preferable because it is easy to obtain a raw material.

Examples of R ⁸² and R ⁸³ which are monovalent aliphatic hydrocarbon groups include alkyl groups such as methyl group, ethyl group and isopropyl group, and alkenyl groups such as vinyl group and allyl group. Examples of the monovalent aromatic hydrocarbon group R ⁸² and R ⁸³ include aryl groups such as a phenyl group and a tolyl group. Examples of the alkoxy groups R ⁸² and R ⁸³ include a methoxy group, an ethoxy group, and an isopropoxy group. Of these, a methyl group and a methoxy group are preferable from the viewpoint of availability of raw materials.

Examples of R ⁸⁴ to R ⁸⁷ which are monovalent hydrocarbon groups of 1 to 6 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and isobutyl groups, cycloalkyl groups such as cyclohexyl, And aryl groups such as phenyl groups. Among them, the methyl group is preferable in view of the raw material availability and reactivity.

Each of R ¹⁸ and R ¹⁹ is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms (that is, a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms and a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, Aromatic hydrocarbon group). Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and isobutyl, cycloalkyl groups such as cyclohexyl, vinyl, allyl An aryl group such as a phenyl group, and the like. Of these, a hydrogen atom and a methyl group are preferable in terms of raw material availability.

Each of R ²⁰ and R ²¹ is preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms (that is, a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms and a monovalent aromatic hydrocarbon group having 1 to 6 carbon atoms )to be. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and isobutyl, cycloalkyl groups such as cyclohexyl, vinyl, allyl An aryl group such as a phenyl group, and the like. Examples of the alkoxy group represented by R ²⁰ and R ²¹ include a methoxy group, an ethoxy group, and an isopropoxy group. Among them, the methyl group is preferable from the viewpoint of raw material availability.

The compounding molar ratio of the compound of the formula (7) to the compound of the formula (8) is in a preferred range, and the content of the compound of the formula (8) is preferably 3 to 30 mol% 5 to 20 mol%. When the content is within the above range, the viscosity of the obtained composition becomes excessively high, resulting in a deterioration of fluidity and deterioration of moldability and a phenomenon in which the resultant cured product is too hard and insufficient crack resistance is hard to occur, .

The weight average molecular weight of the component (A1) in terms of polystyrene is usually 500 to 20,000, preferably 1,000 to 10,000, more preferably 2,000 to 8,000. If the molecular weight is less than 500, the obtained silicon compound is hardly solidified. If the molecular weight exceeds 20,000, the obtained composition may have an excessively high viscosity, resulting in deterioration of fluidity and deterioration of moldability.

(A1), a trifunctional organosilane having an oxygen-containing functional group capable of condensation reaction with a silphenylene skeleton-containing organosilicon compound containing an alkoxy group or a hydroxyl group or a combination thereof, or a hydrolysis-condensation product thereof (Siloxane oligomer) or a combination thereof is preferably 10 to 100 ° C, more preferably 20 to 80 ° C.

(7) obtained by hydrolytic condensation of a trifunctional organosilane represented by the above formula (6), such as a siloxane oligomer having a functional group capable of condensation reaction among raw materials of the component (A1) ), A (co) hydrolytic condensation product of one or more hydrolyzable group-containing silane compounds represented by the following formula (11) may also be used.

(Wherein R ³⁰ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y independently represents a halogen atom such as a chlorine atom or an alkoxy group having 1 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms And an aryloxy group having 6 to 8 carbon atoms, and k is 0, 1 or 2,

Examples of R ³⁰ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group, cycloalkyl groups such as cyclohexyl group and aryl groups such as phenyl group. Of these, the methyl group is preferable from the viewpoint of raw material availability.

Examples of the alkoxy group having 1 to 4 carbon atoms in Y include a methoxy group, an ethoxy group, and an isopropoxy group. Examples of the alkenyloxy group having 2 to 4 carbon atoms include a vinyloxy group and an allyloxy group. Examples of the aryloxy group having 6 to 8 carbon atoms include phenyloxy, have. Y is preferably a halogen atom, particularly a chlorine atom, from the standpoint of obtaining a solid organopolysiloxane.

Examples of the hydrolyzable group-containing silane compound represented by the above formula (11) include organotrichlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane and phenyltrichlorosilane; Organotrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane and the like; Diorganodichlorosilane such as dimethyldichlorosilane; Diorganoalkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane and methylphenyldiethoxysilane; Tetrachlorosilane; Tetramethoxysilane and the like.

Hydrolysis and condensation of the hydrolyzable group-containing silane compound can be carried out by a conventional method, but examples thereof include acid catalysts such as acetic acid, hydrochloric acid, and sulfuric acid, and organic bases such as sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide It is preferably carried out in the presence of an alkali catalyst. For example, when a silane containing a chloro group is used as the hydrolyzable group, a desired hydrolysis condensate having a desired molecular weight can be obtained by using hydrogen chloride gas generated by hydrogenation and hydrochloric acid as a catalyst.

The amount of water used for the hydrolysis and condensation is generally 0.9 to 1.6 moles, preferably 1.0 to 1.3 moles, per 1 mole of the hydrolyzable group (particularly chloro group) in the hydrolyzable group-containing silane compound. When the amount is in the range of 0.9 to 1.6 moles, the workability of the resulting composition and the toughness of the cured product of the composition tend to be excellent.

The hydrolysis and condensation of the hydrolyzable group-containing silane compound is usually carried out in an organic solvent such as an alcohol, a ketone, an ester, a cellosolve, or an aromatic compound. The organic solvent may be used alone or in combination of two or more. Specifically, the organic solvent is preferably an alcohol such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, n-butanol or 2-butanol, or an aromatic compound such as toluene or xylene, Isopropyl alcohol, toluene, and an isopropyl alcohol / toluene combination system are more preferable because toughness tends to be excellent.

The reaction temperature for hydrolysis and condensation is preferably 10 to 120 캜, more preferably 20 to 100 캜. When the reaction temperature satisfies this range, the hydrolysis-condensation product of a solid which can be used in the subsequent step is not easily gelated but easily obtained.

The content of the hydroxy group in the component (A1) is preferably 1.0 to 8.0% by mass, and more preferably 2.5 to 5.0% by mass.

2. A combination of (A2) - (a) and (A2) -b

(A2) - (a) a resin-bound organopolysiloxane

(A) of the component (A2) is an organopolysiloxane represented by the following average composition formula (1) and having a weight average molecular weight in terms of polystyrene of 500 to 20,000 as described above, and is a resin phase (i.e., a branched or three- ). (A2) The component (a) contains a hydroxyl group and forms a crosslinked structure in the presence of a curing catalyst of the component (D) described later. The component (A2) - (a) may be used alone or in combination of two or more.

A, b and c satisfy the following relationships: 0.8? A? 1.5, 0? B? 0.3, 0.001? C? 0.5 and 0.801 a + b + c <2 Lt; / RTI &gt;

When the value of a, which indicates the content of the methyl group (that is, the molar ratio with respect to the number of silicon atoms in the molecule, the same applies hereinafter) is less than 0.8, the resulting cured product of the silicone resin composition containing the resinous organopolysiloxane is too hard, A problem such as a shortage is likely to occur, which is not preferable. On the other hand, when a exceeds 1.5, the resulting resinous organopolysiloxane is hardly solidified. Preferably 0.9? A? 1.2, more preferably 0.9? A? 1.1.

When b, which represents the content of the organoxy group such as an alkoxy group, an alkenyloxy group or an aryloxy group, is more than 0.3, the molecular weight of the resulting resinous organopolysiloxane tends to be small and crack resistance is often lowered. Preferably 0.001? B? 0.2, and more preferably 0.01? B? 0.1.

When the content c of the hydroxyl group bonded to the Si atom is more than 0.5, the condensation reaction of the obtained resinous organopolysiloxanes or the condensation reaction between the organopolysiloxane and the organosilicon compound of the component (A2) - (b) The reaction or a combination of these condensation reactions tends to excess during heating and curing, and as a result, the resultant cured product exhibits high hardness and tends to have insufficient cracking resistance. On the other hand, if c is less than 0.001, the resulting resinous organopolysiloxane tends to have a high melting point, and there may be a problem in workability. If no bond is formed between the component (A2) - (a) and the component (A2) - (b), these components are not immobilized in the resulting cured product. As a result, the cured product has a low hardness, There is a tendency to deteriorate. Preferably 0.01? C? 0.3, more preferably 0.05? C? 0.2. In order to control the value of c, it is preferable to maintain the complete condensation ratio of the organoxy group such as an alkoxy group in the raw material at 86 to 96 mol%. When the above-mentioned complete condensation ratio is within the above-mentioned range, the melting point of the resulting resinous organopolysiloxane tends to become an appropriate value.

From the above point of view, it is preferable that 0.911? A + b + c? 1.8, more preferably 1.0? A + b + c? 1.5.

R is preferably an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group or an isopropyl group, an alkenyl group such as a vinyl group or an allyl group, A monovalent hydrocarbon group represented by the following formula Of these, a methyl group and an isopropyl group are preferable from the viewpoint of availability of raw materials.

The weight average molecular weight of the component (A2) - (a) in terms of polystyrene is usually 500 to 20000, preferably 1000 to 10000, and more preferably 2000 to 8000. If the molecular weight is less than 500, the resulting resinous organopolysiloxane is hardly solidified. If the molecular weight exceeds 20,000, the obtained composition may have an excessively high viscosity, resulting in reduced fluidity and poor moldability.

(A2) - (a) component, typically Q unit (SiO _4/2 units), T units of (CH ₃ SiO _3/2 units, and so on) and a D unit _{((CH 3) 2 SiO 2} /2 unit, and so on) . &Lt; / RTI &gt; (70 to 100 mol%) and more preferably 75 to 75 mol% (75 to 100 mol%) of the total siloxane unit when the component (A2) - (a) Mol%), and particularly preferably 80 mol% or more (80 to 100 mol%). If the molar ratio is less than 70 mol%, the overall balance of hardness, adhesion, and outline may be lost in the resulting cured product. The remainder may be D and Q units, and it is preferable that the total molar ratio of these units to the total siloxane units is 30 mol% or less (0 to 30 mol%).

(A2) - The component (a) can be obtained as a hydrolyzed condensate of a hydrolyzable group-containing silane compound represented by the following chemical formula (12). The hydrolyzable group-containing silane compounds may be used alone or in combination of two or more.

(Wherein Y 'is independently an aryl group such as a halogen atom such as a chlorine atom or an alkoxy group having 1 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, or an aryloxy group having 6 to 8 carbon atoms N is 0, 1 or 2,

Examples of the alkoxy group having 1 to 4 carbon atoms in Y 'include a methoxy group, an ethoxy group, and an isopropoxy group. Examples of the alkenyloxy group having 2 to 4 carbon atoms include a vinyloxy group and an allyloxy group. Examples of the aryloxy group having 6 to 8 carbon atoms include phenyloxy, have. Y 'is preferably a halogen atom, particularly a chlorine atom, from the standpoint of obtaining a solid organopolysiloxane.

Examples of the hydrolyzable group-containing silane compound represented by the above formula (12) include methyltrichlorosilane; Methyltrialkoxysilane such as methyltrimethoxysilane and methyltriethoxysilane; Dimethyldichlorosilane; Dimethyl dialkoxysilane such as dimethyl dimethoxysilane and dimethyl diethoxysilane; Tetrachlorosilane; Tetraalkoxy silane such as tetramethoxy silane and tetraethoxy silane, and the like.

Hydrolysis and condensation of the hydrolyzable group-containing silane compound may be carried out by a conventional method. For example, an acid catalyst such as acetic acid, hydrochloric acid or sulfuric acid, or an alkali such as sodium hydroxide, potassium hydroxide or tetramethylammonium hydroxide It is preferably carried out in the presence of a catalyst. For example, when a silane containing a chloro group is used as the hydrolyzable group, a desired hydrolysis condensate having a desired molecular weight can be obtained by using hydrogen chloride gas generated by hydrogenation and hydrochloric acid as a catalyst.

The amount of water used for the hydrolysis and condensation is generally 0.9 to 1.6 moles, preferably 1.0 to 1.3 moles, per 1 mole of the hydrolyzable group (particularly chloro group) in the hydrolyzable group-containing silane compound. When the amount is in the range of 0.9 to 1.6 moles, the workability of the resulting composition and the toughness of the cured product of the composition tend to be excellent.

The hydrolysis and condensation of the hydrolyzable group-containing silane compound is usually carried out in an organic solvent such as an alcohol, a ketone, an ester, a cellosolve, or an aromatic compound. The organic solvent may be used alone or in combination of two or more. Specifically, the organic solvent is preferably an alcohol such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, n-butanol or 2-butanol, or an aromatic compound such as toluene or xylene, Isopropyl alcohol, toluene, and an isopropyl alcohol / toluene combination system are more preferable because toughness tends to be excellent.

The reaction temperature for hydrolysis and condensation is preferably 10 to 120 캜, more preferably 20 to 100 캜. When the reaction temperature satisfies this range, gelation hardly occurs and a solid hydrolysis-condensation product usable in the next step can be easily obtained.

[(A2) - (b) Organosilicon compound having a silphenylene moiety]

(A2) - (b) is an organosilicon compound having a silphenylene moiety represented by the following formula (2) as described above. The components (A2) - (b) have a silylene moiety or siloxane moiety, or a combination thereof, together with a silphenylene moiety. An organosilicon compound having a silphenylene moiety such as the components (A2) - (b) contributes to improvement of substrate adhesion, heat resistance and mechanical strength of the resulting cured product. The components (A2) - (b) may be used singly or in combination of two or more.

Wherein R ¹ independently represents an alkoxy group or a hydroxy group, each of R ² and R ³ independently represents a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or a hydroxy group, and R ⁴ to R ⁷ Each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms; X independently represents a structural unit represented by the following formula (3) or (4); and X ' (4 '), and n is independently an integer of 0 to 9)

(Wherein each of R ⁸ and R ⁹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group)

Wherein each of R ¹⁰ and R ¹¹ represents a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or a hydroxy group, carbon atoms or other oxygen atoms are bonded to the left binding hand, and carbon Atoms or other silicon atoms are bonded)

(Wherein R &lt; ¹⁰ &gt; and R &lt; ¹¹ &gt; are as defined above)

(A2) - (b) may be added to the composition of the present invention in advance without being assembled in the resin (that is, without previously reacting with the components (A2) - (b) as the resin components) In addition, the component (A2) - (b) plays a role of a wetter, so that the composition has a high fluidity, and the moldability of the composition is improved and the composition is easily manufactured .

Examples of the alkoxy group R ¹ include a methoxy group, an ethoxy group, and an isopropoxy group. Among them, a methoxy group is preferable because it is easy to obtain a raw material.

Examples of R &lt; ² &gt; and R &lt; ³ &gt; which are monovalent aliphatic hydrocarbon groups include alkyl groups such as methyl group, ethyl group and isopropyl group, and alkenyl groups such as vinyl group and allyl group. Examples of the monovalent aromatic hydrocarbon group R ² and R ³ include an aryl group such as a phenyl group and a tolyl group. Examples of the alkoxy groups R ² and R ³ include a methoxy group, an ethoxy group, and an isopropoxy group. Of these, a methyl group and a methoxy group are preferable from the viewpoint of availability of raw materials.

When at least one of R ¹ to R ³ is an alkoxy group or a hydroxy group, when the component (A2) - (b) is reacted with the resinous organopolysiloxane of the component (A2) - (a), the adherence of the obtained cured product to the substrate, And the mechanical strength are improved by the contribution of the silphenylene moiety of the component (A2) - (b), and the occurrence of protruded portions at the time of molding is effectively prevented.

Examples of R ⁴ to R ⁷ which are monovalent hydrocarbon groups of 1 to 6 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and isobutyl groups, cycloalkyl groups such as cyclohexyl, And aryl groups such as phenyl groups. Among them, the methyl group is preferable in view of the raw material availability and reactivity.

Each of R ⁸ and R ⁹ is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms (that is, a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms and a monovalent hydrocarbon group having 1 to 6 carbon atoms, Aromatic hydrocarbon group). Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and isobutyl, cycloalkyl groups such as cyclohexyl, vinyl, allyl An aryl group such as a phenyl group, and the like. Of these, a hydrogen atom and a methyl group are preferable in terms of raw material availability.

Each of R ¹⁰ and R ¹¹ is preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms (that is, a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms and a monovalent aromatic hydrocarbon group having 1 to 6 carbon atoms )to be. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and isobutyl, cycloalkyl groups such as cyclohexyl, vinyl, allyl An aryl group such as a phenyl group, and the like. Examples of the alkoxy groups R ¹⁰ and R ¹¹ include a methoxy group, an ethoxy group, and an isopropoxy group. Among them, the methyl group is preferable from the viewpoint of raw material availability.

The amount of the component (A2) - (b) is usually from 1 to 30 parts by mass, preferably from 5 to 20 parts by mass, in total of 100 parts by mass of the components (A2) - (a) to be. If the amount is less than 1 part by mass, it is difficult to obtain a cured product having sufficient strength and toughness. When the blending amount exceeds 30 parts by mass, the silicone resin composition before curing tends to become excessively soft, which tends to make handling difficult.

[(B) white pigment]

The white pigment of component (B) is incorporated into the composition of the present invention to increase the whiteness of the cured product. The white pigment as the component (B) may be one usually used in a silicone resin composition for producing a cured product used for applications such as a reflector (reflector) of an optical semiconductor device. Examples of the component (B) include titanium dioxide, alumina, rare earth oxides (for example, yttrium oxide or lanthanum oxide), zinc sulfate, zinc oxide, magnesium oxide and hollow particles. The component (B) may be used alone or in combination of two or more.

As the white pigment of the component (B), it is preferable to use titanium dioxide in order to further enhance whiteness. The unit lattice of titanium dioxide may be any of a rutile type, an anatase type and a brookite type, but a rutile type is more preferable in terms of thermal stability.

The average particle diameter and shape of the component (B) are not limited. The average particle diameter of the component (B) is typically 0.05 to 5.0 mu m. The component (B) can be surface-treated in advance with a hydrated oxide of a metal such as Al or Si in order to enhance the compatibility with the resin component and the inorganic filler and the dispersibility. The average particle diameter can be obtained as the cumulative mass average value D ₅₀ (or median diameter) in the particle size distribution measurement by the laser diffraction method.

The blending amount of the component (B) is usually 3 to 200 parts by mass, preferably 5 to 150 parts by mass, more preferably 50 to 150 parts by mass, relative to 100 parts by mass of the total of the component (A) [component (A1) To 120 parts by mass. When the blending amount is less than 3 parts by mass, sufficient whiteness may not be obtained. When the blending amount exceeds 200 parts by mass, not only the proportion of other components added for the purpose of improving the mechanical strength is reduced but also the moldability is remarkably lowered. The proportion of the component (B) in the whole white thermosetting silicone resin composition of the present invention is preferably in the range of 1 to 50 mass%, more preferably 3 to 30 mass%.

[(C) Inorganic filler]

In the silicone resin composition of the present invention, an inorganic filler other than the component (B) is further blended as the component (C). As the inorganic filler of the component (C), those which are usually compounded in a silicone resin composition can be used. For example, silica such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, antimony trioxide and the like can be mentioned, but the white pigment (white coloring agent) . The component (C) may be used alone or in combination of two or more.

The average particle size and shape of the inorganic filler as the component (C) are not particularly limited, but the average particle size is preferably 3 to 40 占 퐉. The average particle diameter can be obtained as the cumulative mass average value D ₅₀ (or median diameter) in the particle size distribution measurement by the laser diffraction method.

Particularly, silica-based inorganic fillers such as fused silica and fused spherical silica are preferably used, and the particle size thereof is not particularly limited, but the average particle diameter is preferably 4 to 40 占 퐉 in view of moldability and fluidity of the composition, To 35 mu m. Further, in order to promote the high-temperature homogenization of the composition, it is preferable to use an inorganic filler having a fine particle size of 0.1 to 3 μm, a medium particle size of 4 to 8 μm, and an average particle size of a coarse particle size of 10 to 40 μm desirable.

The inorganic filler of the component (C) is surface-treated in advance with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to strengthen the bonding strength between the resin component such as the component (A) and the white pigment of the component (B) It may be something.

Examples of such coupling agents include epoxy functionalities such as? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Mercapto functional alkoxysilanes such as alkoxysilane, alkoxysilane, and alkoxysilane, and mercapto functional alkoxysilanes such as gamma-mercaptopropyltrimethoxysilane. It is not so desirable to cause discoloration of the surface-treated inorganic filler when it is left at 150 DEG C or more like an amine-based silane coupling agent. The amount of the coupling agent used in the surface treatment and the surface treatment method are not particularly limited.

The amount of the component (C) is preferably 300 to 1,000 parts by mass, more preferably 400 to 1,000 parts by mass, further preferably 400 to 950 parts by mass, particularly preferably 400 to 600 parts by mass, per 100 parts by mass of the total amount of the component (A). If the amount of the curing agent is less than 300 parts by mass, it may be impossible to obtain a cured product having sufficient strength. If the amount of the curing agent is more than 1,000 parts by mass, defective filling and loss of flexibility of the cured product may occur, Defects such as peeling of the reflector may occur in the semiconductor device. The proportion of the component (C) in the whole white thermosetting silicone resin composition of the present invention is preferably in the range of 10 to 90 mass%, and particularly preferably in the range of 20 to 80 mass%.

[(D) Curing Catalyst]

The curing catalyst of the component (D) is a condensation catalyst for use in curing the component (A), and is selected in consideration of the stability of the component (A), the curability of the composition, and the hardness and non-sulfur modification of the coating. The component (D) may be used alone or in combination of two or more. As the component (D), for example, an organic metal condensation catalyst such as an organic acid zinc, a Lewis acid catalyst, an organoaluminum compound, or an organic titanium compound is preferably used, and specifically, zinc benzoate, zinc octylate, p- But are not limited to, zinc benzoate, zinc laurate, zinc stearate, aluminum chloride, aluminum perchlorate, aluminum phosphate, aluminum triisopropoxide, aluminum acetylacetonate, ethylacetoacetate aluminum di (n-butyrate) Ethyl acetoacetic acid ester, tetrabutyl titanate, tetraisopropyl titanate, tin octylate, cobalt naphthenate, and tin naphthenate. Among them, zinc benzoate is preferably used.

The amount of the component (D) to be added is usually 0.01 to 10 parts by mass, more preferably 0.1 to 1.6 parts by mass, and particularly preferably 1.0 to 1.5 parts by mass based on 100 parts by mass of the total amount of the component (A). When the addition amount is less than 0.01 part by mass, it is difficult to obtain a composition stably having good curability. Even if the addition amount exceeds 10 parts by mass, the curability of the composition hardly improves, and it is difficult to save resources.

In addition to the above components, the following components may be incorporated into the composition of the present invention.

[(E) Release agent]

In the silicone resin composition of the present invention, an internal release agent can be incorporated. The component (E) may be used alone or in combination of two or more. The component (E) is blended so as to increase the releasability at the time of molding. The blending amount of the component (E) is 0.2 to 5.0 mass% with respect to the total composition of the present invention. As the internal mold release agent, for example, synthetic waxes such as natural wax and acid wax, polyethylene wax and fatty acid wax can be mentioned. Among them, calcium stearate having a melting point of 120 to 140 DEG C is preferably used.

[(F) coupling agent]

To the silicone resin composition of the present invention, a coupling agent such as a silane coupling agent or a titanate coupling agent may be added in order to strengthen the bonding strength between the resin and the inorganic filler. The component (F) may be used alone or in combination of two or more.

Examples of the component (F) include epoxy-based compounds such as? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Mercapto functional alkoxysilanes such as functional alkoxysilane and? -Mercaptopropyltrimethoxysilane, and the like are preferably used. It is not so desirable to cause discoloration of the silicone resin when it is left at 150 DEG C or more like an amine-based silane coupling agent.

The amount of the component (F) is not particularly limited, but is preferably 0.1 to 8.0 parts by mass, more preferably 0.5 to 6.0 parts by mass based on 100 parts by mass of the total amount of the component (A). When the blending amount is within the above range, the viscosity of the obtained composition tends to be maintained in an appropriate range, so that voids are less likely to be generated, and the adhesive effect of the obtained cured product and the substrate tends to be sufficient.

[(G) Organopolysiloxane Having a Straight Diorganopolysiloxane Residue]

The component (G) is an organopolysiloxane having a diorganopolysiloxane residue of a linear structure represented by the following formula (13) and containing a hydroxyl group. The component (G) is characterized by having the above-mentioned diorganopolysiloxane residue, and is used as a low stress agent. The component (G) may be used alone or in combination of two or more.

(Wherein each of R ³¹ and R ³² independently represents a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a vinyl group, a phenyl group or an allyl group, and m is an integer of 5 to 50)

Examples of R ³¹ and R ³² which are alkyl groups having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group and an isopropyl group. As R ³¹ and R ³² , a methyl group and a phenyl group are preferable.

m is an integer of usually 5 to 50, preferably 8 to 40, more preferably 10 to 35. When m is within the above range, crack resistance and mechanical strength of the resulting cured product are likely to be sufficient, and warping of the device is particularly unlikely to occur.

(G) component is the D unit represented by General Formula ^{(13) (R 31 R 32} SiO 2/2) M units in addition to the (R ₃ SiO _1/2) and the T units include (RSiO _3/2) . The molar ratio of D units: M units: T units is 90 to 24:75 to 0:50 to 1, particularly 70 to 28:70 to 20:10 to 2 (the sum of these units is 100) . Wherein R represents a hydroxyl group, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, a vinyl group or an allyl group. Further, the component (G) may contain a Q unit (SiO ₂ ).

(For example, 30 to 90 mol%), particularly 50 mol% or more (for example, 50 to 80 mol%) of the total siloxane units in the component (G) (Straight-chain diorganopolysiloxane structure) is preferably formed.

The weight average molecular weight of the component (G) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 10,000 to 100,000. When the molecular weight is in this range, the component (G) is a solid or a semi-solid, and is preferable from the viewpoints of workability and curability of the obtained composition.

The component (G) can be synthesized by condensing a compound serving as a raw material of each unit in such a manner that the molar ratio of the units becomes a desired molar ratio, for example, in the presence of an acid to effect condensation.

Examples of the raw material for the T unit include chlorosilanes such as MeSiCl ₃ , EtSiCl ₃ , PhSiCl ₃ , propyltrichlorosilane and cyclohexyltrichlorosilane, alkoxysilanes such as methoxysilane corresponding to each of these chlorosilanes Can be exemplified. Me, Et, Ph and Vi represent a methyl group, an ethyl group, a phenyl group and a vinyl group, respectively (hereinafter the same).

As the raw material of the D unit represented by the above formula (13)

(M = 3 to 48 integer (average value), n = 0 to 48 integer (average value), and m + n 3 to 48 (average value)).

Examples of the raw material of the M unit include chlorosilanes such as Me ₂ PhSiCl, Me ₂ ViSiCl, Ph ₂ MeSiCl and Ph ₂ ViSiCl, and alkoxysilanes such as methoxysilane corresponding to each of these chlorosilanes .

(G) can be obtained by combining these compounds as raw materials in a predetermined molar ratio, for example, as follows. First, the raw material mixture is obtained by mixing silane and siloxane as raw materials and an organic solvent such as toluene, dropping the raw material mixture into water, and hydrolyzing the mixture at 30 to 50 ° C for 1 hour. Subsequently, the reaction mixture is aged at 50 DEG C for 1 hour, washed with water, and the organic layer is separated. The organic layer is subjected to azeotropic dehydration or ammonia polymerization at 25 to 40 占 폚, followed by filtration and vacuum stripping to obtain a component (G).

In addition, the component (G) produced by the above cohydrolysis and condensation may contain a siloxane unit having a silanol group. The organopolysiloxane of component (G) contains such silanol group-containing siloxane units in an amount of preferably 0.5 to 10 moles, more preferably 1 to 5 moles, based on the total siloxane units. Examples of the silanol-containing siloxane units to play, for example, may be R '(HO) SiO _{2/2 units, R' (HO) 2 SiO} 1/2 unit, the R _'2 (HO) SiO _1/2 units ( Wherein R 'is as defined above, but not a hydroxyl group. Since the organopolysiloxane of the component (G) contains a silanol group, it reacts with an organosilicon compound having a silphenylene skeleton of the component (A) or a resin-bound organopolysiloxane structure.

The amount of the component (G) is preferably 2 to 50 parts by mass, more preferably 3 to 30 parts by mass based on 100 parts by mass of the component (A). When the blending amount is in the above range, the effect of improving the continuous formability is easily obtained, and the low warpage property and the cracking resistance are easily attained. In addition, the obtained composition hardly increases in viscosity, and is easily molded without trouble.

[Other additives]

In the silicone resin composition of the present invention, other various additives may be further added, if necessary. These additives may be used alone or in combination of two or more. For example, additives such as various silicone powders, silicone oils, thermoplastic resins, thermoplastic elastomers, and organic synthetic rubbers can be added to the composition of the present invention to the extent that the effects of the present invention are not impaired for the purpose of improving the properties of the resin have.

[Preparation and molding of composition]

The composition of the present invention can be obtained by mixing one or more of the components (A) to (D), and optionally (E) to (G) and other additives in a predetermined composition ratio, , Followed by melting and mixing treatment by a heat roll, a kneader, an extruder, etc., followed by cooling and solidification, followed by pulverization to an appropriate size.

The most common forming methods of the composition of the present invention include transfer molding and compression molding. The transfer molding process is carried out under the conditions of a molding pressure of 5 to 20 N / mm ² , a molding temperature of 120 to 190 ° C and a molding time of 30 to 500 seconds using a transfer molding machine, in particular a molding pressure of 5 to 20 N / mm ² , And a molding time of 30 to 180 seconds. The compression molding method is preferably performed under the conditions of a molding temperature of 120 to 190 占 폚 and a molding time of 30 to 600 seconds using a compression molding machine, particularly at a molding temperature of 130 to 160 占 폚 and a molding time of 120 to 300 seconds. In any molding method, post-curing can be performed at 150 to 185 캜 for 2 to 20 hours.

The cured product of the silicone resin composition of the present invention preferably has a linear expansion coefficient of 30 ppm / K or less, more preferably 25 ppm / K or less in a temperature range exceeding the glass transition temperature.

[Optical semiconductor device]

The optical semiconductor device of the present invention comprises a photo semiconductor device and a reflector including a cured product of the composition of the present invention. Examples of the optical semiconductor element include a light emitting element such as an LED and a light receiving element such as a photodiode, an optical sensor, and a CMOS image sensor. The reflector may be composed of only the cured product of the composition of the present invention, or may be a combination of the cured product and another reflector material.

[Example]

Hereinafter, the present invention will be described in detail by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

The raw materials used in Examples and Comparative Examples are shown below.

(A1) Organosilicon compounds having a silphenylene skeleton and a resin-like organopolysiloxane structure

A1-1: The organosilicon compound prepared in Synthesis Example 1

A1-2: The organosilicon compound prepared in Synthesis Example 2

A1-3: Organosilicon compound prepared in Synthesis Example 3

(A1 ') an organosilicon compound having an organopolysiloxane structure and no silphenylene skeleton (resin-bound organopolysiloxane)

A1-4: Organosilicon compound prepared in Synthesis Example 4

(A2-a) Resin-phase organopolysiloxane

A2-a-1: Resin-phase organopolysiloxane prepared in Synthesis Example 5

(A2-b) an organosilicon compound having a silphenylene moiety

A2-b-1: An organosilicon compound having a silphenylene moiety prepared in Synthesis Example 6

A2-b-2: An organosilicon compound having a silphenylene moiety prepared in Synthesis Example 7

(B) White pigment

B: rutile titanium dioxide: CR-95, average particle diameter 0.28 占 퐉 (manufactured by Ishihara Sangyo Co., Ltd.)

(C) Inorganic filler

C-1: Fused spherical silica: ES-105, average particle diameter 45 占 퐉 (manufactured by Tokai Mineral Co., Ltd.)

C-2: Fused spherical silica: N-MSR-04, average particle diameter 4 탆 (manufactured by Datsumori Co., Ltd.)

C-3: Fused spherical silica: SO-25R, average particle diameter 0.5 占 퐉 (manufactured by Adma Tech Co., Ltd.)

C-4: Fused spherical silica: CS-6103 53C2, average particle diameter 15 占 퐉 (manufactured by Tatsumori Co., Ltd.)

(D) Curing catalyst

D: zinc benzoate (manufactured by Wako Pure Chemical Industries, Ltd.)

(E) Releasing agent

E: Calcium stearate (manufactured by Wako Pure Chemical Industries, Ltd.)

(F) Coupling agent

F: 3-mercaptopropyltrimethoxysilane: KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[Synthesis Example 1] Synthesis of organosilicon compound A1-1 having a silphenylene skeleton and a resin-like organopolysiloxane structure

815.0 g (3.6 mol) of the compound of the following structural formula (14) obtained by methoxylation of methyltrichlorosilane, addition reaction of 1,4-bis (dimethylhydrogensilyl) benzene with vinyldimethoxymethylsilane with a platinum catalyst 183.6 g (0.40 mol) of the organosilicon compound represented by the following structural formula (15), 167 g of isopropyl alcohol and 1300 g of toluene were placed in a 5 L flask, and 26.2 g of methanesulfonic acid Thereafter, 173 g of water was added dropwise at 30 占 폚 or lower, and the mixture was stirred for 30 minutes. 1000 g of water was added to the reaction mixture and stirred, and then the organic layer was separated. The organic layer was washed with water until it became neutral. The organic layer was subjected to azeotropic dehydration, filtration and vacuum stripping to obtain 608 g of an organosilicon compound A-1 having a silphenylene skeleton and a resin-bound organopolysiloxane structure as a colorless transparent solid (weight average molecular weight 4,940). The content of the hydroxyl group in the organosilicon compound was 3.2% by mass.

[Synthesis Example 2] Synthesis of organosilicon compound A1-2 having a silphenylene skeleton and a resin-like organopolysiloxane structure

724.5 g (3.2 moles) of the compound of the above structural formula (14) obtained by methoxylation of methyltrichlorosilane, addition reaction of 1,4-bis (dimethylhydrogensilyl) benzene and vinyldimethoxymethylsilane with a platinum catalyst 367.1 g (0.60 mol) of the organosilicon compound represented by the structural formula (15) obtained above, 197 g of isopropyl alcohol and 1685 g of toluene were placed in a 5 L flask and 30.8 g of methanesulfonic acid was added dropwise at room temperature Thereafter, 173 g of water was added dropwise at 30 占 폚 or lower, and the mixture was stirred for 30 minutes. 1000 g of water was added to the reaction mixture and stirred, and then the organic layer was separated. The organic layer was washed with water until it became neutral. The organic layer was subjected to azeotropic dehydration, filtration and vacuum stripping to obtain 654 g of an organosilicon compound A1-2 having a silphenylene skeleton and a resin-like organopolysiloxane structure as a colorless transparent solid (weight average molecular weight 7,670). The content of the hydroxyl group in the organosilicon compound was 3.0% by mass.

Synthesis Example 3 Synthesis of organosilicon compound A1-3 having a silphenylene skeleton and a resin-like organopolysiloxane structure

815.0 g (3.6 moles) of the compound of the above structural formula (14) obtained by methoxylation of methyltrichlorosilane, addition reaction of 1,4-bis (dimethylhydrogensilyl) benzene and vinyltrimethoxysilane with a platinum catalyst 207.6 g (0.40 mol) of the organosilicon compound represented by the following structural formula (16), 167 g of isopropyl alcohol and 1300 g of toluene were placed in a 5 L flask, and 26.2 g of methanesulfonic acid Then, 181 g of water was added dropwise at 30 DEG C or lower, and the mixture was stirred for 30 minutes. 1000 g of water was added to the reaction mixture and stirred, and then the organic layer was separated. The organic layer was washed with water until it became neutral. The organic layer was subjected to azeotropic dehydration, filtration and vacuum stripping to obtain 622 g of an organosilicon compound A1-3 having a silphenylene skeleton and a resin-like organopolysiloxane structure as a colorless transparent solid (weight average molecular weight 7,520). The content of the hydroxyl group in the organosilicon compound was 3.0% by mass.

[Synthesis Example 4] Synthesis of organosilicon compound A1-4 having a resin-bound organopolysiloxane structure and no silphenylene skeleton

905.6 g (4.0 mol) of the compound of the above structural formula (14) obtained by methoxylation of methyltrichlorosilane, 137 g of isopropyl alcohol and 920 g of toluene were mixed in a 5 L flask, and to the resulting mixture was added methanesulfonic acid , 173 g of water was added dropwise at 30 占 폚 or lower, and the mixture was stirred for 30 minutes. 1000 g of water was added to the reaction mixture and stirred, and then the organic layer was separated. The organic layer was washed with water until it became neutral. The organic layer was subjected to azeotropic dehydration, filtration and vacuum stripping to obtain an organosilicon compound A1-4 having a resin-bound organopolysiloxane structure and no silphenylene skeleton (i.e., an organopolysiloxane on a resin) as a colorless transparent solid (Weight average molecular weight: 3,600).

[Synthesis Example 5] Synthesis of resin-bound organopolysiloxane A2-a

100 parts by mass of methyltrichlorosilane and 200 parts by mass of toluene were mixed in a 1 L flask, and a mixture of 8 parts by mass of water and 60 parts by mass of isopropyl alcohol was added dropwise to the obtained mixture under ice-cooling. The inner temperature was dropped over 5 to 20 hours while maintaining the temperature at -5 to 0 占 폚. Then, the reaction mixture was heated and stirred at a reflux temperature for 20 minutes, and then cooled to room temperature. To the reaction mixture, 12 parts by mass of water was added dropwise at 30 DEG C or lower over 30 minutes, and the mixture was stirred for 20 minutes. Further, 25 parts by mass of water was further added dropwise, and the mixture was stirred at 40 to 45 DEG C for 60 minutes. Further, 200 parts by mass of water was further added and stirred, and then the organic layer was separated. The organic layer was washed with water until it became neutral. The organic phase was subjected to azeotropic dehydration, filtration and vacuum stripping to obtain a resin-phase organopolysiloxane A2-a represented by the following formula (A2-a) as a colorless transparent solid (melting point 76 캜, weight average molecular weight 3,060) Mass part.

[Synthesis Example 6] Synthesis of organosilicon compound A2-b-1 having a silphenylene moiety

583.3 g (3.00 mol) of silphenylene (C) (1,4-bis (dimethylhydrogensilyl) benzene, manufactured by Kakogaku K.K.) and 200 g of toluene were mixed in a 5 L flask, , And a mixed solution of 933.8 g (6.30 mols) of KBM-1003 (vinyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.), 990 g of toluene and 1.05 g of 1 mass% of octyl alcohol- Dropwise. Thereafter, the reaction mixture was stripped under reduced pressure to obtain 1471.1 g (yield 100%) of an organosilicon compound A2-b-1 having a silphenylene moiety represented by the following structural formula (A2-b-1).

[Synthesis Example 7] Synthesis of organosilicon compound A2-b-2 having a silphenylene moiety

194.4 g (1.00 mol) of silphenylene (C) and 70 g of toluene were mixed in a 3 L flask, and heated to 100 占 폚. Then, 111.5 g (1.05 mol) of vinylsilanetriol, 330 g of toluene and 1 Mass% chloroplatinic acid octyl alcohol-modified solution (0.35 g) was added dropwise to the solution. Thereafter, the reaction mixture was stripped under reduced pressure to obtain 406.3 g (100% yield) of an organosilicon compound A2-b-2 having a silphenylene moiety represented by the following structural formula (A2-b-2).

[Examples 1 to 3 and Comparative Example 1]

(A1) an organosilicon compound having a silphenylene skeleton and a resin-bound organopolysiloxane structure or (A1 ') an organopolysiloxane structure having a resin-bound organopolysiloxane structure and having no silphenylene skeleton (B) a white pigment, (C) an inorganic filler, (D) a curing catalyst, (E) a releasing agent and (F) a coupling agent, mixing the mixture with a bus cone, Followed by pulverization to obtain a white silicone resin composition.

The following various properties were measured using the obtained composition. The results are shown in Table 1. Both were subjected to molding under the following conditions: using a transfer molding machine, molding temperature of 175 ℃, a molding pressure of 6.9 N / mm ^2, the molding time of 120 seconds.

Spiral flow value

The molds conforming to the EMMI standard were used and measured under the above conditions.

ㆍ Bending strength at room temperature, bending elastic modulus

Molding was performed under the above conditions using a mold conforming to the JIS-K6911 standard, and the obtained cured product was post-cured at 180 DEG C for 4 hours. The flexural strength and flexural modulus of the cured product after curing were measured at room temperature (25 캜) in accordance with JIS K 6911 standard.

ㆍ Light reflectance

Molding was performed under the above conditions to prepare a cured product of a circular plate having a diameter of 80 mm and a thickness of 0.20 mm. The cured product was measured for light reflectance at 450 nm using X-rite 8200 manufactured by S-Day & Respectively.

From Table 1, it can be seen that the strength is improved by using the component (A1). Further, it was confirmed that the cured product of the composition containing the component (A1) exhibits a good light reflectance value, and thus is effective as a reflector of the optical semiconductor device.

[Examples 4 to 6 and Comparative Example 2]

(A2-a) resin-bound organopolysiloxane, (A2-b) a silphenylene-containing compound, (B) a white pigment, (C) an inorganic filler, (D) a curing catalyst and (E) a releasing agent were mixed and melt-mixed by a heat roll, and then the obtained compound was cooled and pulverized to obtain a white silicone resin composition.

The following various properties were measured using the obtained composition. The results are shown in Table 2. Both were subjected to molding under the following conditions: using a transfer molding machine, molding temperature of 175 ℃, a molding pressure of 6.9 N / mm ^2, the molding time of 120 seconds.

Spiral flow value

The molds conforming to the EMMI standard were used and measured under the above conditions.

ㆍ Bending strength and flexural modulus at room temperature

Molding was performed under the above conditions using a mold conforming to JIS K 6911 standard, and the obtained cured product was post-cured at 180 ° C for 4 hours. The flexural strength and flexural modulus of the cured product after curing were measured at room temperature (25 캜) in accordance with JIS K 6911 standard.

ㆍ Light reflectance

Molding was carried out under the above conditions to prepare a cured product of a square plate having a side length of 50 mm and a thickness of 0.35 mm. Using a X-rite 8200 manufactured by S-date Co., Ltd., the cured product had a light reflectance Were measured.

ㆍ Linear expansion coefficient

Molding was performed under the above conditions to prepare a cured product of 5 mm x 5 mm x 15 mm, and the cured product was post cured at 180 ° C for 4 hours. The cured product after curing was measured for TMA8140C manufactured by Rigaku Corporation under the conditions of a temperature raising rate of 5 占 폚 / min and a temperature range of 50 to 100 占 폚.

From Table 2, it was found that the addition of the component (A2-b) improves flowability and strength. Further, it was confirmed that the cured product of the composition containing the component (A2-b) exhibits a good light reflectance value and tends to have a lower coefficient of linear expansion, and thus is effective as a reflector of an optical semiconductor device.

Claims (7)

(A) an organosilicon compound having a silphenylene skeleton and a resin-bound organopolysiloxane structure and having a weight average molecular weight of 500 to 20,000 in terms of polystyrene containing a hydroxyl group, or
(A2) 100 parts by mass of the combination of (a) and (b) below:
(a) 70 to 99 parts by mass of a resin-like organopolysiloxane represented by the following average composition formula (1) and having a weight average molecular weight in terms of polystyrene of 500 to 20,000,

A, b and c satisfy the following relationships: 0.8? A? 1.5, 0? B? 0.3, 0.001? C? 0.5 and 0.801 a + b + c <2 Lt; / RTI &gt;
(b) 1 to 30 parts by mass of an organosilicon compound having a silphenylene moiety represented by the following formula (2) (provided that the total amount of the components (a) and (b) is 100 parts by mass)

(Wherein R ¹ independently represents an alkoxy group or a hydroxy group, each of R ² and R ³ independently represents a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or a hydroxy group, and each of R ⁴ to R ⁷ Represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 6 carbon atoms, X independently represents a structural unit represented by the following formula (3) or (4), and X ' 4 '), and n is independently an integer of 0 to 9,

(Wherein each of R ⁸ and R ⁹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group)

Wherein each of R ¹⁰ and R ¹¹ represents a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or a hydroxy group, carbon atoms or other oxygen atoms are bonded to the left binding hand, and carbon Atoms or other silicon atoms are bonded)

(Wherein R &lt; ¹⁰ &gt; and R &lt; ¹¹ &gt; are as defined above)
(B) 3 to 200 parts by mass of a white pigment,
(C) 300 to 1000 parts by mass of an inorganic filler other than the component (B), and
(D) Curing catalyst 0.01 to 10 parts by mass
And a thermosetting silicone resin composition. The composition of claim 1, wherein the curing catalyst of component (D) is an organometallic condensation catalyst. The composition of claim 1 further comprising (E) a release agent in an amount of 0.2 to 5.0 percent by weight of the total composition. The composition according to claim 2, further comprising (E) a release agent in an amount of 0.2 to 5.0 mass% of the total composition. The composition according to claim 3, wherein the mold release agent of component (E) is calcium stearate. 5. The composition of claim 4, wherein the mold release agent of component (E) is calcium stearate. An optical semiconductor device comprising an optical semiconductor element and a reflector including a cured product of the composition according to any one of claims 1 to 6.