KR102498396B1 - Curable silicone composition and optical semiconductor device using the same - Google Patents

Abstract

A curable silicone composition that provides a cured product having excellent curability, high thermal shock resistance and low gas permeability. Furthermore, by applying the curable silicone composition to an optical semiconductor device, an optical semiconductor device having the advantages of being excellent in thermal shock resistance and maintaining high luminous efficiency is provided. An organopolysiloxane having an alkylphenylvinylsiloxane unit (R ² R ³ R ⁴ SiO _0.5 ; where R ² is an alkyl group such as methyl group, R ³ is a phenyl group, and R ⁴ is an alkenyl group such as vinyl group), and the content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is greater than 0.0% by mass and less than 3.0% by mass with respect to the entire composition. and an optical semiconductor device using the same.

Description

Curable silicone composition and optical semiconductor device using the same

The present invention relates to a curable silicone composition, and in detail, a curable silicone composition that can be preferably used as a sealing material or a protective coating material for an optical semiconductor element in an optical semiconductor device such as a light emitting diode (LED), and an optical semiconductor device using the same It is about.

BACKGROUND OF THE INVENTION Curable silicone compositions are used for sealing materials or protective coating materials for optical semiconductor elements in optical semiconductor devices such as light emitting diodes (LEDs). However, since the cured product of the curable silicone composition has high gas permeability, the intensity of light is strong, and when used in a high-brightness LED with high heat generation, there is a problem of discoloration of the encapsulant due to corrosive gas or decrease in luminance due to corrosion of silver plated on the LED substrate. It is becoming. It is because these become a cause of the luminous efficiency attenuation of an optical semiconductor device.

On the other hand, Patent Document 1 and Patent Document 2 propose a curable silicone composition comprising a branched organopolysiloxane having a methylphenylvinylsiloxane unit, an organohydrogenpolysiloxane, and a catalyst for an addition reaction, and these compositions have gas permeability It is disclosed to impart a low cured product. However, these curable silicone compositions have insufficient curability and thermal shock resistance of a cured product to be obtained, and further improvement has been desired.

Japanese Unexamined Patent Publication No. 2012-052045 Japanese Unexamined Patent Publication No. 2014-084417

An object of the present invention is to provide a curable silicone composition that gives a cured product having high hydrosilylation reactivity, excellent curability and thermal shock resistance, and low gas permeability. Moreover, the objective of this invention is providing the optical semiconductor device etc. which are excellent in thermal shock resistance and maintain high luminous efficiency by using the said curable silicone composition.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that an organopolysiloxane containing an alkylphenylvinylsiloxane unit is contained, and 1,3-divinyl-1,3-diphenyl-1,3-dimethyl It was found that the above problems can be solved by a curable silicone composition characterized in that the content range of disiloxane is greater than 0.0% by mass and less than 3.0% by mass, and the present invention has been reached. 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is a compound that remains in organopolysiloxane during the synthesis of branched or resinous organopolysiloxanes containing alkylphenylvinylsiloxane units. Although it is a component, the said subject is solvable by using the curable silicone composition whose content was controlled so that it might fall within the said range.

The curable silicone composition of the present invention

Organopolysiloxane having an alkylphenylalkenylsiloxane unit (R ² R ³ R ⁴ SiO _1/2 ; R ² is an alkyl group having 1 to 12 carbon atoms; R ³ is a phenyl group; R ⁴ is an alkenyl group having 2 to 12 carbon atoms) In addition, the content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is greater than 0.0% by mass and less than 3.0% by mass with respect to the entire composition. .

Preferably, the curable silicone composition of the present invention

(A) average unit formula:

(R ¹ ₃ SiO _1/2 ) _a (R ² R ³ R ⁴ SiO _1/2 ) _b (R ⁵ ₂ SiO _2/2 ) _c (R ³ SiO _3/2 ) _d

(Wherein, R ¹ is the same or different C 1 to C 12 alkyl group or C 2 to C 12 alkenyl group, provided that at least one R ¹ in one molecule is a C 2 to C 12 alkenyl group; R ² is C 1 ~12 alkyl group; R ³ is a phenyl group; R ⁴ is an alkenyl group having 2 to 12 carbon atoms; R ⁴ is an alkenyl group having 2 to 12 carbon atoms; R ⁵ is the same or different alkyl group having 1 to 12 carbon atoms; Alkenyl group or phenyl group of; a, b, c, and d are numbers satisfying 0.00≤a≤0.45, 0.01≤b≤0.45, 0≤c≤0.7, 0.1≤d<0.9, and a+b+c+d = 1, respectively. am.)

An organopolysiloxane represented by

(B) a straight-chain organopolysiloxane having at least two alkenyl groups in one molecule and no silicon atom-bonded hydrogen atoms (0 to 70% by mass relative to the present composition);

(C) organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {the silicon-bonded hydrogen atoms in this component are 0.1 to 5 per mole of the total of alkenyl groups in component (A) and component (B) amount to be a mole},

(D) an effective amount of a catalyst for the hydrosilylation reaction, and

Optionally, (E) adhesion imparting agent {0.01 to 10 parts by mass relative to 100 parts by mass in total of the components (A) to (D) above}

It is made by containing, and also,

It is characterized in that the content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is in the range of 0.05% by mass to 2.50% by mass with respect to the entire composition.

The cured product of the present invention is characterized in that it is obtained by curing the curable silicone composition.

The optical semiconductor device of the present invention is characterized in that an optical semiconductor element is sealed with a cured product of the curable silicone composition.

The curable silicone composition of the present invention is characterized by forming a cured product having high hydrosilylation reactivity, excellent curability and thermal shock resistance, and low gas permeability. Furthermore, the cured product of the present invention is characterized by low gas permeability and excellent thermal shock resistance, and the optical semiconductor device of the present invention equipped with the cured product is characterized by excellent reliability and sustained high luminous efficiency.

1 is a cross-sectional view of an LED as an example of an optical semiconductor device of the present invention.

First, the curable silicone composition of the present invention will be described in detail.

The curable silicone composition of the present invention is an alkylphenylalkenylsiloxane unit (R ² R ³ R ⁴ SiO _1/2 ; R ² is an alkyl group having 1 to 12 carbon atoms; R ³ is a phenyl group; R ⁴ is an alkenyl group having 2 to 12 carbon atoms) The organopolysiloxane characterized as first by containing an organopolysiloxane having a) has excellent hydrosilylation reactivity and can form a cured product having low gas permeability. The organopolysiloxane may contain other siloxane units, and particularly preferably has a branched chain or resin molecular structure. Such an organopolysiloxane is preferably,

Mean unit formula:

(R ¹ ₃ SiO _1/2 ) _a (R ² R ³ R ⁴ SiO _1/2 ) _b (R ⁵ ₂ SiO _2/2 ) _c (R ³ SiO _3/2 ) _d

represented by

In formula, R ^<1> is the same or different C1-C12 alkyl group or C2-C12 alkenyl group. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group, and a methyl group is preferred. Examples of the alkenyl group for R ¹ include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group, and preferably It is a vinyl group. However, at least one R ¹ in one molecule is an alkenyl group having 2 to 12 carbon atoms. In addition, R ² is an alkyl group having 1 to 12 carbon atoms, and the same alkyl group as the above R ¹ is exemplified, preferably a methyl group. In addition, R ³ is a phenyl group. R ⁴ is an alkenyl group having 2 to 12 carbon atoms, and the same alkenyl group as the above R ¹ is exemplified, preferably a vinyl group. Moreover, R ^<5> is the same or different C1-C12 alkyl group, C2-C12 alkenyl group, or a phenyl group. Examples of the alkyl group for R ⁵ include the same alkyl groups as those for R ¹ above. As the alkenyl group for R ⁵ , the same alkenyl groups as those for R ¹ are exemplified.

In the formula, a, b, c, and d are numbers satisfying 0.00≤a≤0.45, 0.01≤b≤0.45, 0≤c≤0.7, 0.1≤d<0.9, and a+b+c+d = 1, respectively; Preferably, it is a number that satisfies 0.00≤a≤0.45, 0.05≤b≤0.45, 0≤c≤0.5, 0.4≤d<0.85, and a+b+c+d = 1, more preferably 0.00≤a≤0.4, 0.05 ≤b≤0.4, 0≤c≤0.4, 0.45≤d<0.8, and a number that satisfies a+b+c+d=1. This is because low gas permeability of a hardened|cured material can be realized if a is below the upper limit of the said range. When b is equal to or greater than the lower limit of the above range, low gas permeability of the cured product can be achieved, while when b is equal to or less than the upper limit of the above range, it is difficult to cause stickiness in the cured product. Moreover, it is because the hardness of hardened|cured material becomes favorable and reliability improves that c is below the upper limit of the said range. In addition, it is because the refractive index of hardened|cured material becomes favorable when d is more than the lower limit of the said range, and on the other hand, it is because the mechanical properties of hardened|cured material improve when it is less than the upper limit of the said range.

The organopolysiloxane according to the present invention is represented by the above average unit formula, but within a range that does not impair the object of the present invention, a siloxane unit represented by formula: R ² ₂ R ³ SiO _1/2 , formula: R ² R ³ ₂ A siloxane unit represented by SiO _1/2 , a siloxane unit represented by formula: R ³ ₃ SiO _1/2 , a siloxane unit represented by formula: R ² SiO _3/2 , a siloxane unit represented by formula: R ⁴ SiO _3/2 , or Formula: You may have a siloxane unit represented by SiO _4/2 . In the formula, R ² is an alkyl group having 1 to 12 carbon atoms, R ³ is an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ⁴ is an alkenyl group having 2 to 12 carbon atoms, respectively. The same groups as are exemplified. In addition, the organopolysiloxane of the present invention may have a silicon atom-bonded alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group, or a silicon-bonded hydroxyl group, as long as the object of the present invention is not impaired.

As a method for preparing such an organopolysiloxane, for example, formula (I):

R ³ SiX ₃

A silane compound represented by Formula (II-1):

R ¹ ₃ SiOSiR ¹ ₃

A disiloxane represented by and/or formula (II-2):

R ¹ ₃ SiX

A silane compound represented by and formula (III-1):

R ² R ³ R ⁴ SiOSiR ² R ³ R ⁴

A disiloxane represented by and/or formula (III-2):

R ² R ³ R ⁴ SiX

The method of carrying out the hydrolysis and condensation reaction of the silane compound represented by in the presence of an acid or an alkali is mentioned.

Formula (I):

R ³ SiX ₃

The silane compound represented by is a raw material for introducing a siloxane unit represented by formula: R ³ SiO _3/2 into organopolysiloxane. In the formula, R ³ is an aryl group of 6 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms, and the same groups as described above are exemplified, and preferably a phenyl group or a naphthyl group. In addition, in formula, X is an alkoxy group, an acyloxy group, a halogen atom, or a hydroxyl group. As an alkoxy group of X, a methoxy group, an ethoxy group, and a propoxy group are illustrated. Moreover, as an acyloxy group of X, an acetoxy group is illustrated. Moreover, as a halogen atom of X, a chlorine atom and a bromine atom are illustrated.

Examples of such silane compounds include alkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; acyloxysilanes such as phenyltriacetoxysilane; halosilanes such as phenyltrichlorosilane; Hydroxysilanes, such as phenyl trihydroxysilane, are illustrated.

Also, formula (II-1):

R ¹ ₃ SiOSiR ¹ ₃

The disiloxane represented by is a raw material for introducing a siloxane unit represented by formula: R ¹ ₃ SiO _1/2 into organopolysiloxane. In formula, R ^<1> is the same or different C1-C12 alkyl group or C2-C12 alkenyl group. As the alkyl group for R ¹ , groups similar to those described above are exemplified, and a methyl group is preferred. Moreover, as an alkenyl group of R ^<1> , the group similar to the above is illustrated, Preferably it is a vinyl group.

As such disiloxane, 1,1,1,3,3,3-hexamethyldisiloxane, 1,1,1,3,3,3-hexaethyldisiloxane, 1,3-divinyl-1,1 ,3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetraethyldisiloxane, 1,1,3,3-tetravinyl-1,3-dimethyldisiloxane, 1 , 1,1,3,3,3-hexavinyldisiloxane is exemplified. Although two or more of these disiloxanes may be used in combination, at least 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3-divinyl-1,1,3,3-tetra It is necessary to include a 1,3-dialkenyl-1,1,3,3-tetraalkyldisiloxane such as ethyldisiloxane.

Also, formula (II-2):

R ¹ ₃ SiX

The silane compound represented by is also a raw material for introducing a siloxane unit represented by formula: R ¹ ₃ SiO _1/2 into organopolysiloxane. In formula, R ^<1> is the same or different C1-C12 alkyl group or C2-C12 alkenyl group. As the alkyl group for R ¹ , groups similar to those described above are exemplified, and a methyl group is preferred. Moreover, as an alkenyl group of R ^<1> , the group similar to the above is illustrated, Preferably it is a vinyl group. In addition, in formula, X is an alkoxy group, an acyloxy group, a halogen atom, or a hydroxyl group, and the group similar to the above is illustrated.

Such silane compounds include trimethylmethoxysilane, trimethylethoxysilane, dimethylvinylmethoxysilane, diethylvinylmethoxysilane, dimethylvinylethoxysilane, diethylvinylethoxysilane, divinylmethylmethoxysilane, and trimethylmethoxysilane. alkoxysilanes such as vinylmethoxysilane; acyloxysilanes such as dimethylvinylacetoxysilane, diethylvinylacetoxysilane, divinylmethylacetoxysilane, and trivinylacetoxysilane; halosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, diethylvinylchlorosilane, divinylmethylchlorosilane, and trivinylchlorosilane; and hydroxysilanes such as dimethylvinylhydroxysilane, diethylvinylhydroxysilane, divinylmethylhydroxysilane, and trivinylhydroxysilane. Although two or more of these silane compounds may be used in combination, at least alkenyldialkylsilane compounds such as divinylmethylmethoxysilane, divinylmethylacetoxysilane, divinylmethylchlorosilane, and divinylmethylhydroxysilane are used. need something

Formula (III-1):

R ² R ³ R ⁴ SiOSiR ² R ³ R ⁴

The disiloxane represented by is a raw material for introducing a siloxane unit represented by the formula: R ² R ³ R ⁴ SiO _1/2 into organopolysiloxane. In the formula, R ² is an alkyl group having 1 to 12 carbon atoms, and the same groups as described above are exemplified, preferably a methyl group. In the formula, R ³ is a phenyl group. In addition, in formula, R ^<4> is an alkenyl group of 2-12 carbon atoms, the group same as the above is illustrated, Preferably it is a vinyl group.

Examples of such disiloxane include 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane.

Formula (III-2):

R ² R ³ R ⁴ SiX

The silane compound represented by is also a raw material for introducing a siloxane unit represented by the formula: R ² R ³ R ⁴ SiO _1/2 into organopolysiloxane. In the formula, R ² is an alkyl group having 1 to 12 carbon atoms, and the same groups as described above are exemplified, preferably a methyl group. In the formula, R ³ is a phenyl group. In the formula, R ⁴ is an alkenyl group having 2 to 12 carbon atoms, and the same groups as described above are exemplified, preferably a vinyl group. In addition, in formula, X is an alkoxy group, an acyloxy group, a halogen atom, or a hydroxyl group, and the group similar to the above is illustrated.

Examples of such silane compounds include alkoxysilanes such as methylphenylvinylmethoxysilane and methylphenylvinylethoxysilane; acetoxysilanes such as methylphenylvinylacetoxysilane; chlorosilanes such as methylphenylvinylchlorosilane; Hydroxysilanes such as methylphenylvinylhydroxysilane are exemplified.

In the preparation method described above, as needed, a silane compound or cyclic silicone compound for introducing a siloxane unit represented by the formula: R ⁵ ₂ SiO _2/2 into the organopolysiloxane, or a siloxane unit represented by the formula: SiO _4/2 A silane compound or silane oligomer for introducing may be reacted. In formula, R ^<5> is the same or different C1-C12 alkyl group, C2-C12 alkenyl group, or a phenyl group. Examples of the alkyl group for R ⁵ include the same alkyl groups as those for R ¹ above. As the alkenyl group for R ⁵ , the same alkenyl groups as those for R ¹ are exemplified.

Examples of such silane compounds include dimethyldimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, tetramethoxysilane, dimethyldiethoxysilane, methylethyldiethoxysilane, methylphenyldiethoxysilane, and dimethoxysilane. Alkoxysilanes, such as phenyl diethoxysilane, tetramethoxysilane, and tetraethoxysilane; acetoxysilanes such as dimethyldiacetoxysilane, methylphenyldiacetoxysilane, diphenyldiacetoxysilane, and tetraacetoxysilane; halosilanes such as dimethyldichlorosilane, methylphenyldichlorosilane, diphenyldichlorosilane, and tetrachlorosilane; Hydroxysilanes, such as dimethyldihydroxysilane, methylphenyldihydroxysilane, and diphenyldihydroxysilane, are illustrated. Moreover, as such a cyclic silicone compound, a cyclic dimethylsiloxane oligomer, a cyclic phenylmethylsiloxane oligomer, and a cyclic diphenylsiloxane oligomer are illustrated. Furthermore, as a silane oligomer, the partial hydrolyzate of tetramethoxysilane and the partial hydrolyzate of tetraethoxysilane are illustrated.

In the above preparation method, silane compound (I), disiloxane (II-1) and/or silane compound (II-2), and disiloxane (III-1) and/or silane compound (III-2), furthermore, if necessary Accordingly, it is characterized by subjecting other silane compounds, cyclic silicone compounds, or silane oligomers to hydrolysis/condensation reactions in the presence of acids or alkalis.

Examples of acids that can be used include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids, trifluoromethanesulfonic acid, and ion exchange resins. Examples of alkalis that can be used include inorganic alkalis such as potassium hydroxide and sodium hydroxide; organic base compounds such as triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, aqueous ammonia, tetramethylammonium hydroxide, alkoxysilane having an amino group, and aminopropyltrimethoxysilane.

In addition, in the above preparation method, an organic solvent can be used. Examples of organic solvents that can be used include ethers, ketones, acetates, aromatic or aliphatic hydrocarbons, γ-butyrolactone, and mixtures of two or more thereof. Preferred organic solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, and γ-butyro Lactone, toluene, and xylene are exemplified.

In the above preparation method, it is preferable to add water or a mixture of water and alcohol in order to promote the hydrolysis/condensation reaction of each of the above components. As this alcohol, methanol and ethanol are preferable. This reaction is accelerated by heating, and when using an organic solvent, it is preferable to carry out the reaction at the reflux temperature.

Since the organopolysiloxane of the present invention has good hydrosilylation reactivity, an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule and a catalyst for hydrosilylation reaction using this as a main agent By adding it, a hydrosilylation reaction curable silicone composition can be prepared.

The curable silicone composition of the present invention includes 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, and 1,3-divinyl-1,3-diphenyl-1,3- The second characteristic is that the content of dimethyldisiloxane in the composition is greater than 0.0% by mass and less than 3.0% by mass. 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is a compound that remains in organopolysiloxane during the synthesis of branched or resinous organopolysiloxanes containing alkylphenylvinylsiloxane units. Although it is a component, thermal shock resistance is improved by using the curable silicone composition whose content is controlled so as to be within the above range. In particular, from the standpoint of improving thermal shock resistance, the content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in the composition is more preferably in the range of 0.05% by mass to 2.50% by mass. When the said content is less than the said lower limit or the said content exceeds the said upper limit, as shown in the comparative example of this specification, thermal shock resistance will fall. Moreover, when the said content exceeds the said upper limit, it may cause deterioration of hardenability, surface tack, etc. That is, the content needs to be within the range of the present invention, and it is known that curable silicone compositions containing branched or resinous organopolysiloxanes containing known alkylphenylvinylsiloxane units satisfy these conditions. There is not. On the other hand, when 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is completely removed (0% by mass), thermal shock resistance decreases as shown in the comparative example of this specification. In view of the technical effect of the invention, it is necessary to maintain a constant content.

Preferably, the curable silicone composition of the present invention contains the above components (A) to (D), and optionally contains (E) component. Here, the organopolysiloxane of component (A) is as described above. Further, from the standpoint of improving thermal shock resistance, it is particularly preferred that the content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in the composition is in the range of 0.05% by mass to 2.50% by mass. .

Component (B) is an optional component for imparting flexibility, extensibility, and flexibility to the cured product, and is a straight-chain organopolysiloxane having at least two alkenyl groups in one molecule and having no silicon atom-bonded hydrogen atoms. . Examples of the alkenyl group in component (B) include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group having 2 carbon atoms. -12 alkenyl groups are exemplified, and vinyl groups are preferred. Examples of groups bonded to silicon atoms other than alkenyl groups in component (B) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups. C1-C12 alkyl groups, such as; A phenyl group, a tolyl group, a xylyl group, a naphthyl group, anthracenyl group, a phenanthryl group, a pyrenyl group, and the hydrogen atom of these aryl groups can be converted to an alkyl group such as a methyl group or an ethyl group; Alkoxy groups, such as a methoxy group and an ethoxy group; aryl groups having 6 to 20 carbon atoms, such as groups substituted with halogen atoms such as chlorine atoms and bromine atoms; A benzyl group, a phenethyl group, a naphthylethyl group, a naphthylpropyl group, anthracenylethyl group, a phenanthrylethyl group, a pyrenylethyl group, and the hydrogen atom of these aralkyl groups are selected from an alkyl group such as a methyl group and an ethyl group; Alkoxy groups, such as a methoxy group and an ethoxy group; aralkyl groups having 7 to 20 carbon atoms, such as groups substituted with halogen atoms such as chlorine atoms and bromine atoms; or a halogenated alkyl group having 1 to 12 carbon atoms, such as a chloromethyl group and a 3,3,3-trifluoropropyl group, and the same groups as described above, respectively. Preferred examples are a methyl group and a phenyl group.

Examples of the component (B) include a dimethylsiloxane/methylvinylsiloxane copolymer capped with trimethylsiloxy groups at both molecular ends, a methylvinylpolysiloxane capped with trimethylsiloxy groups at both molecular ends, and a dimethylsiloxane/methylvinyl capped with trimethylsiloxy groups at both molecular ends. Siloxane/methylphenylsiloxane copolymer, dimethylpolysiloxane with dimethylvinylsiloxy groups blocked at both ends of the molecular chain, dimethylvinylpolysiloxane with dimethylvinylsiloxy groups blocked at both molecular ends, dimethylvinylsiloxane copolymer with dimethylvinylsiloxy groups blocked at both molecular ends, Dimethylsiloxane/methylvinylsiloxane/methylphenylsiloxane copolymers capped with dimethylvinylsiloxy groups at both ends of the molecular chain, and mixtures of two or more of these organopolysiloxanes are exemplified.

In the present composition, the content of component (B) is within the range of 0 to 70% by mass, preferably within the range of 0 to 50% by mass, particularly preferably 0 to 40% by mass, relative to the present composition. is within range This means that when the content of component (B) is below the upper limit of the above range, the cured product does not increase gas permeability, flexibility, extensibility, and flexibility can be imparted to the cured product, and furthermore, light produced using the present composition can be obtained. This is because the reliability of the semiconductor device can be improved.

Component (C) is a crosslinking agent of the present composition and is an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule. (C) As a bonding position of the silicon atom-bonded hydrogen atom in component, molecular chain terminals and/or molecular chain side chains are illustrated. (C) Other groups bonded to silicon atoms in component include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. Alkyl group of 1 to 12 carbon atoms; A phenyl group, a tolyl group, a xylyl group, a naphthyl group, anthracenyl group, a phenanthryl group, a pyrenyl group, and the hydrogen atom of these aryl groups can be converted to an alkyl group such as a methyl group or an ethyl group; Alkoxy groups, such as a methoxy group and an ethoxy group; aryl groups having 6 to 20 carbon atoms, such as groups substituted with halogen atoms such as chlorine atoms and bromine atoms; A benzyl group, a phenethyl group, a naphthylethyl group, a naphthylpropyl group, anthracenylethyl group, a phenanthrylethyl group, a pyrenylethyl group, and the hydrogen atom of these aralkyl groups are selected from an alkyl group such as a methyl group and an ethyl group; Alkoxy groups, such as a methoxy group and an ethoxy group; aralkyl groups having 7 to 20 carbon atoms, such as groups substituted with halogen atoms such as chlorine atoms and bromine atoms; or a halogenated alkyl group having 1 to 12 carbon atoms, such as a chloromethyl group and a 3,3,3-trifluoropropyl group, and the same groups as described above, respectively. Preferred examples are a methyl group and a phenyl group. Examples of the molecular structure of component (C) include linear, branched, cyclic, network, and partially branched linear structures.

As such component (C), methylhydrogenpolysiloxane capped with trimethylsiloxy groups at both molecular ends, dimethylsiloxane-methylhydrogensiloxane copolymer capped with trimethylsiloxy groups at both molecular ends, and dimethylsiloxane capped with trimethylsiloxy groups at both molecular ends. Methylhydrogensiloxane/methylphenylsiloxane copolymer, blocking dimethylhydrogensiloxy groups at both molecular ends Dimethylpolysiloxane, blocking dimethylhydrogensiloxy groups at both molecular ends Dimethylsiloxane/methylphenylsiloxane copolymer, dimethylhydrogensiloxy groups at both molecular ends Blocked methylphenylpolysiloxane, an organopolysiloxane copolymer composed of a siloxane unit represented by the formula: R' ₃ SiO _1/2 and a siloxane unit represented by the formula: R' ₂ HSiO _1/2 and a siloxane unit represented by the formula: SiO _4/2 ; An organopolysiloxane copolymer composed of a siloxane unit represented by formula: R' ₂ HSiO _1/2 and a siloxane unit represented by formula: SiO _4/2 , a siloxane unit represented by formula: R'HSiO _2/2 and formula: R'SiO An organopolysiloxane copolymer composed of a siloxane unit represented by _3/2 or a siloxane unit represented by the formula: HSiO _3/2 , and a mixture of two or more of these organopolysiloxanes are exemplified. Here, R' in the formula is an alkyl group of 1 to 12 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or a halogenated alkyl group of 1 to 12 carbon atoms, and groups similar to those described above are exemplified.

In the present composition, the content of component (C) is an amount within the range of 0.1 to 5 moles of silicon-bonded hydrogen atoms in the present component relative to the total of 1 mole of alkenyl groups in component (A) and component (B). , It is an amount that is preferably within the range of 0.5 to 2 moles. This is because the composition is sufficiently cured when the content of the component (C) is equal to or greater than the lower limit of the above range, while when the content of the component is equal to or less than the upper limit of the above range, the heat resistance of the cured product is improved, and consequently, an optical semiconductor device produced using the present composition. This is because the reliability of

In addition, component (D) is a catalyst for hydrosilylation reaction for accelerating curing of the present composition, and a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst are exemplified. In particular, it is preferable that the component (D) is a platinum-based catalyst in terms of remarkably accelerating the curing of the present composition. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, alcohol solutions of chloroplatinic acid, platinum-alkenylsiloxane complexes, platinum-olefin complexes, and platinum carbonyl complexes, preferably platinum-alkenylsiloxane complexes. . Particularly, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable in view of the good stability of the platinum-alkenylsiloxane complex. Here, as a catalyst for accelerating the hydrosilylation reaction, a non-platinum metal catalyst such as iron, ruthenium, or iron/cobalt may be used.

In addition, in the present composition, the content of component (D) is an effective amount to promote curing of the present composition. Specifically, the content of the component (D) is an amount in which the catalytic metal in the component (D) is in the range of 0.01 to 500 ppm, in terms of mass, relative to the present composition, from the point that the curing reaction of the present composition can be sufficiently accelerated. It is preferable, and furthermore, it is preferable that it is an amount within the range of 0.01 to 100 ppm, and it is particularly preferable that it is an amount within the range of 0.01 to 50 ppm.

The composition may contain (E) an adhesion imparting agent in order to improve the adhesion of the cured product to the substrate in contact during curing. As the component (E), an organosilicon compound having at least one alkoxy group bonded to a silicon atom in one molecule is preferable. As this alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group are illustrated, and a methoxy group is especially preferable. Examples of groups other than the alkoxy group bonded to the silicon atom of the organic silicon compound include substituted or unsubstituted monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and halogenated alkyl groups; glycidoxyalkyl groups such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; epoxycyclohexylalkyl groups such as 2-(3,4-epoxycyclohexyl)ethyl group and 3-(3,4-epoxycyclohexyl)propyl group; epoxy group-containing monovalent organic groups such as oxiranylalkyl groups such as 4-oxiranylbutyl group and 8-oxiranyloctyl group; acrylic group-containing monovalent organic groups such as 3-methacryloxypropyl group; A hydrogen atom is exemplified. This organosilicon compound preferably has a silicon atom-bonded alkenyl group or a silicon-bonded hydrogen atom. In view of being able to impart good adhesion to various substrates, the organosilicon compound preferably has at least one epoxy group-containing monovalent organic group in one molecule. As such an organosilicon compound, an organosilane compound, an organosiloxane oligomer, and an alkyl silicate are illustrated. Examples of the molecular structure of the organosiloxane oligomer or alkyl silicate include linear, partially branched linear, branched, cyclic, and network structures, and particularly preferably linear, branched, and network structures. Examples of such organosilicon compounds include silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane; A siloxane compound having at least one silicon atom-bonded alkenyl group or silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy group in one molecule, a silane compound or siloxane compound having at least one silicon atom-bonded alkoxy group, and a silicon atom bond in one molecule A mixture of siloxane compounds having at least one hydroxyl group and at least one silicon atom-bonded alkenyl group, methyl polysilicate, ethyl polysilicate, and ethyl polysilicate containing an epoxy group are exemplified.

In the present composition, the content of component (E) is not limited, but it is 0.01 parts by mass relative to the total of 100 parts by mass of components (A) to (D) in terms of good adhesion to the substrate in contact during curing. It is preferably within the range of to 10 parts by mass.

In addition, as other optional components in the present composition, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, etc. of alkyne alcohol; enein compounds such as 3-methyl-3-penten-1-in and 3,5-dimethyl-3-hexene-1-in; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane , reaction inhibitors such as benzotriazole may be contained. In this composition, although the content of this reaction inhibitor is not limited, It is preferable to fall within the range of 0.0001-5 mass parts with respect to 100 mass parts of the total of said component (A) - (D) component.

In addition, the composition may contain a fluorescent material as other optional components. Examples of the phosphor include yellow, red, green, and blue, which are composed of oxide-based phosphors, oxynitride-based phosphors, nitride-based phosphors, sulfide-based phosphors, and oxysulfide-based phosphors, which are widely used in light emitting diodes (LEDs), for example. A light emitting phosphor is mentioned. Examples of the oxide phosphor include cerium ion-containing yttrium, aluminum, and garnet-based YAG-based green to yellow light-emitting phosphors, terbium, aluminum, and garnet-based TAG-based yellow light-emitting phosphors containing cerium ions, and cerium and europium ions. Silicate-based green to yellow light emitting phosphors containing are exemplified. As the oxynitride phosphor, silicon, aluminum, oxygen, and nitrogen-based sialon-based red to green light-emitting phosphors containing europium ions are exemplified. Examples of nitride-based phosphors include calcium, strontium, aluminum, silicon, and nitrogen-based Casun-based red light-emitting phosphors containing europium ions. As the sulfide-based phosphor, ZnS-based green phosphor containing copper ions or aluminum ions is exemplified. Examples of the oxysulfide-based phosphor include a Y ₂ O ₂ S-based red light-emitting phosphor containing europium ions. These fluorescent materials may use 1 type or a mixture of 2 or more types. In the present composition, the content of the fluorescent material is not particularly limited, but is preferably within the range of 0.1 to 70% by mass, more preferably 1 to 20% by mass, in the present composition.

In addition, the present composition includes inorganic fillers such as silica, glass, alumina, and zinc oxide as other optional components as long as the object of the present invention is not impaired; organic resin fine powders such as polymethacrylate resin; A heat resistant agent, a dye, a pigment, a flame retardant imparting agent, a solvent, and the like may be contained.

Although this composition is cured at room temperature or by heating, it is preferable to heat it in order to cure it rapidly. As this heating temperature, it is preferable that it exists in the range of 50-200 degreeC. The curable silicone composition of the present invention is suitable for an optical semiconductor device encapsulant or the like, and can provide an optical semiconductor device formed by encapsulating an optical semiconductor element with a cured product of the curable silicone composition.

Next, the hardened|cured material of this invention is demonstrated in detail.

The cured product of the present invention is characterized in that it is obtained by curing the curable silicone composition. The shape of the cured product is not particularly limited, and examples thereof include a sheet shape and a film shape. Although the cured product can be handled as a single unit, it is also possible to handle it in a state in which an optical semiconductor element or the like is covered or sealed.

Next, the optical semiconductor device of the present invention is explained in detail.

The optical semiconductor device of the present invention is characterized in that an optical semiconductor element is sealed with a cured product of the curable silicone composition. As such an optical semiconductor device of this invention, a light emitting diode (LED), a photocoupler, and CCD are illustrated. Moreover, as an optical semiconductor element, a light emitting diode (LED) chip and a solid-state imaging element are illustrated. However, the use of the curable silicone composition of the present invention is not limited to these.

Fig. 1 shows a cross-sectional view of a single surface-mounted LED as an example of the optical semiconductor device of the present invention. In the LED shown in FIG. 1, the LED chip 1 is die-bonded on the lead frame 2, and the LED chip 1 and the lead frame 3 are wire-bonded by the bonding wire 4. A frame material 5 is formed around the LED chip 1, and the LED chip 1 inside the frame material 5 is sealed with a cured product 6 of the curable silicone composition of the present invention. .

In the method of manufacturing the surface-mounted LED shown in Fig. 1, the LED chip 1 is die-bonded to the lead frame 2, and the LED chip 1 and the lead frame 3 are connected with a gold bonding wire ( A method of wire bonding by 4), then filling the inside of the frame member 5 formed around the LED chip 1 with the curable silicone composition of the present invention, and then curing it by heating at 50 to 200 ° C is exemplified. do. By using the curable silicone composition, it is possible to provide an optical semiconductor device and the like that are excellent in thermal shock resistance and maintain high luminous efficiency.

Example

The curable silicone composition of the present invention, a cured product thereof, and an optical semiconductor device are described in detail with reference to examples. A viscosity is a value at 25 degreeC. Here, in Examples, Me, Vi, Ph, and Ep respectively represent a methyl group, a vinyl group, a phenyl group, and a 3-glycidoxypropyl group.

[Reference Example: Synthesis Example of Adhesion Agent]

In a four-necked flask with stirrer, reflux condenser, and thermometer, 82.2 g 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 143 g water, 0.38 g trifluoromethanesulfonic acid, and 500 g toluene. was added, and 524.7 g of phenyltrimethoxysilane was added dropwise over 1 hour while stirring. After completion of the dropping, the mixture was heated to reflux for 1 hour. Thereafter, it was cooled, the lower layer was separated, and the toluene solution layer was washed three times. 314 g of methylglycidoxypropyldimethoxysilane, 130 g of water, and 0.50 g of potassium hydroxide were added to the washed toluene solution layer, and heated to reflux for 1 hour. Next, methanol was distilled off and excess water was removed by azeotropic dehydration. After heating to reflux for 4 hours, the toluene solution was cooled and neutralized with 0.55 g of acetic acid, followed by washing three times. After removing the water, toluene was distilled off under reduced pressure, and the average unit formula of a viscosity of 8,500 mPa s:

(ViMe2SiO1/2)0.18(PhSiO3/2)0.53(EpMeSiO2/2)0.29

An adhesion imparting agent represented by was prepared. (Wherein, Vi represents a vinyl group, Ph represents a phenyl group, Ep represents an epoxy group, and Me represents a methyl group)

Hereinafter, silicone resins A to C containing methylphenylvinylsiloxane units having different contents of 1,3-divinyl-1,3-diphenyldimethyldisiloxane were obtained according to Synthesis Examples 1 to 3.

[Synthesis Example 1: Silicone Resin A]

In a reaction vessel, 100 g (0.5 mol) of phenyltrimethoxysilane and 23.39 g (0.075 mol) of 1,3-divinyl-1,3-diphenyldimethyldisiloxane were added, mixed in advance, and then trifluoromethane 0.83 g (5.5 mmol) of sulfonic acid was added, and 29.95 g (1.6 mol) of water was added while stirring, followed by heating under reflux for 2 hours. Thereafter, heating and atmospheric distillation was performed until the temperature reached 85°C. Then, 22.1 g of toluene and 0.4 g (10 mmol) of sodium hydroxide were introduced, heated and atmospheric distillation was performed until the reaction temperature reached 120°C, and the mixture was reacted at this temperature for 6 hours. After cooling to room temperature, neutralization was performed by adding 0.95 g (15.8 mmol) of acetic acid. After the resulting salt was separated by filtration, a transparent resin solution was obtained. This resin had a number average molecular weight of 1,500, a mass average molecular weight of 1,900, and a content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane of 0.47% by mass.

[Synthesis Example 2: Silicone Resin B]

The resin prepared in Synthesis Example 1 was washed 5 times with a mixed solvent of toluene and methanol in a mass ratio of 1:2 to obtain substantially 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane. A resin not containing (= 0.0% by mass) was obtained.

[Synthesis Example 3: Silicone Resin C]

A transparent resin solution was obtained in the same manner as in Synthesis Example 1, except that 0.488 g (8.7 mmol) of potassium hydroxide was added instead of sodium hydroxide. This resin had a number average molecular weight of 1,530, a mass average molecular weight of 1,830, and a content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane of 5.90% by mass.

In Examples 1 to 4 and Comparative Examples 1 to 4, the content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in the evaluation or composition was quantified by the method shown below. did The results are shown in Table 1 and Table 2.

[Measurement method for 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane]

An internal standard substance of a prescribed mass was added to a sample whose mass was measured in advance, diluted with toluene, and the mass% in the sample was calculated from the peak area ratio of the toluene solution and the internal standard substance in the gas chromatography.

[Shore-D of cured product]

The hardness of the cured product was measured by a type D durometer specified in JIS K 7215-1986 "Testing method for durometer hardness of plastics".

[Thermal shock resistance of optical semiconductor device]

Using the curable silicone composition, 20 optical semiconductor devices as shown in FIG. 1 were produced by heating at 150°C for 2 hours. After holding this optical semiconductor device at -40°C for 30 minutes, the process of raising the temperature to 125°C within 2 minutes and holding for 30 minutes was repeated, and the number of unlit optical semiconductor devices at each cycle number was counted.

[Luminous Efficiency of Optical Semiconductor Device]

Using a curable silicone composition, as component (G), 50 parts by mass of phosphor GAL530-L (manufactured by INTEMATIX) and 3.91 parts by mass of ER6535 (manufactured by INTEMATIX) were mixed with a dental mixer with respect to 100 parts by mass, to obtain a phosphor-containing curing property. A silicone composition was prepared, and it heated at 150 degreeC for 2 hours using this curable silicone composition, and produced 5 optical semiconductor devices similar to FIG. An electric charge of 400 mA was applied to this optical semiconductor device, and the light was turned on for 1000 hours under conditions of 85° C. and 85% relative humidity. After that, the average value was made into the luminous efficiency of the optical semiconductor device.

[Example 1]

6.83 parts by mass of silicone resin B prepared in Synthesis Example 2, 0.82 parts by mass of methylphenylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of the molecular chain having a viscosity of 3,000 mPa s, formula: H(CH3)2SiO(C6H5)2SiOSi(CH3)2H 2.10 parts by mass of organotrisiloxane (an amount in which the number of silicon-bonded hydrogen atoms in this component is 1 relative to the total of 1 mole of vinyl groups in the silicone resin and in the methylphenylpolysiloxane), 0.25 parts by mass of the adhesion imparting agent of Reference Example 1 0.02 parts by mass of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and platinum-1,3-divinyl-1,1,3,3-tetramethyl 0.00063 parts by mass of a 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane solution of a disiloxane complex (containing 4.0 mass% of platinum), 1,3-divinyl-1, A curable silicone composition having a viscosity of 7,700 mPa·s was prepared by mixing 0.01 part by mass of 3-diphenyldimethyldisiloxane. As a result of curing this composition at 150°C for 1 hour, a cured product of Shore-D 73 was obtained. The surface of the cured product was smooth without tack. Its characteristics are shown in Table 1. 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in this curable silicone composition was 0.10% by mass.

[Example 2]

A curable silicone composition having a viscosity of 6,200 mPa·s was prepared in the same manner as in Example 1 except that the amount of 1,3-divinyl-1,3-diphenyldimethyldisiloxane added was 0.10 parts by mass. As a result of curing this composition at 150°C for 1 hour, a cured product of Shore-D 69 was obtained. The surface of the cured product was smooth without tack. Its characteristics are shown in Table 1. 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in this curable silicone composition was 0.99% by mass.

[Example 3]

A curable silicone composition having a viscosity of 5,000 mPa·s was prepared in the same manner as in Example 1 except that the amount of 1,3-divinyl-1,3-diphenyldimethyldisiloxane added was 0.20 parts by mass. As a result of curing this composition at 150°C for 1 hour, a cured product of Shore-D 64 was obtained. The surface of the cured product was smooth without tack. Its characteristics are shown in Table 1. The amount of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in this curable silicone composition was 1.96% by mass.

[Comparative Example 1]

A curable silicone composition having a viscosity of 7,700 mPa s was prepared in the same manner as in Example 1 except that 1,3-divinyl-1,3-diphenyldimethyldisiloxane was not added (= 0.0 part by mass) did As a result of curing this composition at 150°C for 1 hour, a cured product of Shore-D 73 was obtained. The surface of the cured product was smooth without tack. Its characteristics are shown in Table 1. 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in this curable silicone composition was 0.0% by mass.

[Comparative Example 2]

A curable silicone composition having a viscosity of 2300 mPa·s was prepared in the same manner as in Example 1 except that the amount of 1,3-divinyl-1,3-diphenyldimethyldisiloxane added was 0.50 parts by mass. As a result of curing this composition at 150°C for 1 hour, a cured product of Shore-D 44 was obtained. The surface of the cured product was smooth without tack. Its characteristics are shown in Table 1. The amount of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in this curable silicone composition was 4.75% by mass.

[Comparative Example 3]

A curable silicone composition having a viscosity of 1100 mPa·s was prepared in the same manner as in Example 1 except that the amount of 1,3-divinyl-1,3-diphenyldimethyldisiloxane added was 0.91 parts by mass. Although this composition was cured at 150°C for 1 hour, the surface of the cured product was tacky and Shore-D could not be measured. Its characteristics are shown in Table 1. The amount of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in this curable silicone composition was 8.33% by mass.

[Example 4]

The content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is 0.47% by mass, and 5.95 parts by mass of a silicone resin containing a vinylmethylphenylsiloxy group, molecular chain viscosity of 3,000 mPa s 1.80 parts by mass of methylphenylpolysiloxane capped with dimethylvinylsiloxy groups at both ends, 1.98 parts by mass of organotrisiloxane represented by the formula: H(CH3)2SiO(C6H5)2SiOSi(CH3)2H (of the vinyl groups in the silicone resin and in the methylphenylpolysiloxane) 0.25 parts by mass of the adhesion imparting agent of Reference Example 1, 1,3,5,7-tetramethyl-1,3,5,7- 0.02 parts by mass of tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5 of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex A curable silicone composition having a viscosity of 2300 mPa·s was prepared by mixing 0.00063 parts by mass of a 7-tetravinylcyclotetrasiloxane solution (containing 4.0 mass% of platinum). As a result of curing this composition at 150°C for 1 hour, a cured product of Shore-D 53 was obtained. The surface of the cured product was smooth without tack. The content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in this curable silicone composition was 0.28% by mass. As a result of evaluating the luminous efficiency of the optical semiconductor device using the cured product by the above method, the luminous efficiencies after 566 hours and 997 hours were 99.07% and 96.13%, respectively.

[Comparative Example 4]

The content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is 5.90% by mass, 5.95 parts by mass of silicone resin containing a vinylmethylphenylsiloxy group, molecular chain viscosity of 3,000 mPa s 1.80 parts by mass of methylphenylpolysiloxane capped with dimethylvinylsiloxy groups at both ends, 1.98 parts by mass of organotrisiloxane represented by the formula: H(CH3)2SiO(C6H5)2SiOSi(CH3)2H (of the vinyl groups in the silicone resin and in the methylphenylpolysiloxane) 0.25 parts by mass of the adhesion imparting agent of Reference Example 1, 1,3,5,7-tetramethyl-1,3,5,7- 0.02 parts by mass of tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5 of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex A curable silicone composition having a viscosity of 2200 mPa·s was prepared by mixing 0.00063 parts by mass of a 7-tetravinylcyclotetrasiloxane solution (containing 4.0 mass% of platinum). As a result of curing this composition at 150°C for 1 hour, a cured product of Shore-D 52 was obtained. The surface of the cured product was smooth without tack. The content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane in this curable silicone composition was 3.51% by mass. As a result of evaluating the luminous efficiency of the optical semiconductor device using the cured product by the above method, the luminous efficiencies after 566 hours and 997 hours were 95.47% and 91.48%, respectively.

[Overall of Examples and Comparative Examples]

As shown in Examples 1 to 3 (Table 1), it is a curable silicone composition containing a silicone resin containing a methylphenylvinylsiloxane unit, and the content of 1,3-divinyl-1,3-diphenyldimethyldisiloxane is 0.10% by mass, 0.99% by mass, or 1.96% by mass shows that the number of defects is 2 or less even at the time of 401 cycles, and exhibits excellent thermal shock resistance. On the other hand, as shown in Comparative Examples 1 to 3 (Table 1), it is the same curable silicone composition, and the content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is 0.0% by mass; In the case of 4.57% by mass, the number of defects is 8 or more even at the time of 401 cycles, and the thermal shock resistance is clearly inferior. Moreover, hardenability is clearly inferior to the thing whose copper content is 8.33 mass %.

Similarly, the optical semiconductor device using the curable silicone composition of Example 4 (the content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is 0.28% by mass) is Comparative Example 4 (the same content 3.51% by mass), the luminous efficiency after 566 hours and 997 hours is excellent.

The curable silicone composition of the present invention can be used as an electrical/electronic adhesive, potting agent, protective agent, coating agent, or underfill agent, and forms a cured product having particularly high reactivity, low gas permeability, and high thermal shock resistance. Since it can be done, it is suitable as a sealing material or a protective coating material for an optical semiconductor element in an optical semiconductor device such as a light emitting diode (LED), and an optical semiconductor device in which high luminous efficiency continues can be provided.

1 optical semiconductor element
2 lead frame
3 lead frame
4 bonding wires
5 frame materials
6 Cured product of curable silicone composition

Claims (5)

Organopolysiloxane having an alkylphenylalkenylsiloxane unit (R ² R ³ R ⁴ SiO _1/2 ; R ² is an alkyl group having 1 to 12 carbon atoms; R ³ is a phenyl group; R ⁴ is an alkenyl group having 2 to 12 carbon atoms) It is made by containing, and also,
A curable silicone composition wherein the content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is greater than 0.0% by mass and less than 3.0% by mass with respect to the entire composition. According to claim 1,
(A) average unit formula:
(R ¹ ₃ SiO _1/2 ) _a (R ² R ³ R ⁴ SiO _1/2 ) _b (R ⁵ ₂ SiO _2/2 ) _c (R ³ SiO _3/2 ) _d
(Wherein, R ¹ is the same or different C 1 to C 12 alkyl group or C 2 to C 12 alkenyl group, provided that at least one R ¹ in one molecule is a C 2 to C 12 alkenyl group; R ² is C 1 ∼12 alkyl group; R ³ is a phenyl group; R ⁴ is an alkenyl group having 2 to 12 carbon atoms; R ⁵ is an identical or different C 1 to 12 alkyl group, an alkenyl group having 2 to 12 carbon atoms, or a phenyl group; a, b , c, and d are numbers satisfying 0.00≤a≤0.45, 0.01≤b≤0.45, 0≤c≤0.7, 0.1≤d<0.9, and a+b+c+d=1, respectively)
An organopolysiloxane represented by
(B) a straight-chain organopolysiloxane having at least two alkenyl groups in one molecule and no silicon atom-bonded hydrogen atoms (0 to 70% by mass relative to the present composition);
(C) organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {the silicon-bonded hydrogen atoms in this component are 0.1 to 5 per mole of the total of alkenyl groups in component (A) and component (B) molar amount}, and
(D) an effective amount of a catalyst for the hydrosilylation reaction
It is made by containing, and also,
A curable silicone composition wherein the content of 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane is in the range of 0.05% by mass to 2.50% by mass with respect to the entire composition. According to claim 1 or 2,
Further, (E) a curable silicone composition containing an adhesion imparting agent (0.01 to 10 parts by mass based on 100 parts by mass in total of the components (A) to (D)). A cured product obtained by curing the curable silicone composition according to claim 1 or 2. An optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable silicone composition according to claim 1 or 2.

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