KR101472829B1 - Curable composition, cured product, photo-semiconductor device, and polysiloxane - Google Patents

Abstract

(A) a polysiloxane (A) having an alkenyl group and an adhesive group, a polysiloxane (B) having at least two silicon atom-bonded hydrogen atoms per molecule (excluding the polysiloxane (A)) and a hydrosilylation reaction Wherein the content of the polysiloxane (A) is 40 to 90% by mass, when the total content of the components in the curable composition is 100% by mass Curable composition.
(Effect) The curable composition of the present invention is a hydrosilyl-based polysiloxane composition capable of forming a cured product having high adhesiveness to a substrate or metal wiring and high initial luminance such as LED. Therefore, in the optical semiconductor device obtained by covering the semiconductor light emitting element with the cured product obtained from the curable composition, the initial luminance is high, and even when the heat cycle is applied, the cured product is not peeled from the package, high.

Description

CURABLE COMPOSITION, CURED PRODUCT, PHOTO-SEMICONDUCTOR DEVICE, AND POLYSILOXANE BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition,

The present invention relates to a curable composition, a cured product, an optical semiconductor device, and a polysiloxane.

A hydrosilylation reaction curing type polysiloxane composition (hereinafter also referred to as a hydrosilyl polysiloxane composition) used for an encapsulating material of a semiconductor light emitting device (LED) is required to have a technique for enhancing adhesiveness to an LED package or the like.

As a technique for improving the adhesiveness of the hydrosilyl-based polysiloxane composition, there is known a technique of adding an adhesion promoter such as an epoxy group-containing polysiloxane to the hydrosilyl-based polysiloxane composition.

Patent Document 1 describes a hydrosilyl-based polysiloxane composition containing an epoxy group-containing polysiloxane having an alkenyl group as an adhesion promoter in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of an organopolysiloxane as a main agent.

Patent Document 2 describes a hydrosilyl-based polysiloxane composition containing an epoxy group-containing polysiloxane as an adhesion promoter in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of an organopolysiloxane resin containing an alkenyl group as a main agent and a phenyl group.

Patent Document 3 discloses a hydrosilyl-based polysiloxane composition containing an epoxy group-containing polysiloxane having an alkenyl group as an adhesion promoter in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of an organopolysiloxane component containing an alkenyl group as a main component .

Japanese Patent Application Laid-Open No. 2007-327019 Japanese Patent Application Laid-Open No. 2007-008996 Japanese Patent Application Laid-Open No. 2010-229402

It is necessary to increase the epoxy group content of the epoxy group-containing polysiloxane, which is an adhesion promoter, in order to improve the adhesiveness between the substrate and the metal wiring and the sealing material. However, when a large amount of such an adhesion promoter is used, the luminance may be lowered.

It is an object of the present invention to provide a curable composition capable of forming a cured product capable of achieving both adhesion and luminance for a substrate or a metal wiring in a hydrosilyl-based polysiloxane composition.

The present invention relates to a polysiloxane (A) having an alkenyl group and an adhesive group, a polysiloxane (B) having at least two silicon atom-binding hydrogen atoms per molecule (excluding polysiloxane (A) Wherein the content of the polysiloxane (A) is 40 to 90% by mass, when the total content of the components in the curable composition is 100% by mass Curable composition.

The content of the alkenyl group in the polysiloxane (A) is 3 to 50 mol%, and the content of the adhesive group in the polysiloxane (A) is 0.01 to 10 mol%, based on 100 mol% of the total Si atoms contained in the polysiloxane (A) And more preferably 10 mol%.

In the curable composition, it is preferable that the adhesive group is a group having an epoxy group.

In the curable composition, the polysiloxane (A) is a compound represented by the following formula (2):

(2)

( ^Wherein R ^Vi represents a group having an alkenyl group; R ^Ep represents a group having an epoxy group; R ¹ represents, independently of each other, a monovalent hydrocarbon group (excluding groups having an alkenyl group); B is an integer of 0 or more, c is an integer of 0 or more, d is an integer of 1 or more, e is an integer of 0 or more, f is an integer of 0 or more, X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, h represents an integer of 0 or more; i represents an integer of 0 or more, provided that a + c is an integer of 1 or more;

Lt; / RTI >

In the curable composition, it is preferable that the polysiloxane (A) has an aryl group and the content of the aryl group contained in the polysiloxane (A) is from 30 to 120, when the total number of Si atoms contained in the polysiloxane (A) Mol%.

Another invention is a cured product obtained from the above-mentioned curable composition.

In another aspect of the present invention, there is provided an optical semiconductor device characterized by comprising a semiconductor light emitting element and the above cured product which covers the semiconductor light emitting element.

Another invention is a compound represented by the following formula (2):

(2)

( ^Wherein R ^Vi represents a group having an alkenyl group; R ^Ep represents a group having an epoxy group; R ¹ represents, independently of each other, a monovalent hydrocarbon group (excluding groups having an alkenyl group); B is an integer of 0 or more, c is an integer of 0 or more, d is an integer of 1 or more, e is an integer of 0 or more, f is an integer of 0 or more, X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, h represents an integer of 0 or more; i represents an integer of 0 or more, provided that a + c is an integer of 1 or more;

Lt; / RTI >

The curable composition of the present invention is a hydrosilyl-based polysiloxane composition capable of forming a cured product capable of achieving both adhesion and luminance for a substrate or metal wiring.

Therefore, the optical semiconductor device obtained by covering the semiconductor light emitting element with the cured product obtained from the curable composition is an optical semiconductor device having excellent reliability.

1 is a schematic diagram showing one specific example of an optical semiconductor device.

(Mode for carrying out the invention)

≪ Curable composition >

The curable composition of the present invention comprises a polysiloxane (A) having an alkenyl group and an adhesive group, a polysiloxane (B) (excluding polysiloxane (A)) having at least two silicon atom-binding hydrogen atoms per molecule, A curable composition containing a silylation catalyst (C), wherein the content of the polysiloxane (A) is 40 to 90 mass%, when the total content of the components in the curable composition is 100 mass% .

In the present invention, "polysiloxane" means a siloxane having a molecular skeleton in which two or more siloxane units (Si-O) are bonded.

Polysiloxane (A)

The polysiloxane (A) is a polysiloxane having an alkenyl group and an adhesive group. The polysiloxane (A) is the main component of the composition and is cured by the hydrosilylation reaction with the polysiloxane (B) to become the main component of the cured product. The polysiloxane (A) also has a function of enhancing the adhesiveness between the cured product and an LED package in view of having an adhesive group.

Examples of the alkenyl group of the polysiloxane (A) include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, . Of these, a vinyl group, an allyl group and a hexenyl group are preferable.

The content of the alkenyl group in the polysiloxane (A) is preferably from 3 to 50 mol%, more preferably from 5 to 40 mol%, based on 100 mol% of all the Si atoms contained in the polysiloxane (A) Mol%, and more preferably 10 to 30 mol%. When the content of the alkenyl group is within the above range, the hydrosilylation reaction of the polysiloxane (A) and the polysiloxane (B) takes place within a suitable range, and a cured product having high strength can be obtained.

The term "adhesiveness" as used herein means a group having adhesion to a metal or an organic resin which is a material such as a substrate of a semiconductor device or the like.

Examples of the adhesive group possessed by the polysiloxane (A) include groups having an epoxy group, thionyl group, isocyanate group, triallyl isocyanate group and the like.

Among them, a group having an epoxy group is preferable in that it is difficult to inhibit the hydrosilylation reaction that occurs when the curable composition is cured, and a cured product capable of highly bonding both the adhesion and the brightness to a substrate or metal wiring is formed.

Examples of the group having an epoxy group include a glycidoxy group, a glycidoxyalkyl group such as a 3-glycidoxypropyl group, a 3,4-epoxycyclohexyl group, a 3,4-epoxycyclohexyl group, a 2- (3,4-epoxycyclopentyl) ethyl group and 2- (3,4-epoxycyclohexyl) ethyl group, and the like. Specific examples of the group having an epoxy group include groups represented by the following structural formulas (1) to (4). If the group having an epoxy group is such a group, it is possible to form the cured product at a millimeter order.

[In the structural formula (1), R ² represents a methylene group or a divalent straight chain alkylene group having 2 to 10 carbon atoms or a branched chain alkylene group having 3 to 10 carbon atoms];

[In the structural formula (2), R ³ represents a methylene group or a divalent straight chain alkylene group having 2 to 10 carbon atoms or a branched chain alkylene group having 3 to 10 carbon atoms];

[In the structural formula (3), R ⁴ represents a methylene group or a divalent straight chain alkylene group having 2 to 10 carbon atoms or a branched chain alkylene group having 3 to 10 carbon atoms];

[In the structural formula (4), R ⁵ represents a methylene group or a divalent straight chain alkylene group having 2 to 10 carbon atoms or a branched chain alkylene group having 3 to 10 carbon atoms].

Specific examples of the group represented by the structural formula (1) include a 2- (3,4-epoxycyclohexyl) ethyl group and the like.

Specific examples of the group represented by the structural formula (2) include a glycidyl group and the like.

Specific examples of the group represented by the structural formula (3) include a 3-glycidoxypropyl group and the like.

Specific examples of the group represented by the structural formula (4) include a 2- (4-methyl-3,4-epoxycyclohexyl) ethyl group and the like.

The content of the adhesive group in the polysiloxane (A) is preferably 0.01 to 10 mol%, more preferably 0.05 to 5 mol%, based on 100 mol% of the total Si atoms contained in the polysiloxane (A) Mol%, and more preferably 0.05 to 3 mol%. When the content of the adhesive agent is within the above range, a cured film having high adhesion and high brightness between the cured product obtained from the present composition and the LED package or the like can be obtained.

The content of the polysiloxane (A) contained in the curable composition of the present invention is preferably from 40 to 90 mass%, more preferably from 50 to 85 mass%, based on 100 mass% of the total content of the components contained in the composition. By mass, and more preferably 65 to 85% by mass.

In the conventional hydrosilyl-based polysiloxane composition, an epoxy group-containing polysiloxane as an adhesion promoter was added in an amount of about 0.01 to 20 mass% with respect to the whole composition in addition to the polysiloxane as the main agent, in order to improve the adhesiveness. On the contrary, in the curable composition of the present invention, polysiloxane (A) which is an epoxy group-containing polysiloxane is used as a main preparation and its content is 40 to 90 mass% as described above. When the content of the polysiloxane (A) is within the above range, the cured product obtained from the present composition has a high adhesiveness to a substrate or a metal wiring and maintains a high initial luminance of the LED or the like when used as an encapsulant such as an LED.

It is also preferable that the polysiloxane (A) has an aryl group. When the polysiloxane (A) has an aryl group, a characteristic that a high luminance can be obtained when used as an LED encapsulant is exhibited. When the total number of Si atoms contained in the polysiloxane (A) is 100 mol%, the content of the aryl group in the polysiloxane (A) is preferably 30 to 120 mol%, more preferably 50 to 110 mol% %, More preferably 70 to 100 mol%. When the content of the aryl group is within the range of 30 to 120 mol%, a cured film having a high luminance and a high refractive index can be obtained from the composition. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

The polysiloxane (A) preferably has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of 100 to 50,000, more preferably 500 to 5,000. When the weight average molecular weight of the polysiloxane (A) is within the above range, the sealant is easily handled when the sealant is produced using the composition, and the cured product obtained from the composition has sufficient material strength and characteristics as the optical semiconductor encapsulant.

As the polysiloxane (A), the following structural formula (1):

[Chemical Formula (1)

( ^Wherein , R ^Vi represents a group having an alkenyl group; R ^Ad represents a group having a bonding group; R ¹ independently represents a monovalent hydrocarbon group (excluding groups having an alkenyl group); B is an integer of 0 or more, c is an integer of 0 or more, d is an integer of 0 or more, e is an integer of 0 or more, f is an integer of 0 or more, X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, g is an integer of 0 or more, h is an integer of 0 or more, i represents an integer of 0 or more, provided that a + c is an integer of 1 or more, and d +

And the like.

The ratio of a to the total of a, b, c, d, e, f, g, h and i is preferably 0% or more and 60% or less, 5% or more and 40% or less. b is preferably 0% or more and 50% or less, and more preferably 0% or more and 20% or less. c is preferably 0% or more and 30% or less, and more preferably 0% or more and 20% or less. d is preferably 0% or more and 10% or less, and more preferably 0% or more and 5% or less. The ratio of e is preferably 0% or more and 50% or less, and more preferably 0% or more and 30% or less. The ratio of f is 0% or more and 90% or less, preferably 20% or more and 90% or less, and more preferably 40% or more and 80% or less. g is preferably 0% or more and 10% or less, and more preferably 0% or more and 5% or less. h is preferably 0% or more and 50% or less, and more preferably 0% or more and 30% or less. i is preferably 0% or more and 10% or less, and more preferably 0% or more and 5% or less. However, the ratio of a + c is larger than 0%, and the ratio of d + g is larger than 0%.

Of the polysiloxanes represented by the above formula (1), polysiloxanes represented by the following formula (2) are preferable in that they form a cured product capable of highly bonding both the adhesion and the brightness to a substrate or a metal wiring.

(2)

( ^Wherein R ^Vi represents a group having an alkenyl group; R ^Ep represents a group having an epoxy group; R ¹ represents, independently of each other, a monovalent hydrocarbon group (excluding groups having an alkenyl group); B is an integer of 0 or more, c is an integer of 0 or more, d is an integer of 1 or more, e is an integer of 0 or more, f is an integer of 0 or more, X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, h represents an integer of 0 or more; i represents an integer of 0 or more, provided that a + c is an integer of 1 or more.

As the group having an alkenyl group, the same groups as the above-mentioned groups having an alkenyl group are exemplified. As the group having a bonding group, there is exemplified a group having the same group as the above-mentioned bonding group. As the group having an epoxy group, the same group as the group having the above-mentioned epoxy group is exemplified. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl groups; aryl groups such as phenyl, Substituted alkyl groups such as a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, and a nonafluorobutyl ethyl group are exemplified.

As a method for producing the polysiloxane (A), there are known methods for producing the polysiloxane (A) in JP-A 6-9659, JP-A 2003-183582, JP-A 2007-008996, JP-A 2007-106798, 2007-169427 and JP-A-2010-059359, for example, a method of co-hydrolyzing chlorosilane or alkoxysilane as each unit source, a method of hydrolyzing a cohydrolyzate by an alkali metal catalyst or the like And a method of performing equilibration reaction.

By using such a polysiloxane, the cured product obtained from the curable composition of the present invention can obtain a required strength, exhibits adhesion with a metal or an organic resin film, and can obtain a high luminance when used as an LED encapsulant .

Polysiloxane (B)

The polysiloxane (B) is a polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule (except for the polysiloxane (A)). That is, the polysiloxane (B) has at least two Si-H groups (hydrosilyl groups) per molecule. The polysiloxane (B) is a crosslinking agent for the polysiloxane (A) and forms a cured product by hydrosilylation reaction with the polysiloxane (A).

As the polysiloxane (B), a polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule, which is used as a crosslinking agent in a conventional hydrosilyl-based polysiloxane composition, can be used without particular limitation.

Specific examples of the polysiloxane (B) include organohydrogenpolysiloxanes described in Patent Documents 1 to 3 and the like.

As the polysiloxane (B), for example, alkoxysilanes such as phenyltrimethoxysilane, diphenyldimethoxysilane and the like and hydrogen siloxanes such as 1,1,3,3-tetramethyldisiloxane can be obtained by a known method .

The content of the polysiloxane (B) in the curable composition of the present invention is preferably such that the molar ratio of the amount of silicon atom-bonded hydrogen atoms in the polysiloxane (B) to the amount of alkenyl groups in the polysiloxane (A) is 0.1 to 5, Preferably 0.5 to 2, and more preferably 0.7 to 1.4. When the content of the polysiloxane (B) is within the above range, the composition is sufficiently cured and sufficient heat resistance can be obtained in the resulting cured product.

Hydrosilylation  The reaction catalyst (C)

The hydrosilylation reaction catalyst (C) is a catalyst for the hydrosilylation reaction of the polysiloxane (A) and the polysiloxane (B).

The hydrosilylation reaction catalyst (C) can be used without particular limitation, as long as it is a catalyst that is used as a hydrosilylation reaction catalyst in a conventional hydrosilyl-based polysiloxane composition.

Specific examples of the hydrosilylation reaction catalyst (C) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Among these, platinum-based catalysts are preferable from the viewpoint of promoting curing of the composition. Examples of the platinum-based catalyst include platinum-alkenylsiloxane complexes and the like. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl Cyclotetrasiloxane, and the like. Particularly, from the viewpoint of stability of the complex, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable.

The catalyst (C) for hydrosilylation reaction in the curable composition of the present invention utilizes an amount in which the hydrosilylation reaction between the polysiloxane (A) and the polysiloxane (B) proceeds practically.

As long as the object of the present invention is achieved, the curable composition of the present invention may contain, in addition to the above components, fine particles of silica such as fumed silica and quartz powder, titanium oxide, zinc oxide and the like An inorganic filler, a retarder such as cyclo-tetramethyltetravinyltetrasiloxane, a diluent such as diphenylbis (dimethylvinylsiloxy) silane or phenyltris (dimethylvinylsiloxy) silane, a pigment, a flame retardant, a heat resistance agent, ≪ / RTI >

The curable composition of the present invention can be prepared by uniformly mixing the above components by a known method such as a mixer.

The viscosity of the curable composition of the present invention at 25 占 폚 is preferably 1 to 1000000 mPa 占 퐏, and more preferably 10 to 10000 mPa 占 퐏. When the viscosity is within this range, the operability of the composition is improved.

The curable composition of the present invention may be prepared as a single solution, or may be prepared by dividing into two solutions, and two solutions may be mixed at the time of use. If necessary, a small amount of a curing inhibitor such as acetylene alcohol may be added.

<Hard goods>

A cured product can be obtained by curing the curable composition of the present invention. When a semiconductor element is encapsulated with the curable composition of the present invention and cured, a cured product that is an encapsulating material can be obtained.

Examples of the method for curing the curable composition of the present invention include a method in which the curable composition is coated on a substrate and then heated at 100 to 180 캜 for 1 to 13 hours.

As described above, the cured product obtained by curing the curable composition of the present invention has high adhesiveness to a substrate or metal wiring, and realizes a high initial luminance of an LED or the like.

<Optical Semiconductor Device>

The optical semiconductor device of the present invention has a semiconductor light emitting element and the cured product covering the semiconductor light emitting element. The optical semiconductor device of the present invention can be obtained by covering the curable composition with a semiconductor light emitting element and curing the composition. The method of curing the curable composition is as described above.

Examples of the optical semiconductor device include an LED (Light Emitting Diode) and an LD (Laser Diode).

1 is a schematic diagram of one embodiment of the optical semiconductor device of the present invention. The optical semiconductor device 1 includes an electrode 6, a semiconductor light emitting element 2 provided on the electrode 6 and electrically connected to the electrode 6 by a wire 7, And a sealing material 4 filled in the reflector 3 to seal the semiconductor light emitting element 2. The sealing material 4 can be obtained by curing the curable composition of the present invention. Particles 5 such as silica and fluorescent material are dispersed in the sealing material 4.

As described above, the sealing material obtained by curing the curable composition of the present invention has a strong adhesive force to the organic resin film, which is the material of the reflector, and the metal, which is the material of the electrode, so that even when a heat cycle is applied, There is no work. Further, the sealing material maintains a high initial luminance of the LED or the like. That is, high adhesion and high initial brightness can be achieved at the same time.

(Example)

(1) Synthesis of polysiloxane

(1-1) Synthesis of polysiloxane

[Synthesis Example 1] Synthesis of polysiloxane (AR1)

Necked flask equipped with a stirrer, reflux condenser, inlet and thermometer was charged with 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 525 g of phenyltrimethoxysilane, 143 g of water, And 500 g of toluene were charged and mixed, and the mixture was heated under reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was water-filtered. To the water-washed toluene solution layer was added 0.4 g of potassium hydroxide, and the mixture was refluxed while removing water from the water separation tube. After completion of the removal of water, the solution was concentrated to a solid content concentration of 75% by mass and further refluxed for 5 hours. After cooling, 0.6 g of acetic acid was added to neutralize the solution, and the resulting toluene solution was filtered. Thereafter, the resultant was concentrated under reduced pressure to obtain a polysiloxane (AR1). The polystyrene-reduced weight average molecular weight of the polysiloxane (AR1) in the gel permeation chromatography was measured and found to be 2000. The formula of the polysiloxane (AR1) is (ViMe ₂ SiO _1/2 ) ₂₅ (PhSiO _3/2 ) ₇₅ (Vi represents vinyl group, Me represents methyl group, Ph represents phenyl group, and the suffix represents mol%).

[Synthesis Example 2] Synthesis of polysiloxane (A1)

Necked flask equipped with a stirrer, a reflux condenser, an inlet and a thermometer was charged with 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 143 g of water, 521 g of phenyltrimethoxysilane, And 500 g of toluene were charged and mixed, and the mixture was heated under reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was water-filtered. To the water-washed toluene solution layer, 4 g of 3-glycidoxypropylmethyldimethoxysilane and 0.5 g of potassium hydroxide were added and the mixture was heated under reflux for 1 hour. Then, the methanol was distilled off, and excess water was removed by azeotropic dehydration. The mixture was heated under reflux for 4 hours. After the reaction, the toluene solution was cooled, neutralized with 0.6 g of acetic acid and water-filtered. After the water was removed, the toluene was distilled off and concentrated under reduced pressure to obtain a polysiloxane (A1) having 25 mol% of an alkenyl group and 0.5 mol% of an epoxy group (the total number of Si atoms contained in the polysiloxane was 100 mol%). The polystyrene reduced weight average molecular weight of the polysiloxane (A1) in the gel permeation chromatography was measured and found to be 2000. The formula of the polysiloxane (A1) is (ViMe ₂ SiO _1/2 ) ₂₅ (PhSiO _3/2 ) _74.5 (EpMeSiO _2/2 ) _0.5 (Vi is vinyl group, Me is methyl group, Ph is phenyl group, Ep is glycidoxypropyl And the subscript indicates mol%). When the total number of Si atoms contained in the polysiloxane (A1) was 100 mol%, the content of the alkenyl group was 25 mol%, the content of the epoxy group was 0.5 mol%, and the content of the aryl group was 74.5 mol%.

[Synthesis Example 3] Synthesis of polysiloxane (A2)

A four-necked flask equipped with a stirrer, reflux condenser, inlet and thermometer was charged with 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 518 g of phenyltrimethoxysilane, 143 g of water, And 500 g of toluene were charged and mixed, and the mixture was heated under reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was water-filtered. 8 g of 3-glycidoxypropylmethyldimethoxysilane and 0.5 g of potassium hydroxide were added to the water-washed toluene solution layer, and the mixture was heated under reflux for 1 hour. Then, the methanol was distilled off, and excess water was removed by azeotropic dehydration. The mixture was heated under reflux for 4 hours. After the reaction, the toluene solution was cooled, neutralized with 0.6 g of acetic acid and water-filtered. After the water was removed, toluene was distilled off and concentrated under reduced pressure to obtain a polysiloxane (A2) having 25 mol% of an alkenyl group and 1 mol% of an epoxy group (the total number of Si atoms contained in the polysiloxane was 100 mol%). The polystyrene-reduced weight average molecular weight of the polysiloxane (A2) in the gel permeation chromatography was measured and found to be 2000. The formula of the polysiloxane (A2) is _{(ViMe 2 SiO 1/2)} 25 (PhSiO 3/2) 74 (EpMeSiO 2/2) 1 (Vi is a vinyl group, Me is a methyl group, Ph is a phenyl group, Ep is glycidoxypropyl And the subscript indicates mol%). When the total number of Si atoms contained in the polysiloxane (A2) was 100 mol%, the content of the alkenyl group was 25 mol%, the content of the epoxy group was 1 mol%, and the content of the aryl group was 74 mol%.

[Synthesis Example 4] Synthesis of polysiloxane (A3)

Necked flask equipped with a stirrer, a reflux condenser, an inlet and a thermometer was charged with 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 511 g of phenyltrimethoxysilane, 143 g of water, And 500 g of toluene were charged and mixed, and the mixture was heated under reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was water-filtered. 16 g of 3-glycidoxypropylmethyldimethoxysilane and 0.5 g of potassium hydroxide were added to the water-washed toluene solution layer, and the mixture was heated under reflux for 1 hour. Then, the methanol was distilled off, and excess water was removed by azeotropic dehydration. The mixture was heated under reflux for 4 hours. After the reaction, the toluene solution was cooled, neutralized with 0.6 g of acetic acid and water-filtered. After the water was removed, toluene was distilled off and concentrated under reduced pressure to obtain a polysiloxane (A3) having 25 mol% of an alkenyl group and 2 mol% of an epoxy group (the total number of Si atoms contained in the polysiloxane was 100 mol%). The polystyrene reduced weight average molecular weight of the polysiloxane (A3) in the gel permeation chromatography was measured and found to be 2000. The formula of the polysiloxane (A3) is (ViMe ₂ SiO _1/2 ) ₂₅ (PhSiO _3/2 ) ₇₃ (EpMeSiO _2/2 ) ₂ (Vi is vinyl group, Me is methyl group, Ph is phenyl group, Ep is glycidoxypropyl And the subscript indicates mol%). When the total number of Si atoms contained in the polysiloxane (A3) was 100 mol%, the alkenyl group content was 25 mol%, the epoxy group content was 2 mol%, and the aryl group content ratio was 73 mol%.

[Synthesis Example 5] Synthesis of polysiloxane (A4)

In a four-necked flask equipped with a stirrer, a reflux condenser, an inlet and a thermometer, 49 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 442 g of phenyltrimethoxysilane, 85 g of dimethyldimethoxysilane, , 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were charged and mixed, and the mixture was refluxed for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was water-filtered. 8 g of 3-glycidoxypropylmethyldimethoxysilane and 0.5 g of potassium hydroxide were added to the water-washed toluene solution layer, and the mixture was heated under reflux for 1 hour. Then, the methanol was distilled off, and excess water was removed by azeotropic dehydration. The mixture was heated under reflux for 4 hours. After the reaction, the toluene solution was cooled, neutralized with 0.6 g of acetic acid and water-filtered. After the water was removed, toluene was distilled off and concentrated under reduced pressure to obtain a polysiloxane (A4) having 15 mol% of an alkenyl group and 1 mol% of an epoxy group (the total number of Si atoms contained in the polysiloxane was 100 mol%). The polystyrene reduced weight average molecular weight of the polysiloxane (A4) in the gel permeation chromatography was 1800. The formula of the polysiloxane (A4) is (ViMe ₂ SiO _1/2 ) ₁₅ (PhSiO _3/2 ) ₆₄ (Me ₂ SiO _2/2 ) ₂₀ (EpMeSiO _2/2 ) ₁ Is a phenyl group, Ep is a glycidoxypropyl group, and the suffix indicates mol%). When the total number of Si atoms contained in the polysiloxane (A4) was 100 mol%, the content of the alkenyl group was 15 mol%, the content of the epoxy group was 1 mol%, and the content of the aryl group was 64 mol%.

[Synthesis Example 6] Synthesis of polysiloxane (A5)

Necked flask equipped with a stirrer, reflux condenser, inlet and thermometer was charged with 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 525 g of phenyltrimethoxysilane, 143 g of water, And 500 g of toluene were charged and mixed, and the mixture was heated under reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was water-filtered. To the water-washed toluene solution layer, 314 g of 3-glycidoxypropylmethyldimethoxysilane, 130 g of water and 0.5 g of potassium hydroxide were added, and the mixture was heated under reflux for 1 hour. Then, the methanol was distilled off, and excess water was removed by azeotropic dehydration. The mixture was heated under reflux for 4 hours. After the reaction, the toluene solution was cooled, neutralized with 0.6 g of acetic acid and water-filtered. After the water was removed, toluene was distilled off and concentrated under reduced pressure to obtain a polysiloxane (A5) having 25 mol% of an alkenyl group and 40 mol% of an epoxy group (the total number of Si atoms contained in the polysiloxane was 100 mol%). The polystyrene reduced weight average molecular weight of the polysiloxane (A5) in the gel permeation chromatography was 1600. The formula of the polysiloxane (A5) is (ViMe ₂ SiO _1/2 ) ₂₅ (PhSiO _3/2 ) ₃₅ (EpMeSiO _2/2 ) ₄₀ (Vi is vinyl group, Me is methyl group, Ph is phenyl group, Ep is glycidoxypropyl And the subscript indicates mol%). When the total number of Si atoms contained in the polysiloxane (A5) was 100 mol%, the content of the alkenyl group was 25 mol%, the content of the epoxy group was 40 mol%, and the content of the aryl group was 35 mol%.

 [Synthesis Example 7] Synthesis of polysiloxane (A6)

Necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer was charged with 33 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 442 g of phenyltrimethoxysilane, 85 g of dimethyldimethoxysilane, 43 g of dimethoxysilane, 155 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were added and mixed, and the mixture was refluxed for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was water-filtered. 8 g of 3-glycidoxypropylmethyldimethoxysilane and 0.5 g of potassium hydroxide were added to the water-washed toluene solution layer, and the mixture was heated under reflux for 1 hour. Then, the methanol was distilled off, and excess water was removed by azeotropic dehydration. The mixture was heated under reflux for 4 hours. After the reaction, the toluene solution was cooled, neutralized with 0.6 g of acetic acid and water-filtered. After the water was removed, the toluene was distilled off and concentrated under reduced pressure to obtain a polysiloxane (A6) having 10 mol% of an alkenyl group and 1 mol% of an epoxy group (the total number of Si atoms contained in the polysiloxane was 100 mol%). The polystyrene reduced weight average molecular weight of the polysiloxane (A6) in the gel permeation chromatography was 1800. The formula of the polysiloxane (A6) is _{(ViMe 2 SiO 1/2)} 10 (PhSiO 3/2) 64 (Ph 2 SiO 2/2) 5 (Me 2 SiO 2/2) 20 (EpMeSiO 2/2) 1 (Vi Represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, and Ep represents a glycidoxypropyl group, and the suffix indicates mol%). When the total number of Si atoms contained in the polysiloxane (A6) was 100 mol%, the alkenyl group content was 10 mol%, the epoxy group content was 1 mol%, and the aryl group content was 74 mol%.

[Synthesis Example 8] Synthesis of polysiloxane (B1)

195 g of phenyltrimethoxysilane and 0.2 g of trifluoromethanesulfonic acid were added to a four-necked flask equipped with a stirrer, reflux condenser, inlet and thermometer, and 13 g of water was added dropwise over 15 minutes while stirring. The time was refluxed. After cooling to room temperature, 119 g of 1,1,3,3-tetramethyldisiloxane was added, and 88 g of acetic acid was added dropwise with stirring. After completion of dropwise addition, the mixture was heated to 50 캜 while stirring, and reacted for 3 hours. After cooling to room temperature, toluene and water were added, mixed well and allowed to stand, and the aqueous layer was separated and removed. The upper toluene solution layer was washed with water and concentrated under reduced pressure to obtain methylphenylhydrogenpolysiloxane (B1). The chemical formula of the polysiloxane (B1) was (HMe ₂ SiO _1/2 ) ₆₀ (PhSiO _3/2 ) ₄₀ (Me represents methyl group, Ph represents phenyl group, and the suffix represents mol%).

[Synthesis Example 9] Synthesis of polysiloxane (B2)

220 g of diphenyldimethoxysilane and 0.6 g of trifluoromethanesulfonic acid were added to a four-necked flask equipped with a stirrer, a reflux condenser, an inlet and a thermometer, and 147 g of 1,1,3,3-tetramethyldisiloxane was added thereto, While stirring, 108 g of acetic acid was added dropwise over 30 minutes. After completion of dropwise addition, the mixture was heated to 50 캜 while stirring, and reacted for 3 hours. After cooling to room temperature, toluene and water were added, mixed well and allowed to stand, and the aqueous layer was separated and removed. The toluene solution layer as the upper layer was washed with water three times, and then concentrated under reduced pressure to obtain diphenylhydrogenpolysiloxane (B2). Polysiloxane of formula (B2) is _{(HMe 2 SiO 1/2)} 50 (Ph 2 SiO 2/2) 50 was (Me is a methyl group, Ph represents a phenyl group, a subscript represents a mol%).

(1-2) Weight average molecular weight

The weight average molecular weight (Mw) of the obtained polysiloxane was measured by gel permeation chromatography (GPC) under the following conditions and found to be a value in terms of polystyrene.

Apparatus: HLC-8120C (manufactured by TOSO CORPORATION)

Column: TSK-gel Multipore HXL-M (manufactured by Toso K.K.)

Eluent: THF, flow rate 0.5 mL / min, loading 5.0%, 100 μL

(1-3) a content ratio of an alkenyl group, an epoxy group and an aryl group, and a chemical formula of the polysiloxane.

The content of the alkenyl group, epoxy group and aryl group contained in the obtained polysiloxane (the total number of Si atoms contained in the polysiloxane was 100 mol%) and the chemical formula of the polysiloxane were calculated by ²⁹ Si NMR and ¹³ C NMR.

(2) Preparation of a curable composition

[Examples 1 to 5 and Comparative Examples 1 and 2]

The curable compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were obtained by mixing the components shown in the following Table 1 at the compounding amounts shown in Table 1 at 95 캜 under atmospheric pressure. The numerical values in Table 1 represent mass parts. Details of each component in Table 1 are as follows.

C1: Complex of platinum with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (amount of platinum metal: 4% by mass)

D1: cyclo-tetramethyl tetravinyl tetrasiloxane

D2: diphenylbis (dimethylvinylsiloxy) silane

D3: phenyl tris (dimethylvinylsiloxy) silane

(3) Evaluation of curable composition

The curable compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated by the following methods (3-1) to (3-6). The evaluation results are shown in Table 2.

(3-1) Viscosity

The viscosity of the curable composition was measured at 25 캜 using an E-type viscometer.

(3-2) Hardness

The curable composition was coated on a flat plate of Teflon (registered trademark) so that the frame having a thickness of 2 mm was the height of the frame, and heated in a hot air circulating oven at 150 캜 for 5 hours to produce a cured product of 50 mm x 50 mm x 1 mm. The hardness of the cured product was measured by a Type D durometer specified in JIS K6253.

(3-3) Refractive index

Using a cured product prepared for hardness measurement of the curable composition, the refractive index at 25 캜 was measured by a refractive index meter of Model 2010 total refractive index meter manufactured by Metricon. The measurement wavelength is 408 nm.

(3-4) Change in light transmittance

(2 cm in diameter, 1 mm in thickness) on a 1 mm quartz plate, filled with the curable composition, and cured by heating in a hot-air circulating oven at 150 ° C for 5 hours 1.0 mm) at 25 DEG C was measured at a wavelength of 460 nm. Next, in order to investigate the degree of coloring after the accelerated deterioration test, the cured product was heat-aged in a thermocycling oven at 150 ° C for 1000 hours, and the light transmittance at a wavelength of 460 nm at 25 ° C was measured in the same manner. From the ratio of light transmittance after heat aging to light transmittance before heat aging, the change in light transmittance was evaluated on the basis of the following criteria.

A: above 98%

B: above 90% to less than 98%

C: The above ratio is less than 90%

(3-5) Adhesive strength

A curable composition was applied to the bottom surface of a 5 mm diameter and 5 mm high aluminum circle and adhered to various test panels and allowed to stand in a hot air circulating oven at 150 캜 for 1 hour to prepare a test piece with a 5 mm diameter, &Lt; / RTI &gt; The aluminum cylinder closely adhered to various test panels was peeled off at a rate of 50 占 퐉 / sec using a measuring apparatus, series-4000PXY manufactured by Dage, and the load at that time was measured to determine the adhesive strength.

A: Adhesive strength of 10kg or more

B: Adhesive strength of 5kg or more and less than 10kg

C: Adhesive strength less than 5kg

(3-6) Heat resistance

The curable composition was coated on quartz glass to a dry film thickness of 1 mm, dried and cured at 100 占 폚 for 1 hour, and then dried and cured at 150 占 폚 for 5 hours to prepare a cured product. The cured product was stored at 150 DEG C for 500 hours, and the appearance of the cured product after storage was visually observed to evaluate the heat resistance based on the following criteria.

(Color change)

A: No color change

B: A little yellowed

C: Obviously yellowed

(3-7) Measurement of forward flux (total radiant flux) (luminance evaluation)

The curable composition is composed of a surface mount type (Top-View type, optical semiconductor 2 in Fig. 1, electrode 6, wire 7, and reflector 3) , And heated at 150 캜 for 1 hour to prepare a sample for evaluation.

The radial velocity measurement of the sample for evaluation was carried out using a forward flux measuring device (instantaneous multi-photometer MCPD-3700, Φ300 mm integral sphere (hemispherical integral sphere)). The package before the sealing material was applied was energized to emit light. The ratio of the above-mentioned initial sample to the radiated sample in the radiation was calculated as%, and the result was evaluated according to the following criteria.

A: The above ratio is 110% or more

B: the above ratio is less than 110%, 100% or more

C: The above ratio is less than 100%

From the results shown in Table 2, in Comparative Examples 1 and 2 using the polysiloxane (A) which is an epoxy group-containing polysiloxane as an adhesion promoter, in Comparative Example 1 using the polysiloxane (A5) having a large number of epoxy groups, In Comparative Example 2 using the polysiloxane (A3) having a small number of hydroxyl groups, the bonding strength was lowered and the compatibility between high luminance and high adhesiveness was not realized. On the contrary, in Examples 1 to 5 containing a polysiloxane (A) which is an epoxy group-containing polysiloxane as a main component, it was found that both front shear rate and adhesive strength were both high, and both high luminance and high adhesiveness were realized.

The curable composition of the present invention is excellent in adhesiveness to optical semiconductor elements and optical semiconductor members, adhesives, and potting agents (for example, glass, ceramics, etc.) because the cured product of the present invention is transparent and low in light transmittance even when placed in a high- potting agents, protective coatings, underfill agents, and the like. The cured product of the present invention is characterized by being low in light transmittance and excellent in long-term reliability even in a manufacturing process under a high temperature condition since a decrease in light transmittance is small even when exposed to high temperatures. The cured product of the present invention is useful as an optical member used in the vicinity of a high-luminance light source, because the cured product of the present invention is used in an optical semiconductor device such as a high-luminance light emitting device.

1: optical semiconductor device
2: Semiconductor light emitting element
3: Reflector
4: Encapsulation material
5: Particle
6: Electrode
7: Wire

Claims (8)

(B) (except polysiloxane (A)) having at least two silicon atom-binding hydrogen atoms per molecule, and a hydrosilylation reaction catalyst (C) having an alkenyl group and a bonding group, and a polysiloxane ), Wherein the content of the polysiloxane (A) is 40 to 90% by mass when the total content of the components in the curable composition is 100% by mass. The method according to claim 1,
Wherein the polysiloxane (A) has a content of an alkenyl group of 3 to 50 mol% and a content of an adhesive group of 0.01 to 10 mol%, wherein the total number of Si atoms contained in the polysiloxane (A) is 100 mol% Composition. 3. The method of claim 2,
Wherein the adhesive group is a group having an epoxy group. The method of claim 3,
Wherein the polysiloxane (A) is represented by the following formula (2):
(2)

( ^Wherein R ^Vi represents a group having an alkenyl group; R ^Ep represents a group having an epoxy group; R ¹ represents, independently of each other, a monovalent hydrocarbon group (excluding groups having an alkenyl group); B is an integer of 0 or more, c is an integer of 0 or more, d is an integer of 1 or more, e is an integer of 0 or more, f is an integer of 0 or more, X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, h represents an integer of 0 or more; i represents an integer of 0 or more, provided that a + c is an integer of 1 or more;
&Lt; / RTI &gt; 5. The method of claim 4,
Wherein the polysiloxane (A) has an aryl group and the content of the aryl group in the polysiloxane (A) is 30 to 120 mol%, when the total number of Si atoms contained in the polysiloxane (A) is 100 mol%. A cured product obtained from the curable composition according to any one of claims 1 to 5. A semiconductor device comprising: a semiconductor light emitting element; and a cured product according to claim 6, which covers the semiconductor light emitting element. (2): &lt; EMI ID =
(2)

( ^Wherein R ^Vi represents a group having an alkenyl group; R ^Ep represents a group having an epoxy group; R ¹ represents, independently of each other, a monovalent hydrocarbon group (excluding groups having an alkenyl group); B is an integer of 0 or more, c is an integer of 0 or more, d is an integer of 1 or more, e is an integer of 0 or more, f is an integer of 0 or more, X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, h represents an integer of 0 or more; i represents an integer of 0 or more, with the proviso that a + c is an integer of 1 or more.

Images