JP2013239506A - Polysiloxane based composition, and optical semiconductor device using the composition as sealant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polysiloxane based compound causing no discoloration around a lead frame and having excellent adhesiveness to a reflector.SOLUTION: This optical semiconductor device includes an optical semiconductor element 1, a silver-plated lead frame 4, and a hardened material of a polysiloxane based composition 3 for sealing the optical semiconductor element and the silver-plated lead frame. The polysiloxane based composition is composed of (A) a polyhedral structure modified polysiloxane obtained by subjecting a compound (b) having a polyhedral structure polysiloxane and a hydrosilyl group and an organic silicon compound (a') having one alkenyl group in one molecule to hydrosilylated reaction, (B) a compound having two or more alkenyl groups in one molecule, and (C) an organic compound expressed by the specific formula, and total luminous flux retention of an LED is 80% or higher after continuous energization for 500 hours at 85°C and relative humidity of 85%.

Description

  The combination of the composition and the silver-plated LED lead frame suppresses the generation of silver microparticles generated by prolonged exposure to light or heat, and discolors the silver-plated surface, encapsulating resin layer, and reflector. Semiconductor device that does not cause

  Polysiloxane composition is excellent in heat resistance, cold resistance, weather resistance, light resistance, chemical stability, electrical properties, flame resistance, water resistance, transparency, colorability, non-adhesiveness, non-corrosion It is used in various industries. Among them, a composition composed of polysiloxane having a polyhedral structure is known to exhibit further excellent heat resistance, light resistance, chemical stability, low dielectric property, etc. from its specific chemical structure. .

  Among them, a compound using polysiloxane having a polyhedral structure is known to exhibit particularly excellent heat resistance, light resistance, chemical stability, low dielectric constant, and the like. Development to use as a stopper is known.

  However, these polysiloxane-based compositions have poor adhesion to reflectors, and in the long-term reliability test, there is a problem that peeling occurs during the test and changes in optical properties.

  In addition, while the polysiloxane composition has excellent characteristics, there is a problem in that the periphery of the lead frame is generally discolored when used for an optical semiconductor element sealant, resulting in a decrease in luminance of the LED.

  For example, Patent Document 1 discloses a technique for suppressing discoloration of a silver electrode by blending a hydrazide derivative into a curable composition. However, in a curing system using a hydrosilylation reaction, it is known that a hydrazide derivative causes a curing failure by inhibiting a catalytic reaction.

  As described above, it has been desired to develop a polysiloxane compound that does not cause discoloration around the lead frame and has good adhesion to a reflector.

JP2011-159912

  To provide a polysiloxane composition that does not cause discoloration around a lead frame and has good adhesion to a reflector.

As a result of intensive studies, the present inventors have
The above-described problems can be solved by an optical semiconductor device comprising an optical semiconductor element, a silver-plated lead frame, a package on which the optical semiconductor element is mounted, and a cured product of a polysiloxane composition that seals the optical semiconductor element. And found the present invention.

  That is, the present invention has the following configuration.

1). An optical semiconductor device comprising an optical semiconductor element, a lead frame plated with silver, and a cured product of a polysiloxane composition that seals the optical semiconductor element and the lead frame plated with silver The polysiloxane composition is
(A) Polyhedral polysiloxane modification obtained by hydrosilylation reaction of polyhedral polysiloxane, compound (b) having a hydrosilyl group, and organosilicon compound (a ′) having one alkenyl group in one molecule Compound (B) Compound having two or more alkenyl groups in one molecule (C) Organic compound represented by general formula (1) (wherein R ¹⁰ , R ¹¹ and R ¹² have 1 to 50 carbon atoms) Represents a monovalent organic group or a hydrogen atom, at least one of R ¹⁰ , R ¹¹ and R ¹² has one or more glycidyl groups, and at least one has one or more alkenyl groups and / or hydrosilyl groups a. However, any one of R ^10, R ¹¹ and R ^12, but may have a glycidyl group and an alkenyl group and / or a hydrosilyl group at the same time. Moreover, R ^10, R ¹¹ And R ¹² may be the same or different.)

Consists of
An optical semiconductor device characterized in that the total luminous flux retention of the LED after 500 hours of continuous energization at 85 ° C. and 85% relative humidity is 80% or more.

  2). The optical semiconductor device according to 1), wherein the polyhedral polysiloxane is a polyhedral polysiloxane compound (a) having an alkenyl group.

  3). The optical semiconductor device according to 1) or 2), wherein the polyhedral polysiloxane-modified product (A) is a polysiloxane-based composition that is liquid at a temperature of 20 ° C.

  4). Any one of 1) to 3), wherein the organosilicon compound (a ′) having one alkenyl group in one molecule is an organosilicon compound having one or more aryl groups. An optical semiconductor device according to claim 1.

5). The polyhedral polysiloxane compound (a) having an alkenyl group is represented by the formula: [AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group A polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by an aryl group or a group linked to another polyhedral skeleton polysiloxane) 5. The optical semiconductor device according to any one of 1) to 4), which is a composition.

  6). 1 is a polysiloxane composition wherein the compound (b) containing a hydrosilyl group is a cyclic siloxane containing a hydrosilyl group and / or a linear siloxane containing a hydrosilyl group at the molecular end. The optical semiconductor device according to any one of 1) to 5).

  7). The optical semiconductor device according to any one of 1) to 5), wherein the compound (b) containing a hydrosilyl group is a polysiloxane-based composition, which is a cyclic siloxane containing a hydrosilyl group.

  8). The compound (b) containing a hydrosilyl group is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane. 7) The optical semiconductor device described in 7).

9). An optical semiconductor device comprising an optical semiconductor element, a lead frame plated with silver, and a cured product of a polysiloxane composition that seals the optical semiconductor element and the lead frame plated with silver The polysiloxane-based composition is (A) [XR ³ ₂ SiO—SiO _3/2 ] _c R ⁴ ₃ SiO—SiO _3/2 ] _d
[{C + d is an integer of 6 to 24, c is an integer of 1 or more, d is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, an aryl Group or a group linked to other polyhedral skeleton polysiloxane, X has a structure of either of the following general formula (2) or general formula (3), and when there are a plurality of X, the general formula ( The structure of 2) or general formula (3) may be different, and the structure of general formula (2) or general formula (3) may be mixed.

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain In which at least one of Y or Z is a hydrogen atom, and at least one has the structure of the following general formula (4).
-[CH ₂ ] _p -R ⁵ (4)
(P is an integer of 2 or more; R ⁵ is a group containing an organosilicon compound); R is an alkyl group or an aryl group}] as a structural unit, modified polyhedral polysiloxane (B) 2 in one molecule Compound (C) having the above alkenyl group Organic compound represented by general formula (1) (wherein R ¹⁰ , R ¹¹ and R ¹² represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom. , R ¹⁰ , R ¹¹ and R ¹² have at least one glycidyl group and at least one has at least one alkenyl group and / or hydrosilyl group, provided that R ¹⁰ , R ¹¹ and Any one of R ¹² may have a glycidyl group, an alkenyl group and / or a hydrosilyl group at the same time, and R ¹⁰ , R ¹¹ and R ¹² may be different or the same. ),

And the total luminous flux retention of the LED after 500 hours of continuous energization at 85 ° C. and 85% relative humidity is 80% or more.

10). 9. The optical semiconductor device according to 9), which is a polysiloxane composition, wherein R ⁵ has one or more aryl groups.

  11). 11. The optical semiconductor device according to any one of 1) to 10), which is a polysiloxane composition containing a compound (B) having two or more alkenyl groups in one molecule.

  12). 11. The optical semiconductor device according to 11), which is a polysiloxane composition, wherein the compound (B) is a polysiloxane (B1) having two or more alkenyl groups in one molecule.

  13). 12. The optical semiconductor device according to 12), wherein the polysiloxane (B1) having two or more alkenyl groups in one molecule has one or more aryl groups.

  14). Compound (B) is an organic compound represented by the following general formula (5),

(Wherein R ⁶ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ⁶ may be different or the same), and 2 alkenyl groups in one molecule. The optical semiconductor device according to 11), which is a polysiloxane composition, which is an organic compound (B2) having at least one.

  15). 14. The optical semiconductor device according to 14), which is a polysiloxane composition, wherein the organic compound (B2) has a number average molecular weight of less than 900.

  16). 14) or 15), wherein the organic compound (B2) is at least one compound selected from the group consisting of triallyl isocyanurate, diallyl isocyanurate, and diallyl monomethyl isocyanurate. An optical semiconductor device according to 1.

  17). The optical semiconductor device according to 14) or 15), which is a polysiloxane composition, wherein the organic compound (B2) is diallyl monomethyl isocyanurate.

  18). The organic compound (C) is an isocyanuric acid derivative containing one or more glycidyl groups in one molecule and one or more alkenyl groups and / or hydrosilyl groups in one molecule. The optical semiconductor device according to any one of 1) to 17).

  19). The organic compound (C) is a compound having an alkenyl group and a glycidyl group, and is at least one compound selected from the group consisting of diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl monoglycidyl monomethyl isocyanurate 18) The optical semiconductor device according to 18).

  20). The organic compound (C) is a compound having a hydrosilyl group and a glycidyl group, and is at least one compound selected from the group consisting of diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl monoglycidyl monomethyl isocyanurate 18) The optical semiconductor device according to 18), which is a compound (D) obtained by hydrosilylating a hydrosilyl group-containing compound (b).

  21). 21. The optical semiconductor device according to any one of 1) to 20), which is a polysiloxane-based curable composition containing a hydrosilylation catalyst.

  22). The optical semiconductor device according to any one of 1) to 21), which is a polysiloxane-based curable composition containing a curing retarder.

  23). The optical semiconductor device according to any one of 1) to 22), further comprising an inorganic filler.

  It is possible to provide a polysiloxane composition that does not cause discoloration around the lead frame and has good adhesion to the reflector.

It is a schematic sectional drawing of the surface mount type light emitting diode (LED) which is an example of the optical semiconductor device of this invention.

  The present invention will be described in detail below.

<Optical semiconductor device>
The optical semiconductor device of the present invention is not particularly limited, but for example, the structure shown in FIG. FIG. 1 is a schematic cross-sectional view of an optical semiconductor device.

  The optical semiconductor element 1 in FIG. 1 of the present invention is not particularly limited, and those widely used as LEDs of semiconductor light emitting devices can be used. For example, a phosphor is excited by emitted light to emit visible light, and examples thereof include a visible light emitting type LED and an ultraviolet light emitting type LED. In the optical semiconductor element 1 of the present invention, a plurality of the same or different types of LEDs may be mounted per semiconductor light emitting device.

  The reflector 2 in FIG. 1 of the present invention may be used as necessary, and is intended to efficiently reflect the optical semiconductor device from the optical semiconductor element 1. As the material, thermoplastic resin, thermosetting resin, glass epoxy, ceramics, and the like can be used, but are not particularly limited.

  The cured product 3 of the polysiloxane composition in FIG. 1 of the present invention efficiently penetrates the optical semiconductor device from the optical semiconductor element 1 to the outside, and protects the optical semiconductor element and wires from external force and dust. It has the effect of preventing the corrosive gas from entering the apparatus.

  The lead 4 in FIG. 1 of the present invention is for ensuring conductivity when mounting the LED and enhancing the reflection efficiency of the LED. In particular, since the reflectance in the visible light region is high, a metal surface plated with silver is used.

  The wire 5 in FIG. 1 of the present invention electrically connects the optical semiconductor element 1 and the lead 4 and is not particularly limited as long as the material is conductive, but gold, gold alloy, copper, etc. Is mentioned. Further, instead of using the wire 5, an electrical connection may be made using a conductive adhesive or eutectic solder.

  As a result of intensive studies to provide a polysiloxane compound that does not cause discoloration around the lead frame and has good adhesion to the reflector, the following has been found.

  As a method for improving adhesiveness, for example, it is known to add a silane coupling agent represented by 3-glycidoxypropyltrimethoxysilane. However, as a result of detailed studies, it has been found that when these silane coupling agents are blended, discoloration around the lead frame is promoted, and as a result, brightness reduction of the LED may be promoted.

In addition, it is known that by setting the SiH group / alkenyl group ratio in the curable composition to be within a specific range, precipitation of copper on the electrode substrate is suppressed, and as a result, discoloration is suppressed. However, as a result of detailed analysis, absorption of visible light may occur and discoloration may occur due to the formation of fine silver particles on the lead frame surface or in the vicinity of the lead frame or in the sealing resin. I found
The polysiloxane composition used in the present invention will be described in detail.

<Polyhedral polysiloxane>
The polysiloxane composition in the present invention contains polyhedral polysiloxane. As the polyhedral polysiloxane used in the present invention, known polyhedral polysiloxanes can be widely used. The general formula [RSiO _3/2 ] _a and the general formula [R ₃ SiO—SiO _3/2 ] _a ( R is an arbitrary organic group, which may be the same or different; a is an integer of 6 to 24), and is exemplified by a polyhedral polysiloxane composed of siloxane units. A partially cleaved polyhedral polysiloxane containing [R ₂ SiO _2/2 ] units and [R ₃ SiO _1/2 ] units therein may also be used.

  In addition, polyhedral polysiloxane averages hydrosilyl groups in one molecule from the viewpoint of strength, heat resistance, light resistance, and gas barrier properties of the resulting cured product when reacted with the component (B) described below. 3 or more are preferable.

  The polyhedral polysiloxane used in the present invention includes a polyhedral polysiloxane compound (a) having an alkenyl group, a compound (b) having a hydrosilyl group, and an organosilicon compound having one alkenyl group in one molecule ( It is a polyhedral polysiloxane modified product (A) obtained by hydrosilylation reaction with a ′), and the resulting curable composition has heat resistance, light resistance, gas barrier properties, and thermal shock resistance. From the viewpoint of handling property (viscosity) and the like, it is more preferable.

<Polyhedral polysiloxane compound (a) having an alkenyl group>
The polyhedral polysiloxane compound (a) having an alkenyl group used in the curable composition of the present invention is not particularly limited as long as it is a polysiloxane having an alkenyl group in the molecule and having a polyhedral skeleton. Specifically, for example, the following formula:
[R ⁷ SiO _3/2 ] _x [R ⁸ SiO _3/2 ] _y
(X + y is an integer of 6 to 24; x is an integer of 1 or more, y is 0 or an integer of 1 or more; R ⁷ is an alkenyl group or a group having an alkenyl group; R ⁸ is any organic group, or An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by a group linked to other polyhedral skeleton polysiloxanes can be preferably used,
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by an aryl group or a group linked to another polyhedral skeleton polysiloxane) is exemplified.

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

R ¹ is an alkyl group or an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ¹ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

R ² is a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ² in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

  a is not particularly limited as long as it is an integer of 1 or more, but is preferably 2 or more, and more preferably 3 or more, from the handleability of the compound and the physical properties of the resulting cured product. Further, b is not particularly limited as long as it is 0 or an integer of 1 or more.

  The sum of a and b (= a + b) is an integer from 6 to 24, but from the viewpoint of the stability of the compound and the stability of the resulting cured product, it should be 6 to 12, and more preferably 6 to 10. preferable.

The method for synthesizing the component (a) is not particularly limited, and the component can be synthesized using a known method. As a synthesis method, for example, a silane of R ⁹ SiX ^a ₃ (wherein R ⁹ represents R ⁷ and R ⁸ described above, and X ^a represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). Obtained by hydrolysis condensation reaction of compounds. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolysis condensation reaction of R ⁹ SiX ^a _3, the ring is closed by further reacting the same or different trifunctional silane compounds, and polyhedral Methods for synthesizing structural polysiloxanes are also known.

  In addition, for example, there is a method of hydrolytic condensation of tetraalkoxysilane such as tetraethoxysilane in the presence of a base such as quaternary ammonium hydroxide. In this synthesis method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. It is possible to obtain a polyhedral polysiloxane in which Si atoms and alkenyl groups forming a polyhedral structure are bonded through a siloxane bond. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

<Compound (b) having hydrosilyl group>
The compound (b) having a hydrosilyl group used in the curable composition of the present invention is not particularly limited as long as it has one or more hydrosilyl groups in the molecule, but the obtained polyhedral polysiloxane modified product is not limited. From the viewpoints of transparency, heat resistance, and light resistance, a siloxane compound having a hydrosilyl group is preferable, and a cyclic siloxane or a linear polysiloxane having a hydrosilyl group is more preferable. In particular, from the viewpoint of heat resistance, light resistance, and gas barrier properties, a cyclic siloxane is preferable.

  The linear polysiloxane having a hydrosilyl group includes a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. Copolymers, copolymers of methylphenylsiloxane units and methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane blocked at the end with dimethylhydrogensilyl groups, polyblocked at the ends with dimethylhydrogensilyl groups Examples thereof include diphenylsiloxane and polymethylphenylsiloxane blocked at the end with a dimethylhydrogensilyl group.

  In particular, as a linear polysiloxane having a hydrosilyl group, a polysiloxane having a molecular end blocked with a dimethylhydrogensilyl group from the viewpoints of reactivity during modification, heat resistance of the resulting cured product, light resistance, etc. Furthermore, polydimethylsiloxane having a molecular end blocked with a dimethylhydrogensilyl group can be suitably used. Specific examples thereof include tetramethyldisiloxane and hexamethyltrisiloxane.

  Examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1. , 3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen -1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7, Examples include 9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. Specific examples of the cyclic siloxane in the present invention include, for example, 1,3,5,7-tetrahydro, from the viewpoints of industrial availability and reactivity, or heat resistance, light resistance, strength, and the like of the resulting cured product. Gen-1,3,5,7-tetramethylcyclotetrasiloxane can be preferably used.

  These compounds (b), which have a hydrosilyl group, may be used alone or in combination of two or more.

<Organic silicon compound having one alkenyl group in one molecule (a ')>
The organosilicon compound (a ′) having one alkenyl group in one molecule used in the curable composition of the present invention reacts with the hydrosilyl group of the aforementioned compound (b) having a hydrosilyl group. By using the component (a ′), the elastic modulus of the obtained cured product can be reduced, and the thermal shock resistance can be improved.

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

  The component (a ′) in the present invention is not particularly limited as long as it is an organosilicon compound having one alkenyl group in one molecule, but it contains at least one aryl group in one molecule. From the viewpoints of gas barrier properties and refractive index, it is more preferable that the aryl group is directly bonded to a silicon atom from the viewpoints of heat resistance and light resistance.

  The component (a ′) in the present invention is preferably silane or polysiloxane from the viewpoint of heat resistance and light resistance. When the component (a ′) is a silane having one alkenyl group in one molecule, specifically, for example, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethylphenyl Examples include vinyl silane, ethyl diphenyl vinyl silane, allyl trimethyl silane, allyl dimethyl phenyl silane, allyl methyl diphenyl silane, allyl triphenyl silane, allyl triethyl silane, allyl diethyl phenyl silane, allyl ethyl diphenyl silane, and the like. Among these, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are preferable examples from the viewpoint of heat resistance and light resistance, and dimethylphenylvinylsilane and methyldiphenylvinylsilane are also preferable from the viewpoint of gas barrier properties and refractive index. Triphenylvinylsilane is a preferred example.

  Further, when the component (a ′) is a polysiloxane, examples include a linear polysiloxane having one alkenyl group, a polysiloxane having one alkenyl group at the molecular end, and a cyclic siloxane having one alkenyl group. The

  When the component (a ′) is a linear polysiloxane having one alkenyl group, specifically, for example, polydimethylsiloxane, dimethyl dimethylvinylsilyl group and trimethylsilyl group, each of which is blocked at one end. Polymethylphenylsiloxane blocked with a vinylsilyl group and a trimethylsilyl group each at one end, polydiphenylsiloxane blocked with a dimethylvinylsilyl group and a trimethylsilyl group respectively, and a dimethylvinylsilyl group and a trimethylsilyl group. A copolymer of a dimethylsiloxane unit and a methylphenylsiloxane unit each having one end blocked, and a dimethylsiloxane unit and a diphenylsiloxane unit each blocked one by one with a dimethylvinylsilyl group and a trimethylsilyl group, And a copolymer of a methylphenylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group.

In the case of a polysiloxane having one alkenyl group at the molecular end, specifically, for example, polysiloxane having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group as exemplified above, SiO ₂ unit, SiO _{3 /} Examples include at least one siloxane unit selected from the group consisting of ₂ units, SiO units, and SiO _1/2 units, and polysiloxane composed of one dimethylvinylsiloxane unit.

  When the component (a ′) is a cyclic siloxane having one alkenyl group, specifically, for example, 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-vinyl Vinyl-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, Examples include 1-vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane.

  These (a ′) components, which are organosilicon compounds having one alkenyl group in one molecule, may be used alone or in combination of two or more.

<Modified polyhedral polysiloxane (A)>
The modified polyhedral polysiloxane (A) used in the curable composition of the present invention is a polyhedral polysiloxane compound (a) having an alkenyl group and a compound having a hydrosilyl group in the presence of a hydrosilylation catalyst described later ( It can be obtained by hydrosilylation reaction between b) and an organosilicon compound (a ′) having one alkenyl group in one molecule.

  The method for obtaining the modified polyhedral polysiloxane is not particularly limited and can be variously set, but after reacting the component (a) and the component (b) in advance, the component (a ′) may be reacted, The component (a ′) and the component (b) may be reacted in advance, and then the component (a) may be reacted, or the component (a) and the component (a ′) may be allowed to coexist and react with the component (b). May be. After completion of each reaction, for example, volatile unreacted components may be distilled off under reduced pressure and heating conditions, and used as a target product or an intermediate for the next step. In order to suppress the formation of a compound containing only the component (a ′) and the component (b) and not including the component (a), the component (a) and the component (b) are reacted and the unreacted (b The method of reacting the component (a ′) after distilling off the component) is preferred. Suppression of the formation of a compound containing only the component (a ′) and the component (b) and not containing the component (a) is preferable from the viewpoint of heat resistance.

  In the polyhedral polysiloxane modified product thus obtained, a part of the alkenyl group of the component (a) used for the reaction may remain.

  Component (b) is preferably added so that the number of hydrosilyl groups is 2.5 to 20 with respect to one alkenyl group of component (a). When the addition amount is small, gelation proceeds due to a crosslinking reaction, so that the handleability of the modified polyhedral polysiloxane may be inferior, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  The amount of component (a ′) added is preferably such that the number of alkenyl groups is 0.01 to 0.4 with respect to one hydrosilyl group of component (b). When the addition amount is small, the effect of improving the thermal shock resistance of the resulting cured product may be small. When the addition amount is large, the resulting cured product may be poorly cured.

The addition amount of the hydrosilylation catalyst used in the synthesis of the modified polyhedral polysiloxane is not particularly limited, but it is 10 ⁻¹ to 10 to 1 mol of the alkenyl group of the component (a) and the component (a ′) used in the reaction. ^It is good to use in the range of ^-10 mol. Preferably, it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. There is also a risk of foaming. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

The modified polyhedral polysiloxane (A) used in the curable composition of the present invention has the formula
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
[A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, or an aryl group Or a group linked to another polyhedral skeleton polysiloxane, X has a structure represented by the following general formula (2) or general formula (3), and when there are a plurality of X, the general formula (2 ) Or the structure of the general formula (3) may be different, or the structure of the general formula (2) or the general formula (3) may be mixed.

{L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Which may be the same or different. Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain, which may be the same or different. However, at least one of Y or Z is a hydrogen atom, and at least one has the structure of the following general formula (4).
-[CH ₂ ] _p -R ⁵ (4)
(P is an integer of 2 or more; R ⁵ is a group containing an organosilicon compound); R is an alkyl group or an aryl group}]
A polyhedral polysiloxane compound composed of siloxane units represented by

Here, R ⁵ is not particularly limited as long as it is a group containing a silicon compound, but preferably contains at least one aryl group in one molecule from the viewpoint of gas barrier properties and refractive index. From the viewpoint of heat resistance and light resistance, it is preferable that the aryl group is directly bonded to a silicon atom.

  Such a polyhedral polysiloxane modified body can ensure compatibility with various compounds, specifically, the later-described component (B), and further includes, for example, a hydrosilyl group in the molecule. It is possible to react with compounds having various alkenyl groups. Specifically, a cured product having excellent heat resistance, light resistance, gas barrier properties, and the like is obtained by reacting with polysiloxane (B1) or organic compound (B2) having two or more alkenyl groups in one molecule described later. be able to.

  The modified polyhedral polysiloxane may be liquid at a temperature of 20 ° C. It is preferable that the polyhedral polysiloxane modified is in a liquid form because of excellent handling properties.

<Compound (B) having two or more alkenyl groups in one molecule>
The curable composition of the present invention may contain a compound (B) having two or more alkenyl groups in one molecule. When the curable composition used for this invention contains a compound (B) and polyhedral structure polysiloxane has a hydrosilyl group, it can be set as hardened | cured material by making these hydrosilylate-react. In the hydrosilylation reaction, it is preferable to use a hydrosilylation catalyst. As the hydrosilylation catalyst that can be used in this reaction, those described below can be used.

  The addition amount of the compound (B) can be variously set, but when the polyhedral polysiloxane has a hydrosilyl group, the hydrosilyl group contained in the modified polyhedral polysiloxane is 0.3 per alkenyl group of the compound (B). It is desirable to add in a ratio of ˜5, preferably 0.5-3. When the proportion of alkenyl groups is small, appearance defects due to foaming or the like are likely to occur, and when the proportion of alkenyl groups is large, physical properties after curing may be adversely affected.

  Here, as the compound (B), for example, polysiloxane (B1) having two or more alkenyl groups in one molecule, an organic compound (B2) described later, and the like are preferable. In addition, you may use together (B1) component and (B2) component.

<Polysiloxane (B1) having two or more alkenyl groups in one molecule>
The number of siloxane units of the polysiloxane (B1) having two or more alkenyl groups in one molecule that can be contained in the curable composition of the present invention is not particularly limited, but preferably two or more, more preferably 2 to 10 pieces. When the number of siloxane units in one molecule is small, the composition tends to volatilize, and desired physical properties may not be obtained after curing. Moreover, when there are many siloxane units, the gas barrier property of the obtained hardened | cured material may fall.

  The polysiloxane having two or more alkenyl groups in one molecule preferably has an aryl group from the viewpoint of gas barrier properties. In addition, in the polysiloxane having two or more alkenyl groups in one molecule having an aryl group, the aryl group is preferably bonded directly to the Si atom from the viewpoint of heat resistance and light resistance. In addition, the aryl group may be present at either the side chain or the end of the molecule, and the molecular structure of such an aryl group-containing polysiloxane is not limited. For example, the aryl group-containing polysiloxane has a straight chain, branched chain, or partially branched chain. In addition to the chain shape, it may have a cyclic structure.

  Examples of such aryl groups include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, and 4-ethylphenyl. Group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 3-isobutylphenyl group, 4-isobutylphenyl group, 3-tbutylphenyl group, 4-tbutylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,3-dimethylphenyl Group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group, biphenyl group, 2,3,4-trimethyl Examples include phenyl group, 2,3,5-trimethylphenyl group, 2,4,5-trimethylphenyl group, 3-epoxyphenyl group, 4-epoxyphenyl group, 3-glycidylphenyl group, 4-glycidylphenyl group and the like. . Among these, a phenyl group is a preferred example from the viewpoint of heat resistance and light resistance. These may be used alone or in combination of two or more.

  The polysiloxane having two or more alkenyl groups in one molecule in the present invention is a linear polysiloxane having two or more alkenyl groups from the viewpoint of heat resistance and light resistance, and two or more alkenyl groups at the molecular ends. Preferred examples include polysiloxanes having a cyclic structure and cyclic siloxanes having two or more alkenyl groups.

  Specific examples of the linear polysiloxane having two or more alkenyl groups include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Copolymer, methylphenylsiloxane unit, copolymer of methylvinylsiloxane unit and terminal trimethylsiloxy unit, polydimethylsiloxane blocked with dimethylvinylsilyl group, endblocked with dimethylvinylsilyl group Examples thereof include polydiphenylsiloxane and polymethylphenylsiloxane whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular terminals include polysiloxanes whose ends are blocked with dimethylvinylsilyl groups exemplified above, two or more dimethylvinylsiloxane units and SiO ₂ units, SiO _{3 /} Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group consisting of ₂ units and SiO units.

Examples of the cyclic siloxane compound having two or more alkenyl groups include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-vinyl-1-phenyl. -3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5 -Diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-tri Nyl-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11 -Hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane and the like are exemplified.
These polysiloxanes having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

<Organic compound (B2)>
The organic compound (B2) that can be contained in the curable composition of the present invention is an organic compound represented by the following general formula (5), and having two or more alkenyl groups in one molecule If it is, it will not be specifically limited.

(Wherein R ⁶ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ⁶ may be different or the same.)
Since the component (B2) contains two or more alkenyl groups on average in one molecule, the strength, gas barrier property, heat resistance, light resistance and the like of the resulting cured product are excellent. Further, from the viewpoint of gas barrier properties, the number average molecular weight is preferably less than 900.

  The skeleton of the component (B2) may have a functional group other than an alkenyl group, but from the viewpoint of compatibility with the polyhedral polysiloxane, a straight chain such as a methyl group, an ethyl group, or a propyl group. A functional group having low polarity such as the above aliphatic hydrocarbon group is preferred, and a methyl group is particularly preferred from the viewpoint of heat resistance and light resistance.

  The component (B2) is represented by the above general formula (5), for example, from the viewpoint of adhesion to the substrate when the composition is cured with the substrate, and two or more alkenyl groups in one molecule. It is preferably an isocyanuric acid derivative to be contained, and more preferably, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate is used from the viewpoint of the balance between heat resistance and light resistance, and particularly from the viewpoint of thermal shock resistance To diallylmonomethyl isocyanurate is more preferred. These may be used alone or in combination of two or more.

<Organic compound (C)>
The component (C) in the present invention is an organic compound represented by the following general formula (1), and has at least one alkenyl group and / or hydrosilyl group in one molecule, and in one molecule. There is no particular limitation as long as it is an organic compound having one or more glycidyl groups.

(Wherein R ¹⁰ , R ¹¹ and R ¹² represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and at least one of R ¹⁰ , R ¹¹ and R ¹² represents one or more glycidyl groups. And at least one has at least one alkenyl group and / or hydrosilyl group, provided that any one of R ¹⁰ , R ¹¹ and R ¹² has a glycidyl group and an alkenyl group and / or hydrosilyl group simultaneously. R ¹⁰ , R ¹¹ and R ¹² may be different or the same.)
The component (C) in the present invention contains two or more alkenyl groups and / or hydrosilyl groups in one molecule from the viewpoint of the strength, gas barrier properties, heat resistance, light resistance, etc. of the resulting cured product. preferable. In addition, the skeleton of the component (C) may have a functional group other than an alkenyl group or a hydrosilyl group, but from the viewpoint of compatibility with the component (A), a methyl group, an ethyl group, a propyl group A functional group having a low polarity such as a linear aliphatic hydrocarbon group such as a straight chain is preferred, and a methyl group is particularly preferred from the viewpoint of heat resistance and light resistance.

  Examples of the component (C) containing an alkenyl group include diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl monoglycidyl isocyanurate, monoallyl monoglycidyl monomethyl isocyanurate, and the like. From the viewpoint of gas barrier properties, diallyl monoglycidyl isocyanurate and monoallyl diglycidyl isocyanurate are preferable examples.

  The amount of the component (C) having an alkenyl group can be variously set, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on 100% by weight of the polysiloxane composition. 1 to 3% by weight is even more preferred. If the addition amount is too small, the adhesion and the thermal shock resistance are not improved, and if it is too much, the physical properties of the cured product may be adversely affected.

  The component (C) containing a hydrosilyl group includes at least one compound selected from the group consisting of diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl monoglycidyl isocyanurate, monoallyl monoglycidyl monomethyl isocyanurate and Examples of the modified products obtained by hydrosilylating the above-mentioned hydrosilyl group-containing compound (b) include diallyl monoglycidyl isocyanurate and monoallyl diglycidyl isocyanurate from the viewpoints of heat resistance, light resistance, gas barrier properties and the like. A preferred example is a modified product obtained by hydrosilylating at least one compound selected from the group consisting of the above-mentioned compound (b) having a hydrosilyl group.

The amount of the component (C) having a hydrosilyl group can be variously set, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight in 100% by weight of the polysiloxane composition. 1 to 3% by weight is even more preferred. If the addition amount is too small, the adhesion and the thermal shock resistance are not improved, and if it is too much, the physical properties of the cured product may be adversely affected.
These compounds may be used alone or in combination of two or more.

<Hydrosilylation catalyst>
As the hydrosilylation catalyst that can be used in the present invention, a known hydrosilylation catalyst can be usually selected, and there is no particular limitation.

Specifically, a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum; a platinum-vinylsiloxane complex such as Pt _n ( ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex such as Pt [P ( OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer), Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al U.S. Pat. Platinum Arcola described in JP 3220972 specification - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

<Curing retarder>
The curing retarder is a component that can be used to improve the storage stability of the curable composition used in the present invention or to adjust the hydrosilylation reactivity during the curing process. In the present invention, as the retarder, known compounds used in addition-type curable compositions with hydrosilylation catalysts can be used. Specifically, compounds containing aliphatic unsaturated bonds, organophosphorus compounds , Organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the like. These may be used alone or in combination of two or more.

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

  Specific examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

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

  Specific examples of nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, and N, N-dibutyl. -1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, 2,2 Examples include '-bipyridine.

  Specific examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like.

  Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferred curing retarders.

The addition amount of the curing retarder is not particularly limited, but is preferably used in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 100 mol, with respect to 1 mol of the hydrosilylation catalyst. preferable. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

<Silane coupling agent>
The silane coupling agent is a component that can be used for improving adhesiveness as long as the effects of the present invention are not impaired. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Specific preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldisilane. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Alkoxysilanes having an epoxy functional group such as (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysila Alkoxysilanes having a methacrylic group or an acrylic group such as 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Is mentioned. These may be used alone or in combination of two or more.

  In order to prevent coloration on the silver-plated lead frame, the addition amount of the silane coupling agent is 100 weights of a polyhedral polysiloxane modified product and a polysiloxane having two or more alkenyl groups in one molecule. The amount is preferably 1 part by weight or less, and more preferably 0.5 parts by weight or less based on parts.

  In order to increase the adhesiveness, the amount of the silane coupling agent needs to be a certain amount. When the silane coupling agent is used, it is preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.5 part by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product and the coloring of the silver surface may be adversely affected.

  In the present invention, a known adhesion promoter can be used to enhance the effect of the adhesion promoter. Adhesion promoters include, but are not limited to, epoxy-containing compounds, epoxy resins, boronic ester compounds, organoaluminum compounds, and organotitanium compounds.

<Polysiloxane composition>
The polysiloxane composition of the present invention can be obtained by adding a component (A), a component (B) and a component (C) and, if necessary, a hydrosilylation catalyst, a curing retarder and the like. The polysiloxane composition of the present invention can be handled as a liquid resin composition. By using a liquid resin composition, it is possible to easily obtain a molded body according to the application by injecting or applying to a mold, package, substrate or the like and curing.

  When adding temperature when making it harden | cure, Preferably it is 30-400 degreeC, More preferably, it is 50-250 degreeC. If the curing temperature is too high, the resulting cured product tends to have poor appearance, and if it is too low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, for example, by raising the curing temperature stepwise such as 70 ° C., 120 ° C., and 150 ° C., a preferable cured product can be obtained, which is preferable.

  The curing time can be appropriately selected depending on the curing temperature, the amount of the hydrosilylation catalyst to be used and the amount of the reactive group, and other combinations of the composition of the present application. Preferably, a cured product can be obtained by performing the treatment for 10 minutes to 8 hours.

  An inorganic filler can be added to the curable composition of this invention as needed. By using an inorganic filler, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance, flame retardancy, fire resistance, gas barrier properties, etc. of the molded product obtained Various physical properties can be improved.

  The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specifically, for example, quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, etc. Silica-based inorganic filler, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black, Examples thereof include ferrite, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, and silver powder. These may be used alone or in combination of two or more.

  The inorganic filler may be appropriately subjected to a surface treatment. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited.

As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape can be used. The average particle size and particle size distribution of the inorganic filler are not particularly limited, but from the viewpoint of gas barrier properties, the average particle size is preferably 0.005 to 50 μm, more preferably 0.01 to 20 μm. More preferably. Similarly, the BET specific surface area, although not particularly limited, from the viewpoint of gas barrier properties, it is preferably 70m ² / g or more, more preferably 100 m ² / g or more, further 200 meters ² / It is especially preferable that it is g or more.

  Although the addition amount of an inorganic filler is not specifically limited, It is 1-1000 weight part with respect to 100 weight part of curable compositions, More preferably, it is 3-500 weight part, More preferably, it is 5-300 weight part. . When the amount of the inorganic filler added is large, the fluidity may be deteriorated, and when the amount of the inorganic filler added is small, desired physical properties may not be obtained.

  The means for mixing the inorganic filler is not particularly limited. Specifically, for example, a two-roll or three-roll, a planetary stirring and defoaming device, a homogenizer, a dissolver, a planetary mixer, or the like, Examples thereof include a melt kneader such as a plast mill. The mixing of the inorganic filler may be performed at normal temperature, may be performed by heating, may be performed under normal pressure, or may be performed under reduced pressure. If the temperature during mixing is high, the composition may be cured before molding.

  In addition, various additives such as colorants and heat resistance improvers, reaction control agents, mold release agents, dispersants for fillers, and the like are optionally added to the curable composition in the present invention as necessary. Can do. Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

  The curable composition in the present invention is a mixture of the above components using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring and defoaming machine, and heat-treated as necessary. May be.

  The semiconductor light emitting device using the curable composition of the present invention can be used for various conventionally known applications. Specifically, for example, backlights such as light receiving and emitting device liquid crystal display devices, illumination, sensor light sources, instrument light sources for vehicles, signal lights, indicator lights, display devices, light sources of planar light emitters, displays, decorations, various lights, etc. Can be mentioned.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereby.

(SiH value)
A mixed solution of 0.200 g of modified polyhedral polysiloxane, 0.200 g of dibromoethane, and 1.000 g of deuterated chloroform was prepared. The SiH value of the modified polyhedral polysiloxane was determined by measuring the obtained solution using 400 MHz NMR manufactured by Varian Technologies Japan Limited. The following calculation formula (1)
SiH value (mol / kg) = [integral value of peak attributed to SiH group of polyhedral polysiloxane modified product] / [integral value of peak attributed to methyl group of dibromoethane] × 4 × [in the mixture Dibromoethane weight] / [Molecular weight of dibromoethane] / [Modified polyhedral polysiloxane weight in mixture] (1)
It was calculated by using.
(LED continuous energization test)
A 12 mil x 13 mil square blue LED chip (product number: B1213AAA0 S46C-20) manufactured by Genelites Co., Ltd. is mounted on an LED package (model number: SMD6721) manufactured by Echuen Co., Ltd. did. A polysiloxane-based composition was injected here, and a sample was prepared by thermosetting in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 180 ° C. × 1 hour.

  Using the total light flux measurement (φ300 mm) system (product number: HM-0930) manufactured by Otsuka Electronics Co., Ltd., the obtained optical semiconductor device was energized at a temperature of 25 ° C., a current of 30 mA, and a standby time of 30 seconds to emit light. The total luminous flux was measured (initial total luminous flux).

  This optical semiconductor device was bonded to a 0.95 mm pitch surface of a glass epoxy substrate (product number: D006) manufactured by Daisen Electronics Industry, using a conductive paste (FA-705BN) manufactured by Fujikura Kasei Co., Ltd., heated at 150 ° C. for 40 minutes. Connect to the constant current power supply 6240A, put it in a constant temperature and humidity chamber (LH43-13M manufactured by Nagano Science), and conduct an LED continuous energization test at 85 ° C and relative humidity 85% for 500 hours at 20mA. It was.

  The optical semiconductor element after the test was subjected to a total luminous flux measurement at a current value of 20 mA using a total luminous flux measuring apparatus using an integrating sphere at a temperature of 23 ° C. (total luminous flux after the continuous energization test). The total luminous flux retention was calculated using the following formula using the initial total luminous flux and the total luminous flux after the continuous energization test. Total luminous flux retention rate = (total luminous flux after continuous energization test / initial total luminous flux) × 100. A total luminous flux retention of 80% or more was evaluated as ◯, and less than 80% was evaluated as ×.

  In addition, after the continuous energization test, the cured product was evaluated as “◯” when there was no peeling from the package / lead frame, and “X” when there was peeling.

  Furthermore, after the continuous energization test, when the discoloration was observed in the lead frame, the sealing resin in the vicinity of the lead frame, or the reflector in the vicinity of the lead frame, it was marked as ◯.

(Production Example 1)
To 1262 g of a 48% choline aqueous solution (trimethyl-2hydroxyethylammonium hydroxide aqueous solution), 1083 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1000 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.

  The methanol solution was slowly added dropwise while vigorously stirring a solution of 716 g of dimethylvinylchlorosilane, 516 g of trimethylsilyl chloride and 1942 mL of hexane. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, the produced solid is washed by stirring vigorously in methanol and filtered to obtain tetrakis (polysiloxane compound containing alkenyl groups having 16 Si atoms and 4 vinyl groups). 601 g of vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane (Fw = 1178.2) was obtained as a white solid.

(Production Example 2)
20 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, is dissolved in 40 g of toluene, and further a xylene solution of a platinum vinylsiloxane complex. (Platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 3.82 μL was dissolved. 40.83 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (tetrakis (vinyldimethylsiloxy) tetrakis (trimethyl used) was obtained. Siloxy) To an alkenyl group of octasilsesquioxane, an amount of 10.0 hydrosilyl groups) and 13.61 g of toluene were slowly added dropwise and reacted at 105 ° C. for 2 hours. When this solution was subjected to ¹ H-NMR measurement, it was confirmed that alkenyl groups derived from polyhedral polysiloxane compounds having alkenyl groups had disappeared. Toluene and unreacted components were distilled off from this solution, 33 g of toluene was added again to dissolve the product, and a solution prepared by dissolving 19.0 g of vinyldiphenylmethylsilane separately prepared in 19.0 g of toluene was slowly added. The solution was added dropwise and reacted at 105 ° C. for 2 hours. When this solution was subjected to ¹ H-NMR measurement, it was confirmed that the peak of the alkenyl group derived from vinyldiphenylmethylsilane disappeared. After completion of the reaction, 7.30 μl of ethynylcyclohexanol and 1.70 μl of dimethyl maleate were added, and toluene was distilled off to obtain a modified liquid polyhedral polysiloxane 52.0 (SiH value 1.36 mol / kg). It was.

(Production Example 3)
30 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, and 31.42 g of vinyldiphenylmethylsilane (1,3 used) , 5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane is dissolved in 120 g of toluene in an amount of 0.34 alkenyl groups with respect to one hydrosilyl group. 3.82 μL of a xylene solution of the complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was added to 24.5 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (tetrakis (vinyldimethylsiloxy) tetrakis (trimethyl used). Siloxy) An amount of 4 hydrosilyl groups per 1 alkenyl group of octasilsesquioxane) was slowly added dropwise to a solution of 24.5 g of toluene and reacted at 105 ° C. for 2 hours. When this solution was subjected to ¹ H-NMR measurement, it was confirmed that the peaks of both the alkenyl group derived from the polyhedral polysiloxane compound having an alkenyl group and the alkenyl group derived from vinyldiphenylmethylsilane disappeared. After completion of the reaction, 7.30 μl of ethynylcyclohexanol and 1.70 μl of dimethyl maleate were added, and toluene was distilled off to obtain 83.1 g of a modified liquid polyhedral polysiloxane (SiH value: 1.70 mol / kg). It was.

(Production Example 4)
362 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 362 g of toluene were mixed uniformly and stirred at 105 ° C. in a nitrogen atmosphere. 90 ml of a mixed solution of 100 g of diallyl monoglycidyl isocyanurate, 100 g of toluene, and a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, Pt-VTSC-3X, manufactured by Umicore Precious Metals Japan) 90 The solution was added dropwise over a period of minutes, and reacted at 105 ° C. for 4 hours. Unreacted components and toluene were distilled off under reduced pressure to obtain a reaction product (reactant II) of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and diallylmonoglycidyl isocyanurate. ) Was obtained 203 g (SiH valence 7.74 mol / kg).

(Formulation example 1)
To 10.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 2.28 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, platinum vinylsiloxane complex 0.61 μL of a xylene solution (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X), 1.17 μl of ethynylcyclohexanol, and 0.27 μl of dimethyl maleate are uniformly added. Mix and stir to obtain a formulation.

(Formulation example 2)
To the polyhedral polysiloxane modified product obtained in Production Example 2 (10.00 g), diallyl monomethyl isocyanurate (1.38 g) and a platinum vinylsiloxane complex xylene solution (platinum vinylsiloxane complex containing 3 wt% as platinum, Umicore Precious Metals Japan) Manufactured, Pt-VTSC-3X) 0.57 μL, ethynylcyclohexanol 1.09 μl and dimethyl maleate 0.25 μl were added and mixed uniformly and stirred to obtain a blend.

(Formulation example 3)
To 10.00 g of the modified polyhedral polysiloxane obtained in Production Example 3, 2.85 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, platinum vinylsiloxane complex Uniformly by adding 0.64 μL of a xylene solution (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X), 1.23 μl of ethynylcyclohexanol, and 0.28 μl of dimethyl maleate Mix and stir to obtain a formulation.

(Formulation example 4)
The modified polyhedral polysiloxane obtained in Production Example 3 was added to 1.0.00 g of diallyl monomethyl isocyanurate, 1.73 g of diallyl monomethyl isocyanurate, a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, Umicore Precious Metals Japan) Manufactured, Pt-VTSC-3X), 0.59 μL, 1.12 μl of ethynylcyclohexanol, and 0.26 μl of dimethyl maleate were added and mixed uniformly and stirred to obtain a blend.

Example 1
0.25 g of diallyl monoglycidyl isocyanurate was added to the formulation obtained in Formulation Example 1, mixed uniformly and stirred to obtain a polysiloxane composition. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Example 2)
0.23 g of diallyl monoglycidyl isocyanurate was added to the formulation obtained in Formulation Example 2, and the mixture was uniformly mixed and stirred to obtain a polysiloxane composition. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Example 3)
0.26 g of diallyl monoglycidyl isocyanurate was added to the formulation obtained in Formulation Example 3, mixed uniformly, and stirred to obtain a polysiloxane composition. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

Example 4
0.23 g of diallyl monoglycidyl isocyanurate was added to the formulation obtained in Formulation Example 4, and the mixture was uniformly mixed and stirred to obtain a polysiloxane composition. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Example 5)
0.23 g of the reaction product obtained in Production Example 4 was added to the formulation obtained in Formulation Example 4, and the mixture was uniformly mixed and stirred to obtain a polysiloxane composition. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Example 6)
0.23 g of monoallyl diglycidyl isocyanurate was added to the formulation obtained in Formulation Example 4, and the mixture was uniformly mixed and stirred to obtain a polysiloxane composition. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Example 7)
10.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 0.86 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, diallyl monomethyl isocyanurate 0.86 g and diallyl monoglycidyl isocyanurate 0.23 g were added, and a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 59 μL, 1.12 μl of ethynylcyclohexanol and 0.26 μl of dimethyl maleate were added and mixed uniformly and stirred to obtain a polysiloxane-based blend. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Example 8)
10.00 g of the modified polyhedral polysiloxane obtained in Production Example 3, 1.08 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, diallyl monomethyl isocyanurate 1.08 g and diallyl monoglycidyl isocyanurate 0.24 g were added, and a xylene solution of a platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 61 μL, 1.16 μl of ethynylcyclohexanol and 0.27 μl of dimethyl maleate were added and mixed uniformly and stirred to obtain a polysiloxane-based blend. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Comparative Example 1)
Various evaluations described above were performed using the formulation obtained in Formulation Example 1, and the results are shown in Table 1.

(Comparative Example 2)
The various evaluations described above were performed using the formulation obtained in Formulation Example 2, and the results are shown in Table 1.

(Comparative Example 3)
The various evaluations described above were performed using the formulation obtained in Formulation Example 3, and the results are shown in Table 1.

(Comparative Example 4)
The various evaluations described above were performed using the formulation obtained in Formulation Example 4, and the results are shown in Table 1.

(Comparative Example 5)
To the formulation obtained in Formulation Example 1, 0.25 g of 3-glycidoxypropyltrimethoxysilane was added, mixed uniformly, and stirred to obtain a formulation. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Comparative Example 6)
To the formulation obtained in Formulation Example 2, 0.23 g of 3-glycidoxypropyltrimethoxysilane was added, mixed uniformly, and stirred to obtain a formulation. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Comparative Example 7)
To the formulation obtained in Formulation Example 3, 0.26 g of 3-glycidoxypropyltrimethoxysilane was added, mixed uniformly, and stirred to obtain a formulation. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Comparative Example 8)
To the formulation obtained in Formulation Example 4, 0.23 g of 3-glycidoxypropyltrimethoxysilane was added, mixed uniformly, and stirred to obtain a formulation. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

  As shown in Table 1, the semiconductor light-emitting device using the manufacturing method of the present invention does not cause discoloration around the lead frame and has good adhesiveness with the reflector.

DESCRIPTION OF SYMBOLS 1 LED chip 2 Reflector 3 Cured material of polysiloxane type composition 4 Lead 5 Bonding wire

Claims (23)

An optical semiconductor device comprising an optical semiconductor element, a lead frame plated with silver, and a cured product of a polysiloxane composition that seals the optical semiconductor element and the lead frame plated with silver The polysiloxane composition is
(A) Polyhedral polysiloxane modification obtained by hydrosilylation reaction of polyhedral polysiloxane, compound (b) having a hydrosilyl group, and organosilicon compound (a ′) having one alkenyl group in one molecule Compound (B) Compound having two or more alkenyl groups in one molecule (C) Organic compound represented by general formula (1) (wherein R ¹⁰ , R ¹¹ and R ¹² have 1 to 50 carbon atoms) Represents a monovalent organic group or a hydrogen atom, at least one of R ¹⁰ , R ¹¹ and R ¹² has one or more glycidyl groups, and at least one has one or more alkenyl groups and / or hydrosilyl groups a. However, any one of R ^10, R ¹¹ and R ^12, but may have a glycidyl group and an alkenyl group and / or a hydrosilyl group at the same time. Moreover, R ^10, R ¹¹ And R ¹² may be the same or different.)
Consists of
An optical semiconductor device characterized in that the total luminous flux retention of the LED after 500 hours of continuous energization at 85 ° C. and 85% relative humidity is 80% or more. 2. The optical semiconductor device according to claim 1, wherein the polyhedral polysiloxane is a polyhedral polysiloxane compound (a) having an alkenyl group. 3. The optical semiconductor device according to claim 1, wherein the modified polyhedral polysiloxane (A) is a polysiloxane-based composition that is liquid at a temperature of 20 ° C. 3. 4. The polysiloxane composition according to claim 1, wherein the organosilicon compound (a ′) having one alkenyl group in one molecule is an organosilicon compound having one or more aryl groups. An optical semiconductor device according to claim 1. The polyhedral polysiloxane compound (a) having an alkenyl group is represented by the formula: [AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group A polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by an aryl group or a group linked to another polyhedral skeleton polysiloxane) It is a composition, The optical semiconductor device of any one of Claims 1-4. The polysiloxane composition, wherein the compound (b) containing a hydrosilyl group is a cyclic siloxane containing a hydrosilyl group and / or a linear siloxane containing a hydrosilyl group at the molecular end. Item 6. The optical semiconductor device according to any one of Items 1 to 5. The optical semiconductor device according to any one of claims 1 to 5, wherein the compound (b) containing a hydrosilyl group is a polysiloxane composition, which is a cyclic siloxane containing a hydrosilyl group. The compound (b) containing a hydrosilyl group is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane. The optical semiconductor device according to claim 7. An optical semiconductor device comprising an optical semiconductor element, a lead frame plated with silver, and a cured product of a polysiloxane composition that seals the optical semiconductor element and the lead frame plated with silver The polysiloxane-based composition is (A) [XR ³ ₂ SiO—SiO _3/2 ] _c R ⁴ ₃ SiO—SiO _3/2 ] _d
[{C + d is an integer of 6 to 24, c is an integer of 1 or more, d is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, an aryl Group or a group linked to other polyhedral skeleton polysiloxane, X has a structure of either of the following general formula (2) or general formula (3), and when there are a plurality of X, the general formula ( The structure of 2) or general formula (3) may be different, and the structure of general formula (2) or general formula (3) may be mixed.
(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain In which at least one of Y or Z is a hydrogen atom, and at least one has the structure of the following general formula (4).
-[CH ₂ ] _p -R ⁵ (4)
(P is an integer of 2 or more; R ⁵ is a group containing an organosilicon compound); R is an alkyl group or an aryl group}] as a structural unit, modified polyhedral polysiloxane (B) 2 in one molecule Compound (C) having the above alkenyl group Organic compound represented by general formula (1) (wherein R ¹⁰ , R ¹¹ and R ¹² represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom. , R ¹⁰ , R ¹¹ and R ¹² have at least one glycidyl group and at least one has at least one alkenyl group and / or hydrosilyl group, provided that R ¹⁰ , R ¹¹ and Any one of R ¹² may have a glycidyl group, an alkenyl group and / or a hydrosilyl group at the same time, and R ¹⁰ , R ¹¹ and R ¹² may be different or the same. ),
And the total luminous flux retention of the LED after 500 hours of continuous energization at 85 ° C. and 85% relative humidity is 80% or more. The optical semiconductor device according to claim 9, wherein R ⁵ is a polysiloxane composition having one or more aryl groups. The optical semiconductor device according to any one of claims 1 to 10, which is a polysiloxane composition containing a compound (B) having two or more alkenyl groups in one molecule. 12. The optical semiconductor device according to claim 11, wherein the compound (B) is a polysiloxane composition (B1) having two or more alkenyl groups in one molecule. 13. The optical semiconductor device according to claim 12, wherein the polysiloxane (B1) having two or more alkenyl groups in one molecule has one or more aryl groups. Compound (B) is an organic compound represented by the following general formula (5),
(Wherein R ⁶ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ⁶ may be different or the same), and 2 alkenyl groups in one molecule. The optical semiconductor device according to claim 11, wherein the optical semiconductor device is a polysiloxane-based composition which is an organic compound (B2) having at least one. The optical semiconductor device according to claim 14, wherein the organic compound (B2) is a polysiloxane-based composition having a number average molecular weight of less than 900. 16. The polysiloxane composition according to claim 14, wherein the organic compound (B2) is at least one compound selected from the group consisting of triallyl isocyanurate, diallyl isocyanurate, and diallyl monomethyl isocyanurate. An optical semiconductor device according to 1. 16. The optical semiconductor device according to claim 14, wherein the organic compound (B2) is a polysiloxane composition, which is diallyl monomethyl isocyanurate. The organic compound (C) is an isocyanuric acid derivative containing one or more glycidyl groups in one molecule and one or more alkenyl groups and / or hydrosilyl groups in one molecule. The optical semiconductor device according to claim 1. The organic compound (C) is a compound having an alkenyl group and a glycidyl group, and is at least one compound selected from the group consisting of diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl monoglycidyl monomethyl isocyanurate The optical semiconductor device according to claim 18, wherein: The organic compound (C) is a compound having a hydrosilyl group and a glycidyl group, and is at least one compound selected from the group consisting of diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl monoglycidyl monomethyl isocyanurate The optical semiconductor device according to claim 18, wherein the compound is a compound (D) obtained by hydrosilylating a hydrosilyl group-containing compound (b). 21. The optical semiconductor device according to claim 1, which is a polysiloxane-based curable composition containing a hydrosilylation catalyst. The optical semiconductor device according to any one of claims 1 to 21, which is a polysiloxane-based curable composition containing a curing retarder. The optical semiconductor device according to claim 1, further comprising an inorganic filler.