JP2019151768A - Curable silicone composition for light reflecting material, silicone resin cured product, reflector, and led device - Google Patents

Abstract

To provide a curable silicone composition for a light reflecting material which has high fluidity at room temperature and gives a cured product excellent in heat resistance (thermal stability), especially thermal discoloration resistance, and capable of obtaining a high light reflectance.SOLUTION: The curable silicone composition for a light reflecting material contains: (A-1) 30-70 pts.mass of an addition reaction product of (a) a compound represented by general formula (1) having two hydrogen atoms bonded to silicon atoms in one molecule and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, the addition reaction product having at least two addition-reactive carbon-carbon double bonds in one molecule; (A-2) 30-70 pts.mass of a compound represented by general formula (3); (B) an organosilicon compound having three or more hydrogen atoms bonded to silicon atoms in one molecule; (C) a hydrosilylation reaction catalyst; (D) a titanium oxide powder; and (E) an aerosol silica powder.SELECTED DRAWING: None

Description

  The present invention relates to a light-reflective material, particularly a curable silicone composition for light-reflective material (white thermosetting silicone composition) that gives a cured silicone resin useful as a reflector material for white LED (light-emitting diode), The present invention relates to a cured product, and a reflector and an LED device using the cured product.

  In recent years, optical semiconductor elements such as LEDs have been widely used as indicators and light sources because they emit light with high efficiency and are excellent in driving characteristics and lighting repetition characteristics. In particular, white LEDs are widely applied as backlights for display devices and camera flashes, and are also expected as next-generation lighting devices. In such a light emitting device, a component (hereinafter referred to as a reflector) that reflects emitted light is mounted in order to increase the light extraction efficiency in the irradiation direction.

  At present, polyphthalamide resins are widely used as materials used for reflectors (hereinafter referred to as reflector materials). However, the polyphthalamide resin is liable to deteriorate due to long-term use, particularly discoloration, peeling, and mechanical strength reduction, and is difficult to apply to recent high-power light emitting devices.

  In order to solve such problems, Patent Documents 1 to 4 propose a reflector material containing epoxy resin or silicone and a metal oxide as constituents, and Patent Document 5 proposes a ceramic reflector material. However, these solid materials have excellent heat resistance and mechanical properties, but have poor fluidity at room temperature, and thus have problems in handling and workability such as requiring high temperature for molding. In addition, since these solid materials have poor fluidity even at high temperatures, there are problems in processes such as difficulty in forming a fine structure or a large-area structure.

Japanese Patent No. 2656336 JP 2008-106226 A JP 2008-189833 A JP 2013-221075 A JP 2008-117932 A

  The present invention has been made in view of the above circumstances, has a high fluidity at room temperature, is excellent in heat resistance (thermal stability), in particular, heat discoloration resistance, and can obtain a high light reflectance. A curable silicone composition for a light reflecting material is provided. That is, the present invention relates to a light-reflective material, particularly a curable silicone composition for a light-reflective material that gives a cured silicone resin useful as a reflector material for white LEDs, and a reflector comprising the cured product of the composition (particularly, white light emitting The object is to provide a diode).

（式中Ａは下記一般式（２）で表される基から成る群から選ばれる２価の基であり、Ｒ^１は、独立に非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は炭素原子数１〜６のアルコキシ基である。）

（式中Ｐｈはフェニル基であり、Ｒ^２は独立に非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基であり、Ｒ^３は付加反応性炭素−炭素二重結合含有基であり、ｎは１〜２０の整数である。） In order to achieve the above object, in the present invention,
(A-1) (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule; and (b) 1 addition-reactive carbon-carbon double bond. 30 to 70 parts by mass of an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule, which is an addition reaction product with two polycyclic hydrocarbons in the molecule
(A-2) 30 to 70 parts by mass of a compound represented by the following general formula (3) (however, the sum of the component (A-1) and the component (A-2) is 100 parts by mass),
(B) an organosilicon compound having 3 or more hydrogen atoms bonded to silicon atoms in one molecule (the total amount of hydrogen atoms bonded to silicon atoms in the composition is the addition-reactive carbon-carbon 2 in the composition) The amount is 0.5 to 3.0 in terms of molar ratio to the heavy bond)
(C) hydrosilylation reaction catalyst,
Provided is a curable silicone composition for a light reflecting material containing (D) titanium oxide powder and (E) fumed silica powder.

(In the formula, A is a divalent group selected from the group consisting of groups represented by the following general formula (2), and R ¹ is independently an unsubstituted or substituted monovalent carbon atom having 1 to 12 carbon atoms. It is a hydrogen group or an alkoxy group having 1 to 6 carbon atoms.)

(In the formula, Ph is a phenyl group, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is an addition-reactive carbon-carbon double bond-containing group. And n is an integer from 1 to 20.)

  Such a curable silicone composition for a light reflecting material has high fluidity at room temperature, excellent heat resistance (thermal stability), particularly heat discoloration, and high light reflectance. A cured product can be provided.

（式中、Ｒ^４は非置換又は置換の炭素原子数２〜１２のアルケニル基である。） Moreover, it is preferable that said (b) is what is represented by following General formula (4).

(Wherein R ⁴ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)

  In addition, (b) is any one of 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene, and combinations thereof. It is preferable that

  If it is such a raw material (b), intensity | strength can be provided to hardened | cured material more effectively and it can be set as high hardness.

（式中、Ｒ^５は独立に水素原子又はアルケニル基以外の非置換若しくは置換の炭素原子数
１〜１２の一価炭化水素基であり、Ｒ^６はメチル基あるいは水素原子であり、ｐは１〜１０の整数、ｑは０〜７の整数である。ｐが付されたシロキサン単位とｑが付されたシロキサン単位とは互いにランダムに配列している。） Moreover, it is preferable that the said (B) component is a siloxane compound represented by following General formula (5).

(In the formula, R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, R ⁶ is a methyl group or a hydrogen atom, and p is 1 And an integer of 0 to 10 and q is an integer of 0 to 7. The siloxane units marked with p and the siloxane units marked with q are randomly arranged.

  With such a component (B), a cured product having sufficient mechanical properties when used as a reflector material can be obtained.

  At this time, the viscosity at 25 ° C. is preferably 5 to 500 Pa · s.

  With such a viscosity, the fluidity is high and the handling and workability are excellent.

  Moreover, in this invention, the silicone resin hardened | cured material for light reflection materials which is obtained by shape | molding and hardening said curable silicone composition for light reflection materials is provided.

  Such a cured silicone resin for light reflecting material can be suitably used as a reflector material.

  At this time, the reflectance of light having a wavelength of 430 to 800 nm immediately after curing is 95% or more, and the reflectance of light having a wavelength of 430 to 800 nm after 1000 hours exposure in a 170 ° C. environment is 82% or more. It is preferable.

  Such a cured silicone resin for a light reflecting material can be suitably used as a reflector material that is unlikely to deteriorate due to long-term use, particularly discoloration, peeling, and mechanical strength reduction.

  At this time, it is preferable that the Shore D hardness is 65 or more.

  With such Shore D hardness, the cured product, which is a reflector material, has a hardness that is more suitable for cutting into pieces by using a dicing saw or the like.

  Moreover, in this invention, the reflector which consists of said silicone resin hardened | cured material for light reflection materials is provided.

  Furthermore, in this invention, the LED apparatus which mounts said reflector is provided.

  With such a reflector or LED device, high light extraction efficiency can be maintained over a long period of time.

  Since the curable silicone composition for light-reflecting material of the present invention has high fluidity at room temperature, it is excellent in workability and handleability. Moreover, the cured silicone resin for light reflecting material obtained by curing the above composition is excellent in light reflecting performance and heat resistance (thermal stability), particularly heat discoloration. Therefore, the cured product is useful as a light reflecting material, for example, a reflector material for a light emitting device, particularly for a white LED.

  As described above, curability for light reflecting materials that gives a cured product that has high fluidity at room temperature, excellent heat resistance (thermal stability), particularly heat discoloration, and high light reflectivity. The development of silicone compositions has been sought.

  As a result of intensive studies on the above problems, the present inventors have oxidized a thermosetting silicone composition containing a reaction addition product by a hydrosilylation reaction having a specific structure and an organopolysiloxane having a specific structure. Light-reflective material that provides a cured product having high fluidity at room temperature, excellent heat resistance (thermal stability), especially heat-resistant discoloration, and high light reflectivity by compounding titanium powder The present invention has been completed by finding that a curable silicone composition can be obtained.

That is, the present invention
(A-1) (a) a compound having two hydrogen atoms bonded to the silicon atom represented by the general formula (1) in one molecule, and (b) 1 addition-reactive carbon-carbon double bond. 30 to 70 parts by mass of an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule, which is an addition reaction product with two polycyclic hydrocarbons in the molecule
(A-2) 30 to 70 parts by mass of the compound represented by the general formula (3) (however, the total of the component (A-1) and the component (A-2) is 100 parts by mass),
(B) an organosilicon compound having 3 or more hydrogen atoms bonded to silicon atoms in one molecule (the total amount of hydrogen atoms bonded to silicon atoms in the composition is the addition-reactive carbon-carbon 2 in the composition) The amount is 0.5 to 3.0 in terms of molar ratio to the heavy bond)
(C) hydrosilylation reaction catalyst,
It is a curable silicone composition for light reflecting materials containing (D) titanium oxide powder and (E) fumed silica powder.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto. In this specification, Me and Ph represent a methyl group and a phenyl group, respectively, and the viscosity is a value measured by a rotational viscometer.

[(A-1) component]
The component (A-1) of the curable silicone composition for light-reflecting material of the present invention is a component that imparts strength to the cured product after being cured to achieve high hardness.

（式中、Ａは、下記一般式（２）で表される基から成る群から選ばれる２価の基であり、Ｒ^１は、独立に非置換若しくは置換の炭素原子数１〜１２の１価炭化水素基、又は炭素原子数１〜６のアルコキシ基である。）

The component (A-1) includes (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule, and (b) an addition-reactive carbon-carbon double. An addition reaction product with a polycyclic hydrocarbon having two bonds in one molecule, and an addition reaction product having at least two addition-reactive carbon-carbon double bonds in one molecule. Hereinafter, the raw material (a) and the raw material (b) used as the raw material of the component (A-1) will be described.

(In the formula, A is a divalent group selected from the group consisting of groups represented by the following general formula (2), and R ¹ is independently an unsubstituted or substituted 1 having 1 to 12 carbon atoms. A valent hydrocarbon group or an alkoxy group having 1 to 6 carbon atoms.)

（Ｒ^１は独立に非置換もしくは置換の炭素原子数１〜１２の、好ましくは１〜６の、１価炭化水素基又は炭素原子数１〜６のアルコキシ基である） <Raw material (a)>
(A-1) The reaction raw material of component (a) Two hydrogen atoms bonded to the silicon atom represented by the general formula (1) (hereinafter sometimes referred to as “SiH”) per molecule The compound (raw material (a)) is a compound represented by the following general formula (6) because A in the above general formula (1) is a divalent group represented by the above general formula (2). is there.

(R ¹ is independently an unsubstituted or substituted C 1-12, preferably 1-6 monovalent hydrocarbon group or C 1-6 alkoxy group)

In the general formula (6), when R ¹ is a monovalent hydrocarbon group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, an isopentyl group, Alkyl groups such as hexyl group and sec-hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, o-, m- and p-tolyl; benzyl group and 2-phenylethyl group An aralkyl group; an alkenyl group such as a vinyl group, an allyl group, a 1-butenyl group, or a 1-hexenyl group; an alkenyl aryl group such as a p-vinylphenyl group; and one or more hydrogen bonded to a carbon atom in these groups An atom is substituted with a halogen atom, a cyano group, an epoxy ring-containing group, etc., for example, chloromethyl group, 3-chloropropyl group, 3,3,3- A halogenated alkyl group such as a trifluoropropyl group; a 2-cyanoethyl group; a 3-glycidoxypropyl group;

Examples of the case where R ¹ is an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group.

Among these, as R ¹ , those other than alkenyl groups and alkenyl aryl groups are preferable, and those in which all R ^{1 in} one molecule are methyl groups are easy to industrially manufacture, It is preferable because it is easily available.

As the compound represented by the general formula (6), for example,
Structural _{formula: HMe 2 Si-p-C} 6 H 4 -SiMe 2 H
1,4-bis (dimethylsilyl) benzene represented by
Structural _{formula: HMe 2 Si-m-C} 6 H 4 -SiMe 2 H
1,3-bis (dimethylsilyl) benzene represented by
Structural formula: HMe ₂ Si—o—C ₆ H ₄ —SiMe ₂ H
And a silphenylene compound such as 1,2-bis (dimethylsilyl) benzene represented by the formula:

  In addition, the compound represented by the general formula (6) (the raw material (a) which is a reaction raw material of the component (A-1)) can be used alone or in combination of two or more. .

<Raw material (b)>
(B-1) In the polycyclic hydrocarbon (raw material (b)) having two addition-reactive carbon-carbon double bonds in one molecule, which is a reaction raw material of component (A-1), Means a property capable of undergoing the addition of a hydrogen atom bonded to a silicon atom (known as a hydrosilylation reaction).

  In addition, in the raw material (b), an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of (i) polycyclic hydrocarbon. (Ii) a hydrogen atom bonded to a carbon atom forming a polycyclic skeleton of a polycyclic hydrocarbon is substituted with an addition-reactive carbon-carbon double bond-containing group, or (Iii) Of the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon, an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and the polycyclic Any hydrogen atom bonded to the carbon atom forming the hydrocarbon polycyclic skeleton may be substituted with an addition-reactive carbon-carbon double bond-containing group. Here, examples of the addition-reactive carbon-carbon double bond-containing group include alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, norbornyl group, particularly those having 2 to 12 carbon atoms. Etc.

（式中、Ｒ^４は非置換又は置換の炭素原子数２〜１２のアルケニル基である。）

Examples of the component (b) include alkenyl norbornene compounds represented by the following general formula (4). Furthermore, specific examples of the compound represented by the following general formula (4) include 5-vinylbicyclo [2.2.1] hept-2-ene represented by the following structural formula (7), 6-vinylbicyclo [2.2.1] hept-2-ene represented by 8) and a combination of both. (Hereinafter, when it is not necessary to distinguish these three, they may be collectively referred to as “vinyl norbornene”).

(Wherein R ⁴ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)

  In addition, the substitution position of the vinyl group of the vinyl norbornene may be either a cis configuration (exo type) or a trans configuration (end type), and the reaction of the raw material (b) depends on the difference in the arrangement. Since there is no particular difference in sex and the like, a combination of both isomers may be used.

<Preparation of component (A-1)>
The component (A-1) of the curable silicone composition for light-reflecting materials of the present invention is an addition-reactive carbon-carbon double to 1 mol of the raw material (a) having two SiH molecules in one molecule. By subjecting an excess amount of more than 1 mole and not more than 10 moles, preferably more than 1 mole and not more than 5 moles of the raw material (b) having two bonds in one molecule in the presence of a hydrosilylation reaction catalyst, It can be obtained as an addition reaction product having at least two addition-reactive carbon-carbon double bonds in one molecule and having no SiH.

The component (A-1) thus obtained is derived from the raw material (a) in addition to the addition-reactive carbon-carbon double bond derived from the raw material (b) (specifically, in the general formula (1) Since it can contain addition-reactive carbon-carbon double bonds (derived from R ¹ ), it contains at least two addition-reactive carbon-carbon double bonds in one molecule, but this number is preferably 2-6, More preferably, it is two. When the addition reactive carbon-carbon double bond is in such a number, the cured product obtained by curing the curable silicone composition for light-reflecting material of the present invention does not become brittle.

  Any conventionally known hydrosilylation reaction catalyst can be used. For example, carbon powder supporting platinum metal, platinum black, platinous chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of platinum and vinylsiloxane such as divinyltetramethyldisiloxane; Examples include complexes of chloroplatinic acid and olefins, platinum catalysts such as platinum bisacetoacetate; platinum group metal catalysts such as palladium catalysts and rhodium catalysts. Moreover, about addition reaction conditions, use of a solvent, etc., it will not be specifically limited, What is necessary is just to be normal.

  As described above, the component (A-1) is prepared using an excess molar amount of the material (b) relative to the material (a). It has two addition-reactive carbon-carbon double bonds derived from the structure in one molecule. Further, the component (A-1) has a residue derived from the raw material (a), and the residue is derived from the structure of the raw material (b), but has an addition reactive carbon-carbon double bond. It may contain a structure bonded by a divalent residue of a polycyclic hydrocarbon that is not present.

（式中、Ｘは上記原料（ａ）の化合物の二価の残基であり、Ｙは上記原料（ｂ）の多環式炭化水素の一価の残基であり、Ｙ´は上記原料（ｂ）の二価の残基であり、ｍは０〜１０、好ましくは０〜５の整数である） That is, examples of the component (A-1) include compounds represented by the following general formula (9).

Wherein X is a divalent residue of the compound of the raw material (a), Y is a monovalent residue of the polycyclic hydrocarbon of the raw material (b), and Y ′ is the raw material ( b) a divalent residue, and m is an integer of 0 to 10, preferably 0 to 5.

  In addition, about the value of m which is the number of the repeating units represented by said (Y'-X), adjusting the excess molar amount of the said raw material (b) made to react with respect to 1 mol of said raw materials (a). It is possible to set by.

As Y in the general formula (9), specifically, for example, a monovalent residue represented by the following structural formula (hereinafter referred to as “NB” when it is not necessary to distinguish these six members) Generically referred to as “group”, and may be abbreviated as “NB” without distinguishing these six structures.)

Specific examples of Y ′ in the general formula (9) include a divalent residue represented by the following structural formula.

  However, the asymmetrical divalent residue represented by the above structural formula is not limited in the left-right direction as described above. It also includes a structure rotated 180 degrees.

  Although the preferable specific example of the (A-1) component represented by the said General formula (9) is shown below, it is not limited to this. (The meaning of “NB” is as described above.)

（式中、ｒは０〜１０の整数である。）。

(In the formula, r is an integer of 0 to 10).

  Furthermore, the component (A-1) of the curable silicone composition for light reflecting material of the present invention can be used singly or in combination of two or more.

[(A-2) component]
The component (A-2) is highly compatible with the component (A-1), and imparts heat resistance (thermal stability), particularly heat discoloration, without reducing the strength of the cured product after curing. It is.

  The component (A-2) is a linear dimer in which the main chain is composed of repeating diphenylsiloxane units, and both ends of the molecular chain are blocked with a triorganosiloxy group having an addition-reactive carbon-carbon double bond-containing group. Organopolysiloxane. The (A-2) component organopolysiloxane may be used alone or in combination of two or more different molecular weights, types of organic groups bonded to silicon atoms, and the like.

In the general formula (3), the addition-reactive carbon-carbon double bond-containing group as R ³ is the same as that described in the description of <Raw material (b)> above, and is the addition of a hydrogen atom bonded to a silicon atom. It is a group containing a carbon-carbon double bond having a property capable of undergoing (known as a hydrosilylation reaction).

  The said addition reactive carbon-carbon double bond containing group may be used individually by 1 type, or may be used in combination of 2 or more type.

Specific examples of the addition-reactive carbon-carbon double bond-containing group include alkenyl having 2 to 20, preferably 2 to 10, carbon atoms such as vinyl group, allyl group, 5-hexenyl group, propenyl group, and butenyl group. group; alkadienyl group having 4 to 10 carbon atoms such as 1,3-butadienyl group; acryloyloxy group _{(-O (O) CCH = CH} 2), methacryloyloxy group _{(-O (O) CC (CH} 3) = Combinations of the alkenyl group and carbonyloxy group such as CH ₂ ); and combinations of the alkenyl group and carbonylamino group such as acrylamide group (—NH (O) CCH═CH ₂ ).

  Among these, from the viewpoints of productivity and cost when obtaining the raw material of the component (A-2) and reactivity of the component (A-2), the addition reactive carbon-carbon double bond-containing group includes a vinyl group. , An allyl group and a 5-hexenyl group are preferable, and a vinyl group is particularly preferable.

R ² in the general formula (3) is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, alkyl groups such as tert-butyl group, pentyl group, isopentyl group, hexyl group and sec-hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, o-, m- and p-tolyl Aralkyl groups such as benzyl group and 2-phenylethyl group; alkenyl groups such as vinyl group, allyl group, 1-butenyl group and 1-hexenyl group; alkenyl aryl groups such as p-vinylphenyl group; and in these groups 1 or more hydrogen atoms bonded to carbon atoms of the above are substituted with halogen atoms, cyano groups, epoxy ring-containing groups, etc., for example, chloromethyl group, 3 -Halogenated alkyl groups such as chloropropyl group and 3,3,3-trifluoropropyl group; 2-cyanoethyl group; 3-glycidoxypropyl group and the like.

Among these, R ² is particularly preferably a methyl group or a phenyl group because it is easy to produce industrially and is easily available.

  In the component (A-2), the polymerization degree n of the diphenylsiloxane unit is 1 to 20, preferably 1 to 15, and more preferably 2 to 10. When n is larger than 20, a decrease in fluidity and a decrease in compatibility with the component (A-1) occur, which is not preferable.

  The blending amount of the component (A-2) is 30 to 70 parts by weight, preferably 35 to 65 parts by weight, more preferably 100 parts by weight of the total of the components (A-1) and (A-2). Is 40-60 parts by mass. When the blending amount of the component (A-2) is less than 30 parts by mass, the heat discoloration is reduced, and when it exceeds 70 parts by mass, the strength, particularly hardness, of the cured product is reduced.

  Component (A-2) contains, for example, an addition-reactive carbon-carbon double bond after hydrolysis / condensation of a bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane, or simultaneously with hydrolysis / condensation. It can be obtained by sealing the terminal with a terminal sealing agent having a group.

[Component (B)]
The component (B) of the curable silicone composition for light reflecting material of the present invention is an organosilicon compound having 3 or more SiH molecules in one molecule. SiH in the component (B) is added by an addition reactive carbon-carbon double bond having at least two of the components (A-1) and (A-2) in one molecule and a hydrosilylation reaction, A cured product having a three-dimensional network structure is obtained.

（式中、Ｒ^５は独立に水素原子又はアルケニル基以外の非置換若しくは置換の炭素原子数１〜１２の一価炭化水素基であり、Ｒ^６はメチル基あるいは水素原子であり、ｐは１〜１０の整数、ｑは０〜７の整数である。ｐが付されたシロキサン単位とｑが付されたシロキサン単位とは互いにランダムに配列している。） As such (B) component, the siloxane compound represented by following General formula (5) is mentioned, for example.

(In the formula, R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, R ⁶ is a methyl group or a hydrogen atom, and p is 1 And an integer of 0 to 10 and q is an integer of 0 to 7. The siloxane units marked with p and the siloxane units marked with q are randomly arranged.

R ⁵ in the general formula (5) is, for example, alkyl such as methyl group, ethyl, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group and sec-hexyl group. A cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aryl group such as a phenyl group, o-, m-, or p-tolyl; an aralkyl group such as a benzyl group or a 2-phenylethyl group; a p-vinylphenyl group; An alkenylaryl group; and one or more hydrogen atoms bonded to carbon atoms in these groups are substituted with a halogen atom, a cyano group, an epoxy ring-containing group, or the like, for example, a chloromethyl group, a 3-chloropropyl group Halogenated alkyl groups such as 3,3,3-trifluoropropyl group; 2-cyanoethyl group; 3-glycidoxypropyl group and the like. I can get lost.

Among these, R ⁵ is particularly preferably a methyl group or a phenyl group because it is easy to produce industrially and is easily available.

  Although the preferable example of the said (B) component is shown below, it is not limited to this.

HMe ₂ SiO (HMeSiO) ₂ (Ph ₂ SiO) ₂ SiMe ₂ H
HMe ₂ SiO (HMeSiO) ₂ (Ph ₂ SiO) ₂ (Me ₂ SiO) ₂ SiMe ₂ H
HMe ₂ SiO (HMeSiO) ₁ (Ph ₂ SiO) ₁ (Me ₂ SiO) ₄ SiMe ₂ H
HMe ₂ SiO (HMeSiO) ₃ (Me ₂ SiO) ₅ SiMe ₂ H

  (B) component of the curable silicone composition for light reflection materials of this invention can be used even if single 1 type also combines 2 or more types.

  The blending amount of component (B) is preferably set as follows. The curable silicone composition for a light reflecting material of the present invention is a component having SiH other than the component (B) (for example, a component (G) described later), and other than the component (A-1) or (A-2). Any of the components having an addition-reactive carbon-carbon double bond bonded to a silicon atom (for example, vinyl siloxane that can be contained in the present composition in the form of a complex with platinum as component (C) described later) Either or both can be included. Therefore, the amount of hydrogen atoms bonded to the silicon atom in the composition is preferably 0.5 to 3.3 with respect to 1 mole of the addition reactive carbon-carbon double bond bonded to the silicon atom in the composition. 0 mol, more preferably 0.8 to 2.0 mol. When the blending amount of the component (B) satisfies such conditions, a cured product having sufficient mechanical properties when used as a reflector material is obtained from the curable silicone composition for light reflecting materials of the present invention. Can do.

  In the case where only the components (A-1) and (A-2) have an addition reactive carbon-carbon double bond bonded to a silicon atom, and only the component (B) has SiH, The blending amount of the component (B) in the curable silicone composition for light reflecting material is such that the SiH in the component (B) is 1 mol of the addition reactive carbon-carbon double bond in the component (A). The amount is preferably 0.5 to 3.0 mol, more preferably 0.8 to 2.0 mol.

[Component (C)]
Any conventionally known hydrosilylation reaction catalyst that is the component (C) of the curable silicone composition for light-reflecting materials of the present invention can be used. For example, carbon powder supporting platinum metal, platinum black, platinous chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of platinum and vinylsiloxane such as divinyltetramethyldisiloxane; Examples include complexes of chloroplatinic acid and olefins, platinum catalysts such as platinum bisacetoacetate; platinum group metal catalysts such as palladium catalysts and rhodium catalysts.

  The compounding amount of the component (C) in the curable silicone composition for light reflecting material of the present invention is not particularly limited as long as it is an effective amount as a catalyst, but the above (A-1) and (A-2) And (B) component (C) in an amount of about 1 to 500 ppm, particularly preferably about 2 to 100 ppm as a platinum group metal atom, based on the mass as a platinum group metal atom. By setting the blending amount within such a range, the time required for the curing reaction becomes appropriate, and problems such as coloring of the cured product do not occur.

  Component (C) can be used alone or in combination of two or more.

[(D) component]
(D) component of the curable silicone composition for light reflection materials of this invention is a titanium oxide powder. Since the titanium oxide powder (metal compound powder) of component (D) is white, the cured silicone resin for light-reflecting material of the present invention exhibits good light reflectance by blending component (D).

  The particle size of the component (D) is not particularly limited, but as the component (D), in general, many particles having an average particle size in the range of 0.1 to 200 μm are commercially available and easy to handle, and in the range of 0.5 to 100 μm. Those are more preferred. When the average particle size of the component (D) is in the range of 0.1 to 200 μm, the curable silicone composition for a light reflecting material of the present invention tends to have good fluidity, and the cured product of the composition has a surface It is hard to be rough and the light reflection performance is effectively improved. In the present specification, the average particle diameter means a volume-based average particle diameter corresponding to 50% of the cumulative distribution obtained by a particle size distribution measuring apparatus using a laser light diffraction method.

  (D) The compounding quantity of a component becomes like this. Preferably it is 50-1000 mass parts with respect to a total of 100 mass parts with said (A-1), (A-2), and (B) component, More preferably, 60- 900 parts by weight, still more preferably 100 to 800 parts by weight. When the blending amount is in the range of 50 to 1000 parts by mass, the curable silicone composition for light reflecting material of the present invention tends to have good fluidity, and the cured product of the composition tends to have sufficient light reflecting performance.

  (D) A component can be used even if it combines 2 or more types.

[(E) component]
The component (E) of the curable silicone composition for light reflecting material of the present invention is fumed silica powder. By including the component (E) in the composition, sedimentation and aggregation of the component (D), which has a large specific gravity compared to the components (A-1), (A-2) and (B), are prevented. No cured product can be obtained.

  The particle size of the component (E) is not particularly defined, but as the component (E), in general, many particles having an average particle size in the range of 1 to 100 nm are commercially available and easy to handle, and those in the range of 5 to 50 nm are more preferable. . When the average particle diameter of the component (E) is in the range of 1 to 100 nm, it is possible to more effectively prevent the precipitation and aggregation of the component (D) and obtain a cured product without unevenness.

  (E) The compounding quantity of a component becomes like this. Preferably it is 1-50 mass parts with respect to a total of 100 mass parts with said (A-1), (A-2), and (B) component, More preferably, it is 1- 20 parts by mass, still more preferably 1 to 10 parts by mass. When the blending amount is 50 parts by mass or less, the curable silicone composition for light-reflecting material of the present invention exhibits better fluidity, and when it is 1 part by mass or more, precipitation or aggregation of the component (D) occurs. There is nothing.

  (E) A component can be used even if it combines 2 or more types.

（式中、ｓは１〜３の整数であり、ｔは０〜２の整数であり、但しｓ＋ｔは３である。ｓが付されたアミド単位とｔが付されたアミド単位とは互いにランダムに配列している。）

（式中、ｕは１〜２の整数であり、ｖは２〜４の整数であり、但しｕ＋ｖは４〜５の整数である。ｕが付されたシロキサン単位とｖが付されたシロキサン単位とは互いにランダムに配列している。） Moreover, it is preferable to mix | blend an adhesive improvement agent with the curable silicone composition for light reflection materials of this invention. Examples of the adhesion improver include silane coupling agents and oligomers thereof, and silicone having a reactive group similar to the silane coupling agent. Among these, the following (F) component and (G) component Is preferred.
The component (F) is a compound represented by the following general formula (10), and the component (G) is a compound represented by the following general formula (11).

(In the formula, s is an integer of 1 to 3, and t is an integer of 0 to 2, provided that s + t is 3. The amide unit to which s is attached and the amide unit to which t is attached are random to each other. Is arranged in.)

(In the formula, u is an integer of 1 to 2, v is an integer of 2 to 4, provided that u + v is an integer of 4 to 5. A siloxane unit to which u is attached and a siloxane unit to which v is attached. Are randomly arranged with each other.)

  (F) component and (G) component are arbitrary components mix | blended with a composition in order to improve the adhesiveness with respect to the base material of the curable silicone composition for light reflection materials of this invention and its hardened | cured material. Here, the base material refers to metal materials such as gold, silver, copper, and nickel, ceramic materials such as aluminum oxide, aluminum nitride, and titanium oxide, and polymer materials such as silicone resin and epoxy resin. Each of the component (F) and the component (G) can be used singly or in combination of two or more.

  The blending amount of each of the component (F) and the component (G) is preferably 1 to 30 parts by mass with respect to a total of 100 parts by mass of the components (A-1), (A-2), and (B). Yes, more preferably 5 to 20 parts by mass. When the blending amount is 1 to 30 parts by mass, the curable silicone composition for light-reflecting material of the present invention and the cured product thereof are effectively improved in adhesion to the substrate and are not easily colored.

Specific examples of the suitable component (F) include compounds represented by the following formulas, but are not limited thereto.

Specific examples of suitable component (G) include compounds represented by the following formulas, but are not limited thereto.

[Other ingredients]
In addition to the above components, it is optional to add other components to the curable silicone composition for a light reflecting material of the present invention. Examples of other components include those described below.

２−（ビシクロ［２．２．１］ヘプト−２−エン−５−イル）エチル基

２−（ビシクロ［２．２．１］ヘプト−２−エン−６−イル）エチル基 <Antioxidant>
In the cured product of the curable silicone composition for light reflecting material of the present invention, the addition-reactive carbon-carbon double bond in the component (A-1) may remain unreacted, For example, a 2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl group represented by the following structural formula and 2- (bicyclo [2.2.1] represented by the following structural formula are used. ] May contain carbon-carbon double bonds present in either or both of hept-2-en-6-yl) ethyl groups. And when such a carbon-carbon double bond is contained, it will be oxidized by oxygen in air | atmosphere and will cause a hardened material to color. Then, coloring can be prevented beforehand by mix | blending antioxidant with the curable silicone composition for light reflection materials of this invention as needed.

2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl group

2- (bicyclo [2.2.1] hept-2-en-6-yl) ethyl group

  As the antioxidant, all conventionally known antioxidants can be used, and examples thereof include hindered amine compounds and hindered phenol compounds. Specifically, 2,6-di-t-butyl-4- Methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis ( 4-methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol) and the like. These can be used singly or in combination of two or more.

  In addition, when using this antioxidant, the compounding quantity should just be an effective amount as an antioxidant, and although it does not restrict | limit in particular, the said (A-1), (A-2) and (B) component Preferably, about 10 to 10,000 ppm, particularly preferably about 100 to 1,000 ppm is blended on the mass basis. By setting the blending amount within such a range, the antioxidant ability is sufficiently exhibited, and a cured product having excellent light reflection performance without occurrence of coloring or oxidative deterioration can be obtained.

<Others>
Moreover, in order to ensure pot life, addition reaction control agents, such as 1-ethynyl cyclohexanol and 3, 5- dimethyl- 1-hexyn-3-ol, can be mix | blended.
Furthermore, a light stabilizer can be used to impart resistance to light degradation caused by light energy such as light from the light emitting element and sunlight. As the light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidation degradation is suitable, and the antioxidant effect is further improved by using it together with the antioxidant. Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine and the like.

[Curable silicone composition for light reflecting material]
The curable silicone composition for light-reflecting material of the present invention (white thermosetting silicone composition) is liquid before curing, and its viscosity at 25 ° C. is preferably 5 to 500 Pa · s, more preferably 10 ˜400 Pa · s. When the viscosity is in the range of 5 to 500 Pa · s, the resulting composition tends to have good workability and handleability, and bubbles and air are less likely to be entrained during molding and curing.

  The viscosity of the curable silicone composition for light-reflecting materials of the present invention is as follows: (A-1) (A-2) to (E) component and other compounding components, the viscosity of liquid components among these components, And the average particle diameter of the components (D) and (E).

[Hardened silicone resin for light reflecting materials]
By molding and curing the curable silicone composition for light reflecting material of the present invention, a cured silicone resin for light reflecting material can be obtained. The curable silicone composition for a light reflecting material of the present invention can be applied to conventionally used molding methods such as an injection molding method and a transfer molding method. Furthermore, since the curable silicone composition for light reflecting material of the present invention has high fluidity at 25 ° C., it can be molded by a dispensing method or a potting method that could not be applied to the conventional solid reflector materials. The curing conditions of the curable silicone composition for light-reflecting materials of the present invention vary depending on the shape of the molded product, the curing method, etc., and are not particularly limited, but are usually 80 to 200 ° C., preferably 100 to 180 ° C. It is preferable to set the condition for minutes to 24 hours, preferably 5 minutes to 5 hours.

  In general, in order to function as a reflector material, the initial reflectance of visible light (wavelength: 430 to 800 nm) is preferably 95% or more (that is, 95 to 100%), more preferably 97% or more (that is, 97). ~ 100%). When the reflectance is 95% or more, when the cured product is used as a reflector material for a light-emitting device such as a lighting fixture, the light extraction efficiency becomes higher, and sufficient brightness can be easily secured. The reflectance is preferably 82% or more not only in the initial stage of production of the cured product but also after the heat resistance test (performed by leaving the cured product for 1,000 hours at 170 ° C.), and 84% More preferably. The silicone resin cured product for light reflecting material obtained from the curable silicone composition for light reflecting material of the present invention has a reflectivity of visible light (wavelength: 430 to 800 nm) of 95% or more, 170 ° C., 1,000. The light reflectivity after standing for a period of time can be 82% or more, and a sufficient reflectivity as a reflector material can be obtained. In the present specification, the reflectance of light means a value measured by a spectrophotometer device equipped with an integrating sphere.

  The reflector material may be singulated through a cutting process using a dicing saw or the like. In this step, since cutting becomes difficult without sufficient hardness, the cured silicone resin for light reflecting material of the present invention used as the reflector material preferably has a Shore D hardness of 65 or more, more preferably 70 or more. .

[Reflector and LED device]
The curable silicone composition for light reflecting material (white thermosetting silicone resin composition) of the present invention is for a light reflecting material, and the use of the light reflecting material is not particularly limited. For example, a light emitting device such as an LED It can be suitably used as a reflector material for white LEDs (white light emitting diodes). A light emitting device (particularly an LED device, a white LED device, etc.) equipped with a reflector made of a cured silicone resin for a light reflecting material of the present invention can maintain high light extraction efficiency over a long period of time. In addition, since the composition of the present invention has high fluidity and is easy to mold, the cured silicone resin for light reflecting material of the present invention used as a reflector material according to these light-emitting devices including white LEDs has a desired shape. It is easy to do.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the viscosity is a value at 25 ° C. measured using a spiral viscometer (Malcom Co., Ltd., model: PC-1T) which is a rotational viscometer.

In the following examples, symbols indicating the composition of silicone oil or silicone resin are shown below. The number of moles of each silicone oil or each silicone resin indicates the number of moles of vinyl groups or silicon atom-bonded hydrogen atoms contained in each component.
^MH : (CH ₃ ) ₂ HSiO _1/2
M ^Vi : (CH ₂ ═CH) (CH ₃ ) ₂ SiO _1/2
M ^ViΦ : (CH ₂ ^═CH ) (C ₆ H ₅ ) (CH ₃ ) SiO _{1/2
^{D H: (CH 3) HSiO}} 2/2
_{^{D Φ: (C 6 H 5}} ) (CH 3) SiO 2/2
D ^2Φ : (C ₆ H ₅ ) ₂ SiO _2/2

[Synthesis Example 1] Preparation of Component (A-1) Into a 5 L four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5- 1785 g (14.88 mol) of an approximately equimolar amount of an isomer mixture of vinylbicyclo [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene And 455g of toluene was added and it heated at 85 degreeC using the oil bath. To this, 3.6 g of carbon powder supporting 5 mass% platinum was added, and 1698 g (8.75 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 180 minutes while stirring. After completion of the dropwise addition, the mixture was further heated and stirred at 110 ° C. for 24 hours, and then cooled to room temperature. Thereafter, the platinum-supporting carbon was removed by filtration, and toluene and excess vinyl norbornene were distilled off under reduced pressure to obtain 3362 g of a colorless and transparent oily reaction product (viscosity at 25 ° C .: 12820 mPa · s).

（２）ｐ−フェニレン基を３個有する化合物（下記に代表的な構造式の一例を示す）：約３２モル％

（３）ｐ−フェニレン基を４個以上有する化合物：約２７モル％
の混合物であることが判明した。また、混合物全体としての付加反応性炭素−炭素二重結合の含有割合は、０．３６モル／１００ｇであった。 As a result of analyzing the reaction product by FT-IR, NMR, GPC and the like,
(1) Compound having two p-phenylene groups (an example of a typical structural formula shown below): about 41 mol%,

(2) Compound having three p-phenylene groups (an example of a typical structural formula shown below): about 32 mol%

(3) Compound having 4 or more p-phenylene groups: about 27 mol%
It was found to be a mixture of Moreover, the content rate of the addition reactive carbon-carbon double bond as the whole mixture was 0.36 mol / 100g.

[Examples 1-4, Comparative Examples 1-4]
The following (A-1) to (H) components were blended in the blending amounts (unit: parts by mass) shown in Table 1, and compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were obtained. That is, first, Table 1 shows the components (A), (D), (E) and (H) in a 5-liter gate mixer (trade name: 5-liter planetary mixer, manufactured by Inoue Seisakusho Co., Ltd.). Charge in the blending amount, mix for 1 hour at room temperature, then add the components (B), (F) and (G) in the blending amounts shown in Table 1 and mix at room temperature for 30 minutes to be uniform. Finally, component (C) was added in the amount shown in Table 1 and mixed at room temperature under reduced pressure for 30 minutes to obtain a white curable silicone composition. The viscosity of the obtained composition was measured. The results are shown in Table 1.

（Ｇ）下記式で表される化合物

（Ｈ）１−エチニル−１−シクロヘキサノールの５０質量％トルエン溶液（付加反応制御剤） (A-1) the reaction product obtained in Synthesis Example 1,
(A-2-1) Average molecular formula: Organopolysiloxane represented by M ^ViΦ ₂ D ^2Φ ₃ (A-2-2) Average molecular formula: Organopolysiloxane represented by M ^Vi ₂ D ^2Φ ₄ (A-3 ) average molecular ^formula: the organopolysiloxane (B) the average molecular formula represented by _{^{M Vi 2 D Φ 6: M}} H 2 D H 2 D 2Φ 2, in represented by organopolysiloxane (C) a platinum - divinyltetramethyldisiloxane Complex toluene solution (containing 1% by mass of platinum atoms)
(D) titanium oxide powder having an average particle size of 0.5 μm,
(E) fumed silica powder having an average particle size of 14 nm,
(F) Compound represented by the following formula

(G) Compound represented by the following formula

(H) 50% by mass toluene solution of 1-ethynyl-1-cyclohexanol (addition reaction control agent)

Next, the compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were poured into a mold, and 150 ° C., 100
It was cured by pressure at MPa for 15 minutes and then cured in an oven at 150 ° C. and atmospheric pressure for 3 hours to obtain cured products having a thickness of 2 mm (H1 to H4 and H5 to H8 in Table 2 respectively). The properties of the obtained cured product are shown in Table 2. The properties of the cured product were observed or measured as follows.

Appearance: The surface of each cured product was observed using a microscope. The results are shown in Table 2 according to the following criteria.
Uniform appearance (○), unevenness due to filler aggregation (×)

  Hardness (Shore D): The hardness (Shore D) of each cured product was measured according to ASTM D 2240.

Dicing property: Each composition was applied on a copper plate having a thickness of 0.2 mm and cured under the above conditions to prepare a cured product having a thickness of 1 mm. After leaving at room temperature, an adhesive film was attached to the substrate, and cut into a size of 5 mm × 5 mm using a DISCO dicing machine (DAD341 type). The results are shown in Table 2 according to the following criteria.
Good cut surface (○), generation of burrs (×)

Light reflectance: spectrophotometer device U-3310 manufactured by Hitachi, equipped with an integrating sphere
Was measured at 25 ° C. in the wavelength region of 430 to 800 nm.

  Next, the cured products H1 to H8 were left at 170 ° C. for 1,000 hours to conduct a heat resistance test. The heat resistance was evaluated by taking the difference between the initial light reflectance (before the test) and the light reflectance after the test. The evaluation results are shown in Table 3. The smaller the difference in light reflectance, the higher the heat resistance. As a result of visual observation, all the cured products were initially white, but after the heat test, only H5 was clearly changed to brown.

  As shown in Tables 1 to 3, in Examples 1 to 4 using the curable silicone composition for light-reflecting material of the present invention, all the compositions had low viscosity and therefore excellent fluidity. In addition, a high light reflectance was obtained in the initial stage, and the light reflectance was slightly lowered even after the heat resistance test. That is, it was found that heat resistance (particularly, heat discoloration) was also excellent.

  On the other hand, in Comparative Example 1, the light reflectance after the heat test was significantly reduced, and the heat resistance (particularly, heat discoloration) was poor. In Comparative Examples 2 and 3, since the hardness of the cured product was low, the dicing property was poor. Moreover, in the comparative example 4, the favorable external appearance of hardened | cured material was not obtained.

  The above results show that the curable silicone composition for light reflecting material of the present invention has high fluidity at room temperature, and the cured product is not only high in hardness and suitable for the dicing process, but also in the initial light reflection. It shows that it is excellent in rate and heat discoloration. Therefore, the cured product of the curable silicone composition for light reflecting material of the present invention is useful as a light reflecting material, particularly a reflector material for white LED.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Claims (10)

(A-1) (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule; and (b) 1 addition-reactive carbon-carbon double bond. 30 to 70 parts by mass of an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule, which is an addition reaction product with two polycyclic hydrocarbons in the molecule
(A-2) 30 to 70 parts by mass of a compound represented by the following general formula (3) (however, the sum of the component (A-1) and the component (A-2) is 100 parts by mass),
(B) an organosilicon compound having 3 or more hydrogen atoms bonded to silicon atoms in one molecule (the total amount of hydrogen atoms bonded to silicon atoms in the composition is the addition-reactive carbon-carbon 2 in the composition) The amount is 0.5 to 3.0 in terms of molar ratio to the heavy bond)
(C) hydrosilylation reaction catalyst,
A curable silicone composition for light reflectors, comprising (D) titanium oxide powder and (E) fumed silica powder.

(In the formula, A is a divalent group selected from the group consisting of groups represented by the following general formula (2), and R ¹ is independently an unsubstituted or substituted monovalent carbon atom having 1 to 12 carbon atoms. It is a hydrogen group or an alkoxy group having 1 to 6 carbon atoms.)

(In the formula, Ph is a phenyl group, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is an addition-reactive carbon-carbon double bond-containing group. And n is an integer from 1 to 20.) 2. The curable silicone composition for a light reflecting material according to claim 1, wherein the (b) is an alkenyl norbornene compound represented by the following general formula (4).

(Wherein R ⁴ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)   The (b) is any one of 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene, and combinations thereof. The curable silicone composition for a light reflecting material according to claim 1, wherein the curable silicone composition is a light reflecting material. The said (B) component is a siloxane compound represented by following General formula (5), The curable silicone composition for light reflection materials as described in any one of Claims 1-3 characterized by the above-mentioned. .

(In the formula, R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, R ⁶ is a methyl group or a hydrogen atom, and p is 1 And an integer of 0 to 10 and q is an integer of 0 to 7. The siloxane units marked with p and the siloxane units marked with q are randomly arranged.   The curable silicone composition for a light reflecting material according to any one of claims 1 to 4, wherein the viscosity at 25 ° C is 5 to 500 Pa · s.   A cured silicone resin for light-reflective material, which is obtained by molding and curing the curable silicone composition according to any one of claims 1 to 5.   Immediately after curing, the reflectance of light having a wavelength of 430 to 800 nm is 95% or more, and the reflectance of light having a wavelength of 430 to 800 nm after exposure for 1000 hours in a 170 ° C. environment is 82% or more. The cured silicone resin for light reflecting material according to claim 6.   The cured silicone resin for light reflecting material according to claim 6 or 7, wherein the Shore D hardness is 65 or more.   The reflector which consists of a silicone resin hardened | cured material for light reflection materials as described in any one of Claims 6-8.   An LED device comprising the reflector according to claim 9.