JP2010180323A - Curable silicone composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable silicone composition which provides a cured product having large resistance against a stress such as thermal shock, having excellent property of extracting light from a light source because of a high refractive index thereof, and having excellent heat resistance and therefore, is useful as a material for optical devices/optical parts such as an LED element sealing material, an insulating material for electronic devices/electronic parts, or a coating material; and a cured product thereof. <P>SOLUTION: This curable silicone composition includes (A) a specific diphenylsiloxane-based compound having at a molecular chain terminal thereof, an alkenyl group bonded to a silicon atom, (B) an organic silicon compound having at least two hydrogen atoms bonded to a silicon atom, and (C) a catalyst for a hydrosilylation reaction, and provided is also a cured product prepared by curing the composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable silicone resin composition useful as an optical device / optical component material, an electronic device / electronic component insulating material, or a coating material, and a cured product thereof.

  Conventionally, epoxy resin is generally used as a sealing material for optical device / optical component materials, particularly light emitting diode (LED) elements. In addition, regarding silicone resin, attempts have been made to use it as a molding material for LED elements (see Patent Document 1 and Patent Document 2) and as a color filter material (see Patent Document 3). There are few examples of use.

  In recent years, white LEDs have been attracting attention, and it has become an urgent task to deal with yellowing of the epoxy resin encapsulant that has not been a problem until now due to ultraviolet rays and the occurrence of cracks due to an increase in the amount of heat generated by downsizing. ing. As these countermeasures, it has been studied to use a silicone resin having a large amount of phenyl groups in the molecule as a sealing material. However, a cured product of a conventional silicone resin having a phenyl group is weak against stress such as thermal shock, and it is very difficult to reach the level such as thermal shock resistance required by the user. Then, it becomes a material with very poor heat resistance.

Japanese Patent Laid-Open No. 10-228249 Japanese Patent Laid-Open No. 10-242513 JP 2000-123981 A

  The present invention has been made in view of the above circumstances, and is resistant to stress such as thermal shock, and because of its high refractive index, provides a cured product that is excellent in light extraction from a light source and further excellent in heat resistance. An object of the present invention is to provide a curable silicone composition useful as an optical device / optical component material such as an LED element sealing material, an electronic device / electronic component insulating material or a coating material, and a cured product thereof.

  As a result of diligent efforts to achieve the above object, the present inventor cured a curable silicone composition containing the diphenylsiloxane compound of the following component (A) to obtain a cured product having the above characteristics. Based on this finding, the present invention has been completed.

That is, the present invention firstly
(A) The following general formula (1):

（式中、Ｒ¹は脂肪族不飽和結合を含まない非置換の炭素原子数１〜12の一価炭化水素基であり、Ｒ²は炭素原子数１〜12の２価炭化水素基であり、Ｘは非置換の炭素原子数２〜12のアルケニル基であり、ａおよびｂは０〜３の整数であり、ａ＋ｂは２〜６の整数であり、ｎは１以上の正数である）
で表される、ケイ素原子に結合したアルケニル基を分子鎖末端に有するジフェニルシロキサン系化合物、
(B) ケイ素原子に結合した水素原子を少なくとも２個有する有機ケイ素化合物、および
(C) ヒドロシリル化反応触媒
を含む硬化性シリコーン組成物を提供する。

(Wherein, R ¹ is unsubstituted C1-12 monovalent hydrocarbon radicals free of aliphatic unsaturation, R ² is a divalent hydrocarbon group having 1 to 12 carbon atoms X is an unsubstituted alkenyl group having 2 to 12 carbon atoms, a and b are integers of 0 to 3, a + b is an integer of 2 to 6, and n is a positive number of 1 or more)
A diphenylsiloxane compound having an alkenyl group bonded to a silicon atom at the molecular chain end,
(B) an organosilicon compound having at least two hydrogen atoms bonded to a silicon atom, and
(C) A curable silicone composition containing a hydrosilylation reaction catalyst is provided.

  Secondly, the present invention provides a cured product obtained by curing the above composition.

  The curable silicone resin composition of the present invention is resistant to stress such as thermal shock, has a high refractive index, and is excellent in light extraction from a light source, and further provides a cured product excellent in heat resistance and transparency. Can do. Accordingly, it can be suitably used for applications such as protection of light-emitting diode elements, sealing, adhesion, wavelength change or wavelength adjustment, lens materials such as lenses, optical materials and sealing materials for optical components, and display materials. It can also be used as an insulating material for electronic devices and electronic parts, and further as a coating material.

It is a longitudinal cross-sectional view which shows the LED lamp used by the Example and the comparative example.

  Hereinafter, the present invention will be described in more detail. In this specification, the refractive index is a value at 25 ° C. using sodium D-line, the viscosity is a value measured by a rotational viscometer, and ppm is based on mass.

[(A) component]
The component (A) is a diphenylsiloxane compound having an alkenyl group bonded to a silicon atom at the molecular chain end, represented by the general formula (1). The component (A) can be used alone or in combination of two or more having different structures and polymerization degrees.

The number of carbon atoms of R ¹ is from 1 to 12, but preferably from 1 to 8. As the R ^1, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, tert- butyl group, a pentyl group, an isopentyl group, a hexyl group, an alkyl group such as sec- hexyl group; a phenyl group, o Aryl groups such as -tolyl group, m-tolyl group and p-tolyl group; and aralkyl groups such as benzyl group and 2-phenylethyl group. Of these, a methyl group and a phenyl group are preferable, and a phenyl group is particularly preferable.

The R ² has 1 to 12 carbon atoms, preferably 1 to 8, particularly preferably 1 to 4. Examples of R ² include alkylene groups such as methylene group, ethylene group, propylene group, and butylene group; arylene groups such as phenylene group; alkylene aryl groups such as ethylene phenyl group and propylene phenyl group; ethylene phenylethyl group, propylene Examples include alkylene arylalkyl groups such as phenylpropyl group. These may be branched. Among these, an alkylene group is preferable, and an ethylene group is particularly preferable.

  The X has 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms. Examples of X include alkenyl groups such as a vinyl group, an allyl group, a propenyl group, and a butenyl group. Among these, a vinyl group is preferable.

  In the above general formula (1), a and b are integers of 0 to 3, a + b is an integer of 2 to 6, and both a and b are preferably integers of 1 to 3, particularly 1. It is preferable.

  N in the general formula (1) is an integer of 1 or more, preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and particularly preferably an integer of 1 to 10. Is preferred.

The refractive index of the component (A) is preferably 1.54 or more, more preferably 1.54 to 1.65, and particularly preferably 1.58 to 1.63. If the refractive index is too low, the light extraction efficiency from the light source may decrease. The refractive index can be adjusted by appropriately selecting the types of R ¹ , R ² and X and the values of a, b and n, particularly the value of n and the type of R ¹ .

  Preferred specific examples of the component (A) are shown below, but the component (A) is not limited thereto.

(A)成分としては下記一般式で表されるものが特に好ましい。

As the component (A), those represented by the following general formula are particularly preferable.

（式中、Ｒ¹およびｎは前記のとおりである）

(Wherein R ¹ and n are as defined above)

  The component (A) can be obtained, for example, by subjecting compounds corresponding to the units in the component (A) to a hydrosilylation reaction or condensation reaction according to a conventional method.

  Specific examples of the hydrosilylation reaction include the following reaction formula:

（式中、Ｒ¹、Ｘ、ａ、ｂおよびｎは前記のとおりであり、Ｒ²⁰は炭素原子数２〜12の２価炭化水素基であり、ＹはＳｉＨ基と反応してＲ²⁰を生ずる炭素原子数２〜12のアルケニル基含有一価炭化水素基である）
で表されるものが挙げられる。Ｒ²⁰としては、例えば、アルキレン基；アルキレンアリール基；アルキレンアリールアルキル基等が挙げられ、具体的には、Ｒ^２について上記で具体的に例示した２価炭化水素基のうち、炭素原子数２〜12のものが挙げられる。Ｙとしては、例えば、ビニル基、アリル基、プロペニル基、ブテニル基等のアルケニル基；ビニルフェニル基、アリルフェニル基等のアルケニルアリール基；ビニルフェニルエチル基、アリルフェニルプロピル基等のアルケニルアリールアルキル基等が挙げられる。

Wherein R ¹ , X, a, b and n are as defined above, R ²⁰ is a divalent hydrocarbon group having 2 to 12 carbon atoms, and Y reacts with a SiH group to give R ²⁰ The resulting alkenyl group-containing monovalent hydrocarbon group having 2 to 12 carbon atoms)
The thing represented by is mentioned. Examples of R ²⁰ include an alkylene group; an alkylenearyl group; an alkylenearylalkyl group. Specifically, among the divalent hydrocarbon groups specifically exemplified above for R ² , the number of carbon atoms is 2. ˜12. Examples of Y include alkenyl groups such as vinyl, allyl, propenyl, and butenyl; alkenyl aryl such as vinylphenyl and allylphenyl; alkenylarylalkyl such as vinylphenylethyl and allylphenylpropyl Etc.

  In particular, the component (A) in which n = 1 is represented by the following reaction formula:

（上記の各式において、Ｒ¹、Ｒ²⁰、Ｘ、Ｙ、ａおよびｂは前記のとおりである）
で表されるヒドロシリル化反応によっても得ることができる。

(In the above formulas, R ¹ , R ²⁰ , X, Y, a and b are as described above.)
It can obtain also by the hydrosilylation reaction represented by these.

  Further, specific examples of the condensation reaction include the following reaction formula:

（式中、Ｒ¹、Ｒ²、Ｘ、ａおよびｂは前記のとおりであり、ｍ＝ｎ−１（式中、ｎは前記のとおり)である）
で表されるものが挙げられる。

(Wherein R ¹ , R ² , X, a and b are as defined above, and m = n−1 (where n is as defined above)).
The thing represented by is mentioned.

[(B) component]
The organosilicon compound as component (B) is a cross-linking agent for the composition of the present invention, and has at least two hydrogen atoms bonded to silicon atoms (that is, SiH groups) in one molecule. Examples of the component (B) include organohydrogenpolysiloxane having at least two SiH groups and organohydrogensilane having at least two SiH groups. Component (B) can be used alone or in combination of two or more.

  (B) As an organic group couple | bonded with the silicon atom of a component, the number of the same or different unsubstituted or substituted carbon atoms which do not have an aliphatic unsaturated bond becomes like this. Preferably it is 1-12, More preferably, it is 1-10. Even more preferably, a monovalent hydrocarbon group of 1 to 8 is used. Specific examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group; cycloalkyl groups such as cyclohexyl group; phenyl group, tolyl group, xylyl group and naphthyl group. Aryl groups such as benzyl group, phenethyl group and the like; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc., particularly methyl group, phenyl Groups are preferred.

  The viscosity at 25 ° C. of the component (B) is from 0.1 to 1,000 mPa · s because the workability of the resulting composition is good and the physical properties of the resulting cured product are good. It is preferable that it is in the range of 5 to 500 mPa · s.

  Examples of the molecular structure of the organohydrogenpolysiloxane included in the component (B) include linear, cyclic, branched, and three-dimensional networks. In this organohydrogenpolysiloxane, the SiH group may be located only at the end of the molecular chain (ie, only in the M unit) or only in the side chain of the molecular chain (ie, It may be located both at the end of the molecular chain and at the side chain of the molecular chain (even in the D unit, in the T unit or both). The organohydrogenpolysiloxane has at least 2, preferably 3 or more (usually 3 to 300), more preferably about 3 to 100 SiH groups, and 2 to 300 silicon atoms. The number is preferably about 3 to 150.

  The refractive index of the component (B) is preferably 1.45 or more, more preferably 1.45 to 1.65. When the refractive index is 1.45 or more, it is advantageous in terms of light extraction from a light source. In order for the refractive index of the component (B) to be 1.45 or more, the organic group bonded to the silicon atom preferably contains those having 3 or more carbon atoms, and particularly preferably contains a phenyl group. In this case, it is preferable that 10 mol% or more, particularly 10 to 100 mol%, of the substituents other than the hydrogen atom bonded to the silicon atom is a phenyl group.

Specific examples of the organohydrogenpolysiloxane having at least two SiH groups included in the component (B) include tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1,1,3 , 3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, methyl chain-blocked methyl at both ends of the molecular chain Hydrogen polysiloxane, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxy・ Methylphenylsiloxane copolymer, dimethylhydrogensiloxy group-capped dimethylpolysiloxane with molecular chain at both ends, dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer with molecular chain at both ends, and dimethylhydro with molecular chain at both ends Gensiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane; some or all of the methyl groups of these compounds are ethyl groups, propyl groups, etc. Substituted with an aryl group such as an alkyl group or a phenyl group; from a siloxane unit represented by the formula: R ₃ SiO _0.5 , a siloxane unit represented by the formula: R ₂ HSiO _0.5 and a siloxane unit represented by the formula: SiO ₂ A copolymer of the formula Siloxane units represented by the formula R ₂ HSiO _0.5: copolymers comprising siloxane units represented by SiO _2, wherein: the siloxane units of the formula RHSiO: siloxane units and formula represented by RSiO _1.5: In HSiO _1.5 A copolymer comprising any one or both of the siloxane units shown; and a mixture comprising two or more of the above compounds. R in the above formula is an unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms which does not have an aliphatic unsaturated bond. Examples of R include an organic compound bonded to the silicon atom of the component (B). Examples of the group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like, which are given as specific examples above.

  Specific examples of the organohydrogensilane having at least two SiH groups included in the component (B) include diphenylsilane and monophenylsilane.

  The amount of the component (B) is preferably 0.3 to 4.0 mol, more preferably the amount of SiH groups in the component (B) with respect to 1 mol of alkenyl groups bonded to silicon atoms in the entire composition. The amount is in the range of 0.6 to 3.0 mol. When the amount is within this range, the resulting composition is easily cured, and the resulting cured product is likely to have excellent heat resistance.

[Component (C)]
The component (C) hydrosilylation reaction catalyst has an action of promoting the addition reaction (hydrosilylation reaction) between the alkenyl group-containing diphenylsiloxane compound (A) and the SiH group-containing organosilicon compound (B). As long as it is not particularly limited. As the component (C), for example, a conventionally known hydrosilylation reaction catalyst can be used. Specific examples of the component (C) include chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, coordination compounds (complexes) of vinylsiloxane or acetylene compounds, and platinum such as platinum-vinylsiloxane complexes. Compounds such as tetrakis (triphenylphosphine) palladium; rhodium compounds such as chlorotris (triphenylphosphine) rhodium, etc., and platinum compounds are particularly preferred.

  The amount of component (C) added may be an effective amount as a hydrosilylation reaction catalyst, but can be appropriately increased or decreased depending on the desired curing rate. The added amount is usually 0.1 to 1,000 ppm, preferably 1 to 1,000 ppm in terms of the catalytic metal element such as platinum, palladium, rhodium, etc. with respect to the sum of the component (A) and the component (B). It is in the range of 500 ppm. In addition, if this compounding quantity exists in the range of 0.1-1,000 ppm, a cure rate can be raised according to a compounding quantity, and it is economically preferable.

[Component (D)]
Component (D) is represented by the following general formula (2):

（式中、Ｒ^３は非置換の炭素原子数１〜12の一価炭化水素基であり、式中の酸素原子はケイ素原子と結合してシロキサン結合を構成する）
で表される構造単位を有する、ケイ素原子に結合したビニル基を少なくとも２個有するシリコーンオイル、上記一般式（２）で表される構造単位を有する、ケイ素原子に結合したビニル基を少なくとも２個有するシリコーンレジン、またはこれらの組み合わせである。(D)成分は、上記（Ａ）成分とともに上記（Ｂ）成分とのヒドロシリル化を受ける任意成分であるが、より耐熱性が必要とされる場合に配合することが好ましい。(D)成分は１種単独でも構造や分子量の異なる２種以上を組み合わせても使用することができる。

(In the formula, R ³ is an unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and the oxygen atom in the formula combines with a silicon atom to form a siloxane bond)
A silicone oil having at least two vinyl groups bonded to silicon atoms, having a structural unit represented by the formula: at least two vinyl groups bonded to silicon atoms having a structural unit represented by the general formula (2) A silicone resin, or a combination thereof. The component (D) is an optional component that undergoes hydrosilylation with the component (B) together with the component (A), but is preferably blended when more heat resistance is required. Component (D) can be used alone or in combination of two or more having different structures and molecular weights.

The number of carbon atoms of R ³ is 1 to 12, but preferably 1 to 8. Examples of R ³ include alkyl groups such as 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, a hexyl group, and a sec-hexyl group; a phenyl group, o Aryl groups such as -tolyl group, m-tolyl group and p-tolyl group; alkenyl groups such as vinyl group and allyl group; aralkyl groups such as benzyl group and 2-phenylethyl group. Among these, a phenyl group, a methyl group, and a vinyl group are preferable.

  The viscosity at 25 ° C. of the component (D) is from 0.1 to 1,000 mPa · s because the workability of the resulting composition is good and the physical properties of the resulting cured product are good. It is preferable that it is in the range of 5 to 500 mPa · s.

Examples of the molecular structure of component (D) include linear, cyclic, branched, and three-dimensional network. The component (D) has at least 2, preferably 3 or more (usually 3 to 300), more preferably about 3 to 100 structural units represented by the general formula (2). Further, it has 2 to 300 silicon atoms, preferably about 3 to 150 silicon atoms. In the component (D), examples of the structural unit other than the structural unit represented by the general formula (2) include a siloxane unit (M unit) represented by the formula: R ⁴ ₃ SiO _0.5 and a formula: R ⁴ ₂ SiO. in the siloxane units (D units) represented by the ^formula: R 4 siloxane units represented by SiO _1.5 (T unit), wherein: the siloxane units represented by SiO ₂ (Q unit), and the like. R ⁴ in the above formula is an unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. As R ⁴ , for example, alkyl exemplified above for R ³ Group, aryl group, alkenyl group, aralkyl group and the like. Specifically, cyclic silicone oil composed of D unit; linear silicone oil composed of M unit and D unit; combination of D unit and T unit; combination of M unit, D unit and T unit; M unit And a silicone resin comprising a combination of D unit and Q unit. Moreover, it is preferable that vinyl group content in (D) component is 0.01-5 mol%, especially 0.1-1 mol%.

  Specific examples of component (D) include trimethylsiloxy group-capped methylvinylpolysiloxane at both molecular chain ends, trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer at both molecular chain terminals, and trimethylsiloxy group-capped dimethyl at both molecular chain terminals. Siloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / diphenylsiloxane copolymer, cyclic methylvinylsiloxane, methylvinylsilicone resin, phenylvinylsilicone resin, methyl Examples thereof include phenyl vinyl silicone resin.

  (D) As for the compounding quantity of a component, 0-100 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 5-75 mass parts, Most preferably, it is 10-50 mass parts. If the blending amount of the component (D) is too small, the blending effect (heat resistance improving effect) may be insufficient, and if it is too large, the refractive index may decrease and the light extraction from the light source may decrease.

[Other ingredients]
In addition to the components (A) to (D), other components may be added to the composition of the present invention as long as the effects of the present invention are not impaired.

  For example, non-reactive linear or cyclic diorganopolysiloxane or the like may be blended as other components in order to adjust the viscosity of the resulting composition, the hardness of the resulting cured product, and the like.

  In order to ensure the necessary pot life, a reaction control agent such as 1-ethynylcyclohexanol or 3,5-dimethyl-1-hexyn-3-ol can be blended as other components.

  Furthermore, as other components, an inorganic filler such as fumed silica may be blended in order to improve the strength of the cured product within a range that does not affect the transparency, and if necessary, silane coupling. You may mix | blend adhesive improvement agents, such as an agent, dye, a pigment, a flame retardant.

  The curing conditions of the composition of the present invention vary depending on the amount and the like, and are not particularly limited. However, it is usually preferable that the conditions are 60 to 180 ° C. and 5 to 180 minutes. The composition of the present invention can be cured by applying it to a predetermined substrate according to the application and then heating under the above conditions.

[Usage]
The curable silicone composition of the present invention is useful as an optical device / optical component material, an electronic device / electronic component insulating material, or a coating material. Examples of the optical device include optical elements such as LEDs, semiconductor lasers, photodiodes, phototransistors, solar cells, and CCDs. Examples of the optical component include a lens. With the curable silicone composition, for example, the optical element can be protected, sealed, adhered, etc., and the optical component can be produced. Examples of the electronic device include semiconductor elements such as diodes, transistors, ICs, CPUs, and memories other than the optical elements described above. As the coating application, it can be suitably used for applications requiring transparency.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples.

[Example 1]
(A) The following formula (3):

で表されるジフェニルシロキサン系化合物 (屈折率1.61)：100質量部、
(B)下記式：

Diphenylsiloxane compound represented by the above formula (refractive index 1.61): 100 parts by mass,
(B) The following formula:

で表されるオルガノハイドロジェンポリシロキサン(屈折率1.53)：35質量部、および
1-エチニルシクロヘキサノール：0.03質量部
を均一に混合して混合物を得、この混合物に
(C)白金-ビニルシロキサン錯体：(A)成分と(B)成分との合計に対して白金換算で20 ppm
を添加し、さらに均一に混合して組成物を得た。この組成物を、ガラス板で組んだ型の中に２mm厚になるように流し込み、150℃で２時間加熱して硬化成形物を得た。また、上記組成物の硬化物によりＬＥＤチップが封止されたＬＥＤランプを得た。図１は実施例および比較例で用いたＬＥＤランプを示す縦断面図である。図１に示すＬＥＤランプ１において、垂直な壁面２および水平な底面３を有する凹部４がポリフタルアミド製パッケージ５の上面中央部から下方に向かって形成されており、底面３の中央にはＬＥＤチップ６が配置されている。更に、底面３には、壁面２および底面３と接し、ＬＥＤチップ６から分離して、相対向する２個のＡｇ電極７が形成されている。ＬＥＤチップ６とＡｇ電極７おのおのとの間には金線８が接続されている。凹部４は透明硬化物９で埋められている。ＬＥＤランプ１は、底面３にＬＥＤチップ６およびＡｇ電極７を配置し、ＬＥＤチップ６とＡｇ電極７おのおのとの間に金線８を接続した後、凹部４を上記組成物で満たし、該組成物を150℃で２時間加熱して硬化させて透明硬化物９を形成させることにより得た。

An organohydrogenpolysiloxane (refractive index of 1.53): 35 parts by mass, and
1-Ethynylcyclohexanol: 0.03 part by mass is mixed uniformly to obtain a mixture.
(C) Platinum-vinylsiloxane complex: 20 ppm in terms of platinum with respect to the sum of component (A) and component (B)
Was added and further uniformly mixed to obtain a composition. This composition was poured into a mold made of glass plates to a thickness of 2 mm and heated at 150 ° C. for 2 hours to obtain a cured molded product. Moreover, the LED lamp with which the LED chip was sealed with the hardened | cured material of the said composition was obtained. FIG. 1 is a longitudinal sectional view showing an LED lamp used in Examples and Comparative Examples. In the LED lamp 1 shown in FIG. 1, a recess 4 having a vertical wall surface 2 and a horizontal bottom surface 3 is formed downward from the center of the top surface of the polyphthalamide package 5. A chip 6 is arranged. Furthermore, two Ag electrodes 7 which are in contact with the wall surface 2 and the bottom surface 3 and are separated from the LED chip 6 and opposed to each other are formed on the bottom surface 3. A gold wire 8 is connected between the LED chip 6 and each Ag electrode 7. The recess 4 is filled with a transparent cured product 9. In the LED lamp 1, the LED chip 6 and the Ag electrode 7 are arranged on the bottom surface 3, and the gold wire 8 is connected between the LED chip 6 and each of the Ag electrodes 7, and then the recess 4 is filled with the above composition. The product was obtained by heating at 150 ° C. for 2 hours to cure to form a transparent cured product 9.

[Example 2]
In Example 1, as the component (A), the diphenylsiloxane compound represented by the above formula (3):

で表されるジフェニルシロキサン系化合物 (屈折率1.55)：100質量部を用い、(B)成分の配合量を35質量部から18質量部に変更した以外は、実施例１と同様にして組成物を調製し、硬化成形物とＬＥＤチップが硬化物で封止されたＬＥＤランプとを得た。

A diphenylsiloxane compound represented by the formula (refractive index 1.55): A composition as in Example 1 except that 100 parts by mass and the blending amount of component (B) was changed from 35 parts by mass to 18 parts by mass. To obtain an LED lamp in which the cured molded product and the LED chip were sealed with the cured product.

[Example 3]
In Example 1, the amount of component (A) was changed from 100 parts by weight to 80 parts by weight, the amount of component (B) was changed from 35 parts by weight to 32 parts by weight, and component (A), (B ) Component and 1-ethynylcyclohexanol
(D) The following formula (4):

で表されるシロキサン系化合物：20質量部
を均一に混合した以外は、実施例１と同様にして組成物を調製し、硬化成形物とＬＥＤチップが硬化物で封止されたＬＥＤランプとを得た。

A composition is prepared in the same manner as in Example 1 except that 20 parts by mass of the siloxane compound is uniformly mixed, and a cured molded product and an LED lamp in which the LED chip is sealed with the cured product. Obtained.

[Comparative Example 1]
In Example 1, as the component (A), a diphenylsiloxane compound represented by the above formula (3): instead of 100 parts by mass, an organic group bonded to a silicon atom is composed of a methyl group, a phenyl group, and a vinyl group. Phenylvinylmethylpolysiloxane having a phenyl group amount of 30 mol%, a vinyl group amount of 0.02 mol%, a viscosity of 4000 mPa · s, and a refractive index of 1.51 in all organic groups bonded to atoms: Using 80 parts by mass, the blending amount of component (B) was changed from 35 parts by mass to 15 parts by mass, and together with (A) component, (B) component and 1-ethynylcyclohexanol, The composition is prepared in the same manner as in Example 1 except that 20 parts by mass of the siloxane compound is uniformly mixed, and an LED lamp in which the cured molded product and the LED chip are sealed with the cured product. Got.

[Comparative Example 2]
In Example 1, bisphenol A type epoxy resin (trade name: Pernox ME-540, manufactured by Pernox) was used instead of the composition of Example 1, and the thickness poured into a mold assembled with a glass plate was 2 mm to 4 mm thick. The cured molded product and the LED chip in which the LED chip was sealed with the cured product were obtained in the same manner as in Example 1 except that the heating time was changed from 2 hours to 8 hours.

[Comparative Example 3]
In Example 1, instead of the composition of Example 1, a phenyl silicone resin-based curable composition (trade name: X-34-1195, manufactured by Shin-Etsu Chemical Co., Ltd., phenyl group content: about 50 mol%) was used. A cured molded product and an LED lamp in which the LED chip was sealed with a cured product were obtained in the same manner as in Example 1 except that the heating time was changed from 2 hours to 8 hours.

[Performance evaluation method]
About the hardened | cured material and LED lamp which were obtained by the said Example and comparative example, performance was evaluated in accordance with the following method.
<Hardness>
The hardness (Shore D) of the cured product was measured according to ASTM D 2240. The measurement results are shown in Table 1.
<Heat resistance>
The light transmittance at 400 nm of the cured product was measured before and after the cured product was left in a dryer at 150 ° C. for 500 hours and exposed to a high temperature. The measurement results are shown in Table 1.
<Heat shock resistance>
As a thermal shock test, a cycle consisting of an operation in which the LED lamp 1 was allowed to stand at −40 ° C. for 30 minutes and then left at −100 ° C. for 30 minutes was repeated 100 times. In the thermal shock test, the LED lamp was immersed in red ink, and it was observed whether or not the red ink entered the boundary surface between the transparent cured product 9 and the polyphthalamide package 5, Ag electrode 7 or LED chip 6. The observation results are shown in Table 1. The adhesion of the transparent cured product 9 to the polyphthalamide package 5, the Ag electrode 7 or the LED chip 6 after the thermal shock test was evaluated as good when no red ink penetration was observed. When the intrusion of was observed, it was evaluated as defective.

[Evaluation]
By using the (A) component diphenylsiloxane compound, it was possible to develop a curable silicone composition that gives a cured product excellent in heat resistance and thermal shock resistance.

DESCRIPTION OF SYMBOLS 1 LED lamp 2 Wall surface 3 Bottom surface 4 Recess 5 Polyphthalamide package 6 LED chip 7 Electrode 8 Gold wire 9 Transparent cured product

Claims (6)

(A) The following general formula (1):

(Wherein, R ¹ is unsubstituted C1-12 monovalent hydrocarbon radicals free of aliphatic unsaturation, R ² is a divalent hydrocarbon group having 1 to 12 carbon atoms X is an unsubstituted alkenyl group having 2 to 12 carbon atoms, a and b are integers of 0 to 3, a + b is an integer of 2 to 6, and n is a positive number of 1 or more)
A diphenylsiloxane compound having an alkenyl group bonded to a silicon atom at the molecular chain end,
(B) an organosilicon compound having at least two hydrogen atoms bonded to a silicon atom, and
(C) A curable silicone composition containing a hydrosilylation reaction catalyst.   The composition according to claim 1, wherein the component (A) has a refractive index of 1.54 or more.   The composition according to claim 1 or 2, wherein the component (B) has a refractive index of 1.45 or more. (D) The following general formula (2):

(In the formula, R ³ is an unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and the oxygen atom in the formula combines with a silicon atom to form a siloxane bond)
A silicone oil having at least two vinyl groups bonded to silicon atoms, having a structural unit represented by the formula: at least two vinyl groups bonded to silicon atoms having a structural unit represented by the general formula (2) The composition which concerns on any one of Claims 1-3 which further contains the silicone resin which has, or these combination.   The composition according to any one of claims 1 to 4, which is used as a material for an optical device / optical component.   Hardened | cured material obtained by hardening the composition of any one of Claims 1-5.

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