JP2013173891A - White thermosetting silicone composition, and light reflection material for white light emission diode including cured material of the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a white thermosetting silicone composition having high fluidity at room temperature, excellent in light reflection performance and heat resistance (thermal stability), particularly in thermal discoloration resistance, giving a cured material capable of providing a higher light reflectance than conventionally, and good in mold releasability of a cured molding of the molded composition.SOLUTION: A white thermosetting silicone composition includes (A) an addition reaction product, of (a) a compound having two Si-H in one molecule with (b) a polycyclic hydrocarbon having two addition-reactive C=C in one molecule, having at least two addition-reactive C=C in one molecule, (B) a mixture of an organosilicon compound (B-1) having three or more Si-H in one molecule and an organosilicon compound (B-2) having two Si-H in one molecule, (C) a hydrosilylating reaction catalyst, and (D) a titanium oxide whose crystal form is rutile.

Description

  The present invention relates to a light-reflective material, particularly a white thermosetting silicone composition that provides a cured silicone resin useful as a light-reflective material for a white LED (light-emitting diode), and light for a white light-emitting diode comprising the cured product of the composition. It relates to a reflective material.

  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 material that reflects emitted light (hereinafter referred to as a light reflecting material) is mounted in order to increase the light extraction efficiency in the irradiation direction.

  Currently, polyphthalamide resins are widely used as light reflecting 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 these problems, Patent Documents 1 to 3 propose a B-stage type light reflecting material containing epoxy resin and metal oxide as constituent components, and Patent Document 4 proposes a ceramic light reflecting 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 the solid material has poor fluidity even at high temperatures, there is a problem in the process such as difficulty in forming a fine structure or a large-area structure. Patent Document 5 proposes a cured silicone resin that is particularly useful as a light-reflecting material for white LEDs (light-emitting diodes), but there is no description of the crystalline form of titanium oxide powder.

  On the other hand, Patent Document 6 proposes a curable composition containing a polycyclic hydrocarbon skeleton-containing component that gives a cured product having high transparency, but what is described about the problem of improving light reflectivity? Nor.

Japanese Patent No. 2656336 JP 2008-106226 A JP 2008-189833 A JP 2008-117932 A JP 2010-202831 A Japanese Patent No. 4520251

  In addition, the inventor of the present invention provides a light-reflective material, in particular a white thermosetting silicone composition that gives a cured silicone resin useful as a reflector material for white LEDs, and a light-reflective material for white light-emitting diodes comprising the cured product of the composition. Proposed (Japanese Patent Application No. 2011-000706) was inferior in production due to poor mold releasability of the cured molded product of the composition molded by the injection molding method, transfer molding method, compression molding method. It was.

  The present invention has been made in view of the above circumstances, has high fluidity at room temperature, is excellent in light reflection performance, heat resistance (thermal stability), particularly heat discoloration, and has a higher light reflectance than conventional ones. White cured with good mold releasability of the cured molded product (cured product) of the composition molded by the injection molding method, transfer molding method, compression molding method A functional silicone composition is provided. That is, the present invention relates to a white light-emitting diode comprising a light-reflective material, particularly a white thermosetting silicone composition that provides a cured silicone resin useful as a light-reflective material for white LEDs, and a cured product of the composition having excellent productivity. It is an object to provide a light reflecting material.

（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。）で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
（ｂ）付加反応性炭素−炭素二重結合を１分子中に２個有する多環式炭化水素と
の付加反応生成物であって、かつ、付加反応性炭素−炭素二重結合を１分子中に少なくとも２個有する付加反応生成物、
（Ｂ）ケイ素原子に結合した水素原子を１分子中に３個以上有する有機ケイ素化合物（Ｂ−１）、及び、ケイ素原子に結合した水素原子を１分子中に２個有する有機ケイ素化合物（Ｂ−２）からなる混合物：前記(Ｂ−１)成分及び前記(Ｂ−２)成分中のケイ素原子に結合した水素原子の合計量が、前記（Ａ）成分中の付加反応性炭素−炭素二重結合に対してモル比で１．０〜１．５となる量であり、更に、前記(Ｂ−１)成分と前記(Ｂ−２)成分中のケイ素原子に結合した水素原子の合計量は前記(Ｂ−２)成分中のケイ素原子に結合した水素原子量に対して、１．１〜６．５となる量である）、
（Ｃ）ヒドロシリル化反応触媒、並びに
（Ｄ）結晶形態がルチルである酸化チタン粉末
を含有するものであることを特徴とする白色熱硬化性シリコーン組成物を提供する。 In order to solve the above problems, according to the present invention,
(A) (a) The following general formula (1):

(In the formula, A represents the following general formula (2):

And R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or alkoxy having 1 to 6 carbon atoms. It is a group. A compound having two hydrogen atoms bonded to a silicon atom represented by
(B) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the addition-reactive carbon-carbon double bond in one molecule An addition reaction product having at least two
(B) An organosilicon compound (B-1) having three or more hydrogen atoms bonded to a silicon atom in one molecule, and an organosilicon compound (B-1) having two hydrogen atoms bonded to a silicon atom in one molecule -2): The total amount of hydrogen atoms bonded to the silicon atom in the component (B-1) and the component (B-2) is the addition reactive carbon-carbon diene in the component (A). The amount is 1.0 to 1.5 in terms of molar ratio with respect to the heavy bond, and the total amount of hydrogen atoms bonded to silicon atoms in the component (B-1) and the component (B-2). Is an amount of 1.1 to 6.5 with respect to the amount of hydrogen atoms bonded to the silicon atom in the component (B-2)),
(C) A hydrosilylation reaction catalyst, and (D) a white thermosetting silicone composition characterized by containing a titanium oxide powder whose crystal form is rutile.

  Such a white thermosetting silicone composition is excellent in workability and handleability because it has high fluidity at room temperature. In addition, the cured silicone resin obtained by thermosetting the white thermosetting silicone composition has excellent light reflection performance, heat resistance (thermal stability), and particularly heat discoloration. Furthermore, a cured molded product obtained by molding the composition by an injection molding method, a transfer molding method, or a compression molding method is advantageous in terms of production because of good mold releasability.

  Further, in this case, it is preferably for a light reflecting material molded by an injection molding method, a transfer molding method, or a compression molding method.

  Since the white thermosetting silicone composition of the present invention has good mold releasability and is easy to mold, it is suitably used for a light reflecting material molded by an injection molding method, a transfer molding method, or a compression molding method. .

（式中、Ｒ’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。） In this case, examples of the component (b) include alkenyl norbornene compounds represented by the following general formula (3).

(In the formula, R ′ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)

  Thus, (b) the alkenyl norbornene compound represented by the above general formula (3) is exemplified as the polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule. That is, the alkenyl norbornene compound has an addition-reactive carbon-carbon double bond formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon. And the hydrogen atom couple | bonded with the carbon atom which forms the polycyclic skeleton of a polycyclic hydrocarbon is substituted by the addition reactive carbon-carbon double bond containing group.

  In this case, the component (b) is a combination of 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene, and combinations thereof. It is preferable that any one of them.

  Thus, as the compound represented by the general formula (3), 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene Is mentioned.

（式中、Ｒ^１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、ｑは２〜１０の整数、ｒは０〜７の整数である。ｑが付されたシロキサン単位とｒ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。）
で表される環状シロキサン系化合物を含むものとすることができる。またこの場合、該環状シロキサン系化合物が、１，３，５，７−テトラメチルシクロテトラシロキサン、１，３，５，７，９−ペンタメチルシクロペンタシロキサン、及びこれらの組み合わせのうちのいずれかであることが好ましい。 The component (B) is represented by the following general formula (4):

(Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, q is an integer of 2 to 10, and r is 0 to 7) (The siloxane unit with q and the siloxane unit with r are randomly arranged with respect to each other.)
The cyclic siloxane type compound represented by these can be included. In this case, the cyclic siloxane compound is any one of 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, and combinations thereof. It is preferable that

Thus, as said (B) component, what contains the cyclic siloxane type compound represented by the said General formula (4) is mentioned. In the present invention, the cyclic siloxane compound represented by the general formula (4) is defined as the component (B-1) or the component (B-2) according to the definitions of R ¹ , q and r in the formula. Alternatively, when two or more cyclic siloxane compounds represented by the general formula (4) are contained, they can be used as the component (B-1) and the component (B-2). Among the cyclic siloxane compounds represented by the general formula (4), all of R ^{1 in} the general formula (4) are methyl groups, that is, 1,3,5,7-tetramethylcyclohexane. Tetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane and the like are preferred because they are easy to produce industrially and are easily available. In this case, these are used as the component (B-1) and used in combination with another (B-2) organosilicon compound component having two hydrogen atoms bonded to a silicon atom in one molecule. (B) component.

（式中、Ｒ^１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、ｑ’は３〜１０の整数、ｒは０〜７の整数である。Ｒ”は炭素原子数２〜１２のアルキレン基であり、ｎは１〜１００の整数である。ｑ１及びｑ２はそれぞれ０〜８の整数であり、但しｑ１＋ｑ２は１〜８の整数である。ｒ１及びｒ２はそれぞれ０〜７の整数であり、但しｒ１＋ｒ２は０〜７の整数である。）
で表されるノルボルナン環含有環状シロキサン化合物を含むものであることが好ましい。またこの場合、該ノルボルナン環含有環状シロキサン化合物は、５−ビニルビシクロ［２．２．１］ヘプト−２−エン、６−ビニルビシクロ［２．２．１］ヘプト−２−エン及びこれらの組み合わせのうちのいずれかと、１，３，５，７−テトラメチルシクロテトラシロキサン、１，３，５，７，９−ペンタメチルシクロペンタシロキサン及びこれらの組み合わせのうちのいずれかとの付加反応生成物であることが好ましい。 The component (B) is represented by the following general formula (5):

(Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, q ′ is an integer of 3 to 10, and r is 0 to 7) R ″ is an alkylene group having 2 to 12 carbon atoms, n is an integer of 1 to 100. q1 and q2 are each an integer of 0 to 8, provided that q1 + q2 is an integer of 1 to 8. (R1 and r2 are each an integer of 0 to 7, provided that r1 + r2 is an integer of 0 to 7.)
It is preferable that it contains the norbornane ring containing cyclic siloxane compound represented by these. In this case, the norbornane ring-containing cyclic siloxane compound includes 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene, and combinations thereof. And any one of 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, and combinations thereof. Preferably there is.

  Thus, as for the said (B) component, what contains the norbornane ring containing cyclic siloxane compound represented by the said General formula (5) as said (B-1) is mentioned. The norbornane ring-containing cyclic siloxane compound is selected from the group consisting of 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene, and combinations thereof. Any one of 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, and combinations thereof, It is preferable because it can be easily produced industrially.

（式中、Ｒ^２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、Ｍｅはメチル基であり、ｑ３は０〜６０の整数、ｒ３は０〜７の整数である。ｑ３が付されたシロキサン単位とｒ３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。）
で表されるシロキサン化合物を含むものであることが好ましい。 The component (B) is represented by the following general formula (6):

(In the formula, R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, Me represents a methyl group, and q3 represents an integer of 0 to 60. R3 is an integer of 0 to 7. The siloxane unit to which q3 is attached and the siloxane unit to which r3 is attached are randomly arranged.
It is preferable that the siloxane compound represented by these is included.

Thus, as said (B) component, what contains the siloxane compound represented by the said General formula (6) can be mentioned. The siloxane compound represented by the general formula (6) is defined as the component (B-1) or the component (B-2) according to the definitions of R ² , q3, and r3, or in the general formula (6). When 2 or more types of siloxane compounds represented are included, it can be used as said (B-1) component and said (B-2) component.

The titanium oxide as the component (D) is preferably obtained by the chlorine method.
By using titanium oxide obtained by the chlorine method, higher light reflection characteristics can be imparted to the cured product of the composition.

The white thermosetting silicone composition of the present invention preferably further contains (E) a fused quartz glass powder.
Thus, by using together the said (D) component and (E) fused quartz glass powder, a high light reflection characteristic can be provided to the hardened | cured material of a composition.

In particular, the initial light reflectance at a wavelength of 430 to 800 nm of the cured product obtained by curing the white thermosetting silicone composition is 95% or more, and the light reflectance after leaving at 150 ° C. for 2,000 hours is 80%. % Of a white thermosetting silicone composition is preferred.
Such a cured product obtained by curing the white thermosetting silicone composition is more suitable as a light reflecting material, and can be particularly suitably used as a light reflecting material for a white light emitting diode.

Moreover, in this invention, the light reflection material for white light emitting diodes which consists of hardened | cured material of a white thermosetting silicone composition is provided.
A light emitting device such as a white LED using the white thermosetting silicone composition of the present invention can maintain high light extraction efficiency over a long period of time. In addition, since the white thermosetting silicone composition of the present invention is easy to mold because the mold releasability is good, the light reflecting material composed of a cured silicone resin obtained from the white thermosetting silicone composition, It is easy to make a desired shape as a light reflecting material of these light emitting devices including a white LED.

  Since the white thermosetting silicone composition of the present invention has high fluidity at room temperature, it is excellent in workability and handleability. Moreover, the cured silicone resin obtained by thermosetting the composition is excellent in light reflection performance, heat resistance (thermal stability), particularly heat discoloration, and can obtain a higher light reflectance than conventional. it can. Furthermore, since the mold releasability of the cured molded product of the composition molded by the injection mold method, the transfer mold method, and the compression mold method is good, it is excellent in productivity, and the curing excellent in such productivity. The object is useful as a light reflecting material, for example, a light reflecting material for a light emitting device, particularly for a white LED.

Hereinafter, the present invention will be described in more detail.
As described above, the composition for obtaining the conventional light reflecting material has a problem of poor fluidity. Moreover, there existed a problem that the mold release property of the hardened | cured molding of the composition shape | molded by the injection mold method, the transfer mold method, the compression mold method etc. was bad, and it was inferior in terms of production.
Therefore, a cured silicone resin useful as a light reflecting material having high fluidity, light reflecting performance, heat resistance (thermal stability), particularly excellent heat discoloration, and excellent mold releasability. There is a need for a white thermosetting silicone composition that can be applied, the cured product, and a light reflecting material comprising the cured product.

（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。）で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
（ｂ）付加反応性炭素−炭素二重結合を１分子中に２個有する多環式炭化水素と
の付加反応生成物であって、かつ、付加反応性炭素−炭素二重結合を１分子中に少なくとも２個有する付加反応生成物、
（Ｂ）ケイ素原子に結合した水素原子を１分子中に３個以上有する有機ケイ素化合物（Ｂ−１）、及び、ケイ素原子に結合した水素原子を１分子中に２個有する有機ケイ素化合物（Ｂ−２）からなる混合物（前記(Ｂ−１)成分及び前記(Ｂ−２)成分中のケイ素原子に結合した水素原子の合計量が、前記（Ａ）成分中の付加反応性炭素−炭素二重結合に対してモル比で１．０〜１．５となる量であり、更に、前記(Ｂ−１)成分と前記(Ｂ−２)成分中のケイ素原子に結合した水素原子の合計量は前記(Ｂ−２)成分中のケイ素原子に結合した水素原子量に対して、１．１〜６．５となる量である）、
（Ｃ）ヒドロシリル化反応触媒、並びに
（Ｄ）結晶形態がルチルである酸化チタン粉末
を含有するものであることを特徴とする白色熱硬化性シリコーン組成物であれば、室温において、高い流動性を有するため、作業性・取扱い性に優れ、かつ、光反射性能、耐熱性（熱安定性）、特に耐熱変色性に優れ、従来に比べてより高い光反射率が達成できる硬化物を得ることができることを見出し、更に、インジェクションモールド法、トランスファーモールド法、コンプレッションモールド法で成型された該組成物の硬化成型物の金型離型性が良好であることを見出した。 As a result of intensive studies to achieve the above object, the present inventors have completed the present invention. That is, the inventors
(A) (a) The following general formula (1):

(In the formula, A represents the following general formula (2):

And R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or alkoxy having 1 to 6 carbon atoms. It is a group. A compound having two hydrogen atoms bonded to a silicon atom represented by
(B) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the addition-reactive carbon-carbon double bond in one molecule An addition reaction product having at least two
(B) An organosilicon compound (B-1) having three or more hydrogen atoms bonded to a silicon atom in one molecule, and an organosilicon compound (B-1) having two hydrogen atoms bonded to a silicon atom in one molecule -2) (the total amount of hydrogen atoms bonded to silicon atoms in the component (B-1) and the component (B-2) is the addition-reactive carbon-carbon 2 in the component (A)). The amount is 1.0 to 1.5 in terms of molar ratio with respect to the heavy bond, and the total amount of hydrogen atoms bonded to silicon atoms in the component (B-1) and the component (B-2). Is an amount of 1.1 to 6.5 with respect to the amount of hydrogen atoms bonded to the silicon atom in the component (B-2)),
(C) Hydrosilylation reaction catalyst, and (D) A white thermosetting silicone composition characterized by containing a titanium oxide powder whose crystal form is rutile. Therefore, it is possible to obtain a cured product that is excellent in workability and handleability, has excellent light reflection performance, heat resistance (thermal stability), particularly heat discoloration, and can achieve higher light reflectivity than before. It has been found that the mold can be released, and further, the mold releasability of the cured molded product of the composition molded by the injection molding method, transfer molding method and compression molding method is good.

  The present invention will be described in detail below. In this specification, Me and Ph represent a methyl group and a phenyl group, respectively, the viscosity is a value measured by a rotational viscometer at 23 ° C., and the kinematic viscosity is a value measured by an Ostwald viscometer at 25 ° C.

（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。）で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
（ｂ）付加反応性炭素−炭素二重結合を１分子中に２個有する多環式炭化水素と
の付加反応生成物である。以下、これらの（ａ）成分および（ｂ）成分について説明する。 (A) component (A) component of the white thermosetting silicone composition of the present invention is:
(A) The following general formula (1):

(In the formula, A represents the following general formula (2):

And R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or alkoxy having 1 to 6 carbon atoms. It is a group. A compound having two hydrogen atoms bonded to a silicon atom represented by
(B) An addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule. Hereinafter, the component (a) and the component (b) will be described.

（Ｒ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、好ましくは１〜４の、アルコキシ基である。）
で表される化合物が挙げられる。 <(A) component>
(A) Compound which is a reaction raw material of component (a) A compound having two hydrogen atoms bonded to the silicon atom represented by the above general formula (1) (hereinafter sometimes referred to as “SiH”) in one molecule In the general formula (1), A is a divalent group selected from the group consisting of the groups represented by the general formula (2), and the compound (a) includes the following general formula (a -1) to (a-3):

(R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. .)
The compound represented by these is mentioned.

  In the above formulas (a-1) to (a-3), when R is the monovalent hydrocarbon group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group Alkyl groups such as 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; benzyl group, Aralkyl groups such as 2-phenylethyl group; alkenyl groups such as vinyl group, allyl group, 1-butenyl group, 1-hexenyl group; alkenyl aryl groups such as p-vinylphenyl group; and carbon atoms in these groups One or more bonded hydrogen atoms are substituted with a halogen atom, a cyano group, an epoxy ring-containing group, etc., for example, a chloromethyl group, a 3-chloropropyl group Halogenated alkyl groups such as 3,3,3-trifluoropropyl group; a 2-cyanoethyl group; 3-glycidoxypropyl group and the like.

  Moreover, as a case where R is the said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group etc. are mentioned, for example.

  Among the above, as R, those other than alkenyl group and alkenylaryl group are preferable, and those in which all of them are methyl groups are preferable because they are easy to produce industrially and are easily available. .

Examples of the compounds represented by the general formulas (a-1) to (a-3) include, 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 said (a) component which is a reaction raw material of this (A) component can be used even if single 1 type also combines 2 or more types.

<(B) component>
(B) Polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, which is a reaction raw material of component (A), the “addition reactivity” is bonded to a silicon atom. It means the property of being able to undergo the addition of a hydrogen atom (known as a hydrosilylation reaction).
In addition, as the form of the addition-reactive carbon-carbon double bond present in two molecules in the component (b), (i) the carbon atom forming the polycyclic skeleton of the polycyclic hydrocarbon Among them, those having two addition-reactive carbon-carbon double bonds formed between two adjacent carbon atoms, (ii) bonded to a carbon atom forming a polycyclic skeleton of a polycyclic hydrocarbon Those in which two hydrogen atoms are substituted by an addition-reactive carbon-carbon double bond-containing group, or (iii) carbon atoms forming a polycyclic skeleton of a polycyclic hydrocarbon, adjacent to each other An addition-reactive carbon-carbon double bond is formed between two carbon atoms, and the hydrogen atom bonded to the carbon atom forming the polycyclic skeleton of the polycyclic hydrocarbon is an addition-reactive carbon- Any one substituted by a carbon double bond-containing group is acceptable. No. 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’は非置換または置換の炭素原子数２〜１２のアルケニル基である。）
で表されるアルケニルノルボルネン化合物が挙げられる。さらに、該一般式（３）で表される化合物の具体例として、下記構造式（３−１）：

で表される５−ビニルビシクロ［２．２．１］ヘプト−２−エン、
下記構造式（３−２）：

で表される６−ビニルビシクロ［２．２．１］ヘプト−２−エン、およびこれら両者の組み合わせが挙げられる（以下、これら３者を区別する必要がない場合は、「ビニルノルボルネン」と総称することがある）。 Examples of the component (b) include the following general formula (3):

(In the formula, R ′ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)
The alkenyl norbornene compound represented by these is mentioned. Furthermore, as a specific example of the compound represented by the general formula (3), the following structural formula (3-1):

5-vinylbicyclo [2.2.1] hept-2-ene represented by:
The following structural formula (3-2):

6-vinylbicyclo [2.2.1] hept-2-ene, and a combination of the two (hereinafter, when there is no need to distinguish these three, it is generically called “vinyl norbornene”) Sometimes).

  The substitution position of the alkenyl group in the alkenyl norbornene compound (substitution position of the vinyl group of vinyl norbornene in the above structural formulas (3-1) and (3-2)) is a cis configuration (exo configuration) or a trans configuration ( Any of the above-mentioned isomers may be used, and there is no particular difference in the reactivity of the components due to the difference in the arrangement.

<Preparation of component (A)>
The component (A) of the composition of the present invention has two addition-reactive carbon-carbon double bonds in one molecule with respect to 1 mole of the component (a) having two SiH in one molecule. SiH is reacted by adding an excess molar amount of more than 1 mol, for example, 10 mol or less (preferably more than 1 mol, for example 5 mol or less) of the component (b) in the presence of a hydrosilylation reaction catalyst. And an addition reaction product having at least two addition-reactive carbon-carbon double bonds in one molecule.

  The component (A) thus obtained uses an excess molar amount of the component (b) relative to the component (a) for adjustment, so that the addition-reactive carbon-carbon 2 derived from the structure of the component (b) It has two heavy bonds in one molecule. Further, in addition to the addition-reactive carbon-carbon double bond derived from the component (b), an addition reaction derived from the component (a) (specifically, derived from R in the general formula (1)). The component (A) contains at least two addition-reactive carbon-carbon double bonds in one molecule, and this number is preferably 2 to 6, more preferably. Is two. If there are 2 to 6 addition-reactive carbon-carbon double bonds, the cured product obtained by curing the composition of the present invention is not liable to be 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, since the component (A) is prepared using an excess molar amount of the component (b) relative to the component (a), the component (A) has the structure of the component (b). It has two derived addition-reactive carbon-carbon double bonds in one molecule. Furthermore, the component (A) has a residue derived from the component (a), and the residue is derived from the structure of the component (b) but does not have an addition-reactive carbon-carbon double bond. It may contain a structure linked by a divalent residue of a polycyclic hydrocarbon.

That is, as the component (A), for example, the following general formula (A-1):
YX- (Y'-X) pY (A-1)
(In the formula, X is a divalent residue derived from the structure of the component (a), Y is a monovalent residue derived from the structure of the polycyclic hydrocarbon of the component (b), Y ′ is a divalent residue derived from the structure of component (b) above, and p is an integer of 0 to 10, preferably 0 to 5.
The compound represented by these is mentioned.
In addition, about the value of p which is the number of the repeating units represented by said (Y'-X), adjusting the excess molar amount of said (b) component made to react with respect to 1 mol of said (a) component. It is possible to set by.

で表される一価の残基（以下、これら６者を区別する必要がない場合は、これらを「ＮＢ基」と総称し、また、前記６者の構造を区別せずに「ＮＢ」と略記することがある。）が挙げられる。
上記一般式（Ａ−１）中のＹ’としては、具体的には、例えば、下記構造式：

で表される二価の残基が挙げられる。 As Y in the general formula (A-1), specifically, for example, the following structural formula:

(Hereinafter, when it is not necessary to distinguish these six members, they are collectively referred to as “NB group”, and “NB” without distinguishing the structure of the six members) May be abbreviated.).
As Y ′ in the general formula (A-1), specifically, for example, the following structural formula:

The bivalent residue represented by these is mentioned.

  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.

（式中、ｐは０〜１０の整数である。）
更に、本発明の（Ａ）成分は、１種単独でも２種以上を組み合わせても使用することができる。 Although the preferable specific example of (A) component represented by the said general formula (A-1) is shown below, it is not limited to this. The meaning of “NB” is as described above.

(In the formula, p is an integer of 0 to 10.)
Furthermore, the component (A) of the present invention can be used singly or in combination of two or more.

(B) component (B) component of this invention is
(B-1) an organosilicon compound having three or more hydrogen atoms bonded to silicon atoms (ie, SiH) in one molecule, and
(B-2) A mixture composed of an organosilicon compound having two hydrogen atoms bonded to silicon atoms (ie, SiH) in one molecule.
That is, the present invention is characterized in that, as the component (B), the component (B-1) and the component (B-2) are used together as a mixture, and the component (B) And SiH in (B-2) component) is added by an addition reactive carbon-carbon double bond and at least two hydrosilylation reactions that component (A) has in one molecule. Give a cured product.

  The blending amount of the component (B) is such that the total amount of hydrogen atoms bonded to the silicon atoms in the component (B-1) and the component (B-2) is the addition reactivity in the component (A). The molar ratio is 1.0 to 1.5 with respect to the carbon-carbon double bond, and the ratio of the component (B-1) to the component (B-2) is 1) The total amount of hydrogen atoms bonded to silicon atoms in the component (B-2) and the amount of hydrogen atoms bonded to silicon atoms in the component (B-2) is 1.1 to 6. It is a ratio satisfying 5.

  That is, the molar ratio of the total carbon-carbon double bonds in component (A) to the total amount of hydrogen atoms bonded to silicon atoms in component (B) is: total hydrogen atom weight / total carbon-carbon double bonds = 1. (B) component is blended in an amount of 0 to 1.5, and an organosilicon compound having two hydrogen atoms bonded to silicon atoms in the total hydrogen atom weight in component (B) The ratio of the hydrogen atom weight of (B-2) component is the total hydrogen atom weight / hydrogen atom weight of the organosilicon compound having two hydrogen atoms bonded to silicon atoms in one molecule = 1.1 to 6.5. The ratio is more preferably in the range of 1.25 to 6.0. When the said ratio is less than 1.1, the obtained molding may be inferior in terms of mechanical strength. On the other hand, when the ratio is more than 6.5, the mold releasability of the cured molded product of the molded composition is poor and the production is inferior.

（式中、Ｒ^１は、独立に水素原子またはアルケニル基以外の非置換もしくは置換の炭素原子数１〜１２、好ましくは１〜６の一価炭化水素基であり、ｑは２〜１０、好ましくは２〜８の整数、ｒは０〜７、好ましくは０〜３の整数である。ｑ＋ｒの和は好ましくは３〜１０、より好ましくは３〜６の整数である。ｑが付されたシロキサン単位とｒ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。）
で表される環状シロキサン系化合物を前記（Ｂ−１）成分若しくは前記（Ｂ−２）成分として、又は前記（Ｂ−１）成分及び前記（Ｂ−２）成分として含むものが挙げられる。 Examples of the component (B) include the following general formula (4):

(Wherein R ¹ is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms other than a hydrogen atom or an alkenyl group, preferably 1 to 6, and q is preferably 2 to 10, Is an integer of 2 to 8, r is an integer of 0 to 7, preferably 0 to 3. The sum of q + r is preferably an integer of 3 to 10, more preferably an integer of 3 to 6. Siloxanes with q attached The unit and the siloxane unit to which r is attached are randomly arranged to each other.)
And those containing the (B-1) component or the (B-2) component, or the (B-1) component and the (B-2) component.

Examples of the case where R ¹ in the general formula (4) is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert group An alkyl group such as a butyl group, a pentyl group, an isopentyl group, a hexyl group or a 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-, p-tolyl; An aralkyl group such as benzyl group and 2-phenylethyl group; an alkenyl aryl group such as p-vinylphenyl group; and one or more hydrogen atoms bonded to carbon atoms in these groups are a halogen atom, a cyano group, an epoxy group Substituted with a ring-containing group, for example, a halo such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. Genated alkyl group; 2-cyanoethyl group; 3-glycidoxypropyl group and the like.

Among the above, as R ¹ , those in which all of them are methyl groups are particularly preferable because they are easy to produce industrially and are easily available. Examples of those in which all of R ¹ are methyl groups include 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7,9-pentamethylcyclopentasiloxane. (B-1) Used as a component.

（式中、Ｒ^１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、ｑ’は３〜１０の整数、ｒは０〜７の整数である。Ｒ”は炭素原子数２〜１２のアルキレン基であり、ｎは１〜１００の整数である。ｑ１及びｑ２はそれぞれ０〜８の整数であり、但しｑ１＋ｑ２は１〜８の整数である。ｒ１及びｒ２はそれぞれ０〜７の整数であり、但しｒ１＋ｒ２は０〜７の整数である。）
で表されるノルボルナン環含有環状シロキサン化合物を前記（Ｂ−１）成分として含むものを好ましく挙げることができる。 As the component (B), for example, the general formula (5):

(Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, q ′ is an integer of 3 to 10, and r is 0 to 7) R ″ is an alkylene group having 2 to 12 carbon atoms, n is an integer of 1 to 100. q1 and q2 are each an integer of 0 to 8, provided that q1 + q2 is an integer of 1 to 8. (R1 and r2 are each an integer of 0 to 7, provided that r1 + r2 is an integer of 0 to 7.)
The thing containing the norbornane ring containing cyclic siloxane compound represented by these as said (B-1) component can be mentioned preferably.

  The norbornane ring-containing cyclic siloxane compound represented by the general formula (5) is a hydrosilylation reaction between the alkenyl norbornene compound represented by the general formula (3) and the cyclic siloxane compound represented by the general formula (4). Can be manufactured. The alkylene group R ″ in the general formula (5) is generated by the addition reaction of SiH present in the general formula (4) to the alkenyl group R ′ in the general formula (3).

（式中、ｘは１または２であり、ｗは１〜１００、好ましくは１〜１０の整数である）で表される化合物、および、上記ビニルノルボルネン（特に、５−ビニルビシクロ［２．２．１］ヘプト−２−エンや６−ビニルビシクロ［２．２．１］ヘプト−２−エン）の一種または二種と１，３，５，７，９−ペンタメチルシクロペンタシロキサンとをヒドロシリル化反応させて得られる、ＳｉＨを１分子中に３個以上有する付加反応生成物、例えば、下記一般式（ii）：

（式中、ｙは１、２または３であり、ｚは１〜１００、好ましくは１〜１０の整数である。）で表される化合物が挙げられる。 That is, specific examples of the norbornane ring-containing cyclic siloxane compound represented by the general formula (5) include vinyl norbornene (especially 5-vinylbicyclo [2.2.1] hept-2-ene and 6-vinylbicyclo [2. 2.1] Addition obtained by hydrosilylation reaction of one or two kinds of hept-2-ene) and 1,3,5,7-tetramethylcyclotetrasiloxane with 3 or more SiH molecules in one molecule Reaction products such as the following general formula (i):

(Wherein x is 1 or 2, w is an integer of 1 to 100, preferably 1 to 10), and the vinyl norbornene (especially 5-vinylbicyclo [2.2 .1] One or two types of hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene) and 1,3,5,7,9-pentamethylcyclopentasiloxane are hydrosilylated. An addition reaction product having three or more SiHs in one molecule, obtained by the conversion reaction, for example, the following general formula (ii):

(Wherein y is 1, 2 or 3, and z is an integer of 1 to 100, preferably 1 to 10).

（式中、Ｒ^２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、Ｍｅはメチル基であり、ｑ３は０〜６０の整数、ｒ３は０〜７の整数である。ｑ３が付されたシロキサン単位とｒ３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。）で表されるシロキサン化合物を前記（Ｂ−１）成分若しくは前記（Ｂ−２）成分として、又は前記（Ｂ−１）成分及び前記（Ｂ−２）成分として含むものも挙げられる。 Furthermore, as the component (B), for example, the general formula (6):

(In the formula, R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, Me represents a methyl group, and q3 represents an integer of 0 to 60. , R3 is an integer of 0 to 7. The siloxane compound represented by (B-1) is represented by the formula (B-1) wherein the siloxane unit with q3 and the siloxane unit with r3 are randomly arranged. What contains as a component or the said (B-2) component or as said (B-1) component and said (B-2) component is also mentioned.

Although the preferable example of the said (B-1) component is shown below, it is not limited to this.
(HMeSiO) ₄
(HMeSiO) ₅
(HMeSiO) ₃ (Me ₂ SiO)
(HMeSiO) ₄ (Me ₂ SiO)

（式中、ｘは１または２である。）

(Wherein x is 1 or 2)

（式中、ｙは１、２または３である。）
ＨＭｅ_２ＳｉＯ（ＨＭｅＳｉＯ）_２（Ｐｈ_２ＳｉＯ）_２ＳｉＭｅ_２Ｈ
ＨＭｅ_２ＳｉＯ（ＨＭｅＳｉＯ）_２（Ｐｈ_２ＳｉＯ）_２（Ｍｅ_２ＳｉＯ）_２ＳｉＭｅ_２Ｈ
ＨＭｅ_２ＳｉＯ（ＨＭｅＳｉＯ）_１（Ｐｈ_２ＳｉＯ）_１（Ｍｅ_２ＳｉＯ）_４ＳｉＭｅ_２Ｈ
ＨＭｅ_２ＳｉＯ（ＨＭｅＳｉＯ）_３（Ｍｅ_２ＳｉＯ）_５ＳｉＭｅ_２Ｈ
Ｍｅ_３ＳｉＯ（ＨＭｅＳｉＯ）_８ＳｉＭｅ_３
Ｍｅ_３ＳｉＯ（ＨＭｅＳｉＯ）_３８ＳｉＭｅ_３

(Wherein y is 1, 2 or 3)
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
Me ₃ SiO (HMeSiO) ₈ SiMe ₃
Me ₃ SiO (HMeSiO) ₃₈ SiMe ₃

Preferred specific examples of the component (B-2) are shown below, but are not limited thereto.
HMe ₂ SiO (Ph ₂ SiO) SiMe ₂ H

(C) Component The hydrosilylation reaction catalyst which is the (C) component of the present invention is the same as that described in the above “Preparation of the (A) component”.
The blending amount of the component (C) in the composition of the present invention is not particularly limited as long as it is an effective amount as a catalyst, but the platinum group with respect to the sum of the components (A) and (B). The amount of the component (C) is preferably 1 to 500 ppm, particularly preferably about 2 to 100 ppm as the metal atom based on mass. By setting the blending amount within the above range, the time required for the curing reaction becomes appropriate, and it is possible to suppress problems such as coloring of the cured product.
Component (C) can be used alone or in combination of two or more.

(D) Component (D) component of this invention is a titanium oxide powder whose crystal form is a rutile. Production methods of titanium oxide powder having a rutile crystal form are mainly classified into a sulfuric acid method and a chlorine method, but those produced by the chlorine method are particularly preferable in terms of light reflectance. Moreover, although the crystal form of titanium oxide is classified into anatase, rutile and brookite, a cured product having excellent heat discoloration can be obtained by using rutile having the most stable thermal transition. Since the titanium oxide powder of component (D) is white, the cured product exhibits good light reflectance by blending component (D). Particularly, a cured silicone resin having a sufficient reflectivity as a reflector material having an initial light reflectivity of 95% or more at a wavelength of 430 to 800 nm and a light reflectivity of 80% or more after being left at 150 ° C. for 2,000 hours. 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 particle size of the component (D) is not particularly defined, but as the component (D), many particles having an average particle size in the range of 0.1 to 200 μm are generally commercially available and easy to handle, and in the range of 0.5 to 100 μm. 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 of the present invention tends to have good fluidity, and the cured product of the composition has a rough surface. 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.

  The component (D) can be used alone or in combination of two or more, and the blending amount of the component (D) is 100 parts by mass in total of the component (A) and the component (B). Preferably it is 50-1000 mass parts, More preferably, it is 60-900 mass parts, More preferably, it is 100-800 mass parts. When the blending amount is in the range of 50 to 1000 parts by mass, the composition of the present invention tends to have good fluidity, and the cured product of the composition tends to have sufficient light reflection performance and is excellent in balance. Become.

(E) Component Moreover, it is preferable to mix | blend (E) fused quartz glass powder with the said (D) component with the white thermosetting silicone composition of this invention. By using together (E) component, the hardened | cured material of a composition becomes a thing excellent in the light reflectivity more.
The blending amount of the component (E) is preferably 50 to 1500 parts by weight, more preferably 60 to 900 parts by weight, and still more preferably with respect to 100 parts by weight of the total of the components (A) and (B). Is 100-800 parts by mass. When the blending amount is in the range of 50 to 1500 parts by mass, the composition of the present invention has more excellent fluidity, and the cured product of the composition has more excellent light reflection performance.

（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。）
で表される化合物である。 Component (F) In addition to the components (A) to (E), it is preferable to add an adhesion improver to the white thermosetting silicone composition of the present 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 is preferable, and the following general formula (7):

(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.)
It is a compound represented by these.

  Component (F) is an optional component blended in the white thermosetting silicone composition of the present invention and the composition to improve the adhesion of the cured product to the substrate. 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.

が挙げられるが、これらに限定されるものではない。 (F) The compounding quantity of a component becomes like this. Preferably it is 1-30 mass parts with respect to a total of 100 mass parts of the said (A) component and (B), More preferably, it is 5-20 mass parts. When the blending amount is 1 to 30 parts by mass, the curable silicone composition of the present invention and the cured product thereof are effectively improved in adhesion to the substrate and are not easily colored.
As a preferable specific example of the component (F),

However, it is not limited to these.

Other Compounding Components In addition to the above components, it is optional to add other components to the white thermosetting silicone composition of the present invention within a range that does not impair the objects and effects of the present invention. Examples of other components include those described below.

で表される２−（ビシクロ［２．２．１］ヘプト−２−エン−５−イル）エチル基および
下記構造式：

で表される２−（ビシクロ［２．２．１］ヘプト−２−エン−６−イル）エチル基のいずれか一方または両方の中に存在する炭素−炭素二重結合が含まれている場合がある。そして、前記炭素−炭素二重結合が含まれていると、大気中の酸素により酸化され前記硬化物が着色する原因となる。そこで、本発明の組成物に、必要に応じ、酸化防止剤を配合することにより前記着色を未然に防止することができる。 <Antioxidant>
In the cured product of the white thermosetting silicone composition of the present invention, the addition reactive carbon-carbon double bond in the component (A) may remain unreacted, and the following structural formula:

2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl group represented by the following structural formula:

A carbon-carbon double bond present in one or both of 2- (bicyclo [2.2.1] hept-2-en-6-yl) ethyl group represented by There is. And when the said carbon-carbon double bond is contained, it will be oxidized by oxygen in air | atmosphere and will cause the said hardened | cured material to color. Then, the said coloring can be prevented beforehand by mix | blending antioxidant with the composition of this invention as needed.

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, With respect to the sum total of the said (A) component and (B) component, Preferably, about 10 to 10,000 ppm, particularly preferably about 100 to 1,000 ppm is added on a mass basis. By setting the blending amount within the above range, the antioxidant ability is sufficiently exhibited, and a cured product excellent in light reflection performance without coloration or oxidative deterioration is 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, it is also possible to use a light stabilizer in order 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.

White thermosetting silicone composition The white thermosetting silicone composition of the present invention is liquid before curing, and its viscosity at 23 ° C is preferably 0.1 to 500 Pa · s, more preferably 10 to 400 Pa. -S. When the viscosity is in the range of 0.1 to 500 Pa · s, the resulting composition tends to have particularly good workability and handleability, and bubbles and air are less likely to be entrained during molding and curing.
The viscosity of the white thermosetting silicone composition of the present invention is the blending ratio of the components (A) to (D) and other blending components, the viscosity of liquid components among these components, and the average particle size of the component (D). It is adjusted by. Since the white thermosetting silicone composition of the present invention has high fluidity at room temperature, it is excellent in workability and handleability.

Silicone resin cured product A silicone resin cured product can be obtained by molding and curing the white thermosetting silicone composition of the present invention. The white thermosetting silicone composition of the present invention can be applied to conventionally used molding methods such as an injection molding method, a transfer molding method, and a compression molding method. Furthermore, since the composition has a high fluidity at 25 ° C., it can be molded by a dispensing method or a potting method that could not be applied to conventional solid reflector materials. The curing conditions of the white thermosetting silicone composition 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. for 1 minute to The condition is 24 hours, preferably 5 minutes to 5 hours. Moreover, the cured silicone resin obtained by thermosetting the composition is excellent in light reflection performance, heat resistance (thermal stability), particularly heat discoloration, and can obtain a higher light reflectance than conventional. it can. Furthermore, since the mold releasability of the cured molded product of the composition molded by the injection mold method, the transfer mold method, and the compression mold method is good, it is excellent in productivity, and the curing excellent in such productivity. The object is useful as a light reflecting material, for example, a light reflecting material for a light emitting device, particularly for a white LED.

  Generally, in order to function as a light reflecting 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 reflectivity is 95% or more, when the cured product is used as a light reflecting material of 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 80% or more not only in the initial stage of production of the cured product but also after a heat resistance test (performed by leaving the cured product to stand at 150 ° C. for 2,000 hours). 82% or more is more preferable. The cured silicone resin obtained from the white thermosetting silicone resin composition of the present invention has a visible light (wavelength: 430 to 800 nm) reflectance of 95% or more, and light after standing at 150 ° C. for 2,000 hours. The reflectance is 80% or more, and a sufficient reflectance as a light reflecting 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 silicone resin cured product obtained from the white thermosetting silicone resin composition of the present invention has a softening point of preferably 30 ° C or higher, more preferably 40 ° C or higher. When the softening point is 30 ° C. or higher, the cured product is not easily brittle even in a high-temperature environment, and the generation of cracks is effectively suppressed. In addition, in this specification, a softening point means the temperature measured based on the softening point test method (ring ball method) prescribed | regulated to JISK2207.

  The cured silicone resin obtained from the white thermosetting silicone resin composition of the present invention preferably has a linear expansion coefficient of 200 ppm / ° C. or less, more preferably 150 ppm / ° C. or less. When the linear expansion coefficient is 200 ppm / ° C. or less, the cured product is less likely to warp and tends to have excellent long-term reliability. The coefficient of linear expansion generally shows values different from each other at a temperature below the softening point and at a temperature above the softening point, but it is preferably 200 ppm / ° C. or less at both temperatures, more preferably 150 ppm / ° C. or less. preferable. In addition, in this specification, a linear expansion coefficient means the numerical value measured by the thermomechanical analysis (TMA) measuring method according to JISK7197.

Light reflecting material (light reflecting material for white light emitting diode)
The white thermosetting silicone resin composition of the present invention can be used for a light reflecting material. Although the use of this light reflection material is not specifically limited, For example, it can use suitably as light reflection materials for light-emitting devices, such as LED, especially white LED. A light emitting device such as a white LED using this light reflecting material can maintain high light extraction efficiency over a long period of time. Moreover, since the composition of this invention is easy to shape | mold, in these light-emitting devices containing white LED, it is easy to make a light reflection material into a desired shape.

  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 23 ° C. measured using a spiral viscometer (Malcom Co., Ltd., model: PC-1T) which is a rotational viscometer.

および、
（３）ｐ−フェニレン基を３個有する化合物：約４モル％（下記に代表的な構造式の一例を示す）

の混合物であることが判明した。また、前記混合物全体（１００ｇ中）としての付加反応性炭素−炭素二重結合（ＮＢ基）の含有割合は、０．３２モル／１００ｇであった。 (Synthesis Example 1) Preparation of Component (A) Into a 500 mL 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-vinylbicyclo (2.2.1) Hemo-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene in an equimolar amount of isomer mixture) 60 g (0.5 mol) is added, Heated to 85 ° C. using an oil bath. To this, 0.02 g of carbon powder supporting 5% by mass of platinum metal was added, and 38.8 g (0.2 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 25 minutes while stirring. After completion of dropping, the mixture was further stirred at 90 ° C. for 24 hours, and then cooled to room temperature. Thereafter, platinum metal-supported carbon was removed by filtration, and excess vinylnorbornene was distilled off under reduced pressure to obtain 79 g of a colorless and transparent oily reaction product (kinematic viscosity at 25 ° C .: 1220 mm ² / s).
As a result of analyzing the reaction product by FT-IR, NMR, GPC and the like,
(1) p-phenylene group one compound _{having: NBMe 2 Si-p-C} 6 H 4 -SiMe 2 NB about 72 mole%,
(2) Compound having two p-phenylene groups: about 24 mol% (an example of a typical structural formula is shown below),

and,
(3) Compound having three p-phenylene groups: about 4 mol% (an example of a typical structural formula is shown below)

It was found to be a mixture of Moreover, the content rate of the addition reactive carbon-carbon double bond (NB group) as the whole mixture (in 100 g) was 0.32 mol / 100 g.

で表される化合物と下記式

で表される化合物の混合物（付加反応性炭素―炭素二重結合含有量：０．４８５モル／１００ｇ）、
（Ｇ）下記式：

で表される化合物、および
（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）
を表１に示す配合量（単位：質量部）で配合し、実施例１〜４、比較例１、２のおのおのの組成物を得た。即ち、まず、５リットルゲートーミキサー（井上製作所（株）製、商品名：５リットルプラネタリミキサー）に（Ａ）成分、（Ｄ）成分、（Ｅ）成分および（Ｈ）成分を表１に示す配合量で仕込み、室温にて１時間混合し、次に（Ｂ）成分、必要に応じて（Ｆ）成分および（Ｇ）成分を表１に示す配合量で加えて均一になるように室温にて３０分混合し、最後に（Ｃ）成分を表１に示す配合量で加えて均一になるように室温にて減圧下３０分混合して白色熱硬化性シリコーン組成物を得た。得られた組成物の粘度を測定した。金型離型性の評価は１００ｍｍ×１００ｍｍ×２ｍｍ金型枠に白色熱硬化性シリコーン組成物を流し込み、１５０℃、１００ＭＰａで５分間加圧硬化させ、プレス型や金型枠から成型物を剥がす時に破損しない連続脱型回数を観察した。結果を下記表１に示す。 (Examples 1-4, Comparative Examples 1-2)
Metal releasability evaluation (A) Reaction product obtained in Synthesis Example 1
(B-2) HMe ₂ SiO (Ph ₂ SiO) ₂ SiMe ₂ H,
(B-1 (i)) Me ₃ SiO (HMeSiO) ₈ SiMe ₃ ,
(B-1 (ii)) HMe ₂ SiO (HMeSiO) ₂ (Ph ₂ SiO) ₂ SiMe ₂ H,
(C) 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 and produced by the chlorine method and having a crystal form of rutile,
(E) spherical fused silica glass powder having an average particle size of 10.1 μm,
(F) The following formula:

And the following formula

A mixture of compounds represented by (addition reactive carbon-carbon double bond content: 0.485 mol / 100 g),
(G) The following formula:

(H) 50% by mass toluene solution of 1-ethynyl-1-cyclohexanol (addition reaction control agent)
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 and 2 were obtained. That is, first, (A) component, (D) component, (E) component, and (H) component are shown in Table 1 in a 5-liter gate mixer (product name: 5-liter planetary mixer manufactured by Inoue Seisakusho Co., Ltd.). Charge the mixture at room temperature and mix for 1 hour at room temperature. Finally, the 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 thermosetting silicone composition. The viscosity of the obtained composition was measured. Evaluation of mold releasability is carried out by pouring a white thermosetting silicone composition into a 100 mm × 100 mm × 2 mm mold frame, press-curing at 150 ° C. and 100 MPa for 5 minutes, and peeling the molded product from the press mold or mold frame. The number of times of continuous demolding that sometimes did not break was observed. The results are shown in Table 1 below.

Next, each composition of Examples 1 to 4 and Comparative Examples 1 to 2 was poured into a mold frame of 100 mm × 100 mm × 2 mm, and cured by pressure at 150 ° C. and 100 MPa for 5 minutes, and then 150 ° C. and normal pressure. Was cured in an oven for 3 hours to obtain 2 mm thick cured products (R1 to R6, 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.

Softening point / linear expansion coefficient / light reflectance evaluation / softening point / linear expansion coefficient: The temperature was increased from room temperature at a rate of 10 ° C./min using a thermomechanical analyzer TMA / SDTA841 manufactured by Mettler.

^ａ） α_１：軟化点未満の温度における線膨張係数
α_２：軟化点を超える温度における線膨張係数 -Light reflectance: It measured at 25 degreeC in the wavelength range of 430-800 nm using Hitachi Ltd. spectrophotometer apparatus U-3310 carrying an integrating sphere.

^a) α ₁ : Linear expansion coefficient at a temperature below the softening point α ₂ : Linear expansion coefficient at a temperature above the softening point

Evaluation of heat resistance Next, the cured products R1 to R6 and a representative polyamide resin-based reflector A (Amodel A-4422HR manufactured by Solvay Advanced Polymers), B (Gensta TA112 manufactured by Kuraray Co., Ltd.) and C (DSM Japan) Engineering Plastics Stanyl NC155a) was allowed to stand at 150 ° C. for 2,000 hours for 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, the cured products R1 to R6 were kept white before and after the test, but the polyamide resin-based light reflecting materials A to C were initially white, but changed to brown after the test. Was.

  From the above results (Tables 1 to 3), the white thermosetting silicone composition of the present invention has high fluidity at room temperature, and the cured product (R1 to R4) is excellent in initial light reflectance, It shows excellent heat resistance, particularly heat discoloration after thermosetting. Moreover, it has shown that the white curable silicone composition of this invention was excellent in productivity because the frequency | count of continuous demolding improved. On the other hand, the hardened | cured material (R5, R6) of the composition which does not use (B-1) component and (B-2) component together in this invention had bad metal mold release property. As described above, the cured product of the white thermosetting silicone composition of the present invention is useful as a light reflecting material, particularly a white LED light reflecting material.

  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. It is contained in the technical range.

Claims (13)

(A) (a) The following general formula (1):

(In the formula, A represents the following general formula (2):

And R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or alkoxy having 1 to 6 carbon atoms. It is a group. A compound having two hydrogen atoms bonded to a silicon atom represented by
(B) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the addition-reactive carbon-carbon double bond in one molecule An addition reaction product having at least two
(B) An organosilicon compound (B-1) having three or more hydrogen atoms bonded to a silicon atom in one molecule, and an organosilicon compound (B-1) having two hydrogen atoms bonded to a silicon atom in one molecule -2) (the total amount of hydrogen atoms bonded to silicon atoms in the component (B-1) and the component (B-2) is the addition-reactive carbon-carbon 2 in the component (A)). The amount is 1.0 to 1.5 in terms of molar ratio with respect to the heavy bond, and the total amount of hydrogen atoms bonded to silicon atoms in the component (B-1) and the component (B-2). Is an amount of 1.1 to 6.5 with respect to the amount of hydrogen atoms bonded to the silicon atom in the component (B-2)),
(C) Hydrosilylation reaction catalyst, and (D) White thermosetting silicone composition characterized by containing titanium oxide powder whose crystal form is rutile.   2. The white thermosetting silicone composition according to claim 1, wherein the white thermosetting silicone composition is used for a light reflecting material molded by an injection molding method, a transfer molding method, or a compression molding method. The white thermosetting silicone composition according to claim 1 or 2, wherein the component (b) is an alkenyl norbornene compound represented by the following general formula (3).

(In the formula, R ′ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)   The component (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 white thermosetting silicone composition according to any one of claims 1 to 3, wherein the composition is a white thermosetting silicone composition. The component (B) is represented by the following general formula (4):

(Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, q is an integer of 2 to 10, and r is 0 to 7) (The siloxane unit with q and the siloxane unit with r are randomly arranged with respect to each other.)
5. The white thermosetting silicone composition according to claim 1, wherein the white thermosetting silicone composition comprises a cyclic siloxane compound represented by the formula:   The cyclic siloxane compound is any one of 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, and combinations thereof. The white thermosetting silicone composition according to claim 5, wherein The component (B) is represented by the following general formula (5):

(Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, q ′ is an integer of 3 to 10, and r is 0 to 7) R ″ is an alkylene group having 2 to 12 carbon atoms, n is an integer of 1 to 100. q1 and q2 are each an integer of 0 to 8, provided that q1 + q2 is an integer of 1 to 8. (R1 and r2 are each an integer of 0 to 7, provided that r1 + r2 is an integer of 0 to 7.)
5. The white thermosetting silicone composition according to claim 1, comprising a norbornane ring-containing cyclic siloxane compound represented by the formula:   The norbornane ring-containing cyclic siloxane compound 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 an addition reaction product of any one of 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane and combinations thereof. The white thermosetting silicone composition according to claim 7. The component (B) is represented by the following general formula (6):

(In the formula, R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, Me represents a methyl group, and q3 represents an integer of 0 to 60. R3 is an integer of 0 to 7. The siloxane unit to which q3 is attached and the siloxane unit to which r3 is attached are randomly arranged.
The white thermosetting silicone composition according to claim 1, comprising a siloxane compound represented by the formula:   The white thermosetting silicone composition according to any one of claims 1 to 9, wherein the component (D) is obtained by a chlorine method.   The white thermosetting silicone composition according to claim 1, further comprising (E) fused quartz glass powder.   The cured product obtained by curing the white thermosetting silicone composition has an initial light reflectance of 95% or more at a wavelength of 430 to 800 nm, and a light reflectance of 80% or more after being left at 150 ° C. for 2,000 hours. The white thermosetting silicone composition according to any one of claims 1 to 11, wherein the composition is a white thermosetting silicone composition.   The light reflection material for white light emitting diodes which consists of hardened | cured material of the white thermosetting silicone composition of any one of Claims 1 thru | or 12.