JP2018184579A - Addition curable type silicone composition, method for producing the same, silicone cured product, and optical element - Google Patents

Abstract

The present invention provides an addition-curable silicone composition containing a phenyl group, which is capable of providing a cured product having a small weight change at a high temperature, a small discoloration, and excellent heat resistance. (A-1) a branched organopolysiloxane; (A-2) a linear organopolysiloxane having an unsaturated group and an aromatic ring; (B) at least two silicon atom bonds in one molecule. An organohydrogenpolysiloxane having a hydrogen atom, (C) containing a Si-O-Ce bond and a Si-O-Ti bond, and having a Ce content of 50 to 5,000 ppm and a Ti content of 50 to 5,000 ppm. A polyorganometallosiloxane having a viscosity of 10 to 10,000 mPa · s at 25 ° C. and having at least 10 mol% or more of an aryl group based on the total number of organic groups contained in one molecule, and (D) An addition-curable silicone composition comprising a hydrosilylation catalyst containing a platinum group metal. [Selection diagram] None

Description

  The present invention relates to an addition-curable silicone composition, a method for producing the composition, a cured silicone product, and an optical element sealed with the cured product.

  An LED lamp having a light emitting diode (LED) as an optical semiconductor element and known as an optical semiconductor device has a configuration in which an LED mounted on a substrate is sealed with a sealing material made of a transparent resin. As a sealing material for sealing this LED, an epoxy resin-based composition has been widely used.

  However, in epoxy resin-based sealing materials, cracks and yellowing occur due to the recent reduction in size of semiconductor packages, the increase in the amount of heat generated with the increase in brightness of LEDs, and the shortening of light wavelengths, resulting in reduced reliability. Was invited.

  Therefore, a silicone resin composition is used as a sealing material from the viewpoint of having excellent heat resistance. In particular, the addition reaction curable silicone resin composition is cured in a short time by heating and thus has good productivity and is suitable as an LED sealing material (Patent Document 1). In addition, the LED encapsulating material is required to have a high refractive index and strength, but a composition using phenylsiloxane as the main skeleton can give a higher refractive index than conventional silicone (Patent Document). 2, Patent Document 3). In addition, the sealing material having such a phenyl group has high sulfidation resistance, can suppress corrosion of the silver substrate of the LED due to hydrogen sulfide, and provides a highly reliable LED package. It is known.

  However, such a composition containing a phenyl group is yellowed at a high temperature and the light transmittance is lowered, so that the brightness of the LED is lowered. Since the temperature of the sealing material has increased with the recent increase in the output of the LED, the heat discoloration resistance of phenyl silicone for this problem is still insufficient. In addition, cracks are generated due to the weight loss of the silicone resin, resulting in non-lighting, and there is a further demand for a material having a low weight loss rate at high temperatures and low transmittance deterioration, that is, a high heat resistance. .

JP 2004-292714 A JP 2005-105217 A JP 2010-132895 A

  The present invention has been made in view of the above circumstances, and is a silicone composition containing a phenyl group, in order to improve the reliability of the LED, the change in weight at a high temperature is small, in particular, there is little discoloration. An object of the present invention is to provide an addition-curable silicone composition capable of giving a cured product having excellent heat resistance.

（式中、Ｒ^１’は同一又は異なっていてもよい、アルケニル基を含まない置換又は非置換の一価炭化水素基であり、Ｒ^３はメチル基又はフェニル基であり、ｈは０〜５０の数であり、ｉは０〜１００の数である。但し、ｈが０の時、Ｒ^３はフェニル基であり、かつ、ｉは１〜１００の数である。ｈが付された括弧内にあるシロキサン単位及びｉが付された括弧内にあるシロキサン単位は、互いにランダムに配列していても、ブロックで配列していてもよい。）
（Ｂ）１分子中に少なくとも２個以上のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサン：前記（Ａ−１）成分及び（Ａ−２）成分中のケイ素原子結合アルケニル基１個に対して前記（Ｂ）成分中のケイ素原子結合水素原子の数が、０．１〜５．０個となる量、
（Ｃ）Ｓｉ−Ｏ−Ｃｅ結合及びＳｉ−Ｏ−Ｔｉ結合を含有し、Ｃｅ含有量が５０〜５，０００ｐｐｍ、Ｔｉ含有量が５０〜５，０００ｐｐｍであり、２５℃における粘度が１０〜１０，０００ｍＰａ・ｓであり、一分子中に含まれる有機基の全数に対して少なくとも１０モル％以上のアリール基を有するポリオルガノメタロシロキサン：前記（Ａ−１）成分、（Ａ−２）成分、及び（Ｂ）成分の合計１００質量部に対して０．０１〜２０質量部、及び、
（Ｄ）白金族金属を含むヒドロシリル化触媒、
を含むものである付加硬化型シリコーン組成物を提供する。 In order to solve the above problems, in the present invention,
(A-1) a branched organopolysiloxane represented by the following average composition formula (1):
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g (1)
(In the formula, each R ¹ may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, and at least 10 mol% of all R ¹ is an aryl group; ² is an alkenyl group, a, b, c, d, e, f, and g are a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0, and g, respectively. It is a number satisfying ≧ 0, provided that b + c + e> 0, e + f + g> 0, and a + b + c + d + e + f + g = 1.)
(A-2) Linear organopolysiloxane represented by the following formula (2): 10 to 40 parts by mass with respect to 100 parts by mass in total of the component (A-1) and the component (A-2),

(In the formula, R ^{1 ′} may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, R ³ is a methyl group or a phenyl group, and h is 0-50. I is a number from 0 to 100, provided that when h is 0, R ³ is a phenyl group and i is a number from 1 to 100. In parentheses marked with h (The siloxane units in the brackets and the siloxane units in parentheses to which i is attached may be arranged randomly or in blocks.)
(B) Organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule: for one silicon-bonded alkenyl group in the components (A-1) and (A-2) The amount of silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5.0,
(C) Si—O—Ce bond and Si—O—Ti bond are contained, Ce content is 50 to 5,000 ppm, Ti content is 50 to 5,000 ppm, and viscosity at 25 ° C. is 10 to 10 Polyorganometallosiloxane having an aryl group of at least 10 mol% based on the total number of organic groups contained in one molecule: (A-1) component, (A-2) component, And (B) 0.01 to 20 parts by mass with respect to 100 parts by mass in total, and
(D) a hydrosilylation catalyst containing a platinum group metal,
An addition-curable silicone composition is provided.

  With such an addition-curable silicone composition, a weight change at high temperatures is small, and in particular, a cured product with little discoloration and excellent heat resistance can be provided.

Moreover, it is preferable that R ¹ in the formula (1) and R ^{1 ′} in the formula (2) are a phenyl group or a methyl group.

  If it is such, it can use suitably as (A-1) and (A-2) component.

Furthermore, the present invention is a method for producing the above addition-curable silicone composition,
The following (a), (b) and (c) components are reacted at a temperature of 150 ° C. or higher to produce the (C) component polyorganometallosiloxane,
(A) Polyorganosiloxane having a viscosity of 10 to 10,000 mPa · s at 25 ° C. and having at least 10 mol% of aryl groups based on the total number of organic groups contained in one molecule: 100 parts by mass
(B) a rare earth element carboxylate represented by the following general formula (3): an amount of 0.05 to 5 parts by mass in terms of cerium in terms of 100 parts by mass of the component (a),
(R ⁴ COO) _j M ¹ (3)
(In the formula, R ⁴ is the same or different monovalent hydrocarbon group, M ¹ is cerium or a rare earth element containing cerium, and j is an integer of 3 to 4.)
(C) One or both of the titanium compound represented by the following general formula (4) and its hydrolysis condensate: 0.05 to 5 parts by mass in terms of mass of titanium with respect to 100 parts by mass of the component (a) The amount,
(R ⁴ O) ₄ M ² (4)
(Wherein R ⁴ is the same or different monovalent hydrocarbon group and M ² is titanium),
And a step of mixing the components (A-1), (A-2), (B), (C), and (D), and a method for producing an addition-curable silicone composition.

  With such a production method, a polyorganometallosiloxane having a predetermined Ce content and Ti content (that is, the component (C)) can be easily synthesized. The composition can be easily produced.

  Furthermore, this invention provides the silicone hardened | cured material which is a hardened | cured material of the said addition curable silicone composition.

  Such a cured silicone product is highly transparent, has a high refractive index, and is excellent in heat resistance at high temperatures.

  Furthermore, the present invention provides an optical element that is sealed with the cured silicone.

  The cured silicone of the present invention is highly transparent, has a high refractive index, and is excellent in heat resistance at high temperatures. Therefore, the optical element sealed with such a silicone cured product is highly reliable.

  As described above, the addition-curable silicone composition of the present invention is highly transparent, has a higher refractive index than dimethylpolysiloxane, has a small weight change at high temperatures, and has particularly little discoloration. A cured product having excellent heat resistance can be provided. Accordingly, a cured product obtained from such an addition-curable silicone composition can be suitably used for an optical element sealing material.

  As described above, development of an addition-curable silicone composition containing a phenyl group, which has a small weight change at high temperatures, and can give a cured product with particularly low discoloration and excellent heat resistance. Was demanded.

  As a result of intensive studies on the above problems, the present inventors have found that the addition-curable silicone composition containing the components (A-1), (A-2), and (B) to (D) described later is a phenyl group. It is found that the above-mentioned problems can be achieved by improving the heat resistance by including a specific silicone resin containing a polyorganometallosiloxane containing a Si—O—Ce bond and a Si—O—Ti bond. Was completed.

（式中、Ｒ^１’は同一又は異なっていてもよい、アルケニル基を含まない置換又は非置換の一価炭化水素基であり、Ｒ^３はメチル基又はフェニル基であり、ｈは０〜５０の数であり、ｉは０〜１００の数である。但し、ｈが０の時、Ｒ^３はフェニル基であり、かつ、ｉは１〜１００の数である。ｈが付された括弧内にあるシロキサン単位及びｉが付された括弧内にあるシロキサン単位は、互いにランダムに配列していても、ブロックで配列していてもよい。）
（Ｂ）１分子中に少なくとも２個以上のケイ素原子結合水素原子を有するオルガノハイドロジェンポリシロキサン：前記（Ａ−１）成分及び（Ａ−２）成分中のケイ素原子結合アルケニル基１個に対して前記（Ｂ）成分中のケイ素原子結合水素原子の数が、０．１〜５．０個となる量、
（Ｃ）Ｓｉ−Ｏ−Ｃｅ結合及びＳｉ−Ｏ−Ｔｉ結合を含有し、Ｃｅ含有量が５０〜５，０００ｐｐｍ、Ｔｉ含有量が５０〜５，０００ｐｐｍであり、２５℃における粘度が１０〜１０，０００ｍＰａ・ｓであり、一分子中に含まれる有機基の全数に対して少なくとも１０モル％以上のアリール基を有するポリオルガノメタロシロキサン：前記（Ａ−１）成分、（Ａ−２）成分、及び（Ｂ）成分の合計１００質量部に対して０．０１〜２０質量部、及び、
（Ｄ）白金族金属を含むヒドロシリル化触媒、
を含む付加硬化型シリコーン組成物である。 That is, the present invention
(A-1) a branched organopolysiloxane represented by the following average composition formula (1):
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g (1)
(In the formula, each R ¹ may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, and at least 10 mol% of all R ¹ is an aryl group; ² is an alkenyl group, a, b, c, d, e, f, and g are a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0, and g, respectively. It is a number satisfying ≧ 0, provided that b + c + e> 0, e + f + g> 0, and a + b + c + d + e + f + g = 1.)
(A-2) Linear organopolysiloxane represented by the following formula (2): 10 to 40 parts by mass with respect to 100 parts by mass in total of the component (A-1) and the component (A-2),

(In the formula, R ^{1 ′} may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, R ³ is a methyl group or a phenyl group, and h is 0-50. I is a number from 0 to 100, provided that when h is 0, R ³ is a phenyl group and i is a number from 1 to 100. In parentheses marked with h (The siloxane units in the brackets and the siloxane units in parentheses to which i is attached may be arranged randomly or in blocks.)
(B) Organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule: for one silicon-bonded alkenyl group in the components (A-1) and (A-2) The amount of silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5.0,
(C) Si—O—Ce bond and Si—O—Ti bond are contained, Ce content is 50 to 5,000 ppm, Ti content is 50 to 5,000 ppm, and viscosity at 25 ° C. is 10 to 10 Polyorganometallosiloxane having an aryl group of at least 10 mol% based on the total number of organic groups contained in one molecule: (A-1) component, (A-2) component, And (B) 0.01 to 20 parts by mass with respect to 100 parts by mass in total, and
(D) a hydrosilylation catalyst containing a platinum group metal,
Is an addition-curable silicone composition.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[Addition-curing silicone composition]
The addition-curable silicone composition of the present invention comprises the following components (A-1), (A-2), and (B) to (D). Hereinafter, each component will be described in detail.

<(A-1) component>
The component (A-1) in the addition-curable silicone composition of the present invention is a branched organopolysiloxane represented by the following average composition formula (1).
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g (1)
(In the formula, each R ¹ may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, and at least 10 mol% of all R ¹ is an aryl group; ² is an alkenyl group, a, b, c, d, e, f, and g are a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0, and g, respectively. It is a number satisfying ≧ 0, provided that b + c + e> 0, e + f + g> 0, and a + b + c + d + e + f + g = 1.)

The component (A-1) is a component necessary for obtaining the reinforcing property of the silicone composition and has a branched structure. The component (A-1) is composed of SiO _4/2 units and / or SiO _3/2 units (that is, SiO _4/2 units, R ² SiO _3/2 units _, and / or R ¹ SiO _3/2 units). Although a branched structure as essential, furthermore methyl vinyl siloxy units, SiO _2/2 units such as dimethylsiloxy units, dimethylvinylsiloxy units may include SiO _1/2 units, such as trimethylsiloxy units. The content of SiO _4/2 units and / or SiO _3/2 units is preferably 5 mol% or more of all siloxane units in the organopolysiloxane resin of component (A-1), more preferably 10 mol to 95 mol. %, Particularly preferably 20 to 60 mol%.

  The component (A-1) is preferably a waxy or solid three-dimensional network organopolysiloxane resin at 23 ° C. The term “wax” means that it is a gum (raw rubber) having a self-fluidity of 10,000 Pa · s or more, particularly 100,000 Pa · s or more, at 23 ° C.

In the average composition formula (1), at least 10 mol%, preferably 20 mol% or more of all R ¹ are aryl groups. Due to the presence of the aryl group, the refractive index can be improved, the light extraction efficiency in the LED package can be improved, and the sulfur resistance for suppressing the blackening of the silver substrate can be imparted. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, and a phenyl group is particularly preferable.

In R ¹ , a group other than an aryl group is not particularly limited as long as it is a substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group. For example, a methyl group, an ethyl group, a propyl group, a butyl group, Alkyl groups such as pentyl group, hexyl group and heptyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group In general, an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 12, preferably 1 to 10, and more preferably 1 to 8 carbon atoms is used. A methyl group is particularly preferable.

R ² is an alkenyl group, preferably an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, an allyl group or an ethynyl group, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group.

Specific examples of the component (A-1) include the following branched organopolysiloxanes.
(CH ₂ = CH (CH ₃ ) (C ₆ H ₅ ) SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) _3.8 (SiO ₂ ) _4.3
((CH ₃ ) ₃ SiO _1/2 ) _2.5 (CH ₂ ═CH (CH ₃ ) ₂ SiO _1/2 ) _1.2 ((C ₆ H ₅ ) ₂ SiO) _1.3 (SiO ₂ ) _{5 .0}

  The component (A-1) may be used alone or in combination of two or more.

（式中、Ｒ^１’は同一又は異なっていてもよい、アルケニル基を含まない置換又は非置換の一価炭化水素基であり、Ｒ^３はメチル基又はフェニル基であり、ｈは０〜５０の数であり、ｉは０〜１００の数である。但し、ｈが０の時、Ｒ^３はフェニル基であり、かつ、ｉは１〜１００の数である。ｈが付された括弧内にあるシロキサン単位及びｉが付された括弧内にあるシロキサン単位は、互いにランダムに配列していても、ブロックで配列していてもよい。） <(A-2) component>
The component (A-2) is a linear organopolysiloxane represented by the following formula (2).

(In the formula, R ^{1 ′} may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, R ³ is a methyl group or a phenyl group, and h is 0-50. I is a number from 0 to 100, provided that when h is 0, R ³ is a phenyl group and i is a number from 1 to 100. In parentheses marked with h (The siloxane units in the brackets and the siloxane units in parentheses to which i is attached may be arranged randomly or in blocks.)

  The component (A-2) is a component having two vinyl groups in one molecule and causing stress relaxation after the composition is cured. Usually, the main chain is composed of repeating diorganosiloxane units, It is an organopolysiloxane having a linear molecular structure that is blocked with a triorganosiloxy group containing a vinyl group at the end.

In the component (A-2), examples of R ^{1 ′} in formula (2) include the same as those exemplified as R ^{1 in the} component (A-1).

In formula (2), h is a number from 0 to 50, i is a number from 0 to 100, preferably h is a number from 3 to 20, and i is a number from 0 to 30. When h is 0, R ³ is a phenyl group, and i is a number from 1 to 100. If h and i are out of the above ranges, the sulfur resistance and light extraction efficiency of the optical element sealed with the cured product of the composition of the present invention may be lowered.

  The viscosity of the component (A-2) at 25 ° C. is preferably in the range of 10 to 100,000 mPa · s, more preferably 10 to 10,000 mPa · s. If the viscosity is within this range, there is no fear that this component will function as a soft segment more than necessary, and sufficient hardness can be obtained. Moreover, there is no fear that the viscosity of the composition becomes extremely high and the workability is poor.

  Specific examples of the component (A-2) include: both-end methylphenylvinyl group-capped diphenylsiloxane, one-end methylphenylvinyl group-one-end diphenylvinyl group-capped diphenylsiloxane, both-end diphenylvinyl-group-capped diphenylsiloxane, both-end diphenylvinyl Blocked diphenylsiloxane / methylphenylsiloxane copolymer, dimethylvinyl-blocked diphenylsiloxane at both ends, dimethylvinyl-blocked at one end, methylphenylvinyl-blocked diphenylsiloxane at both ends, dimethylvinyl-blocked methylphenylsiloxane at both ends, dimethylvinyl at one end Examples include a group-terminal terminal methylphenylvinyl group-capped methylphenylsiloxane.

More specifically, examples of the component (A-2) include the following linear organopolysiloxane.
(CH ₂ = CH (CH ₃ ) (C ₆ H ₅ ) SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) ₃
(CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) ₁₅ ((CH ₃ ) ₂ SiO) ₆₅

  The component (A-2) may be used alone or in combination of two or more.

  (A-2) The compounding quantity of a component is 10-40 mass parts with respect to a total of 100 mass parts of (A-1) component and (A-2) component, Preferably it is 30-40 mass parts.

<(B) component>
Component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule.

  (B) There is no restriction | limiting in particular in the molecular structure of a component, For example, various organohydrogen polysiloxane manufactured conventionally, such as linear, cyclic, branched, and three-dimensional network structure, can be used. . Further, the component (B) may be liquid at room temperature (25 ° C.), waxy or solid.

  The component (B) preferably has at least one aryl group from the viewpoint of compatibility with the components (A-1) and (A-2). As an aryl group, the thing similar to what was illustrated by (A-1) component is mentioned.

  The organohydrogenpolysiloxane of component (B) is at least 2, preferably 3 to 300, particularly preferably 3 to 100 silicon atom-bonded hydrogen atoms in one molecule (that is, hydrosilyl group (SiH group)). Have When the organohydrogenpolysiloxane of the component (B) has a linear structure, these SiH groups may be located only at either the molecular chain end or the molecular chain middle (molecular chain non-terminal) It may be located in both of them.

  The number (degree of polymerization) of silicon atoms in one molecule of component (B) is preferably 2 to 300, more preferably 3 to 200, and still more preferably 4 to 150.

As the component (B), for example, an organohydrogenpolysiloxane represented by the following average composition formula (5) can be used.
R ⁵ _l H _k SiO _{(4-1k) / 2} (5)
Wherein R ⁵ is a monovalent hydrocarbon group bonded to a substituted or unsubstituted silicon atom which does not contain an alkenyl group and may be the same or different, and l and k are 0.7 ≦ l ≦ 2 0.1, 0.001 ≦ k ≦ 1.0, and a positive number satisfying 0.8 ≦ l + k ≦ 3.0.)

In the average composition formula (5), the carbon number of the monovalent hydrocarbon group of R ⁵ is preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 8, and as a specific example of R ⁵ include the same ones as exemplified as R ^{1 'for R 1} or (a-2) component in the component (a-1).

Specific examples of the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, tris ( (Hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-capped methylhydrogenpolysiloxane at both ends, trimethylsiloxy group-capped dimethylsiloxane / methylhydro at both ends Disiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane di, both ends dimethylhigh Dioxysiloxane group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer blocked at both ends, trimethylsiloxy-blocked methylhydrogensiloxane / diphenylsiloxane copolymer at both ends, trimethylsiloxy-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane at both ends Polymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydro Gensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / methylphenylsiloxane copolymer, (CH ₃ ) _A copolymer comprising ₂ HSiO _1/2 units, (CH ₃ ) ₃ SiO _1/2 units and SiO _4/2 units, and a copolymer comprising (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units. Examples thereof include a polymer, a copolymer composed of (CH ₃ ) ₂ HSiO _1/2 units, SiO _4/2 units, and (C ₆ H ₅ ) ₃ SiO _1/2 units.

More specifically, examples of the component (B) include organohydrogenpolysiloxanes described below.
(H (CH ₃ ) (C ₆ H ₅ ) SiO _1/2 ) ₃ ((C ₆ H ₅ ) SiO _3/2 ) ₁
((CH ₃ ) ₃ SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) ₂ (H (CH ₃ ) SiO) ₆

  The (B) component organohydrogenpolysiloxane may be used alone or in combination of two or more.

  The blending amount of component (B) is such that the number of silicon atom-bonded hydrogen atoms in component (B) is 0 with respect to one silicon atom-bonded alkenyl group in component (A-1) and component (A-2). 0.1 to 5.0, preferably 0.5 to 3.0, and more preferably 0.5 to 2.0. If it is outside this range, high strength cannot be imparted to the silicone cured product, and it cannot be suitably used as a sealing material.

<(C) component>
The component (C) contains a Si—O—Ce bond and a Si—O—Ti bond, has a Ce content of 50 to 5,000 ppm, a Ti content of 50 to 5,000 ppm, and a viscosity at 25 ° C. The polyorganometallosiloxane is 10 to 10,000 mPa · s, and has at least 10 mol% of aryl groups based on the total number of organic groups contained in one molecule.

  Component (C) is an additive for imparting heat resistance to the resulting silicone composition. (C) The compounding quantity of a component is 0.01-20 mass parts with respect to a total of 100 mass parts of (A-1) component, (A-2) component, and (B) component, Preferably it is 0.1. -10 parts by mass, more preferably 0.5-5 parts by mass. When the compounding amount of the component (C) exceeds the above range, the resulting silicone composition may be colored or the hardness of the cured product may be reduced. Moreover, when the compounding quantity of (C) component is less than the said range, sufficient heat-resistant discoloration property will not be obtained.

  The component (C) contains 10 mol% or more of aryl groups in one molecule from the viewpoint of compatibility with the components (A) and (B). When the aryl group content is less than 10 mol%, a highly transparent composition cannot be obtained. As an example of this aryl group, the thing similar to what was illustrated in the said (A-1) component is mentioned.

The component (C) is preferably a reaction product obtained by heat-treating the following components (a), (b) and (c) at a temperature of 150 ° C. or higher.
(A) Polyorganosiloxane having a viscosity of 10 to 10,000 mPa · s at 25 ° C. and having at least 10 mol% of aryl groups based on the total number of organic groups contained in one molecule: 100 parts by mass
(B) a rare earth element carboxylate represented by the following general formula (3): (a) an amount of 0.05 to 5 parts by mass in terms of the mass of cerium with respect to 100 parts by mass of the component,
(R ⁴ COO) _j M ¹ (3)
(In the formula, R ⁴ is the same or different monovalent hydrocarbon group, M ¹ is cerium or a rare earth element containing cerium, and j is an integer of 3 to 4.)
(C) One or both of the titanium compound represented by the following general formula (4) and its hydrolysis condensate: (a) 0.05 to 5 parts by mass in terms of mass of titanium with respect to 100 parts by mass of the component The amount of
(R ⁴ O) ₄ M ² (4)
(In the formula, R ⁴ is the same or different monovalent hydrocarbon group, and M ² is titanium.)

  The polyorganosiloxane (a) has a viscosity of 10 to 10,000 mPa · s at 25 ° C. and has at least 10 mol% of aryl groups with respect to the total number of organic groups contained in one molecule. Any known one can be used.

  Examples of the carboxylate of the rare earth element (b) include cerium salts such as 2-ethylhexanoic acid, naphthenic acid, oleic acid, lauric acid, and stearic acid.

  Examples of the titanium compound as the component (c) include tetraalkoxytitanium such as tetra n-butyl titanate and its hydrolysis condensate.

<(D) component>
The hydrosilylation catalyst containing the platinum group metal of component (D) promotes the addition reaction between the alkenyl group in components (A-1) and (A-2) and the silicon atom-bonded hydrogen atom in component (B). Any catalyst can be used. Specific examples thereof include platinum group metals such as platinum, palladium and rhodium, chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid and olefins, vinyl siloxane or acetylene compounds, tetrakis (triphenylphosphine). ) Platinum group metal compounds such as palladium and chlorotris (triphenylphosphine) rhodium are exemplified, and platinum compounds are particularly preferred.

  (D) A component may be used individually by 1 type, or may use 2 or more types together.

  (D) The compounding quantity of a component is an effective amount as a catalyst, and it converts into a catalytic metal element with respect to the total amount of (A-1) component, (A-2) component, and (B) component. It is preferably in the range of 1 to 500 ppm, more preferably in the range of 1 to 100 ppm on a mass basis. If it is in the said range, the reaction rate of addition reaction will become appropriate, and the hardened | cured material which has high intensity | strength can be obtained.

<Other ingredients>
Components such as an adhesion improver and a reaction inhibitor may be added to the addition-curable silicone composition of the present invention depending on the purpose.

  As an adhesion improver, from the viewpoint of imparting self-adhesiveness to the composition of the present invention that is an addition reaction curable type, organosilicon compounds such as silane and siloxane containing a functional group imparting adhesiveness, non-silicone type Organic compounds and the like are used.

  Specific examples of the functional group imparting adhesiveness include vinyl groups bonded to silicon atoms, alkenyl groups such as allyl groups, or hydrogen atoms; epoxy groups bonded to silicon atoms via carbon atoms (for example, γ-glycid Alkoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, etc.), acryloxy group (eg, γ-acryloxypropyl group, etc.), or methacryloxy group (eg, γ-methacryloxypropyl group, etc.); alkoxysilyl Groups (for example, alkoxysilyl such as trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, etc. bonded to a silicon atom via an alkylene group which may contain 1 to 2 ester structures, urethane structures or ether structures) Group).

  Examples of the organosilicon compound containing a functional group that imparts adhesiveness include a silane coupling agent, a siloxane having an alkoxysilyl group and an organic functional group, a compound in which an alkoxysilyl group is introduced into an organic compound having a reactive organic group, etc. Is exemplified.

  Examples of non-silicone organic compounds include organic acid allyl esters, epoxy group ring-opening catalysts, organic titanium compounds, organic zirconium compounds, and organic aluminum compounds.

  Reaction inhibitors include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene-based compounds; hydroperoxy compounds; maleic acid derivatives; Such as cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, ethynylmethyldecylcarbinol, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, The well-known compound which has a hardening inhibitory effect with respect to the hydrosilylation catalyst of the said (D) component is illustrated.

  Since the degree of the curing inhibitory effect of the reaction inhibitor varies depending on the chemical structure of the reaction inhibitor, it is desirable to adjust the blending amount of the reaction inhibitor to an optimum amount for each reaction inhibitor used. Preferably, it is 0.001-5 mass parts with respect to 30 mass parts in total of (A-1) component, (A-2) component, (B) component, (C) component, and (D) component. If the amount is 0.001 part by mass or more, the long-term storage stability of the composition at room temperature can be sufficiently obtained. When the blending amount is 5 parts by mass or less, there is no fear that the curing of the composition is inhibited.

  In addition, in order to improve the reinforcing property, the composition of the present invention includes, for example, fine powder silica, crystalline silica, hollow filler, silsesquioxane and other inorganic fillers, and these fillers as organoalkoxysilanes. A compound, an organochlorosilane compound, an organosilazane compound, a filler hydrophobized with an organosilicon compound such as a low molecular weight siloxane compound, etc .; silicone rubber powder, silicone resin powder, etc. may be blended.

The fine powder silica preferably has a specific surface area (BET method) of 50 m ² / g or more, more preferably 50 to 400 m ² / g, particularly preferably 100 to 300 m ² / g. If the specific surface area is 50 m ² / g or more, sufficient reinforcement can be imparted to the cured product.

  As such fine powdered silica, known ones conventionally used as reinforcing fillers for silicone rubber can be used, for example, fumed silica (dry silica), precipitated silica (wet silica) and the like. Can be mentioned. Fine powder silica may be used as it is, but in order to give good fluidity to the composition, methylchlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane, dimethylpolysiloxane, hexamethyldisilazane, divinyl It is preferable to use those treated with an organosilicon compound such as hexaorganodisilazane such as tetramethyldisilazane and dimethyltetravinyldisilazane. Such reinforcing silica may be used alone or in combination of two or more.

[Method for producing addition-curable silicone composition]
Moreover, in this invention, the method of manufacturing the above-mentioned addition-curable silicone composition is provided.
In the addition-curable silicone composition of the present invention, the following components (a), (b) and (c) are reacted at a temperature of 150 ° C. or higher to produce a polyorganometallosiloxane of component (C), It can manufacture by mixing A-1), (A-2), (B), (C), and (D) component.
(A) Polyorganosiloxane having a viscosity of 10 to 10,000 mPa · s at 25 ° C. and having at least 10 mol% of aryl groups based on the total number of organic groups contained in one molecule: 100 parts by mass
(B) a rare earth element carboxylate represented by the following general formula (3): an amount of 0.05 to 5 parts by mass in terms of cerium in terms of 100 parts by mass of the component (a),
(R ⁴ COO) _j M ¹ (3)
(In the formula, R ⁴ is the same or different monovalent hydrocarbon group, M ¹ is cerium or a rare earth element containing cerium, and j is an integer of 3 to 4.)
(C) One or both of the titanium compound represented by the following general formula (4) and its hydrolysis condensate: 0.05 to 5 parts by mass in terms of mass of titanium with respect to 100 parts by mass of the component (a) The amount,
(R ⁴ O) ₄ M ² (4)
(In the formula, R ⁴ is the same or different monovalent hydrocarbon group, and M ² is titanium.)

  Examples of the components (a), (b) and (c) used as the raw material for the component (C) are as described above.

  With such a production method, a polyorganometallosiloxane having a predetermined Ce content and Ti content can be easily synthesized. Therefore, the addition-curable silicone composition of the present invention can be easily produced. it can.

[Silicone cured product]
Furthermore, the present invention provides a cured product (silicone cured product) obtained by curing the addition-curable silicone composition.

  As the curing method and conditions for the silicone resin composition of the present invention, known curing methods and conditions can be employed. As an example, it can be cured at 100 to 180 ° C. for 10 minutes to 5 hours.

  The refractive index of the silicone cured product at a wavelength of 589 nm is preferably 1.44 or more.

  The silicone cured product obtained by curing the addition-curable silicone composition of the present invention has a high refractive index, excellent heat resistance at high temperatures, and particularly high light transmittance. It can be used as a coating material and sealing material for semiconductor devices, and a protective coating material for electricity and electronics.

[Optical element]
Furthermore, the present invention provides an optical element that is sealed with the cured silicone.

  As described above, the cured silicone of the present invention is highly transparent, has a high refractive index, and is excellent in heat resistance at high temperatures. Therefore, the optical element sealed with such a silicone cured product is highly reliable.

  Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. In the following, the viscosity is a value at 25 ° C. measured using a rotational viscometer.

[Synthesis Example 1]
((CH ₃ ) ₃ SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) _3.9 ((CH ₃ ) ₂ SiO) Methylphenylorganopolysiloxane having a viscosity of 400 mPa · s represented by _8.6 130 parts by mass, terpene solution of 2-ethylhexanoate containing cerium as a main component (rare earth element content 6% by mass) 13 parts by mass (cerium content 0.55 parts) and tetra n-butyl titanate 2.7 A mixture in which mass parts (titanium mass is 0.3 times the mass of cerium in the 2-ethylhexanoate) was mixed in advance was added with stirring to obtain a yellowish white dispersion. While flowing a small amount of nitrogen gas, the turpentine was heated to flow out, and then heated at 300 ° C. for 1 hour. As a result, a homogeneous composition of polyorganometallosiloxane (C-1) that was dark yellowish brown and transparent was obtained. It was. When the obtained polyorganometallosiloxane was analyzed by ICP-OES (high frequency inductively coupled plasma emission spectroscopy), the Ce content was 3,200 ppm and the Ti content was 2,700 ppm. The viscosity of the polyorganometallosiloxane (C-1) was 175 mPa · s.

[Synthesis Example 2]
((CH ₃ ) ₃ SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) _3.9 ((CH ₃ ) ₂ SiO) Methylphenylorganopolysiloxane having a viscosity of 400 mPa · s represented by _8.6 To 130 parts by weight, 13 parts by weight of a terpene solution of 2-ethylhexanoate mainly containing cerium (rare earth element content: 6% by weight) (0.55 parts as cerium content) was added with stirring. A dispersion was obtained. While flowing a small amount of nitrogen gas through this, the terpene was heated to flow out, and then heated at 300 ° C. for 1 hour. As a result, a homogeneous composition of polyorganometallosiloxane (C-2) that was dark yellowish brown and transparent was obtained. It was. When the obtained polyorganometallosiloxane was analyzed by ICP-OES (high frequency inductively coupled plasma emission spectroscopy), the Ce content was 3,300 ppm. The viscosity of the polyorganometallosiloxane (C-2) was 220 mPa · s.

[Synthesis Example 3]
2-methylhexanoic acid containing cerium as a main component in 100 parts by mass of methylorganopolysiloxane having a viscosity of 100 mPa · s represented by ((CH ₃ ) ₃ SiO _1/2 ) ₂ ((CH ₃ ) ₂ SiO) ₅₇ 10 parts by weight of terpene solution of salt (rare earth element content: 6% by mass) (0.43 parts as cerium content) and 2.1 parts by mass of tetra n-butyl titanate (mass of titanium is cerium in 2-ethylhexanoate) What was mixed in advance (0.3 times the mass) was added while stirring to obtain a yellowish white dispersion. While flowing a small amount of nitrogen gas through this, the terpene was heated to flow out, and then heated at 300 ° C. for 1 hour. As a result, a uniform composition of polyorganometallosiloxane (C-3) that was dark reddish brown and transparent was obtained. . When the obtained polyorganometallosiloxane was analyzed by ICP-OES (high frequency inductively coupled plasma emission spectroscopy), the Ce content was 3,400 ppm and the Ti content was 3,700 ppm. The viscosity of the polyorganometallosiloxane (C-3) was 115 mPa · s.

[Synthesis Example 4]
A methylphenylorganoorganism having a viscosity of 700 mPa · s containing 30 mol% of a phenyl group so that a reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane has a platinum content of 1.0 mass%. A platinum catalyst was prepared by diluting with polysiloxane.

[Examples 1-4, Comparative Examples 1-4]
The following components were mixed in the blending amounts shown in Table 1 to prepare addition-curable silicone compositions. In addition, the numerical value of each component in Table 1 represents a mass part. [Si-H] / [Si-Vi] value is the value of the hydrogen atom bonded to the silicon atom in component (B) relative to the all-silicon-bonded alkenyl group in component (A-1) and component (A-2). Represents the molar ratio.

(A-1) Component:
(A-1-1) (CH ₂ = CH (CH ₃ ) (C ₆ H ₅ ) SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) _3.8 (SiO ₂ ) _4.3 Branched phenyl silicone resin (A-1-2) ((CH ₃ ) ₃ SiO _1/2 ) _2.5 (CH ₂ ═CH (CH ₃ ) ₂ SiO _1/2 ) _1.2 ((C ₆ Branched methylphenyl silicone resin (A-2) component represented by H ₅ ) ₂ SiO) _1.3 (SiO ₂ ) _5.0 :
(A-2-1) (CH ₂ ═CH (CH ₃ ) (C ₆ H ₅ ) SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) ₃ , viscosity 2,000 mPa · s Linear phenyl silicone oil (A-2-2) (CH ₂ ═CH (CH ₃ ) ₂ SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) ₁₅ ((CH ₃ ) ₂ SiO) ₆₅ A linear methylphenyl silicone oil (B) component having a viscosity of 700 mPa · s represented by:
(B-1) Organohydrogenpolysiloxane (B-2) represented by (H (CH ₃ ) (C ₆ H ₅ ) SiO _1/2 ) ₃ ((C ₆ H ₅ ) SiO _3/2 ) ₁ Organohydrogenpolysiloxane (C) component represented by ((CH ₃ ) ₃ SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) ₂ (H (CH ₃ ) SiO) ₆ :
(C-1) Polyorganometallosiloxane obtained in Synthesis Example 1 (C-2) Polyorganometallosiloxane obtained in Synthesis Example 2 (C-3) Polyorganometallosiloxane obtained in Synthesis Example 3 (D ) Component: Platinum catalyst obtained in Synthesis Example 4

（Ｆ−２）接着性向上剤：下記式（７）で表されるシロキサン

Other ingredients:
(E) Reaction inhibitor: Ethynylcyclohexanol (F-1) Adhesion improver: Siloxane represented by the following formula (6)

(F-2) Adhesion improver: siloxane represented by the following formula (7)

  The addition-curable silicone compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated as follows, and the results are shown in Table 2.

[appearance]
Each composition was cured by heating at 150 ° C. for 2 hours, and the appearance of the obtained cured product was visually confirmed.

[Refractive index]
Each composition was cured by heating at 150 ° C. for 2 hours, and the refractive index of the cured product at a wavelength of 589 nm at 25 ° C. was measured using an ATAGO digital refractometer RX-5000.

[Light transmittance]
The addition-curable silicone composition was poured into a mold to a thickness of 2 mm and cured under conditions of 150 ° C. × 4 hours. The initial linear light transmittance T ₀ of the cured product at a wavelength of 400 nm was measured with a spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.). Furthermore, after exposing the cured product at 180 ° C. for 1000 hours, the linear light transmittance T at a wavelength of 400 nm was measured. The smaller the difference (T ₀ -T) from the initial light transmittance, the better the heat discoloration. The value of (T ₀ -T) is preferably 10 points or less.

[Weight after heat test]
The addition-curable silicone composition was cured at 150 ° C. for 2 hours, and the weight after exposure to 180 ° C. for 1000 hours was compared with the case where the initial weight of the cured product was 100. . The smaller the difference from the initial, the smaller the weight loss and the better the heat resistance.

  As shown in Table 2, the silicone cured products of Examples 1 to 4 were excellent in transparency, had little deterioration in transmittance after 180 ° C. × 1000 hours, and were excellent in heat discoloration. In addition, it was confirmed that Examples 1 and 2 were smaller than Comparative Example 1 and Examples 3 and 4 were smaller than Comparative Example 2 in that the weight change after the heat test was small and the heat resistance was excellent.

  On the other hand, in Comparative Examples 1 and 2 not including the component (C) and Comparative Example 3 in which the component (C) does not include the Si—O—Ti bond, although the initial transparency is high, the transmission after 180 ° C. × 1000 hours The rate deterioration and weight change were large as compared with Examples 1 to 4, and the material was low in reliability. Moreover, in the comparative example 4 in which (C) component does not have an aryl group, compatibility with the composition containing a phenyl group is bad, initial transparency falls remarkably, and it turns out that it is not suitable for a LED use.

  From the above, it was shown that the addition-curable silicone composition of the present invention can provide a cured product suitable for LED applications that has a small weight change at high temperatures and is excellent in heat discoloration.

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

Specific examples of the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, tris ( (Hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-capped methylhydrogenpolysiloxane at both ends, trimethylsiloxy group-capped dimethylsiloxane / methylhydro at both ends siloxane copolymers, both ends endcapped with dimethyl hydrogen siloxy group dimethylpolysiloxane, both end dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane siloxanyl down, both ends dimethyl Hyde Gensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer Combined, trimethylsiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydrogen siloxy groups at methylhydrogensiloxane-dimethylsiloxane-methylphenylsiloxane copolymers, (CH ₃₎ HSiO _1/2 units and _{(CH 3) 3 SiO 1/2} units and _{SiO 4/2 units,} copolymers composed _of copolymerization consisting of _(CH 3) 2 _{HSiO 1/2} units and _{SiO 4/2} units And a copolymer composed of (CH ₃ ) ₂ HSiO _1/2 unit, SiO _4/2 unit, and (C ₆ H ₅ ) ₃ SiO _1/2 unit.

Claims (5)

(A-1) a branched organopolysiloxane represented by the following average composition formula (1):
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g (1)
(In the formula, each R ¹ may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, and at least 10 mol% of all R ¹ is an aryl group; ² is an alkenyl group, a, b, c, d, e, f, and g are a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, e ≧ 0, f ≧ 0, and g, respectively. It is a number satisfying ≧ 0, provided that b + c + e> 0, e + f + g> 0, and a + b + c + d + e + f + g = 1.)
(A-2) Linear organopolysiloxane represented by the following formula (2): 10 to 40 parts by mass with respect to 100 parts by mass in total of the component (A-1) and the component (A-2),

(In the formula, R ^{1 ′} may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group, R ³ is a methyl group or a phenyl group, and h is 0-50. I is a number from 0 to 100, provided that when h is 0, R ³ is a phenyl group and i is a number from 1 to 100. In parentheses marked with h (The siloxane units in the brackets and the siloxane units in parentheses to which i is attached may be arranged randomly or in blocks.)
(B) Organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule: for one silicon-bonded alkenyl group in the components (A-1) and (A-2) The amount of silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5.0,
(C) Si—O—Ce bond and Si—O—Ti bond are contained, Ce content is 50 to 5,000 ppm, Ti content is 50 to 5,000 ppm, and viscosity at 25 ° C. is 10 to 10 Polyorganometallosiloxane having an aryl group of at least 10 mol% based on the total number of organic groups contained in one molecule: (A-1) component, (A-2) component, And (B) 0.01 to 20 parts by mass with respect to 100 parts by mass in total, and
(D) a hydrosilylation catalyst containing a platinum group metal,
An addition-curable silicone composition comprising: 2. The addition-curable silicone composition according to claim 1, wherein R ¹ in the formula (1) and R ^{1 ′} in the formula (2) are a phenyl group or a methyl group. A method for producing the addition-curable silicone composition according to claim 1 or 2,
The following (a), (b) and (c) components are reacted at a temperature of 150 ° C. or higher to produce the (C) component polyorganometallosiloxane,
(A) Polyorganosiloxane having a viscosity of 10 to 10,000 mPa · s at 25 ° C. and having at least 10 mol% of aryl groups based on the total number of organic groups contained in one molecule: 100 parts by mass
(B) a rare earth element carboxylate represented by the following general formula (3): an amount of 0.05 to 5 parts by mass in terms of cerium in terms of 100 parts by mass of the component (a),
(R ⁴ COO) _j M ¹ (3)
(In the formula, R ⁴ is the same or different monovalent hydrocarbon group, M ¹ is cerium or a rare earth element containing cerium, and j is an integer of 3 to 4.)
(C) One or both of the titanium compound represented by the following general formula (4) and its hydrolysis condensate: 0.05 to 5 parts by mass in terms of mass of titanium with respect to 100 parts by mass of the component (a) The amount,
(R ⁴ O) ₄ M ² (4)
(Wherein R ⁴ is the same or different monovalent hydrocarbon group and M ² is titanium),
And a step of mixing the components (A-1), (A-2), (B), (C), and (D), and a method for producing an addition-curable silicone composition.   A cured silicone product, which is a cured product of the addition-curable silicone composition according to claim 1 or 2.   An optical element sealed with the silicone cured product according to claim 4.