JP2014077092A - Resin composition containing surface-modified composite metal oxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable silicone resin composition containing a surface-modified composite metal oxide, for obtaining a cured product having a high refractive index and high weather resistance.SOLUTION: The curable silicone resin composition contains a curable polyorganosiloxane compound (A) and a surface-modified composite metal oxide (B). The surface-modified composite metal oxide (B) is obtained by surface-modifying a composite metal oxide (b2) with a modifier containing a surface modifier (b1) represented by general formula (1): RRRSi-Y-SiRX{wherein Rto Rare each independently a C1-C18 hydrocarbon group or a substituted or unsubstituted siloxy group, Ris a saturated alkyl group, Y is a divalent bonding group, X is a hydrogen atom, a halogen atom, a C1-C6 alkoxy group, a C3-C6 cycloalkoxy group, or an acetoxy group, and n is an integer of 0-2}.

Description

  The present invention relates to a curable resin composition containing a surface-modified composite metal oxide.

  Conventionally, a cured product of a composition mainly based on an epoxy resin or the like has been widely used for a semiconductor peripheral insulating member of an optical semiconductor device typified by an LED. This is because, from the viewpoint of workability when applying the composition before curing, the composition has a low viscosity, the LED emits heat during use, and the semiconductor peripheral member undergoes a cooling cycle. The cured product has high crack resistance, the hardened product has a high hardness in order to obtain a smooth cut surface during dicing, and the cured product has a high hardness in order to improve the light extraction efficiency. This is because it is required to be transparent.

  However, the epoxy resin has a problem in that the resin itself is yellowed due to an increase in the amount of heat generated with the recent increase in brightness of the LED and shortening of the excitation wavelength and emission wavelength of the phosphor. . In recent years, in order to solve such problems, silicone compositions containing polyorganosiloxane as a main component and cured products thereof have been used. However, such a silicone resin has a low refractive index, and the light extraction efficiency is reduced. For these reasons, development of a technology for increasing the refractive index while maintaining the resin properties such as transparency and weather resistance of these sealing resins is desired. As one of them, metal oxide fine particles are contained in these resins. A method to disperse the material in the water has been studied. For example, zirconium oxide and titanium oxide, which are metal oxides, have a high refractive index of 2.0 or more, and by making their particle size 20 nm or less, the refractive index can be increased while ensuring transparency. However, since these metal oxides have poor compatibility with the resin as a matrix and the metal oxides aggregate, there is a concern that transparency may deteriorate.

  In Patent Document 1, the formula (I):

（式中、ｍは２〜１４の整数を表す）
で表される化合物、式（ＩＩ）：

(In the formula, m represents an integer of 2 to 14)
A compound represented by formula (II):

(Wherein R represents —H, — (CH ₂ ) ₂ Si (OCH ₃ ) ₃ or (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , n represents an integer of 2 to 15). And a method for preparing a composition for a silicone resin, comprising metal oxide fine particles.

  In Patent Document 2, an organic compound (A) containing two or more carbon-carbon double bonds having reactivity with SiH groups in one molecule (S), a silicon compound containing two or more SiH groups in one molecule (B), a metal oxide fine particle-containing curable resin composition comprising a hydrosilylation catalyst (C) and a metal oxide fine particle (D), the metal oxide fine particles having a controlled particle size and dispersibility A curable resin composition is described which is dispersed therein and has improved light diffusibility or refractive index.

JP 2009-173866 A JP 2010-138270 A

  However, in the metal oxide-containing resin composition described in Patent Document 1, zirconium oxide is used as the metal oxide. However, the refractive index of zirconium oxide is lower than that of titanium oxide or barium titanate, and the refractive index is not necessarily high. It is not optimal as a filler.

  In the metal oxide-containing resin composition described in Patent Document 2, it is considered that the transparency is good because the metal oxide particles are nano-order. However, since the organic compound (A) containing two or more carbon-carbon double bonds having reactivity with the SiH group is used in one molecule, a considerable heat load is applied to the resin for weather resistance. The requirements for high-brightness LEDs are not fully satisfied.

  In view of the above-described prior art, the problem to be solved by the present invention is a curable silicone containing a surface-modified composite metal oxide for obtaining a cured product having a high refractive index and a high weather resistance. It is to provide a resin composition.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and conducted experiments. As a result, they have found that the above-mentioned problems can be solved by the following solution means, and have completed the present invention. That is, the present invention is as follows.

[1] A curable silicone resin composition comprising a curable polyorganosiloxane compound (A) and a surface-modified composite metal oxide (B),
The surface-modified composite metal oxide (B) is obtained by converting the composite metal oxide (b2) into the following general formula (1):
R ¹ R ² R ³ Si—Y—SiR ⁴ _n X _(3-n) (1)
{Wherein R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, R ⁴ is a saturated alkyl group, and Y is a divalent linking group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, and n is an integer of 0 to 2. }
A curable silicone resin composition obtained by surface modification with a modifying agent containing a surface modifying agent (b1) represented by
[2] As the curable polyorganosiloxane compound (A), a polyorganosiloxane compound (a1) having a functional group selected from the group consisting of a vinyl group, an allyl group and an acrylic group, and a hydrogen atom directly bonded to silicon The curable silicone resin composition according to the above [1], further comprising a polyorganosiloxane compound (a2) having a hydrosilation catalyst (C).
[3] A polyorganosiloxane compound having a group having an unsaturated carbon double bond capable of photoradical polymerization, selected from the group consisting of an acryl group, a methacryl group and a styryl group, as the curable polyorganosiloxane compound (A). The curable silicone resin composition according to the above [1], comprising (a3) and further comprising a radical photopolymerization initiator (D).
[4] The curable silicone resin composition according to any one of [1] to [3], wherein in the surface modifier (b1), n is 0 or 1.
[5] The curable silicone resin composition according to any one of [1] to [4], wherein Y is a divalent hydrocarbon group having 1 to 6 carbon atoms in the surface modifier (b1).
[6] The curable silicone resin composition according to any one of [1] to [5], wherein the composite metal oxide (b2) is barium titanate.
[7] The curable silicone resin composition according to any one of [1] to [6], wherein the composite metal oxide (b2) has an average primary particle size of 1 to 50 nm.
[8] The volume ratio of the composite metal oxide (b2) to the total volume of 100% by volume of the curable polyorganosiloxane compound (A) and the surface-modified composite metal oxide (B) is 10 to 70% by volume. The curable silicone resin composition according to any one of the above [1] to [7].

  ADVANTAGE OF THE INVENTION According to this invention, the curable silicone resin composition containing the surface-modified complex metal oxide for obtaining the hardened | cured material which has a high refractive index and high weather resistance can be provided.

  Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

This embodiment
A curable silicone resin composition comprising a curable polyorganosiloxane compound (A) and a surface-modified composite metal oxide (B),
The surface-modified composite metal oxide (B) is obtained by converting the composite metal oxide (b2) into the following general formula (1):
R ¹ R ² R ³ Si—Y—SiR ⁴ _n X _(3-n) (1)
{Wherein R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, R ⁴ is a saturated alkyl group, and Y is a divalent linking group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, and n is an integer of 0 to 2. }
The curable silicone resin composition obtained by carrying out surface modification with the modifier containing the surface modifier (b1) represented by these is provided.

≪Curable polyorganosiloxane compound (A) ≫
The structure of the curable polyorganosiloxane compound (A) of the present embodiment is not particularly limited, but preferably has a structure represented by the following average composition formula (2).
R ⁵ _a R ⁶ _b SiO _{(4-ab) / 2} (2)
{Wherein R ⁵ represents a saturated aliphatic hydrocarbon group; an aryl group; or an alkoxy group; R ⁶ represents a hydrogen atom, a hydroxyl group, or an unsaturated carbon double bond-containing group having 1 to 8 carbon atoms; And 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, where 0 ≦ a + b ≦ 3. }

In the above formula (2), R ⁵ is, for example, an alkyl group up to C20 such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, and a cycloalkyl group. Groups; aryl groups such as phenyl groups; alkoxy groups such as methoxy groups, ethoxy groups, and isopropoxy groups; and the like. Of these, methyl group, ethyl group, phenyl group, methoxy group, ethoxy group, and isopropoxy group are preferable from the viewpoint of transparency, ease of synthesis, and availability, and methyl group, phenyl group, methoxy group, ethoxy group are preferable. And isopropoxy groups are more preferred.

In the above formula (2), as R ⁶ , for example, vinyl group, allyl group, hexenyl group, cyclohexenyl group, cyclohexenylethyl group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, Examples include unsaturated carbon double bond-containing groups such as a methacryl group, an acryl group, a styryl group, a methacrylopropyl group, and an acrylopropyl group; a hydroxyl group; a hydrogen atom and the like. Of these, vinyl group, allyl group, methacryl group, acrylic group, methacrylopropyl group, acrylopropyl group, styryl group, hydroxyl group, and hydrogen atom are preferable from the viewpoint of transparency, synthesis ease, and availability.

The curable polyorganosiloxane compound (A) is typically used in combination with a hydrosilylation catalyst (C) described later or a photoradical polymerization initiator (D). The R ⁶ contributes to good weather resistance and curability of the heat resistant composition. From the viewpoint of obtaining good weather resistance and good curability by heat or light, the amount of R ⁶ is preferably 0.1 to 8.0 mmol per gram of resin (ie, curable polyorganosiloxane compound (A)). More preferably, it is 0.3-7.0 mmol, More preferably, it is 0.5-6.5 mmol.

  The content of the curable polyorganosiloxane compound (A) in the curable silicone resin composition is preferably 1 to 80% by volume. The content is preferably 1% by volume or more from the viewpoint of curability, more preferably 5% by volume or more, from the viewpoint of heat resistance, preferably 80% by volume or less, and more preferably 70% by volume or less.

  The weight average molecular weight of the curable polyorganosiloxane compound (A) of this embodiment is preferably 300 or more and 20,000 or less, and more preferably 500 or more and 15,000 or less. In the present disclosure, the weight average molecular weight is a value obtained by converting standard polystyrene by gel permeation chromatography (GPC). The weight average molecular weight of the curable polyorganosiloxane compound (A) is preferably 300 or more from the viewpoint of heat resistance and curability, and is preferably 20,000 or less because the viscosity is low.

  The viscosity of the curable polyorganosiloxane compound (A) of the present embodiment is preferably 2 mPa · s or more and 200 Pa · s or less, and more preferably 2 mPa · s or more and 100 Pa · s or less. When it is 2 mPa · s or more, it is preferable from the viewpoint of dispersion maintaining property of the surface-modified composite metal oxide (B), and when it is 200 Pa · s or less, it is preferable from the viewpoint of handleability.

The method for producing the curable polyorganosiloxane compound (A) of the present embodiment is not particularly limited, but as an example, one or more kinds of compounds represented by the following general formula (3) are hydrolyzed and A method obtained by condensation is mentioned.
R ⁵ _c R ⁶ _d Si (OR ⁷ ) _(4-cd) (3)
{Wherein R ⁵ and R ⁶ are as defined in the general formula (2), R ⁷ is a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and c and d are integers, 0 ≦ c ≦ 3, 0 ≦ d ≦ 3, where 0 ≦ c + d ≦ 3. }
In the above formula (3), as R ⁷ , for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, and the like, an alkyl group up to C6 and a cycloalkyl group Groups and the like. Among these, from the viewpoint of hydrolyzability of alkoxide, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group and hexyl group are preferable, methyl group, ethyl group, propyl group, isopropyl group, butyl group. Is more preferable.

The amount of water added for hydrolysis is preferably 0.1 to 10 times in molar ratio to the group represented by OR ⁷ in the compound represented by the general formula (3). 0.4 to 8 times is more preferable, and 0.8 to 5 times is more preferable. When the amount of water added is 0.1 times or more, the molecular weight of the curable polyorganosiloxane compound (A) is increased, and it is preferably 10 times or less from the viewpoint of workability.

  From the viewpoint of adjusting the reaction rate of hydrolysis and condensation, it is more preferable to hydrolyze and condense the compound represented by the general formula (3) in the presence of a catalyst.

  Examples of the catalyst include an acid catalyst and a base catalyst. For example, examples of the acid catalyst include inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid and the like. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, benzoic acid, and p-aminobenzoic acid. Examples include acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, citraconic acid, malic acid, glutaric acid and the like. Examples of the base catalyst include inorganic bases and organic bases. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; lithium carbonate, potassium carbonate, and carbonate Examples thereof include alkali or alkaline earth metal carbonates such as sodium; metal hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate; and the like. Examples of the organic base include trialkylamines such as triethylamine and ethyldiisopropylamine; N, N-dialkylaniline derivatives having 1 to 4 carbon atoms such as N, N-dimethylaniline and N, N-diethylaniline; pyridine, 2,6 -Pyridine derivatives which may have an alkyl substituent having 1 to 4 carbon atoms, such as lutidine;

  These catalysts can be used alone or in combination of two or more. During the production of the curable polyorganosiloxane compound (A), it is possible to add a catalyst in such an amount that the pH of the reaction system is in the range of 0.01 to 6.0. This is preferable.

  Hydrolysis and condensation for producing the curable polyorganosiloxane compound (A) can also be performed in an organic solvent. Examples of the organic solvent that can be used for the condensation reaction include alcohols, esters, ketones, ethers, aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, amide compounds, and the like.

  Examples of the alcohol include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, B propylene glycol monopropyl ether, mono ethers of polyhydric alcohols such as propylene glycol monobutyl ether; and the like.

  Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, and γ-butyrolactone. Examples of ketones include acetone, methyl ethyl ketone, and methyl isoamyl ketone.

  Examples of the ether include, in addition to the above monoethers of polyhydric alcohols, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene Examples include polyhydric alcohol ethers obtained by alkyl etherifying all hydroxyl groups of polyhydric alcohols such as glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; tetrahydrofuran; 1,4-dioxane; anisole and the like.

  Examples of the aliphatic hydrocarbon compound include hexane, heptane, octane, nonane, decane, and the like.

  Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene and the like.

  Examples of the amide compound include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  Among these solvents, methanol, ethanol, isopropanol, butanol, etc. as alcohols; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. as ketones; ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. as ethers , And amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferable because they are easily mixed with water.

  These solvents may be used alone or in combination of a plurality of solvents.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of manufacturing a curable polyorganosiloxane compound (A), -50 to 200 degreeC is preferable and 0 to 150 degreeC is more preferable. From the viewpoint of increasing the reaction rate of the hydrolysis and condensation reaction, the reaction temperature is preferably −50 ° C. or higher, and from the viewpoint of suppressing gelation of the curable polyorganosiloxane compound (A), the reaction temperature is 200 ° C. or lower. It is preferable that

  The reaction time for producing the curable polyorganosiloxane compound (A) is not particularly limited, but is preferably 30 minutes to 24 hours, and more preferably 1 to 6 hours. In order to sufficiently progress hydrolysis of a hydrolyzable group (for example, alkoxy group), the reaction time is preferably 30 minutes or more, from the viewpoint of suppressing gelation of the curable polyorganosiloxane compound (A), The reaction temperature is preferably 24 hours or less.

(Silanol group sealing)
The curable polyorganosiloxane compound (A) may be, for example, a hydrolysis condensate obtained by the above-described method, and the silanol group is converted by organosilylation treatment of the silanol group of the hydrolysis condensate. It may be sealed.

In a preferred embodiment, the silanol group of the hydrolysis condensate can be sealed with a silanol group sealing agent. The example of a preferable silanol group sealing agent is a compound represented by following General formula (4).
P ¹ _n R ⁸ _(3-n) SiQ (4)
{Wherein P ¹ is an alkenyl group, a cycloalkenyl group, or a hydrogen atom, R ⁸ is a monovalent hydrocarbon group, Q is a halogen atom, and n is 1 or 2 is there. }
By the treatment using such a compound, a curable polyorganosiloxane compound (A) in which silanol groups are sealed can be obtained.

P ¹ can act as an unsaturated bond functional group in the curable polyorganosiloxane compound (A). Preferred examples of P ¹ are alkenyl groups having 1 to 8 carbon atoms or cycloalkenyl groups having 3 to 8 carbon atoms from the viewpoint of reactivity, and more preferred examples are vinyl groups, allyl groups, hexenyl groups, cyclohexane groups. A hexenyl group, a methacryl group, an acrylic group, and a styryl group, and particularly preferred examples are a vinyl group, an allyl group, a methacryl group, an acrylic group, and a styryl group.

Preferred examples of R ⁸ are alkyl group and cycloalkyl group up to C20 such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, hexyl group and cyclohexyl group from the viewpoint of heat resistance. An aryl group such as a phenyl group, and more preferred examples are a methyl group and a phenyl group.
A preferable example of Q is a chlorine atom from the viewpoint of enabling a low viscosity of the reactive and curable silicone resin composition.

  The amount of the compound represented by the general formula (4) is not particularly limited as long as the amount of the silanol group is adjusted, but there is no particular limitation. By changing the amount, the curable polyorganosiloxane compound (A ) Can be adjusted. For example, when chlorosilane is used as the compound represented by the general formula (4), the addition amount is 0.2 to 1. mol in terms of a molar ratio with respect to the silanol group of the compound before the treatment (for example, the aforementioned hydrolysis condensate). It is preferably about 1.

  In order to adjust the amount of silanol groups, the compound represented by the general formula (4) and a silanol having neither an unsaturated carbon double bond such as trimethylchlorosilane nor a hydrogen atom directly bonded to a silicon atom. A base sealant can also be used in combination.

  When the silanol group is sealed by organosilylation treatment of the silanol group, a solvent may be used. Examples of the solvent include esters, ketones, ethers, aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, and the like.

Examples of the ester include methyl acetate, ethyl acetate, butyl acetate and the like.
Examples of the ketone include acetone, methyl ethyl ketone, methyl isoamyl ketone, and the like.

  Examples of the ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl. Monoethers of polyhydric alcohols such as ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol Polyhydric alcohol ethers obtained by alkyl etherifying all hydroxyl groups of polyhydric alcohols such as cold dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether; Tetrahydrofuran; 1,4-dioxane; anisole and the like.

  Examples of the aliphatic hydrocarbon compound include hexane, heptane, octane, nonane, decane, and the like.

  Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene and the like.

  When the silanol group is sealed by organosilylation treatment of the silanol group, the acid generated is preferably neutralized with a Lewis base. Examples of the Lewis base include pyridine, piperidine, triethylamine and the like.

  20-150 degreeC is preferable and, as for the reaction temperature at the time of sealing a silanol group, 20-50 degreeC is more preferable. A reaction temperature of 20 ° C. or higher is preferable from the viewpoint of reaction rate, and a reaction temperature of 150 ° C. or lower is preferable from the viewpoint of workability.

≪Surface modified composite metal oxide (B) ≫
In the surface-modified composite metal oxide (B) of the present embodiment, the composite metal oxide (b2) is represented by the following general formula (1):
R ¹ R ² R ³ Si—Y—SiR ⁴ _n X _(3-n) (1)
{Wherein R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, R ⁴ is a saturated alkyl group, and Y is a divalent linking group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, and n is 0 to 2. }
It is obtained by surface modification with a modifying agent containing a surface modifying agent (b1) represented by

  In the present embodiment, a curable silicone resin composition having excellent weather resistance can be obtained by using the composite metal oxide. Further, in this embodiment, due to the contribution of the surface modification using at least the surface modifier (b1), the affinity between the curable polyorganosiloxane compound (A) and the surface modified composite metal oxide (B) is good, and the surface Since the modified composite metal oxide (B) is well dispersed in the curable silicone resin composition, a curable silicone resin composition giving a cured product having a high refractive index is obtained.

(Surface modifier (b1))
In the general formula (1), R ^{1 to} R ³ are each a hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted siloxy group, which may be the same or different. Examples of the hydrocarbon group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl group. 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, cyclopentyl group, n -Acyclic or cyclic saturated hydrocarbon groups such as hexyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, n-octyl group, n-nonyl group, n-decyl group, octadecyl group, phenyl Group, aromatic hydrocarbon group such as tolyl group, xylyl group, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, Acyclic and cyclic unsaturated hydrocarbon groups such as chlorhexenylethyl group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, styryl group, etc., and benzyl group, phenethyl group, 2-methyl Examples thereof include arylalkyl groups such as benzyl group, 3-methylbenzyl group and 4-methylbenzyl group. Examples of the substituted or unsubstituted siloxy group include trimethylsiloxy group, methyldiethylsiloxy group, dimethylethylsiloxy group, dimethylbutylsiloxy group, dimethylcyclohexylsiloxy group, dimethylphenylsiloxy group, and methyldiphenylsiloxy group. It is done.

Among these, from the viewpoint that the surface modification reaction with the composite metal oxide (typically fine particles) easily proceeds and suppresses the decrease in the refractive index due to the surface modification group, R ^{1 to} R ³ are: A methyl group, an ethyl group, a trimethylsiloxy group, or a dimethylphenylsiloxy group is preferable, and a methyl group or a trimethylsiloxy group is more preferable.

In the general formula (1), R ⁴ is a saturated alkyl group, preferably a saturated alkyl group having 1 to 4 carbon atoms. Examples of the saturated alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Among these, R ⁴ is preferably a methyl group from the viewpoint that the surface modification reaction with the composite metal oxide proceeds easily.

  In the general formula (1), Y is a divalent linking group, preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, and is a divalent hydrocarbon group having 2 to 6 carbon atoms. It is more preferable. As a C1-C6 bivalent hydrocarbon group, a C1-C6 linear or branched alkylene group is mentioned, for example. Among these, from the viewpoint of ease of synthesis, Y is preferably a linear or branched alkylene group having 2 or 3 carbon atoms, more preferably a linear or branched alkylene group having 2 carbon atoms. is there.

  In the general formula (1), X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group. Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a t-butoxy group, and an n-hexyloxy group. A cyclohexyloxy group etc. are mentioned as a C3-C6 cycloalkoxy group.

  Among these, X is preferably a hydrogen atom or an alkoxy group from the viewpoint of easy reaction control, and more preferably a hydrogen atom, a methoxy group, or an ethoxy group.

  In the said General formula (1), n is 0-2. From the viewpoint that the surface modification reaction with the composite metal oxide proceeds easily, n is preferably 0 or 1.

  The surface modifier (b1) represented by the general formula (1) includes, for example, hydrosilylation of a corresponding hydrosilane compound and a silane compound having an unsaturated carbon double bond (also referred to as an alkenylsilane compound in the present disclosure). It can be produced by reaction. Specifically, in a hydrocarbon-based organic solvent or in the absence of a solvent, the hydrosilane compound and the alkenylsilane compound are dissolved so that an equimolar amount or one compound is slightly excessive, and a metal catalyst is added and heated and stirred. It is manufactured by.

The hydrosilane compound and alkenylsilane compound correspond to the silicon compound represented by the general formula (1), and the following general formula (5):
R ¹ R ² R ³ Si—H (5)
{Wherein R ^{1 to} R ³ are as defined in the general formula (1). }
And the following general formula (6):
R ⁹ -SiR ¹⁰ _n X ¹ _(3-n) (6)
{Wherein R ⁹ is an unsaturated carbon double bond-containing hydrocarbon group having 2 to 6 carbon atoms, R ¹⁰ is a saturated alkyl group having 1 to 4 carbon atoms, and X ¹ is a halogen atom or carbon number An alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, and n is 0 to 2, preferably 0 or 1. }
An alkenylsilane compound represented by:
Or the following general formula (7):
R ¹ R ² R ³ Si-R ⁹ (7)
{Wherein R ^{1 to} R ³ are as defined in the general formula (1), and R ⁹ is an unsaturated carbon double bond-containing hydrocarbon group having 2 to 6 carbon atoms. }
And an alkenylsilane compound represented by the following general formula (8):
H-SiR ¹⁰ _n X ¹ _(3-n) (8)
{Wherein, R ¹⁰ is a saturated alkyl group having 1 to 4 carbon atoms, X ¹ is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, N is 0 to 2, preferably 0 or 1. }
The hydrosilane compound represented by these can be used in combination. Preferred examples of R ⁹ are vinyl group, allyl group, hexenyl group, cyclohexenyl group, methacryl group, acrylic group, and styryl group, and particularly preferred examples include vinyl group, allyl group, acrylic group, and the like. . In the above case, R ^{4 in} the general formula (1) is derived from each R ¹⁰ described above. Preferred examples of R ¹⁰ are the same as those exemplified as saturated alkyl having 1 to ⁴ carbon atoms for R ⁴ . Preferred examples of X ¹ are the same as those exemplified for X in the general formula (1) as a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group.

  Although there is no restriction | limiting in particular in the molar ratio of the said hydrosilane compound and an alkenylsilane compound, Generally, an alkenylsilane compound should be used in 0.9-1.1 mol with respect to 1 mol of hydrosilane compounds. Is preferred.

  Examples of the hydrocarbon-based organic solvent include hexane, octane, toluene, xylene and the like. The organic solvent can be used in any amount.

  Examples of the metal catalyst include platinum group metals such as platinum, palladium, rhodium, and ruthenium, supported catalysts in which the platinum group metal is supported on a carrier such as carbon, alumina, silica, and polymer, chloroplatinic acid, and alcohol-modified platinum chloride. Examples include acids, olefins or acetylene complexes of chloroplatinic acid, vinylsiloxane complexes of platinum, tetrakis (triphenylphosphine) palladium, and chlorotris (triphenylphosphine) rhodium. Among these, chloroplatinic acid (Speier catalyst), platinum tetramethyldivinyldisiloxane complex (Karsttedt catalyst), and chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst) are preferable. These metal catalysts may be used alone or in combination of two or more.

The amount of the metal catalyst used can be in the range of 1 × 10 ^{−6 to} 0.01 mol with respect to 1 mol of the hydrosilane compound.

  The reaction temperature of the hydrosilylation reaction is preferably in the range of 0 to 150 ° C., and the reaction time is preferably in the range of 0.5 to 48 hours.

  When the surface modifier (b1) represented by the general formula (1) is synthesized by the hydrosilylation reaction, a cis isomer and a trans isomer are formed when the hydrosilane is added to the unsaturated bond site of the alkenyl silane. May be obtained. This isomer mixture can be separated by a separation operation such as distillation or column chromatography, but even a cis-trans isomer mixture is preferably used in a surface modification reaction with a composite metal oxide described later. be able to.

  Of the surface modifier (b1) represented by the general formula (1), for the silicon compound in which X in the general formula (1) is a hydrogen atom, for example, X in the general formula (1) is a halogen atom. A silicon compound that is an alkoxy group, a cycloalkoxy group, or an acetoxy group is manufactured by the above-described method, and then manufactured by performing a reduction reaction using a reducing agent such as lithium aluminum hydride or sodium borohydride. it can.

  The surface modifier (b1) may be used alone or in combination. Further, the modifying agent used in the present embodiment may be only the surface modifying agent (b1) or a combination of the surface modifying agent (b1) and an additional modifying agent component. Additional modifier components include organic phosphonic acids, organic carboxylic acid compounds, tetraalkoxysilanes, and the like. When an additional modifier component is used, the ratio of the surface modifier (b1) in the total amount of the modifier is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of weather resistance and dispersibility. More preferably, it is 70 mass% or more, Most preferably, it is 100 mass%.

(Composite metal oxide (b2))
In this embodiment, a composite metal oxide (b2) is used. The composite metal oxide (b2) contains two or more kinds of metal atoms and oxygen atoms. Examples of the composite metal oxide include barium titanate, strontium titanate, lead titanate, zirconium silicate, lead zirconate, indium tin oxide, antimony tin oxide, lithium niobate, and lithium cobaltate. Among these, from the viewpoint of improving the refractive index, barium titanate and strontium titanate are preferable. These may be used alone or in combination of two or more.

  The composite metal oxide (b2) preferably has a spherical shape, a rod shape, a plate shape, a fiber shape, or a shape in which two or more of these are combined, and more preferably has a spherical shape. In addition, the spherical shape here means a substantially spherical shape including a spheroid, an oval and the like in addition to a true spherical shape.

  The average primary particle diameter of the composite metal oxide (b2) is preferably equal to or less than the wavelength of light used in the intended application in order to avoid adverse effects on transparency due to light scattering. The average primary particle size is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 50 nm or less, and still more preferably 1 nm or more and 40 nm or less. If the average primary particle size is 1 nm or more, the dispersibility of the composite metal oxide (b2) is good, and if it is 100 nm or less, the composite metal oxide (b2) is dispersed in an organic solvent or resin. Transparency is good. In the present disclosure, the average primary particle diameter means a number average value. The average primary particle diameter can be determined by direct observation with a transmission electron microscope (TEM). Specifically, for example, the major axis of 50 particles is measured, and the number average is obtained.

  The composite metal oxide (b2) can be produced by a hydrothermal method, a sol-gel method, a coprecipitation method or the like, and the average primary particle size can be controlled by changing the production conditions.

  As for a specific method for producing the composite metal oxide (b2), for example, in the case of barium titanate, equimolar amounts of metal barium and tetraethyl orthotitanate were heated and dissolved in 2-methoxyethanol. Thereafter, a method of obtaining a dispersion of barium titanate fine particles by adding water to cause hydrolysis reaction and condensation reaction to proceed. If necessary, powdery barium titanate fine particles can be obtained by performing a drying treatment such as spray drying or vacuum drying. In addition, by performing the sintering process in an electric furnace or the like, the surface hydroxyl group amount of the barium titanate fine particles can be controlled according to the sintering process time.

  In the present embodiment, the surface modification agent containing the surface modification agent (b1) is allowed to act on the composite metal oxide (b2) to perform a surface modification reaction, and the surface has a structural site derived from the surface modification agent (b1) on the surface. A method for producing the modified composite metal oxide (B) is disclosed.

  Specifically, for example, it is produced by a step of adding the surface modifier (b1) to a uniform dispersion of a composite metal oxide (b2) containing alcohol and water.

  The uniform dispersion may contain water used in the hydrolysis step when producing the composite metal oxide (b2) as it is, and by removing a part of the water or adding water, The amount can also be controlled. The surface modifier (b1) may be added as it is, or may be added after dilution with alcohol, water or other organic solvent.

  The reaction temperature of the surface modification reaction is preferably 0 to 120 ° C, more preferably 30 to 100 ° C. Moreover, it is preferable that reaction time is 0.5 to 24 hours, More preferably, it is 0.5 to 3 hours.

  The composite metal oxide (b2) used for the surface modification reaction may be dispersed in water, an organic solvent, or a mixture thereof, or may be a powder obtained by a drying process. When the surface modification reaction is performed using the powdered composite metal oxide (b2), the surface modification reaction may be performed in a dispersing apparatus such as a bead mill.

  The bead mill is a dispersing device including a bead separation mechanism that separates beads, which are a rotor, a stator, and stirring particles. The beads that are stirring particles are required to be ultrafine beads, and the particle diameter is preferably 3 to 300 μm, more preferably 10 to 50 μm. If the particle diameter is 3 μm or more, impact energy required for dispersion can be obtained, and if it is 300 μm or less, reaggregation due to excessive impact energy can be suppressed.

  Examples of the stirring particles include zirconia, alumina, silica, glass, silicon carbide, and silicon nitride. Among these, zirconia is preferably used from the viewpoint of excellent strength and stability as stirring particles.

  The addition amount of the surface modifier (b1) to the composite metal oxide (b2) is the total surface area of the composite metal oxide (b2) and the area that the surface modifier (b1) can modify by a single molecule (theoretical coating surface area). It can be determined from the ratio.

The surface area (m ² / g) per unit mass of the composite metal oxide (b2) is measured by the BET method. The theoretical coating surface area (m ² / g) per unit mass of the surface modifier (b1) is calculated by 6.02 × 10 ²³ × 1.3 × 10 ⁻¹⁹ ÷ (molecular weight of the surface modifier).

The quantity ratio between the surface modifier (b1) and the composite metal oxide (b2) is as follows: theoretical surface area of the surface modifier (b1) (m ² ) / total surface area of the composite metal oxide (b2) (m ² ) The ratio is preferably 0.3 to 3.0, more preferably 0.7 to 2.0. The ratio is preferably 0.3 or more from the viewpoint of dispersibility of the composite metal oxide (b2), and preferably 3.0 or less from the viewpoint of workability.

  Examples of a method for separating the surface-modified composite metal oxide (B) from the curable silicone resin composition described later for various measurements of the surface-modified composite metal oxide (B) include, for example, centrifugation at a rotational speed of 15000 rpm or more. A method of precipitating and isolating the dispersed surface-modified composite metal oxide (B) by centrifuging with a machine can be used. The isolated surface-modified composite metal oxide (B) can be measured by a known method.

≪Curable silicone resin composition≫
The curable silicone resin composition of this embodiment can be obtained by dispersing the surface-modified composite metal oxide (B) in the curable polyorganosiloxane compound (A). As the dispersion step, the surface-modified composite metal oxide (B) is isolated from the solvent, mixed with the curable polyorganosiloxane compound (A), and processed using a ball mill, jet mill, bead mill or the like mill. Or performing sonication. It is more dispersible with respect to the curable polyorganosiloxane compound (A) and has excellent transparency, so that the dispersion is obtained by dispersing the surface-modified composite metal oxide (B) in water or an organic solvent. A curable silicone resin in which the surface-modified composite metal oxide (B) is dispersed in the curable polyorganosiloxane compound (A) by sufficiently dissolving the polyorganosiloxane compound (A) and then removing the solvent with an evaporator or the like. It is further preferred to prepare the composition.

The content of the surface-modified composite metal oxide (B) is that of the composite metal oxide (b2) relative to 100% by volume of the total volume of the curable polyorganosiloxane compound (A) and the surface-modified composite metal oxide (B). The volume ratio is preferably 10 to 70% by volume. The volume ratio is more preferably 15 to 50% by volume. The volume ratio is preferably 10% by volume or more from the viewpoint of realizing a high refractive index, and preferably 70% by volume or less from the viewpoint of avoiding brittleness of the cured product of the curable silicone resin composition. The volume ratio is such that the density of the curable polyorganosiloxane compound (A) is 1 g / mL, the density of the surface modifier (b1) is 1 g / mL, and the density of the composite metal oxide (b2) is a literature value, for example, If it is barium titanate, it will be 6.02 g / mL and it will be calculated by the following formula.
Volume ratio of composite metal oxide (b2) = (mass of b2 / density of b2) / {(mass of A / density of A) + (mass of b1 / density of b1) + (mass of b2 / density of b2) )}

≪Additional ingredients≫
The curable silicone resin composition may contain an additional component in addition to the curable polyorganosiloxane compound (A) and the surface-modified composite metal oxide (B). Hereinafter, suitable examples of the additional component will be described.

  It is preferable that the curable silicone resin composition further contains an adhesion-imparting agent in terms of adhesion to various materials. Examples of the adhesion imparting agent include an epoxy functional group-containing compound, a thiol group-containing compound, and alkoxysilane. A preferred adhesion-imparting agent is an organohydrogenpolysiloxane compound containing an epoxy group and / or an alkoxy group, and a particularly preferred adhesion-imparting agent is an epoxy group-containing organohydrogenpolysiloxane compound.

  The compounding amount of the adhesion-imparting agent is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the curable polyorganosiloxane compound (A) and the surface-modified composite metal oxide (B). Is preferred. The blending amount is preferably 0.01 parts by mass or more from the viewpoint of adhesiveness, and is preferably 20 parts by mass or less from the viewpoint of transparency and crack resistance.

  The curable silicone resin composition may contain an inorganic filler. The inorganic filler preferably has an average primary particle diameter equal to or smaller than the wavelength used in the intended application in order to avoid an adverse effect on light transmittance. The average primary particle diameter is more preferably 100 nm or less. In the cured resin, the inorganic filler may improve, for example, mechanical properties and thermal conductivity. Although the minimum of the average primary particle diameter of an inorganic filler is not specifically limited, From the point that the viscosity of a resin composition is low and it has favorable moldability, it is preferable that it is 0.1 nm or more. In addition, the said average primary particle diameter is a number average value calculated | required by calculation from the specific surface area of BET. Although the compounding quantity of an inorganic filler can be selected according to the objective, Preferably it is 1-60 with respect to 100 mass parts of total amounts of a curable polyorganosiloxane compound (A) and a surface modification complex metal oxide (B). The amount may be 3 parts by mass, more preferably 3 to 50 parts by mass, and still more preferably 5 to 40 parts by mass.

  The curable silicone resin composition may contain one or more selected from a curing retardant, a thermosetting resin, a thermoplastic resin, an antioxidant, and an ultraviolet absorber.

  Furthermore, the curable silicone resin composition may contain a phosphor or a phosphor for the purpose of converting the color of the emission wavelength. These materials are preferably mixed with a resin component or any other component using a known method such as centrifugation. The obtained mixture may be defoamed by vacuum defoaming or the like.

  A thermosetting silicone composition is mentioned as one aspect | mode of the curable silicone resin composition of this embodiment. As the thermosetting silicone composition, as the curable polyorganosiloxane compound (A), a polyorganosiloxane compound (a1) having a functional group selected from the group consisting of vinyl group, allyl group and acrylic group, silicon A composition containing a polyorganosiloxane compound (a2) having a hydrogen atom directly bonded to and further containing a hydrosilylation catalyst (C) as a curing agent is preferred from the viewpoint of the weather resistance of the cured product. Each functional group of the polyorganosiloxane compound (a1) is preferably an unsaturated bond functional group, and these functional groups undergo an addition reaction with a hydrogen atom of the polyorganosiloxane compound (a2) by the action of the hydrosilylation catalyst (C). Thus, a cured product having excellent heat resistance can be provided.

  By curing the molded body or thin film of the thermosetting silicone composition using heat, a transparent cured product preferable as an optical material can be obtained.

Preferred examples of the polyorganosiloxane compound (a1) include compounds in which R ^{6 in} the general formula (2) is a vinyl group, an allyl group, a butenyl group, a propenyl group, a hexenyl group, a cyclohexenyl group, or an acrylic group. Is mentioned.

  From the viewpoint of obtaining good weather resistance and thermosetting properties, the total content of functional groups selected from the group consisting of vinyl groups, allyl groups and acrylic groups of the polyorganosiloxane compound (a1) is preferably a resin (ie It is 0.1-5.0 mmol / g per gram of organosiloxane compound (a1)).

Preferable examples of the polyorganosiloxane compound (a2) include compounds in which R ^{6 in} the general formula (2) is a hydrogen atom.

  From the standpoint of obtaining good weather resistance and thermosetting properties, the amount of hydrogen atoms directly bonded to silicon of the polyorganosiloxane compound (a2) is preferably about 0.001 per gram of resin (ie, polyorganosiloxane compound (a2)). 1 to 5.0 mmol / g.

  The content of the polyorganosiloxane compound (a1) in the thermosetting silicone composition is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 45 parts by mass or less, based on 100 parts by mass of the entire composition. preferable. 5 parts by mass or more is preferable from the viewpoint of transparency of the cured product, and 50 parts by mass or less is preferable from the viewpoint of refractive index.

  The mixing ratio of the polyorganosiloxane compound (a1) and the polyorganosiloxane compound (a2) in the thermosetting silicone composition is [group consisting of vinyl group, allyl group and acrylic group of the polyorganosiloxane compound (a1). The total number of functional groups selected from:] / [number of hydrogen atoms directly bonded to silicon atoms of the polyorganosiloxane compound (a2)] is preferably 0.5 to 2, and 0.7 to 1.3. Particularly preferred. 0.5 or more is preferable from the viewpoint of weather resistance and adhesiveness of the curable silicone resin composition, and 2 or less is preferable in that a hydrogen atom directly bonded to a silicon atom does not cause a dehydrogenation reaction during curing.

  In the present embodiment, the curable polyorganosiloxane compound (A) is a compound corresponding to both the polyorganosiloxane compound (a1) and the polyorganosiloxane compound (a2), that is, a vinyl group, allyl in one molecule. A compound having both a functional group selected from the group consisting of a group and an acrylic group and a hydrogen atom directly bonded to silicon may be used. Such a compound can be manufactured by the manufacturing method of the curable polyorganosiloxane compound (A) described above. In this case, the amount of the compound is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 45 parts by mass or less, based on 100 parts by mass of the entire composition. 5 mass parts or more are preferable from the point of transparency of hardened | cured material, and 50 mass parts or less are preferable from the point of refractive index. In a preferred embodiment, the compound can be used in combination with a hydrosilylation catalyst (C) described later.

The thermosetting silicone composition preferably further contains a hydrosilylation catalyst (C). The hydrosilylation catalyst (C) is a catalyst for promoting an addition reaction between an unsaturated hydrocarbon in the unsaturated hydrocarbon group and a hydrogen atom directly bonded to a silicon atom in the SiH group. A known hydrosilylation catalyst can be used as the hydrosilylation catalyst (C). Examples of hydrosilylation catalysts include platinum group metals such as platinum (including platinum black), rhodium and palladium; H ₂ PtCl ₄ · nH ₂ O, H ₂ PtCl ₆ · nH ₂ O, NaHPtCl ₆ · nH ₂ O, KHPtCl ₆ · nH ₂ O, Na ₂ PtCl ₆ · nH ₂ O, K ₂ PtCl ₄ · nH ₂ O, PtCl ₄ · nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · nH ₂ O {where n is 0 It is an integer of ˜6, preferably 0 or 6. }, Such as platinum chloride, chloroplatinic acid and chloroplatinate; alcohol-modified chloroplatinic acid; complex of chloroplatinic acid and olefins; platinum group metals such as platinum black and palladium supported on a support such as alumina, silica and carbon Rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane, divinyltetramethyldisiloxane platinum complex or vinyl group-containing And a complex with a cyclic siloxane. These hydrosilylation catalysts may be used alone or as a mixture of two or more hydrosilylation catalysts.

  The content of the hydrosilylation catalyst (C) in the thermosetting silicone composition is preferably 0.01 to 1000 ppm based on the weight of the platinum group metal, based on the curable polyorganosiloxane compound (A), 2-100 ppm is more preferable. The content is preferably 0.01 ppm or more from the viewpoint of reaction efficiency, and preferably 1000 ppm or less from the viewpoint of transparency of the cured product.

  As another aspect of the curable silicone resin composition of the present embodiment, a photocurable silicone composition may be mentioned. The photocurable silicone composition includes a group having an unsaturated carbon double bond capable of photoradical polymerization selected from the group consisting of an acryl group, a methacryl group, and a styryl group as the curable polyorganosiloxane compound (A). The composition which contains the polyorganosiloxane compound (a3) which has and further contains radical photopolymerization initiator (D) as a hardening | curing agent is preferable from a viewpoint of a cure rate.

  A transparent cured product preferable as an optical material can be obtained by curing the molded body or thin film of the photocurable silicone composition using light.

Preferable examples of the polyorganosiloxane compound (a3) include compounds in which R ^{6 in} the general formula (2) is an acryl group, a methacryl group or a styryl group.

  A group having an unsaturated carbon double bond capable of radical photopolymerization selected from the group consisting of an acryl group, a methacryl group and a styryl group of the polyorganosiloxane compound (a3) from the viewpoint of obtaining good weather resistance and photocurability The total content of is preferably 0.1 to 5.0 mmol / g per gram of resin (that is, polyorganosiloxane compound (a3)).

  The content of the polyorganosiloxane compound (a3) in the photocurable silicone composition is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 45 parts by mass or less, based on 100 parts by mass of the entire composition. preferable. 5 parts by mass or more is preferable from the viewpoint of transparency of the cured product, and 50 parts by mass or less is preferable from the viewpoint of refractive index.

Preferred examples of the radical photopolymerization initiator (D) include the following compounds that absorb light having a wavelength of 365 nm.
(1) benzophenone derivatives; for example, benzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, etc. (2) acetophenone derivatives For example, trichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-
ON, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl)
-Benzyl] -phenyl} -2-methylpropan-1-one, methyl phenylglyoxylate, (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl } -2-methyl-propan-1-one) (IRGACURE127 manufactured by Ciba Japan Co., Ltd.) and the like (3) thioxanthone derivatives; for example, thioxanthone, 2-methylthioxanthone, 2
-Isopropylthioxanthone, diethylthioxanthone and the like (4) benzyl derivatives; for example, benzyl, benzyldimethyl ketal, benzyl-β-
(5) benzoin derivatives such as methoxyethyl acetal; for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1phenylpropan-1-one, etc. (6) oxime compounds such as 1-phenyl-1,2 -Butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O- Ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl)
Oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (Ciba Japan OXE-01), ethanone-1- [9-ethyl-
6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (IRGACURE OXE02 manufactured by Ciba Japan) and the like

(7) α-hydroxy ketone compounds; for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- {4- [4- (2
-Hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane and the like (8) α-aminoalkylphenone compounds; for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1 (Ciba Japan IR
GACURE 369), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-
(9) phosphine oxide compounds such as morpholin-4-yl-phenyl) butan-1-one; for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxy) Benzoyl) -2
, 4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (DAOCURE TPO manufactured by Ciba Japan) and the like (10) titanocene compounds; for example, bis (η5-2,4 -Cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like (11) benzoate derivatives; for example, ethyl-p- (N, N-dimethyl) (Aminobenzoate) and the like (12) acridine derivatives; for example, 9-phenylacridine and the like. These may be used alone or in combination with a plurality of photoradical initiators.

  The amount of the radical photopolymerization initiator (D) is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less when the entire composition is 100 parts by mass. preferable. More preferably, they are 0.2 mass part or more and 3 mass parts or less. Curing proceeds favorably when the amount is 0.01 parts by mass or more, and it is preferable for the amount to be 10 parts by mass or less because there is little coloring after photocuring or baking with heat.

  In the case of performing a curing treatment with light, for example, visible light, ultraviolet light, far ultraviolet light, or the like can be used. Examples of the light source include a low-pressure or high-pressure mercury lamp, deuterium lamp, or discharge light of a rare gas such as argon, krypton, or xenon, YAG laser, argon laser, carbon dioxide laser, or XeF, XeCl, XeBr, KrF, An excimer laser such as KrCl, ArF or ArCl can be used. The output of these light sources is preferably 10 to 5,000 W.

  Another aspect of the present embodiment provides various articles that are cured products of the curable silicone resin composition described above. The cured product can be preferably used as a sealing material for optical semiconductors, a die attach material, and a lens, and particularly preferably used as a sealing material for optical semiconductors.

  The cured product is obtained by heating, exposing, or heating the curable silicone resin composition disclosed in the present embodiment.

  Various curing temperatures can be set for producing these cured products, but 30 ° C to 300 ° C is preferable, and 70 ° C to 200 ° C is more preferable from the viewpoint of curing speed and moldability.

  Curing may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than performing curing at a constant temperature, it is preferable that the reaction is carried out while raising the temperature in a multistage or continuous manner in that a uniform cured product with less distortion is easily obtained and cracks are less likely to occur.

There is no restriction | limiting in particular about the formation method of the crosslinked structure by a hydrocarbon group at the time of hardening, A condensation reaction, an addition reaction, etc. can be illustrated. The Si— (CH ₂ ) ₂ —Si structure is particularly preferable from the viewpoint of the heat resistance of the cured product. This structure includes, for example, a compound having an ethenyl group directly bonded to a silicon atom as a polyorganosiloxane compound (a1), a polyorganosiloxane compound (a2) having a hydrogen atom directly bonded to a silicon atom, and hydrosilylation It can be obtained by using a curable silicone resin composition containing a platinum catalyst as the catalyst (C) and hydrosilylating the ethenyl group and the hydrogen atom with the platinum catalyst.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these.

  The curable polyorganosiloxane compounds synthesized in the following examples were measured according to the following (1) and (2).

(1) Measurement of weight average molecular weight (Mw) An isopropyl alcohol solution or a propylene glycol methyl ether acetate solution of a silicone resin (as a curable polyorganosiloxane compound) is added to tetrahydrofuran so that the concentration of the silicone resin component is 1% by mass. And measured by gel permeation chromatography (GPC) (EcoSEC HLC-8320, manufactured by Tosoh Corporation). The weight average molecular weight (Mw) was determined as a value in terms of polystyrene as a standard substance.
[GPC measurement conditions]
-Column: TSKgel G1000H-HR, G3000H-HR, and G5000H-HR (all manufactured by Tosoh Corporation) in series-Eluent: Toluene (flow rate: 1 mL / min)
Column operating temperature: 40 ° C

(2) Measurement of functional group concentration of unsaturated bond functional group and hydrogen atom directly reacted with silicon atom 1H NMR was measured by the following method, and the unsaturated bond functional group and silicon atom for 1 g of polyorganosiloxane compound were measured. The functional group concentration (mmol) of the directly reacted hydrogen atom was calculated.

  Sample preparation: Each polyorganosiloxane compound was weighed, and toluene was weighed to 10 wt%. Furthermore, it diluted with 1% tetramethylsilane containing heavy chloroform so that a polymer concentration might be 1 mass%.

  From the 1H NMR measurement result of the prepared sample solution, the ratio of the peak area of the hydrogen atom of the vinyl group (3H) or the peak area of the hydrogen atom of the SiH group (1H) and the peak area of the methyl group of toluene (3H) The concentration of the unsaturated bond functional group per 1 g of the polymer and the concentration of the functional group of the hydrogen atom that reacted directly with the silicon atom were calculated.

  1HNMR measurement: Integration was performed using an NMR (Nuclear Magnetic Resonance) apparatus GSX400 manufactured by JEOL, with a pulse width of 0.5 seconds, a waiting time of 2 seconds, and an integration count of 16.

[Synthesis Example 1]
In a 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer, 149.9 g of methyltrimethoxysilane, 32.5 g of ethoxytrimethylsilane, and 120 g of isopropyl alcohol (IPA) were added and stirred. A mixture with 128.7 g of ion-exchanged water was added dropwise and heated in an oil bath set at 80 ° C. for 2 hours to obtain a reaction mixture.

  The reaction mixture was transferred to a 1 L flask, 360 g of propylene glycol methyl ether acetate (PGMEA) was added, and IPA and water were distilled off with an evaporator. Furthermore, it concentrated until the silicone resin component became 33.3 mass%, and the PGMEA solution of silicone resin was obtained.

  Into a 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer prepared separately, 288 g of the above PGMEA solution of silicone resin, 90.1 g of pyridine, and 100 g of PGMEA were stirred and further 137.6 g of vinyldimethylchlorosilane was added dropwise. And stirred at room temperature for 1 hour.

  After adding 100 g of cyclohexane and 100 g of ion-exchanged water, the aqueous layer was removed by a liquid separation operation, and the obtained organic layer was washed twice with 100 g of ion-exchanged water. The organic solvent was distilled off with an evaporator to obtain 146 g of the target silicone resin (methyl-modified silicone-SiVi). The weight average molecular weight (Mw) of the obtained silicone resin was 1,020. The vinyl group concentration calculated from 1H-NMR was 3.85 mmol / g.

[Synthesis Example 2]
In a 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer, 149.9 g of methyltrimethoxysilane, 32.5 g of ethoxytrimethylsilane, and 120 g of IPA were added and stirred, and 58 mg of 1M hydrochloric acid and ion-exchanged water 128. 7 g of the mixture was added dropwise and heated in an oil bath set at 80 ° C. for 2 hours to obtain a reaction mixture.

  The above reaction mixture was transferred to a 1 L flask, 360 g of PGMEA was added, and IPA and water were distilled off with an evaporator. Furthermore, it concentrated until the silicone resin component became 33.3 mass%, and the PGMEA solution of silicone resin was obtained.

  Into a 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer prepared separately, 288 g of the above PGMEA solution of silicone resin, 90.1 g of pyridine, and 100 g of PGMEA were stirred, and 107.8 g of dimethylchlorosilane was further added dropwise. And stirred at room temperature for 1 hour.

  After adding 100 g of cyclohexane and 100 g of ion-exchanged water, the aqueous layer was removed by a liquid separation operation, and the obtained organic layer was washed twice with 100 g of ion-exchanged water. The organic solvent was distilled off with an evaporator to obtain 140 g of the target silicone resin (methyl-modified silicone-SiH). The weight average molecular weight (Mw) of the obtained silicone resin was 980. The concentration of SiH groups calculated from 1H-NMR was 3.95 mmol / g.

[Synthesis Example 3]
A 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer was charged with 135.9 g of methacryloxypropyltrimethoxysilane, 69.3 g of methyltrimethoxysilane, 25.6 g of ethoxytrimethylsilane, and 187.5 g of IPA. Further, a mixture of 58 mg of 1M hydrochloric acid and 144.1 g of ion-exchanged water was added dropwise, and heated in an oil bath set at 80 ° C. for 2 hours to obtain a reaction mixture.

  The above reaction mixture was transferred to a 1 L flask, 300 g of PGMEA was added, and IPA and water were distilled off with an evaporator. Furthermore, it concentrated until the silicone resin component became 33.3 mass%, and the PGMEA solution of silicone resin was obtained.

  Into a 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer prepared separately, 288 g of the above PGMEA solution of silicone resin, 90.1 g of pyridine, and 100 g of PGMEA were added and stirred, and 123.8 g of trimethylchlorosilane was further added dropwise. And stirred at room temperature for 1 hour.

  After adding 100 g of cyclohexane and 100 g of ion-exchanged water, the aqueous layer was removed by a liquid separation operation, and the obtained organic layer was washed twice with 100 g of ion-exchanged water. The organic solvent was distilled off with an evaporator to obtain 150 g of the target silicone resin (methyl-modified silicone-methacrylic). The obtained silicone resin had a weight average molecular weight (Mw) of 1080. The concentration of the methacryl group calculated from 1H-NMR was 2.83 mmol / g.

[Synthesis Example 4]
In a 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer, 136.23 g of phenyltrimethoxysilane, 16.67 g of ethoxytrimethylsilane, and 308 g of IPA were added and stirred, and 1 mL of 1M hydrochloric acid and 55 g of ion-exchanged water The mixture was added dropwise and heated in an oil bath set at 80 ° C. for 2 hours to obtain a reaction mixture.

  The above reaction mixture was transferred to a 1 L flask, 600 g of PGMEA was added, and IPA and water were distilled off with an evaporator. Furthermore, it concentrated until the silicone resin component became 33.3 mass%, and the PGMEA solution of silicone resin was obtained.

  Into a 1 L separable flask equipped with a reflux tube, a dropping funnel and a stirrer prepared separately, 141 g of the above PGMEA solution of silicone resin and 44.56 g of pyridine were stirred, and 56.71 g of vinyldimethylchlorosilane was further added dropwise. And stirred at room temperature for 1 hour.

After adding 100 g of cyclohexane and 100 g of ion-exchanged water, the aqueous layer was removed by a liquid separation operation, and the obtained organic layer was washed twice with 100 g of ion-exchanged water. The organic solvent was distilled off with an evaporator to obtain 67.8 g of the target silicone resin (phenyl-modified silicone-SiVi). The weight average molecular weight (Mw) of the obtained silicone resin was 930. The concentration of the vinyl group calculated from 1H-NMR was 4.14 mmol / g.
[Synthesis Example 5]
In a 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer, 136.23 g of phenyltrimethoxysilane, 16.67 g of ethoxytrimethylsilane, and 308 g of IPA were added and stirred, and 1 mL of 1M hydrochloric acid and 55 g of ion-exchanged water The mixture was added dropwise and heated in an oil bath set at 80 ° C. for 2 hours to obtain a reaction mixture.

  The above reaction mixture was transferred to a 1 L flask, 600 g of PGMEA was added, and IPA and water were distilled off with an evaporator. Furthermore, it concentrated until the silicone resin component became 33.3 mass%, and the PGMEA solution of silicone resin was obtained.

  Into a 1 L separable flask equipped with a reflux tube, a dropping funnel, and a stirrer separately prepared, 141 g of the above PGMEA solution of silicone resin and 44.56 g of pyridine were stirred, and 44.5 g of dimethylchlorosilane was further added dropwise. Stir at room temperature for 1 hour.

  After adding 100 g of cyclohexane and 100 g of ion-exchanged water, the aqueous layer was removed by a liquid separation operation, and the obtained organic layer was washed twice with 100 g of ion-exchanged water. The organic solvent was distilled off with an evaporator to obtain 67.2 g (phenyl-modified silicone-SiH) of the desired silicone resin. The weight average molecular weight (Mw) of the obtained silicone resin was 930. The concentration of SiH groups calculated from 1H-NMR was 4.10 mmol / g.

  The composite metal oxide synthesized in the following examples was measured according to the following (3) to (5).

(3) Measurement of the particle diameter of the composite metal oxide The particle dispersion is dropped on a fine sample capturing film (collodion film), dried, and then observed using a JEOL 2000-FX transmission electron microscope (TEM). The number average of the primary particle diameter of 50 particles was calculated.

(4) Identification of composite metal oxide particles Part of the particle dispersion is dried, powder X-ray diffraction is performed using a Rigaku X-ray diffractometer RU-200X, and the crystals are compared with the diffraction patterns described in the literature. The structure was confirmed. The crystallite size was also determined.

(5) Identification and pretreatment of the surface area of the composite metal oxide: A composite metal obtained by taking 0.5 g of a sample into a sample tube and drying under reduced pressure in a main body pretreatment apparatus under conditions of RT to 200 ° C., 0.01 mmHg or less, about 12 hr. The surface area of the oxide was measured using the BET method.
<Specific surface area / pore distribution measurement>
・ Device: Autosorb-3MP (manufactured by Yuasa Ionics)
・ Adsorption gas: N2 gas
・ Measurement temperature: Liquid nitrogen (77.4 ° K)

[Synthesis Example 6]
288 mL of 2-methoxyethanol (manufactured by Wako Pure Chemical Industries, Ltd., purity 99% or more) was placed in a 1 L separable flask that was replaced under a nitrogen atmosphere. Degassed by bubbling 2-methoxyethanol with nitrogen for 2 hours under a nitrogen atmosphere. 6.56 g (0.08M) of metal barium (manufactured by Kanto Chemical, purity 99% or more) and 10.05 mL (0.08M) of tetraethoxytitanium (manufactured by Tokyo Chemical Industry, purity 97% or more) were added to the mixture while stirring. Heating at 130 ° C. for 2 hours completely dissolved the metal barium and tetraethoxytitanium. Two hours later, a solution obtained by dissolving 43.2 mL (4M) of ion-exchanged water with 2-methoxyethanol was bubbled with N 2 and added so that the total amount of the solution became 600 mL. The mixture was stirred at 130 ° C. for 3 hours using an oil bath to obtain a barium titanate dispersion (BT-01). Nanoparticles with an average of 7 nm were obtained by TEM, and it was confirmed that the XRD diffraction peak coincided with barium titanate, and the crystallite size was identified as 7 nm. The surface area measured by the BET method was 130 m ² / g.

[Synthesis Example 7]
855 mL of ethanol (manufactured by Wako Pure Chemical Industries, Ltd., purity 99% or more) was placed in a separable flask having a volume of 2 L that was replaced under a nitrogen atmosphere. Under a nitrogen atmosphere, 24.7 g (0.1M) of metal barium and 37.7 mL (0.1M) of tetraethoxytitanium are placed therein and heated at 70 ° C. for 2 hours with stirring. Was completely dissolved. Two hours later, a solution obtained by dissolving 324 mL (10 M) of ion-exchanged water with ethanol was added so that the total amount of the solution was 1800 mL. The mixture was stirred at 70 ° C. for 3 hours using an oil bath to obtain barium titanate. After cooling the reaction solution at room temperature, it was centrifuged at 8000 rpm for 30 minutes to isolate the precipitate. The isolate was washed with ethanol and dried under reduced pressure at 70 ° C. and 0.5 kPa for 8 hours. Nanoparticles with an average of 7 nm were obtained by TEM, confirming that the XRD diffraction peak coincided with barium titanate, and the crystallite size was identified as 6.7 nm (BT-02). The surface area measured by the BET method was 150 m ² / g.

[Synthesis Example 8]
833 mL of ethanol was placed in a separable flask having a volume of 2 L that was replaced under a nitrogen atmosphere. Under a nitrogen atmosphere, 37.1 g (0.15 M) of metal barium and 56.5 mL (0.1 M) of tetraethoxytitanium are put therein and heated at 70 ° C. for 2 hours with stirring. Was completely dissolved. Two hours later, a solution obtained by dissolving 648 mL (20 M) of ion-exchanged water with ethanol was added so that the total amount of the solution was 1800 mL. The mixture was stirred at 70 ° C. for 3 hours using an oil bath to obtain barium titanate. After cooling the reaction solution at room temperature, it was centrifuged at 8000 rpm for 30 minutes to isolate the precipitate. The isolate was washed with ethanol and dried under reduced pressure at 70 ° C. and 0.5 kPa for 8 hours. Nanoparticles with an average of 18 nm were obtained by TEM, confirming that the XRD diffraction peak coincided with barium titanate, and the crystallite size was identified as 17.3 nm (BT-03). The surface area measured by the BET method was 76 m ² / g.

  The surface modifiers synthesized in the following examples were measured according to the following (6) to (8).

(6) Tracking of raw material conversion rate The raw material conversion rate was determined using gas chromatography.
[GC measurement conditions]
-GC device: GC-14B (manufactured by Shimadzu Corporation)
Column: DB-1 (30 m × 250 μm × 0.25 μmF) (manufactured by Agilent Technologies)
Column temperature: Hold for 5 minutes at 50 ° C., then increase to 300 ° C. by 10 ° C. per minute Carrier gas: He (flow rate 1.0 mL / min)

(7) Purity determination of surface modifier The purity was determined using gas chromatography.
[GC measurement conditions]
-GC device: GC-14B (manufactured by Shimadzu Corporation)
Column: DB-1 (30 m × 250 μm × 0.25 μmF) (manufactured by Agilent Technologies)
Column temperature: Hold for 5 minutes at 50 ° C., then increase to 300 ° C. by 10 ° C. per minute Carrier gas: He (flow rate 1.0 mL / min)

(8) Confirmation of product Using 1H-NMR, the structure of the product was identified, and the production ratio of the positive adduct and the reverse adduct was determined.

[Synthesis Example 9]
Toluene (made by Wako Pure Chemicals, dehydrated) 800 g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 128.6 g (made by Shin-Etsu Silicone) in a 2 L separable flask substituted under a nitrogen atmosphere Then, 71.4 g of trimethoxyvinylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was weighed, and 110 μL of a 2 wt% xylene solution (manufactured by Gelest) of a tetramethyldivinyldisiloxane complex of platinum (Karstedt catalyst) was added. A reflux tube was set, and the reaction was heated at 60 ° C. using an oil bath in a nitrogen atmosphere. After 8 hours, it was cooled to room temperature. The conversion rate of trimethoxyvinylsilane by GC was 100%. Toluene was distilled off at 4 kPa and 70 ° C. using an evaporator. Further purification was carried out by distillation under reduced pressure at 0.57 kPa and 120 ° C. (boiling point 103 ° C., 0.57 kPa) to obtain bis (trimethylsiloxy) methylsilylethyltrimethoxysilane (D-TMS). The production ratio of bis (trimethylsiloxy) methylsilylethyltrimethoxysilane and bis (trimethylsiloxy) methylsilylethyltrimethoxysilane identified by 1H-NMR was 90:10 by mass ratio, and the purity measured by GC was 99. %Met.

[Synthesis Example 10]
Weigh 3.8 g of lithium aluminum hydride (manufactured by Tokyo Chemical Industry Co., Ltd., LAH) into a 1 L four-necked flask that has been dried under reduced pressure, and cool it in an ice bath. And added under a nitrogen atmosphere. Prepare a mixed solution of 26.4 g of D-TMS and 50 mL of ultra-dehydrated diethyl ether in a dropping funnel under a nitrogen atmosphere. It was dripped slowly so as not to exceed. After everything was dropped, the temperature was returned to room temperature and reacted at room temperature for 1 hour. It was confirmed by GC that (trimethylsiloxy) dimethylsilylethyltrimethoxysilane was quantitatively reduced. The mixture was ice-cooled again, and 17.6 g of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was slowly dropped using a dropping funnel so that the internal temperature did not exceed 15 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours under a nitrogen atmosphere. The reaction solution was filtered under reduced pressure using a Celite 545 (manufactured by Wako Pure Chemical Industries) with a Kiriyama funnel to remove LAH, and then diethyl ether and ethyl acetate were distilled off. The remaining reaction solution was distilled under reduced pressure at 0.5 kPa under nitrogen at 70 ° C. (boiling point: 58 ° C., 0.5 kPa) and purified to obtain bis (trimethylsiloxy) methylsilylethylsilane (D-SiH 3). The production ratio of 2-bis (trimethylsiloxy) methylsilylethylsilane and 1-bis (trimethylsiloxy) methylsilylethylsilane identified by 1H-NMR was 90:10 by mass ratio, and the purity measured by GC was 99. %Met.

[Synthesis Example 11]
640 g of toluene, 78.0 g of trimethoxyvinylsilane, and 82.0 g of pentamethyldisiloxane (manufactured by Shin-Etsu Silicone) were weighed in a separable flask having a volume of 2 L that was replaced under a nitrogen atmosphere, and platinum tetramethyldivinyldisiloxane complex (Karstedt) 90 μL of a 2 wt% xylene solution of (catalyst) was added. A reflux tube was set, and the reaction was heated at 60 ° C. using an oil bath in a nitrogen atmosphere. After 2 hours, it was cooled to room temperature. The conversion rate of trimethoxyvinylsilane by GC was 100%. Toluene was distilled off at 4 kPa and 70 ° C. using an evaporator. Further purification was carried out by distillation under reduced pressure at 0.7 kPa and 100 ° C. (boiling point 86 ° C., 0.7 kPa) to obtain (trimethylsiloxy) dimethylsilylethyltrimethoxysilane. The production ratio of 2- (trimethylsiloxy) dimethylsilylethyltrimethoxysilane and 1- (trimethylsiloxy) dimethylsilylethyltrimethoxysilane identified by 1H-NMR was 79:21 by mass ratio.

Separately, 15.2 g of LAH was weighed into a 1 L four-necked flask dried under reduced pressure, and 400 mL of ultra-dehydrated diethyl ether was added under a nitrogen atmosphere using a syringe while cooling in an ice bath. Prepare a mixture of 84.4 g of (trimethylsiloxy) dimethylsilylethyltrimethoxysilane and 100 mL of super-dehydrated diethyl ether in a dropping funnel under a nitrogen atmosphere. Was slowly added dropwise so that the internal temperature did not exceed 15 ° C. After everything was dropped, the temperature was returned to room temperature and reacted at room temperature for 1 hour. It was confirmed by GC that (trimethylsiloxy) dimethylsilylethyltrimethoxysilane was quantitatively reduced. The mixture was ice-cooled again, and 52.9 g of ethyl acetate was slowly added dropwise using a dropping funnel so that the internal temperature did not exceed 15 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours under a nitrogen atmosphere. The reaction solution was filtered under reduced pressure using Celite 545 with a Kiriyama funnel to remove LAH, and then diethyl ether and ethyl acetate were distilled off. The remaining reaction solution was distilled under reduced pressure at 4.4 ° C. under a reduced pressure of 90 ° C. (boiling point: 65 ° C., 4.4 kPa) to obtain (trimethylsiloxy) dimethylsilylethylsilane (M-SiH ₃ ). The production ratio of 2- (trimethylsiloxy) dimethylsilylethylsilane and 1- (trimethylsiloxy) dimethylsilylethylsilane identified by 1H-NMR is 79:21 by mass ratio, and the purity measured by GC is 99%. there were.

[Synthesis Example 12]
800 g of toluene, 73.5 g of trimethylvinylsilane, and 126.5 g of triethoxysilane (manufactured by Tokyo Chemical Industry) are weighed in a separable flask having a volume of 2 L that has been substituted under a nitrogen atmosphere, and platinum tetramethyldivinyldisiloxane complex (Karstedt catalyst). 110 μL of 2 wt% xylene solution was added. A reflux tube was set, and the reaction was heated at 60 ° C. using an oil bath in a nitrogen atmosphere. After 2 hours, it was cooled to room temperature. The conversion rate of trimethylvinylsilane by GC was 100%. Toluene was distilled off at 4 kPa and 70 ° C. using an evaporator. Further, it was purified by distillation under reduced pressure (boiling point 65 ° C., 0.3 kPa) at 0.3 kPa and 90 ° C. to obtain trimethylsilylethyltriethoxysilane. The production ratio of 2-trimethylsilylethyltriethoxysilane and 1-trimethylsilylethyltriethoxysilane identified by 1H-NMR was 87:13 in mass ratio.

  Separately, 15.2 g of LAH was weighed into a 1 L four-necked flask dried under reduced pressure, and 400 mL of ultra-dehydrated diethyl ether was added under a nitrogen atmosphere using a syringe while cooling in an ice bath. A mixture of 75.2 g of trimethylsilylethyltriethoxysilane and 100 mL of ultra-dehydrated diethyl ether was prepared in a dropping funnel under a nitrogen atmosphere, and the internal temperature of the LAH diethyl ether suspension was 15 under ice-cooling under a nitrogen atmosphere. The solution was slowly added dropwise so as not to exceed ℃. After everything was dropped, the temperature was returned to room temperature and reacted at room temperature for 1 hour. It was confirmed by GC that trimethylsilylethyltriethoxysilane was quantitatively reduced. The mixture was ice-cooled again, and 36.0 g of methyl formate (manufactured by Wako Pure Chemical Industries, Ltd.) was slowly added dropwise using a dropping funnel so that the internal temperature did not exceed 15 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours under a nitrogen atmosphere. The reaction solution was filtered under reduced pressure using Celite 545 with a Kiriyama funnel to remove LAH, and then diethyl ether and methyl formate were distilled off. The remaining reaction solution was purified by repeated atmospheric distillation (boiling point 96 ° C.) twice at 120 ° C. under nitrogen to obtain trimethylsilylethylsilane (Z—SiH 3). The production ratio of 2-trimethylsilylethylsilane and 1-trimethylsilylethylsilane identified by 1H-NMR was 87:13 by mass ratio, and the purity measured by GC was 99%.

  Regarding the dispersion of the surface modified composite metal oxide (B) produced by surface modification of the composite metal oxide (b2) with the surface modifier (b1) produced in the following example, the following (9) to (9) Measurement was performed according to (11).

(9) Reaction rate of surface modifier Determined using a calibration curve method using gas chromatography.
[GC measurement conditions]
-GC device: GC-14B (manufactured by Shimadzu Corporation)
Column: DB-1 (30 m × 250 μm × 0.25 μmF) (manufactured by Agilent Technologies)
Column temperature: Hold for 5 minutes at 50 ° C., then increase to 300 ° C. by 10 ° C. per minute Carrier gas: He (flow rate 1.0 mL / min)

(10) Determination of alkoxysilane surface modification rate 1.0 g of powder of composite metal oxide fine particles with surface modification and 2.0 g of crystalline cellulose (trade name: Avicel, manufactured by Funakoshi) are mixed and stirred for 30 minutes in an automatic agate mortar. did. The obtained powder is filled into a 25 mmφ vinyl chloride ring, a sample is prepared with a tablet molding machine, and FP order analysis is performed using a Rigaku scanning X-ray fluorescence analyzer, ZSX Primus II. The molar ratio of silicon atoms was measured, and the amount of silicon compound present on the surface of the composite metal oxide fine particles was calculated.

When the surface area of the composite metal oxide fine particles is calculated from the average primary particle diameter and the occupied area per molecule of the silicon compound is 1.3 × 10 ⁻¹⁹ m ² , the entire surface of the composite metal oxide fine particles is The coated state was defined as a surface modification rate of 100%, and the state in which no silicon compound was present was defined as a surface modification rate of 0%.

(11) Transmittance measurement The dispersion was placed in a 1 cm quartz cell, and the transmittance of light having a wavelength of 400 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Tech).

[Synthesis Example 13]
By adding 3.31 g of D-TMS synthesized in Synthesis Example 9 to the dispersion of fine barium titanate particles (BT-1) obtained in Synthesis Example 6 above and heating at 70 ° C. for 1 hour, a white suspension is obtained. A liquid was obtained. After removing the solvent by treating at 7,000 rpm for 30 minutes using a centrifuge, the obtained solid component was washed with acetone and ethanol, toluene was added, and 4.0% by mass of toluene dispersed in a solid content concentration A liquid was obtained. The reaction rate of the surface modifier was 29% by mass, and the surface modification rate was 29%. The transmittance of light having a wavelength of 450 nm was 85%. (Dispersion 1)

[Synthesis Example 14]
In a 500 mL separable flask with a reflux tube set, 10 g of barium titanate (primary particle diameter 7 nm) of Synthesis Example 7 having a surface area of 150 m ² / g, 323 g of toluene, (M-SiH ₃ of Synthesis Example 11 + Synthesis Example 12) Z-SiH ₃ ) 1.18 g (5.7 mmol) of M-SiH ₃ and 33.0 g (22.9 mmol) of Z-SiH ₃ so that the ratio of theoretical coating surface area / barium titanate surface area is 1.49. The mixture was added and reacted at 40 ° C. for 1 hour in an oil bath. Further, the reaction solution was put into a slurry tank of a bead mill (UAM-015, manufactured by Kotobuki Industries), and 100 g of toluene was added. Zirconia beads DZB 15 micrometer diameter (Daiken Chemical Industry Co., Ltd.) 350 g, beads rotating speed 12 m / sec, flow rate 110 mL / min, 32 ° C., N 2 atmosphere, 1.5 hours dispersion treatment in a bead mill and collecting the dispersion liquid Treated with ultrasound for 30 minutes. The reaction rates of M-SiH ₃ and Z-SiH ₃ were 46% by mass and 72% by mass, respectively, and the total surface modification rate was 100% (respectively M-SiH ₃ / Z-SiH ₃ = 12% / 88%). It was. Toluene was added to the obtained dispersion to make the solid content concentration of the dispersion 1.5% by mass (dispersion 2). The transmittance of light having a wavelength of 450 nm was 87%.

[Synthesis Example 15]
In a 500 mL separable flask with a reflux tube set, 10 g of barium titanate (primary particle diameter 7 nm) of Synthesis Example 7 having a surface area of 150 m ² / g, 323 g of toluene, M-SiH ₃ theoretical surface area of Synthesis Example 11 / barium titanate Then, 5.9 g (28.5 mmol) of M-SiH ₃ was added so that the surface area ratio was 1.49, and the mixture was reacted at 40 ° C. for 1 hour in an oil bath. Further, the reaction solution was put into a slurry tank of a bead mill, and 100 g of toluene was added. Zirconia DZB 15 micrometer diameter 350g, bead rotation speed 12m / sec, flow rate 90mL / min, 32 ° C, N2 atmosphere, 1.5 hours dispersion treatment with bead mill, the dispersion liquid was collected and treated with ultrasonic wave for 30 minutes . The reaction rate of M-SiH ₃ was 60% by mass, and the total surface modification rate was 90%. Toluene was added to the obtained dispersion to adjust the solid content concentration of the dispersion to 1.5% by mass (dispersion 3). The transmittance of light having a wavelength of 450 nm was 89%.

[Synthesis Example 16]
In a 500 mL separable flask equipped with a reflux tube, 10 g of barium titanate (primary particle diameter 18 nm) of Synthesis Example 8 having a surface area of 75 m ² / g, 323 g of toluene, [D-SiH ₃ + phenylsilane of Synthesis Example 10 (Shin-Etsu Silicone) , Hereinafter Ph-SiH ₃ )] D-SiH ₃ 2.0 g (7.2 mmol) and Ph-SiH 0.77 g (7.2 mmol) so that the ratio of theoretical coating surface area / barium titanate surface area is 1.49. Was added and allowed to react at 40 ° C. for 1 hour in an oil bath. Further, the reaction solution was put into a slurry tank of a bead mill, and 100 g of toluene was added. Zirconia beads DZB 15 micrometer diameter 350 g, bead rotation speed 12 m / sec, flow rate 100 mL / min, 32 ° C., N 2 atmosphere, dispersion treatment was performed with a bead mill for 2 hours, and the dispersion was collected and treated with ultrasonic waves for 30 minutes. The reaction rates of D-SiH ₃ and Ph-SiH ₃ were 35% by mass and 68% by mass, respectively, and the total surface modification rate was 99% (respectively D-SiH ₃ / Ph-SiH ₃ = 74% / 26%). It was. Toluene was added to the obtained dispersion to make the solid content concentration of the dispersion 1.5% by mass (dispersion 4). The transmittance of light having a wavelength of 450 nm was 88%.

[Synthesis Example 17]
In a 500 mL separable flask set with a reflux tube, 10 g of barium titanate (primary particle diameter 7 nm) of Synthesis Example 7 having a surface area of 150 m ² / g, 323 g of toluene, [D-SiH ₃ + phenylsilane of Synthesis Example 10 (Shin-Etsu Silicone) Manufactured, hereinafter referred to as Ph-SiH ₃ )] The ratio of the theoretical coating surface area / barium titanate surface area is 1.49, so that 4.0 g (14.3 mmol) of D-SiH ₃ and 1.54 g (14.3 mmol) of Ph-SiH _{3 are} obtained. And the mixture was allowed to react at 40 ° C. for 1 hour in an oil bath. Further, the reaction solution was put into a slurry tank of a bead mill, and 100 g of toluene was added. Zirconia beads DZB 15 micrometer diameter 350 g, bead rotation speed 12 m / sec, flow rate 95 mL / min, 32 ° C., N 2 atmosphere, dispersion treatment was performed in a bead mill for 2 hours, and the dispersion was recovered and treated with ultrasonic waves for 30 minutes. The reaction rates of D-SiH ₃ and Ph-SiH ₃ were 36% by mass and 68% by mass, respectively, and the total surface modification rate was 100% (D-SiH ₃ / Ph-SiH ₃ = 74% / 26%, respectively). It was. Toluene was added to the obtained dispersion to adjust the solid content concentration of the dispersion to 1.5% by mass (dispersion 5). The transmittance of light having a wavelength of 450 nm was 87%.

[Synthesis Example 18]
By adding 3.4 g of bis (trimethylsiloxy) methylsilylpropyltrimethoxysilane to the dispersion (BT-1) of barium titanate fine particles obtained in Synthesis Example 6 above, the mixture was heated at 70 ° C. for 1 hour. A suspension of was obtained. After removing the solvent by treating at 7,000 rpm for 30 minutes using a centrifuge, the obtained solid component was washed with acetone and ethanol, toluene was added, and 4.0% by mass of toluene dispersed in a solid content concentration A liquid was obtained (Dispersion 6). The reaction rate of the surface modifier was 34% by mass, and the surface modification rate was 34%. The transmittance of light having a wavelength of 450 nm was 85%.

[Synthesis Example 19]
By adding 3.4 g of [bis (trimethylsiloxy) methylsilyl] ethylmethyldimethoxysilane to the barium titanate fine particle dispersion (BT-1) obtained in Synthesis Example 6, and heating at 70 ° C. for 1 hour, A white suspension was obtained. After removing the solvent by treating at 7,000 rpm for 30 minutes using a centrifuge, the obtained solid component was washed with acetone and ethanol, toluene was added, and 4.0% by mass of toluene dispersed in a solid content concentration A liquid was obtained (Dispersion 7). The reaction rate of the surface modifier was 31% by mass, and the surface modification rate was 31%. The transmittance of light having a wavelength of 450 nm was 85%.

[Synthesis Example 20]
27 g of ethanol was added to 3.0 g of an aqueous dispersion of zirconia oxide fine particles having an average particle diameter of 7 nm (trade name: NZD-3005, manufactured by Sumitomo Osaka Cement Co., Ltd., solid content concentration: 30% by mass). By adding 3.31 g of D-TMS synthesized in Synthesis Example 9 and heating at 70 ° C. for 1 hour, a white suspension was obtained. After removing the solvent by treating at 7,000 rpm for 30 minutes using a centrifuge, the obtained solid component was washed with acetone and ethanol, toluene was added, and 4.0% by mass of toluene dispersed in a solid content concentration A liquid was obtained (dispersion 8). The reaction rate of the surface modifier was 35% by mass, and the surface modification rate was 35%. The transmittance of light having a wavelength of 450 nm was 85%.

  The curable silicone resin compositions prepared in the following examples were measured according to the following (12) to (15).

(12) Calculation of volume ratio of composite metal oxide in curable silicone resin composition The density of the curable polyorganosiloxane compound (A) is 1 g / mL, the density of the surface modifier (b1) is 1 g / mL, From the literature values of the density of the composite metal oxide (b2) (6.02 g / mL for barium titanate), the total volume of the curable polyorganosiloxane compound (A) and the surface-modified composite metal oxide (B) is 100. The volume ratio of the composite metal oxide (b2) to the volume% was calculated by the following formula. The mass ratio of (b1) and (b2) was calculated from the reaction rate of the surface modifier.
Volume% of composite metal oxide = (mass of b2 / density of b2) / {(mass of A / density of A) + (mass of b1 / density of b1) + (mass of b2 / density of b2)}

(13) Refractive index measurement of cured film Each composition was apply | coated on the board | substrate of an alkali free glass, and the cured film with a film thickness of 150 micrometers was produced by heating at 150 degreeC for 2 hours. This cured film was peeled off from the alkali-free glass substrate using the cutter blade, and the refractive index at a wavelength of 589 nm was measured using a multiwavelength Abbe refractometer (DR-M2 manufactured by Atago). The measurement was performed by sandwiching the produced cured film between a prism and a daylighting glass. At that time, monobromonaphthalene was dropped as an intermediate liquid on the interface between the cured film and the prism and on the interface between the cured film and the daylighting glass. Those having a refractive index of 1.6 or higher were evaluated as １．５, those having a refractive index of 1.55 or higher as ◯, and those having a refractive index lower than 1.55 as ×.

(14) Transparency (transmittance) of the cured product
A 50 mm × 50 mm × 150 μm mold was filled with the prepared composition, and heat-cured in an oven at 80 ° C. × 30 minutes, then 100 ° C. × 30 minutes, and then 150 ° C. × 2 hours. About the hardened | cured material after heat-curing, the transmittance | permeability of the light whose wavelength is 400 nm was measured. A transmittance of 80% or more was evaluated as ◯, a transmittance of 70% or more and less than 80% was evaluated as Δ, and a transmittance of less than 70% was evaluated as ×.

(15) Weather resistance (transmittance) of the cured product
A 50 mm × 50 mm × 150 μm mold was filled with the prepared composition, and heat-cured in an oven at 80 ° C. × 30 minutes, then 100 ° C. × 30 minutes, and then 150 ° C. × 2 hours. The cured product after heat curing was left in an oven at 180 ° C. in the air for 10 days, and further subjected to a 144 hour exposure test to a 7 W 365 nm light source. About the hardened | cured material after a test, the transmittance | permeability of the light whose wavelength is 400 nm was measured. A transmittance of 85% or more was evaluated as ◯, a transmittance of 55% or more and less than 85% as Δ, and a transmittance of less than 55% as ×.

[Example 1]
190 g of the dispersion liquid of Synthesis Example 13 was taken into a 500 mL eggplant flask, and 1 g of methyl-modified silicone-SiVi of Synthesis Example 1 and methyl-modified silicone-SiH of Synthesis Example 2 were weighed and dissolved in the dispersion liquid. Toluene was removed until the viscosity of the mixture became 20 Pa · s at 70 ° C. and 0.5 kPa, and a 2 wt% xylene solution of karsted catalyst was added so as to be 2 ppm with respect to the silicone resin in terms of pure Pt. A 50 mm × 50 mm × 150 μm mold was filled with the prepared composition, and heat-cured in an oven at 80 ° C. × 30 minutes, then 100 ° C. × 30 minutes, and then 150 ° C. × 2 hours.

[Example 2] and [Example 4] to [Example 7]
The preparation method and curing were in accordance with Example 1, and the compositions were prepared at the blending ratios in Table 1 and thermally cured.

[Example 3]
190 g of the dispersion liquid of Synthesis Example 13 was taken in a 500 mL eggplant flask, and 2 g of methyl silicone-methacrylic acid of Synthesis Example 3 was weighed and dissolved in the dispersion liquid. Toluene was removed until the viscosity of the mixture became 20 Pa · s at 70 ° C. and 0.5 kPa, and 0.01 g of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (DAOCURE TPO manufactured by BASF) was added. A 50 mm × 50 mm × 150 μm mold is filled with the prepared composition, and irradiated with UV light at a light intensity of 1000 mJ / cm ² using a metal halide lamp (CV-110Q-G manufactured by Fusion UV Systems Japan), and cured to a thickness of 100 μm. A membrane was prepared. Further, the remaining solvent was removed by baking at 150 ° C.

[Comparative Example 1]
The preparation method and curing were in accordance with Example 1, and the compositions were prepared at the blending ratios in Table 1 and thermally cured. The Abbe refractive index of the cured product was 1.52, and a cured product having a refractive index of 1.55 or more was not obtained.

[Comparative Example 2]
In a 100 mL eggplant flask, 4 g of the barium titanate nanoparticle powder of Synthesis Example 7 was taken, and 1 g of methyl-modified silicone-SiVi of Synthesis Example 1 and methyl-modified silicone-SiH of Synthesis Example 2 were weighed and dissolved in the dispersion. Toluene was removed until the viscosity of the mixture became 20 Pa · s at 70 ° C. and 0.5 kPa, and a 2 wt% xylene solution of karsted catalyst was added so as to be 2 ppm with respect to the silicone resin in terms of pure Pt. A 50 mm × 50 mm × 150 μm mold was filled with the prepared composition, and heat-cured in an oven at 80 ° C. × 30 minutes, then 100 ° C. × 30 minutes, and then 150 ° C. × 2 hours. Barium titanate was not dispersed in the silicone resin, and the cured film became cloudy.

[Comparative Example 3]
The preparation method and curing were in accordance with Example 1, and the compositions were prepared at the blending ratios in Table 1 and thermally cured. Triallyl isocyanurate (manufactured by Evonik Degussa Japan, TAICROS (registered trademark)) and the surface-modified barium titanate were incompatible, and the cured film became cloudy.

  The curable silicone resin composition of the present invention is useful as a material for light-emitting diode elements and other optical devices or optical components. Specifically, it can be suitably used for protective films on light-emitting elements, optical lenses that change or adjust the wavelength of light obtained from the elements, die bonding materials that are fixed to lead terminals or packages, underfill, substrate materials, etc. It is.

Claims (8)

A curable silicone resin composition comprising a curable polyorganosiloxane compound (A) and a surface-modified composite metal oxide (B),
The surface-modified composite metal oxide (B) is obtained by converting the composite metal oxide (b2) into the following general formula (1):
R ¹ R ² R ³ Si—Y—SiR ⁴ _n X _(3-n) (1)
{Wherein R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, R ⁴ is a saturated alkyl group, and Y is a divalent linking group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, and n is an integer of 0 to 2. }
A curable silicone resin composition obtained by surface modification with a modifying agent containing a surface modifying agent (b1) represented by   As the curable polyorganosiloxane compound (A), a polyorganosiloxane compound (a1) having a functional group selected from the group consisting of a vinyl group, an allyl group and an acrylic group, and a polyorganosiloxane having a hydrogen atom directly bonded to silicon. The curable silicone resin composition according to claim 1, comprising an organosiloxane compound (a2) and further comprising a hydrosilylation catalyst (C).   As the curable polyorganosiloxane compound (A), a polyorganosiloxane compound (a3) having a group having an unsaturated carbon double bond capable of radical photopolymerization selected from the group consisting of an acryl group, a methacryl group and a styryl group The curable silicone resin composition according to claim 1, further comprising a radical photopolymerization initiator (D).   The curable silicone resin composition according to any one of claims 1 to 3, wherein n is 0 or 1 in the surface modifier (b1).   The curable silicone resin composition of any one of Claims 1-4 whose Y is a C1-C6 bivalent hydrocarbon group in the said surface modifier (b1).   The curable silicone resin composition according to any one of claims 1 to 5, wherein the composite metal oxide (b2) is barium titanate.   The curable silicone resin composition of any one of Claims 1-6 whose average primary particle diameter of the said composite metal oxide (b2) is 1-50 nm.   The volume ratio of the composite metal oxide (b2) to the total volume of 100% by volume of the curable polyorganosiloxane compound (A) and the surface-modified composite metal oxide (B) is 10 to 70% by volume. Item 8. The curable silicone resin composition according to any one of items 1 to 7.