JP5780003B2 - COMPOSITION COMPOSITION AND TRANSPARENT COMPOSITION OF INORGANIC OXIDE PARTICLES AND SILICONE RESIN - Google Patents

Description

  The present invention relates to a composite composition and a transparent composite of inorganic oxide particles and a silicone resin, and more specifically, is suitably used as a filler material for a silicone resin, and is transparent with improved refractive index, mechanical properties, and gas barrier properties. Composition of inorganic oxide particles and silicone resin capable of preventing dispersibility when dispersed in silicone resin and phase separation / whitening during curing of inorganic oxide particles capable of maintaining the property And a transparent composite obtained by molding and solidifying the composite composition.

In the past, attempts have been made to improve the mechanical properties and the like of a resin by compounding an inorganic oxide such as silica with a resin as a filler. As a method of combining the filler and the resin, a method of mixing a dispersion liquid in which an inorganic oxide is dispersed in a solution containing one or both of water and an organic solvent, and the resin is generally used. By mixing the dispersion and the resin by various methods, an inorganic oxide particle composite plastic in which the inorganic oxide particles are combined as the second phase can be produced (for example, see Patent Document 1).
In addition, coating compositions and coating films that have optical properties such as refractive index and transparency adjustment in addition to mechanical properties have been proposed by coating the surface of inorganic oxide particles with a polymer (for example, , See Patent Document 2).

Among polymer materials, silicone resins have excellent weather resistance such as heat resistance and cold resistance, as well as excellent electrical properties and low toxicity, so they range from cosmetic materials and medical materials to electrical and electronic materials. Used throughout. Further, in recent years, attention has also been paid to the transparency, and it is also used for a member requiring transparency, such as a transparent sealing material for a light emitting diode.
Properties required for such applications include transparency, optical properties such as refractive index, mechanical properties such as hardness, thermal stability such as heat resistance, and gas barrier that suppresses the permeability of water vapor and various gases. Sex.

  For example, zirconium oxide particles can be produced in the presence of a chelating agent by improving the optical properties and thermal stability by combining a conventionally proposed silicone resin and an inorganic material such as an inorganic oxide. A composition comprising a polysiloxane mixed with a hydroxyl group-containing polysiloxane (Patent Document 3), a composition for coating a light emitting device comprising a composite of zirconium oxide particles and polyfunctional polysiloxane (Patent Document 4), and coating inorganic nanoparticles with an organic compound A large number of materials such as a filling material for a light emitting element mixed with phenyl group-containing silicone (Patent Document 5) have been proposed.

Japanese Patent Laying-Open No. 2005-161111 JP 2003-292826 A JP 2006-316264 A JP 2009-91380 A JP 2007-70603 A

However, conventionally, when the inorganic oxide particles are combined with a hydrophobic resin, the surface of the inorganic oxide particles is hydrophilic, and therefore, particularly between the highly hydrophobic silicone resin and the inorganic oxide particles. In the meantime, the silicone resin and the inorganic oxide particles are separated, making it difficult to form a composite.
Therefore, as a general solution, in order to hydrophobize the surface of the inorganic oxide particles, a surface modifier such as an organic polymer dispersant is added to the surface of the inorganic oxide particles to thereby form a silicone resin and an inorganic oxide. There has been a contrivance to increase the compatibility with physical particles, but there has been a problem that it is difficult to sufficiently hydrophobize the surface of the inorganic oxide particles until they are compatible with the silicone resin.
In addition, the particle size of the inorganic oxide particles is as large as 20 nm or more. Therefore, there is a problem that transparency is lowered and devitrification occurs depending on the case.

For example, in a high viscosity silicone resin, even if a conventional hydrophobic polymer dispersant is used, it is difficult to be compatible with inorganic oxide particles, and the surface of inorganic oxide particles can be sufficiently hydrophobized. Even if it was possible, there was a problem that a transparent dispersion of inorganic oxide particles could not be obtained.
In addition, when a hydroxyl group-containing polysiloxane is used, water is generated with the progress of crosslinking, and in some cases, there is a possibility that the inorganic oxide particles and the polysiloxane may be phase-separated. There was a risk of pores and cracks.
On the other hand, when polyfunctional polysiloxane is used, there is a limitation in the blending of inorganic oxide particles and polysiloxane, and there is a problem that pores and cracks become prominent particularly when the amount of inorganic oxide particles is large. It was. When the polyfunctional polysiloxane is used, there is a problem that unreacted functional groups are likely to remain, so that the composite characteristics after crosslinking are likely to change with time, and the durability is inferior.

Further, when the inorganic oxide particles and the silicone resin are made compatible with each other using a chelating agent, there is a problem that coloring occurs due to a change with time or thermal deterioration.
In addition, as a high refractive index filling material for light-emitting elements, a transparent dispersion in which nanoparticles are dispersed in methylphenyl silicone that easily interacts with various organic molecules has been proposed. The transparent dispersion and the cured product cannot be achieved.
In addition, when addition reaction type dimethyl silicone is used, the silicone before curing is transparently dispersed, but phase separation may occur in the curing step and whitening may occur.

  On the other hand, a method of treating the surface of the conventional metal oxide particles with a modified silicone has also been proposed, but since the modified silicone is generally polyfunctional, it is possible to reliably treat the surface of the inorganic oxide particles. In some cases, the unreacted modified site may adversely affect the compatibility with the silicone resin. Thus, in order to solve this problem, attempts have been made to improve the surface treatment (secondary or tertiary surface treatment), but there have been problems such as complicated processes.

  The present invention has been made to solve the above-described problems, and inorganic oxide particles capable of maintaining the transparency as well as improving the refractive index, mechanical properties, and gas barrier properties are dispersed in the silicone resin. In this case, an object is to provide a composite composition and a transparent composite of inorganic oxide particles and a silicone resin, which have high dispersibility and can prevent phase separation and whitening during curing.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that an inorganic oxide particle having an average dispersed particle diameter of 1 nm or more and 20 nm or less is a polydimethylsiloxane skeleton having one functional group at one end. By surface modification with a polymer and further compounding with a silicone resin and a reaction catalyst, when the inorganic oxide particles are dispersed in the silicone resin, the dispersibility of the inorganic oxide particles is greatly increased. While improving transparency and maintaining transparency, while maintaining the heat resistance and light resistance of a silicone resin, it discovered that the transparent composite body by which the refractive index was controlled can be obtained, and it came to complete this invention.

That is, the inorganic oxide composite composition of the particles and the silicone resin of the present invention, a port re polydimethylsiloxane backbone average dispersed particle diameter as surface modified by polymer binds less 1nm or more and 20nm inorganic oxide particles A composite composition comprising a silicone resin and a reaction catalyst, wherein the silicone resin comprises a vinyl-modified silicone and a hydrogen-modified silicone, and the reaction catalyst comprises a hydrosilylation reaction catalyst. The polydimethylsiloxane skeleton polymer is one or two selected from the group consisting of a monoglycidyl ether-terminated polydimethylsiloxane and a monohydroxyether-terminated polydimethylsiloxane .

The polydimethylsiloxane skeleton polymer is preferably one or two selected from the group of monoglycidyl ether-terminated polydimethylsiloxane and monohydroxy ether-terminated polydimethylsiloxane.
The vinyl-modified silicone includes vinyl dimethyl silicone at both ends, vinyl diphenyl-dimethyl silicone at both ends, vinyl phenylphenyl silicone at both ends, vinyl diethyl silicone at both ends, vinyl dimethyl silicone at side chain, vinyl methyl silicone, vinyl methoxy silicone. 1 type or 2 types or more selected from the group of vinyl resin dispersions are preferred.

  The hydrogen-modified silicone is one selected from the group consisting of hydrogen-dimethylsilicone at both ends, methylhydrogen-dimethylsilicone, methylhydrogensilicone, ethylhydrogensilicone, methylhydrogen-phenylmethylsilicone, and hydride resin. Or it is preferable that they are 2 or more types.

（但し、Ｒ_１〜Ｒ_８は相互に独立な任意の有機基（Ｈを除く）、ｍは１以上の整数、ｎは０を含む正の整数である）
に示す側鎖ハイドロジェン変性シリコーンを含有してなり、該側鎖ハイドロジェン変性シリコーンにおけるｍとｎとの比（ｍ／（ｍ＋ｎ））は０．２５以上かつ１以下であることが好ましい。 The hydrogen-modified silicone has the following formula (1):

(Where R _{1 to} R ₈ are mutually independent arbitrary organic groups (excluding H), m is an integer of 1 or more, and n is a positive integer including 0)
It is preferable that the ratio (m / (m + n)) of m to n in the side chain hydrogen-modified silicone is 0.25 or more and 1 or less.

（但し、Ｒ _１ 〜Ｒ _８ は相互に独立な任意の有機基（Ｈを除く）、ｍは１以上の整数、ｎは０を含む正の整数である）
に示す側鎖ハイドロジェン変性シリコーンであることが好ましい。
前記無機酸化物粒子の形成材料が酸化ジルコニウム（ＺｒＯ_２）、酸化チタン（ＴｉＯ_２）、酸化ケイ素（ＳｉＯ_２）、酸化アルミニウム（Ａｌ_２Ｏ_３）、酸化鉄（Ｆｅ_２Ｏ_３、ＦｅＯ、Ｆｅ_３Ｏ_４）、酸化銅（ＣｕＯ、Ｃｕ_２Ｏ）、酸化亜鉛（ＺｎＯ）、酸化イットリウム（Ｙ_２Ｏ_３）、酸化ニオブ（Ｎｂ_２Ｏ_５）、酸化モリブデン（ＭｏＯ_３）、酸化インジウム（Ｉｎ_２Ｏ_３、Ｉｎ_２Ｏ）、酸化スズ（ＳｎＯ_２）、酸化タンタル（Ｔａ_２Ｏ_５）、酸化タングステン（ＷＯ_３、Ｗ_２Ｏ_５）、酸化鉛（ＰｂＯ、ＰｂＯ_２）、酸化ビスマス（Ｂｉ_２Ｏ_３）、酸化セリウム（ＣｅＯ_２、Ｃｅ_２Ｏ_３）、酸化アンチモン（Ｓｂ_２Ｏ_３、Ｓｂ_２Ｏ_５）酸化ゲルマニウム（ＧｅＯ_２、ＧｅＯ）、スズ添加酸化インジウム（ＩＴＯ：Indium Tin Oxide）、イットリア安定化ジルコニア（ＹＳＺ：Yttria Stabilized Zirconia）から選択される１種または２種以上であることが好ましい。
前記無機酸化物粒子の前記複合組成物中の含有率が、１質量％以上かつ９０質量％以下であることが好ましい。 The vinyl-modified silicone is a side chain vinyl-dimethyl silicone, and the hydrogen-modified silicone is represented by the following formula (1):

(Where R _{1 to} R ₈ are mutually independent arbitrary organic groups (excluding H), m is an integer of 1 or more, and n is a positive integer including 0)
The side chain hydrogen-modified silicone shown in FIG.
The material for forming the inorganic oxide particles is zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ , FeO, Fe ₃ O ₄ ), copper oxide (CuO, Cu ₂ O), zinc oxide (ZnO), yttrium oxide (Y ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), molybdenum oxide (MoO ₃ ), indium oxide (In ₂ O ₃ , In ₂ O), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ , W ₂ O ₅ ), lead oxide (PbO, PbO ₂ ), bismuth oxide (Bi) ₂ O ₃ ), cerium oxide (CeO ₂ , Ce ₂ O ₃ ), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ) germanium oxide (GeO ₂ , GeO), tin-added It is preferable that it is 1 type, or 2 or more types selected from indium oxide (ITO: Indium Tin Oxide) and yttria stabilized zirconia (YSZ: Yttria Stabilized Zirconia).
The content of the inorganic oxide particles in the composite composition is preferably 1% by mass to 90% by mass.

The transparent composite of the present invention is formed by molding and solidifying the composite composition of the inorganic oxide particles of the present invention and the silicone resin into a predetermined shape, or molding the composite composition and then forming silicone. The inorganic oxide particles whose surface is modified by bonding the polydimethylsiloxane skeleton polymer in the resin are dispersed with an average dispersed particle diameter of 1 nm or more and 20 nm or less, and a hydrosilylation reaction catalyst is contained in the silicone resin. The polydimethylsiloxane skeleton polymer is one or two selected from the group consisting of a monoglycidyl ether-terminated polydimethylsiloxane and a monohydroxyether-terminated polydimethylsiloxane .

According to the composite composition of the inorganic oxide particles and the silicone resin of the present invention, the average dispersed particle size whose surface is modified by binding a polydimethylsiloxane skeleton polymer having one functional group at one end is 1 nm or more. In addition, the inorganic oxide particles of 20 nm or less, a silicone resin, and a reaction catalyst are included. The silicone resin is a resin that includes vinyl-modified silicone and hydrogen-modified silicone. The reaction catalyst is a hydrosilylation reaction catalyst. Since it is made to contain, the dispersibility of the inorganic oxide particle in a silicone resin can be improved significantly.
Therefore, when this composite composition is used, when the inorganic oxide particles and the silicone resin are combined, the dispersibility is high, and phase separation and whitening at the time of curing can be prevented. A transparent composite with a controlled refractive index can be obtained while maintaining heat resistance and light resistance.

  According to the transparent composite of the present invention, inorganic oxide particles whose surface is modified by bonding a polydimethylsiloxane skeleton polymer having one functional group at one end in a silicone resin has an average dispersed particle diameter of 1 nm or more and 20 nm. In addition to dispersing in the following, the silicone resin contains a hydrosilylation reaction catalyst, so that the inorganic oxide particles and the silicone resin in which the refractive index is controlled while maintaining transparency, heat resistance and light resistance are maintained. A transparent complex with can be easily obtained.

  According to the transparent composite of the present invention, the composite composition of the inorganic oxide particles and the silicone resin of the present invention is molded into a predetermined shape and solidified, or molded after the composite composition is solidified. It is possible to easily obtain a transparent composite of inorganic oxide particles having a controlled refractive index and a silicone resin while maintaining the properties, heat resistance and light resistance.

The form for implementing the composite composition and transparent composite_body | complex of the inorganic oxide particle | grains and silicone resin of this invention are demonstrated.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

[Composite composition of inorganic oxide particles and silicone resin]
The composite composition of inorganic oxide particles and silicone resin of the present embodiment (hereinafter sometimes simply referred to as “composite composition”) is a composite composition in which inorganic oxide particles are dispersed in a silicone resin. And an inorganic oxide particle having an average dispersed particle diameter of 1 nm to 20 nm, which is surface-modified by bonding with a polydimethylsiloxane skeleton polymer having one functional group at one end, a silicone resin, and a reaction catalyst Is a composite composition.

Here, the “composite composition” does not have a specific shape, has irreversible deformability that does not return to the original shape once deformed, and serves as a raw material for the transparent composite described later It is.
As a state of this composite composition, for example, a state in a liquid state or a gel state having thixotropy shall be shown.

  The inorganic oxide that is a component of the inorganic oxide particles is not particularly limited, but is an oxide of a nonmetallic element such as silicon (Si), zirconium (Zr), titanium (Ti), aluminum (Al), iron (Fe ), Copper (Cu), zinc (Zn), yttrium (Y), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), tantalum (Ta), tungsten (W), lead (Pb) ), Bismuth (Bi), cerium (Ce), antimony (Sb), germanium (Ge) and other metal element oxides.

Examples of such inorganic oxides include zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ , FeO). , Fe ₃ O ₄ ), copper oxide (CuO, Cu ₂ O), zinc oxide (ZnO), yttrium oxide (Y ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), molybdenum oxide (MoO ₃ ), indium oxide (In ₂ O ₃ , In ₂ O), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ , W ₂ O ₅ ), lead oxide (PbO, PbO ₂ ), bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ , Ce ₂ O ₃ ), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ) germanium oxide (GeO ₂ , GeO) Etc.

Such inorganic oxides also include composite oxides such as tin-added indium tin oxide (ITO) and yttria stabilized zirconia (YSZ).
Such inorganic oxides may be used alone or in combination of two or more.
In particular, when increasing the refractive index of a composite composition with a silicone resin, zirconium oxide (ZrO ₂ ) or titanium oxide (TiO ₂ ) having a high refractive index, being colorless and transparent to visible light, and having high hardness. ₂ ) is preferred.

  Further, when reducing the refractive index of a composite composition with a silicone resin, for example, an inorganic oxide that has a low refractive index as a whole particle by having voids in the particles such as hollow silica particles and porous silica particles. It is preferable to use physical particles.

The average dispersed particle size in the composite composition of the inorganic oxide particles is preferably 1 nm or more and 20 nm or less.
Here, the reason why the average dispersed particle diameter of the inorganic oxide particles is limited to 1 nm or more and 20 nm or less is that when the average dispersed particle diameter is less than 1 nm, the primary particle diameter of the particles constituting the particles is extremely less than 1 nm. This is because the crystallinity becomes poor, and it becomes difficult to express particle characteristics such as refractive index. On the other hand, when the average dispersed particle diameter exceeds 20 nm, the influence of Rayleigh scattering becomes large, and the composite composition This is because the transparency of the product is lowered, or the transparency of the transparent composite obtained by molding and solidifying the composite composition is lowered.

  Thus, since the inorganic oxide particles are nanometer-sized particles, a composite composition in which the inorganic oxide particles are dispersed in a silicone resin, or a transparent product formed by molding and solidifying the composite composition. Even in the composite, light scattering is small, and the transparency of the composite composition and the transparent composite can be maintained.

The content of the inorganic oxide particles in the composite composition is preferably 1% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 90% by mass or less, and further preferably 10% by mass or more. And it is 85 mass% or less.
Here, the reason why the content of the inorganic oxide particles is limited to 1% by mass or more and 90% by mass or less is that when the content is less than 1% by mass, the amount of the inorganic oxide particles is too small, and the inorganic oxide particles When the oxide particles are combined with the silicone resin, it is not preferable because changes in the optical properties and mechanical properties of the silicone resin are hardly exhibited, and as a result, the effect of combining the inorganic oxide particles cannot be obtained. On the other hand, when the content exceeds 90% by mass, the dispersibility of the inorganic oxide particles cannot be ensured sufficiently, the fluidity in the composite composition is lowered, and the moldability is deteriorated.

Next, the surface modification of the inorganic oxide particles will be described.
The surface of the inorganic oxide particles is modified with a surface modifier made of a polydimethylsiloxane skeleton polymer having one functional group at one end.
This surface modifier has a polydimethylsiloxane skeleton, in particular, a linear polydimethylsiloxane skeleton in the main chain, and has only one polar group as a functional group at one end (one end side) of the main chain. ing. Therefore, when this functional group (polar group) is selectively bonded to the surface of the inorganic oxide particle, the other end, that is, the siloxane skeleton part is aligned and faces the outside of the particle (the direction away from the surface of the inorganic oxide particle). It becomes.

  Moreover, since the siloxane skeleton portion and the silicone resin are highly compatible and have good affinity, the inorganic oxide particles surface-modified with the surface modifier made of the polydimethylsiloxane skeleton polymer are contained in the silicone resin. Can be uniformly dispersed, and a good composite composition can be formed.

Here, the “linear polydimethylsiloxane skeleton” means that the polydimethylsiloxane skeleton has no branches (branches).
Here, the polydimethylsiloxane skeleton is branched (branched), or the polar group which is a functional group is located in the middle of the siloxane skeleton (the silicon in which the functional group is located in the middle of the siloxane skeleton). In the case of bonding, at least a part of the siloxane skeleton is likely to face the surface direction of the inorganic oxide particles or the direction parallel to the particle surface. In this case, the amount of the siloxane skeleton directed to the outside of the inorganic oxide particles is reduced, and the compatibility and affinity between the inorganic oxide particles and the silicone resin may be reduced. Furthermore, since the uniformity of the direction of the siloxane skeleton is lost, entanglement and steric hindrance between the siloxane skeletons may occur, and the compatibility and affinity between the inorganic oxide particles and the silicone resin may also decrease.

  Further, this surface modifier is a monofunctional group having only one polar group, and since this functional group is used for bonding with the inorganic oxide particles, the surface bonded to the inorganic oxide particles. There are no functional groups in the modifier. Therefore, when using a conventional polyfunctional polysiloxane, there is no risk of deterioration of compatibility with the silicone resin generated due to unreacted functional groups, such as white turbidity, A stable composite composition can be obtained.

As such a surface modifier, it is preferable to have one or two of monoglycidyl ether-terminated polydimethylsiloxane and monohydroxyether-terminated polydimethylsiloxane.
Among the terminal groups possessed by these surface modifiers, the monoglycidyl ether terminal is one in which the epoxy group part of the glycidyl group is ring-opened and bonded to the hydroxyl group on the surface of the inorganic oxide particle. The monohydroxy ether terminal is bonded by dehydration condensation between the terminal hydroxyl group and the surface hydroxyl group of the inorganic oxide particles.

  Of these surface modifiers, monoglycidyl ether-terminated polydimethylsiloxane does not naturally contain hydroxyl groups, and monohydroxyether-terminated polydimethylsiloxane has hydroxyl groups only on functional groups that bind to inorganic oxide particles. Have. Therefore, in any surface modifier, after bonding to the surface of the inorganic oxide particle, it does not have a hydroxyl group or exists in the vicinity of the surface of the inorganic oxide particle, and does not prevent compatibility with the silicone resin. It is in a state.

  Moreover, the transparent composite_body | complex obtained from the composite composition of the inorganic oxide particle surface-modified by these surface modifiers and a silicone resin has a small shrinkage rate. As a result, there is no generation of pores or cracks in the transparent composite, and the dispersibility of the inorganic oxide particles in the cured silicone resin is maintained well, and a transparent composite free from defects is obtained.

Since the inorganic oxide particles of this embodiment are surface-modified with a polydimethylsiloxane skeleton polymer having one functional group at one end, the silicone resin has excellent compatibility and dispersibility. Yes. Accordingly, the silicone resin itself is not particularly limited, and any ordinary silicone resin can be used without any problem.
Among these silicone resins, particularly preferred are silicone resins using a hydrosilylation reaction in which a cured product is obtained at room temperature (25 ° C.) or more and about 150 ° C. or less. Examples of such silicone resins include vinyl-modified silicones and Hydrogen-modified silicone is preferred.

  As vinyl-modified silicones, both terminal vinyl-dimethyl silicone, both terminal vinyl diphenyl-dimethyl silicone, both terminal vinyl-phenyl methyl silicone, both terminal vinyl-diethyl silicone, side chain vinyl-dimethyl silicone, vinyl methyl silicone, vinyl methoxy silicone And vinyl resin dispersion. One kind of these vinyl-modified silicones may be selected and used, or two or more kinds may be used in combination.

  Examples of the hydrogen-modified silicone include both-end hydrogen-dimethylsilicone, methylhydrogen-dimethylsilicone, methylhydrogensilicone, ethylhydrogensilicone, methylhydrogen-phenylmethylsilicone, and hydride resin. One type of these hydrogen-modified silicones may be selected and used, or two or more types may be used in combination.

（但し、Ｒ_１〜Ｒ_８は相互に独立な任意の有機基（Ｈを除く）、ｍは１以上の整数、ｎは０を含む正の整数である）
に示す側鎖ハイドロジェン変性シリコーンを含有していることが好ましい。
ここで、側鎖ハイドロジェン変性シリコーンが好ましい理由は、ビニル変性シリコーンとヒドロシリル化反応等により重合硬化してシリコーン樹脂重合体を形成する際に、末端ハイドロジェン変性シリコーンに比べて反応性が高く、さらに反応基であるハイドロジェン変性シリコーンの量が多くできることから架橋密度が高くなり、結果として得られたシリコーン樹脂重合体の特性を向上させることができるからである。 In this hydrogen-modified silicone, the following formula (1)

(Where R _{1 to} R ₈ are mutually independent arbitrary organic groups (excluding H), m is an integer of 1 or more, and n is a positive integer including 0)
It is preferable to contain the side chain hydrogen-modified silicone shown in FIG.
Here, the reason why the side chain hydrogen-modified silicone is preferable is that, when a silicone resin polymer is formed by polymerization and curing with a vinyl-modified silicone and a hydrosilylation reaction, the reactivity is higher than the terminal hydrogen-modified silicone, Furthermore, since the amount of the hydrogen-modified silicone as a reactive group can be increased, the crosslinking density is increased, and the characteristics of the resulting silicone resin polymer can be improved.

Furthermore, the ratio (m / (m + n)) of m to n in the side chain hydrogen-modified silicone represented by the above formula (1) is preferably 0.25 or more and 1 or less.
Here, the reason why the ratio of m to n (m / (m + n)) is limited to 0.25 or more and 1 or less is that when this ratio is less than 0.25, the crosslinking density during curing is too low. In addition, the aggregation / phase separation rate of the inorganic oxide particles becomes faster than the curing rate of the silicone resin, and as a result, the transparency is lost upon curing with the silicone resin.

に示すハイドロジェン含有ユニットの含有率が高くなり、透明複合体を形成した後もビニル変性シリコーンと未反応のユニットの割合が増加すると考えられるが、この未反応ハイドロジェン含有ユニットが透明複合体の特性に及ぼす影響はほとんど無い。したがって、側鎖ハイドロジェン変性シリコーンにおけるｍとｎの比（ｍ／（ｍ＋ｎ））の最大値は１であってよい。 As the ratio of m to n (m / (m + n)) increases, the following formula (2)

The content of hydrogen-containing units shown in (2) is high, and the proportion of vinyl-modified silicone and unreacted units is expected to increase even after forming a transparent composite. There is almost no influence on the characteristics. Therefore, the maximum value of the ratio of m to n (m / (m + n)) in the side chain hydrogen-modified silicone may be 1.

In the above formula (1), R _{1 to} R ₈ are mutually independent arbitrary organic groups (excluding H), and part or all of them may be the same. Here, “partially the same” means, for example, that R ₁ , R ₃ , R ₄ and H ₆ are the same, and R ₁ , R ₂ , R ₅ , R ₇ and R ₈ are mutually Not only in the case where only some are of the same species, for example, R ₁ , R ₃ and R ₄ are the same and R ₂ , R ₅ , R ₇ and R ₈ are the same, and R ₁ , R ₂ and R ₆ may be different from each other, and some of them may be the same combination.
Further, the “organic group” represents all groups composed of organic substances such as a characteristic group, a functional group, and a substituent, and includes, for example, an alkyl group and an alkoxy group.

  This silicone resin does not have a specific shape as a characteristic of the composite composition after mixing with inorganic oxide particles or the like, and has irreversible deformability that does not return to the original shape once deformed. Any material can be used as a raw material for the transparent composite, which will be described later, and may be in a liquid state or a gel-like state having thixotropy, for example, and the degree of polymerization is not particularly limited.

That is, as long as the composite composition has the above characteristics, any of a monomer (monomer), an oligomer (2 to several hundreds of polymers), and a polymer (several hundreds or more of polymers) may be used. You may use what gave the width | variety of polymerization degree by combining.
Moreover, in this silicone resin, you may add antioxidant, a mold release agent, a coupling agent, an inorganic filler, etc. in the range which does not impair the characteristic.

The composite composition of this embodiment contains a reaction catalyst.
The reaction catalyst preferably contains a hydrosilylation reaction catalyst. Examples of the hydrosilylation reaction catalyst include a noble metal catalyst, and a noble metal powder, a noble metal salt, a noble metal complex, and the like can be appropriately selected. Among the noble metal catalysts, platinum group catalysts are preferable, and examples thereof include platinum catalysts, rhodium catalysts, palladium catalysts, and the like, and platinum catalysts are particularly preferable. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, a platinum-olefin complex, a platinum-carbonyl complex, and the like. These can be used alone or in combination of two or more.

Moreover, the composite composition of this embodiment can contain an organic solvent.
Here, the following points can be raised as advantages of the composite composition containing an organic solvent.
The first advantage is viscosity control of the composite composition. For example, when the mixture of the inorganic oxide particles and the silicone resin has a high viscosity, the fluidity is deteriorated, and there may be a problem that the moldability and ease of handling of the transparent composite described later are lowered. Therefore, in order to solve these problems, it is possible to reduce the viscosity of the mixture to a desired viscosity by adding an organic solvent to the mixture.

  The second advantage is easy mixing and dispersion. For example, inorganic oxide particles modified with a surface modifier are first dispersed in an organic solvent highly compatible with the silicone resin to be used to form an inorganic oxide particle dispersion, and this inorganic oxide particle dispersion and silicone It is preferable to mix and stir the resin since the dispersibility of the inorganic oxide particles in the silicone resin becomes very high.

As the organic solvent, a hydrophobic solvent is preferably used. The reason is that a hydrophobic solvent is suitable as a solvent having high dispersibility of the surface-modified inorganic oxide and high compatibility with the silicone resin.
As such a hydrophobic solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and chlorine-containing solvents such as dichloromethane, chloroform, and carbon tetrachloride are preferably used. One of these solvents is used. Can be used alone or in admixture of two or more.

  The content of the organic solvent is not particularly limited as long as the above-mentioned solvent addition effect can be obtained, but is usually 400% by mass with respect to the total amount of the surface-modified inorganic oxide particles and the silicone resin. The following is preferable. The reason for this is that if an organic solvent is present in excess, when forming a transparent composite described later using this composite composition, the viscosity is too low, resulting in difficulty in moldability, or removal of the organic solvent. This is because it takes time and is not preferable.

[Method for producing composite composition]
In the production method of the composite composition of the present embodiment, first, the surface of the inorganic oxide particles is modified with a polydimethylsiloxane skeleton polymer having one functional group at one end, and then the surface-modified average dispersed particle size is obtained. Is a method of mixing inorganic oxide particles of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst.

  Here, as a method for modifying the surface of the inorganic oxide particle with a polydimethylsiloxane skeleton polymer having one functional group at one end, first, a specific dispersant is bonded to the surface of the inorganic oxide particle in advance to make it hydrophobic. After imparting dispersibility to an organic solvent (organic solvent), the inorganic oxide particles are dispersed in a hydrophobic solvent, and a polydimethylsiloxane skeleton polymer having one functional group at one end is dispersed in the obtained dispersion. The surface which consists of the specific dispersing agent previously couple | bonded with the surface of the inorganic oxide particle in this hydrophobic solvent, and the polydimethylsiloxane frame | skeleton polymer which has one functional group in one terminal by adding the surface modifier which becomes A method for substituting the modifier may be mentioned.

First, a specific dispersant is bonded to the surface of the inorganic oxide particles so as to have dispersibility in a hydrophobic solvent.
This specific dispersant is a surface modifier comprising a polydimethylsiloxane skeleton polymer in which inorganic oxide particles to which a dispersant is bonded are easily dispersed in a hydrophobic solvent and having one functional group at one end. In the case of coexistence, the specific dispersant already bonded to the surface of the inorganic oxide particle and the surface modifier can easily be substituted.

Specific examples of the dispersant include organic acid compounds and organic base compounds. Examples of the organic acid compound include carboxylic acid, phosphoric acid, and sulfonic acid. Examples of the organic base compound include amine and phosphazene base.
Among these dispersants, carboxylic acids and amines are preferably used because they function as a dispersant for dispersing the inorganic oxide particles and can be favorably eliminated during the reaction with the surface modifier. .

  Examples of the carboxylic acid include 1 selected from saturated fatty acids such as formic acid, acetic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, stearic acid, and unsaturated fatty acids such as oleic acid. A species or two or more species may be selected and used. As the amine, for example, one or more selected from aromatic amines such as pyridine and bipyridine and aliphatic amines such as triethylamine, diethylamine, monoethylamine, and butylamine may be selected and used.

Next, the inorganic oxide particles having a specific dispersant bonded to the surface are dispersed in a hydrophobic solvent.
The hydrophobic solvent is not particularly limited as long as the inorganic oxide particles can be stably dispersed. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and chlorine-containing compounds such as dichloromethane, chloroform, and carbon tetrachloride. A solvent is preferably used, and one or more of these solvents can be used.

Next, the surface modifier composed of a polydimethylsiloxane skeleton polymer having one functional group at one end is added to the hydrophobic solvent in which the inorganic oxide particles are dispersed, and this surface modifier is already applied to the surface of the inorganic oxide. The surface of the inorganic oxide particles is modified by substituting with a specific dispersing agent.
The mass ratio of the surface modifier comprising the polydimethylsiloxane skeleton polymer having one functional group at one end to the inorganic oxide particles is 5% by mass or more and 200% by mass or less with respect to the total mass of the inorganic oxide particles. More preferably, it is 10 mass% or more and 100 mass% or less, More preferably, it is 20 mass% or more and 100 mass% or less.

  Here, the reason why the mass ratio of the surface modifier is limited to 5% by mass or more and 200% by mass or less is that when the mass ratio of the surface modifier is less than 5% by mass, the amount of the surface modifier is too small and inorganic. The surface of the oxide particles cannot be sufficiently modified. Therefore, it becomes difficult for the inorganic oxide particles having insufficient surface modification to be compatible with the silicone resin. On the other hand, when the mass ratio of the surface modifier exceeds 200% by mass, the proportion of the surface modifier in the composite composition increases to a degree that cannot be ignored, and thus greatly affects the properties of the composite composition. This is because there is a risk of deteriorating characteristics.

Thus, by using a surface modifier composed of a polydimethylsiloxane skeleton polymer having one functional group at one end and reacting the surface modifier with inorganic oxide particles in a hydrophobic solvent, The groups (polar groups) are selectively oriented and bonded to the inorganic oxide particles, while the other end side is directed to the outside of the inorganic oxide particles so as to be dispersed in the hydrophobic solvent. Therefore, these surface treatment agents have a shape in which the functional group portion is bonded to the inorganic oxide particles, and the other end side is radially separated from the inorganic oxide particles.
As described above, inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less, the surface of which is modified with a polydimethylsiloxane skeleton polymer having one functional group at one end, are obtained.

Next, the inorganic oxide particles having a surface-modified average dispersed particle diameter of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst are mixed. At this time, an organic solvent may be added as necessary.
Here, the silicone resin itself is not particularly limited, and any combination of vinyl-modified silicone and hydrogen-modified silicone that can be cured by the hydrosilylation reaction described above can be used without any problem.

  That is, as vinyl-modified silicone, both terminal vinyl-dimethylsilicone, both terminal vinyldiphenyl-dimethylsilicone, both terminal vinyl-phenylmethylsilicone, both terminal vinyl-diethylsilicone, side chain vinyl-dimethylsilicone, vinylmethylsilicone, vinyl From methoxysilicone, vinyl resin dispersion, etc., one kind can be selected and used alone or in combination of two or more kinds.

  Examples of the hydrogen-modified silicone include hydrogen-dimethylsilicone at both ends, methylhydrogen-dimethylsilicone, methylhydrogensilicone, ethylhydrogensilicone, methylhydrogen-phenylmethylsilicone, hydride resin, and the like. The types can be selected and used alone or in combination of two or more.

The hydrogen-modified silicone preferably contains a side chain hydrogen-modified silicone represented by the above formula (1).
Here, the reason why the side chain hydrogen-modified silicone is preferable is that, when a silicone resin polymer is formed by polymerization and curing with a vinyl-modified silicone and a hydrosilylation reaction, the reactivity is higher than the terminal hydrogen-modified silicone, Furthermore, since the amount of the hydrogen-modified silicone as a reactive group can be increased, the crosslinking density is increased, and the characteristics of the resulting silicone resin polymer can be improved.

Furthermore, the ratio (m / (m + n)) of m to n in the side chain hydrogen-modified silicone represented by the above formula (2) is preferably 0.25 or more and 1 or less.
Here, the reason that the ratio of m to n (m / (m + n)) is limited to 0.25 or more is that when this ratio is less than 0.25, the crosslinking density at the time of curing is too small, and thus inorganic This is because the aggregation / phase separation rate of the oxide particles becomes faster than the curing rate of the silicone resin, and as a result, the transparency is lost upon curing with the silicone resin.

  In addition, as the ratio of m to n (m / (m + n)) increases, the content of the hydrogen-containing unit represented by the above formula (2) increases, and even after forming the transparent composite, Although the proportion of unreacted units is thought to increase, this unreacted hydrogen-containing unit has little effect on the properties of the transparent composite. Therefore, the maximum value of the ratio of m to n (m / (m + n)) in the side chain hydrogen-modified silicone may be 1.

  The method of mixing the surface-modified inorganic oxide particles and the silicone resin is not particularly limited, and a conventionally known method such as a mixer, various mills, or application of ultrasonic waves may be used.

  Here, the inorganic oxide particles whose surface is modified by the surface modifier can be mixed with the silicone resin in the state of the particles, but the surface-modified inorganic oxide particles in the silicone resin can be mixed. In order to increase dispersibility and ease of mixing, the surface-modified inorganic oxide particles are previously redispersed in an organic solvent (hydrophobic solvent) that is highly compatible with the silicone resin that uses the particles. It is preferable to mix and stir the obtained inorganic oxide particle dispersion and the silicone resin.

  That is, when inorganic oxide particles are directly added to a silicone resin having a certain degree of viscosity and stirred, the inorganic oxide particles are uniformly dispersed in the silicone resin having viscosity while preventing aggregation of the particles. It is difficult, the dispersibility of the inorganic oxide particles in the obtained dispersion is poor, and further, the process itself of dispersing the inorganic oxide particles in the viscous silicone resin requires a great deal of labor.

  On the other hand, when the surface-modified inorganic oxide particles are once redispersed in an organic solvent highly compatible with the silicone resin, the organic solvent itself has a low viscosity. In the form of a low-viscosity inorganic oxide particle dispersion. Therefore, if the dispersion liquid in which the inorganic oxide particles are uniformly dispersed and the silicone resin are mixed, the liquids are mixed with each other, so even if the silicone resin has a certain degree of viscosity, it is uniformly mixed with the dispersion liquid. As a result, the inorganic oxide particles are easily and uniformly dispersed in the silicone resin. Furthermore, since the process itself is a process of mixing the low-viscosity inorganic oxide particle dispersion and the viscous silicone resin, and a process of mixing the solutions, a great deal of labor is not required.

Furthermore, when the mixture of the surface-modified inorganic oxide particles and the silicone resin has a high viscosity, the fluidity of the mixture deteriorates, and as a result, the moldability of the transparent composite described later and ease of handling are reduced. There may be a problem of degradation.
In order to prevent this problem, when mixing the inorganic oxide particles and the silicone resin, an appropriate solvent, for example, an organic solvent having high dispersibility of the surface-modified inorganic oxide and high compatibility with the silicone resin. It is preferable to reduce the viscosity of the resulting mixture.

As such an organic solvent, a hydrophobic solvent is preferably used. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and chlorine-containing solvents such as dichloromethane, chloroform, and carbon tetrachloride are suitably used. Of these solvents, one kind can be used alone, or two or more kinds can be mixed and used.
Further, the content of the organic solvent is not particularly limited as long as the above-mentioned solvent addition effect can be obtained, but usually 400 mass with respect to the total amount of the surface-modified inorganic oxide particles and the silicone resin. % Or less is preferable. The reason for this is that if an organic solvent is present in excess, when forming a transparent composite described later using this composite composition, the viscosity is too low, resulting in difficulty in moldability, or removal of the organic solvent. It takes time.

As a specific method for mixing the surface-modified inorganic oxide particles and the silicone resin, for example, (1) After redispersing the inorganic oxide particles in an organic solvent, the silicone resin is added to the dispersion (2) After mixing the inorganic oxide particles and the silicone resin, an organic solvent is appropriately added to the mixture, and the viscosity is adjusted by stirring and mixing using a mixer or the like. And the like, and the like.
In addition, when the viscosity of the mixture obtained by the addition of the organic solvent is low, the viscosity may be adjusted (high viscosity) by removing part or all of the organic solvent by volatilization or the like.
As described above, the composite composition of the present embodiment can be obtained.

[Transparent composite]
In the transparent composite of this embodiment, the inorganic oxide particles whose surface is modified by bonding a polydimethylsiloxane skeleton polymer having one functional group at one end in a silicone resin have an average dispersed particle diameter of 1 nm or more and 20 nm or less. And a transparent composite containing a hydrosilylation reaction catalyst in the silicone resin. In this transparent composite, an organic solvent, especially a hydrophobic solvent, is not basically contained, and even if it is contained, the amount is very small.

  Here, the “transparent composite” has a specific shape, but this “having a predetermined shape” means that the transparent composite does not have irreversible deformability such as liquid or gel. This shows that a certain shape can be maintained according to the purpose and method. That is, in addition to a normal solid state that hardly deforms, it includes a rubber-like one having elastic deformability (shape restoring property), and does not indicate that the shape itself is a specific shape.

  This transparent composite has a predetermined shape by increasing the degree of polymerization and crosslinking of the silicone resin in the above composite composition, or the number of polymerizations and crosslinking between the silicone resin and the siloxane skeleton of the surface modifier. Can be obtained. Therefore, each component of the transparent composite, that is, the inorganic oxide particles, the silicone resin, and the reaction catalyst, the surface of which is modified with a surface modifier made of a polydimethylsiloxane skeleton polymer having one functional group at one end. About 3 components, it is the same as the above-mentioned composite composition.

  In this transparent composite, the surface-modified inorganic oxide particles constituting the composite itself have high compatibility and affinity with the silicone resin, and good dispersibility in the silicone resin. Therefore, degradation of optical characteristics, mechanical characteristics, thermal stability, etc. caused by phase separation of inorganic oxide particles and silicone resin or aggregation of inorganic oxide particles. There is no possibility of causing it, and good characteristics can be maintained.

  Further, as described above, when this silicone resin is cured by a reaction catalyst, the curing rate of the silicone resin is faster than the aggregation / phase separation rate of the inorganic oxide particles. The oxide particles are not aggregated and the transparency is high. In addition, since the composite composition which is a material for forming the transparent composite does not use a chelating agent, there is no possibility of coloring the transparent composite.

In addition, since the average dispersed particle size of the inorganic oxide particles contained in this transparent composite is 20 nm or less, the occurrence of Rayleigh scattering, which has a large effect when the average dispersed particle size exceeds 20 nm, is suppressed to a low level. The transparency of the composite is not lowered.
Thus, since the inorganic oxide particles are nanometer-sized particles, light scattering is small even in a composite composition or a transparent composite in which the inorganic oxide particles are dispersed in a silicone resin. And the transparency of the transparent composite can be maintained.

Furthermore, since the average dispersed particle diameter of the inorganic oxide particles contained in the transparent composite is 1 nm or more, the average primary particle diameter of the inorganic oxide particles does not become less than 1 nm at which the maintenance of crystallinity is lowered. . Therefore, the inorganic oxide particles are maintained in good crystallinity.
Thus, since the crystallinity of the inorganic oxide particles is maintained, the characteristics of the inorganic oxide particles themselves, that is, characteristics such as refractive index, hardness, and heat resistance do not deteriorate. Therefore, the effect as a transparent composite obtained by combining inorganic oxide particles with a silicone resin can be sufficiently obtained.

Here, the effect of the transparent composite will be described.
"Optical properties"
The optical properties of the transparent composite include refractive index control.
Since the refractive index of the silicone resin is about 1.4, the refractive index of the transparent composite can be increased by compositing with high refractive index oxide particles having a higher refractive index than that of the silicone resin.
In particular, it is effective to form a composite with high refractive index inorganic oxide particles having a refractive index of 2 or more, such as tetragonal zirconium oxide (refractive index: 2.15) or titanium oxide (refractive index: about 2.6). By using these high refractive index inorganic oxide particles, the refractive index of the transparent composite can be increased from about 1.5 to about 1.65, which is about 0.1 to 0.2 higher than that of the silicone resin alone. Is possible.

Regarding the transparency of the transparent composite, as described above, the light scattering can be suppressed sufficiently low by setting the average dispersed particle size of the inorganic oxide particles to 20 nm or less. Therefore, the transparency is sufficiently maintained in this transparent composite.
If inorganic oxide particles such as hollow silica particles and porous silica particles that have voids in the particles and have a low refractive index as a whole are combined with a silicone resin, the refractive index of the transparent composite can be increased. It can also be reduced.

"Mechanical properties"
The mechanical properties of the transparent composite include an improvement in hardness as compared with the resin alone.
Ordinary inorganic oxide particles have a higher hardness than silicone resins, and the surface hardness of the transparent composite can be increased by combining the inorganic oxide particles with a silicone resin. Thereby, the scratch resistance of the transparent composite can be improved, and the dimensional accuracy of the transparent composite itself can be improved.
In particular, since zirconium oxide has a high hardness among oxide-based ceramics, it can exhibit a high effect in improving the surface hardness by combining.

"Thermal and chemical stability"
Since the silicone resin itself contains silicon (Si) in the skeleton, it is superior in thermal stability and chemical stability such as heat resistance and chemical resistance as compared with a normal resin. On the other hand, inorganic oxide particles are superior to silicone resins in terms of heat resistance. Therefore, if inorganic oxide particles with high chemical stability are selected and the inorganic oxide particles with high chemical stability are combined with a silicone resin, the thermal stability and chemical properties of the resulting transparent composite are obtained. Stability can be further increased.

Here, as can be seen from the high compatibility with the hydrophobic solvent, the silicone resin is hydrophobic (water repellency), but has high flexibility and low gas barrier property against water vapor compared to other resins. .
In the transparent composite of the present embodiment, the inorganic oxide particles having excellent gas barrier properties are uniformly dispersed inside the transparent composite, and the bondability between the inorganic oxide particles and the silicone resin is high. The gas barrier property against water vapor in can be improved to a high state.

According to this transparent composite, the refractive index of the obtained transparent composite is increased from, for example, about 1.4 to 1.65 by combining high refractive index inorganic oxide particles, particularly zirconium oxide, with a silicone resin. be able to. In addition, the dimensional accuracy can be improved by improving the hardness. Therefore, the design freedom in the optical element can be improved.
As a result, for example, the optical lens can be reduced in size, thickness, integration, improvement in light collection efficiency, reduction in refractive index wavelength dependency, and the like, and thus an apparatus using such an optical element. Improvements in characteristics of CCD and CMOS cameras, such as higher resolution and higher sensitivity, can be expected.

  In addition, since this transparent composite has a higher refractive index than a single silicone resin, when used as a sealing material for an LED, which is a light-emitting element, A member having a high refractive index, such as a substrate for forming a body (the refractive index of a semiconductor material which is a light emitting body of an LED is about 2.5, and the refractive index of a light-transmitting substrate on which the semiconductor material is formed is 1.76. The degree of refractive index matching can be improved. Therefore, it is possible to reduce internal reflection in the process of extracting light emitted from the LED light emitter.

That is, by using the transparent composite of the present embodiment as an LED sealing material, the light extraction efficiency from the LED can be improved by about 10% to 15%. As a result, the luminance of the LED can be improved.
Furthermore, since this transparent composite has a high gas barrier property against water vapor, it is possible to suppress the intrusion of moisture from the outside and suppress the deterioration of the light emitting region. Therefore, the lifetime of the light emitting element can be extended.

  In addition, when this transparent composite is used as a sealing material for an organic EL element, the gas barrier property against water vapor is high, so that moisture penetration from the outside can be suppressed and deterioration of the light emitting region can be suppressed. In addition, since the inorganic oxide particles in the transparent composite can effectively suppress the permeation of oxygen gas, the deterioration of the light emitting region can be similarly suppressed. Therefore, the lifetime of the light emitting element in the organic EL element can be extended by using the transparent composite of the present embodiment as a sealing material for the organic EL element.

[Method for producing transparent composite]
The transparent composite of the present embodiment can be obtained by molding and solidifying the composite composition of the present embodiment into a predetermined shape, or molding the composite composition into a predetermined shape after solidifying the composite composition. .

In the manufacturing method of this embodiment, the “method of forming into a predetermined shape and solidifying” is as follows.
First, the composite composition of the present embodiment is molded using a mold or a mold, or filled into a mold or a mold-shaped container, thereby forming a molded body or a filling molded into a target shape. Get things.
At this time, if the composite composition to be used has a high viscosity, an organic solvent or the like is added in advance and stirred and mixed so as to reduce the viscosity, so that the viscosity is suitable for molding and filling. Is preferred.
On the other hand, when the viscosity of the composite composition to be used is low, the silicone resins or a part of the silicone resin and the surface modifier are polymerized or crosslinked in advance as described below, or the composite composition contains an organic solvent. In some cases, it is preferable to adjust the viscosity to be suitable for molding and filling by increasing the viscosity by removing part or all of the organic solvent by volatilization.

Subsequently, the molded body or the filling is left at room temperature (about 25 ° C.) or is heated to a predetermined temperature (room temperature to 150 ° C., preferably 80 ° C. to 150 ° C.) and left to stand for a predetermined time. Reactions such as polymerization and crosslinking are caused to occur in the silicone resin and the surface modifier in the composition via a reaction catalyst, and the degree of bonding (degree of polymerization) between the silicone resins and between the silicone resin and the surface modifier is increased.
Further, when an organic solvent remains in the molded body or the filling, the organic solvent is removed by volatilization.
Thereby, even if it applies external force after removing this molded object or filling material from a metal mold | die or a container, it will be in the state which can maintain a fixed shape.
As described above, it is possible to obtain the transparent composite of the present embodiment having no defects, excellent optical characteristics and mechanical characteristics, and having high thermal stability and chemical stability.

Moreover, in the manufacturing method of this embodiment, "the method of shape | molding in a predetermined shape after solidifying a composite composition" is as follows.
First, the composite composition of this embodiment is solidified to obtain a solidified product (unformed transparent composite) of the composite composition. As the solidification method, the composite composition is allowed to stand at room temperature (about 25 ° C.) or at a predetermined temperature (room temperature to 150 ° C., preferably 80 ° C. to 150 ° C.) and left to stand for a predetermined time. What is necessary is just to raise reaction (polymerization degree) between silicone resins or between a silicone resin and a surface modifier by causing a reaction such as polymerization or cross-linking to a silicone resin or a surface modifier in a product via a reaction catalyst. .
Moreover, when an organic solvent remains, it is preferable to volatilize and remove this organic solvent.
This solidified product is in a state in which a certain shape can be maintained even when an external force is applied.

Next, this solidified product is formed into a necessary shape by a machining method such as cutting or die cutting. The silicone resin of the present embodiment has flexibility even after curing and can be easily processed.
Furthermore, the molded body after processing may be further solidified by increasing the degree of bonding (degree of polymerization) between the silicone resins or between the silicone resin and the surface modifier, or by removing the remaining organic solvent. .
As described above, it is possible to obtain the transparent composite of this embodiment having no defects, excellent optical characteristics and mechanical characteristics, and having high thermal stability and chemical stability.

  In addition, when applying this transparent composite to the field where transparency is not a problem, it is not necessary to ensure transparency, and therefore, it is necessary to limit the average dispersed particle size of the inorganic oxide particles to be used to 1 nm or more and 20 nm or less. There is no.

For example, when the purpose is to improve only the surface hardness of a composite containing inorganic oxide particles and a silicone resin, particles having an average dispersed particle size larger than 20 nm, for example, 100 nm inorganic oxide particles should be used. You can also.
Even in such a case, by applying the manufacturing method of the composite composition of the present embodiment, the dispersibility of the inorganic oxide particles in the composite composition is increased, and a molded body or filling having good physical properties. It can be set as the composite composition which can produce a thing.

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

"Example 1"
To a zirconium salt solution in which 2615 g of zirconium oxychloride octahydrate is dissolved in 40 L (liter) of pure water, dilute ammonia water in which 344 g of 28% ammonia water is dissolved in 20 L of pure water is added with stirring, and the zirconia precursor slurry is added. It was adjusted.
Next, an aqueous sodium sulfate solution in which 300 g of sodium sulfate was dissolved in 5 L of pure water was added to this slurry with stirring. The amount of sodium sulfate added at this time was 30% by mass with respect to the zirconia-converted value of zirconium ions in the zirconium salt solution.

Subsequently, this mixture was dried at 130 ° C. for 24 hours in the air using a drier to obtain a solid.
Next, the solid was pulverized using an automatic mortar, and then baked at 500 ° C. for 1 hour in the air using an electric furnace.
Next, the fired product is put into pure water, stirred to form a slurry, washed using a centrifuge, and after sufficiently removing the added sodium sulfate, dried in a dryer, Zirconia particles were obtained.

Next, 85 g of toluene and 5 g of caproic acid were added to and mixed with 10 g of the zirconia particles, and the surface of the zirconia particles was modified with a ligand. Then, the dispersion process was performed and the zirconia transparent dispersion liquid was prepared.
Next, 100 g of this zirconia transparent dispersion was mixed with 10 g of a monoglycidyl ether-terminated polydimethylsiloxane (PDMS-G: number average molecular weight 5000: manufactured by Aldrich) as a polydimethylsiloxane skeleton polymer having one functional group at one end, dibutyltin dilaurate 0 .01 g was added and surface modification was performed under reflux.

  After completion of the reaction, the solvent was removed with an evaporator, and methanol washing and centrifugation were repeated to remove caproic acid detached from the zirconia particles and unreacted monoglycidyl ether-terminated polydimethylsiloxane. The recovered surface-modified zirconia particles were 15 g.

  The obtained surface-treated zirconia particles were measured by proton NMR (in deuterated chloroform). As a result, the signal intensity caused by glycidyl groups in the vicinity of 2.6 to 3.5 ppm was found to be monoglycidyl ether-terminated polydimethylsiloxane alone. Compared to a large decrease. From this result, it was judged that the monoglycidyl ether-terminated polydimethylsiloxane caused ring opening of the epoxy group and bonding with the zirconia particles.

  After 15 g of the surface-modified zirconia particles were redispersed in 35 g of toluene, 14.1 g of side chain vinyl-dimethylsilicone VDT-131 (manufactured by Gelest) as vinyl-modified silicone and methylhydrogen-dimethylsilicone HMS as hydrogen-modified silicone 0.9 g of -151 (manufactured by Gelest) was added, and 6 mg of platinum divinyltetramethyldisiloxane SIP6830.3 (manufactured by Gelest) for room temperature curing was added as a reaction catalyst, and the surface-modified zirconia particles of Example 1-silicone resin A composite composition was obtained.

Next, this surface-modified zirconia particle-silicone resin composite composition was stirred and dissolved, then poured into a mold assembled with a glass plate, and the curing reaction was carried out while removing the organic solvent under vacuum at 40 ° C. A transparent composite having a thickness of 1 of 1 mm was obtained.
The content of zirconia particles in this transparent composite was 25% by mass.

The cross section of the obtained transparent composite of Example 1 was observed using a field emission transmission electron microscope JEM-2100F (manufactured by JEOL Ltd.), and the particle size of 100 particles randomly selected was measured. The average value was defined as the average dispersed particle size of the zirconia particles in the transparent composite. As a result of this measurement, the average dispersed particle size was 7 nm.
From this measurement result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 1 was 7 nm or less.
In addition, as a result of conducting elemental analysis on the obtained transparent composite of Example 1, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, so that it was the transparent composite of the present invention. confirmed.

"Example 2"
Zirconia particles from 10 g (25% by mass) to 14 g (35% by mass), and side chain vinyl-dimethylsilicone VDT-131 as a vinyl-modified silicone from 14.1 g (47% by mass) to 8.4 g (28% by mass). Example 2 according to Example 1 except that methylhydrogen-dimethylsilicone HMS-151 was changed from 0.9 g (3% by mass) to 0.6 g (2% by mass) as the hydrogen-modified silicone. The surface-modified zirconia particle-silicone resin composite composition and a transparent composite having a thickness of 1 mm were obtained.
The content of zirconia particles in this transparent composite was 35% by mass.

As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 2 in the same manner as in Example 1, the average dispersed particle diameter was 8 nm.
From this result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 2 was 8 nm or less.
Further, as a result of conducting elemental analysis on the obtained transparent composite of Example 2, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, so that it was the transparent composite of the present invention. confirmed.

"Example 3"
Zirconia particles from 10 g (25% by mass) to 16 g (40% by mass), and side chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone from 14.1 g (47% by mass) to 5.7 g (19% by mass). , 0.9 g (3 wt%) to 0.3 g (1 wt%) of methylhydrogen-dimethylsilicone HMS-151 as the hydrogen-modified silicone and 6 mg of platinum divinyltetramethyldisiloxane SIP6830.3 as the reaction catalyst ( The surface-modified zirconia particle-silicone resin composite composition of Example 3 and a transparent composite having a thickness of 1 mm are the same as in Example 1 except that the amount is changed from 0.02% by mass to 3 mg (0.01% by mass). Got the body.
The content of zirconia particles in this transparent composite was 40% by mass.

As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 3 in the same manner as in Example 1, the average dispersed particle diameter was 10 nm.
From this result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 3 was 10 nm or less.
In addition, as a result of conducting elemental analysis on the obtained transparent composite of Example 3, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, so that it was the transparent composite of the present invention. confirmed.

Example 4
The side chain vinyl-dimethylsilicone VDT-131 was changed from 14.1 g (47% by mass) to 11.7 g (39% by mass) as the vinyl-modified silicone, and 0.1% of methylhydrogen-dimethylsilicone HMS-151 as the hydrogen-modified silicone. The surface of Example 4 according to Example 1 except that 9 g (3% by mass) was changed to 3.3 g (11% by mass) of methylhydrogen-dimethylsilicone HMS-031 (manufactured by Gelest). A modified zirconia particle-silicone resin composite composition and a transparent composite having a thickness of 1 mm were obtained.
The content of zirconia particles in this transparent composite was 25% by mass.

As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 4 in the same manner as in Example 1, the average dispersed particle diameter was 7 nm.
From this result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 4 was 7 nm or less.
In addition, as a result of conducting elemental analysis on the obtained transparent composite of Example 4, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, so that it was the transparent composite of the present invention. confirmed.

"Example 5"
As vinyl-modified silicone, 14.1 g (47% by mass) of side-chain vinyl-dimethylsilicone VDT-131 was added to 4.8 g (16% by mass) of side-chain vinyl-dimethylsilicone VDT-731 (manufactured by Gelest). Except that 0.9 g (3% by mass) of methylhydrogen-dimethylsilicone HMS-151 was changed to 10.2 g (34% by mass) of methylhydrogen-dimethylsilicone HMS-031 as a gen-modified silicone, According to Example 1, the surface-modified zirconia particle-silicone resin composite composition of Example 5 and a transparent composite having a thickness of 1 mm were obtained.
The content of zirconia particles in this transparent composite was 25% by mass.

As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 5 in the same manner as in Example 1, the average dispersed particle diameter was 7 nm.
From this result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 5 was 7 nm or less.
In addition, as a result of conducting elemental analysis on the obtained transparent composite of Example 5, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, so that it was the transparent composite of the present invention. confirmed.

"Example 6"
As a vinyl-modified silicone, 14.1 g (47% by mass) of side chain vinyl-dimethylsilicone VDT-131 was added to 13.5 g (45% by mass) of both-end vinyl-dimethylsilicone DMS-V21 (manufactured by Gelest). 0.9 g (3% by mass) of methylhydrogen-dimethylsilicone HMS-151 as a gen-modified silicone, and 1.5 g (5% by mass) of methylhydrogen-dimethylsilicone HMS-301 (manufactured by Gelest), respectively. Other than the changes, the surface-modified zirconia particle-silicone resin composite composition of Example 6 and a transparent composite having a thickness of 1 mm were obtained according to Example 1.
The content of zirconia particles in this transparent composite was 25% by mass.

As a result of measuring the particle diameter of zirconia particles in the obtained transparent composite of Example 6 in the same manner as in Example 1, the average dispersed particle diameter was 10 nm.
From this result, it was concluded that the average dispersed particle size of zirconia particles in the composite composition of Example 6 was 10 nm or less.
In addition, as a result of performing elemental analysis on the obtained transparent composite of Example 6, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, so that it was the transparent composite of the present invention. confirmed.

"Example 7"
As a vinyl-modified silicone, 14.1 g (47% by mass) of side chain vinyl-dimethylsilicone VDT-131 was added to 14.7 g (49% by mass) of both-end vinyl-dimethylsilicone DMS-V22 (manufactured by Gelest). Except that 0.9 g (3% by mass) of methyl hydrogen-dimethyl silicone HMS-151 was changed to 0.3 g (1% by mass) of methyl hydrogen-dimethyl silicone HMS-301, respectively, as a gen-modified silicone, According to Example 1, the surface-modified zirconia particle-silicone resin composite composition of Example 7 and a transparent composite having a thickness of 1 mm were obtained.
The content of zirconia particles in this transparent composite was 25% by mass.

The particle diameter of the zirconia particles in the obtained transparent composite of Example 7 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 10 nm.
From this result, it was concluded that the average dispersed particle size of zirconia particles in the composite composition of Example 7 was 10 nm or less.
In addition, as a result of conducting elemental analysis on the obtained transparent composite of Example 7, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, so that it was the transparent composite of the present invention. confirmed.

"Example 8"
The side chain vinyl-dimethylsilicone VDT-131 is changed from 14.1 g (47% by mass) to 14.4 g (48% by mass) as the vinyl-modified silicone, and 0.1% of methylhydrogen-dimethylsilicone HMS-151 as the hydrogen-modified silicone. Surface modified zirconia particles-silicone of Example 8 according to Example 1 except that 9 g (3% by mass) was changed to 0.6 g (2% by mass) of methylhydrogen-dimethylsilicone HMS-301. A resin composite composition and a transparent composite having a thickness of 1 mm were obtained.
The content of zirconia particles in this transparent composite was 25% by mass.

As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 8 in the same manner as in Example 1, the average dispersed particle diameter was 7 nm.
From this result, it was concluded that the average dispersed particle size of zirconia particles in the composite composition of Example 8 was 7 nm or less.
Further, as a result of conducting elemental analysis on the obtained transparent composite of Example 8, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, so that it was the transparent composite of the present invention. confirmed.

"Example 9"
14.1 g (47% by mass) of side-chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone, 11.4 g (38% by mass) of side-chain vinyl-dimethylsilicone VDT-731, and methyl as hydrogen-modified silicone According to Example 1, except that 0.9 g (3% by mass) of hydrogen-dimethylsilicone HMS-151 was changed to 3.6 g (12% by mass) of methylhydrogen-dimethylsilicone HMS-301. Thus, a surface-modified zirconia particle-silicone resin composite composition of Example 9 and a transparent composite having a thickness of 1 mm were obtained.
The content of zirconia particles in this transparent composite was 25% by mass.

The particle diameter of the zirconia particles in the obtained transparent composite of Example 9 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 7 nm.
From this result, it was concluded that the average dispersed particle size of zirconia particles in the composite composition of Example 9 was 7 nm or less.
In addition, as a result of conducting elemental analysis on the obtained transparent composite of Example 9, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, so that it was the transparent composite of the present invention. confirmed.

"Example 10"
14.1 g (47% by mass) of side chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone, 14.7 g (49% by mass) of vinyl-dimethylsilicone DMS-V22 at both ends, and methyl as hydrogen-modified silicone 0.9 g (3% by mass) of hydrogen-dimethylsilicone HMS-151 was added to 0.3 g (1% by mass) of methylhydrogen-dimethylsilicone HMS-301, and platinum divinyltetramethyldisiloxane SIP6830. 3 was changed to platinum cyclovinylmethylsiloxane SIP 6832.2 (manufactured by Gelest Co., Ltd.), respectively, and the surface-modified zirconia particle-silicone resin composite composition of Example 10 and a transparent film having a thickness of 1 mm were used according to Example 1. A complex was obtained.
The content of zirconia particles in this transparent composite was 25% by mass.

As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 10 in the same manner as in Example 1, the average dispersed particle diameter was 9 nm.
From this result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 10 was 9 nm or less.
In addition, as a result of conducting elemental analysis on the obtained transparent composite of Example 10, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, so that it was the transparent composite of the present invention. confirmed.

"Comparative Example 1"
14.1 g (47% by mass) of side chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone, 8.7 g (29% by mass) of vinyl-dimethylsilicone DMS-V21 at both ends, and methyl as hydrogen-modified silicone According to Example 1, except that 0.9 g (3% by mass) of hydrogen-dimethylsilicone HMS-151 was changed to 6.3 g (21% by mass) of methylhydrogen-dimethylsilicone HMS-031, respectively. Thus, a surface-modified zirconia particle-silicone resin composite composition of Comparative Example 1 and a composite having a thickness of 1 mm were obtained.
The content of zirconia particles in this composite was 25% by mass.
As a result of measuring the particle diameter of the zirconia particles in the obtained composite of Comparative Example 1 in the same manner as in Example 1, the average dispersed particle diameter was 35 nm.

"Comparative Example 2"
14.1 g (47% by mass) of side chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone, 13.2 g (44% by mass) of vinyl-dimethylsilicone DMS-V22 at both ends, and methyl as hydrogen-modified silicone According to Example 1, except that 0.9 g (3% by mass) of hydrogen-dimethylsilicone HMS-151 was changed to 1.8 g (6% by mass) of methylhydrogen-dimethylsilicone HMS-031, respectively. Thus, a surface-modified zirconia particle-silicone resin composite composition of Comparative Example 2 and a composite having a thickness of 1 mm were obtained.
The content of zirconia particles in this composite was 25% by mass.
As a result of measuring the particle diameter of the zirconia particles in the obtained composite of Comparative Example 2 in the same manner as in Example 1, the average dispersed particle diameter was 42 nm.

"Evaluation"
The transparency, refractive index, and durability of each of the transparent composites of Examples 1 to 10 and Comparative Examples 1 and 2 were evaluated by the following apparatus or method.

(1) Transparency The transmittance of visible light was measured using a spectrophotometer (manufactured by JASCO Corporation).
Here, the visible light transmittance in the thickness direction (L = 1 mm) of the transparent composite (or composite) was measured, and the visible light transmittance was 80% or more as “◯” and less than 80% as “x”. .
(2) Refractive index The refractive index was measured with an Abbe refractometer in accordance with Japanese Industrial Standard JIS K 7142 “Plastic Refractive Index Measuring Method”.
Here, on the basis of a single resin not added with zirconia particles, a case where the refractive index is improved by 0.03 or more is “◯”, and a case where the refractive index is improved by less than 0.03 is “X”. .

(3) Durability The transparent composite (or composite) is allowed to stand for 24 hours in an environment at a temperature of 150 ° C. and then taken out. The appearance of the transparent composite (or composite) is visually observed, and there is no yellowing. The thing was set as "(circle)" and the thing yellowed was set as "x".
Table 1 shows the composition of each of the composite compositions of Examples 1 to 10 and Comparative Examples 1 and 2 and the evaluation results of the transparent composite (or composite).

According to Table 1, each of the transparent composites of Examples 1 to 10 was excellent in all points of transparency, refractive index and durability.
On the other hand, the composites of Comparative Examples 1 and 2 had an extremely low visible light transmittance of 0% to 20%, and the refractive index could not be measured.
The reason is that both hydrogen-modified silicone and vinyl-modified silicone have low crosslink density, so the aggregation / phase separation rate of inorganic oxide particles is faster than the curing rate of silicone resin, and as a result, when cured with silicone resin. This is thought to be due to the loss of transparency.

  The composite composition of inorganic oxide particles and silicone resin of the present invention is a composite composition obtained by dispersing inorganic oxide particles in a silicone resin, and a polydimethylsiloxane skeleton having at least one functional group at one end. By forming a composite composition comprising inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less, which is surface-modified by bonding with a polymer, a silicone resin, and a reaction catalyst, an inorganic oxide is obtained. Since a transparent composite with a controlled refractive index can be obtained while maintaining the transparency, heat resistance, and light resistance of a composite comprising particles and a silicone resin, a semiconductor light emitting device (LED) Sealing material, liquid crystal display substrate, organic EL display substrate, color filter substrate, touch panel substrate, solar cell substrate optical sheet, transparent plate, Manabu lens, an optical element, an optical waveguide, such as an adhesive, of course, also in various industrial fields other than this, its availability is large.

Claims (8)

A composite composition comprising inorganic oxide particles having an average dispersed particle size of 1 nm or more and 20 nm or less, which is surface-modified by bonding with a polydimethylsiloxane skeleton polymer, a silicone resin, and a reaction catalyst,
The silicone resin contains vinyl-modified silicone and hydrogen-modified silicone,
The reaction catalyst contains a hydrosilylation reaction catalyst,
The polydimethylsiloxane skeleton polymer is one or two selected from the group consisting of a monoglycidyl ether-terminated polydimethylsiloxane and a monohydroxyether-terminated polydimethylsiloxane . Composite composition. The vinyl-modified silicone includes vinyl dimethyl silicone at both ends, vinyl diphenyl-dimethyl silicone at both ends, vinyl phenylphenyl silicone at both ends, vinyl diethyl silicone at both ends, vinyl dimethyl silicone at side chain, vinyl methyl silicone, vinyl methoxy silicone. The composite composition of inorganic oxide particles and a silicone resin according to claim 1 , wherein the composite composition is one or more selected from the group of vinyl resin dispersions. The hydrogen-modified silicone is one selected from the group consisting of hydrogen-dimethylsilicone at both ends, methylhydrogen-dimethylsilicone, methylhydrogensilicone, ethylhydrogensilicone, methylhydrogen-phenylmethylsilicone, and hydride resin. Or it is 2 or more types, The composite composition of the inorganic oxide particle and silicone resin of Claim 1 or 2 characterized by the above-mentioned. The hydrogen-modified silicone has the following formula (1):

(Where R _{1 to} R ₈ are mutually independent arbitrary organic groups (excluding H), m is an integer of 1 or more, and n is a positive integer including 0)
Containing the side chain hydrogen-modified silicone shown in
The inorganic oxidation according to any one of claims 1 to 3 , wherein a ratio (m / (m + n)) of m to n in the side chain hydrogen-modified silicone is 0.25 or more and 1 or less. Composite composition of product particles and silicone resin. The vinyl-modified silicone is a side chain vinyl-dimethyl silicone,
  The hydrogen-modified silicone has the following formula (1):

  (However, R ₁ ~ R ₈ Are arbitrary organic groups independent of each other (excluding H), m is an integer of 1 or more, and n is a positive integer including 0)
The composite composition of inorganic oxide particles and a silicone resin according to claim 2, which is a side chain hydrogen-modified silicone. The material for forming the inorganic oxide particles is zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ , FeO, Fe ₃ O ₄ ), copper oxide (CuO, Cu ₂ O), zinc oxide (ZnO), yttrium oxide (Y ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), molybdenum oxide (MoO ₃ ), indium oxide (In ₂ O ₃ , In ₂ O), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ , W ₂ O ₅ ), lead oxide (PbO, PbO ₂ ), bismuth oxide (Bi) ₂ O ₃ ), cerium oxide (CeO ₂ , Ce ₂ O ₃ ), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ) germanium oxide (GeO ₂ , GeO), tin-added 6. One type or two or more types selected from indium tin oxide (ITO) and yttria stabilized zirconia (YSZ). A composite composition of inorganic oxide particles and a silicone resin.   The inorganic oxide particles and the silicone according to any one of claims 1 to 6, wherein the content of the inorganic oxide particles in the composite composition is 1% by mass or more and 90% by mass or less. Composite composition with resin. The composite composition of inorganic oxide particles according to any one of claims 1 to 7 and a silicone resin is formed into a predetermined shape and solidified, or formed after the composite composition is solidified. A transparent composite characterized by
The inorganic oxide particles whose surface is modified by bonding the polydimethylsiloxane skeleton polymer to the silicone resin are dispersed with an average dispersed particle diameter of 1 nm or more and 20 nm or less, and a hydrosilylation reaction catalyst is contained in the silicone resin. And
The polydimethylsiloxane skeleton polymer is one or two selected from the group consisting of monoglycidyl ether-terminated polydimethylsiloxane and monohydroxy ether-terminated polydimethylsiloxane .