KR20140038983A - Composite composition of inorganic oxide particles and silicone resin, and transparent composite material - Google Patents

Abstract

The composite composition of the inorganic oxide particle and silicone resin of this invention is the inorganic oxide particle whose surface-modified average dispersion particle diameter is 1 nm or more and 20 nm or less by combining the polydimethylsiloxane skeleton polymer which has a monofunctional group to one terminal, It is a composite composition containing a silicone resin and a reaction catalyst, a silicone resin contains vinyl modified silicone and hydrogen modified silicone, and the reaction catalyst contains the hydrosilylation reaction catalyst.

Description

COMPOSITE COMPOSITION OF INORGANIC OXIDE PARTICLES AND SILICONE RESIN, AND TRANSPARENT COMPOSITE MATERIAL}

The present invention relates to a composite composition of an inorganic oxide particle and a silicone resin and a transparent composite.

This application claims priority in accordance with Japanese Patent Application No. 2011-128302 for which it applied to Japan on June 8, 2011, and uses the content here.

In the past, attempts have been made to improve mechanical properties and the like of resins by complexing inorganic oxides such as silica with resins as fillers. As a method of compounding this filler and resin, the dispersion liquid which disperse | distributed the inorganic oxide in the solution containing either or both of water and an organic solvent, and the method of mixing resin are common. By mixing a dispersion liquid and resin by various methods, the inorganic oxide particle composite plastic in which the inorganic oxide particle was compounded as a 2nd phase can be manufactured (for example, refer patent document 1).

Moreover, by coating a polymer on the surface of an inorganic oxide particle, the coating composition and coating film of the optical characteristic, such as adjustment of refractive index and transparency other than a mechanical characteristic, are proposed (for example, refer 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, low toxicity, and the like, and therefore are widely used in cosmetics, medical materials and electrical and electronic materials. In recent years, attention has also been paid to its transparency, and it is also used for members requiring transparency, such as transparent sealing materials for light emitting diodes.

Examples of the properties required in such applications include optical properties such as transparency and refractive index, mechanical properties such as hardness, thermal stability such as heat resistance, and gas barrier properties of suppressing water vapor and various gas permeability.

As an optical property and thermal stability which were improved by compounding conventionally proposed inorganic materials, such as a silicone resin and an inorganic oxide, the composition which combined the zirconium oxide particle with the hydroxyl group containing polysiloxane in presence of a chelating agent, for example. (Patent Document 3), a light emitting device coating composition (patent document 4) in which zirconium oxide particles and polyfunctional polysiloxane are complexed, and a light emitting device filling material in which inorganic nanoparticles are coated with an organic compound and mixed with phenyl group-containing silicon (Patent Document 5) and many others have been proposed.

Japanese Unexamined Patent Application Publication No. 2005-161111 Japanese Patent Laid-Open No. 2003-292826 Japanese Laid-Open Patent Publication No. 2006-316264 Japanese Unexamined Patent Publication No. 2009-91380 Japanese Unexamined Patent Publication No. 2007-70603

However, conventionally, when attempting to complex inorganic oxide particles with a hydrophobic resin, the surface of the inorganic oxide particles is hydrophilic, so that the silicone resin and the inorganic oxide particles are separated particularly between the highly hydrophobic silicone resin and the inorganic oxide particles. There was a problem that it was difficult to combine and discard.

Thus, 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 applied to the surface of the inorganic oxide particles, thereby improving the compatibility of the silicone resin with the inorganic oxide particles. This consists of However, 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.

Moreover, the particle size of an inorganic oxide particle is 20 nm or more, and therefore there exists a problem that transparency falls and it may devitrify in some cases.

For example, in the highly viscous silicone resin, even if a conventional hydrophobic polymer dispersing agent is used, it is difficult to be compatible with the inorganic oxide particles, and even if the surface of the inorganic oxide particles can be sufficiently hydrophobized, the transparent dispersion liquid of the inorganic oxide particles. There was a problem that could not be obtained.

Moreover, when hydroxyl group containing polysiloxane is used, water generate | occur | produces with progress of bridge | crosslinking, and there exists a possibility that inorganic oxide particle and polysiloxane may phase-separate in some cases, Furthermore, a hole and a crack are obtained in the obtained composite material. There was a problem that this might occur.

On the other hand, even when the polyfunctional polysiloxane is used, there are limitations in the mixing of the inorganic oxide particles and the polysiloxane, and there is a problem that the generation of holes and cracks becomes remarkable especially when the amount of the inorganic oxide particles is large. In the case of using the polyfunctional polysiloxane, the unreacted functional group is likely to remain, and therefore, there is a problem that it is likely to change over time in the composite properties after crosslinking, and furthermore, the durability is inferior.

In addition, when the inorganic oxide particles and the silicone resin are commercialized by using a chelating agent, there is a problem in that coloration occurs due to changes over time or thermal degradation.

Moreover, in the high refractive index filling material for light emitting elements, although the transparent dispersion liquid which disperse | distributed nanoparticles in methylphenyl silicone which is easy to interact with various organic molecules is proposed, the transparent dispersion in the low polar dimethylsilicone resin, and It cannot achieve about hardened | cured material.

Moreover, when using addition reaction type dimethylsilicon, although it disperse | distributes transparently to the silicone before hardening, there existed a problem that a phase separation may occur and whiten in the hardening process.

On the other hand, the conventional method of treating the surface of the metal oxide particles with modified silicon has also been proposed, but since the modified silicon is generally polyfunctional, the surface of the inorganic oxide particles cannot be reliably treated. There was a problem that there is a case that adversely affects the compatibility with the silicone resin. Thus, in order to solve this problem, improvements have been attempted such as performing secondary or tertiary surface treatment (surface modification), but there have been problems such as complicated process.

The present invention has been made to solve the above problems. Inorganic oxide particles having a high dispersibility and dispersing in the silicone resin when the inorganic oxide particles which allow the transparency to be maintained together with the improvement of the refractive index, the mechanical properties and the gas barrier properties, and which can prevent phase separation and whitening during curing It is an object to provide a composite composition and a transparent composite of particles and a silicone resin.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject. As a result, surface-modified inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less were subjected to surface modification using a polydimethylsiloxane skeleton polymer having a monofunctional group at one end, and furthermore, using a silicone resin and a reaction catalyst. By complexing, when the inorganic oxide particles are dispersed in the silicone resin, the dispersibility of the inorganic oxide particles is greatly improved, while maintaining transparency, the transparent composite having a controlled refractive index while maintaining the heat resistance and light resistance of the silicone resin is prepared. It discovered what was obtained and came to complete this invention.

That is, the composite composition of the inorganic oxide particle and the silicone resin of the present invention is at least an inorganic oxide particle, the surface of which is modified by bonding a polydimethylsiloxane skeleton polymer having a monofunctional group to one end, and the average dispersed particle diameter is 1 nm or more. In the composite composition containing 20 nm or less of inorganic oxide particles, a silicone resin, and a reaction catalyst, the silicone resin contains vinyl-modified silicone and hydrogen-modified silicone, and the reaction catalyst is hydrosilylation. (C) containing a reaction catalyst.

It is preferable that the said polydimethylsiloxane skeleton polymer is a monoglycidyl ether terminal polydimethylsiloxane and / or a monohydroxyether terminal polydimethylsiloxane.

The vinyl-modified silicones include both terminal vinyl-dimethylsilicone, both terminal vinyldiphenyl-dimethylsilicone, both terminal vinyl-phenylmethylsilicone, both terminal vinyl-diethylsilicone, branched vinyl-dimethylsilicone, vinylmethylsilicone and vinylmethicone. It is preferable that it is 1 type (s) or 2 or more types chosen from the group which consists of a oxysilicone and a vinyl resin dispersion.

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

The hydrogen-modified silicone is the following formula (1)

[Chemical Formula 1]

(Wherein R ₁ to R ₈ are any organic groups independent of each other (except 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 the following, and the ratio (m / (m + n) of m and n in the said side chain hydrogen modified silicone is 0.25 or more and 1 or less.

In the transparent composite of the present invention, the inorganic oxide particles surface-modified by the polydimethylsiloxane skeleton polymer having a monofunctional group at one end in the silicone resin are dispersed at an average dispersed particle diameter of 1 nm or more and 20 nm or less. It is characterized by containing a hydrosilylation reaction catalyst in a silicone resin.

The transparent composite of the present invention is characterized in that 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.

In the method for producing a composite composition of the inorganic oxide particles and the silicone resin of the present invention, the surface of the inorganic oxide particles is modified with a polydimethylsiloxane skeleton polymer having a monofunctional group at one end, and the average dispersed particle diameter whose surface is modified is A process of obtaining inorganic oxide particles of 1 nm or more and 20 nm or less, and a process of mixing inorganic oxide particles of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst with an average dispersed particle diameter of which the surface is modified; It is characterized by including.

The composite composition of the inorganic oxide particle and the silicone resin of the present invention is, at least, an inorganic oxide particle, the surface of which is modified by bonding a polydimethylsiloxane skeleton polymer having a monofunctional group at one end thereof, and the average dispersed particle diameter is 1 nm or more and 20 The inorganic oxide particle which is nm or less, a silicone resin, and a reaction catalyst are contained, a silicone resin contains vinyl modified silicone and hydrogen modified silicone, and a reaction catalyst contains a hydrosilylation reaction catalyst. Thereby, 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, dispersibility is high, and phase separation and whitening during curing can be prevented, thus maintaining transparency, heat resistance and light resistance, A transparent composite with controlled refractive index can be obtained.

According to the transparent composite of the present invention, the inorganic oxide particles surface-modified by the polydimethylsiloxane skeleton polymer having a monofunctional group at one end in the silicone resin are dispersed at an average dispersed particle diameter of 1 nm or more and 20 nm or less, It was assumed that the silicone resin contained a hydrosilylation reaction catalyst. Thereby, the transparent composite of the inorganic oxide particle and silicone resin in which the refractive index was controlled can be obtained easily, maintaining transparency, heat resistance, and light resistance.

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. Thereby, the transparent composite of the inorganic oxide particle and silicone resin in which the refractive index was controlled can be obtained easily, maintaining transparency, heat resistance, and light resistance.

The present invention relates to a composite composition of an inorganic oxide particle and a silicone resin and a transparent composite. More specifically, the inorganic oxide particles which are suitably used as filler materials for silicone resins and which are capable of maintaining transparency while improving refractive index, mechanical properties and gas barrier properties are dispersed in the silicone resin. The present invention relates to a composite composition of inorganic oxide particles and a silicone resin capable of preventing dispersibility and phase separation and whitening at the time of curing, and a transparent composite formed by molding the composite composition.

The preferable aspect for implementing the composite composition and transparent composite of the inorganic oxide particle and silicone resin of this invention is demonstrated.

This form is concretely explained in order to understand the meaning of invention better, and it does not limit this invention unless there is particular designation. Additions, omissions, substitutions, and other modifications of the configuration are possible without departing from the spirit of the present invention.

[Composite Composition of Inorganic Oxide Particles and Silicone Resin]

The composite composition (hereinafter may only be referred to as "composite composition") of the inorganic oxide particles and the silicone resin of the present embodiment is a composite composition obtained by dispersing the inorganic oxide particles in the silicone resin, and at least, as the inorganic oxide particles. A composite composition comprising inorganic oxide particles having a mean dispersed particle diameter of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst while being surface modified by bonding a polydimethylsiloxane skeleton polymer having a monofunctional group to one end thereof. .

Here, the "composite composition" does not have a specific shape, and once deformed, has a irreversible deformability that does not return to the original shape, and becomes a raw material for the transparent composite described later.

As a state of this composite composition, it shall show what is in the gel-like state which has liquid state or thixotropy, for example.

Although it does not specifically limit as an inorganic oxide which is a component of an inorganic oxide particle, Oxide of nonmetallic elements, 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) And oxides of metal elements such as cerium (Ce), antimony (Sb), and germanium (Ge).

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), and the like.

Such inorganic oxides also include complex oxides such as indium tin oxide (ITO) and yttria stabilized zirconia (YSZ).

Such inorganic oxide may be used individually by 1 type, and may mix and use 2 or more types.

In particular, when high refractive index of the composite composition with the silicone resin, zirconium oxide (ZrO ₂ ) and titanium oxide (TiO ₂ ) having high refractive index, colorless and transparent to visible light, and high hardness are suitable.

Moreover, when making a low refractive index composite composition with a silicone resin, it is preferable to use the inorganic oxide particle which becomes a low refractive index whole particle | grains by having a space | gap in particle | grains, such as hollow silica particle and porous silica particle, for example.

It is preferable that the average dispersed particle diameter in the composite composition of this inorganic oxide particle is 1 nm or more and 20 nm or less. The average dispersed particle diameter is more preferably 3 nm or more and 10 nm or less.

Here, the reason which limited the mean-dispersion particle diameter of an inorganic oxide particle to 1 nm or more and 20 nm or less is as follows. When the average dispersed particle diameter is less than 1 nm, the primary particle diameter of the particles constituting the particles is also extremely small, less than 1 nm. For this reason, the crystallinity of inorganic oxide particles becomes small, 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 by inorganic oxide particles becomes large, and the transparency of a composite composition falls, or the transparency of the transparent composite obtained by shape | molding and solidifying this composite composition falls. .

As described above, since the inorganic oxide particles are nanometer-sized particles, the light scattering is small even in the composite composition obtained by dispersing the inorganic oxide particles in the silicone resin or the transparent composite formed by molding and solidifying the composite composition. It is possible to maintain transparency of the composite composition and the transparent composite.

It is preferable that the content rate in the composite composition of this inorganic oxide particle is 1 mass% or more and 90 mass% or less, More preferably, it is 5 mass% or more and 90 mass% or less, More preferably, 10 mass% or more and 85 mass% It is as follows.

Here, the reason which limited the content rate of an inorganic oxide particle to 1 mass% or more and 90 mass% or less is as follows. If the content is less than 1% by mass, the amount of the inorganic oxide particles is too small, and when the inorganic oxide particles are combined with the silicone resin, it is difficult to express changes in the optical and mechanical properties of the silicone resin, and consequently the inorganic oxide. It is not preferable because the effect of compounding the particles is not obtained. On the other hand, when the content is more than 90% by mass, the dispersibility of the inorganic oxide particles cannot be sufficiently secured, or the fluidity in the composite composition is lowered and the moldability deteriorates, which is not preferable.

Next, the surface modification of this inorganic oxide particle is demonstrated.

The surface of this inorganic oxide particle is modified by the surface modifier which consists of a polydimethylsiloxane skeleton polymer which has a monofunctional group at one terminal.

This surface modifier has a polydimethylsiloxane skeleton, in particular, a linear polydimethylsiloxane skeleton as a main chain, and has only one polar group as a functional group at one end (one end side) of the main chain. Therefore, when this functional group (polar group) is selectively bonded to the surface of the inorganic oxide particles, the other end side, that is, the siloxane skeleton portion is aligned to face the particle outside (the direction away from the surface of the inorganic oxide particles). do.

In addition, since the siloxane skeleton portion and the silicone resin have high compatibility and good affinity, the inorganic oxide particles surface-modified by the surface modifier composed of this polydimethylsiloxane skeleton polymer can be uniformly dispersed in the silicone resin. So that good composite compositions can be formed.

Here, "linear polydimethylsiloxane skeleton" has shown that there is no branch (branch) in a polydimethylsiloxane skeleton.

Here, when this polydimethylsiloxane skeleton has a branch (branch), or when the polar group which is a functional group is located in the middle of a siloxane skeleton (the functional group couple | bonds with the silicon located in the middle of a siloxane skeleton), At least one portion is likely to face the surface direction of the inorganic oxide particles or to face the direction parallel to the particle surface. In this case, the amount of the siloxane skeleton toward the outside of the inorganic oxide particles is reduced, which may cause the compatibility and affinity between the inorganic oxide particles and the silicone resin to decrease. In addition, since the unity in the direction of the siloxane skeleton is lost, entanglement and steric hindrance between the siloxane skeletons are generated, and there is a possibility that the compatibility and affinity between the inorganic oxide particles and the silicone resin are lowered.

This surface modifier is a monofunctional group having only one polar group, and since the functional group is used for bonding the inorganic oxide particles, no functional group exists in the surface modifier bonded to the inorganic oxide particles. Therefore, when a conventional polyfunctional polysiloxane is used, there is no fear of deterioration of compatibility with a silicone resin generated due to unreacted functional groups, for example, turbidity, and the like, thereby obtaining a stable composite composition. Can be.

As such a surface modifier, it is preferable to have a monoglycidyl ether terminal polydimethylsiloxane and / or a monohydroxy ether terminal polydimethylsiloxane. It is preferable that the monoglycidyl ether terminal polydimethylsiloxane used for this invention is 500-10000 in molecular weight. Moreover, it is preferable that the monohydroxyether terminal polydimethylsiloxane used for this invention is 500-10000 in molecular weight.

Of the terminal groups possessed by these surface modifiers, the monoglycidyl ether terminal has a ring-opened portion of the epoxy group which is part of the glycidyl group, and is bonded to the hydroxyl group on the surface of the inorganic oxide particle, and the monohydroxyether terminal is And the hydroxyl group on the surface of the inorganic oxide particles are bonded by dehydration condensation.

In these surface modifiers, monoglycidyl ether terminal polydimethylsiloxane does not contain a hydroxyl group originally, and monohydroxyether terminal polydimethylsiloxane has a hydroxyl group only in the functional group couple | bonded with an inorganic oxide particle. . Therefore, in either of the surface modifiers, after bonding to the surface of the inorganic oxide particles, there is no state that does not have a hydroxyl group, or the hydroxyl group is present in the vicinity of the surface of the inorganic oxide particles, and does not prevent compatibility with the silicone resin. It is.

Moreover, the shrinkage rate is small for the transparent composite obtained from the composite composition of the inorganic oxide particle and silicone resin surface-modified by these surface modifiers. As a result, no holes or cracks are generated in the transparent composite, and the dispersibility of the inorganic oxide particles in the cured silicone resin is also maintained well, whereby a transparent composite without defects is obtained.

Since the inorganic oxide particle of this embodiment is surface-modified by the polydimethylsiloxane skeleton polymer which has a monofunctional group at one terminal, it is excellent in compatibility and dispersibility with respect to a silicone resin. Therefore, there is no restriction | limiting in particular in silicone resin itself, If it is a normal silicone resin, it can use without a 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 higher and about 150 ° C or lower. Particularly preferred as such silicone resins are vinyl-modified silicone and hydrogen-modified silicone. This is suitable.

Examples of vinyl-modified silicones include both terminal vinyl-dimethylsilicone, both terminal vinyldiphenyl-dimethylsilicone, both terminal vinyl-phenylmethylsilicone, both terminal vinyl-diethylsilicone, branched vinyl-dimethylsilicone, vinylmethylsilicone and vinylmethoxy Silicone, a vinyl resin dispersion, etc. are mentioned. These vinyl-modified silicones may be used in one kind or in combination of two or more kinds.

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

In this hydrogen-modified silicone, following formula (1)

(2)

(Wherein R ₁ to R ₈ are any organic groups independent of each other (except 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 to.

Here, the side chain hydrogen-modified silicone is preferable because it is more reactive than the terminal hydrogen-modified silicone when the polymer-cured polymer is formed by polymerizing and curing the vinyl-modified silicone with a hydrosilylation reaction or the like. It is because crosslinking density becomes high because the quantity of silicone can be increased, and the characteristic of the resultant silicone resin polymer can be improved.

Moreover, it is preferable that ratio (m / (m + n)) of m and n in the side chain hydrogen modified silicone shown in said Formula (1) is 0.25 or more and 1 or less. The ratio (m / (m + n)) is more preferably 0.30 or more and 0.70 or less.

Here, the reason for limiting the ratio (m / (m + n)) of m and n to 0.25 or more and 1 or less is as follows. First, when the ratio of m and n (m / (m + n)) is less than 0.25, since the crosslinking density during curing is too small, the aggregation and phase separation rates of the inorganic oxide particles are faster than the curing rate of the silicone resin. It is because transparency will be lost at the time of hardening with a silicone resin.

Next, the ratio of m and n (m / (m + n)) is an upper limit, but as the ratio of m and n (m / (m + n)) increases, the following equation (2)

(3)

It is thought that the content rate of the hydrogen containing unit shown to increase, and also the ratio of a vinyl modified silicone and an unreacted unit increases after forming a transparent composite. However, this unreacted hydrogen containing unit has little effect on the properties of the transparent composite. Therefore, the maximum value of the ratio of m and n (m / (m + n)) in side chain hydrogen modified silicone may be one.

In said Formula (1), R <_1> -R <_8> is arbitrary organic groups (except H) independent from each other, and one part or all may be the same. Here, "partly same" means that only a part thereof is the same, for example, R ₁ , R ₃ , R _4, and R ₆ are the same, and R ₁ , R ₂ , R ₅ , R _7, and R ₈ are different from each other. In addition to the same species, for example, R ₁ and R ₃ and R ₄ are the same, and R ₂ and R ₅ , R ₇ and R ₈ are the same, and R ₁ , R ₂ and R ₆ are different from each other. Some combinations may be the same.

In addition, an "organic device" shows the general group which consists of organic substance, such as a characteristic group, a functional group, and a substituent, and an alkyl group, an alkoxy group, etc. are contained, for example.

This silicone resin is a characteristic of the composite composition after mixing with inorganic oxide particles and the like, and has no specific shape, and once deformed, has an irreversible deformation property that does not return to the original shape, and becomes a raw material for the transparent composite described later. For example, what is necessary is just to exist in the gel-like state which has a liquid state or thixotropy, and the polymerization degree is not specifically limited.

That is, as long as the composite composition has the above characteristics, any of monomers (monomers), oligomers (two to several hundred polymers), and polymers (several hundred or more polymers) may be used, and combinations thereof have a wide range in the degree of polymerization. You may use it.

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 the reaction catalyst.

As this reaction catalyst, what contains a hydrosilylation reaction catalyst is preferable. As this hydrosilylation reaction catalyst, a noble metal catalyst is mentioned, The powder of a noble metal, a noble metal salt, a noble metal complex, etc. can be selected suitably. Among the noble metal catalysts, a platinum group catalyst is preferable, and for example, a platinum catalyst, a rhodium catalyst, a palladium catalyst and the like can be cited. Particularly, a platinum catalyst is preferable. Examples of the platinum catalyst include platinum fine powder, chloroplatinic acid, platinum-olefin complex, platinum-carbonyl complex, and the like, and these may be used alone or in combination of two or more thereof.

Moreover, the composite composition of this embodiment can contain an organic solvent.

Here, the following points are mentioned as an advantage that a composite composition contains an organic solvent.

As a 1st advantage, the viscosity control of a composite composition is mentioned. For example, when the mixture of an inorganic oxide particle and a silicone resin is high viscosity, fluidity may deteriorate, and the problem that the moldability of the transparent composite mentioned later and the ease of handling may fall may arise. Thus, in order to solve these problems, it is possible to lower the viscosity of the mixture to the desired viscosity by adding an organic solvent to the mixture. The viscosity of the mixture of the inorganic oxide particles and the silicone resin is preferably 0.05 Pa · s to 10000 Pa · s, more preferably 0.1 Pa · s to 100 Pa · s.

As a 2nd advantage, the ease of mixing and dispersion is mentioned. For example, the inorganic oxide particle modified by the surface modifier is first disperse | distributed in the organic solvent with high compatibility with the silicone resin to be used, and it is set as an inorganic oxide particle dispersion liquid, and this inorganic oxide particle dispersion liquid and silicone resin are mixed and mixed. When it stirs, since the dispersibility to inorganic resin of inorganic oxide particle | grains becomes very high, it is preferable.

It is preferable to use a hydrophobic solvent as this organic solvent. This is because a hydrophobic solvent is suitable as a solvent having high dispersibility of surface-modified inorganic oxide and having high compatibility with a silicone resin.

As such a hydrophobic solvent, chlorine-containing solvents, such as aromatic hydrocarbons, such as benzene, toluene, xylene, and ethylbenzene, dichloromethane, chloroform, carbon tetrachloride, are used suitably, One type of these solvents independently Or 2 or more types can be mixed and used.

Although the content rate of this organic solvent will not be specifically limited if the above-mentioned solvent addition effect is acquired, Usually, it is preferable that it is 400 mass% or less with respect to the total amount of the surface-modified inorganic oxide particle and silicone resin. The content rate of an organic solvent becomes like this. More preferably, it is 100 mass% or less. The reason for this is that when an excessive amount of an organic solvent is present, when forming the transparent composite described later using this composite composition, the viscosity is too low, which causes difficulty in moldability, or requires time for removal of the organic solvent. This is because it is not preferable.

[Method for Producing Composite Composition]

In the method for producing a composite composition of the present embodiment, first, the surface of the inorganic oxide particles is modified with a polydimethylsiloxane skeleton polymer having a monofunctional group at one end, and the average dispersed particle diameter whose surface is modified is 1 nm or more. An inorganic oxide particle of 20 nm or less is formed, and then the surface-modified average dispersed particle diameter is 1 nm or more and 20 nm or less of inorganic oxide particles, a silicone resin, and a reaction catalyst.

Here, the method shown below is mentioned as a method of modifying the surface of an inorganic oxide particle with the polydimethylsiloxane skeleton polymer which has a monofunctional group at one terminal. That is, at first, a specific dispersant is bonded to the surface of the inorganic oxide particles in advance so as to have dispersibility in a hydrophobic solvent (organic solvent). Next, this inorganic oxide particle is disperse | distributed in a hydrophobic solvent, and a dispersion liquid is obtained. Next, the surface modifying agent which consists of a polydimethylsiloxane skeletal polymer which has a monofunctional group at one end is added to the obtained dispersion liquid, the specific dispersing agent previously couple | bonded with the surface of an inorganic oxide particle in this hydrophobic solvent, and a monofunctional group at one end. The method of substituting the surface modifier which consists of a polydimethylsiloxane skeleton polymer which has is mentioned.

The above method is explained in more detail.

Initially, a specific dispersant is bonded to the surface of the inorganic oxide particles to have dispersibility in a hydrophobic solvent.

Inorganic oxide particles bound to this particular dispersant are easily dispersed in a hydrophobic solvent. Moreover, the inorganic oxide particle which this specific dispersing agent couple | bonded has the specific dispersing agent already couple | bonded with the said inorganic oxide particle surface when the surface modifier which consists of a polydimethylsiloxane skeleton polymer which has a monofunctional group at one terminal coexists. Surface modifiers can easily cause substitution.

As a specific dispersing agent, an organic acid compound or an organic base compound is mentioned. Examples of the organic acid compound include carboxylic acid, phosphoric acid and sulfonic acid, and examples of the organic base compound include amine and phosphazene base.

Among these dispersants, carboxylic acids and amines are suitably used because they function as dispersants for dispersing inorganic oxide particles and can be desorbed satisfactorily during reaction with the surface modifier.

Examples of the carboxylic acid include one selected from saturated fatty acids such as formic acid, acetic acid, butyric acid, valeric acid, capric acid, enanthic acid, caprylic acid, capric acid, lauric acid, stearic acid, and oleic acid, or the like. You may select and use 2 or more types. As the amine, for example, one or two or more selected from aromatic amines such as pyridine and bipyridine, and aliphatic amines such as triethylamine, diethyl amine, monoethylamine and butylamine may be selected and used.

Next, the inorganic oxide particle which bound the specific dispersing agent to the surface is disperse | distributed in a hydrophobic solvent.

As the hydrophobic solvent, any inorganic oxide particles having a specific dispersant bound to the surface may be stably dispersed. Examples of the hydrophobic solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, dichloromethane, chloroform and carbon tetrachloride. A chlorine-containing solvent is used suitably, and 1 type, or 2 or more types of these solvent can be used.

Subsequently, a surface modifier made of a polydimethylsiloxane skeleton polymer having a monofunctional group at one end described above is added to a hydrophobic solvent in which inorganic oxide particles having a specific dispersant bound to the surface are dispersed, and the surface modifier is used as an inorganic. It is substituted with a specific dispersant already bound to the oxide surface. Thereby, the surface of an inorganic oxide particle is modified with the surface modifier which consists of a polydimethylsiloxane skeleton polymer which has a monofunctional group at one terminal.

It is preferable that the mass ratio with respect to the inorganic oxide particle of the surface modifier which consists of a polydimethylsiloxane skeleton polymer which has a monofunctional group at this terminal is 5 mass% or more and 200 mass% or less with respect to the total mass of an inorganic oxide particle, More preferably, 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 for limiting the mass ratio of the surface modifier to 5% by mass or more and 200% by mass or less is that if the mass ratio of the surface modifier is less than 5% by mass, the amount of the surface modifier is too small, so that the surface of the inorganic oxide particles is sufficiently filled. This is because it cannot be modified, and therefore, compatibility of the inorganic oxide particles having insufficient surface modification with the silicone resin becomes difficult, and the transparency is lost upon compounding with the silicone resin. On the other hand, when the mass ratio of the surface modifier exceeds 200 mass%, the proportion of the surface modifier in the composite composition is increased to the point that the ratio of the surface modifier is not negligible, and thus, greatly affects the properties of the composite composition, resulting in a decrease in the characteristics. This is because it may cause.

Thus, by using the surface modifier consisting of a polydimethylsiloxane skeleton polymer having a monofunctional group at one end, the surface modifier is reacted with inorganic oxide particles in a hydrophobic solvent, whereby the functional group (polar group) of the surface modifier is an inorganic oxide. The particles are selectively oriented and bonded to the particles, while the other end tries to disperse in the hydrophobic solvent, and forms an outer side of the inorganic oxide particles. Therefore, these surface treating agents become a form in which a functional group part couple | bonds with an inorganic oxide particle, and the other end side moves away radially with respect to an inorganic oxide particle.

As mentioned above, while the surface is modified by the polydimethylsiloxane frame | skeleton polymer which has a monofunctional group at one terminal, the inorganic oxide particle whose average dispersed particle diameter is 1 nm or more and 20 nm or less is obtained.

Subsequently, this surface-modified average dispersion particle diameter mixes the inorganic oxide particle of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst. At this time, you may add an organic solvent as needed.

Here, the silicone resin itself is not particularly limited, and any combination of vinyl-modified silicone and hydrogen-modified silicone curable 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 methoxy silicone, a vinyl resin dispersion, etc., one type can be selected individually or in combination of 2 or more types.

As the hydrogen-modified silicone, there are one type from among both terminal hydrogen-dimethylsilicone, methylhydrogen-dimethylsilicone, methylhydrogensilicone, ethylhydrogensilicone, methylhydrogen-phenylmethylsilicone, and hydride resin. May be used alone or in combination of two or more thereof.

Moreover, in hydrogen modified silicone, it is preferable to contain the side chain hydrogen modified silicone shown in said Formula (1).

Here, the side chain hydrogen-modified silicone is preferable because it is more reactive than the terminal hydrogen-modified silicone when the polymer-cured polymer is formed by polymerizing and curing the vinyl-modified silicone with a hydrosilylation reaction or the like. It is because crosslinking density becomes high because the quantity of silicone can be increased, and the characteristic of the resultant silicone resin polymer can be improved.

Moreover, it is preferable that ratio (m / (m + n)) of m and n in the side chain hydrogen modified silicone shown in said Formula (2) is 0.25 or more and 1 or less. The ratio (m / (m + n)) is more preferably 0.30 or more and 0.70 or less.

Here, the reason for limiting the ratio (m / (m + n)) of m and n to 0.25 or more is as follows. First, when the ratio of m and n (m / (m + n)) is less than 0.25, since the crosslinking density during curing is too small, the aggregation and phase separation rates of the inorganic oxide particles are faster than the curing rate of the silicone resin. It is because transparency will be lost at the time of hardening with a silicone resin.

Next, although the ratio of m and n (m / (m + n)) is an upper limit of 1, as the ratio of m and n (m / (m + n)) becomes larger, the hide represented by the above formula (2) It is thought that the content rate of a rosen containing unit becomes high and the ratio of vinyl modified silicone and an unreacted unit increases even after forming a transparent composite. However, this unreacted hydrogen containing unit has little effect on the properties of the transparent composite. Therefore, the maximum value of the ratio of m and n (m / (m + n)) in side chain hydrogen modified silicone may be one.

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

Here, the inorganic oxide particle whose surface was modified by the surface modifier can also be mixed with a silicone resin in the state as it is. However, in order to improve the dispersibility and the ease of mixing of the surface-modified inorganic oxide particles in the silicone resin, an organic solvent having high compatibility with the silicone resin using the surface-modified inorganic oxide particles in advance (hydrophobic solvent) It is preferable to mix and stir the inorganic oxide particle dispersion liquid and silicone resin which were made to redispersion in ().

In other words, when the inorganic oxide particles are directly added to and stirred with a silicone resin having a certain viscosity, it is difficult to disperse the inorganic oxide particles in a viscous silicone resin uniformly and prevent the aggregation of the particles. The dispersibility of the inorganic oxide particles in the dispersion is also poor, and further, the process itself of dispersing the inorganic oxide particles in the viscous silicone resin requires a great labor.

On the other hand, once the surface-modified inorganic oxide particles are redispersed in an organic solvent having high compatibility with the silicone resin, since the organic solvent itself is low viscosity, the inorganic oxide particles are uniformly dispersed in the organic solvent and thus low viscosity It becomes the inorganic oxide particle dispersion liquid of. Therefore, when the dispersion liquid in which the inorganic oxide particles are uniformly dispersed and the silicone resin are mixed, the liquids are mixed, so that even if the silicone resin has some viscosity, the dispersion is uniformly mixed with the low viscosity dispersion liquid. The inorganic oxide particles are easily and uniformly dispersed in the silicone resin. Moreover, since it is the process itself of mixing a low viscosity inorganic oxide particle dispersion liquid and a viscous silicone resin, and the mixing process of solutions, a large labor force is not needed.

Moreover, when the mixture of the surface-modified inorganic oxide particle and silicone resin has high viscosity, the fluidity | liquidity of this mixture may deteriorate, and also there arise a problem that the moldability of the transparent composite mentioned later and ease of handling fall.

In order to prevent this problem, when mixing the inorganic oxide particles and the silicone resin, a suitable solvent, for example, an organic solvent obtained by adding an organic solvent having high dispersibility of surface-modified inorganic oxide particles and high compatibility with the silicone resin is obtained. It is preferable to reduce the viscosity of the mixture.

As such an organic solvent, it is preferable to use a hydrophobic solvent, and for example, a chlorine-containing solvent such as aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, dichloromethane, chloroform, carbon tetrachloride is suitably used, One of these solvents may be used alone or in combination of two or more thereof.

Moreover, the content rate of this organic solvent will not be specifically limited if the said solvent addition effect is obtained, but it is preferable that it is usually 400 mass% or less with respect to the total amount of the surface-modified inorganic oxide particle and silicone resin normally. The content rate of an organic solvent becomes like this. More preferably, it is 100 mass% or less. The reason for this is that when an excessive amount of an organic solvent is present, when forming the transparent composite described later using this composite composition, the viscosity is too low, which causes difficulty in moldability, or requires time to remove the organic solvent. to be.

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, a silicone resin is added to the dispersion and mixed and stirred, (2 ) After mixing the inorganic oxide particles and the silicone resin, an organic solvent is appropriately added to the mixture, and the mixture is stirred and mixed using a mixer or the like to adjust the viscosity to form a mixture having fluidity.

When the viscosity of the mixture obtained by the addition of the organic solvent is low, the viscosity (high viscosity) may be adjusted 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 complex]

In the transparent composite of the present embodiment, the inorganic oxide particles surface-modified by the polydimethylsiloxane skeleton polymer having a monofunctional group at one end in the silicone resin are dispersed at an average dispersed particle diameter of 1 nm or more and 20 nm or less, It is a transparent composite containing the hydrosilylation reaction catalyst in the said silicone resin. In this transparent composite_body | complex, an organic solvent, especially a hydrophobic solvent is not contained fundamentally but is extremely small even if it contains.

Here, the "transparent composite" has a specific shape, but the "predetermined shape" means that the transparent composite does not have irreversible deformation such as liquid or gel shape, and has a constant shape in accordance with the purpose and method of use. Say something you can keep. That is, in addition to the usual hardly deformed solid shape, those having elastic deformation properties (shape resilience) such as rubber shape are included, and the shape itself is not shown to be a specific shape.

The transparent composite can obtain a state having a predetermined shape by increasing the degree of polymerization or crosslinking degree of the silicone resin or the number of polymerization and crosslinking between the silicone resin and the siloxane skeleton of the surface modifier in the composite composition. . Therefore, each component constituting this transparent composite, that is, the inorganic oxide particles, silicone resins, and reaction catalysts modified by a surface modifier composed of a polydimethylsiloxane skeleton polymer having a monofunctional group at one end thereof, It is the same as that of the composite composition mentioned above.

In this transparent composite, the surface-modified inorganic oxide particle which comprises itself is high in compatibility and affinity with a silicone resin, and its dispersibility in a silicone resin is favorable. Therefore, there is no case where the inorganic oxide particles and the silicone resin cause phase separation or aggregation of the inorganic oxide particles occurs. Therefore, there is no fear of causing deterioration such as optical characteristics, mechanical characteristics, thermal stability, etc. due to these, and good characteristics can be maintained.

As described above, when the silicone resin is cured with a reaction catalyst, the curing rate of the silicone resin is faster than the aggregation and phase separation rates of the inorganic oxide particles. Therefore, inorganic oxide particle | grains do not aggregate in the transparent composite obtained, and it becomes a thing with high transparency. In addition, since the chelating agent is not used for the composite composition which is a formation material of a transparent composite_body | complex, there is no possibility that coloring may arise in a transparent composite material.

Moreover, the average dispersed particle diameter of the inorganic oxide particle contained in this transparent composite_body | complex is 20 nm or less. Therefore, when the average dispersed particle diameter exceeds 20 nm, the generation of Rayleigh scattering, which increases in influence, is also suppressed low, and the transparency of the transparent composite may not be lowered.

As described above, since the inorganic oxide particles are nanometer-sized particles, the light scattering is small even in the composite composition or transparent composite in which the inorganic oxide particles are dispersed in the silicone resin, so that the transparency of the composite composition and the transparent composite is maintained. It is possible.

In addition, since the average dispersed particle diameter of the inorganic oxide particle contained in this transparent composite_body | complex is 1 nm or more, the average primary particle diameter of this inorganic oxide particle does not become less than 1 nm in which crystalline retention falls. Therefore, this inorganic oxide particle has favorable crystallinity.

Thus, since the crystallinity of inorganic oxide particle is maintained, the characteristic which inorganic oxide particle itself has, namely, characteristics, such as refractive index, hardness, and heat resistance, do not deteriorate. Therefore, the effect as a transparent composite which combined the inorganic oxide particle with the silicone resin can be sufficiently obtained.

Here, the effect of a transparent composite is demonstrated.

`` Optical characteristics ''

Refractive index control is mentioned as an optical characteristic of a transparent composite_body | complex.

Since the refractive index of a silicone resin is about 1.4, the refractive index of a transparent composite can be made high compared with the case of single silicone resin by combining a silicone resin and the high refractive index oxide particle which is higher in refractive index than this silicone resin.

In particular, it is effective to complex with a high refractive index inorganic oxide particle having a refractive index of 2 or more, for example, tetragonal zirconium oxide (refractive index: 2.15) and titanium oxide (refractive index: about 2.6), and these high refractive index inorganic oxide particles By using, it is possible to increase the refractive index of the transparent composite from 1.5 to 1.65, which is about 0.1 to 0.2, which is higher than that of the silicone resin alone.

About transparency of this transparent composite, light scattering can be suppressed low enough by making the average dispersion particle diameter of an inorganic oxide particle into 20 nm or less as mentioned above. Therefore, in this transparent composite, transparency is sufficiently maintained.

In addition, when the inorganic oxide particles having a lower refractive index than the silicone resin as a whole are combined with the silicone resin by having voids in the particles, such as hollow silica particles or porous silica particles, the refractive index of the transparent composite is lower than that of the silicone resin alone. It is also possible to reduce.

`` Mechanical characteristics ''

As mechanical property of a transparent composite, the hardness improves compared with resin alone.

Normal inorganic oxide particles have a higher hardness than silicone resins, and by compounding these inorganic oxide particles with silicone resins, the surface hardness of the transparent composite can be increased in comparison with that of the silicone resin alone. Thereby, the scratch resistance of a transparent composite can be improved and the dimensional precision of a transparent composite itself can be improved.

In particular, zirconium oxide has a high hardness among oxide ceramics, and therefore can exhibit a high effect on the improvement of surface hardness by compounding.

`` Thermal and chemical stability ''

Since silicone resin itself contains silicon (Si) in frame | skeleton, compared with normal resin, it is excellent in thermal stability and chemical stability, such as heat resistance and chemical-resistance. On the other hand, inorganic oxide particles are stronger than silicone resins in terms of heat resistance. Therefore, when inorganic oxide particles having high chemical stability are selected and the inorganic oxide particles having high chemical stability are combined with the silicone resin, the thermal stability and chemical stability of the resulting transparent composite can be further increased as compared with the case of the silicone resin alone.

Here, the silicone resin is hydrophobic (water repellent), as can be seen from the high compatibility with the hydrophobic solvent, but is rich in flexibility and low in gas barrier properties against water vapor compared with other resins.

In the transparent composite of the present embodiment, the inorganic oxide particles having excellent gas barrier properties are uniformly dispersed in the inside of the transparent composite, and the bonding property between the inorganic oxide particles and the silicone resin is high, so that the water vapor in the transparent composite The gas barrier property can be improved to a higher state than in the case of the silicone resin alone.

This transparent composite can be suitably used for an optical lens. For this reason, according to the transparent composite, the refractive index of the obtained transparent composite can be increased from about 1.4 to about 1.65, which is the case of the silicone resin alone, by complexing high refractive index inorganic oxide particles, particularly zirconium oxide, with a silicone resin. . Moreover, compared with the silicone resin single case, the hardness is improved, so that the dimensional accuracy can be improved. Therefore, the freedom of design in an optical element can be improved.

As a result, for example, compared with the case where a single silicone resin is used for the optical lens, it is possible to miniaturize, reduce the thickness, integrate, improve the condensing efficiency, reduce the refractive index wavelength dependence, and the like. Therefore, the improvement of characteristics, such as high resolution and high sensitivity, for example, CCD and CMOS camera which are the apparatus using such an optical element can be anticipated.

Moreover, this transparent composite material can be used suitably as a sealing material of LED which is a light emitting element. As a reason, this transparent composite material has a high refractive index compared to a single silicone resin, and therefore, when used as a sealing material for LEDs that are light emitting elements, the transparent composite has a high refractive index such as a light emitting body covered by the sealing material, a substrate for forming the light emitting body, or the like. It is possible to improve the refractive index match with the member (a refractive index of the semiconductor material which is the light emitting body of the LED is about 2.5, and the refractive index of the translucent substrate which forms the semiconductor material is about 1.76). Therefore, the internal reflection in the process of taking out light emission from the light emitting body of LED to the outside can be reduced.

That is, by using the transparent composite of this embodiment for the sealing material of LED, the light extraction efficiency from LED can be improved about 10 to 15%. As a result, the brightness of the LED can be improved.

In addition, since the transparent composite has a high gas barrier property against water vapor, water infiltration from the outside can be suppressed and deterioration of the light emitting region can be suppressed. Therefore, the life of the light emitting element can be extended.

Moreover, this transparent composite material can be used suitably also as a sealing material of organic electroluminescent element. For this reason, when this transparent composite is used as a sealing material of an organic EL element, since the gas barrier property to water vapor is high, it can suppress the water infusion from the outside and suppress deterioration of a light emitting area. Moreover, since the inorganic oxide particle in a transparent composite_body | complex can effectively suppress permeation of oxygen gas, it can similarly suppress deterioration of a light emitting area | region. Therefore, the life span of the light emitting element in an organic EL element can be extended by using the transparent composite of this embodiment as a sealing material of an organic EL element.

[Method for Producing Transparent Composite]

The transparent composite of the present embodiment can be obtained by molding the composite composition of the present embodiment into a predetermined shape to solidify it, or by molding the composite composition and then molding into a predetermined shape.

In the manufacturing method of this embodiment, "the method of shape | molding and solidifying to a predetermined shape" is as follows.

First, the composite composition of this embodiment is shape | molded using a metal mold | die or a mold, or it fills in the container of a metal mold or die shape, and the molded object or filler molded to the target shape is obtained.

At this time, when the viscosity of the composite composition to be used is high, it is preferable to add an organic solvent etc. previously, to stir and mix, to reduce a viscosity, and to adjust so that it may become a viscosity suitable for shaping | molding and filling.

On the other hand, when the viscosity of the composite composition to be used is low, in advance, polymerization or crosslinking of the silicone resins or a part of the silicone resin and the surface modifier is carried out as described below, or when the composite composition contains an organic solvent, It is preferable to raise a viscosity by removing a part or all of an organic solvent by volatilizing etc., and to adjust so that it may become a viscosity suitable for shaping | molding and filling.

Subsequently, the molded article or the filler 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 allowed to stand for a predetermined time. A reaction such as polymerization or crosslinking is caused to the surface modifier through a reaction catalyst to increase the degree of bonding (polymerization degree) between the silicone resins and the silicone resin and the surface modifier.

Moreover, when an organic solvent remains in this molded object or a filler, this organic solvent is volatilized off.

Thereby, after removing this molded object or a filler from a metal mold | die and a container, even if an external force is applied, it will be in the state which can maintain a fixed shape.

By the above, the transparent composite of this embodiment can be obtained which is free from defects, is excellent in optical and mechanical properties, and has high thermal stability and chemical stability.

Moreover, in the manufacturing method of this embodiment, "the method of shape | molding to a predetermined shape after solidifying a composite composition" is as follows.

First, the composite composition of this embodiment is solidified and the solidified material (unformed transparent composite body) of a composite composition is obtained. As the solidification method, the composite composition is left at room temperature (about 25 ° C) or at a predetermined temperature (room temperature-150 ° C, preferably 80 ° C-150 ° C) and left to stand for a predetermined time. What is necessary is just to make reaction of a modification agent, such as superposition | polymerization, crosslinking, etc. through a reaction catalyst, and to raise the bond degree (polymerization degree) between silicone resin, a silicone resin, and a surface modification agent.

Moreover, when an organic solvent remains, it is preferable to also volatilize this organic solvent.

This solid state is a state which can maintain a fixed shape even if external force is applied.

Next, this solid is shape | molded to a required shape by machining methods, such as cutting and a punching. The silicone resin of this embodiment has flexibility after hardening, and can be processed easily.

In the molded article after processing, the solidification may be further advanced by increasing the degree of bonding (polymerization degree) between the silicone resins, the silicone resin and the surface modifier, or by removing the remaining organic solvent.

Also by the above, the transparent composite of this embodiment can be obtained which is free from defects, is excellent in optical and mechanical properties, and has high thermal stability and chemical stability.

In the case where the transparent composite is applied to a field that does not cause transparency, it is not necessary to secure transparency. Therefore, it is not necessary to limit the average dispersed particle diameter of the inorganic oxide particles to be used to 1 nm or more and 20 nm or less.

For example, when it is aimed at improving only the surface hardness of the composite containing an inorganic oxide particle and a silicone resin, you may use the particle | grains whose average dispersed particle diameter is larger than 20 nm, for example, the inorganic oxide particle of 100 nm. have.

Even in such a case, by applying the manufacturing method of the composite composition of this embodiment, the dispersibility of the inorganic oxide particle in a composite composition becomes high, and it can be set as the composite composition which can manufacture the molded object or filler which has favorable physical property.

Example

Although an Example and a comparative example demonstrate this invention concretely below, this invention is not limited by these Examples. Additions, omissions, substitutions, and other modifications of the configuration are possible without departing from the spirit of the present invention.

[Example 1]

The zirconium precursor slurry was adjusted by stirring the dilute ammonia water in which 344 g of 28% ammonia water was dissolved in 20 L of pure water to a zirconium salt solution in which 2615 g of zirconium oxychloride octahydrate was dissolved in 40 L (liter) of pure water.

Subsequently, the sodium sulfate aqueous solution which melt | dissolved 300 g of sodium sulfate in 5 L of pure water was added to this slurry, stirring. The addition amount of sodium sulfate at this time was 30 mass% with respect to the zirconia conversion value of the zirconium ion in a zirconium salt solution.

Subsequently, this mixture was dried at 130 degreeC for 24 hours in air | atmosphere using the dryer, and solid was obtained.

Subsequently, the solid was pulverized by using an automatic mortar, and then fired at 500 ° C. for 1 hour in the air using an electric furnace.

Subsequently, the calcined product was poured into pure water, stirred to a slurry state, washed using a centrifugal separator, and sufficiently added sodium sulfate was removed, followed by drying in a drier to obtain zirconia particles.

Subsequently, 85 g of toluene and 5 g of capronic acid were added and mixed with this 10 g of zirconia particle, and the surface of the zirconia particle was modified with capric acid which is a ligand. Thereafter, a dispersion treatment was performed to prepare a zirconia transparent dispersion.

Subsequently, 10 g of 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 in 100 g of this zirconia transparent dispersion liquid, dibutyl tin 0.01 g of dilaurate was added to perform surface modification under reflux.

After completion | finish of reaction, the solvent was removed by the evaporator, and methanol washing and centrifugation were repeated, and capric acid isolate | separated from zirconia particle and unreacted monoglycidyl ether terminal polydimethylsiloxane were removed. The recovered surface-modified zirconia particles were 15 g.

As a result of measuring the obtained surface-treated zirconia particle in proton NMR (in heavy chloroform), the signal intensity | strength resulting from the glycidyl group of 2.6-3.5 ppm vicinity was compared with the monoglycidyl ether terminal polydimethylsiloxane single body. It was greatly reduced. From this result, it was judged that the monoglycidyl ether terminal polydimethylsiloxane produced the ring-opening of an epoxy group and the bond with zirconia particle.

15 g of this surface-modified zirconia particle is redispersed with 35 g of toluene, and then 14.1 g of branched vinyl-dimethylsilicone VDT-131 (manufactured by Gelest) as vinyl-modified silicone and methylhydrogen-dimethylsilicone HMS-151 as hydrogen-modified silicone 0.9 g of (Gelest) was added, and 6 mg of platinum divinyl tetramethyldisiloxane SIP 6830.3 (manufactured by Gelest) for room temperature curing was further added as a reaction catalyst, and the surface modified zirconia particle-silicone resin of Example 1 was added. A composite composition was obtained.

Subsequently, after stirring and dissolving this surface modified zirconia particle-silicone resin composite composition, it poured into the form piled up by the glass plate, hardening reaction, removing the organic solvent under 40 degreeC vacuum, and the thickness of Example 1 is 1 mm. A phosphorus transparent composite was obtained.

The content rate of the zirconia particle of this transparent composite_body | complex was 25 mass%.

The cross section of the obtained transparent composite of Example 1 was observed using an electrolytic emission transmission electron microscope JEM-2100F (manufactured by Nippon Electronics Co., Ltd.), the particle diameters of 100 randomly picked particles were measured, and the average value thereof was determined as the transparent composite. It was set as the average dispersed particle diameter of the zirconia particle in the inside. As a result of this measurement, the average dispersed particle diameter was 7 nm.

From this measurement result, the average dispersed particle diameter of the zirconia particle in the composite composition of Example 1 was also concluded to be 7 nm thru | or less than that.

Moreover, as a result of performing elemental analysis about the obtained transparent composite of Example 1, since the platinum component of the quantity equivalent to the amount added as a reaction catalyst was detectable, it confirmed that the transparent composite of this invention was obtained.

[Example 2]

From 10 g (25 mass%) to 14 g (35 mass%) of zirconia particles, from 14.1 g (47 mass%) to 8.4 g (28 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl modified silicone, Surface modified zirconia particles of Example 2 according to Example 1, except that methylhydrogen-dimethylsilicone HMS-151 was changed from 0.9 g (3 mass%) to 0.6 g (2 mass%) as modified silicone, respectively. A silicone resin composite composition and a transparent composite having a thickness of 1 mm were obtained.

The content rate of the zirconia particle of this transparent composite_body | complex was 35 mass%.

As a result of measuring the particle diameter of the zirconia particle in the obtained transparent composite of Example 2 similarly to Example 1, the average dispersed particle diameter was 8 nm.

From this result, the average dispersed particle diameter of the zirconia particle in the composite composition of Example 2 was also concluded to be 8 nm thru | or less than that.

Moreover, as a result of performing elemental analysis with respect to the obtained transparent composite of Example 2, since the platinum component of the quantity equivalent to the amount added as a reaction catalyst was detectable, it confirmed that the transparent composite of this invention was obtained.

[Example 3]

From 10 g (25 mass%) to 16 g (40 mass%) of zirconia particles, from 14.1 g (47 mass%) to 5.7 g (19 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl modified silicone, From 0.9 g (3 mass%) to 0.3 g (1 mass%) of methylhydrogen-dimethylsilicone HMS-151 as a modified silicone, 6 mg (0.02 mass%) of platinum divinyl tetramethyldisiloxane SIP 6830.3 as a reaction catalyst The surface modified zirconia particle-silicone resin composite composition of Example 3 and the transparent composite having a thickness of 1 mm were obtained according to Example 1 except having changed to 3 mg (0.01 mass%), respectively.

The content rate of the zirconia particle of this transparent composite_body | complex was 40 mass%.

As a result of measuring the particle diameter of the zirconia particle in the obtained transparent composite of Example 3 similarly to Example 1, the average dispersed particle diameter was 10 nm.

From this result, the average dispersed particle diameter of the zirconia particle in the composite composition of Example 3 was also concluded to be 10 nm thru | or less than that.

Moreover, as a result of performing elemental analysis about the obtained transparent composite of Example 3, since the platinum component of the quantity equivalent to the quantity added as a reaction catalyst was detectable, it confirmed that the transparent composite of this invention was obtained.

[Example 4]

From 14.1 g (47 mass%) to 11.7 g (39 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl modified silicone, 0.9 g (3 mass) of methylhydrogen-dimethylsilicone HMS-151 as hydrogen modified silicone %) Was changed to 3.3 g (11% by mass) of methylhydrogen-dimethylsilicone HMS-031 (manufactured by Gelest), and the surface modification zirconia particle-silicone resin of Example 4 was changed according to Example 1 A composite composition and a transparent composite having a thickness of 1 mm were obtained.

The content rate of the zirconia particle of this transparent composite_body | complex was 25 mass%.

As a result of measuring the particle diameter of the zirconia particle in the obtained transparent composite of Example 4 similarly to Example 1, the average dispersed particle diameter was 7 nm.

From this result, the average dispersed particle diameter of the zirconia particle in the composite composition of Example 4 was also concluded to be 7 nm thru | or less than that.

Moreover, as a result of performing elemental analysis about the obtained transparent composite of Example 4, since the platinum component of the quantity equivalent to the amount added as a reaction catalyst was detectable, it confirmed that the transparent composite of this invention was obtained.

[Example 5]

14.1 g (47 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl modified silicone, 4.8 g (16 mass%) of side chain vinyl-dimethylsilicone VDT-731 (manufactured by Gelest) is used as hydrogen-modified silicone It carried out according to Example 1 except having changed 0.9 g (3 mass%) of methylhydrogen- dimethyl silicone HMS-151 into 10.2 g (34 mass%) of methylhydrogen- dimethyl silicone HMS-031, respectively. The surface modified zirconia particle-silicone resin composite composition of Example 5 and the transparent composite with a thickness of 1 mm were obtained.

The content rate of the zirconia particle of this transparent composite_body | complex was 25 mass%.

As a result of measuring the particle diameter of the zirconia particle in the obtained transparent composite of Example 5 similarly to Example 1, the average dispersed particle diameter was 7 nm.

From this result, the average dispersed particle diameter of the zirconia particle in the composite composition of Example 5 was also concluded to be 7 nm thru | or less than that.

Moreover, as a result of performing elemental analysis with respect to the obtained transparent composite of Example 5, since the platinum component of the quantity equivalent to the amount added as a reaction catalyst was detectable, it confirmed that the transparent composite of this invention was obtained.

[Example 6]

Hydrogen-modified silicone as 14.1 g (47 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl modified silicone, and 13.5 g (45 mass%) of both terminal vinyl-dimethylsilicone DMS-V21 (made by Gelest) As a result, except that 0.9 g (3 mass%) of methylhydrogen-dimethylsilicone HMS-151 was changed to 1.5 g (5 mass%) of methylhydrogen-dimethylsilicone HMS-301 (manufactured by Gelest), respectively. According to Example 1, the surface modified zirconia particle-silicone resin composite composition of Example 6 and a transparent composite having a thickness of 1 mm were obtained.

The content rate of the zirconia particle of this transparent composite_body | complex was 25 mass%.

As a result of measuring the particle diameter of the zirconia particle in the obtained transparent composite of Example 6 similarly to Example 1, the average dispersed particle diameter was 10 nm.

From this result, the average dispersed particle diameter of the zirconia particle in the composite composition of Example 6 was also concluded to be 10 nm thru | or less than that.

Moreover, as a result of performing elemental analysis about the obtained transparent composite of Example 6, since the platinum component of the quantity equivalent to the quantity added as a reaction catalyst was detectable, it confirmed that the transparent composite of this invention was obtained.

[Example 7]

As modified vinyl silicone, 14.1 g (47 mass%) of side chain vinyl-dimethylsilicone VDT-131 is 14.7 g (49 mass%) of both terminal vinyl-dimethylsilicone DMS-V22 (made by Gelest), hydrogen modified silicone As Example 1, except that 0.9 g (3 mass%) of methylhydrogen-dimethylsilicone HMS-151 was changed to 0.3 g (1 mass%) of methylhydrogen-dimethylsilicone HMS-301, respectively. The surface modified zirconia particle-silicone resin composite composition of Example 7 and the transparent composite with a thickness of 1 mm were obtained.

The content rate of the zirconia particle of this transparent composite_body | complex was 25 mass%.

As a result of measuring the particle diameter of the zirconia particle in the obtained transparent composite of Example 7 similarly to Example 1, the average dispersed particle diameter was 10 nm.

From this result, the average dispersed particle diameter of the zirconia particle in the composite composition of Example 7 was also concluded to be 10 nm thru | or less than that.

Moreover, as a result of performing elemental analysis about the obtained transparent composite of Example 7, the platinum component of the quantity equivalent to the amount added as a reaction catalyst was detectable, and it confirmed that the transparent composite of this invention was obtained.

[Example 8]

From 14.1 g (47 mass%) to 14.4 g (48 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl modified silicone, 0.9 g (3 mass) of methylhydrogen-dimethylsilicone HMS-151 as hydrogen modified silicone %) Was changed to 0.6 g (2% by mass) of methylhydrogen-dimethylsilicone HMS-301, respectively, except that the surface modified zirconia particle-silicone resin composite composition and the thickness of Example 8 were A transparent composite having 1 mm was obtained.

The content rate of the zirconia particle of this transparent composite_body | complex was 25 mass%.

The particle size of the zirconia particles in the obtained transparent composite of Example 8 was measured in the same manner as in Example 1, and the average dispersed particle diameter was 7 nm.

From this result, the average dispersed particle diameter of the zirconia particle in the composite composition of Example 8 was also concluded to be 7 nm thru | or less than that.

Moreover, as a result of performing elemental analysis about the obtained transparent composite of Example 8, since the platinum component of the quantity equivalent to the amount added as a reaction catalyst was detectable, it confirmed that the transparent composite of this invention was obtained.

[Example 9]

14.1 g (47 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl modified silicone, and 11.4 g (38 mass%) of side chain vinyl-dimethylsilicone VDT-731, and methylhydrogen-dimethyl as hydrogen modified silicone. Surface modification of Example 9 in accordance with Example 1 except that 0.9 g (3 mass%) of silicon HMS-151 was changed to 3.6 g (12 mass%) of methylhydrogen-dimethylsilicone HMS-301, respectively. A zirconia particle-silicon resin composite composition and a transparent composite having a thickness of 1 mm were obtained.

The content rate of the zirconia particle of this transparent composite_body | complex was 25 mass%.

As a result of measuring the particle diameter of the zirconia particle in the obtained transparent composite of Example 9 similarly to Example 1, the average dispersed particle diameter was 7 nm.

From this result, the average dispersed particle diameter of the zirconia particle in the composite composition of Example 9 was also concluded to be 7 nm thru | or less than that.

Moreover, as a result of performing elemental analysis about the obtained transparent composite of Example 9, since the platinum component of the quantity equivalent to the quantity added as a reaction catalyst was detectable, it confirmed that the transparent composite of this invention was obtained.

[Example 10]

14.1 g (47 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl modified silicone, and 14.7 g (49 mass%) of both terminal vinyl-dimethylsilicone DMS-V22, methylhydrogen- as a hydrogen-modified silicone 0.9 g (3 mass%) of dimethylsilicone HMS-151, 0.3 g (1 mass%) of methylhydrogen-dimethylsilicone HMS-301, platinum divinyl tetramethyldisiloxane SIP 6830.3 as a reaction catalyst, platinum cyclo Except having changed into vinyl methylsiloxane SIP 6832.2 (made by Gelest), respectively, the surface modified zirconia particle-silicone resin composite composition and the transparent composite of thickness 1mm were obtained according to Example 1 according to Example 1.

The content rate of the zirconia particle of this transparent composite_body | complex was 25 mass%.

As a result of measuring the particle diameter of the zirconia particle in the obtained transparent composite of Example 10 similarly to Example 1, the average dispersed particle diameter was 9 nm.

From this result, the average dispersed particle diameter of the zirconia particle in the composite composition of Example 10 was also concluded to be 9 nm or less.

Moreover, as a result of performing elemental analysis about the obtained transparent composite of Example 10, since the platinum component of the quantity equivalent to the quantity added as a reaction catalyst was detectable, it confirmed that the transparent composite of this invention was obtained.

`` Comparative Example 1 ''

14.1 g (47 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl modified silicone, and 8.7 g (29 mass%) of both terminal vinyl-dimethylsilicone DMS-V21, and methylhydrogen- as hydrogen modified silicone The surface of Comparative Example 1 according to Example 1, except that 0.9 g (3 mass%) of dimethylsilicone HMS-151 was changed to 6.3 g (21 mass%) of methylhydrogen-dimethylsilicone HMS-031, respectively. A modified zirconia particle-silicon resin composite composition and a composite having a thickness of 1 mm were obtained.

The content rate of the zirconia particle of this composite_body | complex was 25 mass%.

As a result of measuring the particle diameter of the zirconia particle 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 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone, 13.2 g (44 mass%) of both terminal vinyl-dimethylsilicone DMS-V22, and methylhydrogen- as hydrogen modified silicone The surface of Comparative Example 2 according to Example 1, except that 0.9 g (3 mass%) of dimethylsilicone HMS-151 was changed to 1.8 g (6 mass%) of methylhydrogen-dimethylsilicone HMS-031, respectively. A modified zirconia particle-silicon resin composite composition and a composite having a thickness of 1 mm were obtained.

The content rate of the zirconia particle of this composite_body | complex was 25 mass%.

As a result of measuring the particle diameter of the zirconia particle in the obtained composite of Comparative Example 2 in the same manner as in Example 1, the average dispersed particle diameter was 42 nm.

`` Comparative Example 3 ''

To 10 g of zirconia particles prepared in the same manner as in Example 1, 85 g of toluene and 5 g of capric acid were added and mixed, and the surface of the zirconia particles was modified with capric acid as the ligand. Thereafter, a dispersion treatment was performed to prepare a zirconia transparent dispersion.

After completion | finish of reaction, a solvent was removed by the evaporator and zirconia particle and unreacted capronic acid were removed by repeating acetone washing and centrifugation. The recovered zirconia particles modified with capronic acid whose ligand was the surface was 11 g.

From 10 g (25 mass%) of this capronic acid modified zirconia particle as a zirconia particle, from 14.1 g (47 mass%) to 18.8 g (63 mass%) of side chain vinyl-dimethylsilicone VDT-131 as vinyl modified silicone, Methylhydrogen-dimethylsilicone HMS-151 as a hydrogen-modified silicone from 0.9 g (3 mass%) to 1.2 g (4 mass%) and 6 mg (0.02 mass) of platinum divinyl tetramethyldisiloxane SIP 6830.3 as a reaction catalyst The surface modified zirconia particle-silicone resin composite composition of Comparative Example 3 and a composite having a thickness of 1 mm were obtained in the same manner as in Example 1, except that each was changed to 9 mg (0.03 mass%).

The content rate of the zirconia particle of this composite_body | complex was 25 mass%.

As a result of measuring the particle diameter of the zirconia particle in the obtained composite of Comparative Example 3 in the same manner as in Example 1, the average dispersed particle diameter was 45 nm.

"evaluation"

About each transparent composite of Examples 1-10 and each composite of Comparative Examples 1-3, transparency, refractive index, and durability were evaluated by the following apparatus or method.

(1) transparency

The transmittance | permeability of visible light was measured using the spectrophotometer (made by Nippon spectroscopy).

Here, the visible light transmittance in the thickness direction (L = 1mm) of the transparent composite material (or composite) was measured, and 80% or more of visible light transmittance was "(circle)" and less than 80% was made into "x".

(2) Refractive index

It measured with the Abbe refractometer based on Japanese Industrial Standard JISK7142 "the refractive index measuring method of plastic."

Here, "(circle)" and the case where the refractive index improved only less than 0.03 were made into "x" when the refractive index improved 0.03 or more based on the resin single substance which does not add the zirconia particle.

(3) Durability

After leaving a transparent composite (or composite) for 24 hours in the environment of temperature 150 degreeC, it is taken out, the external appearance of a transparent composite (or composite) is observed visually, and it is "○" that there is no yellowing, and the yellowed thing is "x". I said.

Table 1 shows the evaluation results of the compositions and transparent composites (or composites) of the composite compositions of Examples 1 to 10 and Comparative Examples 1 and 2, respectively.

According to Table 1, each transparent composite of Examples 1-10 was excellent in all the points of transparency, refractive index, and durability.

On the other hand, in the composites of Comparative Examples 1 and 2, the transmittance of visible light was extremely low, 0% to 20%, and the refractive index could not be measured.

This is because both hydrogen-modified silicone and vinyl-modified silicone have a low crosslinking density, so that the aggregation and phase separation rates of the inorganic oxide particles are faster than the curing rate of the silicone resin, and as a result, transparency at the time of curing the inorganic oxide particles and the silicone resin is achieved. It seems to be due to missing.

In the composite of Comparative Example 3, the transmittance of visible light was extremely low at 10% or less, and the refractive index could not be measured. The reason for this is that the surface modification of the inorganic oxide particles is insufficient, so that the inorganic oxide particles aggregate in the composite composition of the inorganic oxide particles and the silicone resin, and as a result, the transparency in the composite is not obtained. In terms of durability, after yellowing at 150 ° C. for 24 hours, micro yellowing was observed, and thus the effect of discoloration by capric acid was confirmed.

[Industrial Availability]

In the present invention, when the inorganic oxide particles capable of improving the refractive index, the mechanical properties and the gas barrier properties are dispersed in the silicone resin, the dispersibility is high, and the phase separation and whitening during curing are prevented, thereby ensuring transparency. The composite composition of an inorganic oxide particle and silicone resin, and a transparent composite can be provided.

The composite composition of the inorganic oxide particle and silicone resin of this invention is a composite composition which disperse | distributes inorganic oxide particle in a silicone resin, At least, as an inorganic oxide particle, the polydimethylsiloxane frame | skeleton polymer which has a monofunctional group in one terminal couple | bonds, The surface-modified and inorganic dispersion particle whose average dispersed particle diameter is 1 nm or more and 20 nm or less, a silicone resin, and the reaction catalyst are contained. Thereby, the transparent composite with controlled refractive index can be obtained, maintaining transparency, heat resistance, and light resistance of the composite which combined the inorganic oxide particle and the silicone resin. Therefore, optical sheets, such as a sealing material of a semiconductor light emitting element (LED), the board | substrate for liquid crystal display devices, the board | substrate for organic electroluminescent display devices, the board | substrate for color filters, the board | substrate for touch panels, the board | substrate for solar cells, a transparent plate, an optical lens, an optical In addition to devices, optical waveguides, adhesives, and the like, as well as various industrial fields other than this, their applicability is great.

Claims (8)

At least, as the inorganic oxide particles, the surface-modified by bonding a polydimethylsiloxane skeleton polymer having a monofunctional group to one end, the inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst In the composite composition which contains
The silicone resin contains vinyl modified silicone and hydrogen modified silicone,
The said reaction catalyst is a composite composition of the inorganic oxide particle and silicone resin which contain a hydrosilylation reaction catalyst. The method according to claim 1,
The said polydimethylsiloxane skeleton polymer is a composite composition of the inorganic oxide particle and silicone resin which are monoglycidyl ether terminal polydimethylsiloxane and / or monohydroxyether terminal polydimethylsiloxane. 3. The method according to claim 1 or 2,
The vinyl-modified silicones include both terminal vinyl-dimethylsilicone, both terminal vinyldiphenyl-dimethylsilicone, both terminal vinyl-phenylmethylsilicone, both terminal vinyl-diethylsilicone, branched vinyl-dimethylsilicone, vinylmethylsilicone and vinylmethicone. Composite composition of the inorganic oxide particle and silicone resin which are 1 type (s) or 2 or more types chosen from the group which consists of a oxysilicone and a vinyl resin dispersion. 4. The method according to any one of claims 1 to 3,
The hydrogen-modified silicone is one selected from the group consisting of both terminal hydrogen-dimethylsilicone, methylhydrogen-dimethylsilicone, methylhydrogensilicone, ethylhydrogensilicone, methylhydrogen-phenylmethylsilicone, and hydride resin. Or a composite composition of two or more kinds of inorganic oxide particles and a silicone resin. 5. The method according to any one of claims 1 to 4,
The hydrogen-modified silicone is the following formula (1)
[Chemical Formula 1]

(Wherein R ₁ to R ₈ are any organic groups independent of each other (except H), m is an integer of 1 or more and n is a positive integer including 0)
It is made by containing the side chain hydrogen modified silicone shown to
The composite composition of the inorganic oxide particle and silicone resin whose ratio (m / (m + n)) of m and n in the said side chain hydrogen modified silicone is 0.25 or more and 1 or less. In the silicone resin, the surface-modified inorganic oxide particles are dispersed at an average dispersed particle diameter of 1 nm or more and 20 nm or less by bonding a polydimethylsiloxane skeleton polymer having a monofunctional group to one end thereof, and hydrosilylation reaction in the silicone resin. Transparent composite containing a catalyst. The transparent composite formed by shape | molding the composite composition of the inorganic oxide particle and silicone resin in any one of Claims 1-5 to a predetermined shape, and solidifying, or shape | molding after solidifying the said composite composition. A step of modifying the surface of the inorganic oxide particles with a polydimethylsiloxane skeleton polymer having a monofunctional group at one terminal, and obtaining 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;
Including the process of mixing the inorganic oxide particle of 1 nm or more and 20 nm or less of the mean-dispersion particle diameter which the said surface was modified, a silicone resin, and a reaction catalyst,
The manufacturing method of the composite composition of the inorganic oxide particle and silicone resin in any one of Claims 1-5.