JP2017155136A - Inorganic oxide-containing curable silicone resin composition and optical member formed by using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inorganic oxide-containing curable silicone resin composition from which an optical member having a high refractive index and excellent optical transparency can be formed.SOLUTION: The inorganic oxide-containing curable silicone resin composition comprises: a first curable silicone resin having a functional group for surface bonding, which participates in bonding to the surface of an inorganic oxide particle, and having a first crosslinking functional group; a second curable silicone resin having a functional group for surface bonding, which participates in bonding to the surface of an inorganic oxide particle, and having a second crosslinking functional group; an inorganic oxide particle on which the first curable silicone resin is bonded to the surface thereof via the functional group for surface bonding; and an inorganic oxide particle on which the second curable silicone resin is bonded to the surface thereof via the functional group for surface bonding. The first crosslinking functional group and the second crosslinking group can be bonded by applying energy; and the inorganic oxide particles have an average primary particle diameter of 1 to 40 nm.SELECTED DRAWING: None

Description

  The present invention relates to an inorganic oxide-containing curable silicone resin composition and an optical member formed using the same.

  In an LED (Light Emitting Diode) device, an LED chip is sealed with a transparent resin such as an epoxy resin or a silicone resin in order to protect the mounted LED chip.

  As an epoxy resin for sealing an LED chip, a bisphenol A type epoxy resin having a phenyl group or a cresol novolac type epoxy resin is used. When such an epoxy resin is used as a sealing resin, the sealing resin is oxidized and deteriorated by radicals generated by heat or light, and yellowing occurs. For this reason, a hydrogenated epoxy resin with improved yellowing resistance may be used as an epoxy resin for LED chip sealing. However, even when such an epoxy resin is used as a sealing resin, when the energy emitted from the LED chip increases with the shortening of the wavelength or the brightness of the LED device, the sealing resin turns yellow, The brightness of the LED device decreases.

  On the other hand, a dimethyl silicone resin may be used as a silicone resin for LED chip sealing. Dimethyl silicone resin is superior in heat resistance and light resistance compared to epoxy resin. However, the refractive index nD of dimethyl silicone resin is as low as about 1.4, which is smaller than the refractive index of the LED chip. For this reason, when the light emitted from the LED chip is incident on the dimethyl silicone resin at an angle smaller than the critical angle, the light is totally reflected at the interface with the dimethyl silicone resin. When total reflection occurs, the light extraction efficiency decreases, and the brightness of the LED device decreases.

  Therefore, in order to increase the refractive index of the silicone resin, a technique using a silicone resin having a phenyl group has been studied. However, since the phenyl group absorbs ultraviolet light and generates radicals, with the shortening of the wavelength of the LED device, the sealing resin is oxidized and deteriorated as in the case of the epoxy resin, resulting in yellowing. Further, when applied to a high power LED device having an output of 1 W or more, it is deteriorated by generated heat.

  Also, in order to increase the refractive index of the silicone resin while maintaining heat resistance and light resistance, there is a method of mixing inorganic oxide particles such as zirconia with excellent thermal stability and high refractive index into the silicone resin. It is being considered. When mixing inorganic oxide particles such as zirconia with a silicone resin, if the particle size of the inorganic oxide particles is several hundred nm or more, light scattering occurs on the particle surface from the difference in refractive index from the silicone resin, The mixture becomes cloudy. In order to obtain a transparent mixture, the particle diameter of the inorganic oxide particles mixed with the silicone resin needs to be several tens of nm or less. However, the surface of the inorganic oxide particles is generally covered with a hydroxyl group and has high hydrophilicity. For this reason, when nanometer-sized inorganic oxide particles having a particle size of several tens of nanometers or less are mixed with a hydrophobic substance such as a silicone resin, the inorganic oxide particles aggregate and the inorganic oxide particles are not uniformly dispersed. . As a result, the mixture becomes cloudy and the transparency required for the optical member cannot be maintained.

  In order to uniformly disperse the inorganic oxide particles in the silicone resin without agglomerating the particles, a method of hydrophobizing the surface of the inorganic oxide particles with a surface treatment agent such as a silane coupling agent is often used. However, when the surface of the inorganic oxide particles is hydrophobized by the surface treatment agent, many hydroxyl groups such as unreacted particle surface hydroxyl groups due to steric hindrance of the surface treatment agent itself and unreacted hydroxyl groups derived from the hydrolyzate of the surface treatment agent. Remains. For this reason, the hydrophobization of the inorganic oxide particles does not proceed. Accordingly, when mixed with a hydrophobic substance such as a silicone resin, the inorganic oxide particles aggregate.

  In Patent Document 1, in order to make the surface of the inorganic oxide particles hydrophobic and to reduce the remaining hydroxyl groups, the inorganic oxide particles are subjected to primary surface modification and secondary surface modification, and then further residual hydroxyl groups are eliminated. Discloses a method of performing tertiary surface modification with an alkylsilazane surface treatment agent. However, this method requires a large amount of a surface modifier and a multi-step surface modification step, so that productivity is lowered. Moreover, in this method, since the surface modifier having a refractive index of about 1.4 is used more than the particle weight, the refractive index of the surface-modified inorganic oxide particles becomes low. In addition, the inorganic oxide particles surface-modified by this method can be dispersed in a low-viscosity silicone resin, but a high-viscosity of 1 to 10 Pa · s generally used for LED chip sealing. It is difficult to disperse in a silicone resin.

  Patent Document 2 discloses a technique in which a silicone resin is used as a surface modifier in order to disperse inorganic oxide particles in a high-viscosity silicone resin that is generally used for LED chip sealing. In this method, a functional group capable of binding to the surface of the inorganic oxide particle is provided at the end of the silicone resin used as the surface modifier, and the high molecular weight silicone resin is bonded to the surface of the inorganic oxide particle. As a result, it is possible to disperse the inorganic oxide particles in the high-viscosity silicone resin serving as a matrix. However, when the surface of the inorganic oxide particles is modified with a silicone resin, the molecular weight of the silicone resin is large, so that the thickness of the modification layer is increased, and the number of inorganic oxide particles that can be dispersed in the silicone resin as a matrix is reduced. The effect of the rise is difficult to come out.

  Non-Patent Document 1 proposes a matrix-free type silicone resin-inorganic oxide particle composite composed of inorganic oxide particles and a silicone resin used as a surface modifier without using a silicone resin as a matrix. Yes. By changing the molecular weight of the silicone resin used as the surface modifier and adjusting the film thickness of the modification layer, the refractive index is increased to 1.6 by adjusting the amount of inorganic oxide particles that can be put into the composite. Can be made. It has also been reported that the resin viscosity increases by crosslinking between the silicone resins that modify the surface of the inorganic oxide particles with a curing agent. In this case, since the curing agent that crosslinks between the silicone resins becomes the matrix, there is a concern that the inorganic oxide particles and the matrix are phase-separated and become cloudy.

JP 2009-173757 A US Patent Application Publication No. 2014/0343333

RSC Adv. , 2015, 5, 14788-14795

  Therefore, the present invention has been made in view of the above-mentioned problems, and forms an optical member having a high refractive index and excellent optical transparency without using a silicone resin or a curing agent as a matrix. An object of the present invention is to provide an inorganic oxide-containing curable silicone resin composition that can be used, and an optical member formed using the same.

  The present inventor has intensively studied to achieve the above-described object, and modifies the surface of the inorganic oxide particles with a specific silicone resin, and bonds and cures between the inorganic oxide particles via the silicone resin. As a result, the inventors have found that nanometer-sized inorganic oxide particles can be uniformly dispersed without agglomeration.

  This invention is made | formed based on this knowledge, and has the following structures.

(Configuration 1)
In an inorganic oxide-containing curable silicone resin composition comprising a curable silicone resin and inorganic oxide particles,
A first curable silicone resin having a functional group for surface binding and a first crosslinkable functional group involved in bonding to the surface of the inorganic oxide particles;
A second curable silicone resin having a functional group for surface binding and a second crosslinkable functional group involved in binding to the surface of the inorganic oxide particles;
Inorganic oxide particles in which the first curable silicone resin is bonded to the surface via the surface-binding functional group;
Inorganic oxide particles in which the second curable silicone resin is bonded to the surface via the surface binding functional group,
The first crosslinkable functional group and the second crosslinkable functional group can be bonded by application of energy,
The inorganic oxide-containing curable silicone resin composition having an average primary particle size of 1 to 40 nm.

(Configuration 2)
The inorganic oxide containing curable silicone resin composition of the structure 1 containing the catalyst which accelerates | stimulates the coupling | bonding of a said 1st crosslinkable functional group and a said 2nd crosslinkable functional group.

(Configuration 3)
A non-curable silicone resin having a functional group for surface binding involved in binding to the surface of the inorganic oxide particles,
The inorganic oxide-containing curable silicone resin composition according to Configuration 1 or 2, wherein the non-curable silicone resin is bonded to the surface of the inorganic oxide particle through the surface-binding functional group.

(Configuration 4)
The inorganic oxide-containing curable silicone resin composition according to Configuration 3, wherein the non-curable silicone resin is composed of a plurality of resins having different molecular weights.

(Configuration 5)
The combination of said 1st and 2nd crosslinkable functional group is the inorganic of any one of the structures 1-4 which are a hydrosilyl group and a vinyl group, an epoxy group, and an acid anhydride group, or an acryl group and an acryl group. Oxide-containing curable silicone resin composition.

(Configuration 6)
The inorganic oxide-containing curable silicone resin composition according to any one of configurations 1 to 5, wherein the surface-bonding functional group is a carboxy group, a sulfonyl group, or a phosphate group.

(Configuration 7)
The inorganic oxide-containing curable silicone resin composition according to any one of configurations 1 to 6, wherein the inorganic oxide particles include at least one selected from the group consisting of zirconia, titania, ceria, and barium titanate. object.

(Configuration 8)
The combination of the first and second crosslinkable functional groups is a hydrosilyl group and a vinyl group,
The inorganic oxide-containing curable silicone resin composition according to Configuration 2, wherein the catalyst is a catalyst that promotes a hydrosilylation reaction.

(Configuration 9)
The inorganic oxide-containing curable silicone resin composition according to Configuration 8, wherein the catalyst contains platinum.

(Configuration 10)
10. The inorganic oxide-containing curable silicone resin composition according to any one of configurations 1 to 9, wherein the energy application is heating.

(Configuration 11)
The inorganic oxide-containing curable silicone resin composition according to any one of Configurations 1 to 10 is cured by bonding the first crosslinkable functional group and the second crosslinkable functional group. An optical member.

(Configuration 12)
The optical member according to Configuration 11, wherein the volume ratio of the inorganic oxide particles is 10% by volume or more.

(Configuration 13)
The optical member according to Configuration 11 or 12, wherein the total light transmittance at a wavelength of 400 nm or more and 800 nm or less is 80% or more.

  As described above, according to the inorganic oxide-containing curable silicone resin composition according to the present invention, the inorganic oxide particles in which the first curable silicone resin is bonded to the surface via the surface-bonding functional group, and the surface Inorganic oxide particles in which the second curable silicone resin is bonded to the surface via a bonding functional group. The first curable silicone resin has a first crosslinkable functional group, and the second curable silicone resin has a second crosslinkable functional group. The average primary particle diameter of the inorganic oxide particles is 1 nm or more and 40 nm or less. For this reason, in this inorganic oxide-containing curable silicone resin composition, the first crosslinkable functional group and the second crosslinkable functional group are bonded to each other, and the first curable silicone resin and the second curable silicone resin composition are combined. It is cured by crosslinking with the silicone resin. At that time, the inorganic oxide particles are bonded to each other through the first curable silicone resin and the second curable silicone resin. Accordingly, nanometer-sized inorganic oxide particles can be uniformly dispersed in the silicone resin at a high concentration.

  Moreover, according to the optical member which concerns on this invention, the inorganic oxide containing curable silicone resin composition mentioned above is hardened by couple | bonding a 1st crosslinkable functional group and a 2nd crosslinkable functional group. It will be. For this reason, since the nanometer-sized inorganic oxide particles are uniformly dispersed at a high concentration in the silicone resin, an optical member having a high refractive index and excellent optical transparency can be obtained.

  Hereinafter, embodiments of the present invention will be specifically described. In addition, the following embodiment is one form at the time of actualizing this invention, Comprising: This invention is not limited within the range.

A. Inorganic Oxide-Containing Curable Silicone Resin Composition The inorganic oxide-containing curable silicone resin composition according to this embodiment includes a functional group for surface bonding and a first crosslinkability involved in bonding to the surface of inorganic oxide particles. A first curable silicone resin having a functional group, a second curable silicone resin having a functional group for surface binding involved in binding to the surface of the inorganic oxide particles and a second crosslinkable functional group; Inorganic oxide particles in which the first curable silicone resin is bonded to the surface via the surface binding functional group, and the second curable silicone resin is bonded to the surface via the surface binding functional group. Inorganic oxide particles. The first crosslinkable functional group and the second crosslinkable functional group can be bonded by applying energy.
In addition, the inorganic oxide-containing curable silicone resin composition of this embodiment includes a first crosslinkable functional group of the first curable silicone resin and a second crosslinkable functional group of the second curable silicone resin. It is preferable to include a catalyst that promotes bonding with the.
Furthermore, the inorganic oxide-containing curable silicone resin composition of this embodiment may include a non-curable silicone resin having a surface-bonding functional group involved in bonding to the surface of the inorganic oxide particles. The non-curable silicone resin is bonded to the surface of the inorganic oxide particle via the surface bonding functional group. The non-curable silicone resin does not have a crosslinkable functional group. By using a non-curable silicone resin, the hardness of the optical member formed using the inorganic oxide-containing curable silicone resin composition of this embodiment can be adjusted.

(1) Curable Silicone Resin The first curable silicone resin has a silicone main chain, a surface-bonding functional group that binds to the silicone main chain, and a first crosslinkable functional group. Similarly, the second curable silicone resin has a silicone main chain, a surface-bonding functional group and a second crosslinkable functional group bonded to the silicone main chain. The surface-bonding functional groups of the first and second curable silicone resins are involved in bonding to the surface of the inorganic oxide particles.
Examples of the structure of the silicone main chain of the first and second curable silicone resins include a dimethyl silicone structure, a methylphenyl silicone structure, and a diphenyl silicone structure. The structure of the silicone main chain may be a combination of these structures (for example, when the silicone main chain is composed of a dimethylsilicone structure portion and a dimethylphenylsilicone structure portion). The first curable silicone resin and the second curable silicone resin may have a silicone main chain having the same structure or may have a silicone main chain having a different structure. The first curable silicone resin having the same silicone main chain structure may be bonded to one inorganic oxide particle, or the first curable silicone resin having a different silicone main chain structure may be used. You may combine. Similarly, the second curable silicone resin having the same silicone main chain structure may be bonded to one inorganic oxide particle, or the second curable resin having a different silicone main chain structure. The case where a silicone resin couple | bonds may be sufficient.
By applying energy to the inorganic oxide-containing curable silicone resin composition, the first crosslinkable functional group of the first curable silicone resin and the second crosslinkable functional group of the second curable silicone resin Can be combined. Examples of such a combination of the first and second crosslinkable functional groups include hydrosilyl group and vinyl group, epoxy group and acid anhydride group, acrylic group and acrylic group. In the inorganic oxide-containing curable silicone resin composition, the first crosslinkable functional group and the second crosslinkable functional group are preferably contained in the same molar amount. The bonding position of the first and second crosslinkable functional groups to the silicone main chain may be the terminal of the silicone main chain, or may be in the middle of the silicone main chain other than the terminal.
The 1st and 2nd curable silicone resins are couple | bonded with the surface of the inorganic oxide particle through the surface bonding functional group. The functional group for surface bonding is bonded to the hydroxyl group on the surface of the inorganic oxide particle. Examples of such surface binding functional groups include a carboxy group, a sulfonyl group, and a phosphate group. When these are used as the functional group for surface bonding, the inorganic oxide-containing curable silicone resin composition tends to be transparent. The first curable silicone resin and the second curable silicone resin may have the same surface-binding functional group or may have different surface-binding functional groups. Moreover, the case where the 1st curable silicone resin which has the same functional group for surface binding may couple | bond with one inorganic oxide particle, and the 1st curable silicone which has a different functional group for surface binding may be sufficient as it. It may be a case where a resin is bonded. Similarly, the second curable silicone resin having the same surface bonding functional group may be bonded to one inorganic oxide particle, or the second curable resin having a different surface bonding functional group. The case where a silicone resin couple | bonds may be sufficient. The bonding position of the functional group for surface bonding to the silicone main chain may be the terminal of the silicone main chain, or may be in the middle of the silicone main chain other than the terminal.
The viscosity of the curable silicone resin is preferably 0.001 Pa · s to 10 Pa · s, and more preferably 0.005 Pa · s to 1 Pa · s. If the viscosity exceeds 10 Pa · s, the inorganic oxide-containing curable silicone resin composition cannot be maintained in a liquid state, which is not preferable. If the viscosity is less than 0.001 Pa · s, it is difficult to disperse the inorganic oxide particles. Moreover, since a volatile component generate | occur | produces that a viscosity is less than 0.005 Pa * s, it is unpreferable. The viscosity of the non-curable silicone resin can be controlled by the molecular weight. That is, as the non-curable silicone resin, a molecular weight having a viscosity in the range of 0.001 Pa · s to 10 Pa · s is used.

(2) Inorganic oxide particles The inorganic oxide particles have a number average average primary particle diameter of 1 nm to 40 nm, preferably 1 nm to 10 nm, more preferably 1 nm to 5 nm. If the average primary particle diameter exceeds 40 nm, Rayleigh scattering tends to occur, which is not preferable. “1 nm” is the lower limit of the size that can exist as inorganic oxide particles.
The inorganic oxide particles are preferably used in a state where they are dispersed in an organic solvent without being aggregated.
As the inorganic oxide particles, particles containing at least one selected from the group consisting of zirconia, titania, ceria, and barium titanate are preferably used.
The inorganic oxide particles to which the first curable silicone resin is bonded and the inorganic oxide particles to which the second curable silicone resin are bonded may include the same material or different materials. May be included.
The inorganic oxide particles are classified into those in which the first curable silicone resin is bonded to the surface and those in which the second curable silicone resin is bonded to the surface. However, as long as the refractive index and optical transparency of the optical member and the hardness of the optical member are not affected, the second curing is applied to the inorganic oxide particles having the first curable silicone resin bonded to the surface. The curable silicone resin may be bonded, or the first curable silicone resin may be bonded to the inorganic oxide particles bonded to the surface of the second curable silicone resin.

(3) Catalyst The catalyst used depends on the combination of the first and second crosslinkable functional groups.
When the combination of the first and second crosslinkable functional groups is a hydrosilyl group and a vinyl group, a catalyst that accelerates the hydrosilylation reaction is used. Among catalysts that promote the hydrosilylation reaction, those that are activated by heat include those containing platinum, those containing palladium, and the like. Since platinum is colorless and transparent even after the hydrosilylation reaction, platinum is preferable as a catalyst for promoting the hydrosilylation reaction.
When the combination of the first and second crosslinkable functional groups is an epoxy group and an acid anhydride group, a catalyst that accelerates the polymerization reaction is used. Examples of the catalyst for promoting the polymerization reaction include tertiary amine, tertiary amine salt, imidazole, and phosphine.
When the combination of the first and second crosslinkable functional groups is an acrylic group and an acrylic group, a catalyst that promotes a radical reaction is used. Examples of the catalyst for promoting the radical reaction include azo compounds and peroxides.

(4) Non-curable silicone resin The non-curable silicone resin has a silicone main chain and a surface-bonding functional group that binds to the silicone main chain. The functional group for surface bonding of the non-curable silicone resin is involved in bonding to the surface of the inorganic oxide particles.
Examples of the structure of the silicone main chain of the non-curable silicone resin include a dimethyl silicone structure, a dimethylphenyl silicone structure, and a diphenyl silicone structure. The structure of the silicone main chain may be a combination of these structures (for example, when the silicone main chain is composed of a dimethylsilicone structure portion and a dimethylphenylsilicone structure portion). When non-curable silicone resin having the same silicone main chain structure is bonded to one inorganic oxide particle, or when non-curable silicone resin having different silicone main chain structure is bonded. There may be.
The non-curable silicone resin is bonded to the surface of the inorganic oxide particle via the surface bonding functional group. Examples of such surface binding functional groups include a carboxy group, a sulfonyl group, and a phosphate group. It may be a case where a non-curable silicone resin having the same surface binding functional group is bonded to one inorganic oxide particle, or a case where a non-curable silicone resin having a different surface binding functional group is bonded. May be.
The non-curable silicone resin may be composed of a plurality of resins having different molecular weights.

(5) Energy application When curing the inorganic oxide-containing curable silicone resin composition of this embodiment, energy is applied. Energy application can be performed by heating, light irradiation, or the like. When the optical member formed using the inorganic oxide-containing curable silicone resin composition of this embodiment is used as a sealing resin for an LED chip mounted on an LED device, energy application is performed by heating. Is preferred.

(6) Content of inorganic oxide particles and silicone resin Inorganic oxide particles and silicone resin in the inorganic oxide-containing curable silicone resin composition of this embodiment (first curable silicone resin, second curing) The content of the curable silicone resin and the non-curable silicone resin) is determined as follows.
First, the target value of the refractive index of the optical member formed using the inorganic oxide-containing curable silicone resin composition of this embodiment is determined.
When the target value is determined, the volume ratio (volume%) of the inorganic oxide particles necessary to reach the target value of the refractive index is determined. This volume ratio (volume%) depends on the type of silicone resin used (first curable silicone resin, second curable silicone resin, non-curable silicone resin).
When the volume ratio (volume%) is determined, the content (% by weight) of inorganic oxide particles necessary for securing the volume ratio (volume%) is determined.
When the content (% by weight) of the inorganic oxide particles is determined, the first curable silicone resin and the second curable silicone resin are ensured so as to ensure the volume ratio (volume%) required by the inorganic oxide particles. The molecular weight and content (% by weight) of each are adjusted. Moreover, when using noncurable silicone resin, the molecular weight and content (weight%) of noncurable silicone resin are also adjusted. When the non-curable silicone resin is composed of a plurality of resins having different molecular weights, the molecular weight and content (% by weight) of each resin constituting the non-curable silicone resin are also adjusted.
If the molecular weight of the silicone resin is increased, the content (% by weight) of the inorganic oxide particles cannot be increased. On the other hand, if the molecular weight of the silicone resin is reduced, the content (% by weight) of the inorganic oxide particles can be increased, but the fluidity of the inorganic oxide-containing curable silicone resin composition is lowered. Further, when only the curable silicone resin is used without using the non-curable silicone resin, the optical member formed using the inorganic oxide-containing curable silicone resin composition becomes too hard. Further, when the volume ratio (volume%) of the inorganic oxide particles is the same, it is necessary to increase the molecular weight of the silicone resin as the particle diameter of the inorganic oxide particles increases. Moreover, when using the optical member formed using the inorganic oxide containing curable silicone resin composition of this embodiment as sealing resin of the LED chip mounted in an LED device, the viscosity of the silicone resin is the LED chip. It is preferable that it is 1-10 Pa.s generally used for sealing. Considering these points, the molecular weight and content (% by weight) of the first curable silicone resin and the second curable silicone resin, the molecular weight and content (% by weight) of the non-curable silicone resin, The molecular weight and content (% by weight) of each resin constituting the non-curable silicone resin are adjusted.
In the examples described later, the target value of the refractive index of the optical member was set to 1.51. In order to reach a refractive index of 1.51, it is necessary to contain 18% by volume or more of zirconia particles. In order to contain 18% by volume or more of zirconia particles, it is necessary to contain 50% by weight or more of silicone resin. Therefore, 100 g of zirconia particles, 54 g of a first curable silicone resin having a number average molecular weight of about 6000, 54 g of a second curable silicone resin having a number average molecular weight of 10,000, and a non-curable silicone resin having a number average molecular weight of 10,000. 16 g of non-curable silicone resin having a number average molecular weight of 1000 was used in an amount of 20 g. In this case, the content of zirconia particles was 52.6% by weight.

B. Optical member The optical member of this embodiment is obtained by using the above-described inorganic oxide-containing curable silicone resin composition, the first crosslinkable functional group of the first curable silicone resin, and the second curable silicone resin. It hardens | cures by couple | bonding with 2 crosslinkable functional groups.
By applying energy to the inorganic oxide-containing curable silicone resin composition, the first crosslinkable functional group of the first curable silicone resin and the second crosslinkable functional group of the second curable silicone resin Join.

  In the optical member, the volume ratio (volume%) of the inorganic oxide particles is preferably 10% by volume or more, and more preferably 15% by volume or more. A refractive index can fully be improved as the volume ratio (volume%) of an inorganic oxide particle is 10 volume% or more.

  The optical member preferably has a total light transmittance of 60% or more at a wavelength of 400 nm or more and 800 nm or less, and more preferably 80% or more.

  In the conventional method of mixing the surface-modified inorganic oxide particles and the silicone resin as the matrix, the distance between the inorganic oxide particles in the obtained optical member varies depending on the presence of the matrix. On the other hand, the inorganic oxide-containing curable silicone resin composition of this embodiment has the inorganic oxide particles surface-modified with the first silicone resin having the first crosslinkable functional group and the second crosslinkability. Inorganic oxide particles surface-modified with a second silicone resin having a functional group are mixed. For this reason, between the inorganic oxide particles in the optical member formed using the inorganic oxide-containing curable silicone resin composition of this embodiment, the first curable silicone resin and the second curable silicone resin are used. And connect through. Therefore, the variation in the distance between the inorganic oxide particles is small.

  In addition, the inorganic oxide-containing curable silicone resin composition of this embodiment includes an oxidation degradation inhibitor and a phosphor within a range that does not affect the refractive index and optical transparency of the optical member and the hardness of the optical member. In addition, other additives may be included.

C. INORGANIC OXIDE-CONTAINING CURABLE SILICONE RESIN COMPOSITION AND OPTICAL MEMBER MANUFACTURING METHOD The inorganic oxide-containing curable silicone resin composition and the optical member of this embodiment are bonded to the surface of inorganic oxide particles. First curable silicone resin forming step for forming a first curable silicone resin having a functional group for use and a first crosslinkable functional group, and for surface bonding involved in bonding to the surface of inorganic oxide particles A second curable silicone resin step for forming a second curable silicone resin having a functional group and a second crosslinkable functional group; a particle dispersion forming step for forming a dispersion of inorganic oxide particles; The first curable silicone resin is added to the dispersion of the inorganic oxide particles, the first curable silicone resin is bonded to the surface of the inorganic oxide particles, and the first curable silicone resin is modified. Inorganic First curable silicone resin-modified particle forming step for forming oxide particles, and first curable silicone resin-modified particle dispersion for forming a dispersion of inorganic oxide particles modified with the first curable silicone resin In the liquid forming step, the second curable silicone resin is added to the dispersion of the inorganic oxide particles, and the second curable silicone resin is bonded to the surface of the inorganic oxide particles. A second curable silicone resin-modified particle forming step for forming inorganic oxide particles modified with a silicone resin, and a second for forming a dispersion of inorganic oxide particles modified with a second curable silicone resin. A curable silicone resin-modified particle dispersion forming step, a dispersion of inorganic oxide particles modified with a first curable silicone resin, and a dispersion of inorganic oxide particles modified with a second curable silicone resin; Mixing, and then distilling off the solvent from the mixture to form a gel-like product, and applying energy to the gel-like product, the first curable silicone resin first It can manufacture by performing the hardened | cured material formation process which couple | bonds a crosslinkable functional group and the 2nd crosslinkable functional group of a 2nd curable silicone resin, and forms hardened | cured material. The gel-like product obtained by the gel-like product forming step corresponds to the inorganic oxide-containing curable silicone resin composition, and the cured product obtained by the cured product-forming step corresponds to the optical member.
Further, the inorganic oxide-containing curable silicone resin composition of this embodiment includes a first crosslinkable functional group of the first curable silicone resin and a second crosslinkable functional group of the second curable silicone resin. In the case where a catalyst that promotes the bonding is included, a predetermined catalyst is added in the gel-like product forming step.
Furthermore, when the inorganic oxide-containing curable silicone resin composition of this embodiment includes a non-curable silicone resin having a functional group for surface binding that is involved in bonding to the surface of the inorganic oxide particles, inorganic oxidation is performed. A non-curable silicone resin forming step of forming a non-curable silicone resin having a functional group for surface binding involved in binding to the surface of the product particles is performed. Then, in the first curable silicone resin modified particle forming step, a non-curable silicone resin is added together with the first curable silicone resin in the dispersion of the inorganic oxide particles, and the surface of the inorganic oxide particles is added. The first curable silicone resin and the non-curable silicone resin are combined. Similarly, in the second curable silicone resin modified particle forming step, a non-curable silicone resin is added together with the second curable silicone resin to the dispersion of inorganic oxide particles, and the surface of the inorganic oxide particles The second curable silicone resin and the non-curable silicone resin are bonded to each other.

  Hereinafter, a phosphoric acid group is used as the functional group for surface bonding, a hydrosilyl group is used as the first crosslinkable functional group, a vinyl group is used as the second crosslinkable functional group, and the catalyst and the non-curable silicone resin are used. Furthermore, about the case where energy application is performed by heating, the manufacturing method of an inorganic oxide containing curable silicone resin composition and an optical member is demonstrated concretely.

(1) First curable silicone resin forming step The first curable silicone resin forming step is a step of forming a first curable silicone resin having a phosphate group and a hydrosilyl group.
In this step, first, a silicone resin having hydrosilyl groups at both ends is dissolved in a solvent. In the solution, vinyl phosphonic acid is added. Vinylphosphonic acid is added in an amount of 0.5 equivalent to the hydrosilyl group. Further, a catalyst for promoting the hydrosilylation reaction is added to the solution. Thereafter, the solution is stirred at a predetermined temperature to bond the hydrosilyl group of the silicone resin and the vinyl group of vinylphosphonic acid. Thereafter, the precipitate is taken out from the solution to obtain a first curable silicone resin having a phosphate group at one end and a hydrosilyl group at the other end.

(2) Second curable silicone resin step The second curable silicone resin step is a step of forming a second curable silicone resin having a phosphate group and a vinyl group.
In this step, first, a silicone resin having a hydrosilyl group at one end and a vinyl group at the other end is dissolved in a solvent. In the solution, vinyl phosphonic acid is added. Vinylphosphonic acid is added in an amount of 5.0 equivalents relative to the hydrosilyl group. Further, a catalyst for promoting the hydrosilylation reaction is added to the solution. Thereafter, the solution is stirred at a predetermined temperature to bond the hydrosilyl group of the silicone resin and the vinyl group of vinylphosphonic acid. Thereafter, the precipitate is taken out from the solution to obtain a second curable silicone resin having a phosphate group at one end and a vinyl group at the other end.

(3) Non-curable silicone resin forming step The non-curable silicone resin forming step is a step of forming a non-curable silicone resin having a phosphate group.
In this step, first, a silicone resin having a methylol group at the end is dissolved in a solvent. Into the solution is added phosphoryl chloride. Phosphoryl chloride is added in excess with respect to methylol groups. Thereafter, the solution is stirred at a predetermined temperature to bond the methylol group of the silicone resin and phosphoryl chloride. Thereafter, water is added to the solution to replace the unreacted chlorine group of phosphoryl chloride with a hydroxyl group. Thereafter, the precipitate is taken out from the solution to obtain a non-curable silicone resin having a phosphate group at the terminal.

(4) Particle dispersion forming step The particle dispersion forming step is a step of forming a dispersion of inorganic oxide particles.
In this step, first, an inorganic oxide particle dispersion in which inorganic oxide particles having a number average average primary particle diameter of 1 nm to 40 nm are dispersed in a predetermined organic solvent is prepared. Aliphatic carboxylic acid is added to the dispersion. Thereafter, the dispersion is stirred at a predetermined temperature to bond the aliphatic carboxylic acid to the surface of the inorganic oxide particles. Thereafter, the precipitate is taken out from the dispersion, and a solvent is added to the taken-out precipitate to obtain a dispersion of inorganic oxide particles modified with an aliphatic carboxylic acid.

(5) First curable silicone resin-modified particle forming step The first curable silicone resin-modified particle forming step includes the steps of first curable silicone resin and non-curable silicone resin in a dispersion of inorganic oxide particles. And bonding the first curable silicone resin and the non-curable silicone resin to the surface of the inorganic oxide particles to form inorganic oxide particles modified with the first curable silicone resin. It is.
In this step, first, a first curable silicone resin and a non-curable silicone resin are added to a dispersion of inorganic oxide particles modified with an aliphatic carboxylic acid. Thereafter, the dispersion is stirred at a predetermined temperature, and the first curable silicone resin and the non-curable silicone resin are made inorganic through the phosphate groups of the first curable silicone resin and the non-curable silicone resin. Bond to the surface of the oxide particles. Thereafter, the precipitate is taken out from the dispersion to obtain inorganic oxide particles modified with the first curable silicone resin.

(6) First Curable Silicone Resin Modified Particle Dispersion Forming Step In the first curable silicone resin modified particle dispersion forming step, a dispersion of inorganic oxide particles modified with the first curable silicone resin is used. It is a process of forming.
In this step, the inorganic oxide particles modified with the first curable silicone resin are added to a solvent to obtain a dispersion of inorganic oxide particles modified with the first curable silicone resin.

(7) Second curable silicone resin-modified particle forming step In the second curable silicone resin-modified particle forming step, the second curable silicone resin is added to the dispersion of inorganic oxide particles, and inorganic oxidation is performed. In this step, the second curable silicone resin is bonded to the surface of the product particles to form inorganic oxide particles modified with the second curable silicone resin.
This step is performed in the same manner as the first curable silicone resin-modified particle forming step described above.

(8) Second curable silicone resin-modified particle dispersion forming step The second curable silicone resin-modified particle dispersion forming step is a process of dispersing inorganic oxide particles decorated with the second curable silicone resin. This is a step of forming a liquid.
This step is performed in the same manner as the first curable silicone resin-modified particle dispersion forming step described above.

(9) Gel-like product forming step The gel-like product forming step includes the dispersion of inorganic oxide particles modified with the first curable silicone resin and the inorganic oxide particles modified with the second curable silicone resin. This is a step of forming a gel-like material by mixing the dispersion and then distilling off the solvent from the mixture.
In this step, first, a dispersion of inorganic oxide particles modified with the first curable silicone resin and a dispersion of inorganic oxide particles decorated with the second curable silicone resin are mixed. Here, the mixing is performed so that the inorganic oxide particles modified with the first curable silicone resin and the inorganic oxide particles decorated with the second curable silicone resin have a predetermined ratio. Furthermore, a catalyst for promoting the hydrosilylation reaction is added. The mixture is then stirred until the mixture is uniform. Thereafter, the solvent is distilled off from the mixture to obtain a gel.

(10) Cured product forming step In the cured product forming step, the first crosslinkable functional group of the first curable silicone resin and the second crosslink of the second curable silicone resin are heated by heating the gel-like product. It is a step of bonding a functional functional group to form a cured product.
In this step, the obtained gel-like product is heated at a predetermined temperature to bond the hydrosilyl group of the first curable silicone resin and the vinyl group of the second curable silicone resin, thereby obtaining a cured product.

D. Effect As in the prior art, in the method of mixing the surface-modified inorganic oxide particles and the silicone resin as the matrix, when the concentration of the inorganic oxide particles is a low concentration of about 1 to 20% by weight, the matrix and The inorganic oxide particles can be uniformly dispersed in the resulting silicone resin. However, when the concentration of the inorganic oxide particles is a high concentration of 20% by weight or more, the distance between the particles becomes small, so that the van der Waals attractive force between the particles becomes large and the particles aggregate. For this reason, in the conventional method, high concentration inorganic oxide particles cannot be uniformly dispersed, and the mixture becomes cloudy.
In contrast, the inorganic oxide-containing curable silicone resin composition of this embodiment includes inorganic oxide particles in which the first curable silicone resin is bonded to the surface via the surface-bonding functional group, and the surface-bonding resin composition. Inorganic oxide particles having a second curable silicone resin bonded to the surface via a functional group. The first curable silicone resin has a first crosslinkable functional group, and the second curable silicone resin has a second crosslinkable functional group. The first crosslinkable functional group and the second crosslinkable functional group can be bonded by application of energy. The average primary particle diameter of the inorganic oxide particles is 1 nm or more and 40 nm or less. For this reason, this inorganic oxide-containing curable silicone resin composition is capable of bonding the first crosslinkable functional group and the second crosslinkable functional group by applying energy, and thereby the first curable silicone. The resin and the second curable silicone resin are cured by crosslinking. At that time, the inorganic oxide particles are bonded to each other through the first curable silicone resin and the second curable silicone resin.
As described above, the inorganic oxide-containing curable silicone resin composition of this embodiment includes the inorganic oxide particles surface-modified with the first silicone resin having the first crosslinkable functional group and the second crosslinkability. The inorganic oxide particles surface-modified with the second silicone resin having a functional group are mixed, and a silicone resin as a matrix is not used. For this reason, the density | concentration of an inorganic oxide particle can be made into the high density | concentration of 50 weight% or more. In addition, since no silicone resin is used as the matrix, the surface of the inorganic oxide particles can be sufficiently modified with the silicone resin even when the concentration of the inorganic oxide particles is 50% by weight or more. Aggregation can be prevented. For this reason, in this embodiment, a transparent inorganic oxide-containing curable silicone resin composition in which inorganic oxide particles are uniformly dispersed at a high concentration can be obtained.

The optical member of this embodiment is obtained by curing the above-described inorganic oxide-containing curable silicone resin composition by bonding the first crosslinkable functional group and the second crosslinkable functional group. Is. For this reason, since the nanometer-sized inorganic oxide particles are uniformly dispersed at a high concentration in the silicone resin, an optical member having a high refractive index and excellent optical transparency can be obtained.
Therefore, when the optical member of this embodiment is used as a sealing resin for an LED chip mounted on an LED device, the refractive index difference from the LED chip is reduced. Therefore, reflection when the light emitted from the LED chip enters the sealing resin is reduced, and the light extraction efficiency is increased. As a result, the light emission luminance of the LED device can be improved.

  Hereinafter, based on an Example and a comparative example, this invention is demonstrated more concretely. The following examples are merely examples of the present invention and do not limit the present invention.

  First, various measurement methods will be described prior to the description of Examples and Comparative Examples.

<Measurement method of refractive index>
The refractive index was measured with an Abbe refractometer (manufactured by Atago Co., Ltd., DR-M2) in accordance with Japanese Industrial Standards: JIS K7142 “Method for Measuring Plastic Refractive Index”.

<Measurement method of total light transmittance>
The total light transmittance was measured with a haze meter (Nippon Denshoku make, NDH7000 (trade name)) in accordance with Japanese Industrial Standards: JIS K 7361 “Testing method for total light transmittance of plastic-transparent material”.

Production Example 1
In Production Example 1, a method for producing a first curable silicone resin having a phosphate group and a hydrosilyl group will be described.
First, in a reaction vessel, 10 g of a silicone resin having a number average molecular weight of 6000 (manufactured by Gelest, DMS-H21 (trade name)) having hydrosilyl groups at both ends is placed in 100 ml of tetrahydrofuran (THF (abbreviation)) at both ends. A silicone resin having a hydrosilyl group was dissolved in tetrahydrofuran. Thereafter, 180 mg of vinylphosphonic acid (manufactured by Tokyo Chemical Industry) was added to the solution. Vinylphosphonic acid was added in an amount of 0.5 equivalent to the hydrosilyl group. Thereafter, the solution was uniformly stirred, and then Karstedt catalyst was added so that the platinum concentration was 50 ppm with respect to the silicone resin. Thereafter, the solution was stirred at 70 ° C. overnight to bind the hydrosilyl group of the silicone resin and the vinyl group of vinylphosphonic acid. After completion of the reaction, the solvent was distilled off from the solution at 40 ° C. under vacuum. Thereafter, methanol was added to wash the precipitate. Thereafter, the methanol used for washing was discarded, and a first curable silicone resin having a phosphate group at one end and a hydrosilyl group at the other end was obtained.

Production Example 2
In Production Example 2, a method for producing a second curable silicone resin having a phosphate group and a vinyl group will be described.
First, in a reaction vessel, 10 g of a silicone resin having a number average molecular weight of 10,000 (manufactured by Gelest, DMS-HV22 (trade name)) having a hydrosilyl group at one end and a vinyl group at the other end is added to tetrahydrofuran (TFT). (Abbreviation)) 100 ml, and a silicone resin having a hydrosilyl group at one end and a vinyl group at the other end was dissolved in tetrahydrofuran. Thereafter, 540 mg of vinylphosphonic acid (manufactured by Tokyo Chemical Industry) was added to the solution. Vinylphosphonic acid was added in an amount of 5.0 equivalents relative to the hydrosilyl group. Thereafter, the solution was uniformly stirred, and then Karstedt catalyst was added so that the platinum concentration was 50 ppm with respect to the silicone resin. Thereafter, the solution was stirred at 70 ° C. overnight to bind the hydrosilyl group of the silicone resin and the vinyl group of vinylphosphonic acid. After completion of the reaction, the solvent was distilled off from the solution at 40 ° C. under vacuum. Thereafter, methanol was added to wash the precipitate. Thereafter, the methanol used for washing was discarded, and a second curable silicone resin having a phosphate group at one end and a vinyl group at the other end was obtained.

Production Example 3
In Production Example 3, a method for producing a non-curable silicone resin having a phosphate group will be described. The following description is based on the method shown in the reference “Langmuir 2013, 29, 1211”.
First, in a reaction container, 20 g of a silicone resin having a methylol group at the end (manufactured by Gelest, MCR-C12 (trade name)) was placed in 100 ml of toluene, and the silicone resin having a methylol group at the end was dissolved in toluene. The inside of the reaction vessel was replaced with nitrogen, 2.5 ml of triethylamine was added to the solution, and 2.0 ml of phosphoryl chloride was further added under ice cooling. An excessive amount of phosphoryl chloride was added to the methylol group. Thereafter, the solution was returned to room temperature and stirred for 3 hours to react the methylol group of the silicone resin with the chlorine group of phosphoryl chloride. Thereafter, 10 ml of pure water was added to the solution to replace the unreacted chlorine group of phosphoryl chloride with a hydroxyl group. The toluene layer was washed by a liquid separation operation using pure water, and excessively added phosphoryl chloride hydrolyzate and triethylamine hydrochloride were removed from the toluene layer. By removing the solvent from the toluene layer under vacuum at 40 ° C., a non-curable silicone resin having a phosphate group at the terminal and having a number average molecular weight of 1000 was obtained.
Further, a non-curable silicone resin having a number average molecular weight of 10,000 having a phosphate group at the terminal was obtained by the same method except that 0.5 ml of triethylamine and the addition amount of phosphoryl chloride were changed to 0.4 ml.

Production Example 4
In Production Example 4, a method for producing a dispersion of zirconia particles will be described.
First, in a reaction vessel, 100 ml of a methanol solution (manufactured by Sakai Chemical Co., Ltd., SZR-M (trade name)) containing 30% by weight in a state where zirconia particles having an average primary particle diameter of 3 to 4 nm are dispersed is contained. Toluene 50 ml and n-octanoic acid 15 ml were added. Thereafter, the solution was stirred overnight at 50 ° C., and n-octanoic acid was bonded to the surface of the zirconia particles via the carboxy group of n-octanoic acid. After completion of the reaction, the solvent was distilled off from the solution at 40 ° C. under vacuum. Thereafter, methanol was added to wash the precipitate. Thereafter, methanol used for washing was discarded, and zirconia particles modified with n-octanoic acid were obtained. Thereafter, 100 ml of toluene was added to the obtained zirconia particles to obtain a dispersion of zirconia particles modified with n-octanoic acid.

Synthesis Example 1
In Synthesis Example 1, a method for synthesizing a dispersion of zirconia particles modified with a first curable silicone resin and a non-curable silicone resin will be described.
First, in a reaction vessel, the first curable silicone resin 54 g obtained in Production Example 1 and the number average molecular weight 10000 obtained in Production Example 3 were added to 100 g of the zirconia particle dispersion obtained in Production Example 4. 16 g of the non-curable silicone resin and 20 g of the non-curable silicone resin having a number average molecular weight of 1000 obtained in Production Example 3 were added. Thereafter, the solution was stirred overnight at 70 ° C., and n-octanoic acid bonded to the surface of the zirconia particles was converted into a first curable silicone resin, a non-curable silicone resin having a number average molecular weight of 10,000, and a number average. It was replaced with a non-curable silicone resin having a molecular weight of 1000. The first curable silicone resin and the non-curable silicone resin are bonded to the surface of the zirconia particles through the phosphate group. After completion of the reaction, the solvent was distilled off from the solution at 40 ° C. under vacuum. Thereafter, methanol was added to wash the precipitate. Thereafter, the methanol used for washing is discarded, and a dispersion of zirconia particles modified with the first curable silicone resin, the non-curable silicone resin having a number average molecular weight of 10,000 and the non-curable silicone resin having a number average molecular weight of 1000 is prepared. Obtained.

Synthesis Example 2
In Synthesis Example 2, a method for synthesizing a dispersion of zirconia particles modified with a second curable silicone resin and a non-curable silicone resin will be described.
First, in a reaction container, the dispersion liquid of zirconia particles obtained in Production Example 4 was added to the second curable silicone resin 54 g obtained in Production Example 2 and the number average molecular weight 10000 obtained in Production Example 3. 16 g of the non-curable silicone resin and 20 g of the non-curable silicone resin having a number average molecular weight of 1000 obtained in Production Example 3 were added. Otherwise, following the same procedure as in Synthesis Example 1, zirconia modified with a second curable silicone resin, a non-curable silicone resin having a number average molecular weight of 10,000, and a non-curable silicone resin having a number average molecular weight of 1000 A dispersion of particles was obtained.

Synthesis Example 3
In Synthesis Example 3, a method for synthesizing a dispersion of zirconia particles modified with a non-curable silicone resin will be described.
First, in a reaction container, 100 g of the dispersion of zirconia particles obtained in Production Example 4, 80 g of the non-curable silicone resin having a number average molecular weight of 10,000 obtained in Production Example 3, and the number obtained in Production Example 3 20 g of non-curable silicone resin having an average molecular weight of 1000 was added. Other than that, following the same procedure as in Synthesis Example 1, a dispersion of zirconia particles modified with a non-curable silicone resin having a number average molecular weight of 10,000 and a non-curable silicone resin having a number average molecular weight of 1000 was obtained.

  Table 1 shows the raw materials used in Synthesis Example 1-3.

Example 1.
First, zirconia modified in the reaction vessel with the first curable silicone resin obtained in Synthesis Example 1, a non-curable silicone resin having a number average molecular weight of 10,000, and a non-curable silicone resin having a number average molecular weight of 1,000. Zirconia particles modified with a dispersion of particles, the second curable silicone resin obtained in Synthesis Example 2, a non-curable silicone resin having a number average molecular weight of 10,000, and a non-curable silicone resin having a number average molecular weight of 1000 The dispersion was mixed. The mixing was performed so that the solid content in the dispersion obtained in Synthesis Example 1 and the solid content in the dispersion obtained in Synthesis Example 2 were each 1 g. Furthermore, the Karstedt catalyst was added so that the platinum concentration was 50 ppm with respect to the entire solid content. Then, it stirred using the rotation revolution mixer until the mixture became uniform. Thereafter, the solvent was distilled off from the mixture at 40 ° C. under vacuum to obtain a colorless and transparent gel. The obtained gel-like product was heated at 150 ° C. for 1 hour to bond the hydrosilyl group of the first curable silicone resin and the vinyl group of the second curable silicone resin to obtain a colorless and transparent cured product. .
The obtained cured product had a refractive index nD of 1.51. The main chains of the first curable silicone resin, the second curable silicone resin, and the non-curable silicone resin used in Example 1 have a dimethyl silicone structure. Since the refractive index nD of dimethyl silicone resin is 1.41, it is recognized that the cured product of Example 1 has improved refractive index by including zirconia particles.
Moreover, in Example 1, the refractive index equivalent to a phenyl silicone resin is implement | achieved using the silicone resin of a dimethyl silicone structure. For this reason, when the hardened | cured material of Example 1 is applied to a high power LED device, the brightness | luminance of an LED device can be improved and the reduction of power consumption can be brought about.
Moreover, the total light transmittance of the obtained hardened | cured material is 87.5%, and even if it contains a zirconia particle, it is recognized that the transparent hardened | cured material was obtained.

Comparative Example 1
First, a dispersion of zirconia particles modified with the first curable silicone resin and the non-curable silicone resin obtained in Synthesis Example 1 and the non-curable silicone resin obtained in Synthesis Example 3 were modified. A dispersion of zirconia particles was mixed. Otherwise, the same procedure as in Example 1 was followed.
In Comparative Example 1, a transparent gel-like material was obtained, but even when heated at 150 ° C., a cured product was not obtained and remained in a gel-like shape.

  As mentioned above, although this invention was demonstrated in detail based on embodiment and an Example, this invention is not limited to this. It is obvious that those having ordinary knowledge in the relevant field can make modifications and improvements within the technical idea of the present invention.

Claims (13)

In an inorganic oxide-containing curable silicone resin composition comprising a curable silicone resin and inorganic oxide particles,
A first curable silicone resin having a functional group for surface binding and a first crosslinkable functional group involved in bonding to the surface of the inorganic oxide particles;
A second curable silicone resin having a functional group for surface binding and a second crosslinkable functional group involved in binding to the surface of the inorganic oxide particles;
Inorganic oxide particles in which the first curable silicone resin is bonded to the surface via the surface-binding functional group;
Inorganic oxide particles in which the second curable silicone resin is bonded to the surface via the surface binding functional group,
The first crosslinkable functional group and the second crosslinkable functional group can be bonded by application of energy,
The inorganic oxide-containing curable silicone resin composition having an average primary particle size of 1 to 40 nm.   The inorganic oxide-containing curable silicone resin composition according to claim 1, further comprising a catalyst that promotes bonding between the first crosslinkable functional group and the second crosslinkable functional group. A non-curable silicone resin having a functional group for surface binding involved in binding to the surface of the inorganic oxide particles,
The inorganic oxide-containing curable silicone resin composition according to claim 1 or 2, wherein the non-curable silicone resin is bonded to the surface of the inorganic oxide particles through the surface-binding functional group.   The inorganic oxide-containing curable silicone resin composition according to claim 3, wherein the non-curable silicone resin is composed of a plurality of resins having different molecular weights.   The combination of the first and second crosslinkable functional groups is a hydrosilyl group and a vinyl group, an epoxy group and an acid anhydride group, or an acrylic group and an acrylic group. Inorganic oxide-containing curable silicone resin composition.   The inorganic oxide-containing curable silicone resin composition according to any one of claims 1 to 5, wherein the surface-bonding functional group is a carboxy group, a sulfonyl group, or a phosphate group.   The inorganic oxide-containing curable silicone resin according to any one of claims 1 to 6, wherein the inorganic oxide particles include at least one selected from the group consisting of zirconia, titania, ceria, and barium titanate. Composition. The combination of the first and second crosslinkable functional groups is a hydrosilyl group and a vinyl group,
The inorganic oxide-containing curable silicone resin composition according to claim 2, wherein the catalyst is a catalyst that promotes a hydrosilylation reaction.   The inorganic catalyst-containing curable silicone resin composition according to claim 8, wherein the catalyst contains platinum.   The inorganic oxide-containing curable silicone resin composition according to any one of claims 1 to 9, wherein the energy application is heating.   The inorganic oxide-containing curable silicone resin composition according to claim 1 is cured by bonding the first crosslinkable functional group and the second crosslinkable functional group. An optical member.   The optical member according to claim 11, wherein a volume ratio of the inorganic oxide particles is 10% by volume or more.   The optical member according to claim 11 or 12, wherein the total light transmittance at a wavelength of 400 nm or more and 800 nm or less is 80% or more.