JP6287747B2 - Light-scattering composition, light-scattering composite, and method for producing the same - Google Patents

Description

  The present invention relates to a light scattering composition, a light scattering composite, and a method for producing the same.

A resin molded body in which inorganic particles are dispersed in a resin is easy to diffuse light, and is therefore often used as a light reflecting plate or a light diffusing plate for road signs, signboards, lighting fixtures and the like. For example, in lighting equipment applications, light emitted from a light source may be reflected by a resin molded body to diffuse light, or light may be transmitted through the resin molded body to diffuse light. In particular, in the case of using a light source with strong directivity, only the place where the light beam is irradiated tends to be bright, and thus light scattering is particularly required.
As a light source with strong directivity, for example, an optical semiconductor light emitting device such as a light emitting diode (LED) can be cited, and for example, a scattering site capable of diffusing light is provided.

  As an optical semiconductor light-emitting device having a scattering portion, a planar light source (Patent Document 1) in which light is scattered in a light guide plate by a scattering layer coated with white powder and the surface brightness is constant, and light passing through the light source is scattered To diffuse, direct, and convert the white light radially to be useful for indoor lighting (Patent Document 2), and to diffuse the light to the sealing material to eliminate the dark spots of adjacent LED devices A method of incorporating particles (Patent Document 3) and a method of reducing scattering unevenness of illumination light by coexisting scattering particles having a particle diameter of 2 μm to 4.5 μm with a phosphor in a sealing material (Patent Document 4) have been proposed. ing. Also proposed is a method (Patent Document 5) in which a filter element having a large number of nanoparticles is arranged behind a luminescence conversion element to selectively reduce the radiation intensity of at least one spectral partial region of unwanted radiation by absorption. Has been.

Japanese Patent No. 3116727 Special table 2003-515899 gazette JP 2007-317659 A JP 2011-150790 A Special table 2007-507089

  However, the purpose of each is to make the distribution of light emitted from the optical semiconductor light emitting device uniform or to reduce color unevenness. Further, with the particle size of Patent Document 4, there is a problem that the translucency of light emitted from the optical semiconductor light emitting element is deteriorated and the luminance of the optical semiconductor light emitting device is lowered. In addition, when the undesired radiation intensity is reduced by absorption as in Patent Document 5, the brightness of the optical semiconductor light-emitting device is reduced, and the radiation is converted into heat by absorption to damage peripheral materials, and optical semiconductor light emission. There arises a problem that the luminous efficiency is lowered due to the heat of the element.

  An object of this invention is to provide the light-scattering composition excellent in the light transmittance and scattering property, a light-scattering composite_body | complex, and its manufacturing method.

As a result of earnest research to solve the above problems, the present inventors have made the light conversion layer containing the phosphor particles contain a specific light scattering composition or on the light conversion layer. We have found that by providing a light-scattering layer containing a specific light-scattering composition, a light-semiconductor light-emitting device capable of reducing the blue light component emitted with white light and improving the luminance can be obtained. An application has been filed (Japanese Patent Application No. 2012-187896).
Here, it is assumed that the cause of the light scattering of the light scattering composition of the same application is Rayleigh scattering caused by the light scattering particles contained in the light scattering composition. For this reason, unless the scattering property of the light scattering particles, in other words, the state of the light scattering particles is changed, the light scattering ability in the light scattering composition increases in proportion to the increase in the content of the light scattering particles. The luminance is expected to improve in proportion to the content of the light scattering particles. However, as a result of further research by the present inventors, the inventors have found that the content of the light scattering particles is reduced to a certain value or less, and that the light transmission and scattering properties are excellent, and the present invention has been conceived. That is, the present invention is as follows.

[1] Average primary particle diameter of 3 nm or more and 50 nm or less, including inorganic oxide particles surface-modified with a surface modifying material having one or more functional groups selected from alkenyl groups, H—Si groups, and alkoxy groups Light scattering particles and a matrix resin composition, wherein the content of the light scattering particles is 0.01% by mass or more and 10% by mass or less.
[2] A light scattering composite obtained by curing the light scattering composition according to [1].
[3] In the above [2], at least a part of the light scattering particles form associated particles, and an average secondary particle diameter of the particles including the associated particles is larger than the average primary particle diameter and 1000 nm or less. The light scattering complex as described.
[4] Average primary particle diameter of 3 nm or more and 50 nm or less, including inorganic oxide particles surface-modified with a surface modifying material having one or more functional groups selected from alkenyl groups, H—Si groups, and alkoxy groups A light scattering composite comprising: a light scattering particle comprising: a matrix resin composition; and a light scattering composition obtained by curing a light scattering composition having a content of the light scattering particles of 0.01% by mass to 10% by mass. A method for producing a light-scattering composite, wherein at least a part of monodispersed light-scattering particles are associated to form associated particles in a matrix resin when the light-scattering composition is cured.

  ADVANTAGE OF THE INVENTION According to this invention, the light-scattering composition excellent in the light transmittance and scattering property, a light-scattering composite_body | complex, and its manufacturing method can be provided.

It is a schematic sectional drawing which shows an example of the optical semiconductor light-emitting device produced using the light-scattering composition of this invention. It is a schematic sectional drawing which shows another example of the optical semiconductor light-emitting device produced using the light-scattering composition of this invention. It is a schematic sectional drawing which shows another example of the optical semiconductor light-emitting device produced using the light-scattering composition of this invention. It is a schematic sectional drawing which shows another example of the optical semiconductor light-emitting device produced using the light-scattering composition of this invention.

[Light scattering composition]
The light scattering composition of the present invention comprises an average primary particle comprising inorganic oxide particles surface-modified with a surface modifying material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups Light scattering particles having a diameter of 3 nm or more and 50 nm or less and an uncured matrix resin composition, and the content of the light scattering particles is 0.01% by mass or more and 10% by mass with respect to the total amount of the light scattering composition. % Or less.
The light scattering composition of the present invention may further contain a solvent, a surfactant, a dispersant, a stabilizer, an antioxidant and the like as long as the effects of the present invention are not impaired.

(Light scattering particles)
The light scattering particles in the present invention include inorganic oxide particles surface-modified with a surface modification material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups, and have an average primary particle size Is 3 nm or more and 50 nm or less. The light scattering particles may further include components other than the surface modifying material, for example, inorganic oxide particles surface-treated with a surfactant, an organic acid, or the like, or particles made of an organic resin. Although it is good, it is preferably composed of inorganic oxide particles surface-modified with the surface-modifying material.

As the inorganic oxide particles constituting the light scattering particles, it is preferable to select particles made of a material that does not absorb light in the wavelength region in which the light scattering composite of the present invention is used. For example, examples of materials that do not absorb light in the near ultraviolet light to visible light region include metal oxides such as ZrO ₂ , TiO ₂ , ZnO, Al ₂ O ₃ , SiO ₂ , and CeO ₂ , and these particles Can be suitably used for white light semiconductor light emitting devices (white light emitting diodes).
On the other hand, wavelength characteristics can also be imparted to the light scattering composite by forming light scattering particles using a material having absorption at a specific wavelength. In addition, by selecting the refractive index of the inorganic oxide particles, it is possible to adjust the light scattering property, the light transmittance, and the like.

  The average primary particle diameter of the light scattering particles is 3 nm or more and 50 nm or less. The average primary particle size is preferably 4 nm or more and 40 nm or less, and more preferably 5 nm or more and 20 nm or less. If the average primary particle diameter is less than 3 nm, the scattering effect is small, and the light scattering composite containing the light scattering particles cannot exhibit sufficient scattering characteristics, and thus the effect of providing the light scattering composite cannot be obtained. . On the other hand, when the average primary particle diameter exceeds 50 nm, the scattering becomes too large especially when the later-described associated particles are formed, and multiple scattering is likely to occur in the light scattering complex. Light is confined in the light scattering complex, and the effect of providing the light scattering complex cannot be obtained.

In particular, the light scattering composite of the present invention is suitably used for a white light semiconductor light emitting device. In this case, the light scattering composite emits light from the optical semiconductor light-emitting element, and returns blue or near-ultraviolet emission light components that have passed through the phosphor layer without being converted in wavelength to the phosphor layer by scattering, Two actions are required, that is, the action of taking out converted light components such as yellow light whose wavelength has been converted by the phosphor layer as it is without being scattered as much as possible.
Here, when the average primary particle diameter of the light-scattering particles is less than 3 nm, the scattering characteristics with respect to the blue or near-ultraviolet light emission component are insufficient, so that the blue or near-ultraviolet emission color component remains as it is (not scattered). To be radiated to the outside. For this reason, since the amount of light incident on the phosphor decreases and the amount of light of the light component wavelength-converted by the phosphor does not increase, the luminance of the white light semiconductor light emitting device cannot be improved. Furthermore, the physiological influence by blue light which has been a problem in recent years is likely to occur. On the other hand, when the average primary particle diameter exceeds 50 nm, the blue or near-ultraviolet light component is sufficiently scattered, but not only that, but also the converted light component wavelength-converted by the phosphor layer is also scattered, resulting in a white light semiconductor. Since it becomes difficult to radiate | emit from a light-emitting device, a brightness | luminance falls too.
That is, even when the light-scattering composite of the present invention is applied to a white light semiconductor light-emitting device, if the average primary particle diameter of the light-scattering particles is 3 nm or more and 50 nm or less, the brightness improvement of the white light semiconductor light-emitting device and the blue color are achieved. Or the near-ultraviolet emission color component can be reduced, and it can be used suitably.

Here, it is preferable that the light-scattering particles in the present invention form associated particles in which at least a part of a plurality of particles are associated in the light-scattering composite (cured body). Since the particle size of the associated particles is larger than the particle size of the monodisperse particles (non-associate particles), the light scattering ability is also increased. Therefore, compared to the case where all the particles are formed of non-associate monodisperse particles. It becomes possible to have sufficient scattering ability with a small amount of light scattering particles. That is, sufficient light scattering characteristics can be obtained even when the ratio of the light scattering particles in the light scattering composite formed by molding the light scattering composition of the present invention is 10% by mass or less. For example, in the light (wavelength 460 nm) from the blue light semiconductor light emitting element used in the white light semiconductor light emitting device, the integrated transmittance is higher than the linear transmittance, and the difference (integrated transmittance−linear transmittance) is 25 points. This can be done. More preferably, the difference is 40 points or more.
The average particle size of all particles including the associated particles and the non-associated monodisperse particles, that is, the average secondary particle size is preferably larger than the average primary particle size and not more than 1000 nm, more than 50 nm and not more than 1000 nm. More preferably, it is more preferably 80 nm or more and 1000 nm or less, and most preferably 100 nm or more and 800 nm or less. If the average secondary particle size is the same as the average primary particle size, the associated particles are not formed, and the effect of forming the associated particles may not be obtained. In addition, when the average secondary particle diameter is 50 nm or less, there is a high possibility that the effect of forming associated particles cannot be obtained because there is little difference from the case where all particles are monodisperse particles. On the other hand, if it exceeds 1000 nm, the scattering ability as particles becomes too strong, so that the light incident on the light scattering complex is trapped in the light scattering complex, and the effect of providing the light scattering complex cannot be obtained. is there.

As described above, it is preferable that at least a part of the light-scattering particles in the light-scattering complex forms associated particles in which a plurality of particles are associated. On the other hand, in consideration of ensuring uniformity of the light scattering composite, the light scattering particles are preferably present in a monodispersed state in which the state of primary particles is maintained in the uncured light scattering composition. In order for the light scattering particles to exhibit such behavior, the dispersion state in the matrix resin and the interface affinity with the matrix resin, which will be described later, and further the dispersion state in the matrix resin composition and the interface affinity with the matrix resin composition It is necessary to control sex.
Here, in order to disperse the light scattering particles in the matrix resin, it is necessary to ensure the interface affinity between the surface of the light scattering particles and the matrix resin. For this reason, it is preferable that the surface of the unmodified particles constituting the light scattering particles is coated with a surface modifying material having a structure that is compatible with the structure of the matrix resin.
Specifically, it is a resin monomer or oligomer for forming a matrix resin, and a reaction used for polymerization of resin monomers or oligomers when a matrix resin composition that is a liquid uncured material forms a matrix resin. The group may be included in the surface modifying material. Here, the silicone-based sealing material that is the matrix resin composition preferably has at least one of an H—Si group, an alkenyl group, and an alkoxy group as a reactive group. Therefore, as the surface modifying material, a surface modifying material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups is used, and the surface of the light scattering particles is modified by the surface modifying material. .

  That is, at least a part of the surface of the inorganic oxide particles constituting the light scattering particles is surface-modified with a surface modifying material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups. ing. That is, at least a part of the surface of the inorganic oxide particles is covered with the surface modifying material.

  Surface modification materials having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups include vinyltrimethoxysilane, alkoxy one-end vinyl one-end dimethyl silicone, alkoxy one-end vinyl one-end methyl Phenyl silicone, alkoxy one-end vinyl one-end phenyl silicone, methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacrylic acid and other carbon-carbon unsaturated bond-containing fatty acids, dimethylhydrogensilicone, methylphenylhydrogensilicone, phenyl Hydrogen silicone, dimethylchlorosilane, methyldichlorosilane, diethyl, chlorosilane, ethyldichlorosilane, methylphenylchlorosilane, diphenylchlorosilane, phenyldichloro Losilane, trimethoxysilane, dimethoxysilane, monomethoxysilane, triethoxysilane, diethoxymonomethylsilane, monoethoxydimethylsilane, methylphenyldimethoxysilane, diphenylmonomethoxysilane, methylphenyldiethoxysilane, diphenylmonoethoxysilane, alkoxy both Examples include terminal phenyl silicone, alkoxy both-end methyl phenyl silicone, alkoxy group-containing dimethyl silicone resin, alkoxy group-containing phenyl silicone resin, alkoxy group-containing methyl phenyl silicone resin, and the like.

The surface modification amount of the surface modification material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups on the surface of the inorganic oxide particles is the metal oxide particles as the inorganic oxide particles. Is preferably 1% by mass to 50% by mass with respect to the mass. By making the amount of surface modification in the range of 1% by mass or more and 50% by mass, the light scattering particles can be uniformly dispersed in a monodispersed state in which the primary particle state is maintained in the matrix resin composition. On the other hand, in the light-scattering composite after curing, it is possible to uniformly disperse the matrix resin in a state where at least a part of the light-scattering particles form associated particles. Therefore, a light scattering composite having high scattering characteristics can be obtained.
On the other hand, when the surface modification amount is less than 1% by mass, the bonding points of the functional groups between the surface modification material and the matrix resin composition are insufficient, so that the light scattering particles are well dispersed in the matrix resin composition. However, even if dispersed, the light scattering particles separate from the matrix resin phase and agglomerate in the process of curing the light scattering composite, resulting in a decrease in light transmission and hardness of the light scattering composite. There is a risk of doing.
Further, when the surface modification amount exceeds 50% by mass, there are many bonding points between the surface modification material and the functional group between the matrix resin composition, so that the light scattering particles are primary particles for the matrix resin composition. In addition to enabling uniform dispersion in a monodispersed state in which the above state is maintained, the monodispersion of the light scattering particles is maintained even in the process of curing the light scattering composite, and partial association does not occur. is there. For this reason, the improvement of the light scattering ability (the effect of having a sufficient scattering ability with a smaller amount of light scattering particles) due to the formation of associated particles in the light scattering conversion layer or the light scattering layer cannot be expected. In addition, in the range where the surface modification amount exceeds 50% by mass and 80% by mass or less, although the effect due to the formation of associated particles is difficult to expect, the bonding state between the light scattering particles and the matrix resin is kept good, The properties as a light scattering complex are maintained. On the other hand, when the surface modification amount exceeds 80% by mass, the bonding points of the functional groups between the surface modification material and the matrix resin composition are excessive, and the cured body may become brittle and cracks may occur.
The surface modification amount is more preferably 3% by mass or more and 50% by mass or less, and further preferably 5% by mass or more and 40% by mass or less.

  The modification method of the surface modification material on the surface of the inorganic oxide particles is a dry method in which the surface modification material is mixed and sprayed directly on the inorganic oxide particles, or unmodified with water and / or an organic solvent in which the surface modification material is dissolved. Examples include a wet method in which particles are introduced and the surface is modified in a solvent. In the present invention, it is preferable to use a wet method in view of excellent controllability of the surface modification amount and high uniformity of the surface modification.

Content of the light-scattering particle in a light-scattering composition is 0.01 mass% or more and 10 mass% or less with respect to the light-scattering composition whole quantity. The content of the light scattering particles is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less, based on the total amount of the light scattering composition. .
When the content of the light scattering particles in the light scattering composition is less than 0.01% by mass, the amount of the light scattering particles in the light scattering composite obtained by curing the light scattering composition is too small, and the light scattering effect. Cannot be obtained. On the other hand, when the content of the light scattering particles in the light scattering composition exceeds 10% by mass, the amount of the light scattering particles is excessively large particularly when the associated particles are formed, so that the scattering becomes excessive, and the light scattering complex. The light incident on the light is confined in the light scattering complex, and the effect of providing the light scattering complex cannot be obtained. That is, when the content of the light scattering particles in the light scattering composition is 0.01% by mass or more and 10% by mass or less, it is possible to obtain a light scattering composite having a good balance between scattering and light transmittance. it can.
When a light scattering composite obtained from such a light scattering composition is applied to a white light semiconductor light-emitting device, the light extraction efficiency from the white light semiconductor light-emitting element is improved, so that a light-semiconductor light-emitting device with higher luminance is obtained. be able to.

[Matrix resin composition]
The matrix resin composition is an uncured liquid matrix resin such as a resin monomer or oligomer constituting a matrix resin including light scattering particles when the light scattering composition is cured to form a light scattering composite. .
The matrix resin applied to the light scattering composite is not particularly limited as long as it is a material that does not absorb light in the wavelength region in which the light scattering composite of the present invention is used, but is basically an optical material. It is preferable to have resistance to light (light resistance). As described above, the light scattering composite of the present invention can be suitably used for a white light semiconductor light emitting device. In this case, however, the visible light region (when a near ultraviolet light semiconductor light emitting element is used as the light semiconductor light emitting element) is used. Is transparent in the near ultraviolet light region to the visible light region), and preferably does not impair the reliability (required performances such as durability) of the optical semiconductor light emitting device. Furthermore, in consideration of increasing the output of the optical semiconductor light emitting element and applying it to lighting applications, it is preferable to use a resin that has been conventionally used as an optical semiconductor light emitting element sealing material. In particular, from the viewpoint of durability of the light scattering composite, it is preferable to use a silicone-based sealing material as the matrix resin, and examples thereof include dimethyl silicone resin, methyl phenyl silicone resin, phenyl silicone resin, and organically modified silicone resin. It is done.
Accordingly, the matrix resin composition is a silicone-based resin such as a resin monomer or oligomer of a dimethyl silicone resin, a resin monomer or oligomer of a methyl phenyl silicone resin, a resin monomer or oligomer of a phenyl silicone resin, or a resin monomer or oligomer of an organically modified silicone resin. It is preferable to contain the resin monomer or oligomer of this.
When a silicone resin is used as the matrix resin of the light scattering composite, it is obtained by polymerizing and curing each silicone resin composition that is a liquid uncured material by, for example, an addition reaction, a condensation reaction, a radical polymerization reaction, or the like. be able to.

The light scattering composite obtained by curing the light scattering composition is preferably uniformly dispersed in the matrix resin as a whole in a state where at least a part of the light scattering particles forms associated particles.
In order to uniformly disperse the light scattering particles in the matrix resin, it is preferable to ensure the interface affinity between the surface of the light scattering particles and the matrix resin. In the present invention, as described above, the structure of the surface modifying material is compatible with the structure of the matrix resin. That is, as the matrix resin composition, it is preferable to select a silicone-based sealing material having at least one of an H—Si group, an alkenyl group, and an alkoxy group as a reactive group. A surface modifying material having one or more functional groups selected from a group, an H—Si group, and an alkoxy group is used.

Thus, when a silicone-based sealing material having at least one of an H—Si group, an alkenyl group, and an alkoxy group is used as the matrix resin composition, the alkenyl group, H—Si group, and the surface modification material have, And the alkoxy group is bonded to the matrix resin composition as follows.
The alkenyl group of the surface modifying material is crosslinked by reacting with the H—Si group in the matrix resin composition. The H-Si group of the surface modifying material is crosslinked by reacting with the alkenyl group in the matrix resin composition. The alkoxy group of the surface modifying material is condensed with the alkoxy group in the matrix resin composition through hydrolysis. By such bonding, the matrix resin and the surface modification material are integrated, so that the light scattering particles are not phase-separated in the process of curing the matrix resin composition and forming the matrix resin. It can be maintained and fixed in the matrix resin, and the denseness of these layers can be improved.

  In addition, in order to further enhance the interface affinity between the surface of the light scattering particle and the matrix resin, and / or to more efficiently modify the surface modifying material having the functional group in the process of modifying the surface of the inorganic oxide particle. In addition, a known surface modifying material other than the surface modifying material having the above functional group can be used in combination.

The matrix resin uncured product contained in the matrix resin composition may be used alone or in combination of two or more.
Moreover, it is preferable that content of the matrix resin composition in a light-scattering composition is a remainder except content of the light-scattering particle in a light-scattering composition.

(Preparation of light scattering composition)
The light scattering composition can be obtained by mixing light scattering particles containing inorganic oxide particles whose surface has been modified as described above and a matrix resin. From the viewpoint of scattering properties, it is preferable that the light scattering particles are uniformly dispersed in the matrix resin.
The light scattering particles can be uniformly dispersed in the binder by mixing and dispersing the light scattering particles and the binder by a mechanical method such as a biaxial kneader, or by dispersing the light scattering particles in an organic solvent. There is a method in which the organic solvent is dried and removed after mixing the dispersed liquid and the binder.

  The transmittance at a wavelength of 460 nm measured with an integrating sphere of the light scattering composition is preferably 40% or more and 95% or less. Since the transmittance at a wavelength of 460 nm is 40% or more, it is possible to prevent a decrease in the translucency of the entire light and improve the luminance of the optical semiconductor light emitting device. Further, when the transmittance is 95% or less, it is possible to prevent the emission color component of the optical semiconductor light emitting element that has not been wavelength-converted by the phosphor from being emitted to the external air phase, and to scatter in a direction different from the external air phase. The color rendering properties of the optical semiconductor light emitting device can be improved. The transmittance at a wavelength of 460 nm is more preferably 45% or more and 90% or less, and further preferably 50% or more and 85% or less.

The transmittance at a wavelength of 550 nm is preferably 50% or more. The transmissivity is 50% or more to prevent a decrease in translucency of white light in which the light emission color of the optical semiconductor light-emitting element and the light of which the light emission color is wavelength-converted by the phosphor are synthesized, and the optical semiconductor The luminance of the light emitting device can be improved. The transmittance at a wavelength of 550 nm is more preferably 80% or more, still more preferably 85% or more, and most preferably 90% or more.
In order to obtain the transmittance as described above, a known amount other than the particle surface modification material of the light scattering particles may be adjusted.

[Light scattering complex]
The light scattering composite of the present invention is formed by curing the light scattering composition of the present invention.
Therefore, the light scattering composite of the present invention includes inorganic oxide particles that are surface-modified with a surface-modifying material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups. It contains light scattering particles having a primary particle size of 3 nm or more and 50 nm or less and a matrix resin, and the content of the light scattering particles is 0.01% by mass or more and 10% by mass or less with respect to the total amount of the light scattering complex. is there.

The contents and preferred embodiments of the light scattering particles are the same as the contents and preferred embodiments of the light scattering particles contained in the light scattering composition.
The matrix resin is a resin obtained by curing the matrix resin composition contained in the light scattering composition, and is preferably a transparent resin. The contents and preferred embodiments of the matrix resin composition are the same as the contents and preferred embodiments of the matrix resin composition contained in the light scattering composition.
In the light-scattering composite of the present invention, from the viewpoint of scattering properties, it is preferable that the light-scattering particles are uniformly dispersed as a whole in the matrix resin in a state in which at least a part thereof forms associated particles. The average particle size of all particles including the associated particles and the non-associated monodisperse particles, that is, the average secondary particle size is preferably larger than the average primary particle size and 1000 nm or less, and more than 50 nm and 1000 nm or less. More preferably, it is more preferably 80 nm or more and 1000 nm or less, and most preferably 100 nm or more and 800 nm or less. If the average secondary particle size is the same as the average primary particle size, the associated particles are not formed, and the effect of forming the associated particles may not be obtained. In addition, when the average secondary particle diameter is 50 nm or less, there is a high possibility that the effect of forming associated particles cannot be obtained because there is little difference from the case where all particles are monodisperse particles. On the other hand, if it exceeds 1000 nm, the scattering ability as particles becomes too strong, so that the light incident on the light scattering complex is trapped in the light scattering complex, and the effect of providing the light scattering complex cannot be obtained. is there.
The associated particles are not formed in the state of the light scattering composition, but are preferably formed at the stage where the light scattering composition is cured to form a light scattering composite.
That is, the light scattering particles in the matrix resin composition are in a monodispersed (primary particle) state, and as the matrix resin hardens, the light scattering particles cause local phase separation in an extremely small region, and the associated particles are separated. It is preferable to form. In addition, this local phase separation preferably occurs in the entire matrix resin composition (light scattering composition), and the associated particles are preferably held in a local region without being bonded to each other.
By forming the associated particles in such a form, the amount of the light scattering particles contained in the light scattering composite of the present invention is 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less. Even in such a small amount, a high light scattering property can be expressed.

The curing method of the light scattering composition is not particularly limited, and for example, it may be cured by applying external energy such as light or heat to the light scattering composition. Moreover, you may make it harden | cure by adding a polymerization catalyst.
The light scattering composite of the present invention may be a molded body formed by applying a solution-like light scattering composition on a substrate or putting it in a mold and then curing it. Alternatively, it may be a molded body obtained by melt-kneading using an extruder or the like and then pouring into a mold and cooling. The light scattering composite of the present invention may be a laminate in which plate-like bodies obtained by curing the light scattering composition of the present invention are laminated.
In the above description, the matrix resin composition is assumed to be “resin monomer or oligomer for forming a matrix resin”, and the formation of the matrix resin is basically performed by polymerization and curing of the composition. It is not limited to. For example, the matrix resin composition may be formed of a solvent-soluble resin and a solvent, and the formation of the matrix resin may be performed by removing (drying) the solvent. In this case, as the surface modifying material for the oxide particles, it is preferable to select a material that is partially solvent-soluble.

  Since the light-scattering composition and the light-scattering composite of the present invention are excellent in light scattering and transparency, the light-scattering composition and the light-scattering composite can be applied to various applications that require light to be scattered while being transmitted. In particular, it is suitable for a device including a light source that emits a highly directional light beam, for example, an optical semiconductor light emitting device.

[Optical semiconductor light emitting device]
An optical semiconductor light emitting device includes an optical semiconductor light emitting element, phosphor particles, and a light scattering complex containing light scattering particles and a matrix resin, and emits white light. ) The light scattering composite includes the phosphor particles to form a light scattering conversion layer, and the light scattering particles in the light scattering conversion layer have a content of 10% by mass or less, and the light scattering particles Is surface-modified by a surface modification material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups, and is made of a material that does not absorb light in the emission wavelength region of the optical semiconductor light emitting device. A photo-semiconductor light-emitting device (hereinafter referred to as “photo-semiconductor light-emitting device A”) that is particles having an average primary particle diameter of 3 nm or more and 50 nm or less, or (B) a light conversion layer is formed by a layer containing the phosphor particles A light scattering layer comprising the light scattering composite is provided on the light conversion layer, and the light scattering particle content in the light scattering layer is 10% by mass or less; , An optical semiconductor light emitting device (hereinafter referred to as “optical semiconductor light emitting device B”) that is the same particle as the optical semiconductor light emitting device A.
In the following description of the present invention, the term “optical semiconductor light emitting device” simply refers to both “optical semiconductor light emitting device A” and “optical semiconductor light emitting device B”.
In the present invention, a structure in which “optical semiconductor light emitting device A” and “optical semiconductor light emitting device B” are combined may be used. That is, the light scattering complex may include the phosphor particles to form a light scattering conversion layer, and the light scattering layer made of the light scattering complex may be provided on the light scattering conversion layer.

  A white light semiconductor light emitting device combining a blue light semiconductor light emitting element and a phosphor is combined with the blue light emitted from the blue light semiconductor light emitting element and the light wavelength-converted by the phosphor to produce white (pseudo white). It will be. This type of white light semiconductor light emitting device includes a combination of a blue light semiconductor light emitting element and a yellow phosphor; a combination of a blue light semiconductor light emitting element and a green phosphor and a red phosphor; Since the light emission color of the optical semiconductor light emitting element is blue light, it becomes white light containing a large amount of blue components. In particular, a white light semiconductor light-emitting device in which a blue light semiconductor light-emitting element and a yellow phosphor are combined contains a very large amount of blue components.

A white light semiconductor light emitting device that combines a blue light semiconductor light emitting element and a phosphor contains a large amount of blue components. Therefore, blue light retinopathy of the eye, physiological damage to the skin, arousal level, autonomic nervous function, biological clock In addition, physiological effects on melatonin secretion have been pointed out. In recent years, the market for lighting applications of optical semiconductor light-emitting devices has expanded, and the brightness of optical semiconductor light-emitting devices has been increasing. Human bodies are often exposed to blue light.
However, the optical semiconductor light-emitting device can be manufactured by using the light scattering composition of the present invention, thereby reducing the blue light component emitted together with the white light and improving the luminance. In addition, the color rendering properties can be improved by reducing the blue light component.

As a combination of the optical semiconductor light emitting element and the phosphor in the optical semiconductor light emitting device, for example, a combination of a blue light semiconductor light emitting element and a yellow phosphor having an emission wavelength of about 460 nm; a blue light semiconductor light emitting element and a red light having an emission wavelength of about 460 nm A combination of a phosphor and a green phosphor; a combination of a near-ultraviolet semiconductor light emitting element having a light emission wavelength of 340 nm to 410 nm and a red phosphor, a green phosphor, and a blue primary phosphor. In this case, known optical semiconductor light-emitting elements and various phosphors can be used.
In addition, various types of optical semiconductor light-emitting elements, sealing resins for sealing various phosphors, and the like can be used.
In the following description, the light having each emission wavelength emitted from the semiconductor light emitting element used in the combination of the above optical semiconductor light emitting element and the phosphor is referred to as “light emitting color component” of the optical semiconductor light emitting element. May be called. In addition, light emitted from the phosphor when the phosphor color component is irradiated to the phosphor, that is, light whose wavelength is converted by the phosphor is referred to as “converted light component” from the phosphor. There is.

The aspect about optical semiconductor light-emitting device A and B is demonstrated using FIGS. 1-4.
First, in the first mode of the optical semiconductor light emitting device A, as shown in FIG. 1, the optical semiconductor light emitting element 10 is disposed in the concave portion of the substrate, and the light scattering containing the light scattering particles and the matrix resin is covered so as to cover the optical semiconductor light emitting element 10. A light scattering conversion layer 14 containing phosphor particles 13 in the composite 12 is provided. At this time, the light scattering particles may be present uniformly in the matrix resin, but it is preferable that the light scattering particles are present more on the outer air phase interface (interface with the outer air layer) 18 side. The surface shape of the external air phase interface 18 is not particularly limited, and may be any of a flat shape, a convex shape, and a concave shape.

  As shown in FIG. 2, the second mode of the optical semiconductor light emitting device A is that phosphor particles 13 in the light scattering conversion layer 14 are present closer to the optical semiconductor light emitting element 10 than in the case of FIG. The light scattering particles are present more on the outer air phase interface 18 side than the phosphor particles. By setting it as such an aspect, since most of the blue light components which permeate | transmitted the existing area | region of the fluorescent substance particle 13 can be scattered and returned to the existing area of the fluorescent substance particle 13, the blue light component emitted with white light And the luminance can be further improved.

The optical semiconductor light emitting device B is an embodiment in which a layer containing phosphor particles (light conversion layer) and a layer containing light scattering particles (light scattering layer) are arranged separately. As a first aspect of the optical semiconductor light emitting device B, as shown in FIG. 3, the optical semiconductor light emitting element 10 is disposed in the concave portion of the substrate, and the phosphor particles 13 are contained in the matrix material 15 so as to cover the optical semiconductor light emitting element 10. The light conversion layer 16 is provided, and on the light conversion layer 16, that is, on the side of the external air phase interface 18 of the light conversion layer 16, the light composed of the light scattering composite 12 containing the light scattering particles and the matrix resin composition. A scattering layer 17 is provided.
By setting it as such an aspect, since most of the blue light components which permeate | transmitted the light conversion layer 16 can be scattered by the light-scattering layer 17, and can be returned to the light conversion layer 16, the blue light component emitted with white light And the luminance can be further improved.

  As shown in FIG. 4, the second mode of the optical semiconductor light emitting device B is provided with a sealing resin layer 11 made of a sealing resin so as to cover the optical semiconductor light emitting element 10, and on the sealing resin layer 11, A light conversion layer 16 and a light scattering layer 17 are sequentially stacked.

  In the optical semiconductor light emitting device B, the thicknesses of the light conversion layer and the light scattering layer are not particularly limited as long as the effects of the present invention can be obtained. However, if the blue component is to be reduced, the thickness of the light scattering layer is increased. It is preferable to design the thickness of the light scattering layer in view of the wavelength conversion efficiency and the addition amount of the phosphor used when the optical semiconductor light emitting device is adjusted to a desired color rendering property.

In the light semiconductor light emitting device A, the content of the light scattering particles is 0.01% by mass or more and 10% by mass or less with respect to the total amount of the light scattering conversion layer. It is 0.01 mass% or more and 10 mass% or less with respect to. The content of the light scattering particles in the light conversion layer or the light scattering layer is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less. preferable.
When the content of the light scattering particles in each layer exceeds 10% by mass, the amount of the light scattering particles is excessively large particularly when the associated particles are formed, resulting in excessive scattering, and the emission color component from the optical semiconductor light emitting element. Not only the converted light component from the phosphor but also the external air phase is hardly emitted, and the luminance of the optical semiconductor light emitting device is lowered. On the other hand, when the content of the light scattering particles in each layer is less than 0.01% by mass, the amount of the light scattering particles is too small to obtain the light scattering effect, and the luminance of the optical semiconductor light emitting device cannot be improved. That is, when the light scattering particle content in each layer is 0.01% by mass or more and 10% by mass or less, in each layer, the light scattering property of the emission color component from the optical semiconductor light emitting element, the emission color component, and The optical transparency of the converted light component is well balanced and a high-brightness optical semiconductor light emitting device can be obtained.
Furthermore, when the content of the light scattering particles in each layer is 0.01% by mass or more and 10% by mass or less, the blue light scattering rate is particularly high. That is, in the light having a wavelength of 460 nm, the integrated transmittance value is particularly larger than the linear transmittance value. As a result, it is possible to reduce blue light and improve luminance in the optical semiconductor light emitting device.

In the optical semiconductor light emitting device, the light scattering composition of the present invention is applied or injected onto the light conversion layer, or phosphor particles are mixed in the light scattering composition, applied onto the optical semiconductor light emitting element, and then cured. Thus, the optical semiconductor light emitting device according to the present invention is manufactured.
For example, the light-semiconductor light-emitting device B is produced by applying or injecting the light-scattering composition of the present invention onto the light conversion layer and then curing to form a light-scattering layer made of a light-scattering composite. . Alternatively, the phosphor particles are mixed in the light scattering composition, applied or injected onto the optical semiconductor light emitting device, and then cured to form a light scattering conversion layer composed of a light scattering composite containing the phosphor. Then, the optical semiconductor light emitting device A is manufactured. Examples of the curing of the light scattering composition of the present invention include a polymerization curing reaction such as an addition reaction, a condensation reaction, and a radical polymerization reaction. This polymerization reaction can be performed by applying external energy such as heating and light irradiation, adding a catalyst (polymerizing agent), and the like.

At the time of curing, at least a part of the light scattering particles monodispersed in the light scattering composition is associated to form associated particles in the matrix resin.
As described above, the formation of the associated particles is relatively light scattering by reducing the surface modification amount of the light scattering particles to 50 mass% or less and suppressing the affinity between the matrix resin (composition) and the light scattering particles. This can be achieved by increasing the bonding force between the particles. Also, by slowing the curing rate of the light scattering composition and maintaining the state in which the light scattering particles can move in the light scattering composition during curing, the cohesive force between the light scattering particles and / or other components in the matrix resin The degree of association of the light scattering particles may be increased by using the exclusion force.

The average particle diameter of all particles, which are the aggregated particles thus formed and the monodispersed particles maintained in a non-associated state, that is, the average secondary particle diameter is larger than the average primary particle diameter and 1000 nm or less. More preferably, it is larger than 50 nm and 1000 nm or less, more preferably 80 nm or more and 1000 nm or less, and most preferably 100 nm or more and 800 nm or less.
In addition, although it is a measuring method of an average secondary particle diameter, since the light-scattering composite is a hardened | cured material, the measurement by a dynamic light-scattering method is difficult. For this reason, for example, a thinned sample of the light scattering complex is observed with a transmission electron microscope (TEM), and the light scattering particles that are present individually have the secondary particle size as it is, The portion where the light scattering particles appear to overlap each other is determined as the associated particles, and the average secondary particle size is determined by setting the particle size of the entire associated particles as the secondary particle size.

[Lighting fixtures and display devices]
The optical semiconductor light-emitting device of the present invention can be used for various applications by taking advantage of its excellent characteristics. The effects of the present invention are particularly noticeable in various lighting fixtures and display devices having the same.
Examples of the lighting fixture include general lighting devices such as an indoor lamp and an outdoor lamp. In addition, the present invention can also be applied to illumination of a switch unit of an electronic device such as a mobile phone or OA device.

  As a display device, for example, a mobile phone, a portable information terminal, an electronic dictionary, a digital camera, a computer, a thin TV, a lighting device, and peripheral devices thereof are reduced in size, reduced in weight, reduced in thickness, reduced in power consumption, and Examples thereof include a light-emitting device in a display device of a device that is particularly required to have high luminance and good color rendering such that good visibility can be obtained even in sunlight. In particular, a display device that is visible for a long time such as a computer display device (display), a flat-screen television, or the like is particularly suitable because the influence on the human body, particularly the eyes, can be suppressed. Further, since the size can be reduced by reducing the distance between the first light emitting element and the second light emitting element to 3 mm or less, and further to 1 mm or less, it is also suitable for a small display device of 15 inches or less.

Various measurement methods and evaluation methods according to this example are as follows.
(Surface modification amount in the surface modified particles in the surface modified particle dispersion)
The surface modification amount of the surface modified particles was calculated based on the measurement by thermogravimetric analysis. The sample powder was prepared by centrifuging the surface-modified particle dispersion to take out the surface-modified particles, and drying and removing the dispersion medium with an evaporator. The obtained sample was subjected to thermogravimetric analysis, and the weight loss from 115 ° C. to 500 ° C. was measured. The weight loss below 115 ° C. was attributed to the remaining dispersion medium (toluene). Based on the weight loss obtained (from 115 ° C. to 500 ° C.) and the content of volatile components (C, H, O, and N) and nonvolatile components (Si) in the surface modifying material, the amount of surface modification Was calculated.

(Measurement of integrated transmittance of light scattering composition)
The transmittance of the light-scattering composition was obtained by using a integrating sphere with a spectrophotometer (V-570, manufactured by JASCO Corporation) using a sample obtained by sandwiching the light-scattering composition in a 0.5 mm thin-layer quartz cell. It was measured. The transmittance at a wavelength (λ) of 460 nm is 40% to 95%, the transmittance at a wavelength (λ) of 550 nm is 80% or more, and the transmittance at a wavelength (λ) of 460 nm is 40% to 95%. The transmittance at a wavelength (λ) of 550 nm was 50% or more and less than 80% was designated as “Δ”, and those outside this range were designated as “x”.
A thin-layer quartz cell with this light scattering composition sandwiched in place of the spectrophotometer reflector and the reflection spectrum returned to the integrating sphere was measured. As a result, a decrease in transmittance on the short wavelength side was reflected. Since it corresponded to the increase in the rate, it was confirmed that the light was not absorbed by the particles and the backscattering by the particles was occurring.

(Measurement of transmittance of light-scattering complex: Comparison between integral transmittance and linear transmittance)
The transmittance of the light-scattering composite is measured by integrating sphere measurement and linear measurement with a spectrophotometer (V-570, manufactured by JASCO Corp.) using a light-scattering composite molded into a 1 mm thick substrate as a sample. The case where the difference in transmittance at a wavelength of 460 nm (integral transmittance−linear transmittance) is 40 points or more is considered to be good when blue light scattering is good, and the case is 25 points or more and less than 40 points. “△” means that it is out of this range, and “x” means.

(Measurement of average primary particle size of light scattering particles)
The average primary particle diameter of the light scattering particles was the Scherrer diameter obtained by X-ray diffraction.

(Measurement of average secondary particle diameter of light scattering particles in light scattering composite)
The average secondary particle diameter of the light-scattering particles in the light-scattering composite was observed with a field emission transmission electron microscope (JEM-2100F, manufactured by JEOL Ltd.) using a sample obtained by slicing the light-scattering composite. This was done by measuring the particle size.
Here, regarding the light scattering particles present individually (without associating), the particles themselves are used as secondary particles, and the particle size is set as the secondary particle size. In addition, the portion where a plurality of light scattering particles appear to overlap each other is defined as secondary particles (association particles), and the particle size of the entire portion determined as secondary particles is defined as the secondary particle size. The value of 50 particles among the secondary particle diameters thus measured was randomly selected, and the average value was taken as the average secondary particle diameter of the light scattering particles in the light scattering composite.

(Emission spectrum evaluation of optical semiconductor light emitting device)
The emission spectrum of the optical semiconductor light emitting device was measured using a spectrophotometric device (PMA-12, manufactured by Hamamatsu Photonics). Here, the emission spectrum peak area from a wavelength of 400 nm to 480 nm was set as a, and the emission spectrum peak area from a wavelength of 480 nm to 800 nm was set as b, and the evaluation was performed based on a / b. Based on Comparative Examples 1 and 2 containing no light scattering particles, in Examples 1 to 4, 6 to 9, and Comparative Examples 3 to 4, the value of a / b is 0. A value of 9 times or more and less than that is “◯”, and a value of 0.6 or more and less than 0.9 times of a / b of Comparative Example 1 is “Δ”. The thing of less than 6 times was made into "x". In Example 5 and Comparative Example 5, the a / b value of Comparative Example 2 was compared.

(Brightness evaluation of optical semiconductor light-emitting devices)
The brightness | luminance of the optical semiconductor light-emitting device was measured using the luminance meter (LS-110, Konica Minolta Sensing company make). Based on Comparative Examples 1 and 2 that do not contain light scattering particles, in Examples 1-4, 6-9, and Comparative Examples 3-4, “◯” indicates that the luminance is higher than that of Comparative Example 1, Comparative Example A value of 0.8 or more times the luminance of 1 and the same value as that of “Δ”, and a value of less than 0.8 times the luminance of Comparative Example 1 was designated as “x”. In Example 5 and Comparative Example 5, the brightness of Comparative Example 2 was compared.

<Preparation of unmodified particles>
As unmodified particles constituting the light scattering particles, the following zirconia particles 1 to 5 and silica particles were prepared.

(Preparation of zirconia particles 1)
To a zirconium salt solution in which 2615 g of zirconium oxychloride octahydrate is dissolved in 40 L (liter) of pure water, dilute ammonia water in which 344 g of 28% ammonia water is dissolved in 20 L of pure water is added with stirring, and the zirconia precursor slurry is added. Prepared.
A sodium sulfate aqueous solution in which 300 g of sodium sulfate was dissolved in 5 L of pure water was added to this slurry with stirring to obtain a mixture. The amount of sodium sulfate added at this time was 30% by mass with respect to the zirconia-converted value of zirconium ions in the zirconium salt solution.
This mixture was dried in the air at 130 ° C. for 24 hours using a dryer to obtain a solid. The solid was pulverized in an automatic mortar and then baked in the atmosphere at 520 ° C. for 1 hour using an electric furnace.
Next, the fired product is put into pure water, stirred to form a slurry, washed using a centrifuge, and after sufficiently removing the added sodium sulfate, dried in a dryer, Zirconia particles 1 having an average primary particle size of 5.5 nm were obtained.

(Preparation of zirconia particles 2)
Zirconia particles 2 having an average primary particle size of 7.8 nm were prepared in the same manner as zirconia particles 1 except that the firing temperature in the electric furnace in the production of zirconia particles 1 was changed from 520 ° C. to 550 ° C.

(Preparation of zirconia particles 3)
Zirconia particles 3 having an average primary particle diameter of 2.1 nm were prepared in the same manner as zirconia particles 1 except that the calcination temperature in the electric furnace in preparation of zirconia particles 1 was changed from 520 ° C. to 500 ° C.

(Preparation of zirconia particles 4)
Zirconia particles 4 having an average primary particle size of 21.1 nm were produced in the same manner as zirconia particles 1 except that the firing temperature in the electric furnace in producing the zirconia particles 1 was changed from 520 ° C. to 620 ° C.

(Preparation of zirconia particles 5)
Zirconia particles 5 having an average primary particle size of 48 nm were produced in the same manner as zirconia particles 1 except that the firing temperature in the electric furnace in producing the zirconia particles 1 was changed from 520 ° C. to 660 ° C.

(Preparation of silica particles)
Silica particles containing silica sol (Snowtex OS manufactured by Nissan Chemical Industries) were used as they were. Since X-ray diffraction measurement cannot be performed in a sol state, and the sol is simply dried and solidified, handling at the time of measurement is inconvenient. Therefore, actual measurement was performed with a silica particle-containing dry powder described later. The average primary particle size was 9.5 nm.

[Example 1]
(Preparation of surface-modified zirconia dispersion 1)
To 10 g of zirconia particles 1, 86 g of toluene and 2 g of methoxy group-containing methylphenyl silicone resin (KR9218 manufactured by Shin-Etsu Chemical Co., Ltd.) were added, mixed, stirred for 5 hours in a bead mill, and subjected to surface modification treatment. The beads were removed. Next, 2 g of vinyltrimethoxysilane (KBM1003 manufactured by Shin-Etsu Chemical Co., Ltd.) is added as an alkenyl group (vinyl group) group-containing modifying material, and modification and dispersion are carried out under reflux at 130 ° C. for 6 hours to obtain a surface-modified zirconia dispersion. 1 was produced.
The surface modification amount by the surface modifying material was 40% by mass with respect to the mass of the zirconia particles 1, and the mass ratio of the methoxy group-containing methylphenylsilicone resin and vinyltrimethoxysilane was 1: 1. Further, the obtained surface-modified zirconia dispersion 1 was transparent.

(Preparation of light scattering composition 1)
For 10 g of surface-modified zirconia dispersion 1, 158.6 g of phenyl silicone resin (OE-6330 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.53, A / B mixture ratio = 1/4) (A solution) 31.7 g and B solution 126.9 g) were added and stirred. Thereafter, toluene was removed from the mixture by drying under reduced pressure to obtain a light scattering composition 1 containing surface-modified zirconia particles and a phenyl silicone resin. The obtained light scattering composition 1 was almost transparent. The transmittance of the light scattering composition 1 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 1)
The light-scattering composition 1 was poured into a concave mold having a depth of 1 mm and heat-cured at 150 ° C. for 2 hours to produce a light-scattering composite 1 having a thickness of 1 mm. The transmittance of the obtained light scattering composite 1 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 1)
10 g of yellow phosphor (GLD (Y) -550A manufactured by Genelite) is added to 15 g of the light scattering composition 1, and then the phosphor-containing light scattering composition 1 is mixed and defoamed with a self-revolving mixer, A phosphor-containing light scattering composition 1 was obtained. Next, the phosphor-containing light scattering composition 1 was dropped on the light emitting device of the package including the unsealed blue light semiconductor light emitting device. Further, after dropping the same amount of the light-scattering composition 1 containing no phosphor on the phosphor-containing light scattering composition 1 as the amount of the phosphor-containing light scattering composition 1, the light-scattering composition 1 is heated at 150 ° C. for 2 hours, 1 was cured. Thereby, the optical semiconductor of Example 1 in which the light-scattering conversion layer including the light-scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light-emitting element was formed on the optical semiconductor light-emitting element. The light emitting device 1 was produced.
In addition, the content of the light scattering particles in the light scattering conversion layer was 0.5% by mass, and the content of the yellow phosphor was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 1 were measured and evaluated as described above. The results are shown in Table 1 below.

[Example 2]
(Preparation of light scattering composition 2)
As the surface-modified zirconia dispersion liquid of Example 2, the surface-modified zirconia dispersion liquid 1 of Example 1 was used as it was.
In the preparation of the light scattering composition, the amount of the surface-modified zirconia dispersion 1 was 100 g, and the amount of the phenyl silicone resin (OE-6330) was 146 g (A liquid 29.2 g, B liquid 116.8 g). In the same manner as in Example 1, a light scattering composition 2 was produced. The obtained light-scattering composition 2 was almost transparent. The transmittance of the light scattering composition 2 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 2)
A light scattering composite 2 was prepared in the same manner as in Example 1 except that the light scattering composition 2 was used in place of the light scattering composition 1 in the preparation of the light scattering composite. The transmittance of the obtained light scattering composite 2 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 2)
In the production of the optical semiconductor light emitting device, the optical semiconductor light emitting device 2 was produced in the same manner as in Example 1 except that the light scattering composition 2 was used instead of the light scattering composition 1. Thus, the optical semiconductor of Example 2 in which the light scattering conversion layer including the light scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light emitting device is formed on the optical semiconductor light emitting device. The light emitting device 2 was obtained.
In addition, the content of the light scattering particles in the light scattering conversion layer was 5% by mass, and the content of the yellow phosphor was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 2 were measured and evaluated as described above. The results are shown in Table 1 below.

[Example 3]
(Preparation of surface-modified zirconia dispersion 3)
In the preparation of the surface-modified zirconia dispersion, zirconia particles 2 were used instead of zirconia particles 1, and methyldichlorosilane (LS-50 manufactured by Shin-Etsu Chemical Co., Ltd.), which is an H-Si group-containing modified material instead of an alkenyl group-containing modified material. The surface-modified zirconia dispersion 3 was prepared in the same manner as in Example 1 except that the bead mill was stirred for 5 hours and the reflux time was changed to 3 hours.
The surface modification amount by the surface modifying material was 40% by mass with respect to the mass of the zirconia particles 2, and the mass ratio of the methoxy group-containing methylphenylsilicone resin and methyldichlorosilane was 1: 1. Further, the obtained surface-modified zirconia dispersion 3 was transparent.

(Preparation of light scattering composition 3)
In the production of the light scattering composition 1, a light scattering composition 3 was produced in the same manner as in Example 1 except that the surface modified zirconia dispersion 3 was used instead of the surface modified zirconia dispersion 1. The obtained light scattering composition 3 was almost transparent. The transmittance of the light scattering composition 3 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 3)
The light scattering composite 3 was prepared in the same manner as in Example 1 except that the light scattering composition 3 was used in place of the light scattering composition 1 in the preparation of the light scattering composite. The transmittance of the obtained light scattering composite 3 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 3)
In the production of the optical semiconductor light emitting device, the optical semiconductor light emitting device 3 was produced in the same manner as in Example 1 except that the light scattering composition 3 was used instead of the light scattering composition 1. Thus, the optical semiconductor of Example 3 in which the light scattering conversion layer including the light scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light emitting device was formed on the optical semiconductor light emitting device. The light emitting device 3 was obtained.
In addition, the content of the light scattering particles in the light scattering conversion layer was 0.5% by mass, and the content of the yellow phosphor was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 3 were measured and evaluated as described above. The results are shown in Table 1 below.

[Example 4]
(Preparation of surface-modified zirconia dispersion 4)
In preparation of the surface-modified zirconia dispersion, tetraethoxysilane (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.), which is an alkoxy group-containing modified material, is used instead of the alkenyl group-containing modified material, and the stirring time of the bead mill is 5 hours. A surface-modified zirconia dispersion 4 was produced in the same manner as in Example 1 except that the time was changed to 3 hours.
The amount of surface modification by the surface modifying material was 40% by mass with respect to the mass of the zirconia particles 1, and the mass ratio of the methoxy group-containing methylphenylsilicone resin and tetraethoxysilane was 1: 1. Further, the obtained surface-modified zirconia dispersion 4 was transparent.

(Preparation of light scattering composition 4)
In the production of the light scattering composition, a light scattering composition 4 was produced in the same manner as in Example 1 except that the surface modified zirconia dispersion 1 was used instead of the surface modified zirconia dispersion 1. The obtained light scattering composition 4 was almost transparent. The transmittance of the light scattering composition 4 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 4)
A light scattering composite 4 was prepared in the same manner as in Example 1 except that the light scattering composition 4 was used instead of the light scattering composition 1 in the preparation of the light scattering composite. The transmittance of the obtained light scattering composite 4 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 4)
In the production of the optical semiconductor light emitting device, the optical semiconductor light emitting device 4 was produced in the same manner as in Example 1 except that the light scattering composition 4 was used instead of the light scattering composition 1. Thus, the optical semiconductor of Example 4 in which the light-scattering conversion layer including the light-scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light-emitting element is formed on the optical semiconductor light-emitting element. The light emitting device 4 was obtained.
In addition, the content of the light scattering particles in the light scattering conversion layer was 0.5% by mass, and the content of the yellow phosphor was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 4 were measured and evaluated as described above. The results are shown in Table 1 below.

[Example 5]
(Preparation of surface-modified silica dispersion)
50 g of a methanol solution in which 5 g of hexanoic acid was dissolved in 50 g of silica sol (Snowtex OS, manufactured by Nissan Chemical Industries, Ltd.) was mixed and stirred, and the solvent was removed from the resulting slurry by an evaporator to obtain a silica particle dry powder. 10 g of the obtained silica particle-containing dry powder was mixed with 80 g of toluene. Next, 5 g of one-end epoxy-modified silicone (X-22-173DX, manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 g of vinyltrimethoxysilane (KBM1003, Shin-Etsu Chemical Co., Ltd.) as an alkenyl group (vinyl group) -containing modifying material are added, and 130 Surface modification and dispersion were performed under reflux at 6 ° C. for 6 hours. 100 g of methanol was added to 100 g of the obtained silica dispersion, and the resulting precipitate was collected and dried. The surface modification amount of the surface-modified silica particles by the surface modification material was 80% by mass with respect to the mass of the silica particles, and the mass ratio of the one-end epoxy-modified silicone and vinyltrimethoxysilane was 1: 1. Subsequently, the surface-modified silica particles were added to toluene in an amount of 18% by mass (10% by mass as silica particles) and redispersed to prepare a surface-modified silica dispersion.
The obtained surface-modified silica dispersion was transparent.

(Preparation of light scattering composition 5)
158.2 g of dimethyl silicone resin (OE-6336 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.41, A / B mixture ratio = 1/1) with respect to 10 g of the surface-modified silica dispersion prepared 79.1 g and B liquid 79.1 g) were added and stirred. Thereafter, toluene was removed from the mixture by drying under reduced pressure to obtain a light scattering composition 5 containing surface-modified silica particles and a dimethyl silicone resin. The obtained light scattering composition 5 was almost transparent. The transmittance of the light scattering composition 5 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 5)
A light scattering composite 5 was prepared in the same manner as in Example 1 except that the light scattering composition 5 was used instead of the light scattering composition 1 in the preparation of the light scattering composite. The transmittance of the obtained light scattering composite 5 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 5)
In the production of the optical semiconductor light emitting device, the optical semiconductor light emitting device 5 was produced in the same manner as in Example 1 except that the light scattering composition 5 was used instead of the light scattering composition 1. Thus, the optical semiconductor of Example 5 in which the light-scattering conversion layer including the light-scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light-emitting element was formed on the optical semiconductor light-emitting element. The light emitting device 5 was obtained.
In addition, the content of the light scattering particles in the light scattering conversion layer was 0.5% by mass, and the content of the yellow phosphor was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 5 were measured and evaluated as described above. The results are shown in Table 1 below.

[Example 6]
(Preparation of surface-modified zirconia dispersion 6)
In the preparation of the surface-modified zirconia dispersion, the amount of toluene used is 89 g, the amount of methoxy group-containing methylphenylsilicone resin is 0.5 g, and the amount of vinyltrimethoxysilane used as an alkenyl group (vinyl group) -containing modifier is A surface-modified zirconia dispersion 6 was prepared in the same manner as in Example 1 except that the amount was changed to 0.5 g.
The surface modification amount by the surface modifying material was 10% by mass with respect to the mass of the zirconia particles 1, and the mass ratio of the methoxy group-containing methylphenyl silicone resin and vinyltrimethoxysilane was 1: 1. Further, the obtained surface-modified zirconia dispersion 6 was transparent.

(Preparation of light scattering composition 6)
159.78 g of phenyl silicone resin (OE-6330 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.53, A / B mixture ratio = 1/4) to 2 g of surface-modified zirconia dispersion 6 31.96 g and Liquid B 127.82 g) were added and stirred. Thereafter, toluene was removed from the mixture by drying under reduced pressure to prepare a light scattering composition 6 containing surface-modified zirconia particles and phenyl silicone resin. The obtained light scattering composition 1 was almost transparent. The transmittance of the light scattering composition 6 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 6)
A light scattering composite 6 was prepared in the same manner as in Example 1 except that the light scattering composition 6 was used in place of the light scattering composition 1 in the preparation of the light scattering composite. The transmittance of the obtained light scattering composite 6 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 6)
In the production of the optical semiconductor light emitting device, the optical semiconductor light emitting device 6 was produced in the same manner as in Example 1 except that the light scattering composition 6 was used instead of the light scattering composition 1. Thus, the optical semiconductor of Example 6 in which the light-scattering conversion layer including the light-scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light-emitting element was formed on the optical semiconductor light-emitting element. The light emitting device 3 was obtained.
The light scattering particle content in the light scattering conversion layer was 0.1% by mass, and the yellow phosphor content was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 6 were measured and evaluated as described above. The results are shown in Table 1 below.

[Example 7]
(Preparation of light scattering composition 7)
As the surface-modified zirconia dispersion of Example 7, the surface-modified zirconia dispersion 1 of Example 1 was used as it was.
For 10 g of surface-modified zirconia dispersion 1, 48.6 g of phenyl silicone resin (OE-6330 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.53, A / B mixture ratio = 1/4) (A solution) 9.7 g and B solution 38.9 g) were added and stirred. Thereafter, toluene was removed from the mixture by drying under reduced pressure to prepare a light scattering composition 7 containing surface-modified zirconia particles and phenyl silicone resin. The obtained light scattering composition 7 was almost transparent. The transmittance of the light scattering composition 7 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 7)
A light scattering composite 7 was prepared in the same manner as in Example 1 except that the light scattering composition 7 was used in place of the light scattering composition 1 in the preparation of the light scattering composite. The transmittance of the obtained light scattering composite 7 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 7)
Phenyl silicone resin (OE-6330 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.53, A / B mixture ratio = 1/4) 15 g (A 3 g, B 12 g), yellow phosphor (Genelite) 10 g of GLD (Y) -550A) was added, and then mixed and defoamed with a self-revolving mixer to obtain phosphor-containing composition 7.
Next, the phosphor-containing composition 7 was dropped on the light-emitting element of the package including the unsealed blue light semiconductor light-emitting element, and then heated at 150 ° C. for 30 minutes to cure the phosphor-containing composition 7. Subsequently, after dripping the light-scattering composition 7 on the phosphor-containing composition 7 after curing, the light-scattering composition 1 is cured by heating at 150 ° C. for 90 minutes to completely cure the phosphor-containing composition 7. Cured. Thereby, the optical semiconductor light emitting device 7 of Example 7 in which the light conversion layer containing the phosphor was formed on the optical semiconductor light emitting element and the light scattering layer containing the light scattering particles was formed thereon was produced. did.
In addition, content of the yellow fluorescent substance in a light conversion layer was 20 mass%, and content of the light-scattering particle in a light-scattering layer was 2 mass%. The obtained light scattering layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 7 were measured and evaluated as described above. The results are shown in Table 1 below.

[Example 8]
(Preparation of surface-modified zirconia dispersion 8)
A surface-modified zirconia dispersion 8 was prepared in the same manner as in Example 1 except that zirconia particles 4 were used instead of zirconia particles 1 in the preparation of the surface-modified zirconia dispersion.
The surface modification amount by the surface modifying material was 40% by mass with respect to the mass of the zirconia particles 4, and the mass ratio of the methoxy group-containing methylphenylsilicone resin and vinyltrimethoxysilane was 1: 1. The obtained surface-modified zirconia dispersion 8 was slightly cloudy and transparent.

(Preparation of light scattering composition 8)
In the production of the light scattering composition, a light scattering composition 8 was produced in the same manner as in Example 1, except that the surface modified zirconia dispersion 1 was used instead of the surface modified zirconia dispersion 1. The obtained light scattering composition 8 was slightly cloudy and translucent. The transmittance of the light scattering composition 8 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 8)
In the production of the light scattering composite, a light scattering composite 8 was produced in the same manner as in Example 1 except that the light scattering composition 8 was used instead of the light scattering composition 1. The transmittance of the obtained light scattering composite 8 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 8)
A photo semiconductor light emitting device 8 was produced in the same manner as in Example 1 except that the light scattering composition 8 was used in place of the light scattering composition 1 in the production of the photo semiconductor light emitting device. Thus, the optical semiconductor of Example 8 in which the light scattering conversion layer including the light scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light emitting device was formed on the optical semiconductor light emitting device. A light emitting device 8 was obtained.
In addition, the content of the light scattering particles in the light scattering conversion layer was 0.5% by mass, and the content of the yellow phosphor was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 8 were measured and evaluated as described above. The results are shown in Table 1 below.

[Example 9]
(Preparation of surface-modified zirconia dispersion 9)
In the preparation of the surface-modified zirconia dispersion, zirconia particles 5 are used instead of zirconia particles 1, the amount of toluene used is 87 g, the amount of methoxy group-containing methylphenylsilicone resin used is 1.5 g, and the alkenyl group (vinyl group) is contained. A surface-modified zirconia dispersion 9 was prepared in the same manner as in Example 1 except that the amount of vinyltrimethoxysilane used as the modifying material was changed to 1.5 g.
The surface modification amount by the surface modifying material was 30% by mass with respect to the mass of the zirconia particles 1, and the mass ratio of the methoxy group-containing methylphenylsilicone resin and vinyltrimethoxysilane was 1: 1. Further, the obtained surface-modified zirconia dispersion 9 was slightly cloudy and transparent.

(Preparation of light scattering composition 9)
To 4 g of the surface-modified zirconia dispersion 9, 159.48 g of phenyl silicone resin (OE-6330 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.53, A / B mixture ratio = 1/4) 31.90 g and B liquid 127.58 g) were added and stirred. Thereafter, toluene was removed from the mixture by drying under reduced pressure to prepare a light scattering composition 9 containing surface-modified zirconia particles and phenyl silicone resin. The obtained light scattering composition 9 was almost transparent. The transmittance of the light scattering composition 9 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 9)
A light scattering composite 9 was prepared in the same manner as in Example 1 except that the light scattering composition 9 was used instead of the light scattering composition 1 in the preparation of the light scattering composite. The transmittance of the obtained light scattering composite 9 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 9)
In the production of the optical semiconductor light emitting device, the optical semiconductor light emitting device 9 was produced in the same manner as in Example 1 except that the light scattering composition 9 was used in place of the light scattering composition 1. Thus, the optical semiconductor of Example 9 in which the light-scattering conversion layer including the light-scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light-emitting element was formed on the optical semiconductor light-emitting element. A light emitting device 9 was obtained.
The light scattering particle content in the light scattering conversion layer was 0.2% by mass, and the yellow phosphor content was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 9 were measured and evaluated as described above. The results are shown in Table 1 below.

[Comparative Example 1]
(Evaluation of matrix resin)
Comparative Examples 1 and 2 do not contain light scattering particles in the matrix resin. Therefore, instead of the light scattering composite, the transmittance of the matrix resin itself was measured and evaluated in the same manner as the light scattering composite.
In Comparative Example 1, 7.6 g of phenyl silicone resin (OE-6330 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.53, A / B mixture ratio = 1/4) (A solution 1.5 g, B solution 6) 0.1 g) was mixed and defoamed with a self-revolving mixer, and the obtained composition was measured and evaluated in the same manner as the light-scattering composition of each Example. Further, the obtained composition was poured into a concave mold having a depth of 1 mm and cured by heating at 150 ° C. for 2 hours to prepare a cured matrix resin having a thickness of 1 mm. Measurement and evaluation were conducted in the same manner as the light scattering complex. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 101)
To 7.6 g (A liquid 1.5 g, B liquid 6.1 g), phenyl silicone resin (OE-6330 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.53, A liquid / B liquid mixture ratio = 1/4) 1 g of yellow phosphor (GLD (Y) -550A manufactured by Genelite) was added, and then mixed and defoamed with a self-revolving mixer. Next, a phosphor-containing phenylsilicone resin composition is dropped on a light-emitting element of a package including an unsealed blue light semiconductor light-emitting element, and the phenylsilicone resin composition not containing a phosphor is further dropped. Heat curing was carried out at 2 ° C. for 2 hours. Thereby, the optical semiconductor light-emitting device 101 of the comparative example 1 by which the light conversion layer containing a fluorescent substance was formed on the optical semiconductor light-emitting element was produced.
In addition, content of the yellow fluorescent substance in a light conversion layer was 11.3 mass%. Moreover, the obtained light conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 101 were measured and evaluated as described above. The results are shown in Table 1 below.

(Evaluation of matrix resin)
In the same manner as in Comparative Example 1, except that dimethyl silicone resin (OE-6336 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.41 A liquid / B liquid blending ratio = 1/1) was used instead of phenyl silicone resin. The transmittance of the cured matrix resin was measured and evaluated. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 102)
[Comparative Example 2]
In the production of an optical semiconductor light emitting device, dimethyl silicone resin (OE-6336 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.41 A / B mixture ratio = 1/1) instead of phenyl silicone resin 7.6 g (A The optical semiconductor light emitting device 102 was produced in the same manner as in Comparative Example 1 except that the liquid 3.8 g and the liquid B 3.8 g) were used.
In addition, content of the yellow fluorescent substance in a light conversion layer was 11.3 mass%. Moreover, the obtained light conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 102 were measured and evaluated as described above. The results are shown in Table 1 below.

[Comparative Example 3]
(Preparation of surface-modified zirconia dispersion 103)
In the preparation of the surface-modified zirconia dispersion, a surface-modified zirconia dispersion 103 was prepared in the same manner as in Example 1 except that the zirconia particles 3 were used instead of the zirconia particles 1.
The surface modification amount by the surface modifying material was 40% by mass with respect to the mass of the zirconia particles 3, and the mass ratio of the methoxy group-containing methylphenylsilicone resin and vinyltrimethoxysilane was 1: 1. Further, the obtained surface-modified zirconia dispersion 103 was transparent.

(Preparation of light scattering composition 103)
A light scattering composition 103 was prepared in the same manner as in Example 1 except that the surface-modified zirconia dispersion liquid 1 was used instead of the surface-modified zirconia dispersion liquid 1 in the preparation of the light scattering composition. The obtained light scattering composition 103 was transparent. The transmittance of the light scattering composition 103 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 103)
A light scattering composite 103 was prepared in the same manner as in Example 1 except that the light scattering composition 103 was used instead of the light scattering composition 1 in the preparation of the light scattering composite. The transmittance of the obtained light scattering composite 103 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 103)
A photo semiconductor light emitting device 103 was produced in the same manner as in Example 1 except that the light scattering composition 103 was used instead of the light scattering composition 1 in the production of the photo semiconductor light emitting device. As a result, the optical semiconductor of Comparative Example 3, in which the light scattering conversion layer including the light scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light emitting element is formed on the optical semiconductor light emitting element. A light emitting device 103 was obtained.
In addition, the content of the light scattering particles in the light scattering conversion layer was 0.5% by mass, and the content of the yellow phosphor was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 103 were measured and evaluated as described above. The results are shown in Table 1 below.

[Comparative Example 4]
(Preparation of surface-modified zirconia dispersion 104)
In the preparation of the surface-modified zirconia dispersion, the same procedure as in Example 1 was used except that stearic acid, which is a saturated fatty acid, was used instead of the alkenyl group-containing modifying material, and that the stirring time of the bead mill was changed to 5 hours. A modified zirconia dispersion 104 was prepared. Since stearic acid is a saturated fatty acid and its carboxyl group is used for bonding with zirconia particles, the stearic acid after bonding with zirconia particles has only an alkyl group, an alkenyl group, an H-Si group. And none of the alkoxy groups.
The amount of surface modification by the surface modifying material was 40% by mass with respect to the mass of the zirconia particles 1. Further, the obtained surface-modified zirconia dispersion 104 was transparent.

(Preparation of light scattering composition 104)
The light scattering composition 104 was prepared in the same manner as in Example 1 except that the surface-modified zirconia dispersion liquid 1 was used instead of the surface-modified zirconia dispersion liquid 1 in the preparation of the light scattering composition. The obtained light-scattering composition 104 was slightly cloudy and translucent. The transmittance of the light scattering composition 104 was measured and evaluated as described above. The results are shown in Table 1 below.

(Preparation of light scattering composite 104)
A light scattering composite 104 was prepared in the same manner as in Example 1 except that the light scattering composition 104 was used instead of the light scattering composition 1 in the preparation of the light scattering composite. The transmittance of the obtained light scattering composite 104 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 104)
A photo semiconductor light emitting device 104 was produced in the same manner as in Example 1 except that the light scattering composition 104 was used in place of the light scattering composition 1 in the production of the photo semiconductor light emitting device. Thus, the optical semiconductor of Comparative Example 4 in which the light scattering conversion layer including the light scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light emitting element is formed on the optical semiconductor light emitting element. The light emitting device 104 was obtained.
In addition, the content of the light scattering particles in the light scattering conversion layer was 0.5% by mass, and the content of the yellow phosphor was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 104 were measured and evaluated as described above. The results are shown in Table 1 below.

[Comparative Example 5]
(Preparation of light scattering composition 105)
As the surface-modified silica dispersion of Comparative Example 105, the surface-modified silica dispersion of Example 5 was used as it was.
To 200 g of this surface-modified silica dispersion, 88 g of dimethyl silicone resin (OE-6336 manufactured by Toray Dow Corning Co., Ltd., refractive index 1.41, A / B mixture ratio = 1/1) (A 44 g, B 44 g) of liquid was added and stirred. Thereafter, toluene was removed from the mixture by drying under reduced pressure to obtain a light scattering composition 105 containing surface-modified silica particles and a dimethyl silicone resin. The obtained light scattering composition 105 was almost transparent. The transmittance of the light scattering composition 105 was measured and evaluated as described above. The results are shown in Table 1 below.

(Production of optical semiconductor light emitting device 105)
A photo semiconductor light emitting device 105 was produced in the same manner as in Example 1 except that the light scattering composition 105 was used in place of the light scattering composition 1 in the production of the photo semiconductor light emitting device. Thus, the optical semiconductor of Comparative Example 5 in which the light-scattering conversion layer including the light-scattering particles and the phosphor and having the phosphor particles in the vicinity of the optical semiconductor light-emitting element is formed on the optical semiconductor light-emitting element. A light emitting device 105 was obtained.
The light scattering particle content in the light scattering conversion layer was 20% by mass, and the yellow phosphor content was 20% by mass. Moreover, the obtained light-scattering conversion layer was convex with respect to the external air layer.
The emission spectrum and luminance of the obtained optical semiconductor light emitting device 105 were measured and evaluated as described above. The results are shown in Table 1 below.

  From the said Table 1, all the optical semiconductor light-emitting devices of Examples 1-7 and 9 were superior to Comparative Examples 1-4 in the emission spectrum peak area ratio. That is, in the optical semiconductor light emitting devices of Examples 1 to 7, the blue light component emitted together with the white light was reduced. Furthermore, the optical semiconductor light-emitting devices of Examples 1 to 7 and 9 all have high luminance, and in particular, the optical semiconductor light-emitting devices of Examples 1 to 4 showed very high luminance. Moreover, although each value of Example 8 was falling compared with the other Examples, it was better than the comparative example. This is presumably because the average secondary particle size is larger than in other examples. Moreover, although the optical characteristic was not bad in the comparative example 5, since there was much content of light-scattering particle | grains, especially the viscosity of the light-scattering composition became high and handling was difficult.

DESCRIPTION OF SYMBOLS 10 Optical semiconductor light-emitting element 11 Sealing resin layer 12 Light scattering composite body 13 Phosphor particle 14 Light scattering conversion layer 15 Matrix material 16 Light conversion layer 17 Light scattering layer 18 External air phase interface

Claims (3)

Light scattering having an average primary particle diameter of 3 nm or more and 50 nm or less, including inorganic oxide particles surface-modified with a surface modifying material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups A light scattering composition comprising particles and a matrix resin composition ,
The matrix resin composition is at least selected from a resin monomer or oligomer of a dimethyl silicone resin, a resin monomer or oligomer of a methyl phenyl silicone resin, a resin monomer or oligomer of a phenyl silicone resin, or a resin monomer or oligomer of an organically modified silicone resin One kind,
Der content 0.01 wt% or more and 10 wt% of the light scattering particles in the total solid content of the light-scattering composition is,
In the light scattering particles, when the light scattering composition is cured, at least a part of the light scattering particles forms associated particles, and the average secondary particle diameter of the particles including the associated particles is the average primary particles. A light scattering composition having a diameter larger than 1000 nm . A light scattering composite obtained by curing the light scattering composition according to claim 1 ,
A light-scattering complex , wherein at least a part of the light-scattering particles form associated particles, and an average secondary particle diameter of particles including the associated particles is larger than the average primary particle diameter and 1000 nm or less . Light scattering having an average primary particle diameter of 3 nm or more and 50 nm or less, including inorganic oxide particles surface-modified with a surface modifying material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups Particles and a matrix resin composition,
The matrix resin composition is at least selected from a resin monomer or oligomer of a dimethyl silicone resin, a resin monomer or oligomer of a methyl phenyl silicone resin, a resin monomer or oligomer of a phenyl silicone resin, or a resin monomer or oligomer of an organically modified silicone resin One kind,
A method for producing a light-scattering composite obtained by curing a light-scattering composition having a content of the light-scattering particles in a total solid content of 0.01% by mass or more and 10% by mass or less,
At the time of curing the light scattering composition, at least a part of the monodispersed light scattering particles are associated to form associated particles in the matrix resin, and the average secondary particle diameter of the particles including the associated particles is A method for producing a light-scattering composite that is larger than the average primary particle size and 1000 nm or less .