JP6468020B2 - Inorganic oxide particle dispersion, resin composition, masterbatch, resin composite, and optical semiconductor light emitting device - Google Patents

Description

  The present invention relates to an inorganic oxide particle dispersion, a resin composition, a master batch, a resin composite, and an optical semiconductor light emitting device.

Resin compositions and masterbatches in which inorganic oxide particles are dispersed in an uncured resin tend to increase in viscosity due to mixing of inorganic ions, inorganic salts, etc. derived from the raw material of the inorganic oxide particles. Workability at the time of using a composition and a masterbatch may fall.
Therefore, a technique for suppressing an increase in viscosity of a resin composition or a master batch is disclosed.
For example, in order to obtain a resin dispersion composition having low viscosity and excellent dispersibility and stability without containing an organic solvent, the average particle diameter is in the range of 5 to 300 nm, and has an aromatic ring as a coating resin. It is disclosed that metal oxide particles coated with a (meth) acrylate monomer or oligomer (A) are dispersed in a resin dispersion medium (B) (for example, see Patent Document 1).

  Further, in order to obtain a zirconium oxide dispersion liquid having a high concentration and a low viscosity and high transparency, the zirconium oxide dispersion liquid has a transmittance of 35% or more at a wavelength of 400 nm and a wavelength of 800 nm. It is disclosed that the composition has a transmittance of 95% or more and a zirconium oxide particle content of 20% by weight or more having a viscosity at a temperature of 25 ° C. of 20 mPa · s or less (see, for example, Patent Document 2).

  In addition, in order to make the metal oxide particle dispersion liquid practically free of impurities, by contacting the metal salt with the basic ion exchange resin in a solvent other than alcohol and water, the metal oxide particles Manufacturing a dispersion liquid is disclosed (for example, refer to Patent Document 3).

JP 2012-072288 A JP 2010-132494 A JP 2008-001578 A

However, even if any method is used, it is difficult to suppress an increase in viscosity of the resin composition or the master batch, and the workability of the resin composition is not excellent.
The present invention relates to an inorganic oxide particle dispersion and a resin composition capable of suppressing an increase in viscosity of a masterbatch containing inorganic oxide particles and a silicone resin-forming component, and a masterbatch having a small viscosity and excellent workability, An object of the present invention is to provide a resin composite using the above and an optical semiconductor light emitting device.

As a result of intensive studies to solve the above problems, the present inventors have found that the resin composition and the masterbatch contain inorganic acids (at least one of an inorganic acid and a salt thereof) generated in the process of producing inorganic oxide particles. Even if included in a specific range, the surface of the inorganic oxide particles is surface-modified with a surface-modifying material containing at least one of a silane compound and a silicone compound and is hydrophobized with a carboxylic acid. It was found that the increase in the viscosity of the batch was suppressed.
That is, the present invention is as follows.

[1] Inorganic oxide particles having an average primary particle diameter of 3 nm or more and 20 nm or less, the surface of which is surface modified with a surface modifying material containing at least one of a silane compound and a silicone compound and hydrophobized with carboxylic acid;
A dispersion medium;
An inorganic oxide particle dispersion containing at least one of an inorganic acid and a salt thereof in an amount of 0.1 ppm to 1000 ppm.
[2] The inorganic oxide particle dispersion according to [1], wherein the surface modification amount of the surface modification material with respect to the inorganic oxide particles (surface modification material / inorganic oxide particles) is 10% by mass or more and 150% by mass or less.
[3] The inorganic oxide according to [1] or [2], wherein the amount of hydrophobicity of the carboxylic acid with respect to the inorganic oxide particles (carboxylic acid / inorganic oxide particles) is 0.001% by mass or more and 50% by mass or less. Particle dispersion.
[4] A resin composition comprising the inorganic oxide particle dispersion liquid according to any one of [1] to [3] and a silicone resin forming component, wherein the content of the dispersion medium is 5% by mass or more of the total amount. object.
[5] Inorganic oxide particles having an average primary particle diameter of 3 nm or more and 20 nm or less, the surface of which is surface modified with a surface modifying material containing at least one of a silane compound and a silicone compound and hydrophobized with carboxylic acid;
A silicone resin-forming component;
At least one of 0.1 ppm or more and 1000 ppm or less of an inorganic acid and a salt thereof,
Furthermore, the masterbatch which does not contain a dispersion medium or whose content of a dispersion medium is less than 5 mass% of the whole quantity.
[6] The master batch according to [5], wherein the dispersion medium is removed from the resin composition according to [4].
[7] The master batch according to [5] or [6], wherein the viscosity at 25 ° C. is 0.01 Pa · s or more and 1000 Pa · s or less.
[8] Inorganic oxide particles having an average primary particle diameter of 3 nm or more and 20 nm or less, the surface of which is surface-modified with a surface-modifying material containing at least one of a silane compound and a silicone compound, and hydrophobized with carboxylic acid;
Silicone resin,
A resin composite containing at least one of 0.1 ppm to 1000 ppm of inorganic acid and a salt thereof.
[9] The resin composite according to [8], which is obtained by curing the masterbatch according to any one of [5] to [7].
[10] An optical semiconductor light emitting device comprising a semiconductor light emitting element sealed with a sealing material layer made of the resin composite according to [8] or [9].

  ADVANTAGE OF THE INVENTION According to this invention, the inorganic oxide particle dispersion liquid and resin composition which can suppress an increase in the viscosity of the masterbatch containing an inorganic oxide particle and a silicone resin formation component, and the master which is small in viscosity and excellent in workability A batch, a resin composite using the same, and an optical semiconductor light emitting device can be provided.

It is sectional drawing which shows typically one Embodiment of the optical semiconductor light-emitting device of this invention. It is sectional drawing which shows typically other embodiment of the optical semiconductor light-emitting device of this invention.

<Inorganic oxide particle dispersion>
The inorganic oxide particle dispersion is an inorganic oxide having an average primary particle size of 3 nm to 20 nm, the surface of which is modified with a surface modifying material containing at least one of a silane compound and a silicone compound, and hydrophobized with a carboxylic acid. Physical particles, a dispersion medium, and at least one of 0.1 ppm to 1000 ppm of inorganic acid and a salt thereof.
The inorganic oxide particle dispersion may further contain other components, but does not contain a silicone resin forming component. That is, the content of the silicone resin forming component in the inorganic oxide particle dispersion is 0% by mass.
Hereinafter, at least one of the inorganic acid and its salt may be referred to as inorganic acids.
In addition, the inorganic oxide particle dispersion may be simply referred to as a dispersion.
The details of the inorganic oxide particle dispersion will be described below.

[Inorganic oxide particles]
The inorganic oxide particles of the present invention are particles made of an inorganic oxide and having an average primary particle size of 3 nm to 20 nm.
The composition of the inorganic oxide particles is not particularly limited as long as it is an inorganic oxide, and may be a metal oxide or a non-metal oxide. Specifically, aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), silicon oxide (SiO ₂ ), titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₃ ), zirconium oxide (ZrO ₂ ), Magnesium oxide (MgO), tellurium oxide (TeO ₂ ), cerium oxide (CeO ₂ ), yttrium oxide (Y ₂ O ₃ ), indium oxide (In ₂ O ₃ ), tantalum oxide (Ta ₂ O ₅ ), hafnium oxide ( HfO ₂ ), bismuth oxide (Bi ₂ O ₃ ), tin oxide (SnO ₂ ) and the like.
When the inorganic oxide particle dispersion is used as a sealing material raw material for a white light semiconductor light-emitting device, the inorganic oxide particles have a light emission wavelength region of a blue semiconductor light-emitting element (wavelength of 400 nm to 480 nm, particularly, wavelength of 460 nm), Alternatively, it is preferable to use a metal oxide which is a material that does not absorb light in the emission wavelength region (wavelength of 340 nm to 410 nm) of the near-ultraviolet semiconductor light-emitting element. Examples of such metal oxides include zirconium oxide, titanium oxide, zinc oxide, aluminum oxide, silicon oxide, and cerium oxide. In particular, zirconium oxide and titanium oxide having a high refractive index are preferable because light extraction efficiency from a semiconductor light emitting device can be improved, and among these, zirconium oxide having a low influence on the resin is particularly preferable.
One kind of inorganic oxide particles may be used, or two or more kinds may be used in combination. Also, composite oxide particles may be used.

The inorganic oxide particles have an average primary particle diameter of 3 nm or more and 20 nm or less.
When the average primary particle diameter of the inorganic oxide particles is less than 3 nm, the inorganic oxide particle dispersion liquid is used for manufacturing an optical semiconductor light emitting device. The effect of adding particles cannot be obtained. On the other hand, when the thickness exceeds 20 nm, the translucency of the encapsulant layer is lowered, and the luminance of the optical semiconductor light emitting device may be lowered.
The average primary particle diameter of the inorganic oxide particles is preferably 4 nm or more and 15 nm or less, and more preferably 5 nm or more and 10 nm or less.
The average primary particle diameter of the inorganic oxide particles can be obtained, for example, by selecting 50 or more arbitrary particles from an image obtained by observing the particles with an electron microscope, and obtaining and averaging the particle diameters. . On the other hand, if the primary particle diameter of the inorganic oxide particles is nanometer size, the average primary particle diameter of the inorganic oxide particles may be the Scherrer diameter obtained by X-ray diffraction. This is because if the primary particle diameter is nanometer size, the possibility that one particle is composed of a plurality of crystallites is reduced, and the average primary particle diameter and the Scherrer diameter are substantially the same. It is.

The method for producing the inorganic oxide particles is not particularly limited, and a known method can be used.
For example, desired inorganic oxide particles can be obtained by using a metal salt or metal alkoxide as a raw material and hydrolyzing in a reaction system containing water. It can also be substituted with other suitable organic solvents after the synthesis of the inorganic oxide particles. Uniform dispersion is possible without impairing dispersibility by using an appropriate dispersant as required.

Moreover, you may employ | adopt the method of producing an inorganic oxide particle in an organic solvent as methods other than the method of hydrolyzing in water. Examples of the organic solvent to be used include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone, anisole and the like. These may be used alone or as a mixture of two or more.
When producing inorganic oxide particles in a solution, it is important to obtain appropriate conditions because the properties, particle diameter, aggregation state, and the like of the inorganic oxide particles differ depending on the temperature at the time of synthesis. When synthesis at a higher temperature is required, the necessary characteristics can be obtained by synthesis under high pressure using a high-pressure kettle such as an autoclave.

In addition to the case where the inorganic oxide particles are synthesized only in the liquid phase as described above, there is a case where a firing step is used to perform further high-temperature treatment. Such a firing method is to increase the crystallinity after forming particles in the liquid phase, when reacting and synthesizing raw materials directly in the firing step, or after forming the particle precursor in the liquid phase, In some cases, desired particles are synthesized in the firing step. As an example of the firing method, Japanese Patent Application Laid-Open No. 2003-19427 discloses spray-pyrolysis of a solution in which raw material components of inorganic oxide particles and other inorganic compounds are dissolved, and then washing with water. A method for obtaining only highly crystalline particles by removing inorganic compounds other than inorganic oxide particles is disclosed.
Alternatively, a method of forming a particle precursor in a liquid phase and then crystallizing by firing while preventing aggregation of the particles with an inorganic salt is described in JP-A-2006-16236.
Furthermore, examples include a method of producing by a vapor phase method using a vacuum process such as a molecular beam epitaxy method and a CVD method, and various general particle synthesis methods described in, for example, JP-A-2006-70069. Can do.

This invention can be conveniently used with respect to the method of synthesize | combining an inorganic oxide particle using metal salts among the synthesis | combining methods of said inorganic oxide particle. As described above, zirconium oxide is particularly preferable as the inorganic oxide particles, and examples of the metal salt include zirconium oxychloride, zirconium sulfate, zirconium nitrate and hydrates thereof. Especially, since it can use suitably with respect to the method of synthesize | combining an unmodified particle | grain using a metal chloride as a starting material, a zirconium oxychloride or its hydrate can be mentioned. When zirconium oxychloride or a hydrate thereof is selected, a hydrated zirconium cake is obtained by neutralizing an aqueous solution of zirconium oxychloride, and this is hydrothermally treated at high temperature and high pressure to obtain zirconium oxide particles. Can be adopted.
When the synthesized inorganic oxide particles aggregate and are difficult to unravel, a small amount of an inorganic acid may be added to the aggregate of inorganic oxide particles to unravel. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid and the like.

  The content of the inorganic oxide particles in the inorganic oxide particle dispersion is preferably 5% by mass or more and 50% by mass or less. By setting the content of the inorganic oxide particles in this range, the particle material can take a good dispersion state. The content of the particulate material is more preferably 10% by mass or more and 30% by mass or less.

[Inorganic acids]
The inorganic oxide particle dispersion contains at least one of an inorganic acid and a salt thereof in an amount of 0.1 ppm to 1000 ppm.
The inorganic acids contained in the inorganic oxide particle dispersion are mainly derived from the raw material of the inorganic oxide particles. Further, when the inorganic acid is added and dissolved as described above, these inorganic acids also become a mixing source. Examples of these inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and alkali metal salts and ammonium salts thereof. That is, the presence of ions such as Cl ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , Na ⁺ , K ⁺ , and NH ₄ ⁺ constituting inorganic acids usually increases the viscosity of the resin composition and the masterbatch ( To increase. Moreover, when the density | concentration of inorganic acids, especially the amount of chlorine is high, the transmittance | permeability of a masterbatch will fall, As a result, the transmittance | permeability fall of a resin composite will arise.
This is because, when there are many inorganic salts that are ionic impurities, these inorganic salts have substantially no affinity for the silicone resin forming component or silicone resin, so the inorganic salts are compatible with the silicone resin forming component or silicone resin. This is due to the occurrence of separation to form fine particles. That is, when the phase-separated inorganic salts are dispersed in an emulsion-like manner in the silicone resin-forming component, the viscosity of the entire system may be significantly increased by the action of the emulsion-like particles. Moreover, when light scattering is caused by the emulsion-like particles, haze is generated, and the transparency of the silicone resin-forming component and the silicone resin may be lowered.

Here, the concentration of the inorganic acids in the inorganic oxide particle dispersion is preferably as low as possible in order to obtain an effect of suppressing increase in viscosity and improving transmittance. However, since a method of synthesizing inorganic oxide particles from salts containing inorganic acid is common, it is difficult to completely remove even after an impurity removal step such as washing in the synthesis step. Contains 1 ppm or more of inorganic acids. On the other hand, as described later, the surface of the inorganic oxide particles is subjected to surface modification and hydrophobization treatment, so that the concentration of inorganic acids is 1000 ppm even if the increase in viscosity due to the presence of the inorganic oxide particles is suppressed. If it exceeds, an increase in viscosity and a decrease in transparency due to inorganic acids will become apparent.
Therefore, in the present invention, even if the inorganic oxide particle dispersion liquid contains 0.1 ppm or more and 1000 ppm or less of inorganic acids, the surface of the inorganic oxide particles contains at least one of a silane compound and a silicone compound. It is possible to suppress an increase in viscosity by being surface-modified by and being hydrophobized by carboxylic acid. The content of inorganic acids is preferably 800 ppm or less, and more preferably 500 ppm or less.

As a method for quantifying inorganic acids in the inorganic oxide particle dispersion, for example, a combustion decomposition-ion chromatography method can be suitably used. The analysis procedure of this method is that the sample is pyrolyzed in a combustion decomposition unit and burned with oxygen gas, the generated gas is collected in an absorption liquid (hydrogen peroxide solution) by an absorption unit, and the collected absorption liquid is ionized. Each ion content is measured by chromatographic analysis.
When measuring the amount of chlorine as an inorganic acid, the measuring device is an automatic combustion halogen / sulfur analysis system (SQ-1 type / HSU-35 type manufactured by Anatech / Yanaco Co., Ltd., ICS-2000 type manufactured by Nippon Dionex Co., Ltd.). Are preferably used.
For inorganic acids that are not suitable for combustion decomposition, the target ions are extracted from inorganic oxide particles and inorganic oxide particle dispersions using acid and alkaline aqueous solutions, and quantified by ion chromatographic analysis. Can be

[Surface modification and hydrophobization of inorganic oxide particles]
The surface of the inorganic oxide particles is surface-modified with a surface modifying material containing at least one of a silane compound and a silicone compound, and is hydrophobicized with carboxylic acid.
Hereinafter, the inorganic oxide particles whose surface is surface-modified with a surface-modifying material containing at least one of a silane compound and a silicone compound and are hydrophobized with carboxylic acid may be referred to as surface-modified inorganic oxide particles.

Here, the order of surface modification and hydrophobization on the surface of the inorganic oxide particles shown below is not particularly limited, and may be hydrophobized after surface modification, or may be performed after hydrophobization. Further, surface modification and hydrophobization may be performed simultaneously.
In the case where the surface modification is performed after hydrophobizing first, it is considered that the following steps are performed. First, when the inorganic oxide particles are treated with carboxylic acid, the carboxylic acid is bonded to a hydroxyl group present on the surface of the inorganic oxide particle, thereby hydrophobizing the surface of the inorganic oxide particle. Thereafter, when the surface modifying material is treated with inorganic oxide particles, the surface modifying material not only binds to the hydroxyl group remaining on the surface of the inorganic oxide particle without carboxylic acid bonding, but also already bonded to the hydroxyl group. Carboxylic acid is also substituted for surface modification. This is because the binding force of the surface modifying material to the hydroxyl group is stronger than the binding force of the carboxylic acid to the hydroxyl group. However, in general, since the surface modifying material has a large molecule and cannot be substituted for all carboxylic acids due to steric hindrance, some of the carboxylic acids are not substituted and are left in place. Through the above steps, inorganic oxide particles (surface-modified inorganic oxide particles) in which the hydroxyl group on the surface is modified with the surface modifying material and the unmodified hydroxyl group is hydrophobized with carboxylic acid can be obtained.
In this case, in the hydrophobization, the amount of carboxylic acid to be hydrophobized (carboxylic acid / inorganic oxide particles) with respect to the inorganic oxide particles is preferably 10% by mass or less. If the amount of hydrophobization is 10% by mass or less, surface modification can be facilitated when surface modification is performed after the surface of the non-modified particle is hydrophobized.

  Next, when the surface modification is performed first and then the surface is hydrophobized, the following steps are considered. First, when the inorganic oxide particles are treated with the surface modifying material, the surface modifying material is bonded to the hydroxyl groups on the surface of the inorganic oxide particles. However, since the surface modifying material generally has a large molecule, it cannot bond to all the hydroxyl groups on the surface of the inorganic oxide particles, and the hydroxyl groups remain. When the inorganic oxide particles treated with the surface modifying material are treated with carboxylic acid, the surface modifying material bonded to the surface of the inorganic oxide particles is hardly substituted with carboxylic acid. On the other hand, since the carboxylic acid has a small molecule, it is hydrophobized by binding to the hydroxyl group remaining on the surface of the inorganic oxide particles (in the form of filling the gap between the surface modifying materials). In the same manner as in the case where the surface modification is performed after the previous hydrophobization by the above steps, the surface hydroxyl group is modified by the surface modifying material, and the unmodified hydroxyl group is hydrophobized by the carboxylic acid. Surface-modified inorganic oxide particles).

Thus, the order of surface modification and hydrophobization is not limited, and the surface-modified oxide particles obtained are substantially the same regardless of which is performed first. Therefore, either surface modification or hydrophobization may be performed first.
Further, surface modification and hydrophobization may be performed simultaneously, that is, the inorganic oxide particles may be treated simultaneously with the surface modification material and the carboxylic acid. In this case, since the surface modifying material has a stronger binding force to the hydroxyl group on the surface of the inorganic oxide particles than the carboxylic acid, it is considered that the process proceeds in a process close to the case where the surface modification is performed first and then the hydrophobicity is performed. .

(Surface modification)
The surface modifying material used for the surface modification of the inorganic oxide particle surface includes at least one of a silane compound and a silicone compound.
As the silane compound and silicone compound that can be contained in the surface modifying material, known silane compounds and silicone compounds that can be bonded to oxygen atoms of the inorganic oxide can be used.
Specific examples of the silane compound include dichlorodiphenylsilane, dichlorodimethylsilane, dichlorodiethylsilane, dichloromethylphenylsilane, dichloroethylphenylsilane, dichloromethylvinylsilane, dichloromethylsilane, dimethoxydiphenylsilane, dimethoxydimethylsilane, Diethyldimethoxysilane, dimethoxymethylphenylsilane, ethyldimethoxyphenylsilane, dimethoxymethylvinylsilane, dimethoxymethylsilane, diethoxydiphenylsilane, diethoxydimethylsilane, diethoxydiethylsilane, diethoxymethylphenylsilane, diethoxyethylphenylsilane, di Ethoxymethyl vinyl silane, diethoxymethyl silane, diphenyl silane diol, trichlorophenyl Run, Trichloromethylsilane, Trichloroethylsilane, Trichlorovinylsilane, Trichlorosilane, Trimethoxyphenylsilane, Trimethoxymethylsilane, Ethyltrimethoxysilane, Trimethoxyvinylsilane, Trimethoxysilane, Triethoxyphenylsilane, Triethoxymethylsilane, Tri Examples include ethoxyethylsilane, triethoxyvinylsilane, triethoxysilane and the like.
Among the above, the silane compound is preferably dimethoxymethylphenylsilane, dimethoxymethylsilane, trimethoxyphenylsilane, and trimethoxymethylsilane.

Examples of the silicone compound include phenyl silicones, methylphenyl silicones, dimethyl silicones and the like that contain alkoxy groups, silanol groups, epoxy groups and the like, which are functional groups having reactivity with inorganic oxide particles. Among these, terminal functional group type silicone is preferable. Furthermore, the alkenyl group and hydrogen group (Si-H) which have the reactivity with the below-mentioned silicone resin formation component may be included.
A silane compound and a silicone compound may each be used by 1 type, and 2 or more types may be mixed and used for them.

Examples of the method of modifying the surface of the inorganic oxide particles with the surface modifying material include a wet method and a dry method.
In the wet method, inorganic oxide particles and surface modifying materials are added to the solvent, and if necessary, a catalyst for reacting the surface modifying materials with the inorganic oxide particles is added, and energy is applied from outside such as heating and stirring, bead media, etc. A method of dispersing oxide particles while surface-modifying them in a solvent is mentioned.
Examples of the dry method include a method in which inorganic oxide particles and a surface modifying material are mixed with a kneader or the like to perform surface modification to obtain inorganic oxide particles modified with the surface modifying material.

What is the surface modification amount of the surface modification material relative to the inorganic oxide particles (surface modification material / inorganic oxide particles)? It is preferable that it is 10 mass% or more and 150 mass% or less. If the amount of surface modification is in this range, the dispersibility of the surface-modified inorganic oxide particles in the resin can be maintained high, and a decrease in transparency can be suppressed.
The surface modification amount is more preferably 20% by mass or more and 120% by mass or less.
The surface modification amount can be calculated, for example, from the amount of mass reduction after heat treatment of the surface-modified inorganic oxide particles after drying. The drying temperature may be a temperature at which the dispersion medium is almost completely volatilized and the surface modifying material and the hydrophobizing agent (carboxylic acid) described below are not thermally decomposed, but are usually selected between 100 ° C. and 200 ° C. Good. The heat treatment temperature may be a temperature at which the surface modifying material and the hydrophobizing agent are almost completely thermally decomposed, but it may be usually selected between 600 ° C and 1000 ° C.
In addition, since the amount of mass reduction after heat treatment is the sum of the amount of reduction based on the surface modification material and the amount of reduction due to the hydrophobizing agent, it is necessary to separately measure and subtract the hydrophobizing agent amount (measurement of hydrophobizing agent amount) The method will be described later). In addition, since silicon contained in the surface modification material is a non-volatile component and remains after heat treatment, the silicon content is determined in consideration of the surface modification material component against the mass loss based on the surface modification material obtained by measurement. Need to add.

(Hydrophobic)
The surface of the inorganic oxide particles is hydrophobized with carboxylic acid.
In the present invention, “hydrophobization” of the inorganic oxide particles means depolarization by bonding carboxylic acid to the particle surface hydroxyl group which is the polarity of the surface of the inorganic oxide particles. By this hydrophobization, interaction (attraction) due to polar groups between inorganic oxide particles is reduced, and an increase in viscosity can be suppressed. The bond between the hydroxyl group and the carboxylic acid is not particularly limited as long as the carboxylic acid is not easily detached and the surface modifying material can be easily substituted.
The kind of carboxylic acid is not limited, and examples thereof include linear, branched, and cyclic monovalent or polyvalent carboxylic acids having 1 to 8 carbon atoms. Examples include formic acid, acetic acid, propionic acid, butanoic acid (butyric acid), hexanoic acid, oxalic acid, and succinic acid. The number of carbon atoms of the carboxylic acid is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less, from the viewpoint of easy hydrophobicity, that is, a small molecule and less steric hindrance. Monovalent carboxylic acids are preferred.
Carboxylic acid is modified with inorganic oxide particles or surface modification material as a carboxylic acid solution dissolved in a known solvent such as alcohols such as methanol, ethanol, n-propanol, isopropanol, aromatic hydrocarbons such as toluene, and water. It is preferable to apply to the inorganic oxide particles.

The hydrophobic amount of carboxylic acid (carboxylic acid / inorganic oxide particles) with respect to the inorganic oxide particles is preferably 0.001% by mass or more and 50% by mass or less. When the hydrophobization amount is 0.001% by mass or more, the resin composition and the masterbatch obtained from the inorganic oxide particle dispersion liquid are unlikely to increase in viscosity, and a decrease in workability is suppressed. Moreover, since the amount of hydrophobicity is 50% by mass or less, the obtained resin composite can prevent deterioration of heat resistance and light resistance due to peroxide radicals and the like, and prevent yellowing of the resin composite. can do.
The amount of carboxylic acid hydrophobized with respect to the inorganic oxide particles is more preferably 0.002% by mass or more and 10% by mass or less, and further preferably 0.005% by mass or more and 5% by mass or less.
In addition, since the surface of the inorganic oxide particles is modified with a surface modifying material, the amount of hydrophobicity of the carboxylic acid is often 0.1% by mass or less. Even if the surface modifying material is small or the surface modifying material has a large molecule (prone to steric hindrance) and the residual hydroxyl group on the surface of the inorganic oxide particles is large, the amount of hydrophobicity of the carboxylic acid is usually 1% by mass or less. It is. In other words, the upper limit (50% by mass or less) of hydrophobicity and the preferable range defined above are ranges required from the viewpoint of the heat resistance and light resistance of the resulting resin composite, and are usually hydrophobized to this range. The amount never increases.

The amount of carboxylic acid to be hydrophobized with respect to the inorganic oxide particles can be determined, for example, by bringing a sample into contact with an aqueous solution of an inorganic alkali to extract carboxylic acid ions into an aqueous phase and measuring the amount of extraction. Specifically, the surface-modified inorganic oxide particles or dispersion thereof as a sample is mixed with an aqueous sodium hydroxide solution, and stirred and shaken for about 30 minutes to extract carboxylate ions into the aqueous phase, and then the solids and oil What is necessary is just to analyze the extract which removed the phase part by an ion chromatograph.
As the measuring device, an ICS-3000 type manufactured by Nippon Dionex Co., Ltd., a Prominence HIC-SP type manufactured by Shimadzu Corporation, etc. are preferably used.
Note that the combustion decomposition-ion chromatography method suitably used as a method for quantifying inorganic acids in an inorganic oxide particle dispersion is not suitable for quantifying carboxylic acids.

[Dispersion medium]
The dispersion medium of the dispersion is not particularly limited as long as it is a medium that does not dissolve and disperse the surface-modified inorganic oxide particles. For example, water, an organic solvent, and a solution obtained by mixing these in an arbitrary ratio are used. Can do.
Organic solvents include methanol, ethanol, 1-propanol, 2-propanol, butanol, octanol and other alcohols; ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyl Esters such as lactones; ethers such as diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; acetone , Methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, cyclohexa Ketones such as emissions; benzene, toluene, xylene, ethyl amide, aromatic hydrocarbons such as; dimethylformamide, N, N- dimethylacetamide, amides such as N- methyl pyrrolidone is preferably used.
One or more of these dispersion media can be used.

In addition, the dispersion of the present invention has a dispersant, a surface treatment agent, a water-soluble binder and the like (hereinafter referred to as “a dispersion agent”) in order to improve the dispersibility of the surface-modified inorganic oxide particles and the stability of the dispersion. (Sometimes referred to as a dispersant or the like).
Dispersing agents and surface treatment agents include cationic surfactants, anionic surfactants, nonionic surfactants, silane coupling agents such as organoalkoxysilanes and organochlorosilanes, polyethyleneimine polymer dispersants, polyurethanes Polymer dispersants such as polymer dispersants and polyallylamine polymer dispersants are preferably used. These dispersants and surface treatment agents may be appropriately selected depending on the particle diameter of the composite fine particles and the type of the desired dispersion medium, and one or more of the above dispersants may be mixed and used. As the water-soluble binder, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), hydroxycellulose, polyacrylic acid, or the like can be used.

As a method for performing the dispersion treatment, a known dispersion apparatus can be used alone or in combination. For example, a bead mill, a nanomizer, a jet mill, a homogenizer, a planetary mill, an ultrasonic disperser or the like can be used alone or in combination. Can be used. Among these, a bead mill that can easily control the dispersed particle size by selecting the bead size is preferably used. The time required for the dispersion treatment may be sufficient as long as the inorganic oxide particles are uniformly dispersed in the dispersion medium.
The content of the dispersion medium in the inorganic oxide particle dispersion is from 40% by mass to 99% by mass with respect to the total mass of the inorganic oxide particle dispersion from the viewpoint of uniform dispersibility of the inorganic oxide particles. It is preferably 50% by mass or more and 90% by mass or less.

<Resin composition>
The resin composition includes an inorganic oxide particle dispersion and a silicone resin forming component, and the content of the dispersion medium is 5% by mass or more of the total amount of the resin composition.
In the present invention, the “resin composition” is a state that does not have a specific shape by having fluidity, that is, a so-called fluid (liquid material), and serves as a raw material for a masterbatch and a resin composite described later. It is.
The “resin-forming component” is a component for forming a resin component in the resin composite described later, and is usually a monomer, oligomer, or prepolymer of the resin component that is liquid.

Examples of the silicone resin-forming component include a phenyl silicone resin-forming component and a methylphenyl silicone resin-forming component.
Examples of the phenyl silicone resin-forming component include those in which a phenyl group is arranged on a siloxane polymer. Examples of the methylphenyl silicone resin forming component include those in which a phenyl group and a methyl group (alkyl group) are arranged on a siloxane polymer. In addition, there is a modified silicone resin in which a siloxane structure having a phenyl group and an epoxy group or another hydrocarbon are combined. In addition to the straight chain, the structure includes a two-dimensional chain, a three-dimensional network resin, and a cage structure.
The phenyl silicone resin forming component and the methyl phenyl silicone resin forming component may be used alone or in combination. Moreover, you may combine what has the above various structures, and also may add the above modified silicone resins.

In the resin composition of the present invention, the surface of the inorganic oxide particles is modified with a surface modifying material containing at least one of a silane compound and a silicone compound, and is hydrophobicized with a carboxylic acid. Even in this case, the increase in viscosity can be suppressed. Thereby, the viscosity in 25 degreeC can be 0.01 Pa.s or more and 1000 Pa.s or less. The viscosity of the resin composition is more preferably 0.01 Pa · s to 500 Pa · s.
The content of the silicone resin-forming component in the resin composition is preferably 40% by mass or more and less than 90% by mass from the viewpoint of easy handling by keeping the viscosity within the above range, and 50% by mass or more and 85% by mass. More preferably, it is not more than mass%.
From the same viewpoint, the content of the dispersion medium in the resin composition is preferably 5% by mass or more and 70% by mass or less, and preferably 10% by mass or more and 50% by mass or less with respect to the total mass of the resin composition. More preferred.

<Master batch>
The master batch has inorganic oxide particles having an average primary particle diameter of 3 nm or more and 20 nm or less, the surface of which is surface-modified with a surface modifying material containing at least one of a silane compound and a silicone compound, and hydrophobized with carboxylic acid. A silicone resin-forming component and at least one of 0.1 ppm to 1000 ppm of an inorganic acid and a salt thereof, and further contains no dispersion medium, or the content of the dispersion medium is 5% by mass of the total amount of the master batch Is less than.
This master batch can be obtained by mixing the surface-modified and hydrophobized inorganic oxide particles and the silicone resin-forming component. More preferably, the dispersion medium is obtained from the resin composition of the present invention by a known method. It can be obtained by removing and making the content of the dispersion medium less than 5% by mass. The master batch is a fluid (liquid material).
Since the masterbatch of the present invention suppresses increase in viscosity even if it contains inorganic acids, the viscosity at 25 ° C. should be 0.01 Pa · s or more and 1000 Pa · s or less even when the dispersion medium is removed. Can do. The viscosity of the master batch is more preferably 0.1 Pa · s or more and 100 Pa · s or less.

<Resin composite>
The resin composite is formed by curing a master batch.
As described above, the master batch can be obtained by mixing the surface-modified inorganic oxide particles and the silicone resin-forming component, but more preferably, the inorganic oxide particle dispersion of the present invention and the silicone resin. A dispersion medium is removed from a resin composition containing a forming component. Therefore, a resin composite can be obtained by curing this master batch.
More specifically, the silicone resin forming component in the masterbatch is polymerized and cured by addition reaction, condensation reaction, etc., and the surface modification material of the inorganic oxide particles and the silicone resin forming component are combined by a crosslinking reaction to form an inorganic oxide. It is obtained by integrating the product particles and the silicone resin.
Here, the “resin composite” maintains a certain shape according to the purpose and method of use. That is, it is not necessary that the shape itself be a specific shape, including a normal solid state that hardly deforms, and a rubber-like one having elastic deformability (shape restoring property).

  The use of the resin composite of the present invention is not particularly limited, and can be suitably used as an optical component using the excellent characteristics of the resin composite. Examples of the optical functional device provided with such an optical component include various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP, liquid crystal projector, etc.), optical fiber communication devices (optical waveguide, optical amplifier, etc.), and cameras. Illuminating fixtures such as light emitting diode (LED) illumination devices, etc., such as photographing devices such as video and video. In particular, it can be suitably used as a sealing material for an optical semiconductor light emitting device or the like.

When the resin composite of the present invention is used for a sealing material such as an optical semiconductor light emitting device, the refractive index is preferably higher than 1.50, more preferably 1.54 or higher, and 1.58 or higher. Is more preferable, and 1.6 or more is most preferable. By increasing the refractive index of the sealing material, the light extraction efficiency from the optical semiconductor light emitting device can be improved and the luminance can be increased.
Further, the transmittance at a wavelength of 450 nm when the optical path length is 0.5 mm is preferably 40% or more, more preferably 60% or more, and further preferably 70% or more. When the transmittance is within this range, for example, when a resin composite is used as an optical component, it is possible to suppress a decrease in light transmission loss as a constituent member.

The refractive index and transmittance of the resin composite are set to a desired range by appropriately adjusting the kind of inorganic oxide particles, the particle diameter, the composition of the silicone resin, the amount of inorganic oxide particles in the resin composite, and the like. be able to.
The refractive index of the resin composite may be measured using a known method. For example, a composite (1 mm thickness) formed on an aluminum substrate is used, and a value at a wavelength of 594 nm is measured at room temperature using a prism coupler. Is required. A method for measuring the transmittance will be described later.

<Optical semiconductor light emitting device>
The optical semiconductor light emitting device includes a semiconductor light emitting element that is sealed with a sealing material layer made of a resin composite.
The configuration of the sealing material layer according to the present invention may be that the entire sealing material layer of the optical semiconductor light emitting device may be a layer of the resin composite of the present invention (first aspect). A part is a layer of the resin composite of the present invention, and other sealing material layers may be laminated (second embodiment). Moreover, you may contain a fluorescent substance in these sealing material layers.

The said optical semiconductor light-emitting device is demonstrated concretely. In addition, this invention is not specifically limited to the following examples.
As shown in FIG. 1, the first aspect (light emitting device 10) according to the present invention is such that the light emitting element 14 is disposed in the concave portion 12 </ b> A of the reflecting cup 12 and the concave portion is embedded in contact with the light emitting element 14. The 1st sealing material layer 16 comprised by the sealing material which consists of this resin composite_body | complex is formed.
According to such an apparatus, the light emitted from the light emitting element 14 passes through the boundary surface with the sealing material, passes through the sealing material, and is reflected directly or by the wall surface of the reflecting cup 12 and is extracted to the outside. It is.

  Examples of the light emitting element constituting the light emitting device include a light emitting diode (LED) and a semiconductor laser. Here, as the light emitting diode, a red light emitting diode that emits red light (for example, light having a wavelength of 640 nm), a green light emitting diode that emits green light (for example, light having a wavelength of 530 nm), and blue light (for example, having a wavelength of 450 nm). An example is a blue light emitting diode that emits light). The light emitting diode may have a so-called face-up structure or a flip chip structure. That is, the light-emitting diode includes a substrate and a light-emitting layer formed on the substrate, and may have a structure in which light is emitted from the light-emitting layer to the outside, or light from the light-emitting layer passes through the substrate. It is good also as a structure radiate | emitted outside.

  More specifically, the light emitting diode includes, for example, a first cladding layer made of a compound semiconductor layer having a first conductivity type (for example, n-type) formed on a substrate, and an active layer formed on the first cladding layer. The first clad layer has a structure in which a second clad layer made of a compound semiconductor layer having a second conductivity type (for example, p-type) formed on the active layer is laminated, and is electrically connected to the first clad layer. An electrode and a second electrode electrically connected to the second cladding layer are provided. The layer constituting the light emitting diode may be made of a known compound semiconductor material depending on the emission wavelength.

In the optical semiconductor light emitting device of the present invention, the refractive index of the sealing material is preferably higher than 1.50, more preferably 1.54 or more, further preferably 1.58 or more, and 1.6. The above is most preferable. Further, the transmittance at a wavelength of 450 nm when the optical path length is 0.5 mm is preferably 40% or more, more preferably 60% or more, and further preferably 70% or more. By increasing the refractive index and the transmittance, the light extraction efficiency from the optical semiconductor light emitting device can be improved and the luminance can be increased.
Alternatively, a first sealing material having a higher refractive index on the light emitting element side may be used, and a second sealing material having a refractive index lower than that of the first sealing material may be used on the outer side thereof. In this case, the refractive index of the resin composite may be adjusted by appropriately adjusting the kind of inorganic oxide particles, the particle diameter, the composition of the silicone resin, the amount of inorganic oxide particles in the resin composite, and the like.

As shown in FIG. 2, the second mode (light emitting device 20) according to the present invention is formed so that the first sealing material layer 16 covers the surface of the light emitting element 14, and the outer side of the first sealing material layer 16 is the present invention. This is the same as the first aspect except that the second sealing material layer 18 having a different composition from that of the optical semiconductor element sealing composition is formed.
Examples of the material of the second sealing material layer 18 having a different composition include resins such as methyl silicone, modified silicone, acrylic resin, epoxy resin, and polyimide resin, or resin composites. The refractive index of the second sealing material layer 18 reduces the interface reflection between the first sealing material layer 16 and the second sealing material layer 18, and the second sealing material layer 18 and the outside. In order to reduce the interfacial reflection, the refractive index of the first sealing material layer 16 is preferably 1 or less and 1 (atmospheric refractive index) or more. Further, for the purpose of adjusting the refractive index of the second sealing material layer 18, the surface-modified metal oxide particles according to the present invention may be contained in the second sealing material layer.

The optical semiconductor light emitting device of the present invention can also be an optical semiconductor light emitting device in which a light emitting element and a phosphor are combined. According to the optical semiconductor light emitting device of the present invention, the first sealing material layer in contact with the optical semiconductor element is the above-described resin composite of the present invention, and the first sealing material layer includes, for example, blue InGaN. A phosphor such as a YAG phosphor for ultraviolet light or an RGB phosphor for ultraviolet light may be contained. This phosphor may be preliminarily contained in the resin composition for forming the resin composite that is the sealing material of the present invention. As the method, the phosphor is directly mixed in the resin composition. Examples thereof include a method of mixing a phosphor in a resin-forming component, a method of mixing a dispersion in which a phosphor is dispersed in an organic solvent and the like, and then removing the organic solvent and the like.
In particular, considering the case of reducing the amount of phosphor used in terms of cost and the case of increasing the light conversion efficiency by intensively arranging the phosphor in the vicinity of the light emitting element, the first sealing material layer in the second mode It is preferable to contain a phosphor. The phosphor is preferably 5 to 80% by mass with respect to the mass of the first sealing material layer, and more preferably 10% by mass to 70% by mass. Note that the second sealing material layer can also contain a phosphor.
As such an optical semiconductor light emitting device combining a light emitting element and a phosphor, a white light emitting diode (for example, a light emitting diode that emits white light by combining an ultraviolet or blue light emitting diode and phosphor particles) is exemplified. be able to.

<1. Preparation of inorganic oxide particles>
(1) Zirconium oxide particles A
While stirring a zirconium salt solution in which 261.5 g of zirconium oxychloride octahydrate was dissolved in 4 L (liter) of pure water, dilute ammonia water in which 34.4 g of 28% ammonia water was dissolved in 2 L of pure water was added dropwise. A zirconia precursor slurry was prepared.
Next, an aqueous sodium sulfate solution in which 30 g of sodium sulfate was dissolved in 0.5 L of pure water was added to this slurry with stirring. The amount of sodium sulfate added at this time was 30% by mass with respect to the zirconia-converted value of zirconium ions in the zirconium salt solution. Subsequently, this mixture was filtered, and the moisture of the obtained cake was dried and removed, and then fired at 500 ° C. for 1 hour in the air using an electric furnace to obtain a fired product.
This fired product is put into pure water, stirred to form a slurry, washed with a centrifuge, sufficiently removed the added sodium sulfate, dried in a drier, and zirconium oxide Particle A was obtained.
When the average primary particle diameter of the obtained zirconium oxide particles A was determined from the Scherrer equation by X-ray diffraction, the average primary particle diameter was 4 nm.

(2) Zirconium oxide particles B
Zirconium oxide particles B were produced in the same manner as zirconium oxide particles A, except that the temperature for firing in the atmosphere using an electric furnace was 600 ° C.
The average primary particle diameter of the obtained zirconium oxide particles B was 15 nm.

(3) Zirconium oxide particles C
Zirconium oxide particles C were produced in the same manner as zirconium oxide particles A, except that the temperature of firing in the atmosphere using an electric furnace was set to 450 ° C.
The average primary particle diameter of the obtained zirconium oxide particles C was 2 nm.

(4) Zirconium oxide particles D
Zirconium oxide particles D were produced in the same manner as zirconium oxide particles A, except that the temperature for firing in the atmosphere using an electric furnace was 650 ° C.
The average primary particle diameter of the obtained zirconium oxide particles D was 25 nm.

(5) Titanium oxide particles 242.1 g of titanium tetrachloride and 111.9 g of tin (IV) chloride pentahydrate are put into 1.5 L (liter) of pure water at 5 ° C., and the mixed solution is stirred. Produced.
Next, the mixed solution is heated to adjust the temperature to 25 ° C., and an aqueous ammonium carbonate solution having a concentration of 10% by mass is added to the mixed solution to adjust the pH to 1.5. Aged for time to remove excess chloride ions.
Next, water was removed from this mixed solution using an evaporator, and then dried to produce titanium oxide particles.
The average primary particle diameter of the obtained titanium oxide particles was 4 nm.

(6) Silica Particles Silica particles of Snowtex OXS manufactured by Nissan Chemical Industries, Ltd. were used. The average primary particle diameter of the silica particles was 5 nm.

<2. Surface modification material>
(1) Modified material A
15 g of dimethoxydimethylsilane, 5 g of trimethoxyphenylsilane, and 10 g of trimethoxymethylsilane (hereinafter referred to as “modifying material A”) are put into a mixed solution of 60 g of methanol / 10 g of water and reacted at a temperature of 50 ° C. for 12 hours. A methanol solution containing 30% by mass was obtained.

(2) Modified material B
15 g of dimethoxymethylphenylsilane, 5 g of trimethoxyphenylsilane, and 10 g of trimethoxymethylsilane (hereinafter referred to as “modifying material B”) are put into a mixed solution of 60 g of methanol / 10 g of water and reacted at a temperature of 50 ° C. for 12 hours. A methanol solution containing 30% by mass was obtained.

(3) Modified material C
10 g of dimethoxymethylphenylsilane, 5 g of trimethoxyphenylsilane, 10 g of trimethoxymethylsilane, 5 g of both-end silanol-type dimethylsilicone (X-21-5841) (hereinafter referred to as modification material C) in a mixed solution of 60 g of methanol / 10 g of water The resulting mixture was reacted at a temperature of 50 ° C. for 12 hours to obtain a methanol solution containing 30% by mass of the modifying material C.

<Example 1>
[Preparation of inorganic oxide particle dispersion]
After dissolving 50 g of a methanol solution containing 30% by mass of the modifying material A in 70 g of toluene, 15 g of zirconium oxide particles A were added. Next, 100 g of 0.1 mm diameter glass beads impregnated with 5 g of a 10% by mass acetic acid aqueous solution were added, and this mixed solution was treated with a sand grinder for 3 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 1) containing 30% by mass of surface-modified zirconium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
With respect to the obtained inorganic oxide particle dispersion 1 (10 g), a silicone resin component [phenyl silicone resin; trade name: OE-6520 (manufactured by Toray Dow Corning Co., Ltd., refractive index 1.54, liquid A / B liquid blended] Ratio = 1/1) 7.0 g (A solution 3.5 g, B solution 3.5 g)] was blended to prepare a resin composition 1.
The dispersion medium was removed from the obtained resin composition 1 by an evaporator, and it was confirmed that the amount of the dispersion medium relative to the solid content in the resin composition was less than 5% by mass.
The obtained master batch 1 was heated and cured at 150 ° C. for 1 hour to obtain a resin composite 1.

<Example 2>
[Preparation of inorganic oxide particle dispersion]
After dissolving 23 g of a methanol solution containing 30% by mass of the modifying material A in 70 g of toluene, 23.1 g of zirconium oxide particles B were added. Next, 100 g of 0.1 mm diameter glass beads impregnated with 5 g of a 10% by mass acetic acid aqueous solution were added, and this mixed solution was treated with a sand grinder for 3 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 2) containing 30% by mass of surface-modified zirconium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
Resin composition 2 was obtained in the same manner as in the preparation of resin composition 1 except that inorganic oxide particle dispersion 1 was changed to inorganic oxide particle dispersion 2.
A master batch 2 was obtained in the same manner as the preparation of the master batch 1 except that the resin composition 1 was changed to the resin composition 2.
Resin composite 2 was obtained in the same manner as in preparation of resin composite 1 except that master batch 1 was changed to master batch 2.

<Example 3>
[Preparation of inorganic oxide particle dispersion]
After dissolving 60 g of a methanol solution containing 30% by mass of the modifying material B in 70 g of toluene, 12 g of zirconium oxide particles A were added. Next, 100 g of 0.1 mm diameter glass beads impregnated with 5 g of a 10% by mass acetic acid aqueous solution were added, and this mixed solution was treated with a sand grinder for 3 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 3) containing 30% by mass of surface-modified zirconium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
Resin composition 3 was obtained in the same manner as in the preparation of resin composition 1 except that inorganic oxide particle dispersion 1 was changed to inorganic oxide particle dispersion 3.
A master batch 3 was obtained in the same manner as the preparation of the master batch 1 except that the resin composition 1 was changed to the resin composition 3.
Resin composite 3 was obtained in the same manner as in the preparation of resin composite 1 except that master batch 1 was changed to master batch 3.

<Example 4>
[Preparation of inorganic oxide particle dispersion]
After dissolving 54.6 g of a methanol solution containing 30% by mass of the modifying material C in 70 g of toluene, 13.6 g of zirconium oxide particles A were added. Next, 100 g of 0.1 mm diameter glass beads impregnated with 5 g of a 10% by mass acetic acid aqueous solution were added, and this mixed solution was treated with a sand grinder for 3 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 4) containing 30% by mass of surface-modified zirconium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
A resin composition 4 was obtained in the same manner as in the preparation of the resin composition 1 except that the inorganic oxide particle dispersion 1 was changed to the inorganic oxide particle dispersion 4.
A master batch 4 was obtained in the same manner as the preparation of the master batch 1 except that the resin composition 1 was changed to the resin composition 4.
Resin composite 4 was obtained in the same manner as in resin composite 1 except that master batch 1 was changed to master batch 4.

<Example 5>
[Preparation of inorganic oxide particle dispersion]
After dissolving 50 g of a methanol solution containing 30% by mass of the modifying material A in 70 g of toluene, 15 g of titanium oxide particles were added. Next, 100 g of 0.1 mm diameter glass beads impregnated with 5 g of a 10% by mass acetic acid aqueous solution were added, and this mixed solution was treated with a sand grinder for 3 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 5) containing 30% by mass of surface-modified titanium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
A resin composition 5 was obtained in the same manner as in the preparation of the resin composition 1 except that the inorganic oxide particle dispersion 1 was changed to the inorganic oxide particle dispersion 5.
A master batch 5 was obtained in the same manner as in the preparation of the master batch 1 except that the resin composition 1 was changed to the resin composition 5.
A resin composite 5 was obtained in the same manner as in the preparation of the resin composite 1 except that the master batch 1 was changed to the master batch 5.

<Example 6>
[Preparation of inorganic oxide particle dispersion]
After dissolving 44.3 g of a methanol solution containing 30% by mass of the modifying material A in 70 g of toluene, 16.7 g of silica particles were added. Next, 100 g of 0.1 mm diameter glass beads impregnated with 5 g of a 10% by mass acetic acid aqueous solution were added, and this mixed solution was treated with a sand grinder for 3 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. From the obtained product, water and methanol were distilled off to obtain a toluene dispersion (inorganic oxide particle dispersion 6) containing 30% by mass of surface-modified silica particles.

[Preparation of resin composition, masterbatch and resin composite]
A resin composition 6 was obtained in the same manner as in the preparation of the resin composition 1 except that the inorganic oxide particle dispersion 1 was changed to the inorganic oxide particle dispersion 6.
A master batch 6 was obtained in the same manner as in the preparation of the master batch 1 except that the resin composition 1 was changed to the resin composition 6.
Resin composite 6 was obtained in the same manner as in the preparation of resin composite 1 except that master batch 1 was changed to master batch 6.

<Example 7>
[Preparation of inorganic oxide particle dispersion]
After dissolving 50 g of a methanol solution containing 30% by mass of the modifying material A in 70 g of toluene, 15 g of zirconium oxide particles A were added. Next, 100 g of 0.1 mm diameter glass beads were added, and this mixed solution was treated with a sand grinder for 3 hours. Next, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 3 hours, then 5 g of a 10% by mass acetic acid aqueous solution was added, and further stirred at 100 ° C. for 5 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 7) containing 30% by mass of surface-modified zirconium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
A resin composition 7 was obtained in the same manner as in the preparation of the resin composition 1 except that the inorganic oxide particle dispersion 1 was changed to the inorganic oxide particle dispersion 7.
A master batch 7 was obtained in the same manner as in the preparation of the master batch 1 except that the resin composition 1 was changed to the resin composition 7.
Resin composite 7 was obtained in the same manner as in preparation of resin composite 1 except that master batch 1 was changed to master batch 7.

<Example 8>
[Preparation of inorganic oxide particle dispersion]
Into 70 g of toluene, 15 g of zirconium oxide particles A were added, and then 100 g of 0.1 mm diameter glass beads impregnated with 5 g of a 10% by mass acetic acid aqueous solution were added, and this mixed solution was treated with a sand grinder for 2 hours. Next, 50 g of a methanol solution containing 30% by mass of the modifying material A was added, and further treated with a sand grinder for 2 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 8) containing 30% by mass of surface-modified zirconium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
A resin composition 8 was obtained in the same manner as in the preparation of the resin composition 1 except that the inorganic oxide particle dispersion 1 was changed to the inorganic oxide particle dispersion 8.
A master batch 8 was obtained in the same manner as the preparation of the master batch 1 except that the resin composition 1 was changed to the resin composition 8.
Resin composite 8 was obtained in the same manner as in the preparation of resin composite 1 except that master batch 1 was changed to master batch 8.

<Comparative Example 1>
[Preparation of inorganic oxide particle dispersion]
After dissolving 71.3 g of a methanol solution containing 30% by mass of the modifying material A in 70 g of toluene, 8.6 g of zirconium oxide particles C were charged. Next, 100 g of 0.1 mm diameter glass beads impregnated with 5 g of a 10% by mass acetic acid aqueous solution were added, and this mixed solution was treated with a sand grinder for 3 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 101) containing 30% by mass of surface-modified zirconium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
A resin composition 101 was obtained in the same manner as in the preparation of the resin composition 1 except that the inorganic oxide particle dispersion 1 was changed to the inorganic oxide particle dispersion 101.
A master batch 101 was obtained in the same manner as in the preparation of the master batch 1, except that the resin composition 1 was changed to the resin composition 101.
A resin composite 101 was obtained in the same manner as in the preparation of the resin composite 1, except that the master batch 1 was changed to the master batch 101.

<Comparative example 2>
[Preparation of inorganic oxide particle dispersion]
After 4.7 g of a methanol solution containing 30% by mass of the modifying material A was dissolved in 70 g of toluene, 28.6 g of zirconium oxide particles D were added. Next, 100 g of 0.1 mm diameter glass beads impregnated with 5 g of a 10% by mass acetic acid aqueous solution were added, and this mixed solution was treated with a sand grinder for 3 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 102) containing 30% by mass of surface-modified zirconium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
A resin composition 102 was obtained in the same manner as in the preparation of the resin composition 1 except that the inorganic oxide particle dispersion 1 was changed to the inorganic oxide particle dispersion 102.
A master batch 102 was obtained in the same manner as in the preparation of the master batch 1, except that the resin composition 1 was changed to the resin composition 102.
A resin composite 102 was obtained in the same manner as the preparation of the resin composite 1 except that the master batch 1 was changed to the master batch 102.

<Comparative Example 3>
[Preparation of inorganic oxide particle dispersion]
After dissolving 50 g of a methanol solution containing 30% by mass of the modifying material A in 70 g of toluene, 15 g of zirconium oxide particles A were added. Next, this mixed solution was treated with a sand grinder for 3 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 103) containing 30% by mass of surface-modified zirconium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
A resin composition 103 was obtained in the same manner as the resin composition 1 except that the inorganic oxide particle dispersion 1 was changed to the inorganic oxide particle dispersion 103.
A master batch 103 was obtained in the same manner as in the preparation of the master batch 1, except that the resin composition 1 was changed to the resin composition 103.
A resin composite 103 was obtained in the same manner as the resin composite 1 except that the master batch 1 was changed to the master batch 103.

<Comparative example 4>
[Preparation of inorganic oxide particle dispersion]
After dissolving 50 g of a methanol solution containing 30% by mass of the modifying material B in 70 g of toluene, 15 g of zirconium oxide particles A were added. Next, 100 g of 0.1 mm diameter glass beads impregnated with 5 g of a 10% by mass acetic acid aqueous solution were added, and this mixed solution was treated with a sand grinder for 3 hours. Subsequently, the slurry collected by removing the glass beads from the treated product was stirred at 100 ° C. for 10 hours. Water and methanol were distilled off from the obtained product to obtain a toluene dispersion (inorganic oxide particle dispersion 104) containing 30% by mass of surface-modified zirconium oxide particles.

[Preparation of resin composition, masterbatch and resin composite]
A resin composition 104 was obtained in the same manner as in the preparation of the resin composition 1 except that the inorganic oxide particle dispersion 1 was changed to the inorganic oxide particle dispersion 104.
A master batch 104 was obtained in the same manner as in the preparation of the master batch 1, except that the resin composition 1 was changed to the resin composition 104.
A resin composite 104 was obtained in the same manner as in the preparation of the resin composite 1, except that the master batch 1 was changed to the master batch 104.

<Reference example>
Resin composition 201 was prepared in the same manner except that toluene was added in place of inorganic oxide particle dispersion 1 in the preparation of resin composition 1.
A master batch 201 was obtained in the same manner as in the preparation of the master batch 1, except that the resin composition 1 was changed to the resin composition 201.
Resin composite 201 was obtained in the same manner except that master batch 1 was changed to master batch 201 in the preparation of resin composite 1.

<Evaluation>
About the inorganic oxide particle dispersion liquid of Examples 1-8 and Comparative Examples 1-4, and Examples 1-8, Comparative Examples 1-4, and the masterbatch of a reference example, various evaluation is performed with the following apparatus or method. went.

(1) Residual amount of inorganic acids (chlorine amount) and carboxylic acid amount The residual amount of inorganic acids (chlorine amount) in the inorganic oxide particle dispersion (toluene dispersion) was quantified by combustion decomposition-ion chromatography. As an analysis procedure, the inorganic oxide particle dispersion is thermally decomposed in a combustion decomposition unit and burned with oxygen gas, and the generated gas is collected in an absorption liquid (hydrogen peroxide solution) by an absorption unit. The content of each collected halogen was measured by ion chromatography.
An automatic combustion halogen / sulfur analysis system SQ-1 type / HSU-35 type (manufactured by Anatech Yanaco) was used as a measuring apparatus.
The amount of carboxylic acid (hydrophobization amount) in the inorganic oxide particle dispersion (toluene dispersion) was quantified by ion chromatography. As an analysis procedure, an inorganic oxide particle dispersion and a sodium hydroxide aqueous solution are mixed, stirred and shaken for about 30 minutes to extract carboxylate ions into an aqueous layer, and then solids and oils (an organic solvent and an organic solvent). The extract from which the organic component dissolved in the organic solvent) was removed was analyzed by ion chromatography.
As a measuring apparatus, an ion chromatography system ICS-3000 type (manufactured by Nippon Dionex) was used.

(2) Viscosity The viscosity of the master batch was measured using a rheometer, Rheo Stress RS-6000 (manufactured by HAAKE). The viscosity was measured at a temperature of 25 ° C. and a shear rate of 1.0 (1 / s), and the ratio (TI) of 5 rotation viscosity / 50 rotation viscosity was calculated.

(3) Transmittance The transmittance was measured with a spectrophotometer V-570 (manufactured by JASCO Corporation) using an integrating sphere in the wavelength range of 350 nm to 800 nm.
In the measurement of the master batch, a sample in which each master batch was sandwiched between thin layer quartz cells having an optical path length of 1 mm was used as a sample. In addition, the measured value only in a quartz cell (air) was made into the blank.
In the measurement of the resin composite, a plate-like molded body having a thickness of 0.5 mm was used as a sample.
The measurement results of the transmittance of the master batch and the resin composite at a wavelength of 450 nm are shown in Table 1 below. In addition, in the wavelength longer than 450 nm, all became a value higher than the transmittance | permeability of 450 nm.

As shown in Table 1 above, the master batches of Examples 1 to 8 contain inorganic oxide particles and accompanying inorganic acids (chlorine), but their viscosities are about 11 Pa · s to 15 Pa · s. , The TI value (ratio of 5 rotational viscosity / 50 rotational viscosity) is about 1.1 to 1.5, and the viscosity of the reference example containing no inorganic oxide particles and inorganic acids (chlorine) is 9.8 Pa · s. And TI value close to 1. That is, although the master batches of Examples 1 to 8 contained inorganic oxide particles and accompanying inorganic acids (chlorine), the viscosity increase was suppressed. Thereby, workability | operativity when obtaining the resin composites 1-8 from the masterbatch of Examples 1-8 did not have a substantial difference with workability | operativity when obtaining the resin composite 201 from the masterbatch of a reference example. .
Moreover, the transmittance | permeability of the masterbatch of Example 1, 3-8 was about 80%-90%, it was close to the transmittance | permeability 90% of a reference example, and transparency was also maintained. The transmittance of the master batch of Example 2 was 63%, which was lower than that of the other examples. This is because the average primary particle size of the inorganic oxide particles used was larger than that of the other examples. It is thought that the scattering caused in

On the other hand, the master batch of Comparative Example 1 had a large specific surface area because the average primary particle diameter of the inorganic oxide particles was as small as 2 nm, and the viscosity did not decrease even when the surface modifying material was increased. Moreover, since the ratio of the surface modifying material is high, an interaction between the surface modifying materials occurs, which is considered to have also acted on the viscosity increase. For this reason, workability was poor, defoaming failure occurred during filling, and it was difficult to obtain a dense resin composite.
In the master batch of Comparative Example 2, the increase in viscosity was suppressed, but the transmittance was extremely reduced. This is because the increase in viscosity is suppressed by the effect of hydrophobicizing the inorganic oxide particles by carboxylic acid, but the inorganic oxide particles have a large particle diameter of 25 nm and the surface modification material is small, so the inorganic oxide particles It is considered that light scattering occurred due to the aggregation of particles.
Moreover, all the master batches of Comparative Examples 3 to 4 had high viscosity, and workability was deteriorated. The reason for the high viscosity is that the masterbatch of Comparative Example 3 is not hydrophobized to inorganic oxide particles by carboxylic acid, and the masterbatch of Comparative Example 4 has an excessive content of inorganic acids (chlorine). This is probably because of this. In particular, in Comparative Example 4, not only the viscosity increased but also the transmittance decreased. This is considered to be because the inorganic acids that are ionic (polar) substances formed emulsion-like particles.

DESCRIPTION OF SYMBOLS 10 Light-emitting device 12 Reflection cup 14 Light-emitting element 16 1st sealing material layer 18 2nd sealing material layer 20 Light-emitting device

Claims (10)

Inorganic oxide particles having an average primary particle diameter of 3 nm or more and 20 nm or less, the surface of which is surface-modified with a surface-modifying material containing a silane compound and a silicone compound, and hydrophobized with carboxylic acid;
A dispersion medium;
An inorganic oxide particle dispersion containing 0.1 ppm or more and 1000 ppm or less of hydrochloric acid and / or a salt thereof.   2. The inorganic oxide particle dispersion according to claim 1, wherein the surface modification amount of the surface modification material with respect to the inorganic oxide particles (surface modification material / inorganic oxide particles) is 10% by mass or more and 150% by mass or less.   The inorganic oxide particle dispersion according to claim 1, wherein the amount of carboxylic acid hydrophobized with respect to the inorganic oxide particles (carboxylic acid / inorganic oxide particles) is 0.001% by mass or more and 50% by mass or less.   A resin composition comprising the inorganic oxide particle dispersion according to any one of claims 1 to 3 and a silicone resin-forming component, wherein the content of the dispersion medium is 5% by mass or more of the total amount. Inorganic oxide particles having an average primary particle diameter of 3 nm or more and 20 nm or less, the surface of which is surface-modified with a surface-modifying material containing a silane compound and a silicone compound, and hydrophobized with carboxylic acid;
A silicone resin-forming component;
At least one of 0.1 ppm to 1000 ppm of hydrochloric acid and a salt thereof,
Furthermore, the masterbatch which does not contain a dispersion medium or whose content of a dispersion medium is less than 5 mass% of the whole quantity.   The master batch according to claim 5, wherein the dispersion medium is removed from the resin composition according to claim 4.   The master batch according to claim 5 or 6, wherein the viscosity at 25 ° C is 0.01 Pa · s or more and 1000 Pa · s or less. Inorganic oxide particles having an average primary particle diameter of 3 nm or more and 20 nm or less, the surface of which is surface-modified with a surface-modifying material containing a silane compound and a silicone compound, and hydrophobized with carboxylic acid;
Silicone resin,
A resin composite comprising 0.1 ppm or more and 1000 ppm or less of hydrochloric acid and / or a salt thereof.   The resin composite according to claim 8, wherein the master batch according to any one of claims 5 to 7 is cured.   An optical semiconductor light-emitting device comprising a semiconductor light-emitting element sealed with a sealing material layer made of the resin composite according to claim 8.