Dispersion, composition, sealing member, light-emitting device, lighting appliance, display device, method for producing dispersion, and method for modifying surface of metal oxide particles

Abstract

The dispersion liquid according to the present application contains metal oxide particles surface-modified with methyl and phenyl at a prescribed ratio, and for metal oxide particles obtained by vacuum drying the dispersion liquid, the transmittance spectrum in the wave number range of 800 cm ‑1 to 3800 cm ‑1 -1 satisfies IA / IB≤3.5, where IA is the normalized spectrum value at 3500 cm ‑1 -1, and IB is the normalized spectrum value at 1100 cm ‑1 -1.

Description

Technical Field

[0001] This invention relates to a dispersion, composition, sealing component, light-emitting device, lighting appliance, display device, method for manufacturing dispersion, and method for surface modification of metal oxide particles containing metal oxide particles surface-modified with silane compounds and silicone compounds.

[0002] This application claims priority based on Japan Patent Application No. 2020-165846 filed on September 30, 2020, the contents of which are incorporated herein by reference. Background Technology

[0003] Light-emitting diodes (LEDs) are widely used as light sources due to their advantages such as small size, long lifespan, and low-voltage operation. The LED chip within the LED package is typically sealed with a resin-containing sealant to prevent contact with deteriorating factors in the external environment, such as oxygen and moisture. Therefore, light emitted from the LED chip passes through the sealant and escapes to the outside. Thus, to increase the beam emitted from the LED package, it is important to efficiently extract the light emitted from the LED chip to the outside of the LED package.

[0004] As a sealing material for improving the extraction efficiency of light emitted from an LED chip, a composition for forming a light scattering composite containing a composition of metal oxide particles and a matrix resin is known, wherein the metal oxide particles are surface-modified with a surface-modifying material containing at least one functional group selected from alkenyl, H-Si, and alkoxy groups (for example, see Patent Document 1).

[0005] In this composition for forming a light-scattering composite, a dispersion containing metal oxide particles is mixed into a silicone resin while maintaining relative transparency. The metal oxide particles used are those with small dispersion size and high refractive index. This structure allows the light-scattering composite obtained by curing the composition to suppress the decrease in light transmittance and improve light scattering properties.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2016 / 142992 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] However, silicone resins used as sealing materials for LEDs typically contain methyl and phenyl groups as hydrocarbon groups, with the ratio of functional groups adjusted depending on the application. For example, in lighting applications, to increase the amount of light extracted from the LED chip, a structure containing a large number of phenyl groups with high refractive index is used. On the other hand, in automotive applications, to suppress the degradation of the silicone sealing resin caused by high-output LEDs, a structure containing a large number of methyl groups with high heat resistance is used.

[0011] Therefore, the surface modification design of the metal oxide particles needs to be tailored to each variety or application of the silicone sealant.

[0012] Furthermore, in recent years, the demand for methyl-based silicone resins containing a large amount of methyl groups with high heat resistance has increased in order to extend the lifespan of LEDs. Compared with conventionally used phenyl-based silicone resins, methyl-based silicone resins have a higher methyl content and a greater degree of hydrophobicity. Therefore, even when metal oxide particles with hydrophobic surfaces, as described in Patent Document 1, are mixed with methyl-based silicone resins, the metal oxide particles tend to aggregate, resulting in a problem where a transparent composition cannot be obtained.

[0013] To address the aforementioned issues, a method was investigated in which metal oxide particles are directly dispersed in a silane compound for primary modification, followed by secondary modification of the silicone compound, thereby obtaining surface-modified metal oxide particles that can be dispersed in methyl-based silicone resins. Hereinafter, "surface-modified metal oxide particles" will sometimes be simply referred to as "surface-modified metal oxide particles."

[0014] However, the surface-modified metal oxide particles obtained by the above method cannot be dispersed in phenyl-based silicone resins containing a large amount of phenyl groups.

[0015] Therefore, it is necessary to have surface-modified metal oxide particles that can be dispersed in both methyl silicone resins and phenyl silicone resins.

[0016] The present invention was made to solve the above-mentioned problems, and its object is to provide a dispersion containing surface-modified metal oxide particles that can be dispersed in both methyl silicone resin and phenyl silicone resin, a composition containing the dispersion, a sealing component formed using the composition, a light-emitting device having the sealing component, an illumination appliance and a display device having the light-emitting device, a method for manufacturing the dispersion, and a method for surface modification of the metal oxide particles.

[0017] Solution for solving the problem

[0018] To address the aforementioned issues, a first aspect of the present invention provides a dispersion comprising metal oxide particles surface-modified with at least one silane compound and at least one silicone compound, and a solvent, wherein the silane compound contains a methyl group, the silicone compound contains a hydrocarbon group having two or more carbon atoms, and the molar ratio (methyl / hydrocarbon group) of the methyl group to the hydrocarbon group in the metal oxide particles is 0.01 or more and 10 or less.

[0019] The metal oxide particles obtained by drying the dispersion under vacuum were measured at 800 cm⁻¹ using a Fourier transform infrared spectrophotometer. -1 Above and 3800cm -1 The following equation (1) is satisfied when the transmission spectrum values ​​in the following wavenumber range are normalized such that the maximum value of the transmission spectrum in the range is 100 and the minimum value is 0.

[0020] IA / IB≤3.5 (1)

[0021] (In the formula, "IA" represents 3500cm) -1 The standardized spectral value below, "IB" represents 1100 cm⁻¹ -1 (The standardized spectral values ​​below.)

[0022] In the first aspect of the present invention, the hydrocarbon group having 2 or more carbon atoms can be an aromatic hydrocarbon group.

[0023] To address the aforementioned issues, a second aspect of the present invention provides a composition comprising the aforementioned dispersion and a silicone resin component.

[0024] To address the aforementioned issues, a third aspect of the present invention provides a sealing component, which is a cured product of the aforementioned composition.

[0025] To address the aforementioned issues, a fourth aspect of the present invention provides a light-emitting device comprising the aforementioned sealing member and a light-emitting element sealed by the aforementioned sealing member.

[0026] To address the aforementioned issues, a fifth aspect of the present invention provides a lighting fixture comprising the aforementioned light-emitting device.

[0027] To address the aforementioned issues, a sixth aspect of the present invention provides a display device comprising the aforementioned light-emitting device.

[0028] To address the aforementioned issues, the seventh aspect of the present invention provides a method for manufacturing a dispersion according to the first aspect.

[0029] To address the aforementioned issues, the eighth aspect of this invention provides a method for surface modification of metal oxide particles.

[0030] The effects of the invention

[0031] According to the present invention, it is possible to provide a dispersion containing surface-modified metal oxide particles that can be dispersed in both methyl silicone resins and phenyl silicone resins, a composition containing the dispersion, a sealing component formed using the composition, a light-emitting device having the sealing component, an illumination appliance having the light-emitting device, a display device, a method for manufacturing the dispersion, and a method for surface modification of the metal oxide particles. Attached Figure Description

[0032] Figure 1 This is a schematic diagram illustrating a preferred example of a light-emitting device according to an embodiment of the present invention.

[0033] Figure 2 This is a schematic diagram illustrating another preferred example of the light-emitting device according to an embodiment of the present invention.

[0034] Figure 3 This is a schematic diagram illustrating another preferred example of the light-emitting device according to an embodiment of the present invention.

[0035] Figure 4 This is a schematic diagram illustrating another preferred example of the light-emitting device according to an embodiment of the present invention. Detailed Implementation

[0036] Examples of preferred embodiments of the dispersion of the present invention, the composition containing the dispersion, the sealing component formed using the composition, the light-emitting device having the sealing component, the lighting fixture and display device having the light-emitting device, the method for manufacturing the dispersion, and the surface modification method for metal oxide particles will be described.

[0037] Furthermore, this embodiment is described in detail to better understand the spirit of the invention, and is not limited to this invention unless otherwise specified. For example, unless there are special limitations, conditions such as materials, quantities, types, quantities, sizes, ratios, sequences, times, and temperatures can be changed, added, or omitted as needed.

[0038] <1. The inventors' concept>

[0039] First, before describing the invention in detail, the inventors' conception for developing the invention will be explained.

[0040] Typically, in the manufacture of sealing materials (compositions) used as raw materials for sealing components, metal oxide particles are modified with surface-modifying materials and dispersed in resins such as silicone resins. However, compared to conventionally used phenyl silicone resins, methyl-based silicone resins have a higher methyl content and greater hydrophobicity. Therefore, as mentioned above, even when using metal oxide particles modified with surface-modifying materials, it is difficult to uniformly disperse the metal oxide particles in methyl-based silicone resins.

[0041] Therefore, the inventors conducted in-depth research to solve the problem. As a result, they found that even simply increasing the amount of surface-modifying material used did not significantly improve the dispersibility of metal oxide particles in methyl silicone resins.

[0042] Having obtained this result, the inventors further investigated the modification state of the surface modification material on the surface of the metal oxide particles. The investigation was based on the following idea: that even when a large amount of surface modification material is used to modify the metal oxide particles, if only a small amount of surface modification material adheres to the surface of the metal oxide particles, the surface of the metal oxide particles will not be sufficiently hydrophobic. On the other hand, it is assumed that even when a small amount of surface modification material is used to modify the metal oxide particles, the adhesion ratio of the surface modification material to the surface of the metal oxide particles is high, and when a large amount of surface modification material adheres to the surface of the metal oxide particles, the surface of the metal oxide particles is sufficiently hydrophobic.

[0043] Furthermore, the inventors discovered that when using silane compounds or silicone compounds as surface modification materials, the degree of adhesion of the surface modification material to the metal oxide particles described above can be measured and observed using a Fourier transform infrared spectrophotometer (FT-IR). They also discovered that when metal oxide particles are surface-modified using silane compounds and silicone compounds via the method described later, the metal oxide particles can be dispersed in methyl-based silicone resins, which are previously difficult to disperse. Moreover, they found that by using a methyl-containing silane compound and a silicone compound containing a hydrocarbon group having two or more carbon atoms, with a molar ratio of methyl to hydrocarbon group of 0.01 or more and 10 or less, surface-modified metal oxide particles that can be dispersed in both methyl-based and phenyl-based silicone resins can be obtained.

[0044] <2. Dispersion>

[0045] The dispersion involved in this embodiment will be described.

[0046] The dispersion involved in this embodiment contains metal oxide particles that have been surface-modified using at least one silane compound and at least one silicone compound, and a solvent. The silane compound contains a methyl group, and the silicone compound contains a hydrocarbon group having two or more carbon atoms. The ratio of the methyl group to the hydrocarbon group in the metal oxide particles (methyl / hydrocarbon group) is 0.01 or more and 10 or less.

[0047] Furthermore, in this embodiment, the metal oxide particles obtained by drying the dispersion through vacuum drying are measured at 800 cm⁻¹ using a Fourier transform infrared spectrophotometer. -1 Above and 3800cm -1 The following equation (1) is satisfied when the measured transmission spectrum values ​​are normalized such that the maximum value of the transmission spectrum in the range is 100 and the minimum value is 0.

[0048] IA / IB≤3.5 (1)

[0049] (In the formula, "IA" represents 3500cm) -1 The standardized spectral value below, "IB" represents 1100 cm⁻¹ -1 (The standardized spectral values ​​below.)

[0050] By satisfying the above conditions, the dispersion involved in this embodiment can be dispersed in both methyl silicone resin and phenyl silicone resin.

[0051] Specifically, in the transmission spectrum measured using a Fourier transform infrared spectrophotometer, the wavenumber is 1100 cm⁻¹. -1 The position is attributed to a siloxane bond (Si-O-Si bond), wavenumber 3500 cm⁻¹ -1 The position is attributed to a silanol group (Si-OH group). Silane compounds and silicone compounds contain Si-OH groups capable of forming Si-O-Si bonds and groups capable of forming Si-OH groups, respectively. Therefore, by comparing 3500cm -1 The spectral values ​​(IA) and 1100 cm⁻¹ below -1 The spectral values ​​(IB) below can be used to observe the degree of reaction of Si-OH groups or groups that can form Si-OH groups in silane and silicone compounds.

[0052] Furthermore, the inventors discovered that when the IA / IB ratio is 3.5 or less, the silane compound sufficiently adheres to the surface of the metal oxide particles. This characteristic allows the metal oxide particles to disperse within the methyl silicone resin without agglomerating.

[0053] In contrast, when the IA / IB ratio exceeds 3.5, the silane and silicone compounds do not sufficiently adhere to the surface of the metal oxide particles, resulting in poor dispersibility of the metal oxide particles in the methyl silicone resin. Consequently, when the dispersion and the methyl silicone resin are mixed, aggregation of the metal oxide particles tends to occur, leading to turbidity in the obtained composition. The IA / IB ratio is, as described above, 3.5 or less, preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less.

[0054] Furthermore, the lower limit of IA / IB is preferably IA = 0, and therefore 0. However, even if a small amount of residual silanol groups (Si-OH groups) remain, it can still be mixed with methyl silicone resins, so the lower limit of IA / IB can be 0, 0.1, 0.2, 0.5, 0.8, 1.0, or 1.5.

[0055] In addition, the determination of the transmission spectrum of metal oxide particles using a Fourier transform infrared spectrophotometer (FT-IR) can be specifically performed as follows.

[0056] The dispersion of this embodiment is dried by vacuum drying. The drying conditions can be adjusted appropriately according to the amount and concentration of the dispersion. For example, if 10g of a dispersion with a solid content of 30% by mass is used, drying at 100°C and below 20hPa for more than 2 hours is sufficient. As a vacuum dryer, for example, the VACUUM OVEN VOS-201SD manufactured by EYELA TOKYO RIKAKIKAI CO,LTD. can be used.

[0057] Next, by using 0.01 g to 0.05 g of metal oxide particles obtained by drying, it is possible to perform measurements using a Fourier transform infrared spectrophotometer (e.g., JASCO Corporation, model: FT / IR-670Plus).

[0058] However, conventional surface-modified metal oxide particles, even those with an IA / IB ratio of 3.5 or less, are difficult to disperse in phenyl silicone resins.

[0059] Therefore, the inventors conducted further research and discovered that by performing surface modification in such a way that the molar ratio of the methyl group to the hydrocarbon group is 0.01 or more and 10 or less, surface-modified metal oxide particles that can be dispersed in both methyl-based silicone resins and phenyl-based silicone resins can be obtained.

[0060] To disperse it in methyl-based silicone resins, surface modification of the metal oxide particles in methyl-containing silane compounds is necessary. However, the metal oxide particles surface-modified using this method have poor affinity for the phenyl groups contained in LED silicone resins. Furthermore, silicone compounds have a higher affinity for silicone resins compared to silane compounds. Therefore, it is hypothesized that by surface treatment with silicone compounds containing hydrocarbon groups with two or more carbon atoms, which have a higher affinity for phenyl groups than for methyl groups, highly versatile surface-modified metal oxide particles that can be dispersed in both methyl-based and phenyl-based silicone resins can be obtained.

[0061] The inventors believed that surface-modified metal oxide particles, which can be dispersed in methyl-based silicone resins, are difficult to disperse in phenyl-based silicone resins due to their increased affinity for methyl groups. Therefore, by adjusting the molar ratio of methyl groups to hydrocarbon groups with two or more carbon atoms, it was unexpected that highly versatile surface-modified metal oxide particles could be dispersed in both methyl-based and phenyl-based silicone resins.

[0062] In this embodiment, the molar ratio (methyl / hydrocarbon group) of the methyl group to the hydrocarbon group in the metal oxide particles is 0.01 or more and 10 or less, preferably 0.03 or more and 8 or less, more preferably 0.05 or more and 5 or less, and even more preferably 0.1 or more and 3 or less. Depending on the requirements, the molar ratio can be 0.2 to 0.8, 0.8 to 2, 2 to 6, 6 to 9, etc.

[0063] With a molar ratio of 0.01 or higher and 10 or lower, metal oxide particles can be transparently dispersed in both methyl and phenyl silicone resins. When the molar ratio of methyl to hydrocarbon groups is less than 0.01, there are too few methyl groups to disperse in methyl silicone resins. On the other hand, if the molar ratio of methyl to hydrocarbon groups exceeds 10, it cannot be dispersed in phenyl silicone resins.

[0064] The molar ratio of methyl groups to hydrocarbon groups with two or more carbon atoms in metal oxide particles refers to the ratio determined using NMR (nuclear magnetic resonance spectroscopy) by the following method. Specifically, it refers to the molar ratio of methyl groups to hydrocarbon groups with two or more carbon atoms contained in surface-modified metal oxide particles. Therefore, it essentially refers to the molar ratio of methyl groups to hydrocarbon groups with two or more carbon atoms contained in silane compounds and silicone compounds.

[0065] 15 g of a dispersion with a solid content adjusted to 30% by mass was mixed with 15 g of methanol to precipitate the surface-modified metal oxide particles. The mixture was then subjected to solid-liquid separation using a centrifuge to recover the solid fraction (surface-modified metal oxide particles). A few milligrams of the recovered surface-modified metal oxide particles were collected and dissolved in dichloroform to a concentration of 1% by mass. Using this solution, an NMR apparatus, such as a benchtop NMR spectrometer (manufactured by Nanalysis Scientific Corp., model NMReady60Pro), was used. 1 H / 19 F)), to determine hydrocarbon groups with 2 or more carbon atoms and methyl groups. 1 H-liquid NMR spectroscopy. The spectral areas (integral values) of hydrocarbon groups with 2 or more carbon atoms and methyl groups are calculated based on the obtained spectra, and the integral value of methyl is divided by the integral value of hydrocarbon groups with 2 or more carbon atoms. Therefore, the molar ratio of methyl to hydrocarbon groups with 2 or more carbon atoms can be calculated.

[0066] In addition, the solid content of the dispersion does not need to be 30% by mass; it is sufficient to collect the amount required for NMR determination.

[0067] (2.1 Metal oxide particles)

[0068] Metal oxide particles scatter light emitted from the light-emitting element within the sealing component described later. Furthermore, the metal oxide particles, depending on their type, increase the refractive index of the sealing component. Thus, the metal oxide particles contribute to increasing the brightness of the light in the light-emitting device.

[0069] There is no particular limitation on the metal oxide particles used. In this embodiment, the metal oxide particles preferably include those selected from zirconium oxide particles, titanium oxide particles, zinc oxide particles, iron oxide particles, copper oxide particles, tin oxide particles, aluminum oxide particles, tantalum oxide particles, niobium oxide particles, tungsten oxide particles, europium oxide particles, yttrium oxide particles, molybdenum oxide particles, indium oxide particles, antimony oxide particles, germanium oxide particles, zinc oxide particles, bismuth oxide particles, and hafnium oxide particles, as well as potassium titanate particles, barium titanate particles, strontium titanate particles, potassium niobate particles, lithium niobate particles, and calcium tungstate particles. Metal oxide particles of at least one of the following groups: ytterbium oxide stabilized zirconia particles, cerium oxide stabilized zirconia particles, calcium oxide stabilized zirconia particles, magnesium oxide stabilized zirconia particles, scandium oxide stabilized zirconia particles, hafnium oxide stabilized zirconia particles, yttrium oxide stabilized zirconia particles, cerium oxide stabilized zirconia particles, indium oxide stabilized zirconia particles, strontium oxide stabilized zirconia particles, samarium oxide stabilized zirconia particles, gadolinium oxide stabilized zirconia particles, antimony-added tin oxide particles, and indium-added tin oxide particles.

[0070] From the viewpoint of improving transparency or compatibility (affinity) with the sealing resin (resin component), the metal oxide particles are preferably selected from at least one of the group consisting of zirconium oxide particles and titanium oxide particles.

[0071] Furthermore, from the viewpoint of improving the refractive index of the sealing component, the metal oxide particles preferably have a refractive index of 1.7 or higher. The upper limit of the refractive index can be arbitrarily chosen, for example, it can be 3.0 or lower, or 2.5 or lower, but is not limited to this.

[0072] The metal oxide particles are more preferably at least one of zirconium oxide particles and titanium oxide particles, and especially preferably zirconium oxide particles.

[0073] The average primary particle size of the metal oxide particles is preferably 1 nm or more and 200 nm or less, more preferably 3 nm or more and 150 nm or less, and even more preferably 10 nm or more and 100 nm or less. Depending on the requirements, it can also be 5–30 nm, 30–50 nm, 50–80 nm, 80–130 nm, etc. By ensuring the average primary particle size of the metal oxide particles is within the above range, the reduction in transparency of the sealing component can be suppressed. As a result, the brightness of the light emitted by the light-emitting device can be further improved.

[0074] The average first diameter of metal oxide particles can be determined, for example, by observation using a transmission electron microscope (TEM). First, inorganic oxide particles are observed using a TEM to obtain TEM images. Next, a predetermined number of inorganic oxide particles are selected from the TEM images, for example, 100. Then, the longest linear dimension (maximum major diameter) of each of these inorganic oxide particles is measured, and these measured values ​​are arithmetically averaged.

[0075] Here, when metal oxide particles aggregate together, the aggregate size is not measured. Instead, the maximum major diameter of a specified number of metal oxide particles constituting the aggregate (primary particles) is measured and taken as the average primary particle size.

[0076] The average dispersed particle size of the metal oxide particles in the dispersion of this embodiment is not particularly limited, but is, for example, 10 nm or more and 300 nm or less, preferably 20 nm or more and 250 nm or less, and more preferably 30 nm or more and 200 nm or less. Depending on the need, it may also be 50 nm or more and 180 nm or less, or 100 nm or more and 150 nm or less. With an average dispersed particle size of 10 nm or more, the brightness of the light emitted by the light-emitting device described later using this dispersion is improved. Furthermore, with an average dispersed particle size of 300 nm or less, the reduction in light transmittance of the dispersion, the composition described later using this dispersion, or the sealing component can be suppressed. As a result, the brightness of the light emitted by the light-emitting device is improved.

[0077] Furthermore, the average dispersed particle size of the metal oxide particles can be the particle size D50 of the metal oxide particles when the cumulative percentage of the scattering intensity distribution obtained by dynamic light scattering is 50%, which can be measured using a dynamic light scattering particle size analyzer (e.g., manufactured by HORIBA, Ltd., model: SZ-100SP). A quartz cell with a path length of 10 mm × 10 mm can be used to measure the dispersion with a solid content adjusted to 5% by mass. In this specification, "solid content" refers to the residue remaining after removing volatile components from the dispersion. For example, by placing 1.2 g of the dispersion in a magnetic crucible and heating it at 150°C for 1 hour using a hot plate, the non-volatile residue (metal oxide particles or surface modification materials, etc.) can be considered as the solid content.

[0078] Furthermore, regardless of whether the metal oxide particles are dispersed in a primary or secondary particle state, the average dispersed particle size of the metal oxide particles is measured and calculated based on the diameter of the dispersed metal oxide particles. In this embodiment, the average dispersed particle size of the metal oxide particles can also be measured as the average dispersed particle size of metal oxide particles with attached surface modification material. In the dispersion, there may be metal oxide particles with and without attached surface modification material. Therefore, typically, the average dispersed particle size of the metal oxide particles is measured as a value in their mixed state.

[0079] The surface modification material described above is attached to the surface of the metal oxide particles. As a result, the metal oxide particles are stably dispersed in dispersions and compositions made using the metal oxide particles.

[0080] (2.2 Silane compounds)

[0081] The surface-modified metal oxide particles involved in this embodiment are formed by surface modification of metal oxide particles with a methyl-containing silane compound. The methyl-containing silane compound can refer to a silane compound containing a methyl group but not a hydrocarbon group with two or more carbon atoms.

[0082] In this embodiment, as long as the methyl / hydrocarbon group of the metal oxide particles is within the specified range, silane compounds containing methyl groups can be used simultaneously, as well as silane compounds containing hydrocarbon groups with 2 or more carbon atoms. Furthermore, silane compounds containing functional groups other than methyl groups or hydrocarbon groups with 2 or more carbon atoms can also be used simultaneously. The number (types) of silane compounds used in this embodiment are not particularly limited; for example, they can be 1 to 10, 2 to 8, 3 to 6, 4 to 5, etc.

[0083] From the viewpoint of enabling more silane compounds to adhere to the metal oxide particles, in this embodiment, it is necessary to modify the surface of the metal oxide particles using a methyl-containing silane compound. However, if the methyl-containing silane compound sufficiently adheres to the surface of the metal oxide particles, subsequent surface modification is not particularly limited as long as it does not hinder or improve compatibility with the silicone resin. Silicone resins for LEDs typically contain methyl and phenyl groups as hydrocarbon groups. Therefore, in this embodiment, the silane compound can be used for both primary and secondary modification using a methyl-containing silane compound, or it can be used for primary modification followed by secondary modification using a silane compound containing a hydrocarbon group with 2 or more carbon atoms. From the viewpoint of improving compatibility with the phenyl groups in the LED silicone resin and improving the stability of the dispersion, it is preferable to modify the surface of the metal oxide particles using a methyl-containing silane compound and a silane compound containing a hydrocarbon group with 2 or more carbon atoms. Therefore, in this embodiment, at least one silane compound preferably contains a methyl group and a hydrocarbon group with 2 or more carbon atoms.

[0084] At least a portion of these silane compounds adheres to the surface of the metal oxide particles, thus preventing particle aggregation by modifying the surface. Furthermore, it improves compatibility with silicone resin components used in LEDs; in other words, it improves compatibility with silicone resin components containing methyl and phenyl groups.

[0085] Here, "attachment" of silane compounds to metal oxide particles refers to the contact or bonding of silane compounds with metal oxide particles through interactions or reactions between them. Examples of contact include physical adsorption. Examples of bonding include ionic bonds, hydrogen bonds, and covalent bonds.

[0086] There are no particular limitations on the silane compound containing methyl groups, as long as it is a compound capable of adhering to the surface of metal oxide particles. Silane compounds containing methyl and alkoxy groups, silane compounds containing methyl and H-Si groups, and silane compounds containing methyl, alkoxy, and H-Si groups can be used.

[0087] A methyl-containing silane compound can be used alone or in combination of two or more. As a methyl-containing silane compound, silane compounds containing alkoxy groups, especially methoxy groups, readily adhere to metal oxide particles and are therefore preferred.

[0088] As a silane compound containing methyl and alkoxy groups, for example, at least one can be used selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, methoxydimethyl(phenyl)silane, ethoxydimethyl(phenyl)silane, dimethyl(methoxy)phenylsilane, and dimethyl(ethoxy)phenylsilane.

[0089] As a silane compound containing methyl and H-Si groups, at least one selected from the group consisting of dimethylchlorosilane, methyldichlorosilane, and methylphenylchlorosilane can be used.

[0090] As a silane compound containing methyl, alkoxy, and H-Si groups, for example, diethoxymethylsilane or ethoxydimethylsilane can be used.

[0091] From the viewpoint that silane compounds containing methyl groups have low viscosity and facilitate the dispersion of metal oxide particles in the dispersion process described later, it is preferable to include silane compounds containing methyl and alkoxy groups.

[0092] In this silane compound containing methyl and alkoxy groups, the number of alkoxy groups is preferably 1 or more and 3 or less, more preferably 3. The number of carbon atoms in the alkoxy groups is preferably 1 or more and 5 or less, and also preferably 2 or more and 4 or less.

[0093] The number of methyl groups in silane compounds containing methyl and alkoxy groups is preferably 1 or more and 3 or less, more preferably 1.

[0094] The total number of alkoxy and methyl groups in silane compounds containing methyl and alkoxy groups is 2 or more and 4 or less, preferably 4.

[0095] Such methyl-containing silane compounds include, for example, at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, and methyltripropoxysilane. From the viewpoint of easy adhesion to the surface of metal oxide particles, methyltrimethoxysilane is preferred, methyltriethoxysilane is more preferred, and methyltrimethoxysilane is more preferably used.

[0096] There are no particular limitations on the hydrocarbon groups containing two or more carbon atoms in silane compounds, as long as they are compatible with silicone resins used in LEDs. For example, they can be aliphatic hydrocarbon groups with two or more carbon atoms, or they can be aromatic hydrocarbon groups.

[0097] The number of carbon atoms in the hydrocarbon group can be appropriately selected based on the types of functional groups contained in the silicone resin for LEDs. Since silicone resins for LEDs typically contain methyl and phenyl groups, the number of carbon atoms is preferably 2 or more and 20 or less, more preferably 3 or more and 16 or less, even more preferably 4 or more and 12 or less, and even more preferably 5 or more and 9 or less.

[0098] As an aliphatic hydrocarbon group, alkyl, alkenyl, and ynyl groups can be used. They can be either chain-type or cyclic aliphatic hydrocarbon groups. Examples of alkyl groups include ethyl, propyl, butyl, pentyl, and hexyl. Examples of alkenyl groups include vinyl, allyl, propenyl, and butenyl. Examples of ynyl groups include ethynyl, propynyl, and butynyl.

[0099] As an aromatic hydrocarbon group, aryl or aralkyl can be used.

[0100] As an aryl group, phenyl, tolyl, xylyl, biphenyl, 1-naphthyl, 2-naphthyl, phenanthrene, etc., can be used.

[0101] As aralkyl groups, for example, triphenylmethyl, benzyl, phenethyl, phenylpropyl, styryl, benzylene, etc. can be used.

[0102] From the viewpoint of excellent compatibility with silicone resins for LEDs, the hydrocarbon group having 2 or more carbon atoms is preferably phenyl or xylyl, and more preferably phenyl.

[0103] As a silane compound containing a hydrocarbon group having two or more carbon atoms, at least one selected from the group consisting of phenyltrimethoxysilane, phenyltriethoxysilane, methylphenylchlorosilane, diphenylchlorosilane, phenyldichlorosilane, methylphenyldimethoxysilane, diphenylmonomethoxysilane, methylphenyldiethoxysilane, and diphenylmonoethoxysilane can be used. From the viewpoint of ease of adjustment to improve compatibility with silicone resins for LEDs, phenyltrimethoxysilane is preferred.

[0104] The content of the silane compound in the dispersion is not particularly limited, but relative to the amount of metal oxide particles, it is preferably 50% by mass or more and 700% by mass or less, more preferably 70% by mass or more and 600% by mass or less, and even more preferably 90% by mass or more and 500% by mass or less. Depending on the need, it can also be 120-400% by mass, 150-300% by mass, etc. This allows the silane compound to adhere densely to the surface of the metal oxide particles, improving both the dispersion stability of the metal oxide particles and the dispersibility in methyl-based and phenyl-based silicone resins.

[0105] (2.3 Silicone Compounds)

[0106] Silicone compounds containing hydrocarbon groups with 2 or more carbon atoms have relatively large molecular weights, which helps to improve their affinity with the silicone resin component described later. These silicone compounds are present near the surface of the metal oxide particles surface-modified with the aforementioned silane compounds. The silicone compounds also act as a mediator between the metal oxide particles surface-modified with the aforementioned silane compounds and the silicone resin component described later. Therefore, there is no particular limitation as long as the silicone compound contains hydrocarbon groups with 2 or more carbon atoms and is compatible with both the metal oxide particles surface-modified with the aforementioned silane compounds and the silicone resin component. Furthermore, the silicone compound may or may not contain methyl groups. The number (types) of silicone compounds used in this embodiment are not particularly limited; for example, it may be 1 to 10 types, 2 to 8 types, 3 to 6 types, 4 to 5 types, etc.

[0107] The aforementioned silicone compound only needs to exist between the metal oxide particles that have been surface-modified with the aforementioned silane compound and the silicone resin component. Therefore, it only needs to exist near the surface of the metal oxide particles that have been surface-modified with the aforementioned silane compound. It can be attached to the metal oxide particles that have been surface-modified with the aforementioned silane compound, or it can be not attached to the metal oxide particles that have been surface-modified with the aforementioned silane compound.

[0108] That is, in this embodiment, "surface modification using silane compounds and silicone compounds" means that the silane compound is attached to the metal oxide particles and the silicone compound exists near the surface of the metal oxide particles to which the silane compound is attached.

[0109] The silicone resin for LEDs contains methyl and phenyl groups; therefore, the silicone compound of this embodiment may contain methyl groups in addition to hydrocarbon groups having 2 or more carbon atoms. The hydrocarbon groups having 2 or more carbon atoms can be the same groups described in the silane compounds above.

[0110] Furthermore, the silicone compound of this embodiment can also be a silicone compound that does not contain a hydrocarbon group having 2 or more carbon atoms and contains a methyl group.

[0111] Examples of silicone compounds containing hydrocarbon groups with two or more carbon atoms include alkoxy-containing phenyl silicones, methylphenyl silicones, methylphenylhydrosilicones, diphenylhydrosilicones, alkoxy-terminated phenyl silicones, alkoxy-terminated methylphenyl silicones, alkoxy-containing methylphenyl silicones, and alkoxy-containing phenyl silicones. These silicone compounds can be used alone or in combination of two or more.

[0112] Examples of silicone compounds that do not contain a hydrocarbon group with two or more carbon atoms but contain a methyl group include dimethyl silicone, methylhydrosilicon, alkoxy-containing dimethyl silicone, and alkoxy-terminated trimethyl-terminated (methyl-terminated) dimethyl silicone. These silicone compounds can be used alone or in combination of two or more.

[0113] The aforementioned silicone compound can be a monomer, an oligomer, or a resin (polymer). Since surface modification is easy, monomers or oligomers are preferred.

[0114] From the viewpoint of ease of reaction and high degree of hydrophobicity, the silicone compound containing a hydrocarbon group having 2 or more carbon atoms preferably contains at least one of the following: alkoxy-containing phenyl silicone, methyl phenyl silicone, alkoxy-terminated phenyl silicone, alkoxy-terminated methyl phenyl silicone, alkoxy-containing methyl phenyl silicone, and alkoxy-containing phenyl silicone; more preferably, it contains methoxy-containing phenyl silicone.

[0115] Furthermore, from the viewpoint of ease of reaction, the methyl-containing silicone compound that does not contain a hydrocarbon group having 2 or more carbon atoms preferably contains dimethyl silicone, alkoxy-containing dimethyl silicone, alkoxy-terminated trimethyl-terminated (methyl-terminated) dimethyl silicone, and more preferably contains at least one selected from the group consisting of dimethyl silicone and methoxy-containing dimethyl silicone.

[0116] The content of silicone compound in the dispersion is not particularly limited, but relative to the metal oxide particles, it is preferably 10% by mass or more and 500% by mass or less, more preferably 15% by mass or more and 400% by mass or less, and even more preferably 100% by mass or more and 300% by mass or less. Depending on the need, it may also be 20% by mass or more and 250% by mass or less, 30% by mass or more and 200% by mass or less, or 50% by mass or more and 100% by mass or less. This allows a sufficient amount of silicone compound to adhere to the surface of the metal oxide particles, improving both the dispersion stability of the metal oxide particles and their dispersibility in methyl silicone resins. Furthermore, it reduces the amount of free silicone compound, suppressing unintended aggregation of metal oxide particles in both methyl and phenyl silicone resins.

[0117] Furthermore, the dispersion may also contain other common surface-modifying materials or dispersants besides the aforementioned silane compounds and silicone compounds as surface-modifying materials.

[0118] The total content of silane and silicone compounds is not particularly limited relative to the amount of metal oxide particles, but is preferably 100% by mass or more and 1000% by mass or less, more preferably 150% by mass or more and 800% by mass or less, and even more preferably 190% by mass or more and 600% by mass or less. It can also be 250-500% by mass, 300-400% by mass, etc., depending on the requirements. If the total amount of silane and silicone compounds is within the above range, the amount of free silane or silicone compounds can be reduced, and the dispersibility of the metal oxide particles can be sufficiently improved.

[0119] (2.4 Solvent)

[0120] The dispersion described in this embodiment contains a solvent for dispersing metal oxide particles as a dispersion medium. This solvent is not particularly limited as long as it can disperse the metal oxide particles to which the silane compound is attached and can be mixed with the silicone resin component described later; a hydrophobic solvent is preferred.

[0121] Examples of such hydrophobic solvents include aromatic hydrocarbons, saturated hydrocarbons, and unsaturated hydrocarbons. These hydrophobic solvents can be used alone or in combination of two or more.

[0122] In the above, hydrophobic solvents are preferably aromatic, and more particularly aromatic hydrocarbons. Aromatic solvents have excellent compatibility with silicone resins for LEDs, which helps to improve the viscosity characteristics of the resulting composition and the quality (transparency, shape, etc.) of the formed sealing components.

[0123] Examples of such aromatic hydrocarbons include benzene, toluene, ethylbenzene, 1-phenylpropane, isopropylbenzene, n-butylbenzene, tert-butylbenzene, sec-butylbenzene, o-xylene, m-xylene, p-xylene, 2-ethyltoluene, 3-ethyltoluene, or 4-ethyltoluene. These aromatic hydrocarbons can be used alone or in combination of two or more.

[0124] From the viewpoint of ease of operation, such as the stability of the dispersion and the removal of the hydrophobic solvent during the manufacture of the composition (described later), the hydrophobic solvent is preferably at least one selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, and benzene, and more preferably toluene.

[0125] The solvent content in the dispersion can be appropriately adjusted to achieve the desired solid composition. The solvent content is preferably 40% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, and even more preferably 60% by mass or more and 80% by mass or less. This makes mixing the dispersion with the resin components described later, especially silicone resins for LEDs, easier.

[0126] The dispersion of this embodiment may contain a hydrophilic solvent. For example, due to the method described later, a hydrophilic solvent may be included in the dispersion. Examples of such hydrophilic solvents include alcohol-based solvents, ketone-based solvents, and nitrile-based solvents. One of these hydrophilic solvents may be used alone, or two or more may be used in combination.

[0127] Examples of alcohol solvents include branched or straight-chain alcohols with 1 to 4 carbon atoms and their ether condensates. These alcohol solvents can be used alone or in combination of two or more. Furthermore, the alcohol compound contained in the alcohol solvent can be any of primary, secondary, and tertiary alcohols. Also, the alcohol compound contained in the alcohol solvent can be any of monohydric, dihydric, and trihydric alcohols. More specifically, examples of alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, methanethiol, 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-buten-1,4-diol, 1,4-butynediol, glycerol, diethylene glycol, and 3-methoxy-1,2-propanediol.

[0128] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0129] Examples of nitrile solvents include acetonitrile.

[0130] From the viewpoint of excellent affinity with both water and hydrophobic solvents, promoting their mixing, the hydrophilic solvent preferably contains an alcohol-based solvent. In this case, the number of carbon atoms in the alcohol compound constituting the alcohol-based solvent is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less.

[0131] Of the above, methanol and ethanol, especially methanol, can fully exhibit the effects of the alcohol-based solvents and are therefore preferred for use.

[0132] Furthermore, the content of the hydrophilic solvent in the dispersion is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. It can also be 1% by mass or less, 0.5% by mass or less, or 0.1% by mass. The content of the hydrophilic solvent can also be 0% by mass.

[0133] (2.5 Other components)

[0134] The dispersion described in this embodiment may also contain components other than those described above. For example, the dispersion described in this embodiment may also contain components other than those described above as needed, such as dispersants, dispersing aids, antioxidants, flow conditioners, thickeners, pH adjusters, preservatives, and other common additives.

[0135] Furthermore, the dispersion involved in this embodiment may also contain components that can be obtained by the methods described later, such as acids, water, alcohols, etc.

[0136] Furthermore, in this specification, the dispersion involved in this embodiment is distinguished from the composition involved in this embodiment, which contains a resin component and can form a sealing component by curing. That is, the dispersion involved in this embodiment does not contain the resin component described later, to the extent that a sealing component can be formed even with simple curing. More specifically, the mass ratio of resin component to metal oxide particles in the dispersion involved in this embodiment, in terms of resin component:inorganic oxide particles, is preferably in the range of 0:100 to 40:60, more preferably in the range of 0:100 to 20:80. Depending on the need, it may also be in the range of 0:100 to 10:90, 0:100 to 5:95, or 0:100 to 2:98. The dispersion involved in this embodiment is further preferably substantially free of the resin component described later, and particularly preferably completely free of the resin component described later.

[0137] The dispersion described in this embodiment contains metal oxide particles surface-modified with a specified silane compound and a solvent, and satisfies the above formula (1). Therefore, it can be dispersed in both methyl-based and phenyl-based silicone resins. Thus, when the dispersion of this embodiment is dispersed in either methyl-based or phenyl-based silicone resin, the generation of turbidity, such as whitening, is suppressed. Furthermore, viscosity changes in LED silicone resins containing surface-modified metal oxide particles are also suppressed.

[0138] <3. Methods for manufacturing dispersions>

[0139] Next, the method for manufacturing the dispersion according to this embodiment will be described.

[0140] The method for manufacturing the dispersion according to this embodiment includes: step B, mixing a first surface-modifying material and metal oxide particles to obtain a mixture; step C, dispersing the metal oxide particles in the mixture; and step F, adding a second surface-modifying material to the mixture to obtain a dispersion. The content of the metal oxide particles in the mixture is 10% by mass or more and 49% by mass or less, and the total content of the first surface-modifying material and the metal oxide particles in the mixture is 65% by mass or more and 98% by mass or less. The first surface-modifying material is a silane compound containing methyl groups, and the second surface-modifying material comprises a silicone compound containing a hydrocarbon group having two or more carbon atoms.

[0141] Depending on the requirements, the content of the metal oxide particles in the mixture may also be 15% by mass or more and 45% by mass or less, 20% by mass or more and 40% by mass or less, 25% by mass or more and 35% by mass or less, or 30% by mass or more and 33% by mass or less. Depending on the requirements, the total content of the first surface modification material and the metal oxide particles in the mixture may also be 68% by mass or more and 97% by mass or less, 69% by mass or more and 96% by mass or less, 70% by mass or more and 95% by mass or less, 75% by mass or more and 90% by mass or less, or 80% by mass or more and 85% by mass or less.

[0142] That is, the method for manufacturing the dispersion according to this embodiment includes: step B, mixing a methyl-containing silane compound and metal oxide particles to obtain a mixture; step C, dispersing the metal oxide particles in the mixture to obtain a dispersion (first dispersion); and step F, adding a silicone compound containing a hydrocarbon group having two or more carbon atoms to the dispersion containing the metal oxide particles to obtain a dispersion (third dispersion).

[0143] Furthermore, the method for manufacturing the dispersion according to this embodiment is also a surface modification method for metal oxide particles. Therefore, it can also be described as follows.

[0144] That is, the surface modification method for metal oxide particles according to this embodiment includes: step B, mixing a first surface modification material and metal oxide particles to obtain a mixture; step C, dispersing the metal oxide particles in the mixture; and step F, adding a second surface modification material to the mixture. The content of the metal oxide particles in the mixture is 10% by mass or more and 49% by mass or less, and the total content of the first surface modification material and the metal oxide particles in the mixture is 65% by mass or more and 98% by mass or less. The first surface modification material is a silane compound containing methyl groups, and the second surface modification material contains a silicone compound containing a hydrocarbon group having two or more carbon atoms.

[0145] In addition, the total content of the methyl-containing silane compounds, the silicone compounds containing hydrocarbon groups with 2 or more carbon atoms, and the metal oxide particles can also be evaluated by solid composition.

[0146] Furthermore, the total content of the aforementioned methyl-containing silane compound, the aforementioned silicone compound containing 2 or more carbon atoms, and the aforementioned metal oxide particles does not include alcohols generated during the hydrolysis of the silane compound (described later). That is, the total content of the aforementioned methyl-containing silane compound, the aforementioned silicone compound containing 2 or more carbon atoms, and the aforementioned metal oxide particles refers to the total content of the silane compound, the hydrolyzed silane compound, the silicone compound, and the metal oxide particles. In addition, the aforementioned total content naturally includes the value of the metal oxide particles that have been surface-modified by the aforementioned methyl-containing silane compound and the aforementioned silicone compound containing 2 or more carbon atoms.

[0147] Furthermore, in this embodiment, before step B, step A (hydrolysis step) may be provided as needed, in which a methyl-containing silane compound and water are mixed to obtain a hydrolysate containing the hydrolyzed methyl-containing silane compound.

[0148] Furthermore, it may also have a process A (hydrolysis process), in which, when the surface of the metal oxide particles is modified using a silane compound containing a hydrocarbon group having 2 or more carbon atoms, the silane compound containing a hydrocarbon group having 2 or more carbon atoms is also used to obtain a hydrolysate in the same way as the silane compound containing a methyl group.

[0149] The following is a detailed description of each process. Furthermore, the process of hydrolyzing silane compounds containing methyl groups is described as the first hydrolysis process, and the process of hydrolyzing silane compounds containing hydrocarbon groups with two or more carbon atoms is described as the second hydrolysis process.

[0150] (Process A (Hydrolysis Process 1))

[0151] In the first hydrolysis step, a methyl-containing silane compound (first silane compound) is mixed with water to obtain a hydrolysate containing the hydrolyzed methyl-containing silane compound. Thus, by using a mixture containing at least a portion of the pre-hydrolyzed methyl-containing silane compound, the methyl-containing silane compound readily adheres to the metal oxide particles in the subsequent dispersion step C. The methyl-containing silane compound does not contain hydrocarbon groups with two or more carbon atoms.

[0152] Furthermore, the content of methyl-containing silane compounds in the hydrolysate is not particularly limited, and can be the remainder of other components in the hydrolysate, for example, preferably 60% or more and 99% or less by mass, more preferably 70% or more and 97% or less by mass, and even more preferably 80% or more and 95% or less by mass.

[0153] In addition, in the first hydrolysis step, the hydrolysate may contain surface modification materials other than silane compounds containing methyl groups.

[0154] Furthermore, in the first hydrolysis step, the hydrolysate includes water. Water serves as the substrate for the hydrolysis reaction of surface-modifying materials such as methyl-containing silane compounds.

[0155] The water content in the hydrolysate is not particularly limited, and can be appropriately set according to the amount of methyl-containing silane compound. For example, relative to 1 mol of methyl-containing silane compound, the amount of water added to the hydrolysate is preferably 0.5 mol or more and 5 mol or less, more preferably 0.6 mol or more and 3 mol or less, and even more preferably 0.7 mol or more and 2 mol or less. This allows the hydrolysis reaction of the methyl-containing silane compound to proceed sufficiently, and more reliably prevents the aggregation of inorganic oxide particles in the dispersion made from excess water.

[0156] Alternatively, the water content in the hydrolysate is preferably 1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less. Depending on the need, it may also be 2% by mass or more and 8% by mass or less, 3% by mass or more and 7% by mass or less, or 4% by mass or more and 6% by mass or less.

[0157] Furthermore, a catalyst can be added to the hydrolysate along with a methyl-containing silane compound and water. For example, an acid or base can be used as a catalyst.

[0158] The acid catalyzes the hydrolysis of methyl-containing silane compounds in the hydrolysate. Conversely, the base catalyzes the condensation reaction between the hydrolyzed methyl-containing silane compounds and functional groups on the surface of the metal oxide particles, such as hydroxyl or silanol groups. Therefore, in the dispersion step (step C) described later, the methyl-containing silane compounds readily adhere to the metal oxide particles, improving the dispersion stability of the metal oxide particles.

[0159] Here, the term "acid" refers to an acid based on the so-called Brønsted-Lourie definition, which is a substance that donates a proton in the hydrolysis reaction of surface-modifying materials such as methyl-containing silane compounds. Similarly, the term "base" refers to a base based on the so-called Brønsted-Lourie definition, which here refers to a substance that accepts a proton in the hydrolysis reaction of methyl-containing silane compounds and the subsequent condensation reaction.

[0160] As an acid, there are no particular limitations as long as it can donate a proton in the hydrolysis reaction of a methyl silane compound. Examples include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, boric acid, and phosphoric acid, or organic acids such as acetic acid, citric acid, and formic acid. These organic acids can be used alone or in combination of two or more.

[0161] As a base, there are no particular limitations as long as it can accept a proton in the hydrolysis reaction of a methyl-containing silane compound; examples include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, ammonia, and amines. These bases can be used alone or in combination of two or more.

[0162] In the above, an acid is preferably used as a catalyst. From the viewpoint of acidity, an inorganic acid is preferred, and hydrochloric acid is more preferred.

[0163] The content of the catalyst in the hydrolysate is not particularly limited, but is preferably 10 ppm or more and 1000 ppm or less, more preferably 20 ppm or more and 800 ppm or less, and even more preferably 30 ppm or more and 600 ppm or less. This allows for sufficient promotion of the hydrolysis of methyl-containing silane compounds and suppression of side reactions of methyl-containing silane compounds.

[0164] Furthermore, the hydrolysate can also contain hydrophilic solvents. These hydrophilic solvents promote the mixing of water and silane compounds in the hydrolysate, further accelerating the hydrolysis reaction of these silane compounds.

[0165] Examples of such hydrophilic solvents include various hydrophilic solvents that can be included in the dispersions described later.

[0166] From the viewpoint of having excellent affinity with both water and hydrophobic solvents and promoting their mixing, the hydrophilic solvent preferably contains at least one selected from the group consisting of alcohol solvents, and more preferably contains at least one selected from methanol and ethanol.

[0167] Furthermore, the content of the hydrophilic solvent in the hydrolysate is not particularly limited, but is preferably 60% by mass or less, more preferably 50% by mass or less. This allows for a sufficiently large increase in the content of the silane compound and water in the hydrolysate. Additionally, the content of the hydrophilic solvent in the hydrolysate is preferably 10% by mass or more, more preferably 15% by mass or more. This further promotes the mixing of the methyl-containing silane compound and water, resulting in efficient hydrolysis of the methyl-containing silane compound. Furthermore, the hydrolysate may not contain any hydrophilic solvent other than the compound derived from the hydrolysis reaction.

[0168] In the hydrolysis process, after preparing the hydrolysate, it can be maintained at a constant temperature for a specified time. This further promotes the hydrolysis of silane compounds.

[0169] In this process, the temperature of the hydrolysate is not particularly limited and can be appropriately changed depending on the type of silane compound. For example, it is preferably 5°C or higher and 65°C or lower, and more preferably 30°C or higher and 60°C or lower.

[0170] Furthermore, there is no particular limitation on the holding time, but it is preferably more than 10 minutes and less than 180 minutes, and more preferably more than 30 minutes and less than 120 minutes.

[0171] In addition, the hydrolysate can be stirred appropriately while maintaining the above-mentioned hydrolysate.

[0172] (Process A (Second Hydrolysis Process))

[0173] Even when using a silane compound containing a hydrocarbon group with two or more carbon atoms (the second silane compound), a second hydrolysis step can be performed to obtain a hydrolysate of a silane compound containing a hydrocarbon group with two or more carbon atoms, provided that the metal oxide particles are surface-modified. The silane compound containing a hydrocarbon group with two or more carbon atoms may or may not have a methyl group.

[0174] In the second hydrolysis step, a silane compound containing hydrocarbon groups with 2 or more carbon atoms is mixed with water to obtain a hydrolysate containing the hydrolyzed silane compound containing hydrocarbon groups with 2 or more carbon atoms. Thus, by using a mixture in which at least a portion of the silane compound containing hydrocarbon groups with 2 or more carbon atoms has been pre-hydrolyzed, the silane compound containing hydrocarbon groups with 2 or more carbon atoms readily adheres to the metal oxide particles in the subsequent addition step F.

[0175] In the second hydrolysis step, the methyl-containing silane compound from the first hydrolysis step can be replaced with a silane compound containing a hydrocarbon group having two or more carbon atoms, and the process can be carried out in the same way.

[0176] (Process B (Mixed Process): One finishing touch)

[0177] In the mixing process, a methyl-containing silane compound (first silane compound) and metal oxide particles are mixed to obtain a mixture. The methyl-containing silane compound can be the compound processed in the first hydrolysis process. In the mixing process, in addition to the methyl-containing silane compound and metal oxide particles, water or a catalyst may also be mixed. Furthermore, if a hydrolysate is obtained through the first hydrolysis process described above, a mixture can be obtained by mixing the hydrolysate and the metal oxide particles.

[0178] Furthermore, the mixture is prepared such that the content of metal oxide particles in the mixture is 10% by mass or more and 49% by mass or less, and the total content of methyl silane compounds and inorganic oxide particles is 65% by mass or more and 98% by mass or less.

[0179] Thus, in this embodiment, the total content of methyl-containing silane compounds and metal oxide particles in the mixture is very high. Furthermore, dispersion media such as organic solvents and water, which are conventionally considered essential, are not included in the mixture, or are only mixed in very small amounts. Alternatively, they may contain a small amount of unavoidable alcohol compounds due to hydrolysis. Even in this case, through the dispersion process, the metal oxide particles can be uniformly dispersed in the mixture while simultaneously achieving uniform adhesion (surface modification) of the methyl-containing silane compounds to the metal oxide particles.

[0180] In detail, when surface-modifying metal oxide particles using surface-modifying materials such as silane compounds in the liquid phase, the mixture is typically prepared by mixing not only the metal oxide particles and the surface-modifying material but also a dispersion medium. This mixture is then dispersed using a disperser. However, when the surface-modified metal oxide particles are mixed with methyl silicone resin, they often fail to disperse sufficiently and instead aggregate, resulting in turbidity or whitening of the methyl silicone resin. In this case, the added inorganic oxide particles cannot fully achieve their intended performance.

[0181] On the other hand, the methyl-containing silane compounds used in this invention are low molecular weight and have relatively low viscosity. Furthermore, the hydrolysis process described above results in good adhesion to metal oxide particles. Therefore, methyl-containing silane compounds are extremely suitable for dispersing metal oxide particles in high concentrations of silane compounds.

[0182] When the total content of the methyl-containing silane compound and the metal oxide particles is less than 65% by mass, components other than the two mentioned above, such as the dispersion medium, become excessive. Therefore, in the dispersion step (step C) described later, there is a tendency for the methyl-containing silane compound to not sufficiently adhere to the surface of the metal oxide particles. As a result, a large number of hydroxyl groups remain on the surface of the metal oxide particles, and when the obtained dispersion is mixed with a hydrophobic material, the metal oxide particles aggregate, causing turbidity in the hydrophobic material. The total content of the methyl-containing silane compound and the metal oxide particles only needs to be 65% by mass or more, preferably 70% by mass or more, and more preferably 75% by mass or more.

[0183] In contrast, when the total content of the methyl-containing silane compound and the metal oxide particles exceeds 98% by mass, the viscosity of the mixture becomes too high, making it impossible for the methyl-containing silane compound to adequately adhere to the surface of the metal oxide particles in the dispersion step (step C) described later. The total content of the methyl-containing silane compound and the metal oxide particles only needs to be 98% by mass or less, preferably 97% by mass or less, and more preferably 95% by mass or less.

[0184] Furthermore, as described above, the content of metal oxide particles in the mixture is 10% by mass or more and 49% by mass or less. This allows the amount of methyl-containing silane compound relative to the metal oxide particles to be within an appropriate range, enabling the methyl-containing silane compound to adhere uniformly to the surface of the metal oxide particles while suppressing the increase in viscosity of the mixture.

[0185] In contrast, when the content of metal oxide particles in the mixture is less than 10% by mass, the amount of methyl-containing silane compound is excessive relative to the metal oxide particles. This excess methyl-containing silane compound induces aggregation of the metal oxide particles in the obtained dispersion. The content of metal oxide particles in the mixture is preferably 20% by mass or more, more preferably 30% by mass or more.

[0186] Furthermore, when the content of metal oxide particles exceeds 49% by mass, the amount of methyl-containing silane compound relative to the metal oxide particles is insufficient, and a sufficient amount of methyl-containing silane compound does not adhere to the metal oxide particles. Moreover, if the content of metal oxide particles becomes excessive, the viscosity of the mixture increases excessively, and the metal oxide particles cannot be sufficiently dispersed in the dispersion step (step C) described later. The content of metal oxide particles in the mixture is preferably 45% by mass or less, more preferably 40% by mass or less.

[0187] The content of the methyl-containing silane compound is not particularly limited relative to the content of the metal oxide particles in the mixture, but is preferably 100% by mass or more and 800% by mass or less, more preferably 140% by mass or more and 600% by mass or less, and even more preferably 180% by mass or more and 400% by mass or less. It may also be 200% by mass or more and 300% by mass or less, depending on the need. This allows the amount of the methyl-containing silane compound relative to the metal oxide particles to be within an appropriate range, enabling the methyl-containing silane compound to adhere uniformly to the surface of the metal oxide particles.

[0188] Furthermore, during the mixing process, an organic solvent can be further mixed into the mixture. By mixing an organic solvent into the mixture, the reactivity of the silane compound and the degree of adhesion of the silane compound to the surface of the metal oxide particles can be controlled. Moreover, the viscosity of the mixture can be adjusted by using the organic solvent.

[0189] Examples of such organic solvents include hydrophobic or hydrophilic solvents, which serve as dispersion media for the dispersions described in this embodiment. One of these organic solvents may be used alone, or two or more may be used in combination.

[0190] The content of organic solvent in the mixture is not particularly limited as long as it meets the requirements for the content of metal oxide particles and methyl-containing silane compounds. Furthermore, it is natural that the mixture may not contain any organic solvent.

[0191] (Process C (Distributed Process))

[0192] In the dispersion process, metal oxide particles are dispersed in the mixture obtained in the mixing process to obtain a first dispersion containing metal oxide particles. In this embodiment, the metal oxide particles are dispersed in a high concentration of methyl-containing silane compound after hydrolysis. Therefore, the obtained first dispersion contains a methyl-containing silane compound that is relatively uniformly attached to the surface of the metal oxide particles, and the metal oxide particles are relatively uniformly dispersed.

[0193] The dispersion of metal oxide particles can be carried out using known dispersers. For example, bead mills, ball mills, homogenizers, dispersers, and agitators are preferred dispersers.

[0194] Here, in the dispersion process, the metal oxide particles in the dispersion are preferably dispersed in the mixture by imparting the minimum required energy, without imparting excessive energy, so that the particle size (dispersion particle size) of the metal oxide particles in the dispersion is approximately uniform.

[0195] Furthermore, it may also include a solvent addition step D (first addition step) after the dispersion step, in which a hydrophobic solvent is added to the first dispersion to obtain a second dispersion.

[0196] Examples of hydrophobic solvents that serve as dispersion media for the dispersions described in this embodiment can be cited. These hydrophobic solvents can be used individually or in combination of two or more.

[0197] (Process D (First Addition Process))

[0198] In the first addition step, a hydrophobic solvent is added to the first dispersion to obtain a second dispersion with the desired solid composition (concentration).

[0199] The first dispersion obtained in dispersion step C has a high solids content (concentration), resulting in high viscosity and poor operability. However, if a hydrophobic solvent is added to the first dispersion to reduce the solids content, the low hydrophobicity of the particle surface leads to particle aggregation, thus preventing the acquisition of a uniform dispersion.

[0200] Therefore, the inventors have also discovered that by heating the obtained first dispersion and slowly adding a hydrophobic solvent, it is possible to adjust it into a dispersion with a low solid content.

[0201] The mechanism is speculated to be as follows.

[0202] By heating the first dispersion, the methyl-containing silane compound attached to the metal oxide particles polymerizes, thereby increasing the hydrophobicity of the particle surface. Even if the polymerization reaction proceeds excessively, the metal oxide particles will aggregate. Therefore, by slowly adding a hydrophobic solvent to the first dispersion in the process of polymerization, excessive polymerization can be suppressed, and the surface can be slowly hydrophobized. Thus, it is possible to slowly mix the hydrophobic solvent into the first dispersion.

[0203] That is, by adding a amount of hydrophobic solvent that prevents metal oxide particles from agglomerating, the polymerization reaction of methyl-containing silane compounds is carried out to a degree that is compatible with the amount of hydrophobic solvent added, thereby obtaining a dispersion with the desired solid composition.

[0204] As described above, a hydrophobic solvent can be added slowly to prevent the aggregation of metal oxide particles. Therefore, the solvent can be added after heating the first dispersion, or the first dispersion can be heated after adding the hydrophobic solvent, or the heating of the first dispersion and the addition of the hydrophobic solvent can be performed simultaneously.

[0205] That is, the first addition step can be step d1, in which the hydrophobic solvent is added at a rate at which the metal oxide particles do not agglomerate after heating the first dispersion; step d2, in which the hydrophobic solvent is added at a rate at which the metal oxide particles do not agglomerate while heating the first dispersion; or step d3, in which the first dispersion is heated after the hydrophobic solvent is added at a rate at which the metal oxide particles do not agglomerate.

[0206] There is no particular limitation on the rate at which metal oxide particles do not agglomerate. For example, the hydrophobic solvent can be added continuously at a rate that reduces the solid content by more than 3% by mass and less than 20% by mass within 1 hour. The amount of hydrophobic solvent added can be adjusted appropriately so that the amount added increases at higher heating temperatures and decreases at lower heating temperatures.

[0207] For example, hydrophobic solvents can be added in stages to reduce the solid content within a range of 3% to 20% by mass every 30 minutes, 1 hour, or 2 hours. The amount of hydrophobic solvent added can be adjusted appropriately to increase the amount added at higher heating temperatures and decrease the amount added at lower heating temperatures.

[0208] The heating temperature is not particularly limited as long as it is the temperature at which the polymerization reaction of the methyl-containing silane compound takes place. For example, a heating temperature of 35°C or higher and 80°C or lower is preferred. By heating at a temperature of 35°C or higher, the polymerization reaction of the methyl-containing silane compound can be carried out. On the other hand, by heating at a temperature of 80°C or lower, the aggregation of metal oxide particles caused by the rapid reaction of the methyl-containing silane compound can be suppressed.

[0209] The heating time only needs to be appropriately extended until the adjustment of the solid composition is completed, preferably 4 hours or more and 12 hours or less. By heating for 4 hours or more, the polymerization reaction of the methyl-containing silane compound can be carried out, allowing it to be mixed with the solvent. On the other hand, by heating for 12 hours or less, the aggregation of metal oxide particles caused by excessive polymerization of the methyl-containing silane compound can be suppressed.

[0210] From the viewpoint of ease of operation, such as the removal of the dispersion medium during the manufacture of the composition, as described later, the hydrophobic solvent is preferably at least one selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, and benzene, and more preferably toluene.

[0211] The content of the hydrophobic solvent in the final second dispersion can be adjusted appropriately to the desired solid composition. The content of the hydrophobic solvent is preferably 40% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, and even more preferably 60% by mass or more and 80% by mass or less.

[0212] The first addition step yields a second dispersion with the desired solid composition. Using the second dispersion improves the operability of the dispersions in subsequent steps.

[0213] (Process E (Removal Process))

[0214] In this embodiment, a step E for removing the alcohol produced by hydrolysis may also be set after step D.

[0215] It is speculated that by incorporating a removal process, the production efficiency of the composition described below is improved.

[0216] There are no particular limitations on the removal method; for example, an evaporator can be used. The removal process can proceed until the alcohol is completely removed, or it can leave approximately 5% by mass remaining.

[0217] (Process F (Second Addition Process): Secondary Refinement)

[0218] In the second addition step, a silicone compound containing a hydrocarbon group having two or more carbon atoms is added to the second dispersion to obtain a third dispersion. As described above, in the second dispersion, a methyl-containing silane compound (the first silane compound) is relatively uniformly attached to the surface of the metal oxide particles. Therefore, the silicone compound exists relatively uniformly near the surface of the metal oxide particles, separated from the aforementioned methyl-containing silane compound.

[0219] In the second addition step, the mixture containing the silicone compound in the second dispersion (the third dispersion) can also be maintained at a specified temperature for a specified time. This further promotes the surface modification of the metal oxide particles by the silicone compound.

[0220] The aforementioned silicone compounds are examples of silicone compounds. These silicone compounds can be used alone or in combination of two or more.

[0221] The aforementioned silicone compound can be added to the second dispersion in such a way that the content of the silicone compound in the second dispersion relative to the amount of metal oxide particles is preferably 10% by mass or more and 500% by mass or less. Furthermore, considering the amount of methyl groups contained in the silane compound and the amount of hydrocarbon groups containing 2 or more carbon atoms contained in the silicone compound, the silicone compound is added in such a way that the ratio of methyl groups to carbon atoms in the metal oxide particles is 0.01 or more and 10 or less. This allows a sufficient amount of silicone compound to adhere to the surface of the metal oxide particles, improving both the dispersion stability of the metal oxide particles and their dispersibility in the silicone resin for LEDs. Moreover, it reduces the amount of free silicone compound and suppresses unintended aggregation of metal oxide particles in the silicone resin for LEDs.

[0222] In the second addition step, the temperature is not particularly limited and can be appropriately changed depending on the type of silicone compound. For example, it is preferably 40°C or higher and 150°C or lower, and more preferably 50°C or higher and 140°C or lower.

[0223] Furthermore, there is no particular limitation on the retention time; for example, it is preferably more than 1 hour and less than 24 hours, and more preferably more than 2 hours and less than 20 hours.

[0224] In addition, the third dispersion can be stirred appropriately during the above-mentioned holding process.

[0225] Furthermore, in the second addition step, one or more silicone compounds can be used for one or more treatments. For example, by using different types of silicone compounds and performing multiple silicone compound-based treatments, it becomes easier to control the surface state of the metal oxide particles corresponding to the type of methyl silicone resin.

[0226] Furthermore, in the second addition step, the solid content can be measured after the silicone compound-based treatment, and a hydrophobic solvent can be added to achieve the desired solid content. By reducing the solid content, mixing with the silicone resin component described later becomes easier.

[0227] Furthermore, in the second addition step, silane compounds containing methyl groups or hydrocarbon groups with two or more carbon atoms can also be added. By adding these silane compounds, adjusting the methyl / hydrocarbon group ratio becomes easier.

[0228] In addition, as the silane compound containing methyl groups or the silane compound containing hydrocarbon groups having two or more carbon atoms, a hydrolysate containing the first silane compound obtained through the first hydrolysis step or a hydrolysate containing the second silane compound obtained through the second hydrolysis step may also be used.

[0229] The amount of silane compound added in the second addition step, including the amount of methyl-containing silane compound mixed in the mixing step B, may be added relative to the amount of metal oxide particles, for example, in a manner that is 100% by mass or more and 700% by mass or less.

[0230] Furthermore, in the second addition step, when adding a silane compound containing a hydrocarbon group having 2 or more carbon atoms, the amount of hydrocarbon group contained in the aforementioned silicone compound is also taken into consideration, and the compound is added in such a way that the molar ratio of methyl to hydrocarbon group having 2 or more carbon atoms is 0.01 or more and 10 or less.

[0231] In addition, in the second addition step, silane compound and silicone compound can be added simultaneously, silicone compound can be added after silane compound, or silane compound can be added after silicone compound.

[0232] Thus, a third dispersion is obtained by surface modification of metal oxide particles with the aforementioned methyl-containing silane compound by using a silicone compound.

[0233] In a dispersion containing surface-modified metal oxide particles manufactured using the manufacturing method of the surface-modified metal oxide particles according to this embodiment, the surface of the metal oxide particles is densely and sufficiently modified by a silane compound containing methyl or methyl groups and hydrocarbon groups having 2 or more carbon atoms, thereby allowing silicone compounds containing hydrocarbon groups having 2 or more carbon atoms to exist near the surface of the metal oxide particles. Furthermore, the surface modification method of the metal oxide particles according to this embodiment can densely and sufficiently modify the surface of the metal oxide particles with silane compounds containing methyl or methyl groups and hydrocarbon groups having 2 or more carbon atoms, thereby allowing silicone compounds containing hydrocarbon groups having 2 or more carbon atoms to exist near the surface of the metal oxide particles. Moreover, the surface-modified metal oxide particles exhibit excellent compatibility with both methyl-based and phenyl-based silicone resins for LEDs, and can be relatively uniformly dispersed in both resins. Therefore, when the surface-modified metal oxide particles are dispersed in either methyl-based or phenyl-based silicone resins, the generation of turbidity such as whitening is suppressed. Furthermore, the viscosity change of the silicone resin for LEDs containing surface-modified metal oxide particles is also suppressed.

[0234] <4. Composition>

[0235] Next, the composition involved in this embodiment will be described.

[0236] The composition according to this embodiment includes a dispersion containing the above-described surface-modified metal oxide particles and a silicone resin component. That is, the composition according to this embodiment is a mixture of the above-described dispersion and silicone resin component. Therefore, in addition to the metal oxide particles and solvent that are surface-modified using a silane compound containing methyl or a hydrocarbon group having two or more carbon atoms, the composition according to this embodiment also contains a silicone resin component.

[0237] Here, silicone resin composition refers to the fluid state of silicone resin before it is cured.

[0238] The composition according to this embodiment can be cured as described below and used as a sealing component for a light-emitting element. By containing metal oxide particles that contribute to improving the refractive index and transparency, the composition according to this embodiment can increase the brightness of the light emitted by the light-emitting device when used as a sealing component.

[0239] Furthermore, the composition according to this embodiment contains surface-modified metal oxide particles that are sufficiently attached to the metal oxide particles to the extent described in formula (1), including the aforementioned methyl-containing silane compound and the silicone compound containing a hydrocarbon group having two or more carbon atoms. Therefore, whether the silicone resin component is present or after the silicone resin component has cured, the aggregation of metal oxide particles is suppressed, thereby suppressing the reduction of transparency. Therefore, when the composition according to this embodiment is used in a sealing component, the brightness of the light emitted by the light-emitting device can be improved.

[0240] From the viewpoint of obtaining a composition with high transparency, the content of metal oxide particles in the composition of this embodiment is preferably 5% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 35% by mass or less.

[0241] Furthermore, the content of methyl silane compounds and silicone compounds containing hydrocarbon groups having 2 or more carbon atoms can correspond to the content in the surface-modified metal oxide particles involved in this embodiment.

[0242] The silicone resin component is the main component of the composition according to this embodiment. When the silicone resin component is used as a sealing material in this embodiment, it cures and seals the light-emitting element, thereby preventing deteriorating factors from the external environment, such as moisture and oxygen, from reaching the light-emitting element. Furthermore, in this embodiment, the cured product obtained from the silicone resin component is substantially transparent, allowing light emitted from the light-emitting element to pass through.

[0243] As for the silicone resin component, there are no particular limitations as long as it is a silicone resin component used for sealing LEDs. The silicone resin component preferably contains methyl and phenyl groups. The silicone resin component can be a methyl-based silicone resin component or a phenyl-based silicone resin component. A methyl-based silicone resin component refers to a silicone resin component containing a large amount of methyl groups. A methyl-based silicone resin component can be a methyl-containing silicone resin component, a methylphenyl silicone resin component, or a dimethyl silicone resin component. From the viewpoint of versatility, a methylphenyl silicone resin component is preferred.

[0244] Phenyl silicone resin components refer to silicone resin components containing a large amount of phenyl groups. Phenyl silicone resin components can be phenyl-containing silicone resin components, methylphenyl silicone resin components, or diphenyl silicone resin components. From the perspective of versatility, methylphenyl silicone resin components are preferred.

[0245] The content of the silicone resin component in the composition involved in this embodiment can be the remainder of other components, for example, preferably 10% by mass or more and 70% by mass or less. The content of the silicone resin component can also be 20% by mass or more and 60% by mass or less, 30% by mass or more and 50% by mass or less, or 35% by mass or more and 45% by mass or less.

[0246] The mass ratio of silicone resin component to surface-modified metal oxide particles in the composition involved in this embodiment, based on silicone resin: surface-modified metal oxide particles, is preferably in the range of 50:50 to 90:10, and more preferably in the range of 60:40 to 80:20.

[0247] The composition described in this embodiment may contain solvent derived from the dispersion described in this embodiment, or it may be removed. That is, the solvent derived from the dispersion may be completely removed, or it may remain in the composition to a degree of 1% or more by mass and 10% or less by mass, or it may remain to a degree of 2% or more by mass and 5% or less by mass.

[0248] To the extent that it does not impede the objectives of the present invention, the composition involved in this embodiment may also contain phosphor particles. Phosphor particles absorb light of a specific wavelength emitted from the light-emitting element and emit light of a predetermined wavelength. That is, the wavelength of light can be converted by phosphor particles, thereby adjusting the hue.

[0249] There are no particular limitations on the use of phosphor particles as long as they can be used in the light-emitting device described below, and they can be appropriately selected and used in such a way that the emission color of the light-emitting device becomes the desired color.

[0250] The content of phosphor particles in the composition of this embodiment can be appropriately adjusted to obtain the desired brightness.

[0251] Furthermore, without hindering the objectives of the present invention, the compositions involved in this embodiment may also contain commonly used additives such as preservatives, polymerization initiators, polymerization inhibitors, curing catalysts, and light diffusing agents. As a light diffusing agent, silica particles with an average particle size of 1 μm or more and 30 μm or less are preferably used.

[0252] The composition of this embodiment contains surface-modified metal oxide particles that are sufficiently attached to the metal oxide particles to the extent described in formula (1), including a methyl-containing silane compound and a silicone compound containing a hydrocarbon group having two or more carbon atoms. Therefore, regardless of whether the silicone resin component is a methyl-based or phenyl-based silicone resin, the aggregation of metal oxide particles is suppressed, thereby inhibiting the reduction of transparency. Thus, using the composition of this embodiment, a sealing component that improves the brightness of the light emitted by the light-emitting device can be formed.

[0253] <5. Method for manufacturing the composition>

[0254] Next, the method for manufacturing the composition according to this embodiment will be described.

[0255] The method for manufacturing the composition according to this embodiment includes step H, in which a silicone resin component is added to the third dispersion obtained by the above-described method for manufacturing surface-modified metal oxide particles to obtain the composition.

[0256] (Process G (3rd Addition Process))

[0257] In the third addition step, a silicone resin component is added to the above-mentioned third dispersion to adjust the composition to the desired solid component (concentration).

[0258] The content of the silicone resin component in the final composition can be appropriately adjusted to the desired solid content. The content of the silicone resin component is preferably, for example, 10% by mass or more and 70% by mass or less.

[0259] Through the third addition step, a composition adjusted to the desired solid composition can be obtained.

[0260] (Process H (Removal Process))

[0261] In this embodiment, a step H for removing the solvent contained in the third dispersion may also be provided after step G.

[0262] There are no particular limitations on the removal method; for example, an evaporator can be used. The removal process can proceed until the solvent is completely removed, or it can leave approximately 5% by mass remaining.

[0263] Thus, the composition involved in this embodiment can be obtained.

[0264] <6. Sealing Components>

[0265] The sealing component involved in this embodiment is a cured product of the composition involved in this embodiment. The sealing component involved in this embodiment is typically used as a sealing component or part thereof disposed on a light-emitting element.

[0266] The thickness or shape of the sealing component involved in this embodiment can be appropriately adjusted according to the desired application or characteristics, and there is no particular limitation.

[0267] As described above, the sealing component according to this embodiment can be manufactured by curing the composition according to this embodiment. The curing method of the composition can be selected according to the characteristics of the silicone resin in the composition according to this embodiment, for example, thermosetting or electron beam curing. More specifically, the sealing component of this embodiment can be obtained by curing the silicone resin in the composition of this embodiment through an addition reaction or a polymerization reaction.

[0268] The average dispersed particle size of the metal oxide particles in the sealing component is preferably 10 nm or more and 300 nm or less, more preferably 20 nm or more and 250 nm or less, and even more preferably 30 nm or more and 200 nm or less.

[0269] Furthermore, the average dispersed particle size of the metal oxide particles in the sealing component is the average particle size (median particle size) based on the number distribution of the sealing component, as determined by transmission electron microscopy (TEM). In this embodiment, the average dispersed particle size of the metal oxide particles in the sealing component is a value determined and calculated based on the dispersed particle size of the metal oxide particles in the sealing component. Regardless of whether the metal oxide particles are dispersed as primary or secondary particles, the average dispersed particle size is determined and calculated based on the diameter of the dispersed metal oxide particles. In this embodiment, the average particle size of the metal oxide particles in the sealing component can also be measured as the average particle size of metal oxide particles surface-modified with the aforementioned silane and silicone compounds. In the sealing component, there may be metal oxide particles surface-modified with the aforementioned silane and silicone compounds and metal oxide particles not surface-modified with the aforementioned silane and silicone compounds; therefore, typically, the average particle size of the metal oxide particles in the sealing component is measured as a value in their mixed state.

[0270] The sealing component described in this embodiment is a cured product of the composition described in this embodiment, and therefore exhibits excellent refractive index and transparency. Therefore, according to this embodiment, a sealing component with excellent extraction efficiency that improves the brightness of light emitted by the light-emitting device can be obtained.

[0271] <7. Light-emitting device>

[0272] Next, the light-emitting device according to this embodiment will be described. The light-emitting device according to this embodiment includes the sealing member described above and a light-emitting element sealed by the sealing member.

[0273] Examples of light-emitting elements include light-emitting diodes (LEDs) and organic light-emitting diodes (OLEDs). In particular, the sealing component described in this embodiment is suitable for sealing light-emitting diodes.

[0274] The following example illustrates the light-emitting device in this embodiment, where the light-emitting element is a light-emitting diode on a chip, i.e., an LED chip, and the light-emitting device is an LED package.

[0275] Figures 1-4 These are schematic diagrams (cross-sectional views) illustrating an example of a light-emitting device according to an embodiment of the present invention.

[0276] Furthermore, for ease of explanation, the sizes of the components in the figures are appropriately emphasized and do not represent actual dimensions or ratios between components. Additionally, in this specification and the accompanying drawings, components with substantially the same functional structure are labeled with the same symbols, thus omitting redundant descriptions.

[0277] Figure 1 The light-emitting device (LED package) 1A shown includes: a substrate 2 having a recess 21; a light-emitting element (LED chip) 3 disposed on the bottom surface of the recess 21 of the substrate 2; and a sealing member 4A for sealing the light-emitting element 3 in the recess 21.

[0278] The sealing component 4A is constituted by the sealing component according to the present embodiment described above. Therefore, metal oxide particles derived from the composition according to the present embodiment are dispersed in the sealing component 4A, resulting in improved light extraction efficiency in the light-emitting device 1A. Furthermore, phosphor particles 5 are dispersed within the sealing component 4A. The phosphor particles 5 convert at least a portion of the wavelength of the light emitted by the light-emitting element 3.

[0279] Figure 2 The difference between the light-emitting device 1B and the light-emitting device 1A is that the sealing member 4B has two layers. That is, the sealing member 4B has a first layer 41B that directly covers the light-emitting element 3 and a second layer 43B that covers the first layer 41B. Both the first layer 41B and the second layer 43B are sealing members according to this embodiment. Phosphor particles 5 are dispersed in the first layer 41B. On the other hand, the second layer 43B does not contain phosphor particles 5. The light-emitting device 1B improves the brightness of light by dispersing metal oxide particles derived from the composition according to this embodiment in the first layer 41B and the second layer 43B constituting the sealing member 4B.

[0280] Figure 3The difference between the light-emitting device 1C and the light-emitting device 1A lies in the structure of the sealing member 4C. The sealing member 4C has a first layer 41C that directly covers the light-emitting element 3 and a second layer 43C that covers the first layer 41C. The first layer 41C is not the sealing member according to this embodiment, but a sealing member made of resin that does not contain the aforementioned metal oxide particles, and is composed of resin or the like suitable for sealing members. Furthermore, phosphor particles 5 are dispersed within the first layer 41C. On the other hand, the second layer 43C is the sealing member according to this embodiment. The light-emitting device 1C improves light extraction efficiency by dispersing metal oxide particles derived from the composition according to this embodiment within the second layer 43C constituting the sealing member 4C.

[0281] exist Figure 4 In the illustrated light-emitting device 1D, the sealing member 4D has a first layer 41D that directly covers the light-emitting element 3, a second layer 43D that covers the first layer 41D, and a third layer 45D that further covers the second layer 43D. The first layer 41D and the second layer 43D are not the sealing members involved in this embodiment, but rather sealing members made of resin that does not contain the aforementioned metal oxide particles, and are composed of resins or the like suitable for sealing members. Furthermore, phosphor particles 5 are dispersed within the second layer 43D. On the other hand, the third layer 45D is the sealing member involved in this embodiment. The light-emitting device 1D increases the brightness of light by dispersing metal oxide particles derived from the composition involved in this embodiment within the third layer 45D constituting the sealing member 4D.

[0282] Furthermore, the light-emitting device according to this embodiment is not limited to the illustrated configuration. For example, the light-emitting device according to this embodiment may not contain phosphor particles in the sealing member. Moreover, the sealing member according to this embodiment can be present at any position within the sealing member.

[0283] In the light-emitting device described in this embodiment, the light brightness is increased because the light-emitting element is sealed by the sealing component of this embodiment.

[0284] Furthermore, the light-emitting device according to this embodiment utilizes the composition according to this embodiment described above to seal the light-emitting element. Therefore, the present invention also relates to a method for manufacturing a light-emitting device, which includes a step of sealing the light-emitting element using the composition according to this embodiment in one aspect. In the same aspect, the above-described manufacturing method may also include a step of mixing the dispersion and resin component according to this embodiment to obtain the above-described composition.

[0285] In addition, the sealing of the light-emitting element can be achieved, for example, by applying the composition involved in this embodiment to the light-emitting element using a dispensing machine or the like, and then curing the composition.

[0286] <8. Lighting fixtures and display devices>

[0287] The light-emitting device described in this embodiment as above can be used, for example, in lighting fixtures and display devices. Therefore, in one aspect, the present invention relates to a lighting fixture or display device having the light-emitting device described in this embodiment.

[0288] As lighting fixtures, examples include general lighting devices such as indoor lights and outdoor lights, and lighting for the switching parts of electronic devices such as mobile phones or OA equipment.

[0289] The lighting fixture according to this embodiment has the light-emitting device according to this embodiment. Therefore, even if the same light-emitting element is used, the emitted light beam is larger than that of the past, which can make the surrounding environment brighter.

[0290] Examples of display devices include mobile phones, mobile information terminals, electronic dictionaries, digital cameras, computers, televisions, and their peripherals.

[0291] The display device according to this embodiment has the light-emitting device according to this embodiment. Therefore, even if the same light-emitting element is used, the emitted light beam is larger than that of the past, and for example, a clearer and brighter display can be performed.

[0292] Example

[0293] The present invention will be further described in detail below through embodiments and comparative examples. Furthermore, the embodiments described below are merely examples of the present invention and do not limit the scope of the invention.

[0294] [Example 1]

[0295] (Preparation of dispersion)

[0296] (1) First hydrolysis process

[0297] As the first silane compound, 90.78 parts by weight of methyltrimethoxysilane (product name: KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.), 9.21 parts by weight of water, and 0.01 parts by weight of hydrochloric acid (1N) were added and mixed to obtain a hydrolysate. Next, the hydrolysate was stirred at 60°C for 30 minutes to perform hydrolysis of methyltrimethoxysilane, yielding a hydrolysate.

[0298] (2) Mixing process (single finishing)

[0299] 30 parts by mass of zirconium oxide (ZrO2) particles (manufactured by Sumitomo Osaka Cement Co., Ltd.) with an average primary particle size of 12 nm were mixed with 70 parts by mass of the above-mentioned hydrolysate to obtain a mixture. The content of zirconium oxide particles in the mixture was 30% by mass, the content of methyltrimethoxysilane was 63.5% by mass, and the total content of zirconium oxide particles and methyltrimethoxysilane was 93.5% by mass.

[0300] (3) Dispersed process

[0301] After dispersing the mixture in a bead mill for 6 hours, the beads were removed to obtain the first dispersion.

[0302] The solid content of the first dispersion was determined (at 100°C for 1 hour), and the result was 70% by mass.

[0303] (4) First Addition Process

[0304] The obtained first dispersion was heated at 60°C for 2 hours. Then, toluene was added to the dispersion to make the solid content 40% by mass, and the mixture was heated at 60°C for 2 hours.

[0305] Next, toluene was added to the dispersion to make the solid content 30% by mass, and the mixture was heated at 60°C for 1 hour.

[0306] Next, toluene was added to the dispersion to make the solid content 20% by mass, and the mixture was heated at 60°C for 1 hour to obtain the second dispersion.

[0307] (FT-IR analysis)

[0308] A portion of the second dispersion was taken and dried using a vacuum dryer. Using 0.01 g to 0.05 g of the obtained surface-modified zirconia particles, the concentration at 800 cm⁻¹ was determined using a Fourier transform infrared spectrophotometer (model: FT / IR-670Plus, manufactured by JASCO Corporation). -1 Above and 3800cm -1 The following wavenumber range is used for transmission spectra. The transmission spectral values ​​are standardized with the maximum value of the transmission spectrum within this measurement range set to 100 and the minimum value to 0. The 3500 cm⁻¹ value is then calculated. -1 Normalized spectral values ​​(IA) and 1100 cm⁻¹ -1 The normalized spectral values ​​(IB) were calculated. The result was an IA / IB ratio of 7.

[0309] (5) Second addition process (secondary modification)

[0310] 66.7 parts by mass of the second dispersion, to which the solid content was adjusted to 15% by mass with toluene, and 33.3 parts by mass of a silicone compound containing methyl and phenyl (trade name: KR213 (high phenyl content), manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and stirred at 100°C for 3 hours to obtain the dispersion of Example 1 (the third dispersion).

[0311] (Evaluation of the dispersion)

[0312] (1)FT-IR analysis

[0313] 10 g of the dispersion described in Example 1, whose solid content was adjusted to 30% by mass with toluene, was dried for 2 hours at 100°C and 20 hPa using a vacuum dryer (manufactured by EYELA TOKYO RIKAKIKAI CO,LTD., device name: VACUUM OVENVOS-201SD). Then, 0.01 g to 0.05 g of the obtained metal oxide particles were measured at 800 cm⁻¹ using a Fourier transform infrared spectrophotometer (model: FT / IR-670Plus, manufactured by JASCO Corporation). -1 Above and 3800cm -1 The following wavenumber range is used for transmission spectra. The spectral values ​​are normalized with the maximum value of the spectrum within this measurement range set to 100 and the minimum value to 0. The 3500 cm⁻¹ value is then calculated. -1 The value (IA) and 1100cm -1 The value of IA / IB is 1.9. The results are shown in Table 1.

[0314] (2) NMR measurement

[0315] 15 g of the dispersion described in Example 1, adjusted to 30% by mass with toluene, and 15 g of methanol were mixed to precipitate the surface-modified zirconia particles. The mixture was then subjected to solid-liquid separation using a centrifuge to recover the solid fraction (surface-modified zirconia particles). A few milligrams of the recovered surface-modified zirconia particles were collected and dissolved in dichloroform to a concentration of 1% by mass. Using this solution, a benchtop NMR apparatus (Nanalysis Scientific Corp., Model NMReady60Pro) was used. 1 H / 19 F)), the determination of phenyl and methyl groups. 1 H-liquid NMR spectroscopy. Based on the obtained spectra, the peak areas (integral values) of phenyl and methyl were calculated separately. The molar ratio of methyl to phenyl was calculated by dividing the integral value of methyl by the integral value of phenyl. The results are shown in Table 1.

[0316] The molar ratio of methyl to phenyl (methyl / phenyl) was 0.45. The results are shown in Table 1.

[0317] (Preparation of Composition A)

[0318] 16.7 g of the dispersion described in Example 1, in which the solid content was adjusted to 30% by mass with toluene, and 95 g of the methyl silicone resin component (trade name: KER-2500-A / B, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed. Then, toluene was removed from the mixture using an evaporator, thereby obtaining composition A of Example 1 containing the methyl silicone resin component.

[0319] The viscosity of the obtained composition A was determined using a rheometer (trade name: RheoStress RS-6000, manufactured by HAAKE) at 25°C and a shear rate of 1 (1 / s).

[0320] As a result, the viscosity A of composition A was 8 Pa·s. The results are shown in Table 1.

[0321] (Preparation of solidified product A)

[0322] The composition was filled into a 1 mm thick SUS container coated with Teflon (registered trademark) to achieve a thickness of 1 mm. Then, it was heated at 100°C for 2 hours, followed by heating at 150°C for 4 hours, thereby obtaining the cured product A described in Example 1. The thickness of cured product A extracted from the container was approximately 1 mm.

[0323] The transmittance of cured product A extracted from the container was determined using a spectrophotometer (JASCO Corporation, model: V-770) and an integrating sphere. The transmittance of cured product A containing methyl silicone resin was 70%. The results are shown in Table 1.

[0324] (Preparation of Composition B and Cured Product B)

[0325] 16.7 g of the dispersion described in Example 1, with the solid content adjusted to 30% by mass using toluene, was mixed with 95 g of the phenyl silicone resin component (trade name: OE-6520, manufactured by Dow Corning Toray Co., Ltd.). Toluene was then removed from the mixture using an evaporator, thereby obtaining composition B of Example 1 containing the phenyl silicone resin component. The viscosity B of composition B, measured in the same manner as composition A, is shown in Table 1.

[0326] Next, cured product B, as described in Example 1, was obtained by curing in the same manner as composition A. The thickness of cured product B extracted from the container was approximately 1 mm. The transmittance B, measured in the same manner as cured product A, is shown in Table 1.

[0327] (Fabrication of LED packages and evaluation of brightness)

[0328] (1) Preparation of the composition

[0329] 5.0 g of the dispersion described in Example 1, in which the solid content was adjusted to 30% by mass with toluene, and 3.5 g of the methyl silicone resin component (trade name: KER-2500-B, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed. That is, the mixture was mixed in a mass ratio of 30:70 between the total mass of zirconium oxide and the surface modification material and the mass of the methyl silicone resin component.

[0330] Next, toluene was removed from the mixture using an evaporator, thereby obtaining composition C, which is described in Example 1, for use in making sealing components.

[0331] (2) Fabrication of LED package

[0332] To the obtained composition C1 by mass, 14 parts by mass of methyl silicone resin (trade name: KER-2500-A / B, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to adjust the composition to have 2% by mass of surface-modified zirconia particles, and the mixture was then stirred. A composition containing 0.38 parts by mass of phosphor particles (yttrium aluminum garnet: YAG) mixed with 1 part by mass of this composition (total ratio of surface-modified zirconia particles and resin: phosphor particles = 100:38) was filled into the LED lead frame to a thickness of 300 μm. The mixture was then held at room temperature for 3 hours. Next, the composition was slowly heated and cured to form a sealed component, thus creating the white LED package described in Example 1.

[0333] (3) Evaluation

[0334] For the obtained white LED package, the luminance was measured by applying a voltage of 3V and a current of 150mA to the LED package using a total luminous flux measurement system (manufactured by Otsuka Electronics Co., Ltd.). The luminance of the white LED package was found to be 74.4 lm. The results are shown in Table 1.

[0335] [Example 2]

[0336] In Example 1, 90.9 parts by mass of the second dispersion and 9.1 parts by mass of the aforementioned silicone compound were mixed instead of 66.7 parts by mass of the second dispersion to which the solid content was adjusted to 15% by mass using toluene and 33.3 parts by mass of the silicone compound containing methyl and phenyl groups. Otherwise, the dispersion involved in Example 2 (the third dispersion) was obtained in exactly the same manner as in Example 1.

[0337] The IA / IB and methyl / phenyl ratios of the dispersion involved in Example 2 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0338] The dispersion described in Example 2 was used instead of the dispersion described in Example 1. Otherwise, compositions A and B, and cured products A and B of Example 2 were obtained in the same manner as in Example 1. The results of measuring the viscosity of the compositions and the transmittance of the cured products in the same manner as in Example 1 are shown in Table 1.

[0339] The dispersion described in Example 2 was used instead of the dispersion described in Example 1. Otherwise, the composition C described in Example 2 and the LED package described in Example 2 were obtained in the same manner as in Example 1. The results of the evaluation, which were performed in the same manner as in Example 1, are shown in Table 1.

[0340] [Example 3]

[0341] In Example 1, 95.2 parts by mass of the second dispersion and 4.8 parts by mass of the above-mentioned silicone compound were mixed instead of 66.7 parts by mass of the second dispersion with the solid content adjusted to 15% by mass using toluene and 33.3 parts by mass of the silicone compound containing methyl and phenyl groups. Otherwise, the dispersion of Example 3 (the third dispersion) was obtained in exactly the same manner as in Example 1.

[0342] The IA / IB and methyl / phenyl ratios of the dispersion involved in Example 3 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0343] The dispersion described in Example 3 was used instead of the dispersion described in Example 1. Otherwise, compositions A and B, and cured products A and B, were obtained in the same manner as in Example 1. The results of measuring the viscosity of the compositions and the transmittance of the cured products, as in Example 1, are shown in Table 1.

[0344] The dispersion described in Example 3 was used instead of the dispersion described in Example 1. Otherwise, the composition C described in Example 3 and the LED package described in Example 3 were obtained in the same manner as in Example 1. The results of the evaluation, which were performed in the same manner as in Example 1, are shown in Table 1.

[0345] [Example 4]

[0346] (Second hydrolysis process)

[0347] As the second silane compound, 91.66 parts by weight of phenyltrimethoxysilane (product name: KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.), 8.33 parts by weight of water, and 0.01 parts by weight of hydrochloric acid (1N) were added and mixed to obtain a hydrolysate. Next, the hydrolysate was stirred at 60°C for 30 minutes to hydrolyze the phenyltrimethoxysilane, yielding a hydrolysate.

[0348] (Preparation of dispersion)

[0349] The solid components obtained during the preparation of Example 1 were adjusted to 15% by mass in 62.5 parts by mass of the second dispersion, 6.3 parts by mass of the hydrolysate of the above-mentioned phenyltrimethoxysilane, and 31.2 parts by mass of a silicone compound containing methyl and phenyl (trade name: KR213 (high phenyl content), manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and stirred at 100°C for 3 hours to obtain the dispersion (third dispersion) involved in Example 4.

[0350] The IA / IB and methyl / phenyl ratios of the dispersion involved in Example 4 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0351] The dispersion described in Example 4 was used instead of the dispersion described in Example 1. Otherwise, compositions A and B, and cured products A and B of Example 4 were obtained in the same manner as in Example 1. The results of measuring the viscosity of the compositions and the transmittance of the cured products in the same manner as in Example 1 are shown in Table 1.

[0352] The dispersion described in Example 4 was used instead of the dispersion described in Example 1. Otherwise, the composition C described in Example 4 and the LED package described in Example 4 were obtained in the same manner as in Example 1. The results of the evaluation, which were performed in the same manner as in Example 1, are shown in Table 1.

[0353] [Example 5]

[0354] In Example 4, instead of mixing 62.5 parts by mass of the second dispersion, 6.3 parts by mass of the hydrolysate of phenyltrimethoxysilane, and 31.2 parts by mass of the silicone compound containing methyl and phenyl, 60.6 parts by mass of the second dispersion, 9.1 parts by mass of the hydrolysate of phenyltrimethoxysilane, and 30.3 parts by mass of the silicone compound containing methyl and phenyl were mixed. Otherwise, the dispersion involved in Example 5 was obtained in the same manner as in Example 4.

[0355] The IA / IB and methyl / phenyl ratios of the dispersion involved in Example 5 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0356] The dispersion described in Example 5 was used instead of the dispersion described in Example 1. Otherwise, compositions A and B, and cured products A and B of Example 5 were obtained in the same manner as in Example 1. The results of measuring the viscosity of the compositions and the transmittance of the cured products in the same manner as in Example 1 are shown in Table 1.

[0357] The dispersion described in Example 5 was used instead of the dispersion described in Example 1. Otherwise, the composition C described in Example 5 and the LED package described in Example 5 were obtained in the same manner as in Example 1. The results of the evaluation, which were performed in the same manner as in Example 1, are shown in Table 1.

[0358] [Example 6]

[0359] In Example 4, instead of mixing 64.5 parts by mass of the second dispersion, 3.2 parts by mass of the hydrolysate of phenyltrimethoxysilane, and 32.3 parts by mass of the silicone compound containing methyl and phenyl, the second dispersion, phenyltrimethoxysilane, and silicone compound containing methyl and phenyl were mixed. Otherwise, the dispersion involved in Example 6 was obtained in the same manner as in Example 4.

[0360] The IA / IB and methyl / phenyl ratios of the dispersion involved in Example 6 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0361] The dispersion described in Example 6 was used instead of the dispersion described in Example 1. Otherwise, compositions A and B, and cured products A and B, were obtained in the same manner as in Example 1. The results of measuring the viscosity of the compositions and the transmittance of the cured products, as in Example 1, are shown in Table 1.

[0362] The dispersion described in Example 6 was used instead of the dispersion described in Example 1. Otherwise, the composition C described in Example 6 and the LED package described in Example 6 were obtained in the same manner as in Example 1. The results of the evaluation, which were performed in the same manner as in Example 1, are shown in Table 1.

[0363] [Example 7]

[0364] In Example 4, instead of mixing 62.5 parts by mass of the second dispersion, 6.3 parts by mass of the hydrolysate of phenyltrimethoxysilane, and 31.2 parts by mass of the silicone compound containing methyl and phenyl, 65.4 parts by mass of the second dispersion, 2.0 parts by mass of the hydrolysate of phenyltrimethoxysilane, and 32.6 parts by mass of the silicone compound containing methyl and phenyl, the dispersion involved in Example 7 was obtained in the same manner as in Example 4.

[0365] The IA / IB and methyl / phenyl ratios of the dispersion involved in Example 7 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0366] The dispersion described in Example 7 was used instead of the dispersion described in Example 1. Otherwise, compositions A and B, and cured products A and B, were obtained in the same manner as in Example 1. The results of measuring the viscosity of the compositions and the transmittance of the cured products, as in Example 1, are shown in Table 1.

[0367] The dispersion described in Example 7 was used instead of the dispersion described in Example 1. Otherwise, the composition C described in Example 7 and the LED package described in Example 7 were obtained in the same manner as in Example 1. The results of the evaluation, which were performed in the same manner as in Example 1, are shown in Table 1.

[0368] [Example 8]

[0369] In Example 4, instead of mixing 62.9 parts by mass of the second dispersion, 5.7 parts by mass of phenyltrimethoxysilane, and 31.4 parts by mass of a silicone compound containing methyl and phenyl, the same method as in Example 4 was used to obtain the dispersion involved in Example 8.

[0370] The IA / IB and methyl / phenyl ratios of the dispersion involved in Example 8 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0371] The dispersion described in Example 8 was used instead of the dispersion described in Example 1. Otherwise, compositions A and B, and cured products A and B of Example 8 were obtained in the same manner as in Example 1. The results of measuring the viscosity of the compositions and the transmittance of the cured products in the same manner as in Example 1 are shown in Table 1.

[0372] The dispersion described in Example 8 was used instead of the dispersion described in Example 1. Otherwise, the composition C described in Example 8 and the LED package described in Example 8 were obtained in the same manner as in Example 1. The results of the evaluation, which were performed in the same manner as in Example 1, are shown in Table 1.

[0373] [Comparative Example 1]

[0374] In Example 1, 95.5 parts by mass of the second dispersion and 4.5 parts by mass of the above-mentioned silicone compound were mixed instead of 66.7 parts by mass of the second dispersion with the solid content adjusted to 15% by mass using toluene and 33.3 parts by mass of the silicone compound containing methyl and phenyl groups. Otherwise, the dispersion of Comparative Example 1 (the third dispersion) was obtained in exactly the same manner as in Example 1.

[0375] The IA / IB and methyl / phenyl ratios of the dispersion involved in Comparative Example 1 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0376] The dispersion described in Comparative Example 1 was used instead of the dispersion described in Example 1. Otherwise, the composition A and the cured product A described in Comparative Example 1 were obtained in the same manner as in Example 1. The results of measuring the viscosity of the composition and the transmittance of the cured product in the same manner as in Example 1 are shown in Table 1.

[0377] In the same manner as in Example 1, the dispersion involved in Comparative Example 1 was used to obtain Composition B and Cured Product B. However, the dispersion of Comparative Example 1 could not be dispersed in the phenyl silicone resin component, and Composition B exhibited turbid agglomeration, thus Cured Product B could not be produced.

[0378] The dispersion described in Comparative Example 1 was used instead of the dispersion described in Example 1. Otherwise, the composition C described in Comparative Example 1 and the LED package described in Comparative Example 1 were obtained in the same manner as in Example 1. The results of the evaluation, which were performed in the same manner as in Example 1, are shown in Table 1.

[0379] [Comparative Example 2]

[0380] In the mixing process of Example 1, 20 parts by mass of the above-mentioned hydrolysate and 50 parts by mass of isopropanol (IPA) were used instead of 70 parts by mass of the hydrolysate of mixed methyltrimethoxysilane. Otherwise, the mixing and dispersion processes were carried out in the same manner as in Example 1, and a dispersion (first dispersion) was obtained.

[0381] The solid content of the dispersion was determined (at 100°C for 1 hour), and the result was 38% by mass.

[0382] (4) First Addition Process

[0383] Toluene was added to the obtained dispersion (dispersion 1) to bring the solid content to 20% by mass, and the mixture was heated at 60°C for 2 hours. Next, toluene was added to the dispersion in the same amount as the amount evaporated, and the mixture was heated at 60°C for 2 hours. Then, toluene was added to the dispersion in the same amount as the amount evaporated, and the mixture was heated at 60°C for 1 hour. Finally, toluene was added to the dispersion in the same amount as the amount evaporated, and the mixture was heated at 60°C for 1 hour, thereby promoting surface modification and obtaining a dispersion in which isopropanol was replaced by toluene (dispersion 2).

[0384] (5) Second addition process

[0385] 89 parts by mass of the second dispersion with a solid content adjusted to 15% by mass and 11 parts by mass of a silicone compound containing methyl and phenyl (trade name: KR213 (high phenyl content), manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and heated at 110°C for 1 hour to obtain the dispersion of Comparative Example 2 (the third dispersion).

[0386] The IA / IB and methyl / phenyl ratios of the dispersion involved in Comparative Example 2 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0387] The dispersion described in Comparative Example 2 was used instead of the dispersion described in Example 1. Otherwise, the composition B and cured product B described in Comparative Example 1 were obtained in the same manner as in Example 1. The results of viscosity and transmittance, measured in the same manner as in Example 1, are shown in Table 1.

[0388] In the same manner as in Example 1, the dispersion involved in Comparative Example 2 was used to obtain composition A and cured product A. However, the dispersion of Comparative Example 2 could not be dispersed in the methyl silicone resin component, and composition A exhibited turbid aggregation, thus curing product A could not be produced.

[0389] [Comparative Example 3]

[0390] In the mixing process of Example 1, 70 parts by mass of the hydrolysate of phenyltrimethoxysilane obtained in the hydrolysis process of Example 4 were used instead of 70 parts by mass of the hydrolysate of methyltrimethoxysilane. Otherwise, the mixing process, dispersion process and first addition process were carried out in the same manner as in Example 1 to obtain a dispersion (second dispersion).

[0391] 89 parts by mass of the second dispersion with a solid content adjusted to 15% by mass and 11 parts by mass of a silicone compound containing methyl and phenyl (trade name: KR213 (high phenyl content), manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and heated at 110°C for 1 hour to obtain the dispersion of Comparative Example 3 (the third dispersion).

[0392] The IA / IB and methyl / phenyl ratios of the dispersion involved in Comparative Example 3 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0393] The dispersion described in Comparative Example 3 was used instead of the dispersion described in Example 1. Otherwise, the composition B and cured product B described in Comparative Example 1 were obtained in the same manner as in Example 1. The results of viscosity and transmittance, measured in the same manner as in Example 1, are shown in Table 1.

[0394] In the same manner as in Example 1, the dispersion involved in Comparative Example 3 was used to obtain composition A and cured product A. However, the dispersion of Comparative Example 3 could not be dispersed in the methyl silicone resin component, and composition A exhibited turbid agglomeration, thus cured product A could not be produced.

[0395] [Comparative Example 4]

[0396] In the mixing process of Example 1, 70 parts by mass of the hydrolysate of the above-mentioned phenyltrimethoxysilane were used instead of 70 parts by mass of the hydrolysate of methyltrimethoxysilane. Otherwise, the mixing process, dispersion process and first addition process were carried out in the same manner as in Example 1 to obtain a dispersion (second dispersion).

[0397] 91 parts by mass of the second dispersion with the solid content adjusted to 15% by mass and 9 parts by mass of the hydrolysate of the above-mentioned methyltrimethoxysilane were mixed and stirred at 130°C for 3 hours to obtain the dispersion of Comparative Example 4 (the third dispersion).

[0398] The IA / IB and methyl / phenyl groups involved in Comparative Example 4 were determined in the same manner as in Example 1. The results are shown in Table 1.

[0399] The dispersion described in Comparative Example 4 was used instead of the dispersion described in Example 1. Otherwise, the composition and cured product described in Comparative Example 4 were to be obtained in the same manner as in Example 1. However, the dispersion of Comparative Example 4 could not be dispersed in either methyl silicone resin or phenyl silicone resin, and compositions A and B both exhibited turbid agglomeration. Therefore, neither cured product A nor cured product B could be produced.

[0400] [Table 1]

[0401]

[0402] By comparing Examples 1 to 8 and Comparative Examples 1 to 4, it was confirmed that zirconia particles with a methyl / phenyl ratio of 0.01 or more and 10 or less, and surface-modified to the extent that 1A / 1B ≤ 3.5 using methyl-containing silane compounds and phenyl-containing silicone compounds, were well dispersed in both methyl-based phenyl silicone resins containing a large amount of methyl groups and phenyl-based silicone resins containing a large amount of phenyl groups.

[0403] Furthermore, by comparing Examples 1 to 3 and Examples 4 to 8, it was confirmed that zirconium oxide particles surface-modified with silane compounds containing methyl and phenyl groups and silicone compounds containing methyl and phenyl groups further improved the brightness of the LED package.

[0404] The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to these examples. Those skilled in the art should understand that various modifications or alterations can be conceived within the scope of the technical concept set forth in the claims, and these, of course, also fall within the technical scope of the present invention.

[0405] Industrial availability

[0406] The present invention can provide a dispersion containing surface-modified metal oxide particles that can be dispersed in both methyl silicone resins and phenyl silicone resins, a composition containing the dispersion, a sealing component formed using the composition, a light-emitting device having the sealing component, an illumination appliance having the light-emitting device, and a display device.

[0407] Label Explanation

[0408] 1A, 1B, 1C, 1D - Light-emitting devices

[0409] 2-Substrate

[0410] 2a-Substrate upper surface

[0411] 2b - Substrate lower surface

[0412] 21-Concave

[0413] 21a-bottom of concave part

[0414] 3-Light-emitting element

[0415] 4A, 4B, 4C, 4D - Sealing components

[0416] 41B, 41C, 41D - Level 1

[0417] 43B, 43C, 43D - Level 2

[0418] 45D - 3rd Floor

[0419] 5-Fluorescent Particles

Claims

1. A dispersion comprising metal oxide particles surface-modified with at least one silane compound and at least one silicone compound, and a solvent, wherein, The silane compound contains a methyl group. The silicone compound contains a hydrocarbon group having two or more carbon atoms. The molar ratio of the methyl group to the hydrocarbon group in the metal oxide particle, i.e., the methyl / hydrocarbon group ratio, is 0.01 or more and 10 or less. The total content of the silane compound and the silicone compound relative to the metal oxide particles is 190% by mass or more and 1000% by mass or less. The metal oxide particles obtained by drying the dispersion under vacuum were measured at 800 cm⁻¹ using a Fourier transform infrared spectrophotometer. -1 Above and 3800cm -1 The following wavenumber range of transmission spectra, when normalized such that the maximum value of the transmission spectrum within the range is 100 and the minimum value is 0, satisfies the following equation (1): IA / IB≤3.5 (1) In the formula, "IA" represents 3500cm -1 The standardized spectral values ​​below, "IB" represents 1100 cm⁻¹. -1 The standardized spectral values ​​below.

2. The dispersion according to claim 1, wherein, The hydrocarbon groups with 2 or more carbon atoms are aromatic hydrocarbon groups.

3. The dispersion according to claim 1, wherein, The metal oxide particles surface-modified using at least one silane compound and at least one silicone compound are secondary modified metal oxide particles obtained by the following modifications. The metal oxide particles are modified once using a first surface modification material, wherein the first surface modification material comprises a silane compound containing a methyl group and not containing a hydrocarbon group having two or more carbon atoms. The metal oxide particles that have undergone primary modification are further modified using a second surface modification material, wherein the second surface modification material comprises at least one of a silicone compound containing a methyl group and a hydrocarbon group having two or more carbon atoms, and a silicone compound that does not contain a methyl group but contains a hydrocarbon group having two or more carbon atoms.

4. The dispersion according to claim 1, wherein, The metal oxide particles are zirconium oxide particles or titanium oxide particles.

5. A composition comprising the dispersion of claim 1 or 2 and a silicone resin component.

6. A sealing component, which is a cured product of the composition of claim 5.

7. A light-emitting device comprising a sealing member as described in claim 6 and a light-emitting element sealed by said sealing member.

8. A lighting fixture comprising the light-emitting device as described in claim 7.

9. A display device comprising the light-emitting device of claim 7.

10. A method for manufacturing the dispersion according to claim 1 or 2, comprising the following steps: The process of mixing a first surface modification material and metal oxide particles to obtain a mixture; The process of dispersing the metal oxide particles in the mixture; and The step of adding a second surface-modifying material to the mixture to obtain a dispersion. The content of the metal oxide particles in the mixture is more than 10% by mass and less than 49% by mass. The total content of the first surface modification material and the metal oxide particles in the mixture is 65% by mass or more and 98% by mass or less. The first surface modification material is a silane compound containing methyl groups. The second surface modification material comprises a silicone compound containing a hydrocarbon group having two or more carbon atoms.

11. The method for manufacturing the dispersion according to claim 10, comprising the following steps: The step of hydrolyzing the first surface modification material before mixing it with the metal oxide particles; and The step of hydrolyzing the second surface modification material prior to its addition to the mixture. The dispersion process is carried out using a disperser.

12. The method for manufacturing the dispersion according to claim 11, wherein, Between the dispersion step and the step of obtaining the dispersion, there is one or both of the steps of adding a hydrophobic solvent to the dispersed mixture and removing the alcohol produced in the hydrolysis step.

13. The method for manufacturing the dispersion according to claim 10, wherein, The methyl-containing silane compound does not contain hydrocarbon groups with two or more carbon atoms.

14. A method for surface modification of metal oxide particles, comprising the following steps: The process of mixing a first surface modification material and metal oxide particles to obtain a mixture; The process of dispersing the metal oxide particles in the mixture; and The step of adding a second surface-modifying material to the mixture. The content of the metal oxide particles in the mixture is more than 10% by mass and less than 49% by mass. The total content of the first surface modification material and the metal oxide particles in the mixture is 65% by mass or more and 98% by mass or less. The first surface modification material is a silane compound containing methyl groups. The second surface modification material comprises a silicone compound containing a hydrocarbon group having two or more carbon atoms. The total content of the silane compound and the silicone compound relative to the metal oxide particles is 190% by mass or more and 1000% by mass or less.

15. The surface modification method for metal oxide particles according to claim 14, comprising the following steps: The step of hydrolyzing the first surface modification material before mixing it with the metal oxide particles; and The step of hydrolyzing the second surface modification material prior to its addition to the mixture. The dispersion process is carried out using a disperser.

16. The surface modification method for metal oxide particles according to claim 15, wherein, Between the dispersion step and the step of obtaining the dispersion, there is one or both of the steps of adding a hydrophobic solvent to the dispersed mixture and removing the alcohol produced in the hydrolysis step.

17. The surface modification method for metal oxide particles according to claim 14, wherein, The methyl-containing silane compound does not contain hydrocarbon groups with two or more carbon atoms.

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