Organic solvent dispersion sol containing conductive tin oxide particles and its manufacturing method

Abstract

As a modified metal oxide particle sol that can exhibit transparency, high particle refractive index, and good film resistivity when coated onto a substrate using a coating agent containing modified metal oxide particles, a modified metal oxide particle sol is provided, comprising modified metal oxide particles (iii) and the modified metal oxide particles dispersed in an organic solvent. The modified metal oxide particles (iii) have tin oxide particles (i) with an average primary particle size of 4 to 50 nm as a core, and are coated with metal oxide particles (ii) with an average primary particle size of 1 to 10 nm and selected from at least one of antimony oxide, tin oxide, and silicon oxide. The average primary particle size has a relationship of core particle (i) ≥ coated particle (ii), and the ratio of (total mass of metal oxides other than tin oxide) to (mass of tin oxide) is 0.005 to 1.0. Furthermore, the sol contains an amine (a) with a water solubility of 0.1 g / L or more and an amine (b) with a water solubility of less than 0.1 g / L.

Description

Technical Field

[0001] This invention relates to an organic solvent dispersion sol containing colloidal particles (also known as modified oxide particles) of conductive tin oxide and a method for manufacturing the same. Background Technology

[0002] High-purity tin oxide is known to be an insulator, but by doping it with indium and antimony, it exhibits electronic conductivity. Furthermore, tin oxide is also known to exhibit electronic conductivity due to oxygen vacancies. Utilizing these properties of tin oxide particles, it has been disclosed, for example, that a transparent conductive coating can be obtained by coating it onto a film (see Patent Document 1).

[0003] In addition, a modified metal oxide sol is disclosed in which an aqueous sol containing water-soluble amines and having an average particle size of 4 to 50 nm is subjected to hydrothermal treatment at a pressure of 0.1 to 40 MPa and a temperature of 100 to 350 °C to produce an aqueous sol containing core particles. Then, an aqueous sol containing antimony pentoxide and silicon dioxide composite colloidal particles with an average particle size of less than 5 nm or an aqueous sol containing water-soluble amines and antimony pentoxide colloidal particles with an average particle size of 1 to 10 nm is mixed with the coating particles to coat the surface of the core particles (see Patent Document 2).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Publication No. 35-6616

[0007] Patent Document 2: Japanese Patent Application Publication No. 2006-176392 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] The present invention provides an organic solvent sol comprising modified metal oxide particles (iii) having tin oxide (i) as a core and coated with metal oxide particles (ii) selected from at least one of antimony oxide, tin oxide and silicon oxide. The modified metal oxide particles (iii) have high conductivity and high refractive index, and are stably dispersed in an organic solvent, thereby enabling them to have transparency, particle refractive index and coating resistivity when coated on a substrate as a coating agent.

[0010] Methods for solving problems

[0011] According to the present invention, as a first point of view, a modified metal oxide sol is provided, which is a sol comprising modified metal oxide particles (iii) and the modified metal oxide particles dispersed in an organic solvent. The modified metal oxide particles (iii) have tin oxide particles (i) having an average primary particle size of 4 to 50 nm as a core and are coated with metal oxide particles (ii) having an average primary particle size of 1 to 10 nm and selected from at least one of antimony oxide, tin oxide and silicon oxide. The average primary particle size has a relationship of core particle (i) ≥ coated particle (ii), and the ratio of (total mass of metal oxides other than tin oxide) to (mass of tin oxide) is 0.005 to 1.0. Moreover, the sol contains an amine (a) with a water solubility of 0.1 g / L or more and an amine (b) with a water solubility of less than 0.1 g / L.

[0012] As a second point of view, a modified metal oxide sol according to the first point of view is provided, wherein the average particle size using dynamic light scattering method is 5 to 100 nm;

[0013] As a third perspective, a modified metal oxide sol according to the first or second perspective is provided, wherein the tin oxide particles (i) serving as the core particles are hydrothermally treated tin oxide particles.

[0014] As a fourth viewpoint, a modified metal oxide sol according to any one of the first to third viewpoints is provided, wherein the tin oxide particles (i) as the core particles have a crystallinity of 60% or more obtained by X-ray diffraction.

[0015] As a fifth point of view, a modified metal oxide sol according to any one of the first to fourth points of view is provided, wherein the metal oxide particles (ii) as coating particles are antimony oxide particles, or composite particles of tin oxide and silicon oxide in a mass ratio of 1:0.1 to 10.0;

[0016] As a sixth point of view, a modified metal oxide sol according to any one of the first to fifth points of view is provided, wherein an amine (a) is contained in the modified metal oxide sol at a ratio of 20 to 3000 ppm;

[0017] As a seventh point of view, a modified metal oxide sol according to any one of the first to sixth points of view is provided, wherein the modified metal oxide sol contains an amine (b) in a proportion of 1,000 to 30,000 ppm;

[0018] As an eighth point of view, a modified metal oxide sol according to any one of the first to seventh points of view is provided, wherein the amine (a) is an amine comprising primary amines, secondary amines, or combinations thereof;

[0019] As a ninth point of view, a modified metal oxide sol according to any one of the first to eighth points of view is provided, wherein the amine (b) is a tertiary amine;

[0020] As a tenth perspective, a modified metal oxide sol according to any one of the first to ninth perspectives is provided, wherein the amine (a) is at least one amine selected from n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, isobutylamine, di-n-butylamine and diisobutylamine;

[0021] As an eleventh perspective, a modified metal oxide sol according to any one of the first to tenth perspectives is provided, wherein the amine (b) is at least one amine selected from tri-n-butylamine, triisobutylamine, tri-n-pentylamine, and triisopentylamine;

[0022] As a twelfth point of view, a modified metal oxide sol according to any one of the first to eleventh points of view is provided, wherein the mass ratio of amine (b) to amine (a) is 3.0 to 200;

[0023] As a thirteenth point of view, a modified metal oxide sol according to any one of the first to twelfth points of view is provided, wherein the modified metal oxide particles (iii) are coated with at least one coating agent selected from formulas (1) to (6):

[0024]

Chemistry 1

[0025] R 1 a si(R 2 ) 4-a (1)

[0026]

[0027] R 5 d Si(R 6 ) 4-d (3)

[0028]

Chemistry 2

[0029]

[0030] In equation (1), R 1 Each of the following is an organic group: alkyl, haloalkyl, alkenyl, aryl, or having a polyether group, epoxy group, (meth)acryloyl group, mercapto group, amino group, urea group, or cyano group, and is bonded to a silicon atom via a Si-C bond. 2 Each represents an alkoxy, acyloxy, or halogen group, and 'a' represents an integer from 1 to 3.

[0031] In equations (2) and (3), R 3 and R 5Each is an alkyl group with 1 to 3 carbon atoms or an aryl group with 6 to 30 carbon atoms, and is bonded to silicon atoms via Si-C bonds. 4 and R 6 Each represents an alkoxy, acyloxy, or halogen group; Y represents an alkylene, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3.

[0032] In formulas (4) to (6), X1, X2, and X3 each represent an alkylene group with 2 to 20 carbon atoms, f, h, and j each represent an integer from 1 to 100, e, g, and i each represent an integer from 1 to 3, and Y1, Y2, and Y3 each represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or a (meth)acryloyl group.

[0033] As the fourteenth point of view, a modified metal oxide sol according to any one of the first to thirteenth points of view is provided, wherein the organic solvent is a solvent comprising alcohol, ketone, ester, ether, amide, hydrocarbon, solvent containing cyano, solvent containing halogen, solvent containing sulfonyl, solvent containing carboxyl, or a mixture thereof.

[0034] As the fifteenth point of view, a modified metal oxide sol according to the fourteenth point of view is provided, wherein the alcohol is a monohydric alcohol with 1 to 20 carbon atoms or a polyhydric alcohol with 1 to 20 carbon atoms;

[0035] As a sixteenth point of view, an antistatic composition is provided, comprising modified metal oxide particles (iii) in a modified metal oxide sol according to any one of the first to fifteenth points of view;

[0036] As the seventeenth point of view, a composition for electron transport materials is provided, comprising modified metal oxide particles (iii) in a modified metal oxide sol according to any one of the first to fifteenth points of view;

[0037] As the eighteenth point, a method for manufacturing an organic solvent sol of modified metal oxide particles according to any one of the first to fifteenth points is provided, comprising the following steps (A) to (D):

[0038] (A) Process: A process for preparing an aqueous sol containing an amine (a) with a water solubility of 0.1 g / L or more and tin oxide particles (i) with an average primary particle size of 4–50 nm.

[0039] (B) Step: A step of preparing an aqueous sol containing an amine (a) with a water solubility of 0.1 g / L or more, and metal oxide particles (ii) having an average primary particle size of 1 to 10 nm and selected from at least one of antimony oxide, tin oxide, and silicon oxide.

[0040] (C) Step: The aqueous sol of tin oxide obtained in step (A) and the aqueous sol of metal oxide particles (ii) obtained in step (B) are mixed at a ratio of (total mass of metal oxides other than tin oxide) / (mass of tin oxide) of 0.005 to 1.0 to manufacture modified metal oxide particles (iii) with tin oxide particles (i) having an average primary particle size of 4 to 50 nm as the core and coated with metal oxide particles (ii) having an average primary particle size of 1 to 10 nm and selected from at least one of antimony oxide, tin oxide and silicon oxide, and an amine (b) with a water solubility of less than 0.1 g / L is added.

[0041] (D) Step: The process of replacing the aqueous medium solvent of the aqueous sol of the modified metal oxide particles (iii) obtained in step (C) with an alcohol having 1 to 5 carbon atoms;

[0042] As the nineteenth point of view, a method for manufacturing an organic solvent sol of modified metal oxide particles (iii) according to the eighteenth point of view is provided, wherein step (A) is to add an amine (a) with a water solubility of more than 0.1 g / L to an aqueous sol of tin oxide particles (i) having an average primary particle size of 4 to 50 nm, and then perform hydrothermal treatment (A-1) at a pressure of 0.1 to 40 MPa and a temperature of 100 to 350 °C for 0.01 to 100 hours.

[0043] As a twentieth viewpoint, a method for manufacturing an organic solvent sol of modified metal oxide particles according to the eighteenth or nineteenth viewpoint is provided, wherein a step (E) and / or a step (F) are added after step (D):

[0044] (E) Process: A process of adding at least one coating agent selected from the following formulas (1) to (6) to the organic solvent sol of the modified metal oxide particles (iii) to perform surface treatment of the modified metal oxide particles (iii).

[0045] (F) Step: A step in which the alcohol solvent of the modified metal oxide particles (iii) having 1 to 5 carbon atoms is replaced with an alcohol, ketone, ester, ether, amide, hydrocarbon, solvent containing a cyano group, solvent containing a halogen, solvent containing a sulfonyl group, solvent containing a carboxyl group, or a mixture thereof, other than those used in step (D).

[0046] R 1 a si(R 2 ) 4-a (1)

[0047]

[0048] R 5 d Si(R 6 ) 4-d (3)

[0049]

[0050] In equation (1), R 1 Each of the following is an organic group: alkyl, haloalkyl, alkenyl, aryl, or having a polyether group, epoxy group, (meth)acryloyl group, mercapto group, amino group, urea group, or cyano group, and is bonded to a silicon atom via a Si-C bond. 2 Each represents an alkoxy, acyloxy, or halogen group, and 'a' represents an integer from 1 to 3.

[0051] In equations (2) and (3), R 3 and R 5 Each is an alkyl group with 1 to 3 carbon atoms or an aryl group with 6 to 30 carbon atoms, and is bonded to silicon atoms via Si-C bonds. 4 and R 6 Each represents an alkoxy, acyloxy, or halogen group; Y represents an alkylene, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3.

[0052] In formulas (4) to (6), X1, X2, and X3 each represent an alkylene group with 2 to 20 carbon atoms, f, h, and j each represent an integer from 1 to 100, e, g, and i each represent an integer from 1 to 3, and Y1, Y2, and Y3 each represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or a (meth)acryloyl group.

[0053] The effects of the invention

[0054] In this invention, modified metal oxide particles (iii) are used, wherein, for tin oxide particles (i) that become core particles, metal oxide particles (ii) selected from at least one of antimony oxide, tin oxide and silicon oxide are used as coating particles to coat the surface of the core particles.

[0055] Both the core particles and the coated particles can be stably dispersed in an aqueous medium using colloidal metal oxide particles in an aqueous sol. These aqueous sols can be mixed. For example, by adding an aqueous sol containing coated particles (ii) to an aqueous sol containing core particles (i), an aqueous sol containing modified metal oxide particles (iii) is obtained. These aqueous sols must contain an amine (a) with a water solubility of 0.1 g / L or higher for stable dispersion in an aqueous medium. Regarding the two aqueous sols containing nuclei (i) and coated particles (ii), a portion of them are removed by cation exchange before or after mixing. Regarding the aqueous sol containing the mixed modified metal oxide particles (iii), in the stage of replacing the dispersion medium from the aqueous medium with an organic solvent to produce an organic solvate of the modified metal oxide particles (iii), the aqueous medium can be replaced with an organic solvent by the coexistence of an amine (a) with a water solubility of more than 0.1 g / L and an amine (b) with a water solubility of less than 0.1 g / L, thereby producing an organic solvate of the modified metal oxide particles (iii) without aggregation.

[0056] In addition, hydrothermal treatment can also be performed on nuclear particles (i). For example, hydrothermal treatment can be performed for 0.01 to 100 hours at a pressure of 0.1 to 40 MPa and a temperature of 100 to 350 °C. It is desirable for the nuclear particles to be stably dispersed in an aqueous medium, so an amine (a) with a water solubility of 0.1 g / L or more is required.

[0057] In this invention, the modified metal oxide particles (iii) are a sol dispersed in an organic solvent. To improve the dispersibility of the modified metal oxide particles (iii) in the organic solvent by replacing the aqueous medium solvent with an organic solvent, an amine (b) with a water solubility of less than 0.1 g / L is required. Detailed Implementation

[0058] The present invention relates to a modified metal oxide sol, which comprises modified metal oxide particles (iii) dispersed in an organic solvent. The modified metal oxide particles (iii) have tin oxide particles (i) with an average primary particle size of 4 to 50 nm as the core and are coated with metal oxide particles (ii) with an average primary particle size of 1 to 10 nm selected from at least one of antimony oxide, tin oxide, and silicon oxide. The average primary particle size has a relationship of core particle (i) ≥ coated particle (ii), and the ratio of (total mass of metal oxides other than tin oxide) to (mass of tin oxide) is 0.005 to 1.0. The sol also contains an amine (a) with a water solubility of 0.1 g / L or more and an amine (b) with a water solubility of less than 0.1 g / L.

[0059] As a method for determining the solubility of a chemical substance in water, column elution is used when the solubility is low, and flask method is used when the solubility is high. For example, the determination method specified in OECD Test Guide 105 (Solubility in Water) can be used.

[0060] The term "metal oxides other than tin oxide" refers to metal oxides whose metallic components are not tin.

[0061] The average primary particle size of tin oxide particles (i) and metal oxide particles (ii) can be observed and determined by transmission electron microscopy.

[0062] The sol containing the modified metal oxide particles (iii) described above can be determined by dynamic light scattering. The average particle size using dynamic light scattering is preferably 5–100 nm, 10–60 nm, or 10–50 nm.

[0063] Tin oxide particles (i) with an average primary particle size of 4 to 50 nm, used as raw materials in this invention, can be prepared as an aqueous sol containing the tin oxide particles (i).

[0064] For example, by using methods such as ion exchange, degelation, hydrolysis, and reaction, it is possible to easily produce sols in the form of colloidal particles with a particle size of about 4 to 50 nm.

[0065] Examples of the aforementioned ion exchange method include treating stannates such as sodium stannate with a hydrogen-form cation exchange resin, or treating tin salts such as tin chloride and tin nitrate with a hydroxyl-form anion exchange resin. Examples of the aforementioned degelling method include neutralizing tin salts with alkali or stannic acid with hydrochloric acid, washing the resulting tin hydroxide gel, and then degelling it with acid or alkali. Examples of the aforementioned hydrolysis method include hydrolyzing tin alkoxides, or removing unwanted acid by hydrolyzing basic tin chloride salts under heating. Examples of the aforementioned reaction method include reacting metallic tin powder with acid.

[0066] In addition, the aqueous sol containing the above-mentioned tin oxide particles (i) can also be obtained by reacting metallic tin with hydrogen peroxide water.

[0067] Metallic tin can be used in powder or granular form. For example, it can be used to produce atomized metallic tin powder obtained by melting an ingot and then spraying it to solidify, or to produce flake-shaped metallic tin powder by cutting an ingot using a turntable, file, or the like.

[0068] Regarding hydrogen peroxide, a commercially available 35% by mass aqueous solution can be used at the desired concentration. For example, by preparing an aqueous solution of an organic acid such as oxalic acid with a concentration of 1-30% by mass or 5-20% by mass, and simultaneously or alternately adding hydrogen peroxide and metallic tin to this aqueous solution, an aqueous solution of stannic acid can be obtained. The aqueous solution of an organic acid such as oxalic acid is placed in a reaction vessel equipped with a stirrer, and hydrogen peroxide and metallic tin are added simultaneously or alternately from their respective inlets while stirring. Since the slurry containing stannin oxide colloids is acidic, glass reaction apparatus or glass-lined (enamel) reaction apparatus is preferred for use in these processes.

[0069] Hydrogen peroxide water and metallic tin (H2O2 / Sn molar ratio) are added to an aqueous solution of organic acids such as oxalic acid while maintaining the ratio at 2–3. More specifically, the following staged addition method can be described: relative to the total mass of hydrogen peroxide water and metallic tin to be added, 1 / 3 to 1 / 30 of the mass of each is taken, and a series of steps is repeated 3 to 30 times, including the addition of hydrogen peroxide water to the aqueous solution of organic acids such as oxalic acid, followed by the addition of metallic tin, and then reacting for 2 to 20 minutes.

[0070] Even if the H₂O₂ / Sn molar ratio is slightly above 3, the reaction can proceed, but it is not preferable to exceed it significantly. When the H₂O₂ / Sn molar ratio is less than 2, oxidation becomes incomplete, and therefore is not preferred. Regarding the addition time of hydrogen peroxide water and metallic tin, it can be added over a period of 0.4 to 10 hours, preferably 0.4 to 5 hours. When the addition time is less than 0.4 hours, the exothermic reaction is violent and cannot be controlled, and unreacted metallic tin is easily left behind, so it is not preferred. Alternatively, it can be added over 10 hours, but this is uneconomical and therefore not preferred.

[0071] The reaction of metallic tin in aqueous solutions of organic acids such as oxalic acid with hydrogen peroxide water is carried out at 30–95°C, preferably 40–85°C. The reaction of hydrogen peroxide with metallic tin is an oxidation reaction, thus exothermic. Additionally, the decomposition of hydrogen peroxide also occurs simultaneously, which is also exothermic. Therefore, careful temperature control is essential, and cooling may be necessary as needed. While the reaction temperature can be below 30°C, excessive cooling is required due to the exothermic nature of the reaction, resulting in excessive reaction time and inefficiency. At reaction temperatures above 95°C, coarse colloidal particles are formed, which is therefore undesirable.

[0072] This process involves removing excess electrolytes (mainly anions) from a coagulated slurry of tin oxide colloids and degelatinizing the tin oxide colloidal particles to obtain a sol. By removing the excess electrolytes, a sol in which the tin oxide colloidal particles are dispersed in a near-primary particle state can be obtained. This cleaning can be performed by methods such as coagulation and precipitation followed by decanting of the supernatant, ultrafiltration, or ion exchange. In cases containing a large amount of electrolyte, a cleaning method involving repeated ultrafiltration followed by water injection and then ultrafiltration again (ultrafiltration-water injection-ultrafiltration) is particularly preferred. The average primary particle size of the tin oxide composite colloidal particles obtained using this process is 4–50 nm or 10–20 nm (nanometers).

[0073] An anion exchange process can be added to the aqueous tin oxide sol. This anion exchange treatment yields a sol that remains stable even at high concentrations. Commercially available anion exchange resins can be used for the anion exchange, prepared in a hydroxyl form. Anion exchange is easily performed by passing the aqueous tin oxide sol through a column packed with anion exchange resin. The preferred flow temperature is 0–60°C, and the preferred flow rate is a space velocity SV1–10 h.

[0074] Before and / or after anion exchange treatment, the stability of the tin oxide aqueous sol can be improved by adding an alkaline substance. As the alkaline substance used, an organic base is preferred; for example, an amine (a) with a water solubility of 0.1 g / L or more, 0.1–5000.0 g / L, 0.1–3000.0 g / L, 0.1–2000.0 g / L, 0.5–2000.0 g / L, 1.0–2000.0 g / L, 10.0–2000.0 g / L, or 100–1000.0 g / L can be used.

[0075] Amine (a) can be added at a ratio of 20 to 3000 ppm or 20 to 1000 ppm. Amine (a) can be an amine comprising primary amines, secondary amines, or combinations thereof. For example, with respect to amine (a), at least one amine selected from n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, isobutylamine, di-n-butylamine, and diisobutylamine can be used.

[0076] In this invention, the crystallinity of the tin oxide particles (i) used as the nucleus particles obtained by X-ray diffraction is preferably 60% or more, or 65% or more and 100% or less. Typically, tin oxide particles in the range of 60 to 95% or 65 to 95% can be used. Preferably, it is 60% or more, and typically it can be set to 60 to 99% or 60 to 95%.

[0077] In this invention, tin oxide aqueous sol with a SnO2 concentration of 1-50% by mass, prepared by the above method, can also be directly used to produce hydrothermally treated tin oxide particles by hydrothermal treatment under pressure, at 100-350°C, and for 0.01-100 hours. For example, the above-mentioned tin oxide aqueous sol can be placed in an autoclave and treated for 0.01-100 hours at a pressure of 0.1-40 MPa and a temperature of 100-350°C.

[0078] The medium for these tin oxide sols can be water or a hydrophilic organic solvent, preferably an aqueous sol. Furthermore, the pH of the sol is a value that stabilizes the sol, typically around 0.2 to 11.5. To achieve the objectives of this invention, the tin oxide sol can contain any components, such as alkaline substances, acidic substances, hydroxycarboxylic acids, etc., used for sol stabilization. The concentration of the tin oxide sol used, based on tin oxide, is approximately 0.5 to 50% by mass, and the lower the concentration, the better; preferably 1 to 30% by mass.

[0079] Regarding the tin oxide sol, an alkaline sol stabilized with an organic base such as the aforementioned amine is particularly preferred. The addition of the amine is preferably carried out at 5–100°C, more preferably at room temperature (20°C)–60°C. Furthermore, regarding the mixing, the amine is added to the tin oxide sol under stirring, and thorough mixing is required, preferably for 0.5–3 hours.

[0080] Regarding the coated particles (ii) used in this invention, an aqueous sol of the coated particles can be used. Regarding the coated particles (ii), either individual antimony oxide particles (ii-1) or composite particles of tin oxide and silicon oxide (ii-2) in a mass ratio of tin oxide:silicon dioxide = 1:0.1 to 10.0 can be used.

[0081] Antimony pentoxide colloidal particles containing alkylamines (ii-1) can be obtained by oxidation, acid decomposition, etc. Examples of acid decomposition include reacting an alkali metal antimonate with an inorganic acid followed by amine decomposition (Japanese Patent Application Publication Nos. 60-41536, 61-227918, and 2001-123115). Examples of oxidation include oxidizing antimony trioxide with hydrogen peroxide in the presence of an amine and an alkali metal (Japanese Patent Application Publication Nos. 57-11848 and 59-232921); and then adding an amine or alkali metal after oxidizing antimony trioxide with hydrogen peroxide. Regarding the amine, for example, an amine (a) with a water solubility of 0.1 g / L or higher can be used. Amine (a) can be added at a ratio of 20–3000 ppm or 20–1000 ppm. The amine (a) can be any amine comprising primary amines, secondary amines, or combinations thereof. For example, with respect to amine (a), at least one amine selected from n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, isobutylamine, di-n-butylamine, and diisobutylamine can be used.

[0082] Antimony pentoxide colloidal particles containing alkylamines (ii-1) are tiny antimony pentoxide colloidal particles. In terms of particle size, observed by electron microscopy, the oligomers or primary particles have a diameter of about 1 to 20 nm. As the amine component, alkylamine salts such as diisopropylamine are preferred, and the molar ratio of amine to Sb₂O₅ is 0.02 to 4.00.

[0083] In the above-mentioned coating, silica particles containing alkylamines can be further added to the antimony pentoxide colloidal particles containing amines.

[0084] The antimony pentoxide and silica composite colloid that can be used as a coating sol can be obtained by a known method as shown below (e.g., Japanese Patent Publication No. 50-40119). That is, it can be obtained by decation using a cation exchange resin after mixing an aqueous solution of alkali metal silicate or silicate with an aqueous solution of alkali metal antimonate.

[0085] Potassium antimony aqueous solution is preferred as the antimony raw material. Sodium silicate, potassium silicate, and active silicic acid obtained by cation exchange of these can be used as the silica raw material. The molar ratio of SiO2 / Sb2O5 is 0.55 to 55. In terms of particle size, the oligomers or average primary particles are less than 5 nm, preferably 1 to 5 nm, as observed by electron microscopy.

[0086] The colloidal particles (ii-2) of the tin oxide and silica composite used in the coating sol of the present invention can be obtained by the method described below.

[0087] The sol is obtained by preparing an aqueous solution containing stannate and silicate at a SiO2 / SnO2 mass ratio of 0.1 to 10, and removing cations present in the resulting aqueous solution. The total concentration of SnO2 and SiO2 in the sol is typically 40% by mass or less, practically preferably 2% by mass or more, and more preferably 5% to 30% by mass.

[0088] The sol can exist stably with virtually no alkali components. However, it can also contain alkali components and be stabilized. Regarding this alkali component, an amine (a) can be added at a ratio of 20–3000 ppm or 20–1000 ppm. The amine (a) can be an amine comprising primary amines, secondary amines, or combinations thereof. For example, at least one amine selected from n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, isobutylamine, di-n-butylamine, and diisobutylamine can be used. These alkali components can be contained in an amount of about 30% by mass or less relative to the total amount of SnO2 and SiO2. Furthermore, two or more of these can be mixed. By adding an amine (a) at a ratio of 20–3000 ppm, the amine dissolved in the sol is adsorbed onto the surface of the modified metal oxide particles, thereby improving the dispersion stability.

[0089] The sol is a colorless, transparent, or slightly colloidal liquid with a pH of 1–9. Furthermore, it is stable for more than 3 months at room temperature and more than 1 month at 60°C, without forming any precipitates. Additionally, the sol does not thicken or gel.

[0090] Examples of stannates and silicates used in the manufacture of this sol include sodium stannate (Na₂SnO₃·3H₂O) and sodium silicate (water glass). Alternatively, substances dissolved in an aqueous solution of an alkali metal hydroxide, such as stannic acid or silicate, can also be used. Examples include methods for preparing an aqueous solution by dissolving powdered stannates and silicates in water; methods for preparing an aqueous solution by mixing aqueous solutions of stannates and silicates; and methods for preparing an aqueous solution by adding powdered stannates and aqueous solutions of silicates to water. For the aqueous solution of stannates, a SnO₂ concentration of approximately 0.1 to 30% by mass is preferred, but concentrations higher are also acceptable. For the aqueous solution of silicates, a SiO₂ concentration of approximately 0.1 to 30% by mass is preferred, but concentrations higher are also acceptable.

[0091] The aqueous solution can be prepared under stirring at room temperature (approximately 20°C) to 100°C, preferably at room temperature (approximately 20°C) to 60°C. The aqueous solution to be mixed, based on the SiO2 / SnO2 mass ratio, is preferably 0.1 to 100. Next, the cations present in the aqueous solution obtained are removed to obtain an aqueous sol. As a method for decation treatment, contact with a hydrogen-form ion exchanger or salting out can be used. The hydrogen-form ion exchanger used here is a commonly used hydrogen-form ion exchanger; if convenient, a commercially available hydrogen-form ion exchange resin can be used.

[0092] Regarding this sol, when the concentration is low, the aqueous sol can be concentrated using conventional methods, such as evaporation or ultrafiltration, as needed to increase the sol concentration. Ultrafiltration is particularly preferred. During this concentration, the temperature of the sol is preferably maintained below approximately 100°C, and particularly below 60°C. Furthermore, there is no particular limitation on its lower limit, but it is preferably maintained above 10°C, and more preferably above 20°C.

[0093] According to the present invention, modified tin oxide colloidal particles (iii-1) coated with amine-containing Sb₂O₅ colloidal particles (ii-1) are negatively charged in a sol. The aforementioned tin oxide particles (i) are positively charged, and the Sb₂O₅ colloid is negatively charged. Therefore, it is assumed that through mixing, the negatively charged Sb₂O₅ colloid (ii-1) is electrically attracted around the positively charged tin oxide colloidal particles (i), and then the Sb₂O₅ is chemically bonded to the surface of the positively charged colloidal particles, with the positively charged particles as the nucleus, and the negatively charged Sb₂O₅ covering its surface, thereby generating modified tin oxide colloidal particles (iii-1).

[0094] When tin oxide colloidal particles (i) with an average primary particle size of 4–50 nm, serving as the core sol, are mixed with amine-containing Sb₂O₅ colloids (ii-1) serving as the coating sol, a stable sol cannot be obtained if the amount of metal oxide in the coating sol is less than 1 part by mass relative to 100 parts by mass of the core sol (SnO₂). This is believed to be because when the amount of Sb₂O₅ colloid is insufficient, the coating of the surface of the colloidal particles in the composite, with tin oxide colloidal particles as the core, becomes inadequate, making it easy for the generated colloidal particles to aggregate, resulting in an unstable sol. Therefore, the amount of Sb₂O₅ colloidal particles to be mixed can be less than the amount covering the entire surface of the tin oxide colloidal particles, but more than the minimum amount required to generate a stable sol of modified tin oxide particles. When an amount of Sb₂O₅ colloidal particles exceeding the amount used for surface coating is used in the above mixing, the resulting sol is merely a stable mixture of the Sb₂O₅ colloid sol and the generated modified tin oxide colloidal particle sol.

[0095] The aforementioned tin oxide colloidal particles (i) are positively charged, while the tin oxide-silica composite colloid (ii-2) is negatively charged. Therefore, it is assumed that through mixing, the negatively charged tin oxide-silica composite colloid (ii-2) is electrically attracted around the positively charged tin oxide colloidal particles (i), and then chemically bonds the tin oxide-silica composite colloid to the surface of the positively charged colloidal particles. With the positively charged particles as the nucleus, the negatively charged tin oxide-silica composite colloid covers its surface, thereby generating modified tin oxide colloidal particles (iii-2).

[0096] When tin oxide colloidal particles (i) with an average primary particle size of 4–50 nm, serving as the core sol, are mixed with a tin oxide and silica composite colloid (ii-2) serving as the coating sol, a stable sol cannot be obtained if the amount of metal oxide (SnO2) in the coating sol is less than 1 part by mass relative to 100 parts by mass of the core sol. This is believed to be because when the amount of the tin oxide and silica composite colloid is insufficient, the surface coating of the colloidal particles using this composite, with tin oxide colloidal particles as the core, becomes insufficient, making it easy for the generated colloidal particles to aggregate, resulting in an unstable sol. Therefore, the amount of tin oxide and silica composite colloidal particles to be mixed can be less than the amount covering the entire surface of tin oxide or tin oxide-zirconia composite colloidal particles, but more than the minimum amount required to generate a stable sol of modified tin oxide colloidal particles. When a quantity of tin oxide and silica composite colloidal particles exceeding the amount used in the surface coating is used in the above mixing, the resulting sol is simply a stable mixture of the sol of the tin oxide and silica composite colloidal particles and the sol of the generated modified tin oxide colloidal particles.

[0097] Preferably, when modifying tin oxide colloidal particles by coating the surface, the amount of the tin oxide and silicon dioxide composite colloid used is 50 parts by mass or less relative to 100 parts by mass of the metal oxide (SnO2) in the nucleus sol, based on the metal oxide in the coated sol.

[0098] The sol of the present invention is obtained by the following method, which includes the following steps (A) to (D):

[0099] (A) Process: A process for preparing an aqueous sol containing an amine (a) with a water solubility of 0.1 g / L or more and tin oxide particles (i) with an average primary particle size of 4–50 nm.

[0100] (B) Step: A step of preparing an aqueous sol containing an amine (a) with a water solubility of 0.1 g / L or more, and metal oxide particles (ii) having an average primary particle size of 1 to 10 nm and selected from at least one of antimony oxide, tin oxide, and silicon oxide.

[0101] (C) Step: The aqueous sol of tin oxide obtained in step (A) and the aqueous sol of metal oxide particles (ii) obtained in step (B) are mixed at a ratio of (total mass of metal oxides other than tin oxide) / (mass of tin oxide) of 0.005 to 1.0 to manufacture modified metal oxide particles (iii) with tin oxide particles (i) having an average primary particle size of 4 to 50 nm as the core and coated with metal oxide particles (ii) having an average primary particle size of 1 to 10 nm and selected from at least one of antimony oxide, tin oxide and silicon oxide, and an amine (b) with a water solubility of less than 0.1 g / L is added.

[0102] (D) Step: The process of replacing the aqueous medium solvent of the aqueous sol of the modified metal oxide particles (iii) obtained in step (C) with an alcohol having 1 to 5 carbon atoms.

[0103] In this invention, regarding step (A), it is possible to use a process (A-1) in which an amine (a) with a water solubility of 0.1 g / L or more is added to an aqueous sol containing tin oxide particles (i) with an average primary particle size of 4 to 50 nm, and then subjected to hydrothermal treatment at a pressure of 0.1 to 40 MPa and a temperature of 100 to 350 °C for 0.01 to 100 hours.

[0104] In this invention, regarding the mixing of the aqueous sol of tin oxide particles (i) obtained in step (A) and the aqueous sol of metal oxide particles (ii) selected from at least one of antimony oxide, tin oxide and silicon oxide obtained in step (B) in step (C), it is preferable to perform the above mixing in a ratio of (total mass of metal oxides other than tin oxide) / (mass of tin oxide) of 0.005 to 1.0, or 0.005 to 0.5, or 0.01 to 0.5, or 0.01 to 0.3, or 0.01 to 0.2, or 0.04 to 0.15.

[0105] Regarding the amines (b) used in process (C) with a water solubility of less than 0.1 g / L, the following can be listed: less than 0.1 g / L, more than 0.00001 g / L but less than 0.1 g / L, more than 0.00002 g / L but less than 0.1 g / L, more than 0.00003 g / L but less than 0.1 g / L, more than 0.00005 g / L but less than 0.1 g / L, more than 0.0001 g / L but less than 0.1 g / L, and more than 0.0001 g / L but less than 0.1 g / L. Tertiary amines up to 0.1 g / L, 0.001 g / L or more, less than 0.1 g / L, 0.01 g / L or more, less than 0.1 g / L, 0.00003 g / L or more, 0.08 g / L, 0.00003 g / L or more, 0.05 g / L, 0.00003 g / L or more, 0.03 g / L, for example, can be exemplified by at least one amine selected from tri-n-butylamine, triisobutylamine, tri-n-pentylamine and triisopentylamine.

[0106] The modified metal oxide sol can contain amines (a) at a ratio of 20–3000 ppm or 20–1000 ppm.

[0107] The modified metal oxide sol can contain amines (b) in proportions of 1,000 to 30,000 ppm or 1,000 to 10,000 ppm.

[0108] It is believed that the amine (b) with a water solubility of less than 0.1 g / L added in step (C) is partially adsorbed onto the surface of the modified metal oxide particles (iii) in the aqueous sol of step (C). When the dispersion medium of the sol is replaced from an aqueous medium solvent to an organic solvent in the subsequent step (D), the presence of the amine (b) improves its compatibility with the organic solvent, preventing the modified metal oxide particles (iii) from agglomerating and allowing them to disperse in the organic solvent. This causes the amine (b) to migrate from the surface of the modified metal oxide particles (iii) into the organic solvent. In the organic solvent-dispersed sol of the modified metal oxide particles (iii), both amine (a) and amine (b) can be detected from the dispersion medium. Because the modified metal oxide particles (iii) are sufficiently dispersed in the organic solvent, the sol exists stably, and when a coating agent containing them is applied to a substrate and cured, the modified metal oxide particles do not become biased on the substrate, thus achieving a high refractive index and good conductivity. The refractive index of such modified metal oxide particles is preferably in the range of 1.75 to 2.00.

[0109] Regarding alcohols with 1 to 5 carbon atoms in the above (D) process, examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, and propylene glycol monomethyl ether.

[0110] In the modified metal oxide sol obtained in this invention, the mass ratio of amine (b) to amine (a) is preferably 3.0 to 200, 3.0 to 100, or 3.0 to 60.

[0111] In this invention, after step (D), steps (E) and / or (F) can be added:

[0112] (E) Process: A process of adding at least one coating agent selected from formulas (1) to (6) to the organic solvent sol of modified metal oxide particles (iii) to perform surface treatment of the modified metal oxide particles (iii).

[0113] (F) Step: A step in which the alcohol solvent of the modified metal oxide particles (iii) having 1 to 5 carbon atoms is replaced with an alcohol, ketone, ester, ether, amide, hydrocarbon, solvent containing cyano, solvent containing halogen, solvent containing sulfonyl, solvent containing carboxyl, or a mixture thereof, other than those used in step (D).

[0114] In the coating agent of the above (E) process, formula (1) to (3) are silane coupling agents, and formula (4) to (6) are phosphate ester compounds. As a coating agent, silane coupling agents, phosphate ester compounds, or combinations thereof can be used.

[0115] For example, it is also possible to perform step (E) after step (D); to perform step (F) after step (D); to perform step (E) after step (D) and then perform step (F).

[0116] As the above-mentioned silane compound, it can be coated with a hydrolysate of at least one silane compound selected from formulas (1) to (3).

[0117] In equation (1), R 1 Each of the following is an organic group: alkyl, haloalkyl, alkenyl, aryl, or having a polyether group, epoxy group, (meth)acryloyl group, mercapto group, amino group, urea group, or cyano group, and is bonded to a silicon atom via a Si-C bond. 2 Each represents an alkoxy, acyloxy, or halogen group, and 'a' represents an integer from 1 to 3.

[0118] In equations (2) and (3), R 3 and R 5 Each is an alkyl group with 1 to 3 carbon atoms or an aryl group with 6 to 30 carbon atoms, and is bonded to silicon atoms via Si-C bonds. 4 and R 6 Each represents an alkoxy, acyloxy, or halogen group; Y represents an alkylene group, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3.

[0119] The alkyl groups mentioned above are alkyl groups having 1 to 18 carbon atoms, and examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclopropyl, etc. Butyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1, 2,2-Trimethyl-n-propyl, 1-Ethyl-1-methyl-n-propyl, 1-Ethyl-2-methyl-n-propyl, Cyclohexyl, 1-Methylcyclopentyl, 2-Methylcyclopentyl, 3-Methylcyclopentyl, 1-Ethylcyclobutyl, 2-Ethylcyclobutyl, 3-Ethylcyclobutyl, 1,2-Dimethylcyclobutyl, 1,3-Dimethylcyclobutyl, 2,2-Dimethylcyclobutyl, 2,3-Dimethylcyclobutyl, 2,4-Dimethylcyclobutyl, 3,3-Dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl 1-Isopropylcyclopropyl, 2-Isopropylcyclopropyl, 1,2,2-Trimethylcyclopropyl, 1,2,3-Trimethylcyclopropyl, 2,2,3-Trimethylcyclopropyl, 1-Ethyl-2-methylcyclopropyl, 2-Ethyl-1-methylcyclopropyl, 2-Ethyl-2-methylcyclopropyl and 2-Ethyl-3-methylcyclopropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, etc., but not limited to these.

[0120] In addition, regarding alkylene groups, examples of alkylene groups derived from the aforementioned alkyl groups can be listed.

[0121] The aryl groups mentioned above are aryl groups with 6 to 30 carbon atoms, such as phenyl, naphthyl, anthracene, pyrene, etc.

[0122] As an alkenyl group, alkenyl groups having 2 to 10 carbon atoms include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-prop ... -Butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, etc., but not limited to these.

[0123] Regarding the aforementioned alkoxy groups, examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl n-butoxy, 2-methyl n-butoxy, 3-methyl n-butoxy, 1,1-dimethyl n-propoxy, 1,2-dimethyl n-propoxy, 2,2-dimethyl n-propoxy, 1-ethyl n-propoxy, and n-hexyloxy, but these are not limited to these.

[0124] The aforementioned acyloxy group is an acyloxy group with 2 to 10 carbon atoms. Examples include methyl carbonyloxy, ethyl carbonyloxy, n-propyl carbonyloxy, isopropyl carbonyloxy, n-butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, n-pentyl carbonyloxy, 1-methyl n-butyl carbonyloxy, 2-methyl n-butyl carbonyloxy, 3-methyl n-butyl carbonyloxy, 1,1-dimethyl n-propyl carbonyloxy, 1,2-dimethyl n-propyl carbonyloxy, 2,2-dimethyl n-propyl carbonyloxy, 1-ethyl n-propyl carbonyloxy, n-hexyl carbonyloxy, 1-methyl n-pentyl carbonyloxy, 2-methyl n-pentyl carbonyloxy, etc., but it is not limited to these.

[0125] Examples of halogen groups include fluorine, chlorine, bromine, and iodine.

[0126] As an organic group containing a polyether group, polyetherpropyl groups containing an alkoxy group can be listed. For example, (CH3O)3SiC3H6(OC2H4)nOCH3 can be listed. n can be used in the range of 1 to 100 or 1 to 10.

[0127] Examples of organic groups with epoxy groups include 2-(3,4-epoxycyclohexyl)ethyl and 3-epoxypropoxypropyl.

[0128] The term "(meth)acryloyl" refers to both acryloyl and methacryloyl groups. Examples of organic groups containing a (meth)acryloyl group include 3-methacryloyloxypropyl and 3-acryloyloxypropyl.

[0129] Organic groups containing thiol groups include, for example, 3-mercaptopropyl.

[0130] Organic groups containing amino groups include, for example, 2-aminoethyl, 3-aminopropyl, N-2-(aminoethyl)-3-aminopropyl, N-(1,3-dimethylbutylene)aminopropyl, N-phenyl-3-aminopropyl, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl, etc.

[0131] Organic groups containing a urea group include, for example, 3-ureopropyl.

[0132] Organic groups containing a cyano group include, for example, 3-cyanopropyl.

[0133] Formulas (2) and (3) above are preferably compounds in which trimethylsilyl groups can be formed on the surface of silica particles. Examples of such compounds are shown below.

[0134]

Transformation 3

[0135]

[0136] In the above formula, R 12 The alkoxy group can be, for example, methoxy or ethoxy. The aforementioned silane compounds can, for example, be silane compounds manufactured by Shin-Etsu Chemical Co., Ltd.

[0137] The process involves the following steps: On the surface of the modified metal oxide particles (iii), hydroxyl groups, or silanol groups (if using silica particles), react with the aforementioned silane compound, thereby coating the silica particles with the silane compound through siloxane bonds. The reaction can be carried out at temperatures ranging from 20°C to the boiling point of the dispersion medium, for example, from 20°C to 100°C. The reaction can be carried out for approximately 0.1 to 6 hours.

[0138] Regarding the aforementioned silane compound, as a coating amount on the surface of the modified metal oxide particles (iii), it is possible to achieve a silicon atom density equivalent to 0.1 atoms / nm in the silane compound. 2 ~6.0 units / nm 2 A certain amount of silane compound is added to the sol of modified metal oxide particles (iii) to coat the surface of silica particles.

[0139] The hydrolysis of the aforementioned silane compounds requires water. When the aqueous medium solvent is replaced with an organic solvent, residual water in the solvent can be used. For example, water present in quantities of 0.01 to 1% by mass can be used. Furthermore, hydrolysis can be carried out using a catalyst or without one.

[0140] As the aforementioned phosphate ester compound, at least one phosphate ester compound selected from formulas (4) to (6) can be listed as a phosphate ester.

[0141] In formulas (4) to (6), X1, X2 and X3 each represent an alkylene group with 2 to 20 carbon atoms, f, h and j each represent an integer from 1 to 100, e, g and i each represent an integer from 1 to 3, and Y1, Y2 and Y3 each represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or a (meth)acryloyl group.

[0142] As a phosphate ester, polyoxyethylene alkyl ether phosphate esters are preferred. For example, the phosphate esters mentioned above can be phosphate esters in which the terminal alkyl group (Y1) in the above formula (4) represents an alkyl group with 6 to 10 or 12 to 15 carbon atoms. As for their products, for example, Phosphhanol RA-600 and RS-610 manufactured by Toho Chemical Industry Co., Ltd. can be used.

[0143] For alkylene groups having 2 to 20 carbon atoms, examples can be given of alkylene groups derived from the alkyl groups described above. For alkenyl groups having 2 to 20 carbon atoms and aryl groups having 6 to 30 carbon atoms, examples can be given as described above.

[0144] Regarding the aforementioned phosphate ester compound, as a coating amount on the surface of the modified metal oxide particles (iii), it is possible to achieve a phosphorus atom density equivalent to 0.1 atoms / nm in the phosphate ester compound. 2 ~6.0 units / nm 2 A certain amount of phosphate ester compound is added to the sol of modified metal oxide particles (iii) to coat the surface of the modified metal oxide particles.

[0145] In this invention, step (F) can be added after step (D).

[0146] (F) Step: A step in which the alcohol solvent of the modified metal oxide particles (iii) with 1 to 5 carbon atoms obtained in step (D) is replaced with alcohols, ketones, esters, ethers, amides, hydrocarbons, solvents containing cyano groups, solvents containing halogens, solvents containing sulfonyl groups, solvents containing carboxyl groups, or mixtures thereof, other than those used in step (D).

[0147] Alcohols other than those used in process (D) that can be used in process (F) are monohydric alcohols with 1 to 20 carbon atoms or 1 to 10 carbon atoms, or polyhydric alcohols with 1 to 20 carbon atoms or 1 to 10 carbon atoms. Examples of monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monomethyl ether, isobutanol, n-pentanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 1-octanol, 1-nonanol, 1-decanol, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, tetrahydrofurfuryl alcohol, etc. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, etc.

[0148] As a ketone, an aliphatic ketone is preferred if it has 1 to 20 carbon atoms or 1 to 10 carbon atoms. Examples include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl pentanyl ketone, cyclohexanone, methyl cyclopentanone, isophorone, 4-hydroxy-4-methyl-2-pentanone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-pentanone, 2-heptanone, and acetylacetone.

[0149] As esters, aliphatic esters are preferred, especially those with 1 to 20 carbon atoms or 1 to 10 carbon atoms. Examples include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl acrylate, ethyl acrylate, propyl acrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, propylene glycol monomethyl ether acetate, methyl benzoate, ethyl benzoate, butyl benzoate, dimethyl phthalate, dibutyl maleate, diethyl oxalate, dibutyl oxalate, hexyl acetate, and benzyl acetate. Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethyl maleate, diethyl fumarate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, propylene glycol diacetate, 1,6-hexanediol diacetate, triacetin, γ-butyrolactone, ethylene carbonate, propylene carbonate, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, phenyl cellosolve acetate, n-butyl acetate, isobutyl acetate, methyl lactate, ethyl lactate, methyl glycolate, ethyl hydroxyacetate Butyl glycolate, methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, methyl-3-hydroxypropionate, ethyl-3-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, methyl-3-ethoxypropionate, ethyl-3-ethoxypropionate, methyl-2-hydroxypropionate, ethyl-2-hydroxypropionate, propyl-2-hydroxypropionate, methyl-2-methoxypropionate, ethyl-2-methoxypropionate Ethyl-2-ethoxypropionate, methyl-2-ethoxypropionate, methyl-2-hydroxy-2-methylpropionate, ethyl-2-hydroxy-2-methylpropionate, methyl-2-methoxy-2-methylpropionate, ethyl-2-ethoxy-2-methylpropionate, 2-hydroxyethylpropionate, 2-hydroxy-2-methylethylpropionate, hydroxyethyl acetate, methyl-2-hydroxy-3-methylbutyrate, ethyl pyruvate, methyl ethyl carbitol, diethyl carbitol, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, etc.

[0150] As an ether, aliphatic ethers are preferred, especially those with 1 to 20 carbon atoms or 1 to 10 carbon atoms. Examples include dimethyl ether, ethyl methyl ether, diethyl ether, tetrahydrofuran, 1,4-dioxane, anisole, 4-methoxytoluene, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tripropylene glycol monomethyl ether, 2-(2-isobutoxyethoxy)ethanol, benzyl ethyl ether, etc.

[0151] As amides, examples of amides with 1 to 20 carbon atoms or 1 to 10 carbon atoms include dimethylacetamide, dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylisobutyramide, 1,3-dimethyl-2-imidazolinone, N-methylformamide, N-methylformaniline, and N-methylacetamide.

[0152] As hydrocarbons, examples include alkane hydrocarbons, cycloalkanes, aromatic hydrocarbons, or mixtures thereof with 6 to 18 or 6 to 40 carbon atoms. Examples of n-alkanes include n-hexane, n-heptane, n-octane, n-nonane, and n-decane. Examples of isoalkanes include isooctane, isononane, and isodecanane. Examples of aromatic hydrocarbons include toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene, and decylbenzene.

[0153] Examples of solvents containing cyanide groups include acetonitrile and 3-methoxypropionitrile.

[0154] Examples of halogen-containing solvents include chloroform and chlorobenzene.

[0155] Examples of solvents containing sulfonyl groups include dimethyl sulfoxide.

[0156] Examples of solvents containing carboxyl groups include formic acid, acetic acid, acrylic acid, methacrylic acid, oleic acid, linoleic acid, linolenic acid, lactic acid, and hexanoic acid.

[0157] In this invention, in step (D), the surface of the modified metal oxide particles (iii) can be coated with a silane compound.

[0158] In this invention, a film-forming composition comprising the above-mentioned modified metal oxide particles (iii), organic solvate, and organic resin is obtained.

[0159] Regarding organic resins, a film-forming composition is obtained by selecting and mixing thermosetting or photocurable resins. Furthermore, cured products can be prepared by containing curing agents such as amine-based curing agents, anhydride-based curing agents, free radical generating curing agents (thermal free radical generating agents, photofree radical generating agents), or acid-generating curing agents (thermal acid-generating agents or photo-acid-generating agents).

[0160] In this composition, a film-forming composition comprising an organic resin and a curing agent is coated or filled onto a substrate, and a cured product is formed by heating, light irradiation, or a combination thereof. Examples of organic resins (curable resins) include resins having functional groups such as epoxy or (meth)acryloyl groups, and isocyanate-based resins. For example, light-curable polyfunctional acrylates are preferably used.

[0161] As a polyfunctional acrylate, examples include polyfunctional acrylates that have 2, 3, 4 or more functional groups in the molecule, such as neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0162] These multifunctional acrylates can also be described below.

[0163]

Chemistry 4

[0164]

[0165]

Transformation 5

[0166]

[0167]

Transformation 6

[0168]

[0169]

Transformation 7

[0170]

[0171] The film-forming composition of the present invention can contain a surfactant (leveling agent).

[0172] As surfactants (leveling agents), anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and silicone surfactants can be used. The surfactant (leveling agent) can be added in the range of 0.01–5 phr or 0.01–1 phr relative to the organic resin.

[0173] Examples of anionic surfactants used in this invention include sodium and potassium salts of fatty acids, alkylbenzene sulfonates, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, α-sulfonyl fatty acid esters, α-olefin sulfonates, monoalkyl phosphates, and alkane sulfonates.

[0174] For example, alkylbenzene sulfonates include sodium, potassium, and lithium salts, such as C10–C16 sodium alkylbenzene sulfonate, C10–C16 alkylbenzene sulfonic acid, and sodium alkylnaphthalene sulfonate.

[0175] As for higher alcohol sulfate salts, there are sodium dodecyl sulfate (sodium lauryl sulfate), triethanolamine lauryl sulfate, and triethanolamine lauryl sulfate, which have 12 carbon atoms.

[0176] Regarding polyoxyethylene alkyl ether sulfates, there are sodium polyoxyethylene styrene phenyl ether sulfate, sodium polyoxyethylene styrene phenyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, and sodium polyoxyethylene oleyl cetyl ether sulfate, etc.

[0177] Regarding α-olefin sulfonates, there are sodium α-olefin sulfonate, etc.

[0178] Examples of alkane sulfonates include sodium 2-ethylhexyl sulfate.

[0179] Examples of cationic surfactants used in this invention include alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl dimethyl benzylammonium salts, and amine salts.

[0180] Alkyltrimethylammonium salts are quaternary ammonium salts with chloride and bromide ions as counterions. Examples include dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, cocoyltrimethylammonium chloride, and alkyl(C16-18)trimethylammonium chloride.

[0181] Dialkyl dimethyl ammonium salts have two lipophilic backbones and two methyl groups. Examples include bis(hydrogenated tallow) dimethyl ammonium chloride. Other examples include dialcyl dimethyl ammonium chloride, dicosyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, and dialkyl (C14-18) dimethyl ammonium chloride.

[0182] Alkyl dimethyl benzyl ammonium salts are quaternary ammonium salts having one lipophilic main chain, two methyl groups, and a benzyl group; examples include benzalkonium chloride. Alkyl chloride (C8-18) dimethyl benzyl ammonium salts are also examples.

[0183] As an amine salt agent, it is a product in which the hydrogen atom of ammonia is replaced by one or more hydrocarbon groups, such as N-methyldihydroxyethylamine fatty acid ester hydrochloride.

[0184] Examples of amphoteric surfactants used in this invention include alkylamino fatty acid salts of the N-alkyl-β-alanine type, alkyl betaines of the alkyl carboxybetaine type, and alkyl amine oxides of the N,N-dimethyldodecylamine oxide type. Examples of these include lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazoline betaine, and lauryl dimethylamine oxide.

[0185] The nonionic surfactants used in this invention are selected from polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and fatty acid chain alkanolamides. For example, examples of polyoxyethylene alkyl ethers include polyoxyethylene dodecyl ether (polyoxyethylene lauryl ether), polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene oil-based ether, polyoxyethylene stearyl ether, polyoxyethylene docosyl ether, polyoxyethylene-2-ethylhexyl ether, and polyoxyethylene isodecyl ether.

[0186] As polyoxyethylene alkylphenol ethers, there are polyoxyethylene styrene phenyl ethers, polyoxyethylene nonylphenyl ethers, polyoxyethylene styrene phenyl ethers, and polyoxyethylene tribenzylphenyl ethers, etc.

[0187] As alkyl glucosides, there are decyl glucoside, lauryl glucoside, etc.

[0188] As polyoxyethylene fatty acid esters, there are polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyethylene glycol distearate, polyethylene glycol dioleate, and polypropylene glycol dioleate, etc.

[0189] As fatty acid esters of sorbitan, there are sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monosesquiolate, and their ethylene oxide adducts, etc.

[0190] As polyoxyethylene sorbitan fatty acid esters, there are polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan triisostearate, etc.

[0191] In addition, as fatty acid chain alkanolamides, there are coconut oil fatty acid diethanolamide, tallow fatty acid diethanolamide, lauric acid diethanolamide, oleic acid diethanolamide, etc.

[0192] Furthermore, examples include polyoxyethylene polyoxypropylene glycol, polyoxyethylene fatty acid esters and other polyoxyalkyl ethers or polyoxyalkyl glycols, polyoxyethylene hydrogenated castor oil ether, sorbitan fatty acid ester alkyl ether, alkyl polyglucoside, sorbitan monooleate, sucrose fatty acid ester, etc.

[0193] Organosilicon surfactants can be used. Organosilicon surfactants are compounds whose main chain has repeating units containing siloxane bonds. The weight-average molecular weight of organosilicon surfactants can range from 500 to 50,000. They can be modified organosilicon surfactants, and examples include structures in which organic groups are introduced into the side chains and / or ends of polysiloxanes. Examples of organic groups include amino, epoxy, alicyclic epoxy, methanol, mercapto, carboxyl, aliphatic ester, aliphatic amide, and polyether groups. As silicone-based surfactants, examples include the following trade names: ToraySilicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), Silwet1-77, L-7280, L-7001, L-7002, L-7200, L-7210, L-7220, L-7230, L7500, L-7600, L-7602, L-7604, L-7605, L-7622, ​​L-7657, L-8500, and L-8610 (all manufactured by Momentive Performance). Materials Corporation), KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Silicone Corporation), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie Corporation), etc. For example, as a polyether-modified silicone, the trade name L-7001 (manufactured by DOWSIL Corporation) can be preferably used.

[0194] In this invention, a film-forming composition comprising the above-mentioned organic solvate and organic resin is obtained. Regarding the film-forming composition, the organic solvent in the organic solvate can be removed, resulting in a film-forming composition comprising modified metal oxide particles (iii) and organic resin.

[0195] Regarding the above-described film-forming compositions, in the case of thermosetting film-forming compositions, a thermosetting agent can be added in the range of 0.01 to 50 phr or 0.01 to 10 phr relative to the resin containing functional groups such as epoxy groups or (meth)acryloyl groups. For example, the thermosetting agent can be contained in a proportion of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to functional groups such as epoxy groups or (meth)acryloyl groups. The equivalent of the thermosetting agent relative to the curable resin is expressed as the equivalent ratio of the thermosetting agent relative to the functional group.

[0196] Examples of thermosetting agents include phenolic resins, amine-based curing agents, polyamide resins, imidazoles, polythiols, acid anhydrides, thermal free radical generators, and thermally induced acid-producing agents. Free radical generator-based curing agents, acid anhydride-based curing agents, and amine-based curing agents are particularly preferred.

[0197] Even if these thermosetting agents are solids, they can be used by dissolving them in a solvent. However, due to the evaporation of the solvent, the density of the cured product decreases, pores are formed, and thus the strength and water resistance decrease. It is preferable that the curing agent itself is liquid at room temperature and pressure.

[0198] Examples of phenolic resins include phenolic varnish resin and cresol varnish resin.

[0199] Examples of amine-based curing agents include piperidine, N,N-dimethylpiperazine, triethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthene diamine, isophorone diamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, xylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine. Among these, liquid forms such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthene diamine, isophorone diamine, diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluene diamine are preferred.

[0200] As a polyamide resin, it is a polyamide amine that has primary and secondary amines in its molecule, generated by the condensation of dimer acid and polyamine.

[0201] Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazoleon trimellitate, and epoxide imidazole adducts.

[0202] Polythiols are, for example, substances with thiol groups at the ends of polypropylene glycol chains or substances with thiol groups at the ends of polyethylene glycol chains, and are preferably in liquid form.

[0203] As an anhydride-based curing agent, anhydrides containing multiple carboxyl groups in one molecule are preferred. Examples of such anhydride-based curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic tetracarboxylic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol dipreptyltrimethacrylate, glycerol trimellitic trimethacrylate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, bridged methylenetetrahydrophthalic anhydride, methylbridged methylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, and chlorhexidine anhydride.

[0204] Examples of thermogenic acid-producing agents include sulfonium salts and phosphonium salts, with sulfonium salts being preferred. For example, the following compounds can be cited.

[0205]

Transformation 8

[0206]

[0207] R can be alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 20 carbon atoms, with alkyl groups having 1 to 12 carbon atoms being particularly preferred.

[0208] Among these, the preferred options are methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride, methylnadic anhydride), hydrogenated methylnadic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, and mixtures of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, which are liquids at room temperature and pressure. The viscosity of these liquid anhydrides is approximately 10–1000 mPa·s when measured at 25°C.

[0209] Examples of thermal free radical generators include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 4,4'-azobis(4-cyanopentanoic acid), dimethyl 2,2'-azobis(2-methylpropionic acid), 2,2'-azobis(2-methylpropanediol) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl hydroperoxide, dicumyl hydroperoxide, benzoyl peroxide, etc. These are available from Tokyo Chemical Industry Co., Ltd.

[0210] Furthermore, when obtaining the above-mentioned cured product, curing aids may be appropriately used in combination. Examples of curing aids include organophosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and diethyl methyltriphenylphosphonium phosphate, quaternary ammonium salts such as 1,8-diazabicyclo(5,4,0)undec-7-ene, 1,8-diazabicyclo(5,4,0)undec-7-ene and octanoic acid salts, zinc octanoate, and tetrabutylammonium bromide. These curing aids can be contained in a ratio of 0.001 to 0.1 parts by mass relative to 1 part by mass of the curing agent.

[0211] In terms of the composition, a resin, a curing agent, and a curing aid as needed are mixed to obtain a thermosetting varnish. The mixing can be carried out in a reaction vessel using stirring blades or a kneader. Mixing is performed by heating at a temperature of 60–100°C for 0.5–1 hour.

[0212] The resulting curable film-forming composition is a thermosetting coating composition, for example, having a suitable viscosity for use as a liquid sealing material. The liquid thermosetting film-forming composition can be prepared to any viscosity, allowing for partial sealing at any location in LEDs and the like using methods such as casting, pouring, dispensing, and printing. By directly applying the liquid thermosetting composition to LEDs and the like in a liquid state using the above method, followed by drying and curing, a cured epoxy resin body is obtained.

[0213] A cured product is obtained by applying a thermosetting film-forming composition (thermosetting coating composition) to a substrate and heating it at a temperature of 80–200°C.

[0214] Regarding the above-described film-forming composition, in the case of a photocurable resin composition, a photocuring agent (photoradical generator, photoacid generator) can be added in the range of 0.01 to 50 phr or 0.01 to 10 phr relative to the resin containing functional groups such as epoxy or (meth)acryloyl groups. For example, the photocuring agent (photoradical generator, photoacid generator) can be contained in a proportion of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to functional groups such as epoxy or (meth)acryloyl groups. The equivalent of the photocuring agent relative to the curable resin is expressed as the equivalent ratio of the photocuring agent relative to the functional group.

[0215] There are no particular limitations on photoradical generators, as long as they generate free radicals directly or indirectly through light irradiation.

[0216] Examples of photoradical generators and photoradical polymerization initiators include imidazole compounds, diazo compounds, diimidazole compounds, N-arylglycine compounds, organic azide compounds, titanocene compounds, aluminate compounds, organic peroxides, N-alkoxypyridinium salts, and thioxanthone compounds. Examples of azide compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzylmethylacetophenone, 4,4'-diazidochalcone, 4,4'-diazidodiphenyl sulfide, and 2,6-bis(4'-azidobenzylmethyl)-4-methylcyclohexanone. Examples of diazo compounds include 1-diazo-2,5-diethoxy-4-p-tolylthiol fluoroborate, 1-diazo-4-N,N-dimethylaminophenyl chloride, and 1-diazo-4-N,N-diethylaminophenyl fluoroborate. Examples of bisimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetra(3,4,5-trimethoxyphenyl)1,2'-bisimidazole and 2,2'-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-bisimidazole. Examples of titanium ceramsite compounds include dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-bisphenyl, dicyclopentadienyl-titanium-bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyl-titanium-bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-titanium-bis(2,4,6-trifluorophenyl), dicyclopentadienyl-titanium-bis(2,6-difluorophenyl), and dicyclopentadienyl-titanium-bis(2,6-difluorophenyl). Dienyl-titanium-bis(2,4-difluorophenyl), bis(methylcyclopentadienyl)-titanium-bis(2,3,4,5,6-pentafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis(2,3,5,6-tetrafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis(2,6-difluorophenyl), and dicyclopentadienyl-titanium-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl), etc.

[0217] Other examples of photoradical generators include 1,3-bis(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone.

[0218] These photoradical polymerizers can be obtained, for example, as BASF's Irgacure TPO (containing 2,4,6-trimethylbenzoyl diphenylphosphine oxide) (c1-1-1), IGM RESINS' Omnirad 819 (containing bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) (c1-1-2), and IGM RESINS' Irgacure 184 (containing 1-hydroxycyclohexylphenyl ketone) (c1-1-3).

[0219]

Chemistry 1

[0220]

[0221] There are no particular limitations on photoacid-producing agents, as long as they generate acid directly or indirectly through light irradiation. Specific examples of photoacid-producing agents include triazine compounds, acetophenone derivatives, disulfone compounds, diazomethane compounds, sulfonic acid derivatives, ononium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts, metallocene complexes, and iron aromatic hydrocarbon complexes.

[0222] Regarding the ononium salts used as the aforementioned photoacid-generating agents, examples of iodonium salts include diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium methanesulfonate, diphenyliodonium toluenesulfonate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium methanesulfonate, bis(p-tert-butylphenyl)iodonium toluenesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, and bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate. Iodonium tetrafluoroborate, bis(p-tert-butylphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate, and further bis(4-tert-butylphenyl)iodonium hexafluorophosphate and other bis(alkylphenyl)iodonium salts, alkoxycarbonylalkoxy-trialkylaryl iodonium salts (e.g., 4-[(1-ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl)-iodonium hexafluorophosphate, etc.), bis(alkoxyaryl)iodonium salts (e.g., (4-methoxyphenyl)phenyliodonium hexafluoroantimonate and other bis(alkoxyphenyl)iodonium salts).

[0223] Examples of sulfonium salts include triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, etc.; (4-phenylthiophenyl)diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl)diphenylsulfonium hexafluorophosphate, bis[4-(diphenylsulfonium)phenyl]sulfide-bis-hexafluoroantimonate, bis[4-(diphenylsulfonium)phenyl]sulfide-bis-hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate, etc.

[0224] Examples of phosphonium salts include triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-chlorobenzyldiazoium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate.

[0225] Examples of examples include selenomonium salts such as triphenylselenomonium hexafluorophosphate and metallocene complexes such as (η5 or η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II)hexafluorophosphate.

[0226] In addition, the following compounds can also be used as photoacid-generating agents.

[0227]

Chemistry 10

[0228]

[0229]

Chemistry 11

[0230]

[0231]

Chemistry 12

[0232]

[0233]

Chemistry 13

[0234]

[0235]

Chemistry 14

[0236]

[0237]

Chemistry 15

[0238]

[0239]

Chemistry 16

[0240]

[0241]

Chemistry 17

[0242]

[0243] [Chemistry 18]

[0244]

[0245] Sulfonium salts and iodonium salts are preferred as photoacid-generating agents. CF3SO3 is an example of one of their anionic species. - C4F9SO3 - C8F 17 SO3 - Camphor sulfonic acid anion, toluene sulfonic acid anion, BF4 - PF6 - AsF6 - and SbF6 - Anionic species such as phosphorus hexafluoride and antimony hexafluoride, which exhibit strong acidity, are particularly preferred.

[0246] The film-forming composition of the present invention may, as needed, contain conventional additives. Examples of such additives include pigments, colorants, thickeners, sensitizers, defoamers, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, solubilizers, fillers, antistatic agents, etc. These additives can be used alone or in combination of two or more.

[0247] Examples of coating methods for the film-forming composition of the present invention include flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roller coating, gravure coating, immersion coating, and slot coating.

[0248] In this invention, a photocoating composition (film-forming composition) can be coated onto a substrate and cured by light irradiation. Additionally, heating can be applied before or after light irradiation.

[0249] The thickness of the coating can be selected from about 0.01 μm to 10 mm depending on the application of the cured material. For example, when used as a photoresist, it can be set to about 0.05 to 10 μm (especially 0.1 to 5 μm). When used as a printed wiring board, it can be set to about 5 μm to 5 mm (especially 100 μm to 1 mm). When used as an optical thin film, it can be set to about 0.1 to 100 μm (especially 0.3 to 50 μm).

[0250] When a transparent coating is obtained, the visible light transmittance of the coating can be set to 80% or more, or 90% or more, typically 90 to 96%.

[0251] The light used for irradiation or exposure when using photoacid-generating agents can be, for example, gamma rays, X-rays, ultraviolet light, or visible light, typically visible light or ultraviolet light, especially ultraviolet light. The wavelength of the light is, for example, 150–800 nm, preferably 150–600 nm, and more preferably around 150–400 nm. The amount of irradiated light varies depending on the thickness of the coating, and for example, can be set to 2–20000 mJ / cm². 2 Preferably 5–5000 mJ / cm 2 The light source can be selected according to the type of light being exposed; for example, in the case of ultraviolet light, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, deuterium lamps, halogen lamps, lasers (helium-cadmium lasers, excimer lasers, etc.) can be used. The curing reaction of the above composition proceeds under such light irradiation.

[0252] In cases where thermogenic acid-generating agents are used, or where photogenic acid-generating agents are used and the coating is heated as needed after light irradiation, the heating temperature is typically around 60–350°C, preferably around 100–300°C. The heating time can be selected from a range of 3 seconds or more (e.g., 3 seconds to about 5 hours), for example, 5 seconds to 2 hours, preferably 20 seconds to 30 minutes, and usually 1 minute to 3 hours (e.g., 5 minutes to 2.5 hours).

[0253] Furthermore, in the case of forming patterns or images (e.g., in the case of manufacturing printed wiring boards), the coating film formed on the substrate can be pattern-exposed. This pattern exposure can be performed by scanning with a laser or by irradiating light through a photomask. By developing (or dissolving) the unexposed areas (unexposed portions) generated by such pattern exposure with a developer, patterns or images can be formed.

[0254] As a developer, it can be used in alkaline aqueous solutions and organic solvents.

[0255] As alkaline aqueous solutions, examples include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine.

[0256] The aforementioned alkaline developer is generally an aqueous solution of 10% by mass or less, preferably an aqueous solution of 0.1% to 3.0% by mass. Furthermore, alcohols and surfactants can also be added to the aforementioned developer, each preferably 0.05 to 10 parts by mass relative to 100 parts by mass of the developer.

[0257] Among them, a 0.1–2.38% (w / w) aqueous solution of tetramethylammonium hydroxide can be used.

[0258] Furthermore, common organic solvents can be used as the developing solution, such as acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, cyclohexanone, etc. These can be used alone or as a mixture of two or more. In particular, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, etc., are preferred.

[0259] In this invention, to improve the adhesion to the substrate after development, an adhesion promoter can be added. Examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazolium; and vinyltrimethylsilylsilanes. The accelerators include silanes such as chlorosilanes, 3-chloropropyltrimethoxysilanes, 3-aminopropyltriethoxysilanes, 3-methacryloyloxypropyltrimethoxysilanes, 3-epoxypropoxypropyltrimethoxysilanes, and 3-(N-piperidinyl)propyltrimethoxysilanes; heterocyclic compounds such as benzotriazoles, benzimidazoles, indazoles, imidazoles, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, urazoles, thiouracil, mercaptoimidazoles, and mercaptopyrimidines; ureas such as 1,1-dimethylurea and 1,3-dimethylurea; and thiourea compounds. One or more of the above-mentioned adhesion promoters can be used in combination. The amount of these adhesion promoters added in the solid content is typically 18% by mass or less, preferably 0.0008 to 9% by mass, and more preferably 0.04 to 9% by mass.

[0260] This invention may include a sensitizer. Examples of usable sensitizers include anthracene, phenothiazine, perylene, thioxanthone, and benzophenone-thioxanthone. Furthermore, examples of sensitized pigments include thiaranonium salt pigments, anthocyanin pigments, quinoline pigments, styrylquinoline pigments, coumarinone pigments, thioxanthone pigments, xanthanol pigments, oxonol pigments, anthocyanin pigments, rhodamine pigments, and pyranonium salt pigments. Anthracene-based sensitizers are particularly preferred, as their sensitivity is dramatically increased when used in conjunction with a cationic curing catalyst (a radiosensitive cationic polymerization initiator), while also possessing free radical polymerization initiation capabilities. For hybrid systems combining the cationic curing system and the free radical curing system of this invention, the catalyst species can be easily obtained. Specific anthracene compounds include dibutoxyanthracene and dipropoxyanthraquinone. Regarding the amount of sensitizer added, it is used in the solid component at a ratio of 0.01 to 20% by mass, preferably 0.01 to 10% by mass.

[0261] The compositions of the present invention can be photocured or thermally cured using photoradicals, thermalradicals, photoacid generators, or thermalacid generators. When using photoacid generators or thermalacid generators, for example, conventional epoxy curing agents (e.g., amines, anhydrides) are not used, or even if they are used, their content is extremely low, thus improving the storage stability of the compositions.

[0262] The above composition has been found to be applicable to photocationic polymerization. It exhibits a high curing speed compared to existing liquid epoxy compounds (e.g., alicyclic epoxy compounds with an epoxy cyclohexyl ring). Due to the fast curing speed, it is also possible to reduce the amount of acid-generating agent added and use weak acid-based acid-generating agents. Regarding the reduction of acid-generating agents, the presence of residual acidic active species after UV irradiation is sometimes important for preventing metal corrosion. Due to the fast curing speed, thick film curing is possible.

[0263] UV curing can be applied to heat-sensitive materials (devices).

[0264] In this invention, it is possible to manufacture an antistatic composition comprising the modified metal oxide particles (iii) in the modified metal oxide sol described above.

[0265] Furthermore, in this invention, it is possible to manufacture an electron transport material composition comprising the modified metal oxide particles (iii) in the modified metal oxide sol described above.

[0266] When a resin varnish that serves as a binder is applied to a substrate with a coating agent containing 300 phr of modified metal oxide particles (iii) from the modified metal oxide sol, resulting in a film thickness of 1.0 μm after drying, a voltage of 1000 V is applied, and a surface resistance value of 10–500 GΩ / □ is observed.

[0267] Example

[0268] The physical properties of the sol (dispersion) were determined using the following methods.

[0269] [Average primary particle size]

[0270] Using a transmission electron microscope (manufactured by Nippon Electron Co., Ltd., trade name JEM-F200), the particles were photographed, and the average primary particle size was set as the average primary particle size of the equivalent circle of 500 arbitrary particles.

[0271] [Average Particle Size Based on Dynamic Light Scattering (Dynamic Light Scattering Method for Particle Size)]

[0272] The sol was diluted with a dispersing solvent, and the parameters of the solvent were measured using a dynamic light scattering method. The apparatus was manufactured by Malvern Instruments Ltd and traded under the name Zetasizer.

[0273] [stability]

[0274] After storing the dispersion at 50°C for 1 week, samples with a dynamic light scattering (DLS) particle size less than 1.2 times larger than before the storage test were designated as unchanged samples and marked as "○", while samples with a dynamic light scattering (DLS) particle size change of more than 1.2 times larger than before the storage test were marked as "×".

[0275] [Determination of Amine Content]

[0276] The amount of amine in the sols obtained in the examples and comparative examples was determined according to steps 1) to 3) below.

[0277] 1) Preparation of standard samples for calibration lines

[0278] Standard samples of isopropylamine and diisopropylamine were prepared by diluting them with 3 mM nitric acid at concentrations of 10 ppm, 100 ppm, and 1000 ppm, respectively.

[0279] Standard samples of tri-n-pentylamine were prepared by diluting it with 3 mM nitric acid containing 20% ​​by mass of acetonitrile in concentrations of 100 ppm, 1000 ppm, and 1% by mass.

[0280] 2) Preparation of samples for quantifying the amine content in the sols obtained in the examples and comparative examples.

[0281] The sols obtained in the examples and comparative examples were diluted with pure water to bring the concentration of colloidal particles to 3% by mass. After adding 0.2 mL of 1M nitric acid to 8.5 g of the diluted sol, the amines adsorbed on the particle surface were stripped from the particle surface by allowing it to stand at room temperature for 24 hours. Next, the resulting solution was centrifuged using a centrifugal ultrafiltration filter unit with a molecular weight cutoff of 10000 Da to recover the filtrate. A sample was prepared for quantifying the amount of amines in the sols obtained in the examples and comparative examples by diluting the recovered filtrate 10-fold with pure water.

[0282] 3) Calculation of the amount of amine in the sols obtained in the examples and comparative examples

[0283] The samples prepared in steps 1) and 2) were determined using an ion chromatography apparatus (Metrohm Japan Co., Ltd., Metrohm Compact IC 761). Calibration lines were constructed by plotting the peak integrated intensities of the standard samples of isopropylamine, diisopropylamine, and tri-n-pentylamine prepared in step 1) against their respective amine concentrations. The amount of amine contained in the sample prepared in step 2) was calculated using the constructed calibration lines.

[0284] [Determination of Crystallinity]

[0285] The crystallinity of the modified metal oxide particles in the sols obtained in the examples and comparative examples was determined using the following steps 1) to 3).

[0286] 1) X-ray diffraction determination of modified metal oxide particles in the sols obtained in the examples and comparative examples

[0287] The sol containing the modified metal oxide particles obtained in the examples was vacuum dried at 60°C for 1 hour. The resulting dried powder was placed in a mortar and pulverized with a pestle. The pulverized particles were mixed with tungsten powder (manufactured by Fujifilm and Koimitsu Chemical Co., Ltd., containing 99.9% by mass or more of tungsten) at a mass ratio of 50:50. The X-ray diffraction of the mixed powder was measured using an X-ray diffraction apparatus (manufactured by Rigaku Co., Ltd., trade name MiniFlex600).

[0288] 2) X-ray diffraction determination of tin oxide (IV) standard samples

[0289] Tin oxide (IV) powder (manufactured by Kanto Chemical Co., Ltd., containing ≥99.0% by mass SnO2) and tungsten powder (manufactured by Fujifilm and Koimitsu Chemical Co., Ltd., containing ≥99.9% by mass tungsten) were mixed at a mass ratio of 50:50. The X-ray diffraction of the mixed powder was measured using an X-ray diffraction apparatus (manufactured by Rigaku Co., Ltd., trade name MiniFlex600).

[0290] 3) Calculation of crystallinity

[0291] Calculate the sum of the peak integral intensities A of tin oxide (IV) (110), (101), (200), (211), and (220) contained in the modified metal oxide particles measured in 1). S1 And the peak integral intensity A of tungsten (110) W1 Secondly, the sum of the peak integral intensities A of tin oxide (IV) (110), (101), (200), (211), and (220) measured in 2) is calculated. S2 And the peak integral intensity A of tungsten (110) W2 The crystallinity of the modified metal oxide particles obtained in the examples and comparative examples was calculated using the following formula.

[0292] Crystallinity = (A S1 / A W1 ) / (A S2 / A W2 )

[0293] [Determination of Refractive Index]

[0294] The refractive index of the modified metal oxides in the sols obtained in the examples and comparative examples was determined using the following steps 1) to 3).

[0295] 1) Preparation of modified metal oxide methanol dispersion sol with varnish

[0296] Weigh 20.00 g of 3-epoxypropoxypropyltrimethoxysilane (manufactured by Momentive, trade name SILQUEST A-187T) into a polyethylene container, add 18.57 g of methanol and 4.57 g of 0.01 N hydrochloric acid aqueous solution, and stir at room temperature for 5 hours. Add 6.00 g of a pre-prepared methanol solution of aluminum 2,4-pentanedione (Al(acac)3) (10% by mass Al(acac)3) as a curing agent, and stir for 10 minutes to prepare a partially hydrolyzed product of 3-epoxypropoxypropyltrimethoxysilane (concentration: 43% by mass).

[0297] A total of 25.00 g of modified metal oxide methanol dispersion varnish was prepared by weighing a partially hydrolyzed product of 3-epoxypropoxypropyltrimethoxysilane, a modified metal oxide dispersion varnish (solids other than water in a mass ratio of 1 / 4), water, methanol, and a methanol solution (10% by mass L-7604) of leveling agent (DOWSIL trade name L-7604) into a brown bottle and stirring at room temperature for 30 minutes. The mixture was then stirred to obtain a modified metal oxide methanol dispersion varnish (solids concentration of 10.0% by mass, modified metal oxide amounts of 50 phr, 100 phr, and 150 phr).

[0298] 2) Preparation of particle-coordinated membranes

[0299] The modified metal oxide methanol dispersion sol obtained in step 1) was mixed with a varnish and dropped onto a UV-O3 treated Si substrate at a depth of approximately 0.5 mL. The mixture was then coated using a spin coater (Mikasa Co., Ltd., trade name Opticoat MS-B100) to a final film thickness of 1.0 μm. The coated film was then baked on a hot plate at 80°C for 5 minutes and then heat-treated in an oven at 120°C for 1 hour to prepare particle-coated films (particle concentrations: 50 phr, 100 phr, 150 phr).

[0300] 3) Determination of the refractive index of particle-coated films and calculation of the refractive index of particles.

[0301] The refractive index of the particle-coated films obtained in step 2) was measured using an ellipsometer (JA Woollam Japan Co., Ltd., trade name Multi-incident Angle Spectroscopic Ellipsometry VASE). The particle-coated amounts were 50 phr, 100 phr, and 150 phr. Additionally, the refractive index of particle-free films prepared similarly using only a partially hydrolyzed product of 3-epoxypropoxypropyltrimethoxysilane was also measured. The measured refractive indices of the coated films were plotted against the particle coagulation amount, and the particle refractive index was determined by extrapolation with the particle coagulation amount set to 100% by mass.

[0302] [Determination of resistivity]

[0303] The resistivity values ​​of the particle-coordinated films obtained in the examples and comparative examples were determined according to the following steps 1) to 3).

[0304] 1) Preparation of modified metal oxide dispersion sol with varnish

[0305] Weigh 37.50 g of 3-epoxypropoxypropyltrimethoxysilane (manufactured by Momentive, trade name SILQUEST A-187T) into a polyethylene container, add 8.57 g of 0.01 N hydrochloric acid aqueous solution, and stir at room temperature for 24 hours. Weigh 4.61 g of the resulting solution into a polyethylene container, add 0.23 g of aluminum 2,4-pentanedione (Al(acac)3) as a curing agent, and add 0.50 g of a methanol solution (10% by mass L-7604) of leveling agent (DOWSIL). Next, with the final solvent composition being water / solvents other than water in a mass ratio of 1 / 4 and the amount of modified metal oxide being 300 phr, the modified metal oxide dispersion sol obtained in the examples and comparative examples, water, and methanol were added, and the mixture was stirred at room temperature for 24 hours to prepare a modified metal oxide dispersion sol-based varnish (solids concentration of 15.0% by mass, amount of modified metal oxide being 300 phr).

[0306] 2) Preparation of particle-coordinated membranes

[0307] The modified metal oxide dispersion sol obtained in step 1) was mixed with a varnish and dropped onto a UV-O3 treated quartz substrate. Approximately 1 mL of the varnish was then applied using a benchtop wire rod coater (manufactured by MST Co., Ltd., trade name PM-9050MC) to achieve a dried film thickness of 1.0 μm. The particle-coated film was then prepared by baking on a hot plate at 80°C for 15 minutes and then heat-treating in an oven at 120°C for 2 hours.

[0308] 3) Measurement of resistivity of particle-coordinated films

[0309] The surface resistivity of the particle-coordinated film (particle coordination amount: 300 phr) obtained in step 2) was measured using a resistivity meter (Mitsubishi Chemical Co., Ltd., trade name Hiresta-UP MCP-HT450) under conditions of 1000 V and 10 seconds. The unit is expressed in Ω / □ (Ohm per square).

[0310] Qualitative and quantitative analysis of tin oxide and other metal oxides.

[0311] For the qualitative and quantitative determination of tin oxide and other metal oxides contained in the particle complexes obtained in the Examples and Comparative Examples, the following steps 1) to 3) are used.

[0312] 1) Fluorescence X-ray analysis of standard samples

[0313] Tin oxide (IV) powder (manufactured by Kanto Chemical Co., Ltd., containing ≥99.0% by mass SnO2), antimony oxide (V) powder (Sigma-Aldrich, containing ≥99.9% by mass Sb2O5), and silica powder (manufactured by Nissan Chemical Co., Ltd., trade name ST-XS, dried under vacuum at 60°C for 1 hour, then pulverized in a mortar with a pestle) were mixed in a mass ratio of SnO2 / Sb2O5 / SiO2 = 1 / 1 / 1. The resulting powder was analyzed using a fluorescence X-ray analysis device (manufactured by Rigaku Co., Ltd., trade name Supermini200). The peak integrated intensity A from tin oxide (IV) was calculated. Sn1 Peak integral intensity A from antimony oxide (V) Sb1 and the peak integral intensity A from silica Si1 .

[0314] 2) Fluorescence X-ray analysis of modified metal oxides in the sols obtained in the examples and comparative examples.

[0315] The sols containing the modified metal oxides obtained in the examples and comparative examples were vacuum dried at 60°C for 1 hour. The resulting dried powder was placed in a mortar and pulverized with a pestle. The pulverized particles were analyzed using a fluorescence X-ray analysis device (manufactured by Rigaku Co., Ltd., trade name Supermini200).

[0316] 3) Qualitative and quantitative analysis of tin oxide and other metal oxides.

[0317] If the peak wavelength of the fluorescent X-rays measured in 2) is the same as the peak wavelength of the standard sample measured in 1), it is determined that the sample contains a metal oxide originating from that peak wavelength. Next, the peak integral intensity A of the fluorescent X-rays from tin oxide (IV) measured in 2) is calculated. Sn2 Peak integral intensity A from antimony oxide (V) Sb2 and the peak integral intensity A from silica Si2 The following calculation formula is used to quantify the tin oxide and other metal oxides contained in the modified metal oxides obtained in the examples and comparative examples.

[0318] Tin oxide content = (A Sn2 / A Sn1 ) / A 合计

[0319] Antimony oxide (V) content = (A Sb2 / A Sb1 ) / A 合计

[0320] Silica content = (ASi2 / A Si1 ) / A 合计

[0321] Among them, A 合计 =(A Sn2 / A Sn1 )+(A Sb2 / A Sb1 )+(A Si2 / A Si1 )

[0322] (Refer to Example 1) Preparation of tin oxide colloidal particles (i) as the core

[0323] 37.5 kg of oxalic acid ((COOH)₂·2H₂O) was dissolved in 363 kg of pure water and heated to 70°C with stirring. 170 kg of 35% hydrogen peroxide solution and 75 kg of metallic tin were added. The addition of hydrogen peroxide solution and metallic tin was carried out alternately. Initially, 10 kg of 35% hydrogen peroxide solution was added, followed by 5 kg of metallic tin. After the reaction was complete (5–10 minutes), this operation was repeated. After all the solution had been added, another 10 kg of 35% hydrogen peroxide solution was added. The addition process took 3 hours. After the addition was complete, the mixture was heated at 95°C for 1 hour to complete the reaction.

[0324] 231 kg of 35% hydrogen peroxide solution and 52 kg of pure water were added to 629 kg of the obtained sol to dilute it to 10% by mass (based on SnO2) and a molar ratio of oxalic acid (H2O2 / (COOH)2) of 8.0 relative to the initial feed. The sol was then aged at 95°C for 5 hours. This process decomposes the oxalic acid into carbon dioxide and water through reaction with hydrogen peroxide. After cooling the resulting tin oxide slurry to approximately 40°C, 2.7 kg of isopropylamine (water solubility 1000 g / L, data cited from the Chemical Book, which can be found at the following URL: https: / / www.chemicalbook.com / ProductList_En.aspx?kwd=isopro pylamine) was added. After desolvation, the sol was circulated through a catalyst tower filled with approximately 15 L of platinum-based catalyst (N-220 (manufactured by Süd-Chemie Catalyst Co., Ltd.)) to decompose excess hydrogen peroxide. The solution was circulated for 5 hours at a flow rate of approximately 30 L / min. Then, after passing the solution through a column packed with anion exchange resin, it was concentrated using ultrafiltration. The resulting sol was an aqueous dispersion of tin oxide colloidal particles (i), with a pH of 11.0 and a SnO2 concentration of 10.0% by mass. Observation using a transmission electron microscope revealed a primary particle size of 10–15 nm.

[0325] (Refer to Example 2) Preparation of silica-tin oxide composite oxide colloidal particles (ii-2) as coating

[0326] 77.2 g of JIS No. 3 sodium silicate (containing 29.8% by mass, converted to SiO2) was dissolved in 668.8 g of pure water. Next, 20.9 g of sodium stannate (NaSnO3·H2O, containing 55.1% by mass, converted to SnO2) was dissolved. The resulting aqueous solution was passed through a column packed with hydrogen-form cation exchange resin. Then, 7.2 g of diisopropylamine (water solubility 100 g / L, data cited from the Chemical Book, which can be found at the following URL: https: / / www.chemicalbook.com / ProductList_En.aspx?kwd=108-18-9) was added to the resulting aqueous dispersion. The resulting sol was an aqueous dispersion of silica-tin oxide composite colloidal particles (ii-2), with a pH of 8.0 and a total metal oxide concentration (SiO2 and SnO2) of 2.5% by mass. Observation using a transmission electron microscope showed a primary particle size of 1–4 nm.

[0327] (Refer to Example 3) Preparation of antimony pentoxide colloidal particles (ii-1) as a coating

[0328] In a 100L container, 12.5 kg of antimony trioxide (containing 99.5% by mass as Sb₂O₃), 66.0 kg of pure water, and 12.5 kg of potassium hydroxide (containing 95% by mass as KOH) were added. 8.4 kg of 35% hydrogen peroxide was slowly added while stirring. 17.6 kg of the resulting potassium antimonate aqueous solution was diluted to 2.2% by mass and passed through a column packed with hydrogen-form cation exchange resin. 0.25 kg of diisopropylamine was added to the antimony acid solution after ion exchange while stirring. The resulting sol was an aqueous dispersion of antimony pentoxide colloidal particles (ii-1) with a pH of 10.8 and an Sb₂O₅ concentration of 1.5% by mass. Observation using a transmission electron microscope showed a primary particle size of 1–10 nm.

[0329] (Manufacturing Example 1) Preparation of tin oxide colloidal particles (iii-2-1) coated with silica-tin oxide composite oxide

[0330] The aqueous dispersion of alkaline tin oxide colloidal particles (i) prepared in Reference Example 1 was subjected to continuous hydrothermal treatment at a treatment temperature of 310°C, a treatment pressure of 20 MPa, and an average flow rate of 0.6 L / min. Next, under stirring, 400 g of the aqueous dispersion of silica-tin oxide composite oxide colloidal particles (ii-2) prepared in Reference Example 2 (total metal oxide concentration (SiO2 and SnO2) of 10 g, 10% by mass relative to the core particles) was added to 1000 g of the obtained aqueous dispersion of alkaline tin oxide colloidal particles (100 g as SnO2). The mixture was then aged at 95°C for 2 hours to obtain an aqueous dispersion of tin oxide colloidal particles (iii-2-1) coated with silica-tin oxide composite oxide. The obtained aqueous dispersion was then passed through a column packed with hydrogen-form cation exchange resin. The obtained aqueous dispersion was concentrated by adding 3.5 g of tri-n-pentylamine (water solubility 0.02 g / L, data cited from Ambeed's homepage, which can be found at the following URL: https: / / www.ambeed.com / products / 621-77-2.html) and then using ultrafiltration. The resulting sol was an aqueous dispersion of tin oxide colloidal particles (iii-2-1) coated with a silica-tin oxide composite oxide, with a pH of 5.5, a total metal oxide (SnO2 and SiO2) concentration of 30.5% by mass, an average particle size (DLS particle size) of 19 nm, and a ratio of (total mass of metal oxides other than tin oxide) to (mass of tin oxide) of 0.065.

[0331] (Manufacturing Example 2) Preparation of tin oxide colloidal particles (iii-2-2) coated with silica-tin oxide composite oxide

[0332] Except that in Manufacturing Example 1, the amount of silica-tin oxide composite oxide colloidal particles added to the aqueous dispersion sol was changed to 800 g (total metal oxide concentration (SiO2 and SnO2) was 20 g, which was 20% by mass relative to the core particles), the sol was prepared in the same manner as in Manufacturing Example 1. The resulting sol was an aqueous dispersion sol of tin oxide colloidal particles (iii-2-2) coated with silica-tin oxide composite oxide, with a pH of 5.5, a total metal oxide (SnO2 and SiO2) concentration of 30.5% by mass, an average particle size (dynamic light scattering particle size) obtained by dynamic light scattering (DLS) of 25 nm, and (total mass of metal oxides other than tin oxide) / (mass of tin oxide) = 0.125.

[0333] (Manufacturing Example 3) Preparation of Tin Oxide Colloidal Particles (iii-1-1) Coated with Antimony Pentoxide Colloidal Particles

[0334] The aqueous dispersion of alkaline tin oxide colloidal particles (i) prepared in Reference Example 1 was subjected to continuous hydrothermal treatment at a treatment temperature of 310°C, a treatment pressure of 20 MPa, and an average flow rate of 0.6 L / min. Next, under stirring, 400 g of an aqueous dispersion of antimony pentoxide colloidal particles (ii-1) prepared in Reference Example 3 (6.0 g of Sb₂O₅, 5.0% by mass relative to the core particles) was added to 1200 g of the obtained aqueous dispersion of alkaline tin oxide colloidal particles (120 g as SnO₂), and the mixture was aged at 95°C for 2 hours to obtain an aqueous dispersion of tin oxide colloidal particles coated with antimony pentoxide colloidal particles (iii-1-1). Next, the obtained aqueous dispersion was passed through a column packed with hydrogen-form cation exchange resin. 3.8 g of tri-n-pentylamine was added to the obtained aqueous dispersion, and the mixture was concentrated using ultrafiltration. The resulting sol was an aqueous dispersion of tin oxide colloidal particles (iii-1-1) coated with antimony pentoxide colloidal particles, with a pH of 4.2, a total metal oxide (SnO2 and Sb2O5) concentration of 20.5% by mass, an average particle size (dynamic light scattering particle size) of 20 nm as determined by dynamic light scattering (DLS), and a ratio of (total mass of metal oxides other than tin oxide) / (mass of tin oxide) of 0.05.

[0335] (Manufacturing Example 4) Preparation of tin oxide colloidal particles (iii-2-3) coated with silica-tin oxide composite oxide

[0336] Except that the hydrothermal treatment temperature was changed to 240°C and the treatment pressure was changed to 7.0 MPa in Manufacturing Example 1, the sol was prepared in the same manner as in Manufacturing Example 1. The obtained sol was an aqueous dispersion of tin oxide colloidal particles (iii-2-3) coated with silica-tin oxide composite oxide, with a pH of 5.5, a total metal oxide (SnO2 and SiO2) concentration of 30.5% by mass, an average particle size (dynamic light scattering particle size) obtained by dynamic light scattering (DLS) of 23 nm, and (total mass of metal oxides other than tin oxide) / (mass of tin oxide) = 0.125.

[0337] (Manufacturing Example 5) Preparation of tin oxide colloidal particles (iii-2-4) coated with silica-tin oxide composite oxide

[0338] Except that the hydrothermal treatment temperature was changed to 150°C and the treatment pressure was changed to 1.0 MPa in Manufacturing Example 1, the sol was prepared in the same manner as in Manufacturing Example 1. The obtained sol was an aqueous dispersion of tin oxide colloidal particles (iii-2-4) coated with silica-tin oxide composite oxide, with a pH of 5.5, a total metal oxide (SnO2 and SiO2) concentration of 30.5% by mass, an average particle size (dynamic light scattering particle size) obtained by dynamic light scattering (DLS) of 21 nm, and (total mass of metal oxides other than tin oxide) / (mass of tin oxide) = 0.125.

[0339] (Manufacturing Example 6) Preparation of tin oxide colloidal particles (iii-2-5) coated with silica-tin oxide composite oxide

[0340] Except that hydrothermal treatment was not performed in Manufacturing Example 1, the sol was prepared in the same manner as in Manufacturing Example 1. The resulting sol was an aqueous dispersion of tin oxide colloidal particles (iii-2-5) coated with a silica-tin oxide composite oxide, with a pH of 5.5, a total metal oxide (SnO2 and SiO2) concentration of 30.5% by mass, an average particle size (dynamic light scattering particle size) obtained by dynamic light scattering (DLS) of 20 nm, and (total mass of metal oxides other than tin oxide) / (mass of tin oxide) = 0.125.

[0341] (Comparative Manufacturing Example 1) Preparation of Tin Oxide Colloidal Particles (iii-3) Coated with Silica-Tin Oxide Composite Oxide

[0342] Except that tri-n-pentylamine was not added in Manufacturing Example 1, the sol was prepared in the same manner as in Manufacturing Example 1. The resulting sol was an aqueous dispersion of tin oxide colloidal particles (iii-3) coated with a silica-tin oxide composite oxide, with a pH of 4.2, a total metal oxide (SnO2 and SiO2) concentration of 20.5% by mass, an average particle size (dynamic light scattering particle size) obtained by dynamic light scattering (DLS) of 28 nm, and (total mass of metal oxides other than tin oxide) / (mass of tin oxide) = 0.125.

[0343] (Example 1)

[0344] 100 g of the aqueous dispersion sol of tin oxide colloidal particles (iii-2-1) coated with silica-tin oxide composite oxide obtained in Manufacturing Example 1 was replaced with methanol using a rotary evaporator to obtain a methanol dispersion sol of tin oxide colloidal particles (iii-2-1) coated with silica-tin oxide composite oxide. The resulting sol had a pH of 4.7 (diluted with water of equal mass to methanol), a total metal oxide (SnO2 and SiO2) concentration of 20.5% by mass, an average particle size based on dynamic light scattering (DLS) of 16 nm, and a stability test result of "0". The residual tri-n-pentylamine in the methanol-dispersed sol of particles (iii-2-1) was 3900 ppm, diisopropylamine 180 ppm, and isopropylamine 24 ppm. The crystallinity of nucleus particle (i) was 92%, the refractive index of particle (iii-2-1) was 1.91, and the resistivity of the coating film formed by particle (iii-2-1) was 1.1 × 10⁻⁶. 11 Ω / □. The mass ratio of amine (b) to amine (a) is 19.1.

[0345] (Example 2)

[0346] 100g of the aqueous dispersion sol of tin oxide colloidal particles (iii-2-2) coated with silica-tin oxide composite oxide obtained in Manufacturing Example 2 was replaced with methanol using a rotary evaporator to obtain a methanol dispersion sol of tin oxide colloidal particles (iii-2-2) coated with silica-tin oxide composite oxide. The resulting sol had a pH of 4.8 (diluted with water of equal mass to methanol), a total metal oxide (SnO2 and SiO2) concentration of 20.5% by mass, an average particle size based on dynamic light scattering (DLS) of 21 nm, and a stability test result of "0". The residual tri-n-pentylamine in the methanol-dispersed sol of particles (iii-2-2) was 4200 ppm, diisopropylamine 190 ppm, and isopropylamine 22 ppm. The crystallinity of nucleus particle (i) was 91%, the refractive index of particle (iii-2-2) was 1.87, and the resistivity of the coating film formed by particle (iii-2-2) was 1.9 × 10⁻⁶. 11 Ω / □. The mass ratio of amine(b) to amine(a) is 19.8.

[0347] (Example 3)

[0348] 100 g of the aqueous dispersion sol of tin oxide colloidal particles (iii-1-1) coated with silica-tin oxide composite oxide obtained in Manufacturing Example 3 was replaced with methanol using a rotary evaporator to obtain a methanol dispersion sol of tin oxide colloidal particles (iii-1-1) coated with silica-tin oxide composite oxide. The obtained sol had a pH of 5.2 (diluted with water of the same mass as methanol), a total metal oxide (SnO2 and Sb2O5) concentration of 30.5% by mass, an average particle size based on dynamic light scattering (DLS) of 16 nm, a stability test result of "0", residual tri-n-pentylamine of 1500 ppm and diisopropylamine of 40 ppm in the methanol dispersion sol of particles (iii-1-1), a crystallinity of 92% for the core particle (i), a refractive index of 1.93 for particles (iii-1-1), and a resistivity of 6.1 × 10⁻⁶ for the coating film. 10 Ω / □. The mass ratio of amine (b) to amine (a) is 37.5.

[0349] (Example 4)

[0350] 100 g of the aqueous dispersion sol of tin oxide colloidal particles (iii-2-3) coated with silica-tin oxide composite oxide obtained in Manufacturing Example 4 was replaced with methanol using a rotary evaporator to obtain a methanol dispersion sol of tin oxide colloidal particles (iii-2-3) coated with silica-tin oxide composite oxide. The resulting sol had a pH of 5.1 (diluted with water of equal mass to methanol), a total metal oxide (SnO2 and SiO2) concentration of 30.5% by mass, an average particle size based on dynamic light scattering (DLS) of 19 nm, and a stability test result of "0". The residual tri-n-pentylamine in the methanol-dispersed sol of particles (iii-2-3) was 3900 ppm, diisopropylamine 180 ppm, and isopropylamine 41 ppm. The crystallinity of nucleus particle (i) was 85%, the refractive index of particle (iii-2-3) was 1.85, and the resistivity of the coating film formed by particle (iii-2-3) was 4.3 × 10⁻⁶. 11 Ω / □. The mass ratio of amine (b) to amine (a) is 17.6.

[0351] (Example 5)

[0352] 100 g of the aqueous dispersion sol of tin oxide colloidal particles (iii-2-4) coated with silica-tin oxide composite oxide obtained in Manufacturing Example 5 was replaced with methanol using a rotary evaporator to obtain a methanol dispersion sol of tin oxide colloidal particles (iii-2-4) coated with silica-tin oxide composite oxide. The resulting sol had a pH of 5.2 (diluted with water of equal mass to methanol), a total metal oxide (SnO2 and SiO2) concentration of 30.5% by mass, an average particle size based on dynamic light scattering (DLS) of 19 nm, and a stability test result of "0". The residual tri-n-pentylamine in the methanol-dispersed sol of particles (iii-2-4) was 4000 ppm, diisopropylamine 160 ppm, and isopropylamine 93 ppm. The crystallinity of nucleus particle (i) was 77%, the refractive index of particle (iii-2-4) was 1.83, and the resistivity of the coating film formed by particle (iii-2-4) was 8.3 × 10⁻⁶. 11 Ω / □. The mass ratio of amine (b) to amine (a) is 15.8.

[0353] (Example 6)

[0354] 100 g of the aqueous dispersion sol of tin oxide colloidal particles (iii-2-5) coated with silica-tin oxide composite oxide obtained in Manufacturing Example 6 was replaced with methanol using a rotary evaporator to obtain a methanol dispersion sol of tin oxide colloidal particles (iii-2-5) coated with silica-tin oxide composite oxide. The resulting sol had a pH of 4.7 (diluted with water of equal mass to methanol), a total metal oxide (SnO2 and SiO2) concentration of 30.5% by mass, an average particle size based on dynamic light scattering (DLS) of 21 nm, and a stability test result of "0". The residual tri-n-pentylamine in the methanol-dispersed sol of particles (iii-2-5) was 3500 ppm, diisopropylamine 140 ppm, and isopropylamine 160 ppm. The crystallinity of nucleus particle (i) was 68%, the refractive index of particle (iii-2-5) was 1.81, and the resistivity of the coating film formed by particle (iii-2-5) was 1.2 × 10⁻⁶. 12 Ω / □. The mass ratio of amine (b) to amine (a) is 11.7.

[0355] (Example 7)

[0356] 100g of the aqueous dispersion sol of tin oxide colloidal particles (iii-2-2) coated with silica-tin oxide composite oxide obtained in Manufacturing Example 2 was replaced with ethanol using a rotary evaporator to obtain an ethanol dispersion sol of tin oxide colloidal particles (iii-2-2) coated with silica-tin oxide composite oxide. The resulting sol had a pH of 5.0 (diluted with water of equal mass to ethanol), a total metal oxide (SnO2 and SiO2) concentration of 20.5% by mass, an average particle size based on dynamic light scattering (DLS) of 22 nm, a stability test result of "0", residual tri-n-pentylamine of 4400 ppm, diisopropylamine of 180 ppm, and isopropylamine of 19 ppm in the ethanol-dispersed sol of particles (iii-2-2), a crystallinity of 91% for nucleus particle (i), a refractive index of 1.87 for particle (iii-2-2), and a resistivity of 2.6 × 10⁻⁶ for the coating film formed by particle (iii-2-2). 11 Ω / □. The mass ratio of amine (b) to amine (a) is 22.1.

[0357] (Example 8)

[0358] 100 g of the aqueous dispersion sol of tin oxide colloidal particles (iii-2-2) coated with silica-tin oxide composite oxide obtained in Manufacturing Example 2 was replaced with 2-propanol using a rotary evaporator to obtain a 2-propanol dispersion sol of tin oxide colloidal particles (iii-2-2) coated with silica-tin oxide composite oxide. The resulting sol had a pH of 5.2 (diluted with water of the same mass as 2-propanol), a total metal oxide (SnO2 and SiO2) concentration of 15.0% by mass, an average particle size based on dynamic light scattering (DLS) of 22 nm, a sol stability test result of "0", residual tri-n-pentylamine of 4800 ppm, diisopropylamine of 170 ppm, and isopropylamine of 19 ppm in the 2-propanol dispersion of particles (iii-2-2), a crystallinity of 92% for nucleus particle (i), a refractive index of 1.87 for particle (iii-2-2), and a resistivity of 2.3 × 10⁻⁶ for the coating film. 11 Ω / □. The mass ratio of amine(b) to amine(a) is 25.4.

[0359] (Example 9)

[0360] 14.6 g of an aqueous dispersion sol of tin oxide colloidal particles (iii-1-1) coated with antimony pentoxide colloidal particles obtained in Manufacturing Example 3 was replaced with ethanol using a rotary evaporator to obtain 20.0 g of an ethanol dispersion sol of tin oxide colloidal particles (iii-1-1) coated with antimony pentoxide colloidal particles with a total metal oxide (SnO2 and Sb2O5) concentration of 15.0% by mass. 1.00 g of polyoxyethylene alkyl ether phosphate (manufactured by Toho Chemical Industry Co., Ltd.: RS-710) diluted with ethanol to a mass ratio of 30% was added to the obtained sol under stirring as a surface modifier, and the particles were surface modified by reflux heating at 90°C for 5 hours. 12.0 g of propylene glycol monomethyl ether was added to the obtained surface-modified ethanol dispersion sol, and the ethanol was evaporated using a rotary evaporator to obtain 15.0 g of propylene glycol monomethyl ether dispersion sol containing tin oxide colloidal particles (iii-1-1) coated with antimony pentoxide colloidal particles. The resulting sol had a pH of 4.7 (diluted with water of equal mass to ethanol), a total metal oxide (SnO2 and Sb2O5) concentration of 20.0% by mass, an average particle size based on dynamic light scattering (DLS) of 25 nm, a stability test result of "0", residual tri-n-pentylamine of 4900 ppm, diisopropylamine of 240 ppm, and isopropylamine of 25 ppm in the propylene glycol monomethyl ether dispersion of particles (iii-1-1), a crystallinity of 92% for nucleus particle (i), a refractive index of 1.91 for particle (iii-1-1), and a resistivity of 8.0 × 10⁻⁶ for the coating film formed by particle (iii-1-1). 11 Ω / □. The mass ratio of amine (b) to amine (a) is 18.5.

[0361] (Comparative Example 1)

[0362] For 100g of the aqueous dispersion sol of tin oxide colloidal particles (iii-3) coated with silica-tin oxide composite oxide obtained in Comparative Manufacturing Example 1, methanol was replaced using a rotary evaporator. As a result, the sol thickened and gelled during the replacement process.

[0363] (Comparative Example 2)

[0364] Except that isopropylamine was not added during the preparation of the tin oxide composite oxide colloidal particles (i) used as the core in Reference Example 1, the sol was prepared in the same manner as in Reference Example 1. The tin oxide slurry was not degellated, and an aqueous dispersion sol was not obtained.

[0365] Industrial availability

[0366] The modified metal oxide particles of the present invention have high conductivity and high refractive index, and they are stably dispersed in organic solvents, thereby enabling the provision of the aforementioned sol as a coating agent that has transparency, high particle refractive index and good film resistivity when coated on a substrate.

Claims

1. A modified metal oxide sol comprising modified metal oxide particles (iii) dispersed in an organic solvent, wherein the modified metal oxide particles (iii) have tin oxide particles (i) having an average primary particle size of 4 to 50 nm as a core, and are coated with metal oxide particles (ii) having an average primary particle size of 1 to 10 nm and selected from at least one of antimony oxide, tin oxide, and silicon oxide, wherein... The average primary particle size has a relationship of tin oxide particles (i) ≥ metal oxide particles (ii), and the ratio of (total mass of metal oxides other than tin oxide) to (mass of tin oxide) is 0.005 to 1.

0. Moreover, the sol contains an amine (a) with a water solubility of more than 0.1 g / L and an amine (b) with a water solubility of less than 0.1 g / L, wherein the amine (a) is an amine including primary amines, secondary amines, or combinations thereof, and the amine (b) is a tertiary amine, and the mass ratio of amine (b) to amine (a) is 3.0 to 200.

2. The modified metal oxide sol according to claim 1, wherein, The average particle size using the dynamic light scattering method is 5–100 nm.

3. The modified metal oxide sol according to claim 1, wherein, The tin oxide particles (i) that serve as the nuclear particles are hydrothermally treated tin oxide particles.

4. The modified metal oxide sol according to claim 1, wherein, The crystallinity of tin oxide particles (i), which are the nuclei, obtained by X-ray diffraction is over 60%.

5. The modified metal oxide sol according to claim 1, wherein, The metal oxide particles (ii) used as coating particles are antimony oxide particles or composite particles of tin oxide and silicon oxide in a mass ratio of 1:0.1 to 10.

0.

6. The modified metal oxide sol according to claim 1, wherein, The modified metal oxide sol contains amines (a) at a ratio of 20–3000 ppm.

7. The modified metal oxide sol according to claim 1, wherein, The modified metal oxide sol contains amines (b) at a ratio of 1000–30000 ppm.

8. The modified metal oxide sol according to claim 1, wherein, The amine (a) is at least one amine selected from n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, isobutylamine, di-n-butylamine and diisobutylamine.

9. The modified metal oxide sol according to claim 1, wherein, Amine (b) is at least one amine selected from tri-n-butylamine, triisobutylamine, tri-n-pentylamine and triisopentylamine.

10. The modified metal oxide sol according to claim 1, wherein, The modified metal oxide particles (iii) are coated with at least one coating agent selected from formulas (1) to (6): 【change 】 【change 】 In equation (1), R 1 Each of the following is an organic group: alkyl, haloalkyl, alkenyl, aryl, or having a polyether group, epoxy group, (meth)acryloyl group, mercapto group, amino group, urea group, or cyano group, and is bonded to a silicon atom via a Si-C bond. 2 Each represents an alkoxy, acyloxy, or halogen group, and 'a' represents an integer from 1 to 3. In equations (2) and (3), R 3 and R 5 Each is an alkyl group with 1 to 3 carbon atoms or an aryl group with 6 to 30 carbon atoms, and is bonded to silicon atoms via Si-C bonds. 4 and R 6 Each represents an alkoxy, acyloxy, or halogen group; Y represents an alkylene, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3. In formulas (4) to (6), X1, X2 and X3 each represent an alkylene group with 2 to 20 carbon atoms, f, h and j each represent an integer from 1 to 100, e, g and i each represent an integer from 1 to 3, and Y1, Y2 and Y3 each represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or a (meth)acryloyl group.

11. The modified metal oxide sol according to claim 1, wherein, Organic solvents include alcohols, ketones, esters, ethers, amides, hydrocarbons, solvents containing cyano groups, solvents containing halogens, solvents containing sulfonyl groups, solvents containing carboxyl groups, or mixtures thereof.

12. The modified metal oxide sol according to claim 11, wherein, Alcohols are monohydric alcohols with 1 to 20 carbon atoms, or polyhydric alcohols with 1 to 20 carbon atoms.

13. An antistatic composition comprising modified metal oxide particles (iii) in a modified metal oxide sol according to any one of claims 1 to 12.

14. A composition for electron transport materials comprising modified metal oxide particles (iii) in a modified metal oxide sol according to any one of claims 1 to 12.

15. A method for manufacturing an organic solvent sol of modified metal oxide particles according to any one of claims 1 to 12, comprising the following steps (A) to (D): (A) Process: A process for preparing an aqueous sol containing an amine (a) with a water solubility of 0.1 g / L or more and tin oxide particles (i) with an average primary particle size of 4–50 nm. (B) Process: A process for preparing an aqueous sol containing an amine (a) with a water solubility of 0.1 g / L or more, and metal oxide particles (ii) having an average primary particle size of 1 to 10 nm and selected from at least one of antimony oxide, tin oxide, and silicon oxide. (C) Step: The aqueous sol of tin oxide obtained in step (A) and the aqueous sol of metal oxide particles (ii) obtained in step (B) are mixed at a ratio of (total mass of metal oxides other than tin oxide) / (mass of tin oxide) of 0.005 to 1.0 to manufacture modified metal oxide particles (iii) with tin oxide particles (i) having an average primary particle size of 4 to 50 nm as the core and coated with metal oxide particles (ii) having an average primary particle size of 1 to 10 nm and selected from at least one of antimony oxide, tin oxide and silicon oxide, and an amine (b) with a water solubility of less than 0.1 g / L is added. (D) Step: The step of replacing the aqueous medium solvent of the aqueous sol of the modified metal oxide particles (iii) obtained in step (C) with an alcohol having 1 to 5 carbon atoms. Wherein amine (a) is an amine comprising primary amines, secondary amines, or combinations thereof, amine (b) is a tertiary amine, and the mass ratio of amine (b) to amine (a) is 3.0 to 200.

16. The method for manufacturing an organic solvent sol of modified metal oxide particles (iii) according to claim 15, wherein, (A) The process involves adding an amine (a) with a water solubility of more than 0.1 g / L to an aqueous sol containing tin oxide particles (i) with an average primary particle size of 4 to 50 nm, followed by hydrothermal treatment (A-1) at a pressure of 0.1 to 40 MPa and a temperature of 100 to 350 °C for 0.01 to 100 hours.

17. The method for manufacturing the organic solvent sol of modified metal oxide particles according to claim 15, wherein, Add steps (E) and / or (F) after step (D): (E) Process: A process of surface treatment of modified metal oxide particles (iii) by adding at least one coating agent selected from formulas (1) to (6) to an organic solvent sol of modified metal oxide particles (iii). 【Transformation 3】 【Chemistry 4】 In equation (1), R 1 Each of the following is an organic group: alkyl, haloalkyl, alkenyl, aryl, or having a polyether group, epoxy group, (meth)acryloyl group, mercapto group, amino group, urea group, or cyano group, and is bonded to a silicon atom via a Si-C bond. 2 Each represents an alkoxy, acyloxy, or halogen group, and 'a' represents an integer from 1 to 3. In equations (2) and (3), R 3 and R 5 Each is an alkyl group with 1 to 3 carbon atoms or an aryl group with 6 to 30 carbon atoms, and is bonded to silicon atoms via Si-C bonds. 4 and R 6 Each represents an alkoxy, acyloxy, or halogen group; Y represents an alkylene, NH group, or oxygen atom; b is an integer from 1 to 3; c is an integer from 0 to 1; and d is an integer from 1 to 3. In formulas (4) to (6), X1, X2, and X3 each represent an alkylene group with 2 to 20 carbon atoms, f, h, and j each represent an integer from 1 to 100, e, g, and i each represent an integer from 1 to 3, and Y1, Y2, and Y3 each represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or a (meth)acryloyl group. (F) Step: A step in which the alcohol solvent of the modified metal oxide particles (iii) having 1 to 5 carbon atoms is replaced with an alcohol, ketone, ester, ether, amide, hydrocarbon, solvent containing cyano, solvent containing halogen, solvent containing sulfonyl, solvent containing carboxyl, or a mixture thereof, other than those used in step (D).

Images