JP2010077409A - Method for producing resin-coated metal oxide particle dispersion sol, application liquid containing the particle for forming transparent coating film, and base material with transparent coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a resin-coated metal oxide particle dispersion sol exhibiting excellent dispersibility and stability even at high concentration. <P>SOLUTION: In the method for producing the resin-coated metal oxide particle dispersion sol, a resin coating material consisting of an acrylic resin and/or a methacrylic resin is added to an organic solvent dispersion liquid of metal oxide particles, which are previously subjected to heat treatment at 100-800°C and have average particle diameter of 5-10 μm, and then, mechanochemical treatment is carried out. The application liquid for forming a transparent coating film comprises a matrix forming component, the resin-coated metal oxide particle dispersion sol obtained by the above method, and an organic solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a metal oxide particle-dispersed sol coated with a resin having excellent dispersibility and stability even at a high concentration, a coating liquid for forming a transparent film containing the resin-coated metal oxide particles, and a substrate with a transparent film About.

  Conventionally, it has been known that a transparent film having a hard coat function is formed on the surface of the base material in order to improve the scratch resistance of the surface of the base material such as glass, plastic sheet, and plastic lens. For example, an organic resin film or an inorganic film is formed on the surface of glass or plastic. Furthermore, it is practiced to further improve the scratch resistance by blending resin particles or inorganic particles such as silica in an organic resin film or an inorganic film.

  However, when fine particles are dispersed in a coating solution for forming a transparent coating to form a transparent coating, if the affinity between the matrix component or the dispersion medium and the particles is low, the particles aggregate or the stability of the coating solution decreases. In addition to the transparency and haze of the transparent film obtained, the scratch resistance, strength, scratch strength, etc. may be insufficient.

For this reason, it is known that the particles are surface-treated with a silane coupling agent in order to improve the dispersibility of the particles to prevent aggregation or to improve the stability of the coating solution. In addition, a resin is coated on the particles by a mechanochemical method, a graft polymerization method, or the like to increase the affinity with a matrix component or a dispersion medium. (JP-A-3-163172 (Patent Document 1), JP-A-6-336558 (Patent Document 2), JP-A-6-49251 (Patent Document 3), JP-A 2000-143230 (Patent Document) 4))
Furthermore, Japanese Patent Application Laid-Open No. 7-118123 (Patent Document 5) and Japanese Patent Application Laid-Open No. 2003-63932 (Patent Document 6) disclose cosmetic powders coated with a resin.

Japanese Patent Laid-Open No. 3-163172 JP-A-6-336558 JP-A-6-49251 JP 2000-143230 A JP 7-118123 A JP 2003-63932 A

  However, the particles surface-treated with the silane coupling agent are often different from the dispersion medium (usually water and / or alcohol) suitable for the silane coupling agent treatment and the dispersion medium used for the coating liquid for forming the transparent film. For this reason, it was necessary to replace the solvent with the dispersion medium for the coating solution. Further, depending on the dispersion medium used in the coating solution, the silane coupling agent may be detached, which may cause the particles to aggregate or the stability of the coating solution to be insufficient.

In addition, in the conventional mechanochemical method, graft polymerization method, etc., it is difficult to uniformly coat the resin on individual particles, and the resin is coated on several or more aggregated particles. May dissolve in the solvent of the coating solution, and the transparent film thus obtained has problems such as a decrease in transparency, an increase in haze, and a decrease in scratch resistance.

As a result of intensive studies in view of such problems, the present inventors have added an acrylic resin to a ketone organic solvent dispersion of heat-treated metal oxide particles, and then individual particles when mechanochemical treatment is performed. The present invention was completed by finding that resin-coated metal oxide particles that can be uniformly coated with a resin and that are excellent in dispersibility and stability even at high concentrations can be obtained.
[1] An organic solvent dispersion of metal oxide particles having an average primary particle diameter in the range of 5 to 300 nm and an average secondary particle diameter in the range of 5 nm to 10 μm preliminarily heat-treated at 100 to 800 ° C. A method for producing a resin-coated metal oxide particle-dispersed sol, in which a resin coating material comprising a methacrylic resin and / or a methacrylic resin is added and then mechanochemically treated.
[2] The method for producing a resin-coated metal oxide particle-dispersed sol according to [1], wherein the organic solvent is at least one selected from ethers, esters, and ketones.
[3] The concentration ratio (C _R ) / (C _MO ) of the concentration (C _R ) as the solid content of the resin coating material and the concentration (C _MO ) as the solid content of the metal oxide fine particles is 0.005 to 0 [1] or [2] in the range of 5
A method for producing a resin-coated metal oxide particle-dispersed sol.
[4] Resin-coated metal oxide particle dispersion of [1] to [3], wherein the total solid content of the metal oxide particles and the resin coating material in the mechanochemical treatment is in the range of 1 to 50% by weight. Method for producing sol. [5] The metal oxide particles include TiO ₂ , SiO ₂ , ZrO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZnO and a composite oxide thereof, tin oxide, tin oxide doped with Sb or P, Indium oxide, Sn
Alternatively, a method for producing a resin-coated metal oxide particle-dispersed sol according to [1] to [4], which is at least one selected from indium oxide doped with F, antimony oxide, and low-order titanium oxide.
[6] The method for producing a resin-coated metal oxide particle-dispersed sol according to [1] to [5], wherein the resin-coated metal oxide particles have an average particle diameter in the range of 5 to 300 nm.
[7] A coating solution for forming a transparent film, comprising a matrix-forming component, a resin-coated metal oxide particle-dispersed sol obtained by the methods [1] to [6], and an organic solvent.
[8] A substrate with a transparent coating, comprising: a substrate; and a transparent coating formed by applying and drying the coating solution for forming a transparent coating according to [7] on the substrate.
[9] The substrate with a transparent coating according to [8], wherein the transparent coating is provided together with another coating.

  According to the present invention, since a specific resin coating material is added to an organic solvent dispersion of metal oxide particles having a specific average particle diameter that has been heat-treated in advance, the solvent is used. A resin-coated metal oxide particle-dispersed sol that can be stably dispersed without agglomerating in the coating solution for forming a transparent coating film and has excellent dispersibility and stability even when the concentration is high is produced. In the coating liquid for forming a transparent film containing the resin-coated metal oxide particles, the coating resin and the matrix-forming component in the coating liquid have binding properties. Therefore, transparency, haze, and adhesion to the substrate It is possible to provide a coating solution for forming a transparent film and a substrate with a transparent film, which can be suitably used for forming a transparent film having excellent film strength and scratch resistance. The mechanochemical treatment in an organic solvent as in the present invention has not been known at all, and the above-described effect achieved by such mechanochemical treatment has not been known.

Hereinafter, first, a method for producing a resin-coated metal oxide particle-dispersed sol will be described.
[Method for producing resin-coated metal oxide particle-dispersed sol]
In the method for producing a resin-coated metal oxide particle-dispersed sol according to the present invention, a specific resin coating agent is added to an organic solvent dispersion of metal oxide particles having an average particle diameter in the range of 5 to 300 nm, and then mechano Chemical treatment.
Metal Oxide Particles As the metal oxide particles used in the present invention, known metal oxide particles conventionally used for transparent coatings can be used.

Specifically, TiO ₂ , SiO ₂ , ZrO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZnO, and composite oxides thereof, tin oxide, tin oxide doped with Sb or P, indium oxide, Sn or 1 selected from indium oxide doped with F, antimony oxide, and low-order titanium oxide
It is preferable that it is a seed or more.

The metal oxide particles can be appropriately selected and used depending on the use of the transparent film. For example, the metal oxide particles used for the antireflection film are usually metal oxides having a refractive index of 1.45 or less, preferably 1.40 or less. things particles are used, specifically SiO _2, particle or the like coated with a metal oxide having a SiO ₂ or conductive thereto, having a cavity inside thereof. As the SiO ₂ particles having a cavity inside, silica-based fine particles having a cavity inside disclosed in JP-A-2001-233611 filed by the applicant of the present application can be suitably employed.

When a transparent coating is used for the hard coat film, the metal oxide particles include ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO, Al ₂ O ₃ , SnO ₂ , or silica having a refractive index of 1.45 or less. System fine particles and the like.

When the transparent coating is a high refractive index film, the metal oxide particles used are usually fine particles having a refractive index of 1.60 or more, more preferably 1.80 or more, specifically ZrO ₂ , TiO _2. Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ , antimony-doped tin oxide, tin-doped indium oxide, phosphorus-doped tin oxide (PTO) and the like. For example, in the case of a PET base material having a high refractive index, titanium oxide particles having a high refractive index can be suitably used in order to approximate the refractive index between the transparent film and the base material.

When imparting conductivity to the transparent coating, the metal oxide particles are usually Sb ₂ O ₅ , SnO ₂ ,
Examples thereof include antimony-doped tin oxide, tin-doped indium oxide, phosphorus-doped tin oxide (PTO), silica-based fine particles whose surfaces are coated with these conductive materials, or silica-based fine particles having a cavity inside.

  The metal oxide particles used in the present invention are preliminarily heat-treated (that is, dried and / or calcined) before being subjected to a mechanochemical treatment described later. The heat treatment temperature is preferably 100 to 800 ° C, more preferably 105 to 750 ° C.

  In preparing the metal oxide particles, if there is already a heating history in the above temperature range, it is not necessary to perform a separate heat treatment. In addition, even if there is a heating history in the temperature range, if there is a water dispersion history after that, it is preferable to perform heat treatment.

  In the present invention, it is preferable to perform heat treatment after drying for solvent removal.

  By such heat treatment, the resin coating amount can be made high and uniform, and as a result, the stability of the resulting resin-coated metal oxide particle-dispersed sol can be enhanced.

  Although the reason is not clear, the heat treatment removes the adhering water that hinders the reaction with the resin, and generates active OH that promotes the reaction with the resin, thereby promoting uniform coating of the particles with the resin. It is thought of.

If the heat treatment temperature is too low, the surface of the metal oxide particles may be active due to residual water remaining, etc., or the bond between the particles and the resin may be insufficient, and the resin coating amount may be insufficient. Yes,
The stability of the resulting resin-coated metal oxide particle-dispersed sol may be insufficient.

  Moreover, even if the heat treatment temperature is too high, the metal oxide particles are excessively aggregated, or depending on the type of the metal oxide particles, sintering is performed, and the stability of the resulting resin-coated metal oxide particle-dispersed sol becomes insufficient. Sometimes.

  As a result, the stability of the paint for forming the transparent film is lowered, and the transparency, haze, film strength, scratch resistance, adhesion to the substrate, etc. of the finally obtained transparent film become insufficient. There is.

  As the average particle size of the metal oxide particles, metal oxide particles having an average particle size such that the average particle size of the obtained resin-coated metal oxide particles is about 5 to 300 nm are used.

  The metal oxide particles may be composed only of primary particles or may be secondary particles composed of a plurality of primary particles. Specifically, metal oxide particles having an average primary particle diameter in the range of 5 to 300 nm, and in the case of secondary particles, metal oxide particles having an average secondary particle diameter in the range of 5 nm to 10 μm (however, The average primary particle size is not exceeded).

  The average primary particle diameter is in the range of 5 to 300 nm, preferably 5 to 200 nm, and the average secondary particle diameter is in the range of more than 5 nm to 10 μm, preferably 10 to 5 μm.

  Even if the secondary particles are particles in which the primary particles are aggregated or particles that are partially bonded and grown, resin-coated metal oxide particles having an average particle diameter in the range of 5 to 300 nm are used. If finally obtained, it can be used without particular limitation.

  In the present invention, the average primary particle diameter is determined by taking a transmission electron micrograph (TEM) of the particles, measuring the particle diameter of 100 particles, and obtaining the average value. The average secondary particle diameter can be determined by a dynamic light scattering method “Microtrack particle size distribution measuring apparatus”.

  If the average primary particle size of the metal oxide particles is too small, excessively agglomerated resin-coated metal oxide particles can be obtained, and the transparency, strength, scratch resistance, adhesion to the substrate, etc. of the transparent film are insufficient. It becomes.

If the average primary particle size is too large, it is difficult to obtain a resin-coated metal oxide particle finally having an average particle size of 300 nm or less, and even if it is strongly ground, it is a crystalline metal oxide. In the case of particles, the crystallinity may decrease. If the average secondary particle size is too large, the pulverization efficiency of the metal oxide particle aggregates or the pulverization of the crystalline metal oxide particles is reduced, or the pulverization becomes difficult. As a result, the average particle diameter of the resulting resin-coated metal oxide particles becomes large, and the stability of the resin-coated metal oxide particle-dispersed sol may be insufficient. Then, the stability of the coating for forming a transparent film using these resin-coated metal oxide particle-dispersed sols decreases, and the transparency, haze, film strength, scratch resistance, and substrate of the finally obtained transparent film In some cases, the adhesiveness of the resin becomes insufficient.

  In the present invention, when the average secondary particle diameter of the metal oxide particles to be used is larger than the above upper limit, the metal oxide particles can be used with a conventionally known agglomeration and pulverization method to 10 μm or less.

As the resin coating material , an acrylic resin and / or a methacrylic resin is used.

Acrylic resins include acrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2 -Acryloyloxyethyl 2-hydroxyethyl-phthalic acid, mono-2-acryloyloxyethyl acid phosphate, di-2-acryloyloxyethyl acid phosphate 2-hydroxybutyl acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, glycerin Diglycidyl ether, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A diglycidyl ether acrylic acid adduct, O-phenylphenol glycidyl ether acrylate, 1,4-butanediol Glycidyl ether diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, dipropylene glycol diglycidyl ether diacrylate, pentaerythritol polyglycidyl ether acrylate, 2-til 2 ethyl 1,3-propanediol diglycidyl ether acrylate, cyclohexanedi Methanol diglycidyl ether acrylate, 1,6 hexanediol diglycidyl ether acrylate, glycerin polyglycidyl ether acrylate, ethylene glycol diglycidyl ether acrylate, polyethylene glycol diglycidyl ether acrylate, dipropylene glycol diglycidyl ether acrylate, polypropylene glycol diglycidyl ether acrylate 2- Examples include acrylic monomers such as droxy, 1-acryloxy, 3-methacryloxypropane, β-carboxyethyl acrylate, homopolymers of these acrylic monomers, and copolymers of acrylic monomers with styrene, silicon, polyester, etc. .

Methacrylic resins include methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, mono-2- Methacryloyloxyethyl acid phosphate, di-2-methacryloyloxyethyl acid phosphate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-3 acryloyloxypropyl methacrylate, bisphenol A diglycidyl ether methacryl Methacrylic monomers such as acid adducts, diglycerin polyglycidyl ether methacrylate, 3-chloro-2-hydroxypropyl methacrylate, these methacrylic monomers Homopolymers of mer, methacrylic monomers and styrene, silicone, and a copolymer of polyester. Furthermore, phosphoric acid ester containing (meth) acrylic group such as di-2-methacryloyloxyethyl acid phosphate, di-2-acryloyloxyethyl acid phosphate, alkali metal salt of (meth) acrylic acid, ammonium salt, phosphonium salt, Esters can also be used.

  The reason why these resin coating materials are preferable is not clear, but since the (meth) acrylic resin is hydrophilic, it is easy to bond to the surface of the metal oxide particles. It is presumed that the resin coating material is easily bonded to the surface of the oxide particles.

The resin coating material may be a monomer, an oligomer or dimer polymerized to some extent, or a polymer that has been further polymerized. Even if the polymerization has not progressed, the polymerization proceeds by mechanochemical treatment or heat treatment.
As the organic solvent , a conventionally known organic solvent can be used.

For example, alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol; glycols such as ethylene glycol and hexylene glycol; diethyl ether, ethylene glycol Ethers such as monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; propyl acetate, isobutyl acetate , Butyl acetate, isopentyl acetate, pentyl acetate, 3-methyl acetate Esters such as xylbutyl, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, Ketones such as acetylacetone and acetoacetate; toluene, xylene and the like.

  Of these, the ethers, esters and ketones are preferred because they have good resin coating efficiency, the resulting resin-coated metal oxide particles have few aggregated particles, are excellent in dispersibility, and are stable without sedimentation.

  The ethers, esters, and ketones are frequently used because they have good coatability and are less likely to cause abnormal appearance when used as a solvent for a coating solution for forming a transparent film. Since it is not necessary to replace the particle-dispersed sol with a solvent for the coating solution, it is preferable from the viewpoint of production efficiency and economy.

  In particular, ethers can be preferably used because metal oxide particles hardly aggregate in mechanochemical treatment and can be uniformly coated with a resin.

Mixing ratio The concentration ratio (C _R ) / (C _MO ) between the concentration (C _R ) as the solid content of the resin coating material and the concentration (C _MO ) as the solid content of the metal oxide particles in the mechanochemical treatment is 0 0.005 to 0.5, more preferably 0.01 to 0.3.

If the concentration ratio (C _R ) / (C _MO ) is too small, dispersibility and stability in the resulting resin-coated metal oxide particle-dispersed sol and a coating solution for forming a transparent film using the resin-coated metal oxide will be insufficient. The obtained transparent film may also have low transparency and high haze. Concentration ratio (C _R ) / (C _MO
) Is too large, dispersibility, stability, transparency of the transparent coating, and haze are not improved, and the characteristics such as the refractive index or conductivity of the metal oxide particles used may not be sufficiently exhibited.

Further, the total solid content concentration of the metal oxide particles and the resin coating material during the mechanochemical treatment is preferably in the range of 1 to 50% by weight, more preferably 2 to 45% by weight. If the total solid concentration is too low, it takes a long time for the treatment, and it becomes difficult to treat all the particles uniformly, the resin coating becomes non-uniform, and the resulting resin-coated metal oxide particle dispersed sol and Dispersibility and stability in a coating solution for forming a transparent film using this become insufficient, and the resulting transparent film may also have low transparency and high haze. If the total solid content is too high, depending on the type of metal oxide particles, solvent, and resin, the viscosity may increase rapidly as the treatment progresses, or the particles may agglomerate. The dispersibility and stability of the product particle-dispersed sol and the coating solution for forming a transparent film using the same become insufficient, and the resulting transparent film may also have low transparency and high haze.
Mechanochemical treatment method The mechanochemical treatment method of the present invention may employ a conventionally known method except that the metal oxide particles, the resin coating material, the ratio and the concentration are employed.

  For example, a predetermined amount of organic solvent, metal oxide particles, and resin coating material are weighed in a Henschel mixer, homomixer, homogenizer, bead mill, etc., and stirred at high speed. In the mechanochemical treatment, a larger particle size can be efficiently treated. Therefore, it is desirable that the particles are relatively large secondary particles, but this is not restrictive.

  The stirring speed varies depending on the apparatus and method used, but if it is too low, if the metal oxide particles are secondary particles, crushing or pulverization will be insufficient, and the resulting resin-coated metal oxide particle particles The diameter may be too large, the resin coating amount may be insufficient, or the bond between the particles and the resin may be insufficient, or the stability of the resin-coated metal oxide particle-dispersed sol may be insufficient. The stability of the coating for forming a transparent film using a resin-coated metal oxide particle-dispersed sol decreases, and the transparency, haze, film strength, scratch resistance, adhesion to the substrate, etc. of the finally obtained transparent film May be insufficient.

  Conventionally, when a resin is coated by the method described above, a polymerization initiator is added, or ultraviolet irradiation or plasma irradiation is performed. However, when a polymerization initiator is added or ultraviolet irradiation is performed, a coating resin is used. If it is not laminated on the particle surface, or if the resin is polymerized and cured too much even if it is coated, or if it is used in a coating liquid for forming a transparent film described later, the binding with the matrix component does not occur. The strength, scratch resistance, scratch resistance, and adhesion to the substrate of the transparent film are unfavorable.

  The average particle diameter of the resin-coated metal oxide particles thus obtained is preferably in the range of 5 to 300 nm, more preferably 5 to 200 nm.

  The coating layer only needs to be attached in a small amount, and the average particle diameter of the metal oxide particles before and after the resin coating may be substantially the same. Of course, the average particle diameter after coating may be large. good. When the average particle diameter of the obtained particles is in the above range, transparency, haze, film strength, scratch resistance, and adhesion to the substrate are high, which is preferable in terms of desired characteristics and applications.

  The concentration of the resulting resin-coated metal oxide particle-dispersed sol is generally in the range of 1 to 50% by weight, preferably 2 to 45% by weight as the solid content.

If the concentration is low, the concentration of the coating solution for forming the transparent film may be too low to form a thick transparent film. In order to obtain a thick film, it is necessary to repeat coating, drying, and curing. If it is too high, the sol stability tends to be insufficient. In the present invention, the obtained resin-coated metal oxide particle-dispersed sol can be used after being concentrated or diluted as necessary.
[Transparent coating solution]
The coating liquid for forming a transparent film according to the present invention comprises a matrix-forming component, the resin-coated metal oxide particle-dispersed sol, and an organic solvent.
Resin-coated metal oxide particle-dispersed sol The resin-coated metal oxide particle-dispersed sol described above is used in the coating liquid for forming a transparent film of the present invention. It is preferable that the density | concentration as solid content in the coating liquid for transparent film formation of the resin coating metal oxide particle is 0.1 to 50 weight%, Furthermore, it is preferable to exist in the range of 0.2 to 40 weight%. Within this range, the sol can be uniformly dispersed together with the matrix component in the coating solution, and the characteristics of the particles can be sufficiently exhibited, so that a desired transparent film can be formed.

If the concentration is too low, the amount of particles is so small that the particle properties (scratch resistance, low refractive index, high refractive index, electrical conductivity, etc.) provide scratch resistance, antireflection performance, antistatic performance, etc. If it is too high, there are few matrix components, and adhesion to the substrate, transparency, haze, scratch resistance, etc. may be insufficient.
Matrix-forming component As the matrix-forming component, an organic resin-based matrix-forming component is preferably used.

As the organic resin matrix forming component, specifically, any of thermosetting resins and thermoplastic resins known as coating resins can be employed. For example, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, silicone rubber and other thermoplastic resins, urethane resins, melamine resins And thermosetting resins such as silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated polyester resin, and thermosetting acrylic resin. Further, it may be a copolymer or modified body of two or more of these resins. In the case of a thermoplastic resin, the matrix-forming component is a matrix component as it is, and in the case of a curable resin, generally, in the matrix-forming component, an uncured (polymerized) monomer is a matrix-forming component, and a cured (polymerized) product is a matrix component.

  These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, it may be a thermosetting resin, an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.

In the present invention, the resin used for the resin-coated metal oxide particles has a binding property with the matrix-forming component, and the film strength and scratch resistance are improved. , Polyfunctional (meth) acrylic acid ester resins having functional groups such as amino group, carboxyl group, sulfo group, etc., specifically, 2-hydroxy-3-acryloyloxypropyl acrylate, 2-hydroxy-3- Acryloyloxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, pentaerythritol poroglycidyl ether acrylate, diethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, Taerythritol triacrylate, trimethylolpropane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, trimethylol propane trimethacrylate, methoxytriethylene glycol dimethacrylate, butoxydiethylene glycol methacrylate, 2 acryloxyethyl succinic acid, 2 acro Iroxyethyl phthalic acid and a mixture thereof, or two or more copolymers or modified products of these resins may be used.

In addition, polyfunctional (meth) acrylic acid ester resins having a functional group such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF ₂ group, and the like, specifically, pentaerythritol tetraacrylate, dipenta Erythritol hexaacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane trimethacrylate, methoxytriethylene glycol dimethacrylate, 1,6- Hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, phenylglycidyl ether acetate Relate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, cresol novolak type epoxy acrylate, bisphenol A diglycidyl ether acrylic acid adduct, pentaerythritol polyglycidyl ether acrylate, neopentyl glycol diglycidyl ether acrylate, Examples include 2-butyl-2ethyl-1,3-propanediol diglycidyl ether acrylate and mixtures thereof.

The concentration of the matrix-forming component in the coating solution for forming a transparent film is preferably in the range of 1 to 60% by weight, more preferably 2 to 50% by weight as the solid content. If the concentration of the matrix-forming component is too low, a predetermined film thickness may not be obtained by a single application, and if application and drying are repeated, adhesion and the like are insufficient, and this is disadvantageous in terms of economy. If the concentration of the matrix forming component is too high, the thickness of the resulting transparent film tends to be non-uniform.
Organic solvent The organic solvent used in the present invention is not particularly limited as long as it can dissolve or disperse the matrix-forming component and the polymerization initiator used as necessary and uniformly disperse the resin-coated metal oxide particles described above. Conventionally known solvents can be used.

  Specifically, alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; methyl acetate , Esters such as ethyl acetate, butyl acetate; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl Ethers such as ether and propylene glycol monoethyl ether; Acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, acetylacetone, ketones such as acetoacetate, toluene, xylene and the like.

  These may be used alone or in combination of two or more. In the present invention, the aforementioned ethers, esters and ketones that can be suitably used for the production of the resin-coated metal oxide particle-dispersed sol are preferred. When these ethers, esters, and ketones are used as organic solvents, the coating solution for forming a transparent film has excellent compatibility with the matrix component, and the transparent film obtained using this has high surface uniformity, transparency, Excellent haze and scratch resistance.

The total concentration of the matrix-forming component and the resin-coated metal oxide particles or the surface-treated resin-coated metal oxide particles in the coating solution for forming a transparent film is 1 to 60% by weight, more preferably 2 to 50% by weight as a solid content. It is preferable that it exists in the range. If the total concentration is too small, a predetermined film thickness may not be obtained by a single application, and if application and drying are repeated, adhesion and the like are insufficient, and this is disadvantageous in terms of economy. If the total concentration is too high, the thickness of the transparent coating obtained may be uneven.
Polymerization initiator In the present invention, a polymerization initiator may be included as necessary together with the resin-coated metal oxide particles and the matrix-forming component. As the polymerization initiator, known ones can be used without particular limitation. For example, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2, 4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-methyl-2-methyl-phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy- Examples include cyclohexyl-phenyl-ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one. The amount of the polymerization initiator used is not particularly limited.

  The above-mentioned coating solution for forming a transparent film is applied to a substrate by a known method such as a dipping method, a spray method, a spinner method, a roll coating method, a bar coating method, a gravure printing method, a micro gravure printing method, dried and cured. In the case of a functional resin, a transparent film can be formed by curing by an ordinary method such as ultraviolet irradiation or heat treatment.

The film thickness of the formed transparent film is preferably in the range of 30 nm to 20 μm.
[Base material with transparent film]
The substrate with a transparent coating according to the present invention comprises a substrate and a transparent coating formed on the substrate, and the transparent coating comprises resin-coated metal oxide particles formed from the coating solution and a matrix component. It is characterized by becoming.
Substrate As the substrate used in the present invention, conventionally known ones can be used without particular limitation, and glass, polycarbonate, acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC). ), Plastic sheets such as cyclopolyolefin and norbornene, plastic films, and plastic panels. Among these, a resin base material can be preferably used. Moreover, the base material with a film in which another film was formed on such a base material can also be used. Examples of other coatings include conventionally known primer films, hard coat films, high refractive index films, and conductive films.
Resin-coated metal oxide particles The resin-coated metal oxide particles are as described above.

The content of the resin-coated metal oxide fine particles in the transparent film is preferably in the range of 0.2 to 90% by weight, more preferably 0.5 to 80% by weight as the solid content. If the content is too small, the amount of particles is so small that the particle properties (improved scratch resistance, low refractive index, high refractive index, electrical conductivity, etc.) have poor scratch resistance, antireflection performance, antistatic performance, etc. In some cases, it is sufficient, and if it is too much, there are few matrix components, and adhesion to the substrate, transparency, haze, scratch resistance, etc. may be insufficient.
Matrix component The matrix component is derived from the organic resin matrix forming component, and the details are as described above.

  The content of the matrix component in the transparent coating is preferably in the range of 10 to 99.8% by weight, more preferably 20 to 99.5% by weight as the solid content.

  If the content of the matrix component in the transparent coating is too small, adhesion to the substrate, transparency, haze, scratch resistance, etc. may be insufficient. If the content is too large, the amount of particles is so small that the particle properties (scratch resistance, low refractive index, high refractive index, conductivity, etc.) are not sufficient for scratch resistance, antireflection performance, antistatic performance, etc. It may become.

  The film thickness of the transparent coating according to the present invention varies depending on the application, but is generally in the range of 30 nm to 20 μm, and more preferably 70 nm to 15 μm.

  If the film thickness of the transparent coating is too thin, film strength and scratch resistance may be insufficient depending on the application. If the film thickness of the transparent coating is too thick, cracks may occur in the transparent coating, or curling (curving or warping) may occur in a substrate such as plastic.

  The substrate with a transparent coating according to the present invention can be produced by applying the above-described coating solution for forming a transparent coating on a substrate, drying and curing.

  Specifically, the transparent film-forming paint is applied to the substrate by a known method such as dipping, spraying, spinner, roll coating, bar coating, slit coater printing, gravure printing, or micro gravure printing. A transparent film can be formed by applying, drying, and curing by an ordinary method such as ultraviolet irradiation or heat treatment. When manufacturing a substrate with a transparent coating having a string-proof property, a roll coating method, a slit coater printing method, a gravure printing method, and a micro gravure printing method are recommended.

Furthermore, in the base material with a transparent film of the present invention, another film different from the transparent film can be provided between the base material and the transparent film. Examples of other coatings include conventionally known primer films, hard coat films, high refractive index films, conductive films, low refractive index films, antiglare films, infrared shielding films, and ultraviolet shielding films.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[Example 1]
Resin coated particles (1) Preparation of dispersion sol
Preparation of P-doped tin oxide fine particles (1) In 8060 g of pure water, 13 g of ammonium nitrate and 20 g of 15% ammonia water were added and stirred, and the temperature was raised to 50 ° C. A solution obtained by dissolving 1519 g of potassium stannate in 4290 g of pure water was added with a roller pump over 10 hours. At this time, nitric acid having a concentration of 10% by weight was added and adjusted so as to maintain the pH at 8.8 with a pH controller. After the addition was completed, the temperature was kept at 50 ° C. for 1 hour, and then 10% by weight nitric acid was added to lower the pH to 3.0. Next, it was washed with pure water until the filtered water conductivity reached 10 μS / cm with an ultrafiltration membrane, and then concentrated with an ultrafiltration membrane. The amount of liquid taken out at this time was 6000 g, and the solid content (SnO ₂ ) concentration was 12% by weight. To this slurry, 264 g of a phosphoric acid aqueous solution having a concentration of 16% by weight was added and stirred for 0.5 hour. This was dried at 105 ° C. for 2 hours and then calcined at 700 ° C. for 2 hours to prepare P-doped tin oxide fine particle (1) powder.

The obtained P-doped tin oxide fine particles (1) have an average primary particle size of 15 nm and an average secondary particle size of 0.
. The volume resistance was 45 Ω · cm at 45 μm.
201 g of resin-coated P-doped tin oxide fine particle powder, 374 g of propylene glycol monomethyl ether (PGME) as an organic solvent, and di-2-methacryloyloxyethyl acid phosphate as a coating resin (manufactured by Kyoeisha Chemical Co., Ltd .: Light Ester P-2M) 14 .5 g was filled into a bead mill containing 1135 g of glass beads (0.4 mm), treated at 1700 rpm for 1 hour, separated from glass beads, and then added with PGME to give a resin with a solid content concentration of 30% by weight. A coated P-doped tin oxide fine particle (1) -dispersed sol was prepared.

  The stability of the resin-coated P-doped tin oxide fine particles (1) dispersed sol and the average particle size of the resin-coated P-doped tin oxide fine particles (1) were measured, and the results are shown in Table 1.

The stability was evaluated by the following method and evaluation criteria. The average particle size was measured with a laser particle size analysis system (PAR-III) manufactured by Otsuka Electronics.
Stability evaluation Resin-coated P-doped tin oxide microparticles with a solid content concentration of 30% by weight (1) Disperse sol is filled in a transparent container and allowed to stand, and the state of precipitated particles is observed at the bottom of the container. The results are shown in Table 1.

No sedimentation layer of particles was observed for more than 1 week. : ◎
A sedimentation layer of particles was observed in 3 to 6 days. : ○
A sedimentation layer of particles was observed in 1 to 2 days. : △
Within 1 day, a sedimentation layer of particles was observed. : ×
Preparation of coating liquid (1) for forming transparent film Resin coated P-doped tin oxide fine particles (1) with a solid content concentration of 30% by weight (1)
6 g of polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Ester A-400) as the glycol acrylate resin and 1,6-hesandiol diacrylate (Nippon Kayaku Co., Ltd.) as the non-glycol bifunctional acrylate resin Made by Kaylad KS-HDD
A) 3 g, 24 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) as a non-glycol-based hexafunctional acrylate resin, 40 g of isopropyl alcohol, 30 g of propylene glycol monomethyl ether, and a photoinitiator A coating liquid (1) for forming a transparent film was prepared by mixing 1.5 g of 4.6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BIAS Japan KK: Lucillin TPO).
Production of substrate with transparent coating (F-1) Coating solution (1) for forming a transparent coating was prepared by using a PET film (thickness: 188 μm, refractive index: 1.65, total light transmittance 90.0%, haze 0.6%). ) By a bar coater method (bar # 14), dried at 80 ° C. for 1 minute, and then applied with an ultraviolet irradiation device (UV irradiation device CS30L21-3 manufactured by Nippon Batteries) equipped with a high pressure mercury lamp (120 W / cm) to 600 mJ / cm ² irradiation cured, transparent film-coated substrate of (F-1) was prepared. At this time, the thickness of the transparent film was 4 μm. The surface resistance of the obtained transparent film was measured with a surface resistance meter (manufactured by Mitsubishi Chemical Corporation: Hiresta), and the results are shown in Table 1.

  Further, the total light transmittance and haze were measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the results are shown in Table 1. Further, pencil hardness, scratch resistance and adhesion were evaluated by the following methods and evaluation criteria, and the results are shown in Table 1.

Measurement of pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.

Measurement of Scratch Resistance Using # 0000 steel wool, sliding 50 times at a load of 500 g / cm ² , visually observing the surface of the film, and evaluating according to the following criteria, the results are shown in Table 1.

Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×
11 parallel scratches were made on the surface of the substrate with adhesive transparent coating (F-1) with a knife at intervals of 1 mm in length and width 1
00 cells were made, cellophane tape (registered trademark) was adhered to this, and then the cellophane tape (registered trademark) was peeled off, and the number of cells remaining without peeling off was determined by the following four steps. The adhesion was evaluated by classifying into The results are shown in Table 1.

Number of remaining cells: 95 or more: ◎
Number of remaining squares 90-94: ○
Number of remaining squares: 85-89:
Number of remaining squares: 84 or less: ×
[Example 2]
Preparation of resin-coated particles (2) dispersed sol In Example 1, except that 7.3 g of di-2-methacryloyloxyethyl acid phosphate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Ester P-2M) was used as the coating resin Similarly, a resin-coated P-doped tin oxide fine particle (2) dispersion sol having a solid content concentration of 30% by weight was prepared. The stability of the resin-coated P-doped tin oxide fine particles (2) dispersed sol having a solid concentration of 30% by weight and the average particle size of the resin-coated P-doped tin oxide fine particles (2) were measured. The results are shown in Table 1.

Preparation of coating liquid (2) for forming transparent film In Example 1, resin-coated resin-coated P-doped tin oxide fine particles (2
) A coating liquid for forming a transparent film (2) was prepared in the same manner except that the dispersion sol was used.

Production of substrate with transparent coating (F-2) A substrate with transparent coating (F-2) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (2) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1.

[Example 3]
Preparation of resin-coated particle (3) dispersion sol In Example 1, except that 29.0 g of di-2-methacryloyloxyethyl acid phosphate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Ester P-2M) was used as the coating resin Similarly, a resin-coated P-doped tin oxide fine particle (3) dispersion sol having a solid concentration of 30% by weight was prepared.

The stability of the resin-coated P-doped tin oxide fine particles (3) dispersed sol having a solid content concentration of 30% by weight and the average particle diameter of the resin-coated P-doped tin oxide fine particles (3) were measured. The results are shown in Table 1.

Preparation of coating liquid for forming transparent film (3) In Example 1, a coating liquid for forming transparent film (3) was used in the same manner except that the resin-coated P-doped tin oxide fine particle (3) dispersion having a solid content of 30% by weight was used. 3) was prepared.

Production of substrate with transparent film (F-3) A substrate with transparent film (F-3) was prepared in the same manner as in Example 1, except that the coating liquid for forming a transparent film (3) was used. did. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1.
[Example 4]
Preparation of Resin Coated Particle (4) Dispersed Sol In Example 1, instead of 14.5 g of di-2-methacryloyloxyethyl acid phosphate as the coating resin, 2-hydroxy-3-phenoxypropyl acrylate (Shin Nakamura Chemical Co., Ltd.) Co., Ltd .: NK ester 702A) A resin-coated P-doped tin oxide fine particle (4) dispersion sol having a solid concentration of 30% by weight was prepared in the same manner except that 14.5 g was mixed.

The stability of the resin-coated P-doped tin oxide fine particles (4) dispersed sol having a solid content concentration of 30% by weight and the average particle size of the resin-coated P-doped tin oxide fine particles (4) were measured. The results are shown in Table 1.

Preparation of coating liquid for forming transparent film (4) To 233.3 g of resin-coated P-doped tin oxide fine particles (4) dispersed sol having a solid content concentration of 30% by weight,
Polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Ester APG-700) as a glycol-based acrylate resin and dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as a non-glycol-based bifunctional acrylate resin: 3 g of light acrylate DCP-A) and pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DPE-4A) as a non-glycol-based tetrafunctional acrylate resin
24 g, 40 g of isopropyl alcohol, 30 g of propylene glycol monomethyl ether and 1.5 g of photoinitiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BIAS JAPAN KK: Lucillin TPO) A coating solution (4) for forming a transparent film was prepared.
Production of substrate with transparent film (F-4) A substrate with transparent film (F-4) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (4) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1. [Example 5]
Preparation of Resin Coated Particle (5) Dispersed Sol In Example 4, the coating resin 2-hydroxy-3-phenoxypropyl acrylate (
A resin-coated P-doped tin oxide fine particle (5) dispersion sol having a solid concentration of 30% by weight was prepared in the same manner except that 7.3 g of NK ester 702A) manufactured by Shin-Nakamura Chemical Co., Ltd. was mixed.

The stability of the resin-coated P-doped tin oxide fine particles (5) dispersed sol having a solid content concentration of 30% by weight and the average particle diameter of the resin-coated P-doped tin oxide fine particles (5) were measured. The results are shown in Table 1.
Preparation of Transparent Film Forming Coating Liquid (5) In Example 4, a transparent film forming coating liquid (5) was used except that a resin-coated P-doped tin oxide fine particle (5) dispersion sol having a solid content concentration of 30% by weight was used. 5) was prepared.
Production of substrate with transparent coating (F-5) A substrate with transparent coating (F-5) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (5) was used. At this time, the thickness of the transparent film was 4 μm.
The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1.
[Example 6]
Preparation of Resin Coated Particle (6) Dispersed Sol In Example 4, the coating resin 2-hydroxy-3-phenoxypropyl acrylate (
A resin-coated P-doped tin oxide fine particle (6) dispersion sol having a solid content concentration of 30% by weight was prepared in the same manner except that 29 g of NK ester 702A) manufactured by Shin-Nakamura Chemical Co., Ltd. was mixed.

The stability of the resin-coated P-doped tin oxide fine particles (6) dispersed sol having a solid content concentration of 30% by weight and the average particle size of the resin-coated P-doped tin oxide fine particles (6) were measured. The results are shown in Table 1.
Preparation of coating liquid for forming transparent film (6) In Example 4, a coating liquid for forming a transparent film was prepared in the same manner as in Example 4 except that a resin-coated P-doped tin oxide fine particle (6) dispersion sol having a solid concentration of 30% by weight was used. 6) was prepared.
Production of substrate with transparent film (F-6) A substrate with transparent film (F-6) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (6) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1. [Example 7]
In Preparation Example 1 of the resin coated particles (7) dispersed sol, using methyl isobutyl ketone (MIBK) 374 g instead of propylene glycol monomethyl ether (PGME) 374 g as an organic solvent, di-2-methacryloyloxyethyl as the coating resin Acid phosphate (manufactured by Kyoeisha Chemical Co., Ltd.)
7.3 g of light ester P-2M) and 7.3 g of 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Ester 702A) were used in the same manner except that they were mixed. A resin-coated P-doped tin oxide fine particle (7) dispersion sol having a partial concentration of 30% by weight was prepared.

The stability of the resin-coated P-doped tin oxide fine particles (7) dispersed sol having a solid content concentration of 30% by weight and the average particle diameter of the resin-coated P-doped tin oxide fine particles (7) were measured. The results are shown in Table 1.
Preparation of coating liquid for forming a transparent film (7) In Example 1, a coating liquid for forming a transparent film (in the same manner as in Example 1 except that a resin-coated P-doped tin oxide fine particle (7) dispersion sol having a solid content concentration of 30% by weight) was used. 7) was prepared.
Production of substrate with transparent film (F-7) A substrate with transparent film (F-7) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (7) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1. [Example 8]
Preparation of Resin Coated Particle (8) Dispersed Sol In Example 1, 2-acryloyloxyethyl succinic acid (Kyoeisha Co., Ltd .: Wright) was used instead of 14.5 g of di-2-methacryloyloxyethyl acid phosphate as the coating resin. A resin-coated P-doped tin oxide fine particle (8) dispersion sol having a solid concentration of 30% by weight was prepared in the same manner except that 14.5 g of (acrylate HOA-MS) was mixed.

The stability of the resin-coated P-doped tin oxide fine particles (8) dispersed sol having a solid content concentration of 30% by weight and the average particle diameter of the resin-coated P-doped tin oxide fine particles (8) were measured. The results are shown in Table 1.
Preparation of coating liquid for forming transparent film (8) In Example 1, a coating liquid for forming a transparent film was prepared in the same manner as in Example 1 except that a resin-coated P-doped tin oxide fine particle (8) dispersion sol having a solid content concentration of 30% by weight was used. 8) was prepared.
Production of substrate with transparent coating (F-8) A substrate with transparent coating (F-4) was prepared in the same manner as in Example 1 except that the coating solution (8) for forming a transparent coating was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1. [Example 9]
Preparation of Resin Coated Particle (9) Dispersed Sol In Example 1, antimony-doped tin oxide (ATO) fine particles (manufactured by JGC Catalysts & Chemicals Co., Ltd .: TL-98FDAR, solid content 20% by weight, average particle size as metal oxide particles) 8 nm) was dried at 105 ° C. for 2 hours, and then heat-treated at 200 ° C. for 2 hours. At this time, the average primary particle diameter was 8 nm, and the average secondary particle diameter was 0.25 μm.

A resin-coated antimony-doped tin oxide fine particle (9) dispersion sol having a solid concentration of 30% by weight was prepared in the same manner except that 201 g of the heat-treated particles were used. The stability of the resin-coated antimony-doped tin oxide fine particles (9) dispersed sol having a solid concentration of 30% by weight and the average particle size of the resin-coated antimony-doped tin oxide fine particles (9) were measured. The results are shown in Table 1.
Preparation of coating liquid for forming transparent film (9) In Example 1, a coating liquid for forming a transparent film (in the same manner as in Example 1) except that the dispersion of resin-coated antimony-doped tin oxide fine particles (9) having a solid content of 30% by weight was used. 9) was prepared.
Production of substrate with transparent film (F-9) A substrate with transparent film (F-9) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (9) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1. [Example 10]
Preparation of Resin Coated Particle (10) Dispersed Sol In Example 1, tin-doped indium oxide (ITO) fine particles (manufactured by JGC Catalysts & Chemicals Co., Ltd .: ELCOM TL-131, average particle size of 20 nm) as metal oxide particles at 200 ° C. Heat-treated for 2 hours. At this time, the average primary particle size was 20 nm, and the average secondary particle size was 0.8 μm.

  A resin-coated tin-doped indium oxide fine particle (10) dispersion sol having a solid content concentration of 30% by weight was prepared in the same manner except that 201 g of the heat-treated particles were used.

The stability of the resin-coated tin-doped indium oxide fine particles (10) dispersed sol having a solid content concentration of 30% by weight and the average particle diameter of the resin-coated tin-doped indium oxide fine particles (10) were measured. The results are shown in Table 1.
Preparation of coating liquid for forming transparent film (10) In Example 1, a coating liquid for forming a transparent film (10) was used in the same manner as in Example 1, except that a resin-coated tin-doped indium oxide fine particle (10) dispersion having a solid content of 30% by weight was used. ) Was prepared.
Production of substrate with transparent film (F-10) A substrate with transparent film (F-10) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (10) was used. At this time, the thickness of the transparent film was 4 μm.

The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1.
[Example 11]
Preparation of resin-coated particles (11) dispersed sol
Preparation of P-doped tin oxide fine particles (2) 1360 g of ammonium nitrate and 20 g of 15% aqueous ammonia were added to 8060 g of pure water and stirred, and the temperature was raised to 50 ° C. A solution obtained by dissolving 1519 g of potassium stannate in 4290 g of pure water was added with a roller pump over 10 hours. At this time, nitric acid having a concentration of 10% by weight was added to adjust the pH to 8.2 with a pH controller. After the addition was completed, the temperature was kept at 50 ° C. for 1 hour, and then 10% by weight nitric acid was added to lower the pH to 3.0. Next, it was washed with pure water until the filtered water conductivity reached 10 μS / cm with an ultrafiltration membrane, and then concentrated with an ultrafiltration membrane. The amount of liquid taken out at this time was 4800 g, and the solid content (SnO ₂ ) concentration was 15% by weight. To this slurry, 264 g of a phosphoric acid aqueous solution having a concentration of 16% by weight was added and stirred for 0.5 hour. This was dried and calcined at 700 ° C. for 2 hours to prepare P-doped tin oxide fine particle (2) powder.

The obtained P-doped tin oxide fine particles (2) have an average primary particle size of 25 nm and an average secondary particle size of 1.
. The volume resistance value was 2 Ωm and 4000 Ω · cm.

A resin-coated P-doped tin oxide fine particle (11) -dispersed sol having a solid concentration of 30% by weight was prepared in the same manner except that 201 g of the P-doped tin oxide fine particle (2) was used.

The stability of the resin-coated P-doped tin oxide fine particles (11) dispersed sol having a solid content concentration of 30% by weight and the average particle size of the resin-coated P-doped tin oxide fine particles (11) were measured. The results are shown in Table 1.

Preparation of coating solution for forming transparent film (11) In Example 1, a coating solution for forming a transparent coating (in the same manner as in Example 1 except that a resin-coated P-doped tin oxide fine particle (11) dispersion sol having a solid content concentration of 30% by weight was used) 11) was prepared.
Production of substrate with transparent film (F-11) A substrate with transparent film (F-11) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (11) was used. At this time, the thickness of the transparent film was 4 μm.

The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1.
[Example 12] (Type of raw material metal oxide particles: titanium oxide)
Preparation of resin-coated particles (12) dispersed sol
Preparation of Titanium Oxide Fine Particles (1) 732 g of titanium tetrachloride was diluted with pure water to obtain an aqueous solution containing 1.0% by weight as TiO ₂ . While stirring this, ammonia water having a concentration of 15% by weight was added to obtain a white slurry having a pH of 9.5. This slurry was washed by filtration to obtain a hydrated titanium oxide gel cake having a concentration of 10.2% by weight as TiO ₂ . This cake was mixed with 16000 g of a 5% hydrogen peroxide solution, and then dissolved by heating at 80 ° C. for 2 hours to obtain a peroxotitanic acid aqueous solution having a concentration of 1.0% by weight as TiO ₂ . Subsequently, the titanium oxide colloidal particle dispersion was prepared by processing at 150 ° C. for 10 hours in an autoclave. Next, after washing with an ultrafiltration membrane and concentrating, this was dried and calcined at 600 ° C. for 2 hours to prepare titanium oxide fine particle (1) powder.

The titanium oxide fine particles (1) had an average primary particle size of 60 nm and an average secondary particle size of 3.0 μm.

A resin-coated titanium oxide fine particle (12) -dispersed sol having a solid concentration of 30% by weight was prepared in the same manner except that 201 g of titanium oxide fine particles (1) were used.

The stability of the resin-coated titanium oxide fine particles (12) dispersed sol having a solid content concentration of 30% by weight and the average particle size of the resin-coated titanium oxide fine particles (12) were measured. The results are shown in Table 1.
Preparation of coating liquid for forming transparent film (12) In the same manner as in Example 1, except that the resin-coated titanium oxide fine particle (12) dispersion sol having a solid concentration of 30% by weight was used, the coating liquid for forming transparent film (12) Was prepared.
Production of substrate with transparent coating (F-12) A substrate with transparent coating (F-12) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (12) was used. At this time, the thickness of the transparent film was 4 μm.

The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1.
[Example 13]
Preparation of resin-coated particles (13) dispersed sol
Preparation of pure water 24320 zirconium oxychloride octahydrate zirconium oxide fine particles _{(ZrOCl 2 · 8H 2 O)} 655g was dissolved, this was added malic acid 27 g, was then added to a concentration of 10 wt% KOH aqueous solution 3130g A zirconium hydroxide hydrogel dispersion (ZrO ₂ concentration 1 wt%) was prepared. At this time, the pH of the dispersion was 10.5 and the temperature was 19 ° C.

Subsequently, it was washed by an ultrafiltration membrane method until the electric conductivity reached 280 μS / cm. Next, 950 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the zirconium hydroxide hydrogel dispersion (ZrO ₂ concentration: 1% by weight) to deionize. Next, after separating the cation exchange resin, 500 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization.

The washed zirconium hydroxide hydrogel dispersion thus obtained (ZrO ₂ concentration 1 wt%) had an electric conductivity of 10 μS / cm and a pH of 6.

Next, the washed zirconium hydroxide hydrogel dispersion (ZrO ₂ concentration: 1% by weight) was irradiated with ultrasonic waves for 1 hour to disperse the hydrogel, filled in an autoclave, and aged at 200 ° C. for 2 hours. At this time, the conductivity was 640 μS / cm and the pH was 2.53.

Subsequently, 1100 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization, and then washed by ultrafiltration membrane method while supplying 37500 g of pure water. The conductivity at this time was 16 μS / cm 2 and pH was 3.9.

Next, after the above-mentioned aged and washed dispersion was adjusted to a ZrO ₂ concentration of 1% by weight, 1340 g of a malic acid aqueous solution having a concentration of 2% by weight was added thereto, and ultrasonic waves were applied for 1 hour to disperse the hydrogel. The mixture was filled in an autoclave and hydrothermally treated at 200 ° C. for 2 hours. At this time, the conductivity was 640 μS / cm and the pH was 2.53.

  Deionization was performed by adding 1100 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) to the hydrothermally treated dispersion, and then washed by ultrafiltration membrane method while supplying 37500 g of pure water. At this time, the conductivity was 47 μS / cm, and the pH was 3.4.

  Subsequently, after concentrating with an ultrafiltration membrane, this was dried at 105 ° C. and further heat-treated at 200 ° C. for 2 hours to prepare zirconium oxide fine particle powder.

  The average primary particle diameter of the zirconium oxide fine particles was 20 nm, and the average secondary particle diameter was 1.5 μm.

  A resin-coated zirconium oxide fine particle (13) dispersion sol having a solid content concentration of 30% by weight was prepared in the same manner except that 201 g of the zirconium oxide fine particles were used.

The stability of the resin-coated zirconium oxide fine particles (13) dispersed sol having a solid content concentration of 30% by weight and the average particle diameter of the resin-coated titanium oxide fine particles (13) were measured. The results are shown in Table 1.
Preparation of Transparent Film Forming Coating Liquid (13) Transparent Coating Film Coating Liquid (13) was prepared in the same manner as in Example 1, except that the resin-coated zirconium oxide fine particles (13) dispersed sol having a solid concentration of 30% by weight was used. Was prepared.
Production of substrate with transparent film (F-13) A substrate with transparent film (F-13) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (13) was used. At this time, the thickness of the transparent film was 4 μm.

The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1.
[Comparative Example 1]
Preparation of Coupling Agent Treated Particle (R1) Dispersed Sol 217 g of P-doped tin oxide fine particle powder prepared in the same manner as in Example 1 and 335 g of ion-exchanged water were placed in a 2 L glass beaker, and 50 g of a 20 wt% KOH aqueous solution was added. After that, 1000 g of quartz beads (0.15 mm) were added, and after sufficiently stirring and pulverizing and dispersing with a bead mill, the quartz beads and the dispersion were separated with a 325 mesh (aperture 44 micron) stainless steel wire mesh. The quartz beads remaining on the wire mesh were washed with 1560 g of ion-exchanged water and mixed well. The solution was heat-treated at 90 ° C. for 1 hour, cooled to room temperature, and 96 g of anion-exchange resin was added and stirred for 1 hour. After that, the anion exchange resin is separated, and then 96 g of the cation exchange resin
After stirring for 1 hour, the cationic resin was separated to obtain a P-doped tin oxide fine particle aqueous dispersion (concentration: 10% by weight).

20.8 g of P-doped tin oxide fine particle water sol having a solid content concentration of 10% by weight as a coupling agent, ie, ethyl orthosilicate (TEOS) (manufactured by Tama Chemicals: ethyl silicate 28, SiO ₂ component 28.8% by weight) The weight ratio of tin oxide fine particles = 3/100) and 2000 g of methanol were added and stirred at 50 ° C. for 18 hours.

Next, γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM)
-5103, placed SiO ₂ component 81.2 wt%) 7.4 g, was subjected to a surface treatment by stirring for 18 hours again 50 ° C.. Thereafter, a P-doped tin oxide fine particle (R1) dispersion sol was prepared by replacing the solvent with ethanol and surface-treating with a silane coupling agent having a solid concentration of 30% by weight.

The stability of the P-doped tin oxide fine particle (R1) dispersion sol surface-treated with a silane coupling agent having a solid concentration of 30% by weight and the average particle size of the P-doped tin oxide fine particle (R1) were measured. Indicated.
Preparation of coating liquid for forming transparent film (R1) Transparent in the same manner as in Example 1, except that P-doped tin oxide fine particle (R1) dispersed sol surface-treated with a silane coupling agent having a solid content of 30% by weight was used. A coating solution (R1) for film formation was prepared.
In the production example 1 of the substrate with a transparent film (RF-1), except that the transparent film-forming coating liquid (R1) was prepared substrate with a transparent film (RF-1) in the same manner. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1. [Comparative Example 2]
Preparation of Resin Coated Particle (R2) Dispersed Sol In Example 1, instead of 14.5 g of di-2-methacryloyloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd .: Light Ester P-2M) as the coating resin, non-acrylic A resin-coated P-doped tin oxide fine particle (R2) -dispersed sol having a solid content concentration of 30% by weight was prepared in the same manner except that 14.5 g of a resin based on polyvinylpyrrolidone (manufactured by Kanto Chemical Co., Inc .: K-30, average molecular weight 10000) was mixed. .

The stability of the resin-coated P-doped tin oxide fine particle (R2) dispersion sol having a solid content concentration of 30% by weight and the average particle diameter of the P-doped tin oxide fine particle (R2) were measured. The results are shown in Table 1.
Preparation of coating liquid for forming transparent film (R2) In Example 1, a coating liquid for forming a transparent film (R2) was used in the same manner except that a resin-coated P-doped tin oxide fine particle (R2) dispersion sol having a solid content of 30% by weight was used. R2) was prepared.
Production of substrate with transparent coating (RF-2) A substrate with transparent coating (RF-2) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R2) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1. [Comparative Example 3]
Preparation of Resin Coated Particle (R3) Dispersed Sol In Example 1, instead of 14.5 g of di-2-methacryloyloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd .: Light Ester P-2M) as a coating resin, non-acrylic A resin-coated P-doped tin oxide fine particle (R3) dispersion sol having a solid concentration of 30% by weight was prepared in the same manner except that 14.5 g of a resin based polyvinyl alcohol (manufactured by Kanto Chemical Co., Ltd .: average molecular weight 10000) was mixed.

The stability of the resin-coated P-doped tin oxide fine particle (R3) dispersion sol having a solid content concentration of 30% by weight and the average particle size of the resin-coated P-doped tin oxide fine particle (R3) were measured. The results are shown in Table 1.
Preparation of coating solution for forming transparent film (R3) In Example 1, a coating solution for forming a transparent coating (R3) was used in the same manner except that a resin-coated P-doped tin oxide fine particle (R3) dispersion sol having a solid concentration of 30% by weight was used. R3) was prepared.
Production of substrate with transparent coating (RF-3) A substrate with transparent coating (RF-3) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R3) was used. At this time, the thickness of the transparent film was 4 μm.

The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1.
[Comparative Example 4]
Preparation of resin-coated particle (R4) dispersion sol
Preparation of P-doped tin oxide fine particles (R1) P-doped tin oxide fine particles (R1) were prepared in the same manner as in Example 1 except that they were dried at 80 ° C. for 2 hours and then not calcined at 700 ° C. for 2 hours.

  The obtained P-doped tin oxide fine particles (R1) had an average primary particle diameter of 15 nm, an average secondary particle diameter of 0.035 μ, and a volume resistance of 6000 Ω · cm.

Next, 217 g of P-doped tin oxide fine particles (1) and 335 g of ion-exchanged water were placed in a 2 L glass beaker, and after adding 50 g of 20 wt% KOH aqueous solution, quartz beads (0.15 m
m) Add 1000 g, thoroughly agitate and disperse in a bead mill, separate the quartz beads from the dispersion with a 325 mesh (44 micron mesh) stainless steel wire mesh, and then leave the quartz beads remaining on the wire mesh The solution washed with 1560 g of ion-exchanged water was thoroughly mixed, and this solution was heat-treated at 90 ° C. for 1 hour, cooled to room temperature, and then 96 g of anion-exchange resin was added and stirred for 1 hour, followed by separation of the anion-exchange resin. Next, 96 g of a cation exchange resin was added and stirred for 1 hour, and then the cation resin was separated to obtain a P-doped tin oxide fine particle aqueous dispersion (concentration: 10% by weight).

Next, P-doped tin oxide fine particle aqueous dispersion was solvent-substituted with propylene glycol monomethyl ether (PGME). At this time, the solid content concentration was 35% by weight. Next, 575 g of a P-doped tin oxide fine particle PGME dispersion having a solid content concentration of 35% by weight and di-2-methacryloyloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd .: Light Ester P-2M) as a coating resin. 5g is filled in a bead mill containing 1135g of glass beads (0.4mm), treated at 1700rpm for 1 hour, glass beads are separated, and then PGME is added to coat resin with a solid content concentration of 30% by weight P-doped tin oxide fine particle (R4) dispersion sol was prepared.

The stability of the resin-coated P-doped tin oxide fine particle (R4) dispersion sol having a solid content concentration of 30% by weight and the average particle diameter of the resin-coated P-doped tin oxide fine particle (R4) were measured. The results are shown in Table 1.
Preparation of coating solution for forming transparent film (R4) In Example 1, a coating solution for forming a transparent coating (R4) was used in the same manner except that a resin-coated P-doped tin oxide fine particle (R4) dispersion sol having a solid content of 30% by weight was used. R4) was prepared.
Production of substrate with transparent coating (RF-4) A substrate with transparent coating (RF-4) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R4) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1. [Reference Example 1]
Preparation of Resin Coated Particle (S1) Dispersed Sol In Example 1, in addition to P-doped tin oxide fine particle powder, organic solvent, and coating resin, 2.4.6-trimethylbenzoyldiphenylphosphine oxide (BIAS) was used as an initiator. A resin-coated P-doped tin oxide fine particle (S1) dispersion sol having a solid concentration of 30% by weight was prepared in the same manner except that 1.4 g of Japan Co., Ltd. (Lucirin TPO) was mixed.

The stability of the resin-coated P-doped tin oxide fine particles (S1) dispersion sol having a solid content concentration of 30% by weight and the average particle diameter of the resin-coated P-doped tin oxide fine particles (S1) were measured. The results are shown in Table 1.
Preparation of coating liquid for forming transparent film (S1) Coating for forming transparent film in the same manner as in Example 1, except that the resin-coated P-doped tin oxide fine particle (S1) dispersion sol having a solid concentration of 30% by weight is used. A liquid (S1) was prepared.
Production of substrate with transparent film (SF-1) A substrate with transparent film (SF-1) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (S1) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1.

[Comparative Example 5]
Preparation of resin-coated particle (R5) dispersion sol
Preparation of P-doped tin oxide fine particles (R2) In the same manner as in Example 11, 13 g of ammonium nitrate and 20 g of 15% ammonia water were added to 8060 g of pure water and stirred, and the temperature was raised to 50C. A solution obtained by dissolving 1519 g of potassium stannate in 4290 g of pure water was added with a roller pump over 10 hours. At this time, nitric acid having a concentration of 10% by weight was added to adjust the pH to 8.2 with a pH controller. After the addition was completed, the temperature was kept at 50 ° C. for 1 hour, and then 10% by weight nitric acid was added to lower the pH to 3.0.
Next, it was washed with pure water until the filtered water conductivity reached 10 μS / cm with an ultrafiltration membrane, and then concentrated with an ultrafiltration membrane. The amount of liquid taken out at this time was 6000 g, and the solid content (SnO ₂ ) concentration was 12% by weight. To this slurry, 264 g of a phosphoric acid aqueous solution having a concentration of 16% by weight was added and stirred for 0.5 hour. Subsequently, this was dried at 80 ° C. for 2 hours to prepare P-doped tin oxide fine particles (R2) powder.

  The obtained P-doped tin oxide fine particles (R2) had an average primary particle size of 25 nm, an average secondary particle size of 0.1 μm, and a volume resistance of 5500 Ω · cm.

Next, 217 g of P-doped tin oxide fine particles (R2) and 335 g of ion-exchanged water were placed in a 2 L glass beaker, 50 g of 20 wt% KOH aqueous solution was added, and then 1000 g of quartz beads (0.15 mm) were added. After stirring and dispersing, the quartz beads and the dispersion are separated with a 325 mesh (mesh opening 44 microns) stainless steel wire mesh, and the quartz beads remaining on the wire mesh are washed with 1560 g of ion-exchanged water. The mixture was heat treated at 90 ° C. for 1 hour, cooled to room temperature, 96 g of anion exchange resin was added and stirred for 1 hour, the anion exchange resin was separated, and then 96 g of cation exchange resin was added. After stirring for 1 hour, the cation resin was separated to obtain a P-doped tin oxide fine particle (R2) aqueous dispersion (concentration: 10% by weight).

Next, the solvent dispersion of the P-doped tin oxide fine particle (R2) aqueous dispersion was replaced with propylene glycol monomethyl ether (PGME). At this time, the solid content concentration was 35% by weight. Next, 575 g of a P-doped tin oxide fine particle PGME dispersion having a solid content concentration of 35% by weight and di-2-methacryloyloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd .: Light Ester P-2M) as a coating resin. 5g is filled in a bead mill containing 1135g of glass beads (0.4mm), treated at 1700rpm for 1 hour, glass beads are separated, and then PGME is added to coat resin with a solid content concentration of 30% by weight P-doped tin oxide fine particle (R5) dispersion sol was prepared.

The stability of the resin-coated P-doped tin oxide fine particle (R5) dispersion sol having a solid content concentration of 30% by weight and the average particle size of the resin-coated P-doped tin oxide fine particle (R5) were measured. The results are shown in Table 1.
Preparation of coating solution for forming transparent film (R5) In Example 1, a coating solution for forming a transparent coating (R5) was used in the same manner except that a resin-coated P-doped tin oxide fine particle (R5) dispersion sol having a solid content of 30% by weight was used. R5) was prepared.
Production of substrate with transparent coating (RF-5) A substrate with transparent coating (RF-5) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R5) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1. [Comparative Example 6]
Preparation of resin-coated particle (R6) dispersion sol
Preparation of Titanium Oxide Fine Particles (R1) 732 g of titanium tetrachloride was diluted with pure water to obtain an aqueous solution containing 1.0% by weight as TiO ₂ . While stirring this, ammonia water having a concentration of 15% by weight was added to obtain a white slurry having a pH of 9.5. This slurry was washed by filtration to obtain a hydrated titanium oxide gel cake having a concentration of 10.2% by weight as TiO ₂ . This cake was mixed with 16000 g of a 5% hydrogen peroxide solution, and then dissolved by heating at 80 ° C. for 2 hours to obtain a peroxotitanic acid aqueous solution having a concentration of 1.0% by weight as TiO ₂ . Subsequently, it was treated in an autoclave at 150 ° C. for 10 hours to prepare a titanium oxide colloid particle dispersion. Subsequently, after washing with an ultrafiltration membrane and concentrating, this was dried at 80 ° C. for 2 hours to prepare titanium oxide fine particles (R1) powder.

The average primary particle diameter of the titanium oxide fine particles (R1) was 60 nm, and the average secondary particle diameter was 0.2 μm.

  A resin-coated titanium oxide fine particle (R6) -dispersed sol having a solid concentration of 30% by weight was prepared in the same manner except that 201 g of titanium oxide fine particles (R1) were used.

The stability of the resin-coated titanium oxide fine particle (R6) dispersion sol having a solid content concentration of 30% by weight and the average particle size of the resin-coated titanium oxide fine particles (R6) were measured. The results are shown in Table 1.
Preparation of coating liquid for forming transparent film (R6) In Example 1, the coating liquid for forming transparent film (R6) was prepared in the same manner as in Example 1, except that the resin-coated titanium oxide fine particle (R6) dispersion sol having a solid content of 30% by weight was used. Was prepared.
Production of substrate with transparent coating (RF-6) A substrate with transparent coating (RF-6) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R6) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1. [Comparative Example 7]
Preparation of resin-coated particle (R7) dispersion sol
Preparation of pure water 24320 zirconium oxychloride octahydrate zirconium oxide particles (R1) a _{(ZrOCl 2 · 8H 2 O)} 655g was dissolved, this was added malic acid 27 g, then the concentration of 10 wt% KOH aqueous solution 3130g A zirconium hydroxide hydrogel dispersion (ZrO ₂ concentration 1% by weight) was prepared by addition. At this time, the pH of the dispersion was 10.5 and the temperature was 19 ° C.

Subsequently, it was washed by an ultrafiltration membrane method until the electric conductivity reached 280 μS / cm. Next, 950 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the zirconium hydroxide hydrogel dispersion (ZrO ₂ concentration: 1% by weight) to deionize. Next, after separating the cation exchange resin, 500 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization.

The washed zirconium hydroxide hydrogel dispersion thus obtained (ZrO ₂ concentration 1 wt%) had an electric conductivity of 10 μS / cm and a pH of 6.

Next, the washed zirconium hydroxide hydrogel dispersion (ZrO ₂ concentration: 1% by weight) was irradiated with ultrasonic waves for 1 hour to disperse the hydrogel, filled in an autoclave, and aged at 200 ° C. for 2 hours. At this time, the conductivity was 640 μS / cm and the pH was 2.53.

Subsequently, 1100 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization, and then washed by ultrafiltration membrane method while supplying 37500 g of pure water. The conductivity at this time was 16 μS / cm 2 and pH was 3.9.

Next, after the above-mentioned ripened and washed dispersion was adjusted to a ZrO ₂ concentration of 1% by weight, 1340 g of a malic acid aqueous solution having a concentration of 2% by weight was added thereto, and ultrasonic waves were applied for 1 hour to disperse the hydrogel. The mixture was filled in an autoclave and hydrothermally treated at 200 ° C. for 2 hours. At this time, the conductivity was 640 μS / cm and the pH was 2.53.

  Deionization was performed by adding 1100 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) to the hydrothermally treated dispersion, and then washed by ultrafiltration membrane method while supplying 37500 g of pure water. At this time, the conductivity was 47 μS / cm, and the pH was 3.4.

  Subsequently, after concentrating with an ultrafiltration membrane, this was dried at 80 ° C. for 2 hours to prepare zirconium oxide fine particle powder (R1).

  The average primary particle diameter of the zirconium oxide fine particles (R1) was 20 nm, and the average secondary particle diameter was 0.5 μm.

  A resin-coated zirconium oxide fine particle (R7) dispersion sol having a solid content concentration of 30% by weight was prepared in the same manner except that 201 g of the zirconium oxide fine particles were used.

The stability of the resin-coated zirconium oxide fine particles (R7) dispersed sol having a solid content concentration of 30% by weight and the average particle size of the resin-coated zirconium oxide fine particles (R7) were measured. The results are shown in Table 1.
Preparation of coating liquid for forming transparent film (R7) In Example 1, the coating liquid for forming transparent film (R7) was prepared in the same manner as in Example 1, except that the resin-coated zirconium oxide fine particle (R7) dispersion sol having a solid concentration of 30% by weight was used. Was prepared.
Production of substrate with transparent film (RF-7) A substrate with transparent film (RF-7) was prepared in the same manner as in Example 1 except that the coating liquid for transparent film formation (R7) was used. At this time, the thickness of the transparent film was 4 μm. The total light transmittance, haze, pencil hardness, scratch resistance and adhesion of the obtained transparent film were measured, and the results are shown in Table 1.

Claims (9)

  An organic resin dispersion of metal oxide particles having an average primary particle diameter in the range of 5 to 300 nm and an average secondary particle diameter in the range of 5 nm to 10 μm preliminarily heat-treated at 100 to 800 ° C., an acrylic resin and A method for producing a resin-coated metal oxide particle-dispersed sol, comprising: adding a resin coating material comprising a methacrylic resin and then performing a mechanochemical treatment. The method for producing a resin-coated metal oxide particle-dispersed sol according to claim 1, wherein the organic solvent is at least one selected from ethers, esters, and ketones. The concentration ratio (C _R ) / (C _MO ) of the concentration (C _R ) as the solid content of the resin coating material and the concentration (C _MO ) as the solid content of the metal oxide fine particles is 0.005 to 0.5. The method for producing a resin-coated metal oxide particle-dispersed sol according to claim 1 or 2, wherein the sol is in a range.   The resin coating according to any one of claims 1 to 3, wherein the total solid content concentration of the metal oxide particles and the resin coating material during the mechanochemical treatment is in the range of 1 to 50 wt%. A method for producing a metal oxide particle-dispersed sol. The metal oxide particles include TiO ₂ , SiO ₂ , ZrO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZnO and composite oxides thereof, tin oxide, tin oxide doped with Sb or P, indium oxide, Sn
The production of a resin-coated metal oxide particle-dispersed sol according to any one of claims 1 to 4, which is at least one selected from indium oxide doped with F, antimony oxide, and low-order titanium oxide. Method.   6. The method for producing a resin-coated metal oxide particle-dispersed sol according to claim 1, wherein the average particle diameter of the resin-coated metal oxide particles is in the range of 5 to 300 nm.   A coating liquid for forming a transparent film, comprising a matrix-forming component, a resin-coated metal oxide particle-dispersed sol obtained by the method according to claim 1, and an organic solvent.   A substrate with a transparent coating, comprising: a substrate; and a transparent coating formed by applying and drying the coating solution for forming a transparent coating according to claim 7 on the substrate.   The substrate with a transparent coating according to claim 8, wherein the transparent coating is provided together with another coating.