JP5466612B2 - Method for producing resin-coated metal oxide particle resin dispersion composition and substrate with transparent coating - Google Patents

Description

  The present invention relates to a resin-coated metal oxide particle resin dispersion composition in which resin-coated metal oxide particles are uniformly dispersed in a resin dispersion medium, a method for producing the resin-coated metal oxide particle resin dispersion composition, and transparent using the resin-coated metal oxide particle resin dispersion composition The present invention relates to a coated substrate.

  Conventionally, in order to improve the scratch resistance of the substrate surface such as glass, plastic sheet, plastic lens, etc., it is known to form a transparent film having a hard coat function on the substrate surface. An organic resin film or an inorganic film is formed on the substrate surface. 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 and 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.

  The applicant of the present application adds an acrylic resin to an organic solvent dispersion in which ethers, esters, and ketones of metal oxide particles that have been heat-treated in advance are used as a dispersion medium, and then performs mechanochemical treatment to obtain individual metal oxides. It is disclosed that resin particles can be uniformly coated on the product particles, and a high-concentration resin-coated metal oxide particle dispersion liquid having an organic solvent as a dispersion medium and a solid content concentration of up to about 50% by weight can be obtained. JP 2010-077409 A (Patent Document 7)

  Further, JP 2007-238759 A (Patent Document 8) discloses a first step of producing a first mixture containing at least inorganic fine particles such as alumina, a first thermoplastic resin, and a first organic solvent. A method for producing a resin composition comprising a second step in which a mechanical load is applied thereto to cause peptization of inorganic fine particles and then a third step in which only the solvent is distilled off is disclosed.

  This resin composition is intended for resination of glass members including window shields of automobiles, etc., and at this time, it has transparency, reduces expansion with respect to heat, and obtains a resin composition having high bending rigidity. For this reason, acicular alumina particles having a small particle diameter and a high aspect ratio are recommended.

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 JP 2010-077409 A JP 2007-238759 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 may be coated on several or more agglomerated particles. The resin of the resin-coated particles may be dissolved in the solvent of the coating solution. For this reason, the obtained transparent film has problems such as a decrease in transparency, an increase in haze, and a decrease in scratch resistance.

  For this reason, it is desirable that the organic solvent is not included. However, when the organic solvent is removed from the resin-coated metal oxide particle-dispersed sol disclosed in Patent Document 7, the stability decreases when the solid concentration exceeds approximately 60% by weight. In some cases, they aggregate and settle. Further, in the example of Patent Document 7, since an organic solvent such as isopropyl alcohol and propylene glycol monomethyl ether is used in preparing the coating solution, the concentration decreases, and after coating, drying is performed to remove the organic solvent. Since a process is required and there is an environmental problem of the removed organic solvent, equipment for preventing this was necessary.

  Conventionally, when used as a coating solution, a resin component is added as a matrix-forming component together with an organic solvent. However, with this coating solution, there is a limit to the film thickness obtained, and the strength and scratch resistance of the coating are also limited. Further improvement in properties and the like has been demanded.

  Furthermore, in the method described in Patent Document 8, the resin composition is obtained by removing the solvent to obtain the resin composition, and then drying, melting and mixing the mixture at a high temperature (250 ° C.), followed by drying and hot pressing. However, the present invention is not intended to obtain a transparent film having a low viscosity, excellent coating properties, no drying process, and excellent transparency as in the present invention.

  As a result of intensive studies in view of such problems, the inventors added a (meth) acrylate-based resin having an aromatic ring to an organic solvent dispersion of metal oxide particles that had been heat-treated in advance, When mechanochemical treatment is performed, the resin can be uniformly coated on individual particles, and then dispersed in a low molecular weight resin dispersion medium having a high affinity with the resin-coated particles. After uniformly dispersing, the organic solvent is removed. A resin-coated metal oxide particle resin-dispersed composition excellent in stability in which resin-coated particles are highly dispersed without curing is obtained, and a polymerization initiator or a curing agent is added to this composition, and then applied and dried. If it is cured without thickening, thick film can be formed and there is no scattering of solvent, so the film thickness at the time of coating is the film thickness of the transparent film as it is, dense and transparent with excellent transparency, haze, scratch resistance, etc. A film can be obtained Was led to the completion of the present invention have found.

The configuration of the present invention is as follows.
[1] Metal oxide particles having an average particle diameter in the range of 5 to 300 nm and coated with a (meth) acrylate monomer or oligomer (A) having an aromatic ring as a coating resin are resin dispersion media (B) A resin dispersion composition characterized by being dispersed in a resin.
[2] The resin dispersion composition according to [1], wherein the concentration of the organic solvent contained in the resin dispersion composition is 1000 ppm or less.
[3] The resin dispersion composition according to [1] or [2], wherein the viscosity is in the range of 10 to 10,000 mPa · s.
[4] The resin dispersion composition of [1] to [3], wherein the weight ratio of the metal oxide particles to the coating resin (A) is in the range of 97/3 to 40/60.
[5] The resin dispersion composition of [1] to [4], wherein the weight ratio of the resin-coated metal oxide particles to the resin dispersion medium is in the range of 10/90 to 90/10.
[6] The resin dispersion composition according to any one of [1] to [5], wherein the (meth) acrylate monomer or oligomer (A) has at least one functional group selected from a hydroxyl group, an amino group, an epoxy group, and a sulfo group. .
[7] The resin dispersion composition of [1] to [6], wherein the resin dispersion medium (B) has an average molecular weight in the range of 400 to 5,000.
[8] The resin dispersion composition of [1] to [7], wherein the resin dispersion medium (B) is a (meth) acrylate resin.
[9] The metal oxide particles are composed of TiO ₂ , SiO ₂ , ZrO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZnO and their composite oxides, tin oxide, tin oxide doped with Sb or P, oxidation The resin dispersion composition of [1] to [8], which is at least one selected from indium oxide doped with indium, Sn, or F, antimony oxide, and low-order titanium oxide.
[10] The resin dispersion composition according to [9], wherein the metal oxide particles are titanium oxide particles and / or zirconium oxide particles.

[11] The resin dispersion composition according to [1] to [10], wherein the metal oxide particles are previously heat-treated at 100 to 800 ° C.
[12] As a coating resin having an aromatic ring as a coating resin, a metal oxide particle dispersion having an average particle diameter in the range of 5 nm to 100 μm and previously heat-treated at 100 to 800 ° C. ) A method for producing a resin dispersion composition comprising adding an acrylate monomer or oligomer (A), followed by a mechanochemical treatment, then mixing a resin dispersion medium (B), and then removing an organic solvent .
[13] The process for producing a resin dispersion composition according to [12], wherein the metal oxide particles are obtained by spray-drying and the metal oxide particles have an average particle diameter in the range of 1 to 100 μm.
[14] Production of resin dispersion composition according to [12] to [13], wherein the organic solvent is at least one selected from alcohols, ethers, esters and ketones having a boiling point of 64.5 ° C to 200 ° C. Method.
[15] The method for producing a resin dispersion composition according to [12] to [14], wherein a weight ratio of the metal oxide particles to the coating resin is in a range of 97/3 to 40/60.
[16] The resin dispersion composition according to [12] to [15], wherein the weight ratio of the total weight of the metal oxide particles and the coating resin to the weight of the resin dispersion medium is in the range of 10/90 to 90/10. Manufacturing method.
[17] The (meth) acrylate monomer or oligomer (A) has at least one functional group selected from a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, an epoxy group, and a sulfo group [12] to [16 ]. The manufacturing method of the resin dispersion composition of.
[18] The method for producing a resin dispersion composition according to [12] to [17], wherein the coating resin has a molecular weight in the range of 400 to 5,000.
[19] The method for producing a resin dispersion composition of [12] to [18], wherein the resin dispersion medium is a (meth) acrylate resin (B).
[20] The method for producing a resin dispersion composition according to [12] to [19], wherein the resin dispersion medium has a molecular weight in the range of 400 to 5,000.

[21] The metal oxide particles are composed of TiO ₂ , SiO ₂ , ZrO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZnO and their composite oxides, tin oxide, tin oxide doped with Sb or P, oxidation A method for producing a resin dispersion composition according to [12] to [20], which is at least one selected from indium oxide doped with indium, Sn or F, antimony oxide, and low-order titanium oxide.
[22] The method for producing a resin dispersion composition according to [21], wherein the metal oxide particles are titanium oxide particles and / or zirconium oxide particles.
[23] A transparent film comprising a base material and a transparent film formed on the base material, wherein the transparent film is formed by applying and curing the resin dispersion composition of [1] to [11] Base material with coating.
[24] The substrate with a transparent coating according to [23], wherein the thickness of the transparent coating is in the range of 100 nm to 2 mm.

  According to the present invention, even if it does not contain an organic solvent, it has a low viscosity, excellent dispersibility and stability, does not contain an organic solvent as a dispersion medium, and does not require an organic solvent when used as a coating solution, thereby forming a transparent film In this case, a drying step is not required, it is sufficient to cure immediately after coating, and it is composed of only resin-coated metal oxide particles and a resin dispersion medium that is a matrix-forming component. The resin-coated metal oxide particle resin dispersion composition that can be used in the present invention, a production method thereof, and a substrate with a transparent coating using the resin-coated metal oxide particle resin dispersion composition can be provided.

  Also, depending on the selection of the metal oxide, a high refractive index film can be obtained. Particularly, since the resin-coated metal oxide particle resin dispersion composition does not contain an organic solvent, it is suitable for various sealing materials such as LEDs and prism sheets. Can be used.

Hereinafter, first, the resin-coated metal oxide particle resin dispersion composition according to the present invention will be described.
[Resin-coated metal oxide particle resin dispersion composition]
The resin-coated metal oxide particle resin dispersion composition according to the present invention is characterized in that the resin-coated metal oxide particles are dispersed in a resin dispersion medium.

Resin-coated metal oxide particles The resin-coated metal oxide particles used in the present invention have metal oxide particles coated with a coating resin.

(i) Metal oxide particles The metal oxide particles are doped with TiO ₂ , SiO ₂ , ZrO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZnO and their complex oxides, tin oxide, Sb or P. One or more selected from tin oxide, indium oxide, indium oxide doped with Sn or F, antimony oxide, and low-order titanium oxide are preferable.

Each of the above metal oxide particles is a metal oxide particle or a composite metal oxide particle having characteristics in refractive index, conductivity and the like, and can be appropriately selected depending on the application.
In the present invention, the metal oxide particles are preferably titanium oxide particles or zirconium oxide particles.

  Titanium oxide particles and zirconium oxide particles have a high refractive index, and those that have been heat-treated in advance have high crystallinity. Therefore, when the particles are mechanochemically treated, the surface of the particles can be uniformly coated with stability. It is possible to obtain a resin-coated metal oxide particle resin dispersion composition excellent in the above.

  The average particle diameter of the metal oxide particles is not particularly limited as long as the average particle diameter of the resulting resin-coated metal oxide particles falls within the above range, and varies depending on the amount of resin coating, but is generally 5 to 300 nm, and more preferably 5 It is preferably in the range of ~ 200 nm.

  When the average particle diameter of the metal oxide particles is smaller than the lower limit of the above range, it is difficult to obtain a resin-coated metal oxide particle resin dispersion composition that is monodispersed and excellent in stability without aggregation.

  If the average particle diameter of the metal oxide particles is too large, even if a stable resin-coated metal oxide particle resin dispersion composition is obtained, the transparency and haze of the transparent film are poor when used for a substrate with a transparent film. It may be insufficient.

  As will be described later, the metal oxide particles used in the present invention are preferably preheated at 100 to 800 ° C., more preferably 105 to 500 ° C., when obtaining the resin-coated metal oxide particles.

Further, crystalline metal oxide particles are preferable.
The average particle diameter of the resin-coated metal oxide particles is preferably in the range of 5 to 300 nm, more preferably 5 to 200 nm (note that the average particle diameter is not smaller than that of the metal oxide particles before coating).

If the average particle diameter of the resin-coated metal oxide particles is smaller than the lower limit of the above range, the stability may be insufficient, and the resin-coated metal oxide particles with a high concentration of the resin-coated metal oxide particles are dispersed in the resin. The composition has a high viscosity, poor applicability and coating properties, and a transparent film having a smooth surface and a uniform film thickness may not be obtained.
If the average particle size of the resin-coated metal oxide particles is too large, the transparency and haze of the transparent coating may be insufficient when used for a substrate with a transparent coating.

(ii) Coating resin As the coating resin for the resin-coated metal oxide particles of the present invention, a (meth) acrylate monomer or oligomer (A) having an aromatic ring is used.

  When a (meth) acrylate monomer or oligomer (A) having an aromatic ring is used, the resin-coated metal oxide particle resin has good dispersibility in the resin dispersion medium described later, low viscosity, and excellent stability. A dispersion composition can be obtained.

Those having no aromatic ring are insufficient in dispersibility and stability.
Of these, a (meth) acrylate monomer or oligomer (A) having at least one functional group selected from a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, an epoxy group, and a sulfo group is preferable.

  The (meth) acrylate monomer or oligomer (A) having such a functional group has a high affinity with the metal oxide particles, strongly adsorbs to the particle surface, and in some cases, bonds to form a dense and uniform resin coating layer. Can be formed.

  Such (meth) acrylate monomers or oligomers (A) include ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diglycidyl ether acrylate, O -Diglycidyl ether phthalate, pt-butylphenyl glycidyl ether acrylate, 9.9-bis-4-acryloyloxyethoxyphenylfluorene, bisphenol A diglycidyl ether (meth) acrylic acid adduct, O-phenylphenol Glycidyl ether acrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A type epoxy acrylate, phenol novolac type epoxy Shi acrylate, cresol novolak epoxy acrylate, phenol novolak type epoxy acrylate, such as carboxylic acid anhydride-modified epoxy acrylate (meth) acrylate resin monomer or oligomer, and the like and mixtures thereof.

These are marketed as NK ester series of Shin-Nakamura Chemical Co., Ltd.
In the resin-coated metal oxide particles, the weight ratio of the metal oxide particles to the coated resin monomer or oligomer (A) is 97/3 to 40/60, more preferably 85/15 to 50/50, particularly 80/20 to 50 /. A range of 50 is preferable.

  If the weight ratio of the metal oxide particles to the coating resin monomer or oligomer exceeds 97/3, the metal oxide particles may not be coated completely and uniformly, depending on the particle diameter of the metal oxide particles, but may be dispersed. In some cases, a resin-coated metal oxide particle resin dispersion composition having excellent properties and stability cannot be obtained.

  When the weight ratio between the metal oxide particles and the coating resin monomer or oligomer is less than 40/60, depending on the blending ratio with the resin dispersion medium described later, the characteristics and effects of the metal oxide particles may not be sufficiently obtained. is there.

(iii) Resin dispersion medium As the resin for the resin dispersion medium used in the present invention, any of known thermosetting resins, thermoplastic resins, electron beam curable resins, and the like 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.

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

In the present invention, the (meth) acrylate resin (B) is preferably used. The (meth) acrylate resin (B) is a monomer or oligomer before polymerization in the resin composition.
As such a resin, specifically, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane trimethacrylate, Methoxytriethylene glycol dimethacrylate, butoxydiethylene glycol methacrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane trimethacrylate, methoxytriethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate , Tylene glycol diglycidyl ether acrylate, polyethylene glycol diglycidyl ether acrylate, dipropylene glycol diglycidyl ether acrylate, polypropylene glycol diglycidyl ether acrylate, 1,6-hexanediol diglycidyl ether acrylate, 2-ethylhexyl glycidyl ether acrylate, penta Erythritol polyglycidyl ether acrylate, neopentyl glycol diglycidyl ether acrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A methacrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, propoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A Acrylate, propoxylated bisphenol A diglycidyl ether acrylate, O-phthalic acid diglycidyl ether acrylate, cyclohexane dimethanol diglycidyl ether acrylate, pt-butylphenyl glycidyl ether acrylate, 9.9-bis-4-acryloyloxyethoxy Phenyl fluorene, bisphenol A diglycidyl ether (meth) acrylic acid adduct, O-phenylphenol glycidyl ether acrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A type epoxy acrylate, phenol novolac type epoxy acrylate, cresol novolac type Such as epoxy acrylate, carboxylic anhydride modified epoxy acrylate and the like, and mixtures thereof. That.

The (meth) acrylate resin (B) may be the same as or different from the above-described (meth) acrylate monomer or oligomer (A).
In the present invention, it is preferable that the coating resin monomer or oligomer used for the resin-coated metal oxide particles and the resin dispersion medium have a functional group capable of bonding to each other.

  The resin dispersion medium preferably has a molecular weight of 400 to 5,000, more preferably 500 to 4,000. Such a resin dispersion medium is usually desirably a monomer or oligomer.

  When the molecular weight of the resin dispersion medium is low, the dispersibility of the particles may be deteriorated, the viscosity in the absence of solvent is high, and the coating property can be lowered, transparency, haze, scratch resistance May be insufficient. If the molecular weight of the resin dispersion medium is too high, the viscosity of the composition is high, the applicability is lowered, the flatness and film thickness of the resulting transparent coating are uneven, and the transparency, haze, scratch resistance, etc. are insufficient. It may become. The molecular weight in the present invention is a polystyrene-equivalent molecular weight.

  Next, the weight ratio of the resin-coated metal oxide particles to the resin dispersion medium in the resin-coated metal oxide particle resin dispersion composition is in the range of 10/90 to 90/10, more preferably 20/80 to 80/20. It is preferable.

  When the weight ratio between the resin-coated metal oxide particles and the resin dispersion medium exceeds 90/10, the dispersibility of the particles may be deteriorated, the viscosity without solvent is increased, and the coating property is decreased. In some cases, the adhesion, transparency, haze, scratch resistance, etc. of the resulting coating may be insufficient.

  When the weight ratio of the resin-coated metal oxide particles to the resin dispersion medium is less than 10/90, the metal oxide particles in the transparent film obtained using the resin-coated metal oxide particle resin dispersion composition of the present invention Since there are few, the effect (high refractive index, electroconductivity, etc.) using a metal oxide particle may not fully be acquired.

  The resin-coated metal oxide particle resin dispersion composition uses an organic solvent in the production process, but the organic solvent derived from the production method described later does not substantially remain in the composition. Even if it remains, it is preferably 1000 ppm or less, more preferably 500 ppm or less.

  When the concentration of the organic solvent in the resin-coated metal oxide particle resin dispersion composition exceeds 1000 ppm, it is necessary to provide a drying step during the formation of the transparent film to remove the organic solvent. Depending on the remaining amount, the denseness and strength of the film In some cases, the effect of improving hardness, scratch resistance and the like cannot be sufficiently obtained.

In the present invention, since the particles are dispersed in the low molecular weight resin dispersion medium as described above, handling such as coating is easy due to low viscosity.
Moreover, the composition of this invention may contain the polymerization initiator and the hardening | curing agent as needed.

Specifically, 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-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one and the like. The amount of the polymerization initiator used is not particularly limited.
Such a resin dispersion composition according to the present invention is produced by the following production method.

[Method for producing resin dispersion composition]
The method for producing a resin dispersion composition according to the present invention has an aromatic ring as a coating resin in an organic solvent dispersion of metal oxide particles that have been heat-treated in the range of an average particle diameter of 5 nm to 100 μm. ) Addition of acrylate resin (A), followed by mechanochemical treatment, mixing of resin dispersion medium, and removal of organic solvent.

(i) First, an organic solvent dispersion of metal oxide fine particles is prepared.
The metal oxide particles are as described above.
The average particle diameter of the metal oxide particles is preferably 5 nm to 100 μm, more preferably in the range of 300 nm to 50 μm.

  If the average particle size of the metal oxide particles is small, the particles may not be opened due to the mechanochemical treatment, and the resin coating will be insufficient. It may become.

  If the average particle size of the metal oxide particles is too large, the pulverization or pulverization efficiency of the metal oxide particles will be reduced, or pulverization will become difficult, and the average particle size of the resulting resin-coated metal oxide particles will increase, The stability of the product may be insufficient. And the transparency of a transparent film using these compositions, haze, film | membrane strength, abrasion resistance, adhesiveness with a base material, etc. may become inadequate.

  In the present invention, when the average particle diameter of the metal oxide particles to be used is larger than 10 μm, it is preferably used in a state of 10 μm or less by a conventionally known agglomeration and pulverization method in the absence of the resin.

The average particle diameter of the metal oxide particles used in the present invention is not particularly limited as long as it is in the above range, and may be primary particles or secondary particles that are aggregates of primary particles.
In the present invention, the metal oxide particles to be used are obtained by spray drying, and the average particle diameter is preferably 1 to 100 μm, more preferably 2 to 50 μm.

  Such metal oxide particles are obtained by spray-drying an aqueous dispersion of metal oxide particles (including primary particles and secondary particles) having an average particle diameter in the range of 5 nm to approximately 10 μm by a conventional method. .

  When such spray-dried metal oxide particles are used, they are easily dispersed in the organic dispersion medium to be described later, and do not thicken at this time, and even when a coating resin is added, it is uniform without thickening. Then, it is easily loosened during mechanochemical treatment, and the metal oxide particles can be uniformly coated with the resin.

  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. Moreover, when the metal oxide particle used for a raw material is an aggregated particle (secondary particle), it can obtain | require with the dynamic light scattering method "microtrack particle size distribution measuring apparatus".

The metal oxide particles are preferably heat-treated in advance at 100 to 800 ° C., more preferably 105 to 500 ° 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.

By such heat treatment, the amount of resin coating can be increased and uniformly coated, and as a result, the stability of the resulting resin-coated metal oxide particle resin dispersion composition can be enhanced.
The reason is not clear, but the heat treatment removes adhering water and increases the activity on the surface of the metal oxide particles, which increases the amount of adsorption of the coating resin, and bonds the metal oxide particles to the resin. Can be promoted.

  If the heat treatment temperature is too low, the surface of the metal oxide particles may be inactive due to the remaining water, etc., or the resin adsorption and bonding between the particles and the resin will be insufficient, resulting in an insufficient amount of resin coating. In some cases, the stability of the resulting composition may be insufficient.

  Further, 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, sintered, or the affinity with the coating resin is greatly reduced, resulting in a resin-coated metal obtained. The stability of the oxide particle resin dispersion composition may be insufficient.

  As a result, the transparency, haze, film strength, scratch resistance, adhesion to the substrate, and the like of the obtained transparent film may be insufficient.

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.

Although it depends on the curing temperature of the resin, the boiling point of the organic solvent used in the present invention is in the range of 64.5 to 200 ° C, preferably 70 to 180 ° C.
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.

In particular, ethers can be preferably used because metal oxide particles hardly aggregate in mechanochemical treatment and can be uniformly coated with a resin.
Although it does not restrict | limit especially as solid content concentration of an organic-solvent dispersion liquid, It is desirable that it is 10 to 50 weight%, Preferably it is 20 to 40 weight%.

Within this range, the resin coating of the obtained particles is uniform, the particles do not aggregate, and a dispersion of resin-coated metal oxide particles excellent in dispersibility and stability can be obtained.
(ii) Next, a (meth) acrylate resin (A) having an aromatic ring as a coating resin is added to the dispersion, and a mechanochemical treatment is performed.

As the coating resin for coating, the (meth) acrylate resin (A) having the aromatic ring described above is used.

  When the (meth) acrylate-based resin (A) having an aromatic ring is used, the dispersibility in the resin dispersion medium described later is good, and after the mechanochemical treatment, the resin dispersion medium is mixed, and then the organic solvent is removed. Thereafter, a resin-coated metal oxide particle resin dispersion composition having a low viscosity and excellent stability can be obtained.

  The (meth) acrylate resin (A) having such a functional group has a high affinity with the metal oxide particles, strongly adsorbs to the particle surface, and in some cases, binds and is dense and uniform in the mechanochemical treatment described later. A simple resin coating layer can be formed.

The weight ratio of the metal oxide particles to the coating resin in the mixing ratio mechanochemical treatment is in the range of 97/3 to 40/60, more preferably 85/15 to 50/50, particularly 80/20 to 50/50. It is preferable.

  If the weight ratio between the metal oxide particles and the coating resin exceeds 97/3, the metal oxide particles may not be completely and uniformly coated, although depending on the particle size of the metal oxide particles. In some cases, a resin-coated metal oxide particle resin dispersion composition having excellent properties cannot be obtained.

  When the weight ratio between the metal oxide particles and the coating resin is less than 40/60, even if the dispersibility and stability are improved, the transparency and haze of the transparent coating are not further improved. Depending on the blending ratio, the content of the metal oxide particles decreases, so that the characteristics of the particles such as refractive index or conductivity 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 content is too low, it may be difficult to treat all particles uniformly or it may take a long time, and the resin coating may become non-uniform. The dispersibility and stability of the composition may be 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 coating resin, the viscosity may suddenly increase or the particles may agglomerate with the progress of the treatment. Dispersibility and stability in the oxide particle dispersion composition and a coating solution for forming a transparent film using the oxide particle dispersion composition may be insufficient, and the resulting transparent film may have low transparency and high haze.

Mechanochemical treatment method The mechanochemical treatment method of the present invention can employ a conventionally known method except that the metal oxide particles, the resin coating material, the mixing 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.
The stirring speed varies depending on the apparatus and method used, but if it is too low, if the particle size of the metal oxide particles is large, the agglomeration or pulverization becomes insufficient, and the resulting resin-coated metal oxide particle particles The diameter may be too large, the amount of resin coating 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 resin dispersion sol may be insufficient. The transparent film obtained may have insufficient transparency, haze, film strength, scratch resistance, adhesion to the substrate, and the like.

  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. Does not cover the particle surface, or even when coated, the polymerization and curing of the resin proceeds too much, so the affinity and binding properties with the resin dispersion medium described later are lowered, and the strength of the transparent film, scratch resistance, scratch resistance And adhesiveness with a substrate tend to be reduced.

The average particle diameter of the resin-coated metal oxide particles obtained at this stage is preferably in the range of 5 to 300 nm, more preferably 5 to 200 nm.
Although the resin coating amount is in the above range, the average particle diameter of the metal oxide particles before and after the resin coating may be substantially the same, and naturally the average particle diameter after the resin coating may be large. . 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 end point of the mechanochemical treatment is not particularly limited as long as the resin-coated metal oxide particles can be obtained, and a partially unreacted (not involved in coating) resin may remain.
(iii) After the mechanical treatment, the resin dispersion medium is mixed and the contained organic solvent is removed.

Resin dispersion medium The resin dispersion medium resin described above is used.
The weight ratio between the resin-coated metal oxide particles and the resin dispersion medium is preferably in the range of 10/90 to 90/10, more preferably 20/80 to 80/20.

  When the weight ratio of the resin-coated metal oxide particles to the resin dispersion medium is less than 10/90, since the resin-coated metal oxide particles are few, the transparent coating obtained using this is used as the metal oxide particles used In some cases, sufficient effects due to the above characteristics (low refractive index, high refractive index, conductivity, etc.) cannot be obtained.

When the weight ratio of the resin-coated metal oxide particles to the resin dispersion medium exceeds 90/10, the resin-coated metal oxide particles are too much and adhesion to the substrate, transparency, haze, scratch resistance, etc. are poor. May be sufficient.
After the resin dispersion medium is added, stirring may be performed so that each component is uniformly dispersed, but mechanochemical can be continued as necessary.

Organic solvent removal The removal method of the organic solvent varies depending on the kind, boiling point, blending amount, etc. of the organic solvent, but is performed under heating, preferably under heating and reduced pressure. The heating temperature varies depending on the resin, but is lower than the temperature at which the polymerization of the resin starts, and is usually preferably 50 ° C. or lower. As the apparatus, a rotary evaporator, a vacuum distillation apparatus or the like is employed.

  The organic solvent is preferably removed until the residual amount of the organic solvent in the resulting resin-coated metal oxide particle resin dispersion composition is 1000 ppm or less, more preferably 500 ppm or less.

  When the residual amount of the organic solvent in the resin-coated metal oxide particle resin dispersion composition exceeds 1000 ppm, it is necessary to provide a drying step when forming the transparent film to remove the organic solvent, depending on the residual amount, The effect of improving strength, hardness, scratch resistance, etc. may not be sufficiently obtained.

Thus, the resin-coated metal oxide particle resin dispersion composition according to the present invention can be obtained.
Furthermore, another resin dispersion medium can be mixed with the obtained resin-coated metal oxide particle resin dispersion composition. Also at this time, the resin-coated metal oxide particles and the resin dispersion medium are mixed so that the weight ratio falls within the above range.
The composition thus obtained has a viscosity in the range of 10 to 10,000 mPa · s, preferably 50 to 9000 mPa · s, more preferably 100 to 8000 mPa · s. Within this range, coating properties and handling properties are excellent.

The composition is usually mixed with a polymerization initiator or a curing agent.
The above resin-coated metal oxide particle resin dispersion composition 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, A transparent film can be formed by curing by an ordinary method such as ultraviolet irradiation or heat treatment.

The substrate with a transparent coating 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 is applied with the resin dispersion composition and cured. It is characterized by that.

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), cyclopolyolefin And plastic sheets such as 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. Moreover, it can also form on a die bond as a sealing material for light emitting diodes (LED).

Transparent coating The transparent coating is obtained by applying and curing the resin dispersion composition.
The film thickness of the transparent film is preferably in the range of 100 nm to 2 mm, more preferably 500 nm to 1.5 mm. The average particle diameter of the resin-coated particles is not more than the film thickness.

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

The weight ratio of the resin-coated metal oxide particles in the transparent coating to the cured dispersion medium resin is preferably in the range of 10/90 to 90/10, more preferably 20/80 to 80/20.
The content of the metal oxide particles in the transparent coating of the present invention is in the range of 20 to 80% by weight, preferably 25 to 75% by weight, and the total of the coating resin and the cured dispersion medium resin is a solid content. 20 to 80% by weight, preferably 25 to 75% by weight.

  Furthermore, the base material with a transparent film of the present invention can be provided with another film different from the transparent film between the base material and the transparent film or on 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]
Preparation of metal oxide particles (1 ) 35 g of zirconium oxychloride octahydrate (ZrOCl ₂ .8H ₂ O (manufactured by Taiyo Mining Co., Ltd .: ZrO ₂ concentration 37.2 wt%)) was dissolved in 1,300 g of pure water. A zirconium hydroxide hydrogel (ZrO ₂ concentration 1% by weight) was prepared by adding 123 g of a 10% by weight aqueous KOH solution, and the conductivity was reduced to 0.5 mS / cm or less by the ultrafiltration membrane method. Washed until

400 g of a 10 wt% KOH aqueous solution was added to 2,000 g of 1 wt% zirconium hydroxide hydrogel as the obtained ZrO ₂ , and after sufficient stirring, 200 g of a 35 wt% hydrogen peroxide aqueous solution was added. At this time, the solution foamed vigorously and the solution became transparent, and the pH was 11.5.

  This solution is filled in an autoclave, hydrothermally treated at 150 ° C. for 11 hours, then taken out, concentrated to 10% using an ultrafiltration membrane, and the conductivity is 0.2 mS / cm or less with pure water. Until washed. Subsequently, it was made into the dispersion liquid of 20 weight% of solid content concentration, and it sprayed in the hot air with an inlet temperature of 400 degreeC, and prepared the spray-dried metal oxide particle (1). At this time, the outlet temperature was 150 ° C.

Subsequently, the metal oxide particle (1) powder which consists of zirconia was prepared by heat-processing with a dryer at 105 degreeC for 20 hours.
The average primary particle diameter of the metal oxide particles (1) was 15 nm, the average secondary particle diameter was 10 μm, and the crystal form was monoclinic as measured by X-ray diffraction. The refractive index was 2.20.

Preparation of resin-coated metal oxide particles (1) organic solvent dispersion, followed by 125.45 g of metal oxide particles (1) powder, 232.999 g of propylene glycol monomethyl ether (PGME) as an organic solvent, and cresol novolak type as a coating resin 100.36 g of epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo EA-7120 / PGMAC, solid content concentration 70%) and 1713.6 g of zirconia beads (diameter 0.05 mm), bead mill (manufactured by Campe Co., Ltd.) : BATCH SAND), disperse, adjust the concentration with PGME solvent, metal oxide particle (1) solid content concentration 20% by weight, total solid content concentration (metal oxide particles (1) + resin) 31.2% by weight of resin-coated metal oxide particles (1) An organic solvent dispersion was prepared.
The average particle diameter of the resin-coated metal oxide particles (1) was measured, and the results are shown in Table 1. The average particle size was measured with a laser particle size analysis system (Otsuka Electronics: FPAR-1000).

Resin Coated Metal Oxide Particles (1-1) Preparation of Resin Dispersion Composition Resin Coated Metal Oxide Particles (1) Neopentyl glycol diglycidyl ether acrylate resin (Shin Nakamura Chemical Co., Ltd.) as a resin dispersion medium in 100 g of organic solvent dispersion ): NK Oligo EA-5320) 20g, and with a rotary evaporator (manufactured by Shibata Chemical Co., Ltd.), the temperature of the warm bath is increased to 60 ° C, the degree of vacuum is gradually increased and PGME is removed in 2 hours to remove the resin-coated metal. A resin dispersion composition of oxide particles (1-1) was prepared.

In this composition, the weight ratio of the resin-coated metal oxide particles (1) to the resin dispersion medium (ZrO ₂ / coating resin / dispersion medium resin) is 39.06 / 21.88 / 39.06.
The remaining amount, stability, and viscosity of the organic solvent of the obtained resin-coated metal oxide particles (1-1) resin dispersion composition were measured, and the results are shown in Table 1. The stability and viscosity were evaluated by the following methods and evaluation criteria.

Stability evaluation Resin-coated metal oxide particles (1-1) Fill the resin dispersion composition in a transparent container and let it stand, observe the state of the precipitated particles at the bottom of the container, and evaluate the results according to the following criteria. 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. : ×

The liquid temperature of the viscosity measurement sample was 25 ° C., and the viscosity was measured with a viscometer (manufactured by Toki Sangyo Co., Ltd .: TBV-10M type).

Production of substrate with transparent coating (1) 100 g of resin-coated metal oxide particles (1-1) resin dispersion composition, 4 g of photoinitiator 1 hydroxy-cyclohexyl-phenyl ketone (manufactured by Ciba Japan Co., Ltd .: Irgacure 184) Were mixed to prepare resin-coated metal oxide particles (1-2) resin dispersion composition for forming a transparent film.

Resin Coated Metal Oxide Particles (1-2) Resin dispersion composition was applied to an easily adhesive PET film (Toyobo Co., Ltd .: Cosmo Shine A-4300, thickness: 188 μm, refractive index: 1.65, total light transmittance 91 0.0%, haze 0.8%) by a bar coater method (bar # 20) and 600 mJ with an ultraviolet irradiation device (manufactured by Nihon Battery: UV irradiation device CS30L21-3) equipped with a high-pressure mercury lamp (120 W / cm). Irradiation was cured under the conditions of / cm ² to prepare a substrate (1) with a transparent coating. The thickness of the transparent film at this time was 35 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.
The total light transmittance and haze of the transparent coating obtained were measured with a haze meter (NDH-2000 manufactured by Nippon Denshoku Industries 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-5600.

Measurement of Scratch Resistance Using # 0000 steel wool, sliding 50 times at a load of 250 g / cm ² , visually observing the surface of the film and evaluating it 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: ×

The surface of the substrate with adhesive transparent coating (1) is made with 11 parallel scratches with a knife at intervals of 1 mm in length and width to make 100 squares, and this is made of cellophane tape (registered cello tape) (manufactured by Nichiban Co., Ltd.) : CT-18) was adhered, and then the cellophane tape (registered trademark cellotape) was peeled off, and the adhesion was evaluated by classifying the number of cells remaining without peeling off into the following four stages. did. 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: ×

Refractive index of coating film In place of the above PET film substrate, a resin-coated metal oxide particle (1-2) resin dispersion composition is applied and cured in the same manner on a silicon wafer to form a coating film having a thickness of 35 μm, The refractive index was measured with an ellipsometer (manufactured by SOPRA: ESVG), and the results are shown in the table.

[Example 2]
Preparation of resin-coated metal oxide particles (2) organic solvent dispersion 125.45 g of zirconia-made metal oxide particles (1) prepared in the same manner as in Example 1, propylene glycol monomethyl ether (PGME) as an organic solvent 232.99 g, 31.63 g of cresol novolac type epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo EA-7120 / PGMAC, solid content concentration 70%) as coating resin, and zirconia beads (diameter 0.05 mm) 1713 .6 g was filled in a bead mill (manufactured by Campe Co., Ltd .: BATCH SAND), dispersed, and then added with PGME to adjust the concentration of the metal oxide particles (1) having a solid content concentration of 20% by weight, the total solid content. A resin-coated metal oxide particle (2) organic solvent dispersion having a concentration of 23.0% by weight was prepared.
The average particle diameter of the resin-coated metal oxide particles (2) was measured, and the results are shown in Table 1.

Resin-coated metal oxide particles (2-1) Preparation of resin dispersion composition Resin-coated metal oxide particles (2) Polyethylene glycol diglycidyl ether acrylate resin as a resin dispersion medium in 100 g of organic solvent dispersion (Shin Nakamura Chemical Co., Ltd.) Product: 20.0 g of NK Oligo EA-5822) was added, and the temperature of the warm bath was increased to 60 ° C. with a rotary evaporator (manufactured by Shibata Chemical Co., Ltd.). A metal oxide particle (2-1) resin dispersion composition was prepared.

At this time, the weight ratio of the resin-coated metal oxide particles (2-1) to the resin dispersion medium (ZrO ₂ / coating resin / dispersion medium resin) is 45.95 / 8.11 / 45.95.
The remaining amount, stability and viscosity of the organic solvent of the obtained resin-coated metal oxide particles (2-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of transparent-coated substrate (2) In Example 1, resin-coated metal oxide particles for forming a transparent film (2-1) were used in the same manner except that the resin-dispersed metal oxide particles (2-1) were used. 2-2) A resin dispersion composition was prepared.

Next, a substrate (2) with a transparent coating was prepared using the resin-coated metal oxide particles (2-2) resin dispersion composition for forming the transparent coating. The thickness of the transparent film at this time was 35 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 Metal Oxide Particles (3) Organic Solvent Dispersion 125.45 g of zirconia metal oxide particles (1) prepared in the same manner as in Example 1, and propylene glycol monomethyl ether (PGME) as the organic solvent 232.99 g, cresol novolac epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo EA-7120 / PGMAC, solid content concentration 70%) as a coating resin, 179.21 g, and zirconia beads (diameter 0.05 mm) 1713 .6 g was filled in a bead mill (manufactured by Campe Co., Ltd .: BATCH SAND), dispersed, and then added with PGME to adjust the concentration of the metal oxide particles (1) having a solid content concentration of 20% by weight, the total solid content. A resin-coated metal oxide particle (3) organic solvent dispersion having a concentration of 40.0% by weight was prepared.
The average particle diameter of the resin-coated metal oxide particles (3) was measured, and the results are shown in Table 1.

Resin-coated metal oxide particles (3-1) Preparation of resin dispersion composition Resin-coated metal oxide particles (3) Neopentyl glycol diglycidyl ether acrylate resin (Shin Nakamura Chemical Co., Ltd.) ): NK Oligo EA-5320) 20g, and with a rotary evaporator (manufactured by Shibata Chemical Co., Ltd.), the temperature of the warm bath is increased to 60 ° C, the degree of vacuum is gradually increased and PGME is removed in 2 hours to remove the resin-coated metal. Oxide particle (3-1) resin dispersion composition was prepared.

At this time, the weight ratio (ZrO ₂ / coating resin / dispersion medium resin) between the resin-coated metal oxide particles (3) and the resin dispersion medium is 33.33 / 33.33 / 33.33.
The remaining amount, stability and viscosity of the organic solvent of the obtained resin-coated metal oxide particles (3-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of transparent-coated substrate (3) In Example 1, resin-coated metal oxide particles for forming a transparent film (3-1) resin-coated metal oxide particles (3-1) were used in the same manner except that the resin dispersion composition was used ( 3-2) A resin dispersion composition was prepared.

Subsequently, a substrate (3) with a transparent coating was prepared using the resin-coated metal oxide particles (3-2) resin dispersion composition for forming a transparent coating. The thickness of the transparent film at this time was 35 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 metal oxide particles (4) In Example 1, metal oxide particles (4) comprising zirconia were similarly prepared except that the spray-dried metal oxide particles (1) were dried at a heat treatment temperature of 200 ° C for 20 hours. A powder was prepared.
The average primary particle size of the metal oxide particles (4) was 15 nm, the average secondary particle size was 10 μm, and the crystal form was monoclinic as measured by X-ray diffraction. The refractive index was 2.20.

Resin Coated Metal Oxide Particles (4) Preparation of Organic Solvent Dispersion Metal Oxide Particles (4) 125.45 g, Organic Solvent 232.99 g, Phenolic Novolac Type Epoxy Acrylate as Coating Resin (Shin Nakamura Chemical Co., Ltd.) Manufactured by: NK Oligo EA-6320 / PGMAC, solid content concentration 80%) and zirconia beads (diameter 0.05 mm) 1713.6 g are filled in a bead mill (Kampe Co., Ltd. product: BATCH SAND) and dispersed. Next, resin-coated metal oxide particles (4) having a solid content concentration of 20% by weight and a total solid content concentration of 31.2% by weight by adjusting the concentration by adding acetone were prepared. .
The average particle diameter of the resin-coated metal oxide particles (4) was measured, and the results are shown in Table 1.

Resin-coated metal oxide particles (4-1) Preparation of resin dispersion composition Resin-coated metal oxide particles (4) Neopentyl glycol diglycidyl ether acrylate resin (Shin Nakamura Chemical Co., Ltd.) as a resin dispersion medium in 100 g of organic solvent dispersion ): NK Oligo EA-5320) 20 g was added, and the temperature of the warm bath was increased to 40 ° C. with a rotary evaporator (manufactured by Shibata Chemical Co., Ltd.). Oxide particle (4-1) resin dispersion composition was prepared.

At this time, the weight ratio (ZrO ₂ / coating resin / dispersion medium resin) between the resin-coated metal oxide particles (4) and the resin dispersion medium is 39.03 / 21.95 / 39.03.
The remaining amount, stability and viscosity of the organic solvent of the obtained resin-coated metal oxide particles (4-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of Transparent Coated Substrate (4) In Example 1 of Resin Coated Metal Oxide Particles (4) Resin Coated Metal Oxide Particles for Formation of Transparent Coat (4) 4-2) A resin dispersion composition was prepared.

Next, a substrate (4) with a transparent film was prepared using the resin-coated metal oxide particles (4-2) resin dispersion composition for forming the transparent film. The thickness of the transparent film at this time was 35 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]
Resin-coated metal oxide particles (5-1) Preparation of resin dispersion composition Resin-coated metal oxide particles having a total solid concentration of 31.2% by weight prepared in the same manner as in Example 1 (1) 100 g of organic solvent dispersion 70 g of neopentyl glycol diglycidyl ether acrylate resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo EA-5320) as a resin dispersion medium is added to a rotary evaporator (manufactured by Shibata Chemical Co., Ltd.), and the temperature of the hot bath is 60 ° C. Then, the degree of vacuum was gradually increased and PGME was removed in 2 hours to prepare a resin-coated metal oxide particle (5-1) resin dispersion composition.

At this time, the weight ratio (ZrO ₂ / coating resin / dispersion medium resin) between the resin-coated metal oxide particles (1) and the resin dispersion medium is 19.8 / 11.0 / 69.2.
The remaining amount, stability and viscosity of the organic solvent of the obtained resin-coated metal oxide particles (5-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of transparent-coated substrate (5) In Example 1, resin-coated metal oxide particles for forming a transparent film (5-1) except that the resin-dispersed composition was used. 5-2) A resin dispersion composition was prepared.

Next, a substrate (5) with a transparent film was prepared using the resin-coated metal oxide particles (5-2) resin dispersion composition for forming the transparent film. The thickness of the transparent film at this time was 35 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]
Resin Coated Metal Oxide Particles (6-1) Preparation of Resin Dispersion Composition Resin Coated Metal Oxide Particles with a Total Solid Concentration of 31.2% by Weight Prepared as in Example 1 (1) 100 g of organic solvent dispersion 9.2 g of neopentyl glycol diglycidyl ether acrylate resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo EA-5320) as a resin dispersion medium, and the temperature of the warm bath with a rotary evaporator (manufactured by Shibata Chemical Co., Ltd.) The temperature was raised to 60 ° C., the degree of vacuum was gradually increased, and PGME was removed in 2 hours to prepare resin-coated metal oxide particles (6-1) resin dispersion composition.

At this time, the weight ratio (ZrO ₂ / coating resin / dispersion medium resin) between the resin-coated metal oxide particles (1) and the resin dispersion medium is 49.50 / 27.72 / 22.77.
The remaining amount, stability and viscosity of the organic solvent of the obtained resin-coated metal oxide particles (6-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of transparent-coated substrate (6) In Example 1, resin-coated metal oxide particles for forming a transparent film were similarly prepared except that the resin-coated metal oxide particles (6-1) resin dispersion composition was used. 6-2) A resin dispersion composition was prepared.

Next, a substrate (6) with a transparent coating was prepared using the resin-coated metal oxide particles (6-2) resin dispersion composition for forming the transparent coating. The thickness of the transparent film at this time was 35 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]
Preparation of Metal Oxide Particles (7) 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. Subsequently, it was washed with an ultrafiltration membrane, then concentrated to a dispersion having a solid content of 20% by weight, and sprayed into hot air having an inlet temperature of 400 ° C. to prepare spray-dried metal oxide particles (7). . At this time, the outlet temperature was 150 ° C.

Subsequently, the metal oxide particle (7) powder which consists of titanium oxide was prepared by heat-processing for 2 hours at 500 degreeC.
The average primary particle size of the metal oxide particles (7) was 60 nm, the average secondary particle size was 15 μm, and the crystal form was anatase type as measured by X-ray diffraction. The refractive index was 2.5.

Preparation of Resin Coated Metal Oxide Particles (7) Organic Solvent Dispersion In Example 1, the solid content concentration of the metal oxide particles (7) was 20% by weight except that the metal oxide particles (7) powder was used. A resin-coated metal oxide particle (7) organic solvent dispersion having a total solid concentration of 31.2% by weight was prepared.
The average particle diameter of the resin-coated metal oxide particles (7) was measured, and the results are shown in Table 1.

Preparation of Resin-Coated Metal Oxide Particles (7-1) Resin Dispersion Composition In Example 1, except that resin-coated metal oxide particles (7) organic solvent dispersion having a total solid concentration of 31.2% by weight were used. Similarly, resin-coated metal oxide particles (7-1) resin dispersion composition was prepared.

At this time, the weight ratio of the resin-coated metal oxide particles (1) to the resin dispersion medium (TiO ₂ / coating resin / dispersion medium resin) is 39.06 / 21.88 / 39.06.
The remaining amount, stability, and viscosity of the organic solvent of the obtained resin-coated metal oxide particles (7-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of transparent coated substrate (7) In Example 1, resin-coated metal oxide particles for forming a transparent film (7-1) were used in the same manner except that the resin-dispersed composition (7-1) was used. 7-2) A resin dispersion composition was prepared.

Subsequently, a substrate (7) with a transparent film was prepared using the resin-coated metal oxide particles (7-2) resin dispersion composition for forming the transparent film. The thickness of the transparent film at this time was 35 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 metal oxide particles (8) Zirconium oxychloride octahydrate (ZrOCl ₂ .8H ₂ O (manufactured by Taiyo Mining Co., Ltd .: ZrO ₂ concentration 37.2 wt%)) was dissolved in 1,300 g of pure water. A zirconium hydroxide hydrogel (ZrO ₂ concentration 1% by weight) was prepared by adding 123 g of a 10% by weight aqueous KOH solution, and the conductivity was reduced to 0.5 mS / cm or less by the ultrafiltration membrane method. Washed until

400 g of a 10 wt% KOH aqueous solution was added to 2,000 g of 1 wt% zirconium hydroxide hydrogel as the obtained ZrO ₂ , and after sufficient stirring, 200 g of a 35 wt% hydrogen peroxide aqueous solution was added. At this time, the solution foamed vigorously and the solution became transparent, and the pH was 11.5.

  This solution is filled in an autoclave, hydrothermally treated at 150 ° C. for 11 hours, then taken out, concentrated to 10% using an ultrafiltration membrane, and the conductivity is 0.2 mS / cm or less with pure water. Until washed. Then, after drying at 105 ° C. for 20 hours with a drier, pulverizing with a mortar, and then sieving with a 44 μm wire mesh, metal oxide particle (8) powder made of zirconia was prepared.

  The average primary particle diameter of the metal oxide particles (8) was 15 nm, the average secondary particle diameter was 35 μm, and the crystal form was monoclinic as measured by X-ray diffraction. The refractive index was 2.20.

Preparation of Resin Coated Metal Oxide Particles (8) Organic Solvent Dispersion In Example 1, the solid content concentration of metal oxide particles (8) was 20% by weight except that the metal oxide particles (8) powder was used. A resin-coated metal oxide particle (8) organic solvent dispersion having a total solid concentration of 31.2% by weight was prepared.
The average particle diameter of the resin-coated metal oxide particles (8) was measured, and the results are shown in Table 1.

Preparation of Resin Coated Metal Oxide Particles (8-1) Resin Dispersion Composition In Example 1, except that resin-coated metal oxide particles (8) organic solvent dispersion composition having a total solid content concentration of 31.2% by weight were used. Similarly, a resin-coated metal oxide particle (8-1) resin dispersion composition was prepared.

At this time, the weight ratio (ZrO ₂ / coating resin / dispersion medium resin) between the resin-coated metal oxide particles (8) and the resin dispersion medium is 39.03 / 21.95 / 39.03.
The remaining amount, stability and viscosity of the organic solvent of the obtained resin-coated metal oxide particles (8-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of transparent coated substrate (8) In Example 1, resin-coated metal oxide particles for forming a transparent film (8-1) were used in the same manner except that the resin-dispersed composition (8-1) was used. 8-2) A resin dispersion composition was prepared.

Next, a substrate (8) with a transparent coating was prepared using the resin-coated metal oxide particles (8-2) resin dispersion composition for forming a transparent coating. The thickness of the transparent film at this time was 35 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 Resin Coated Metal Oxide Particles (R1) Organic Solvent Dispersion 125.45 g of zirconia metal oxide particles (1) prepared in the same manner as in Example 1, and propylene glycol monomethyl ether (PGME) as an organic solvent 232.99 g, neopentyl glycol diglycidyl ether acrylate (Shin-Nakamura Chemical NK Oligo EA− / solid content concentration 100%) 87.82 g and zirconia beads (diameter 0.05 mm) 1713.6 g as a coating resin, Filled and dispersed in Campe Co., Ltd. (BATCH SAND), and then added with PGME to form a resin coating with metal oxide particles (1) having a solid content of 20% by weight and a total solids concentration of 31.2% by weight. A metal oxide particle (R1) organic solvent dispersion was prepared.
The average particle diameter of the resin-coated metal oxide particles (R1) was measured, and the results are shown in Table 1.

Preparation of Resin Coated Metal Oxide Particles (R1-1) Resin Dispersion Composition In Example 1, except that resin-coated metal oxide particles (R1) organic solvent dispersion having a total solid concentration of 31.2% by weight was used. Similarly, resin-coated metal oxide particles (R1-1) resin dispersion composition was prepared.

At this time, the weight ratio of the resin-coated metal oxide particles (R1) to the resin dispersion medium (ZrO ₂ / coating resin / dispersion medium resin) is 39.06 / 21.88 / 39.06.
The remaining amount, stability, and viscosity of the organic solvent of the obtained resin-coated metal oxide particle (R1-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of transparent-coated substrate (R1) In Example 1, resin-coated metal oxide particles for forming a transparent film (R1-1) were used in the same manner except that the resin-dispersed composition (R1-1) resin dispersion composition was used. R1-2) A resin dispersion composition was prepared.

Next, a substrate with transparent coating (R1) was prepared using the resin-coated metal oxide particles (R1-2) resin dispersion composition for transparent coating formation. The thickness of the transparent film at this time was 35 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 Metal Oxide Particles (R2) Organic Solvent Dispersion 125.45 g of zirconia metal oxide particles (1) prepared in the same manner as in Example 1, and propylene glycol monomethyl ether (PGME) as an organic solvent 232.99 g, 2-acryloyloxyethyl succinic acid (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester A-SA, solid content concentration 100%) as a coating resin, 87.82 g, and zirconia beads (diameter 0.05 mm) 1713.6 g was filled in a bead mill (made by Campe Co., Ltd .: BATCH SAND), dispersed, and then added with PGME to adjust the concentration of the metal oxide particles (1) having a solid content concentration of 20% by weight. A resin-coated metal oxide particle (R2) organic solvent dispersion having a partial concentration of 31.2% by weight was prepared.
The average particle diameter of the resin-coated metal oxide particles (R2) was measured, and the results are shown in Table 1.

Preparation of Resin-Coated Metal Oxide Particles (R2-1) Resin Dispersion Composition In Example 1, the resin-coated metal having a metal oxide particle (1) solid content concentration of 20% by weight and a total solid content concentration of 31.2% by weight Resin-coated metal oxide particles (R2-1) resin dispersion composition was prepared in the same manner except that the oxide particle (R2) organic solvent dispersion was used.

At this time, the weight ratio of the resin-coated metal oxide particles (R2) to the resin dispersion medium (ZrO ₂ / coating resin / dispersion medium resin) is 39.06 / 21.88 / 39.06.
The remaining amount, stability, and viscosity of the organic solvent of the obtained resin-coated metal oxide particle (R2-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of Transparent Coated Substrate (R2) In Example 1, resin-coated metal oxide particles for forming a transparent coating (R2-1) were used in the same manner except that the resin dispersion composition (R2-1) resin dispersion composition was used. R2-2) A resin dispersion composition was prepared.

Subsequently, a substrate (R2) with a transparent coating was prepared using the resin-coated metal oxide particles (R2-2) resin dispersion composition for forming a transparent coating. The thickness of the transparent film at this time was 45 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 Metal Oxide Particles (R3-1) Resin Dispersion Composition Metal oxide particles (1) prepared in the same manner as in Example 1 had a solid content concentration of 20% by weight and a total solid content concentration of 31.2% by weight. Resin-coated metal oxide particles (1) 20 g of neopentyl glycol diglycidyl ether acrylate resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo EA-5320) as a resin dispersion medium is added to 100 g of an organic solvent dispersion, and a rotary evaporator ( The resin-coated metal oxide particle (R3-1) resin dispersion composition having a total solid content of 42.7% by weight was prepared by thoroughly mixing with Shibata Chemical Co., Ltd.).

At this time, the weight ratio of the resin-coated metal oxide particles (1) to the resin dispersion medium (ZrO ₂ / coating resin / dispersion medium resin) is 39.06 / 21.88 / 39.06.
The remaining amount, stability, and viscosity of the organic solvent of the obtained resin-coated metal oxide particle (R3-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of substrate with transparent coating (R3) 100 g of resin-coated metal oxide particle (R3-1) resin dispersion composition and photoinitiator 1-hydroxy-cyclohexyl-phenylketone (Ciba Japan Co., Ltd .: Irgacure 184) 4 g was mixed to prepare a resin-coated metal oxide particle (R3-2) resin dispersion composition for forming a transparent film.

Resin-coated metal oxide particles (R3-2) resin dispersion composition was applied to an easily adhesive PET film (manufactured by Toyobo Co., Ltd .: Cosmo Shine A-4300, thickness: 188 μm, refractive index: 1.65, total light transmittance 91 0.0%, haze 0.8%) by a bar coater method (bar # 20), dried at 80 ° C. for 3 minutes, and then an ultraviolet irradiation device equipped with a high-pressure mercury lamp (120 W / cm) (manufactured by Nippon Batteries) : UV irradiation apparatus CS30L21-3) was irradiated and cured under the condition of 600 mJ / cm ² to prepare a substrate (1) with a transparent coating. The thickness of the transparent film at this time was 10 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. Note that slight cracks were observed in the transparent film.

[Comparative Example 4]
Preparation of Resin Coated Metal Oxide Particles (R4-1) Resin Dispersion Composition Metal oxide particles (1) prepared in the same manner as in Example 1 have a solid content concentration of 20% by weight and a total solid content concentration of 31.2% by weight. Resin-coated metal oxide particles (1) 20 g of neopentyl glycol diglycidyl ether acrylate resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo EA-5320) as a resin dispersion medium is added to 100 g of an organic solvent dispersion, and a rotary evaporator ( (Made by Shibata Chemical Co., Ltd.), the temperature of the warm bath is set to 40 ° C., the degree of vacuum is gradually increased, PGME is removed in 2 hours, and resin-coated metal oxide particles having a total solid concentration of 98.0% by weight (R4- 1) A resin dispersion composition was prepared.

At this time, the weight ratio of the resin-coated metal oxide particles (1) to the resin dispersion medium (ZrO ₂ / coating resin / dispersion medium resin) is 39.06 / 21.88 / 39.06.
The remaining amount, stability, and viscosity of the organic solvent of the obtained resin-coated metal oxide particles (R4-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of substrate with transparent coating (R4) 100 g of resin-coated metal oxide particles (R4-1) resin dispersion composition and 4 g of photoinitiator 1 hydroxy-cyclohexyl-phenyl ketone (Ciba Japan Co., Ltd .: Irgacure 184) Were mixed to prepare a resin-coated metal oxide particle (R4-2) resin dispersion composition for forming a transparent film.

Resin-coated metal oxide particles (R4-2) The resin dispersion composition was coated with an easily adhesive PET film (Toyobo Co., Ltd .: Cosmo Shine A-4300, thickness: 188 μm, refractive index: 1.65, total light transmittance 91 0.0%, haze 0.8%) by a bar coater method (bar # 20), and then an ultraviolet irradiation device (Japan Battery: UV irradiation device CS30L21-3) equipped with a high-pressure mercury lamp (120 W / cm) Was cured by irradiation under conditions of 600 mJ / cm ² to prepare a substrate (1) with a transparent coating. The thickness of the transparent film at this time was 30 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. Clear cracks were clearly observed in the transparent film.

[Comparative Example 5]
Preparation of metal oxide particles (R5) In Example 1, metal oxide particles (R5) powder composed of zirconia was prepared by heat treatment in a dryer at 80 ° C for 3 hours.
The average primary particle diameter of the metal oxide particles (R5) was 15 nm, the average secondary particle diameter was 10 μm, and the crystal form was monoclinic as measured by X-ray diffraction. The refractive index was 2.20.

Preparation of Resin Coated Metal Oxide Particles (R5) Organic Solvent Dispersion In Example 1, the solid content concentration of metal oxide particles (R5) was the same as in Example 1 except that metal oxide particles (R5) powder made of zirconia was used. A resin-coated metal oxide particle (R5) organic solvent dispersion with 20 wt% and a total solid content of 31.2 wt% was prepared.
The average particle diameter of the resin-coated metal oxide particles (R5) was measured, and the results are shown in Table 1.

Preparation of Resin-Coated Metal Oxide Particles (R5-1) Resin Dispersion Composition In Example 1, the resin-coated metal having a solid content concentration of 20% by weight and a total solid concentration of 31.2% by weight of the metal oxide particles (R5) Resin-coated metal oxide particles (R5-1) resin dispersion composition was prepared in the same manner except that the oxide particle (R5) organic solvent dispersion was used.

At this time, the weight ratio of the resin-coated metal oxide particles (R5) to the resin dispersion medium (ZrO ₂ / coating resin / dispersion medium resin) is 39.06 / 21.88 / 39.06.
The remaining amount, stability, and viscosity of the organic solvent of the obtained resin-coated metal oxide particle (R5-1) resin dispersion composition were measured, and the results are shown in Table 1.

Production of transparent coated substrate (R5) In Example 1, resin-coated metal oxide particles for forming a transparent coating (R5-1) were used except that the resin dispersion composition (R5-1) resin dispersion composition was used ( R5-2) A resin dispersion composition was prepared.

Next, a substrate (R5) with a transparent coating was prepared using the resin-coated metal oxide particles (R5-2) resin dispersion composition for forming a transparent coating. The thickness of the transparent coating at this time was 40 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. Clear cracks were clearly observed in the transparent film.

Claims (13)

In an organic solvent dispersion of metal oxide particles that have been heat-treated in advance at 100 to 800 ° C., having an average particle diameter in the range of 5 nm to 100 μm,
Coating resins include ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diglycidyl ether acrylate, O-phthalic acid diglycidyl ether acrylate, pt- Butylphenyl glycidyl ether acrylate, 9.9-bis-4-acryloyloxyethoxyphenyl fluorene, bisphenol A diglycidyl ether (meth) acrylic acid adduct, O-phenylphenol glycidyl ether acrylate, 2-hydroxy-3-phenoxypropyl Acrylate, bisphenol A type epoxy acrylate, phenol novolac type epoxy acrylate, cresol novolac type epoxy acrylate Relate, phenol novolak type epoxy acrylate from carboxylic acid anhydride-modified epoxy acrylate of at least one selected of (meth) acrylate resin monomer or oligomer and an aromatic ring consisting of mixtures (meth) Atari rate based monomer or oligomer After adding (A)
The metal oxide particle surface is coated with the coating resin by mechanochemical treatment ,
Next , after mixing the resin dispersion medium (B) ,
A method for producing a resin dispersion composition, wherein the organic solvent is removed, and the concentration of the organic solvent in the resin dispersion composition is 1000 ppm or less . 2. The method for producing a resin dispersion composition according to claim 1 , wherein an average particle diameter of the metal oxide particles coated with the coating resin is in the range of 5 to 300 nm. 2. The method for producing a resin dispersion composition according to claim 1 , wherein the metal oxide particles are obtained by spray drying, and are metal oxide particles having an average particle diameter in the range of 1 to 100 μm. The resin according to any one of claims 1 to 3 , wherein the organic solvent is at least one selected from alcohols, ethers, esters and ketones having a boiling point of 64.5 ° C to 200 ° C. A method for producing a dispersion composition. The weight ratio of the said metal oxide particle and coating resin exists in the range of 97 / 3-40 / 60, The manufacturing method of the resin dispersion composition in any one of Claims 1-4 characterized by the above-mentioned. According to any one of claims 1 to 5, characterized in that the weight ratio of the weight of the total weight and the resin dispersion medium with the coating resin and the metal oxide particles is in the range of 10 / 90-90 / 10 A method for producing a resin dispersion composition. The method for producing a resin dispersion composition according to any one of claims 1 to 6 , wherein the molecular weight of the coating resin is in the range of 400 to 5,000. The method for producing a resin dispersion composition according to any one of claims 1 to 7 , wherein the resin dispersion medium is a (meth) acrylate resin (B). The method for producing a resin dispersion composition according to any one of claims 1 to 8 , wherein the resin dispersion medium has a molecular weight in the range of 400 to 5,000. The metal oxide particles are TiO ₂ , SiO ₂ , ZrO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZnO and their composite oxides, tin oxide, tin oxide doped with Sb or P, indium oxide, Sn The method for producing a resin dispersion composition according to claim 1 , wherein the resin dispersion composition is one or more selected from indium oxide doped with F, antimony oxide, and low-order titanium oxide. The method for producing a resin dispersion composition according to claim 10 , wherein the metal oxide particles are titanium oxide particles and / or zirconium oxide particles. It consists of a base material and the transparent film formed on the base material, and this transparent film apply | coats and hardens the resin dispersion composition obtained by the manufacturing method in any one of the said Claims 1-11. A substrate with a transparent coating, characterized in that. The substrate with a transparent coating according to claim 12 , wherein the thickness of the transparent coating is in the range of 100 nm to 2 mm.