KR20070065858A - Paint for transparent film and transparent film coated substrate - Google Patents

Abstract

Provided are a paint for forming a transparent film, and a transparent film-coated substrate using the paint which has antireflection and excellent adhesive and can be prepared by one step. The paint comprises 0.1-20 wt% of a metal oxide fine particle which is surface-treated with an organic silicon compound represented by R_n SiX_(4-n) and/or a multifunctional acrylate resin having a hydrophobic group and has a surface charge of 5-80 mueq/g; 1-50 wt% of a matrix forming component which comprises an organic silicon compound represented by R_n' SiX_(4-n') or its hydrolyzate, hydrolysis condensate and/or a multifunctional (meth)acrylate resin having a hydrophobic group; and a polar solvent, wherein R is identical to or different from one another and is a C1-C10 unsubstituted or substituted hydrocarbon group; X is a C1-C4 alkoxy group, a silanol group, a halogen atom or H; and n and n' are an integer of 1-3.

Description

Paint for transparent film and transparent film coated substrate

FIG. 1: is a schematic diagram which shows uneven distribution of hydrophobic metal oxide microparticles | fine-particles (A) in a transparent film.

FIG. 2: is a schematic diagram which shows uneven distribution of hydrophobic metal oxide microparticles | fine-particles (A) and hydrophilic metal oxide microparticles | fine-particles (B) in a transparent film.

It is a schematic diagram which shows uneven distribution of hydrophobic metal oxide microparticles (A) and hydrophilic metal oxide (B) in a transparent film.

It is a schematic diagram which shows uneven distribution of hydrophobic metal oxide microparticles | fine-particles (A) and hydrophilic metal oxide microparticles | fine-particles (B) in a transparent film.

Field of technology

The present invention is a coating of one coating material once, and a transparent coating film and a transparent coating film that can be used to form a transparent coating having at least two or more functions, for example, antireflection performance, hard coating function, and the like. It relates to a transparent coating part base material formed using.

Background

It is conventionally known to form a hard coating film on the surface of a substrate in order to improve the scratch resistance of the surface of the substrate such as glass, a plastic sheet, a plastic lens, and the like. It is done. Moreover, in order to mix | blend inorganic particle, such as resin particle or silica, in an organic resin film or an inorganic film, further improving scratch resistance is performed.

In addition, it is known to form an anti-reflection film on the surface of the substrate to prevent reflection of the surface of the substrate such as glass, plastic sheet, plastic lens, etc., for example, by coating, vapor deposition, CVD, etc. A method of forming an antireflection film by forming a film of refractive index material on the surface of a substrate of glass or plastic or by applying a coating liquid containing low refractive index particles such as silica particles to the surface of the substrate (for example, Patent Document 1). (Japanese Patent Application Laid-Open No. 7-133105).

At this time, it is also known to form a high refractive index film containing high refractive index fine particles and the like in the lower layer of the antireflection coating in order to increase the antireflection performance. Moreover, in order to provide antistatic performance and electromagnetic wave shielding performance to a base material, forming the electroconductive film containing electroconductive oxide fine particles, metal fine particles, etc. is also performed. For example, for the purpose of antistatic or antireflection of surfaces of transparent substrates such as display panels such as cathode ray tubes, fluorescent display tubes, and liquid crystal display panels, a transparent film having an antistatic function and an antireflection function is formed on these surfaces. Is done.

In particular, in recent years, such a variety of functional coatings have been laminated and used. For example, a hard coating film is formed on a base material, an electroconductive film or a high refractive index film is formed, and an anti-reflective film is formed.

However, since each film is made of a process of coating, drying, and curing as necessary, a large number of steps are required in forming the multilayer film, and the adhesion between the films is insufficient or there is a problem in productivity and economy.

In addition, the present inventors and the like in Patent Document 2 (Patent No. 2003-12965) disclose a coating liquid containing two different kinds of fine particles having different average particle diameters and conductive particles having a small particle diameter and low refractive index fine particles having a large particle diameter. It has been proposed that a conductive coating having excellent antireflection performance can be formed by one application by using it.

Patent Document 1: Japanese Patent Application Laid-Open No. 7-133105

Patent Document 2: Japanese Patent Laid-Open No. 2003-12965

Problems to be Solved by the Invention

In recent years, in order to simplify the process and to reduce the thickness of the coating itself, a transparent coating having two or more functions is required only by coating the paint once.

Since the coating liquid of the said patent document 2 is a mixture of 2 types of microparticles | fine-particles, only one layer is formed and antireflection performance and antistatic performance are inadequate, adhesiveness to the base materials, such as plastics, is low, and film | membrane strength is insufficient. There was a case to be lost.

Means to solve the problem

The present inventors earnestly examine such a problem, and when a fine particle layer is formed in the coated and formed film, the upper and lower parts are separated completely, the coating can be formed once and a transparent film having two or more functions can be formed. I thought it was.

Therefore, as a result of further investigation, the surface is hydrophobized with a specific organosilicon compound, and the metal oxide particles having a specific surface charge amount are combined with the hydrophobic matrix forming component so that the metal oxide particles are not uniformly dispersed in the transparent film, It has been found that the formation of a layer, that is, the formation of a film having two or more kinds of functions in one film formation, has led to the completion of the present invention.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a transparent film-forming coating material and a transparent coating part base material capable of forming at least two layers having different functions separated up and down by one application. In addition, it is possible to significantly reduce the process for obtaining a transparent film in one coating process, and at the same time, to improve the yield and to provide a transparent film having excellent adhesion.

[1] The surface (A) is surface-treated with an organosilicon compound represented by the following formula (1) and / or a polyfunctional acrylate ester resin having a hydrophobic functional group, and the surface charge amount Q _A is 5 to 80 µeq / metal oxide fine particles (A) in the range of g,

R _n -SiX _{4- n} (1)

Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen, and n is 0 to 3 Integer)

(B) matrix formation comprising a hydrophobic matrix forming component composed of an organosilicon compound represented by the following formula (2) or a hydrolyzate thereof, a hydrolyzed polycondensate and / or a polyfunctional (meth) acrylic acid ester resin having a hydrophobic functional group Ingredients and

R _{n '} -SiX _{4 - n'} (2)

Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen, and n 'is 1 to 3 Is an integer of)

(C) A transparent film-forming paint composed of a polar solvent,

The concentration (C _PA ) of the metal oxide fine particles (A) as a solid content is in the range of 0.1 to 20% by weight, and the concentration (C _M ) as the solid content of the matrix forming component (C) is in the range of 1 to 50% by weight. Transparent film-forming paint.

[2] a hydrophilic matrix composed of a polyfunctional (meth) acrylic acid ester resin having an organic silicon compound represented by the following formula (3) or a hydrolyzate, hydrolyzed polycondensate or a hydrophilic functional group together with a hydrophobic matrix includes a forming component, characterized in that the solid content concentration as a hydrophilic matrix forming component (C _MA) and the solid content concentration as the concentration ratio of the hydrophobic matrix forming component (C _MA) / _(MB C) of (C _MB) in the range of 0.01 to 1 The transparent film formation paint of [1] which is used.

SiX ₄ (3)

(Wherein X is an alkoxy group, silanol group, halogen or hydrogen having 1 to 4 carbon atoms)

[3] The paint for forming a transparent film of [1] or [2], wherein the average particle diameter of the metal oxide fine particles (A) is in the range of 5 to 500 nm.

[4] The surface charge amount (Q _B), the surface charge (Q _B) and the metal oxide fine particles (A) of 25~100 μeq / g further comprises metal oxide fine particles (B) range, and the metal oxide fine particles (B) the surface charge amount (Q _a) of the difference _{(Q B) - (Q a} ) is a transparent film-forming coating material of [1] to [3], characterized in that the range of 20~95 μeq / g.

[5] The paint for forming a transparent film of [1] to [4], wherein the metal oxide fine particles (B) have a concentration (C _PB ) in the range of 0.1 to 20% by weight as solid content.

[6] The paint for forming a transparent film according to [4] or [5], wherein the average particle diameter of the metal oxide fine particles (B) is in a range of 5 to 500 nm.

[7] The hydrophilic functional group is at least one selected from hydroxyl group, amino group, carboxyl group, sulfone group and glycidyl group, and the hydrophobic functional group is selected from (meth) acryloyl group, alkyl group, phenyl group, urethane group and CF ₂ group The coating material for transparent film formation as described in [1] or [2] characterized by the above-mentioned.

[8] The transparent coating part substrate having a transparent coating formed on the substrate,

The transparent film is composed of hydrophobic metal oxide fine particles (A) having a surface charge amount (Q _A ) in the range of 5 to 80 μeq / g and a matrix component,

The metal oxide fine particles (A) form a layer on top of the transparent film, and are localized, and the content (W _PA ) of the metal oxide fine particles (A) in the transparent film is in the range of 0.2 to 90% by weight,

The content (W _M ) of the matrix component is in the range of 10 to 99.8 wt%,

The matrix part is a hydrophobic matrix component selected from a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (4) and / or a polyfunctional (methyl) acrylic acid ester resin having a hydrophobic functional group.

R _n -SiX _{4- n} (4)

(Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen, and n is 0 to 3). Is an integer of)

[9] The matrix component is composed of a hydrophilic matrix component together with a hydrophobic matrix component.

The hydrophilic matrix component is a polyfunctional (meth) acrylic acid ester resin having a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (3) and / or a hydrophilic functional group,

Transparent content of [8], wherein the content ratio (W _MA ) / (W _MB ) of the content (W _MA ) as a solid content of the hydrophilic matrix component and the content (W _MB ) as a solid content of the hydrophobic matrix component is in the range of 0.01 to 1. Coating part base material.

SiX ₄ (3)

(Wherein X is an alkoxy group, silanol group, halogen or hydrogen having 1 to 4 carbon atoms)

[10] The transparent film has a surface charge amount (Q _B ) in the range of 25 to 100 μeq / g, and the surface charge amount (Q _B ) of the metal oxide fine particles ( _B ) and the surface charge amount (Q _A ) of the metal oxide fine particles ( _A ). Further comprises metal oxide fine particles (B) in which the differences (Q _B )-(Q _A ) range from 20 to 95 μeq / g,

[8] or [9], wherein the metal oxide fine particles (B) are localized by forming a layer on the surface of the substrate or dispersed between the layer consisting of the metal oxide fine particles (A) and the surface of the substrate. Part description.

[11] The average particle diameter of the metal oxide fine particles (A) is in the range of 5 to 500 nm, and the average particle diameter of the metal oxide fine particles (B) is in the range of 5 to 500 nm. 10] the transparent coating part base material.

[12] The hydrophilic functional group is at least one selected from hydroxyl group, amino group, carboxyl group and sulfone group, and the hydrophobic functional group is selected from (meth) acryloyl group, alkyl group, phenyl group, urethane group, CF ₂ group or The transparent film part base material of [8]-[11] characterized by two or more types.

EMBODIMENT OF THE INVENTION Hereinafter, the coating material for transparent film formation of this invention is demonstrated concretely.

Paint for forming transparent film

The transparent film-forming paint of the present invention is composed of metal oxide fine particles (A) having a specific surface charge amount, a matrix forming component, and a polar solvent.

Hydrophobic Metal Oxide Fine Particles (A)

The metal oxide fine particles (A) used in the present invention are not particularly limited as long as they have hydrophobicity, and conventionally known hydrophobic metal oxide fine particles can be used, but the surface charge amount (Q _A ) is 5 to 80 μeq / g, moreover 7 to 50 It is preferred that it is in the range of μeq / g. If it is this range, when forming a film in combination with the matrix component demonstrated below, it can be localized in the upper layer.

If the surface charge amount Q _A of the metal oxide fine particles (A) is small because the hydrophobicity is too high, the metal oxide fine particles (A) may aggregate in the paint and may not form a uniform layer on the top of the film.

If the surface charge amount Q _A of the metal oxide fine particles (A) is too high, there is a tendency for the metal oxide fine particles (A) to be dispersed in the film without ubiquitous in the upper layer when forming the film.

As described below, the metal oxide fine particles (A) are surface-treated with an organosilicon compound and / or a resin.

With the metal oxide fine particles may be appropriately selected according to the application, for example, usually a refractive index of 1.45 or less, and further use of fine particles of 1.40 or less As the metal oxide fine particles used in the anti-reflection film, and, specifically, inside the SiO ₂ And fine particles coated with a cavity of SiO ₂ or a metal oxide having conductivity thereon.

The metal oxide fine particles used for the hard coating film include ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ or chain-shaped particles in which these particles are connected in a chain form, or the refractive index described above. And silica-based fine particles of 1.45 or less.

As the metal oxide fine particles used in the high refractive index film, fine particles having a refractive index of 1.60 or more and 1.80 or more are generally used. Specifically, ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ , Antimony-doped tin oxide, tin-doped isodium oxide, tin oxide-doped phosphorus (PTO), and the like.

The metal oxide fine particles used in the conductive film are usually Sb ₂ O ₅ , SnO ₂ , antimony doped tin oxide, tin doped sodium oxide, tin oxide doped phosphorus (PTO) or silica-based fine particles coated on the surface with a conductive material thereof or And silica-based fine particles having a cavity therein.

The metal oxide fine particles (A) are surface-treated with the polyfunctional acrylic acid ester resin in which the said metal oxide fine particles have an organosilicon compound and / or a hydrophobic functional group represented by following formula (1).

R _n -SiX _{4- n} (1)

(Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen, n is an integer of 0 to 3). )

As the organosilicon compound represented by such formula (1), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane , Diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Tris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltrie Oxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrie Cysilane, γ- (β-glycidoxymethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acryloxyoxytriethoxysilane, γ- ( Meta) acryloxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acrylooxypropyl tree Methoxysilane, (gamma)-(meth) acrylooxypropyl triethoxysilane, butyl trimethoxysilane, isobutyl triethoxysilane, hexyl triethoxy silaoctyl triethoxysilane, decyl triethoxysilane, butyl trier Methoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltrie Methoxysilane, perfluorooctylethyltriisopropoxysilane, triple uro Propyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane , γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane and the like.

Polyfunctional acrylic acid ester resins having hydrophobicity include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, Methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1 , 6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, urethane acrylate, and the like.

In the case of using an organosilicon compound, the ratio of the amount to the metal oxide fine particles (weight of the organic silicon compound / metal oxide fine particles) depends on the average particle diameter of the metal oxide fine particles, but is in the range of 0.001 to 2, and more preferably 0.005 to 1.5. desirable.

When using the hydrophobic polyfunctional acrylic acid ester resin, the ratio of the amount (weight of the polyfunctional acrylic acid ester resin having hydrophobicity / weight of the metal oxide fine particles) to the metal oxide fine particles is equal to the average particle diameter of the metal oxide fine particles. Although it depends, it is preferable that it is 0.01-2, Furthermore, it is the range of 0.05-1.5.

Surface treatment with such a weight ratio of an organosilicon compound or a polyfunctional acrylic acid ester resin yields metal oxide fine particles having a predetermined amount of surface charge, resulting in high dispersibility and stability in polar solvents, resulting in a uniform layer on top of the film. Can be formed.

In addition, when the weight ratio is small, the dispersibility and stability in the polar solvent are lowered, the stability of the paint is insufficient, and the film may be whitened when the film is formed. If the weight ratio is too large, the surface charge amount of the metal oxide fine particles (A) is 5 μeq / g or less, and the hydrophobicity is too high. If the metal oxide fine particles (A) are agglomerated in the paint, a uniform layer is not formed on the top of the film. There is.

In the present specification, the arrangement of the metal oxide fine particles (A) on the top of the film means that the metal fine particles exist only on and near the film surface, and the metal oxide fine particles are arranged on the bottom of the film, indicating that the metal fine particles exist only on and around the substrate surface. I say.

In the transparent coating of the present invention, the metal oxide fine particles (A) are unevenly distributed on the upper portion of the transparent coating, but at this time, the metal oxide fine particles (A) may form a multilayer, may form a single layer, or may be dotted on the top. You may do it.

The method for measuring the surface charge amount of the metal oxide fine particles (A) described above is performed by titrating the dispersion of the fine particles using a surface potential titration device (Mutek Co., Ltd. pcd-03) using 0.001 N polydiallyldimethylammonium chloride. The surface charge amount (μeq / g) per unit gram can be obtained.

The average particle diameter of the metal oxide fine particles (A) is preferably in the range of 5 to 500 nm, more preferably 10 to 100 nm.

A small average particle diameter of the metal oxide fine particles (A) is difficult to obtain by itself, and a large average particle diameter of the metal oxide fine particles (A) may not be used as an optical film due to a high base value during film coating. .

The metal oxide fine particles (A) used in the present invention are not particularly limited as long as the surface treatment has been carried out, but is preferably produced by the following method, for example.

In the case of the organosilicon compound, the organosilicon compound described above is added to the alcohol dispersion of the metal oxide fine particles in a predetermined amount, water is added thereto, and acid or alkali is used as a catalyst for hydrolysis of the organosilicon compound, if necessary. It adds and hydrolyzes an organosilicon compound. Or in the case of the polyfunctional acrylic acid ester resin which has hydrophobicity, the above-mentioned hydrophobic polyfunctional acrylic acid ester resin is superposed | polymerized with a thermal or a polymerization initiator, and coat | covers the particle surface of metal oxide fine particle (A). As a polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator which are usually used can be used, Especially a radical polymerization initiator is preferable, For example, polymerization initiators, such as an acetphenol type, a benzoether type, and a titanium type, proper.

The organic solvent dispersion liquid of metal oxide fine particles (A) can be obtained by substituting with an organic solvent. It is preferable to use the polar solvent mentioned below as an organic solvent.

The solid content of the coating is transparent as in the coating composition for the formation of such metal oxide fine particles (A) (C _PA) is in the range of 0.1 to 20% by weight, and further 0.2~15% by weight.

When the concentration of the metal oxide fine particles (A) is small (C _PA ), the amount of particles is small even when unevenly distributed on the top of the film, and thus the antireflection performance and the antistatic performance are insufficient due to the characteristics of the particles (low refractive index or conductivity). There is a case to be done. In addition, even if the concentration (C _PA ) of the metal oxide fine particles (A) is too high, the proportion of particles in the obtained film is too large to substantially form a film in which the metal oxide fine particles are uniformly dispersed throughout the film to provide two or more functions of the present invention. In some cases, no retaining membrane can be obtained.

Metal Oxide Fine Particles (B)

The transparent film-forming paint of the present invention may further contain metal oxide fine particles (B) together with metal oxide fine particles (A).

As the metal oxide fine particles (B), it is preferable to use particles having a less hydrophobicity than the metal oxide fine particles (A) contained simultaneously and a surface charge amount higher than the surface charge amount of the metal oxide fine particles (A). Such metal oxide fine particles form a uniform layer under the film. This also makes it possible to impart additional additional properties to the transparent coating.

The surface charge amount Q _B of the metal oxide fine particles (B) is preferably in the range of 25 to 100 μeq / g, more preferably in the range of 30 to 100 μeq / g. When the surface charge amount Q _{B of} the metal oxide fine particles ( _B ) is low, the metal oxide fine particles (A) and the surface charge amount are close to each other. Therefore, they tend to be mixed with the metal oxide fine particles (A) and located at the top of the film without being ubiquitous at the bottom of the film. Therefore, the effect by the characteristic of a metal oxide fine particle (A), for example, the reflection prevention performance by a low refractive index characteristic may become inadequate. If the surface charge amount Q _B of the metal oxide fine particles (B) is too large, the hydrophobicity is low and the hydrophilicity is approached, so that the metal oxide fine particles (B) may agglomerate in the coating to not form a uniform layer under the film.

Further, the difference (Q _B )-(Q _A ) between the surface charge amount Q _A of the metal oxide fine particles ( _A ) and the surface charge amount Q _B of the metal oxide fine particles (B) is 20 to 95 μeq / g, and furthermore, 25 to It is preferably in the range of 85 μeq / g.

When (Q _B )-(Q _A ) is small, the difference between the surface charge amounts of the metal oxide fine particles (A) and the metal oxide fine particles (B) is small, so that the separation of these fine particles is insufficient, resulting in a film having two or more functions of the present invention. It may not. When (Q _B )-(Q _A ) is large, the film obtained by agglomeration of the metal oxide fine particles (A) and agglomeration of the metal oxide fine particles (B) may whiten, or the adhesion or strength with the substrate may be insufficient.

The metal oxide fine particles (B) are surface-treated with metal oxide fine particles in the same manner as the metal oxide fine particles (A). Usually, as metal oxide microparticles | fine-particles, metal oxide fine particles different from the metal oxide microparticles | fine-particles used for said metal compound microparticles | fine-particles (A) are selected and used according to the objective. Specifically, what is represented by the said metal oxide fine particle (A) is mentioned. In addition, the surface treatment is selected such that the surface charge amount causes a difference in composition (that is, the surface charge amount of the metal oxide fine particles becomes large). For example, a treatment method such as one having higher hydrophilicity or less throughput than that used for the metal oxide fine particles (A) is selected.

It is preferable that the average particle diameter of such metal oxide fine particles (B) is 5-500 nm, Furthermore, it is the range of 10-100 nm. It is difficult to obtain a small average particle diameter by itself, and even if it is too large, the paint stability may become insufficient. Moreover, transparency of the obtained film may fall or the film may whiten.

It is preferable that the density | concentration (C _PB ) as solid content in the coating film for transparent film formation of a metal oxide fine particle (B) is 0.1-20 weight%, Furthermore, it is the range of 0.2-15 weight%. When the concentration (C _PB ) of the metal oxide fine particles (B) is low, the amount of particles is small even when the metal oxide fine particles (B) are unevenly distributed in the lower part of the film, so that the effect of adding the metal oxide fine particles (B) (such as high refractive index and conductivity, Moreover, the antireflection performance improvement effect, antistatic performance, etc.) may become insufficient. When the concentration (C _PB ) of the metal oxide fine particles (B) is too large, the proportion of the particles in the obtained film is too large to be mixed with the metal oxide fine particles (A) or to be a film in which the metal oxide fine particles (B) are dispersed throughout the film. In some cases, a membrane having two or more functions of the invention cannot be obtained.

Matrix forming components

The present invention particularly includes a hydrophobic matrix forming component composed of an organosilicon compound represented by the following formula (2) or a hydrolyzate, hydrolyzed polycondensate or a polyfunctional (meth) acrylic acid ester resin having a hydrophobic functional group as a matrix forming component. A matrix forming component is used.

As the hydrophobic silicone-based (sol-gel-based) matrix forming component, an organosilicon compound represented by the following formula (2), hydrolyzate thereof, or hydrolyzed polycondensate thereof is used.

R _{n '} -SiX _{4 - n'} (2)

(Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen, and n 'is 1 to 1). Is an integer of 3)

Specifically, the thing except n which is 0 among the compounds represented by said Formula (2) is mentioned. Among them, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, hydrolyzates and hydrolyzed polycondensates thereof can be suitably used.

Examples of the hydrophobic organic resin matrix-forming component include polyfunctional (meth) acrylic acid ester resins having hydrophobic functional groups such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, and CF ₂ group, and specifically, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl Methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanedioldi Methacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, urethane acryl Site and the like and mixtures thereof.

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

It is preferable that the matrix formation component used for this invention contains a hydrophilic matrix formation component simultaneously with a hydrophobic matrix formation component.

The hydrophilic matrix forming component includes an organosilicon compound or a hydrolyzate thereof, a hydrolyzed polycondensate, or a hydrophilic matrix forming component made of a polyfunctional (meth) acrylic acid ester resin having a hydrophilic functional group.

SiX ₄ (3)

(Wherein X is an alkoxy group, silanol group, halogen or hydrogen having 1 to 4 carbon atoms)

Specific examples of the organosilicon compound represented by formula (3) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, hydrolyzate thereof, hydrolyzed polycondensate, and the like. Can be used as appropriate.

Examples of the hydrophilic organic resin matrix-forming component include polyfunctional (meth) acrylic acid ester resins having hydrophilic functional groups such as hydroxyl group (OH group), amino group, carboxyl group and sulfone group, and specifically, hydroxyl group (OH group), amino group, Pentaerythritol triacrylate having hydrophilic functional groups such as carboxyl group and sulfone group, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, and the like. In addition to diethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, methoxytriethylene glycol dimethacrylate, butoxydiethylene glycol methacrylate and these And mixtures thereof.

When the hydrophilic matrix forming component is used in combination with the hydrophobic matrix forming component, separation of the metal oxide fine particles (A) and the metal oxide fine particles (B) becomes easy, and a film divided into two layers can be easily obtained.

The concentration ratio (C _MA ) / (C _MB ) of the concentration (C _MA ) as the solid content of the hydrophilic matrix-forming component and the concentration (C _MB ) as the solid content of the hydrophobic matrix-forming component is in the range of 0.01 to 1, moreover, in the range of 0.05 to 0.5. It is preferable.

When the concentration ratio (C _MA ) / (C _MB ) is small, the hydrophilic matrix forming component is small and substantially closes to the hydrophobic matrix forming component, so that the metal oxide fine particles (A) (top) and the metal oxide fine particles (B) (bottom) Separation effect becomes insufficient. When the concentration ratio (C _MA ) / (C _MB ) exceeds 1, the metal oxide fine particles (B) having a high amount of surface charge with a large number of hydrophilic matrix forming components may not be localized in the lower layer.

Polar solvent

As a polar solvent used for this invention, the solvent which can melt | dissolve and easily volatilize said polyfunctional (meth) acrylic acid ester resin is used suitably.

Specifically water; Alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofuryl alcohol, ethylene glycol, hexylene glycol and isopropyl glycol; Esters such as methyl acetate, ethyl acetate and butyl acetate; Ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl ether; Ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, and acetoacetic acid ester, etc. are mentioned. These may be used independently, or may mix and use 2 or more types. Methyl vertical solver, ethyl vertical solver, butyl vertical solver, toluene, cyclohexanone, isophorone and the like can also be used.

The above-mentioned metal oxide fine particles (A), the metal oxide fine particles (B) to be used as necessary, the matrix forming component and the polar solvent are suitably mixed so as to have a desired amount of ratio, so that the paint for forming a transparent film of the present invention can be produced. .

This transparent film-forming coating material is applied to a substrate by known methods such as dipping, spraying, spina, roll coating, bar coating, gravure printing, microgravure printing, and the like, and dried, and irradiated with ultraviolet rays, It can harden | cure by a conventional method, such as heat processing, and can form a transparent film.

When the matrix forming component is an organosilicon compound, an acid or an alkali may be included as the hydrolysis catalyst. Moreover, when a matrix formation component contains polyfunctional (meth) acrylic acid ester resin, you may contain a polymerization initiator. As a polymerization initiator, if it is well-known, it will use without a restriction | limiting and specifically, the same thing as what was used for the said surface treatment is mentioned.

Transparent coating part base material

The substrate to which the transparent coating of the present invention is applied is a transparent coating part substrate in which a transparent coating is formed on the substrate. The hydrophobic metal oxide fine particles (A) and the matrix component having a surface charge amount (Q _A ) of the transparent coating in the range of 5 to 80 μeq / g. Wherein the metal oxide particles (A) are localized by forming a layer on top of the transparent film, and the content (W _PA ) of the metal oxide fine particles (A) in the transparent film is in the range of 0.2 to 90% by weight, It is characterized by the content (W _M ) of 10 to 99.8 weight%. Moreover, it corresponds to the ratio of the quantity of each component in a transparent film, and the ratio of the quantity in a coating liquid.

materials

As a base material used for this invention, a conventionally well-known thing can be used without a restriction | limiting in particular, Glass, a polycarbonate, acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC), cyclopolyolefin, norbornene, etc. Plastic panels, plastic panels, etc. are mentioned. Among these, a resin base material can be used suitably. Moreover, the coating part base material in which the other film was formed on such a base material can also be used.

Metal Oxide Fine Particles (A)

As metal oxide fine particles (A), the same thing as the above-mentioned metal oxide fine particles (A) is used. Transparent content (W _PA) is 0.2~90% by weight of the metal oxide fine particles (A) in the coating film, and further preferably in the range of 5 to 80% by weight.

When the content (W _PA ) of the metal oxide fine particles (A) is small, since the amount of particles is small even when localized on the top of the film, antireflection performance, antistatic performance, etc. based on characteristics of particles such as low refractive index, high refractive index, and conductivity The function of may not be fully expressed. In addition, even if the content (W _PA ) of the metal oxide fine particles (A) is too large, the metal oxide fine particles (A) are substantially present throughout, which is not a transparent coating having two or more functions of the present invention, and the adhesion to the substrate is insufficient. There may be a case.

Hydrophobic metal oxide microparticles | fine-particles (A) are transparently formed in a transparent film in the transparent film, and are unevenly distributed. Such a state is schematically illustrated in FIG. 1.

Metal Oxide Fine Particles (B)

The transparent coating on the base of the transparent coating part of the present invention may further contain metal oxide fine particles (B). The metal oxide fine particles (B) are localized by forming a layer in the film or are dispersed between the layer composed of the metal oxide fine particles (A) and the substrate surface. Such a state is shown typically in FIG. 2, 3, 4. FIG. FIG. 2 is an example which is unevenly distributed in the lower layer of the transparent film, FIG. 3 is an example which is unevenly distributed in the layer immediately below the metal oxide fine particles (A) layer, and FIG. 4 is unevenly distributed under the metal oxide fine particles (A) layer. It is shown to be dispersed without.

As metal oxide fine particles (B), the same thing as the above-mentioned metal oxide fine particles (B) can be used.

The content (W _PB ) of the metal oxide fine particles (B) in the transparent coating is preferably in the range of 0.1 to 40% by weight, more preferably 0.2 to 30% by weight. When the content (W _PB ) of the metal oxide fine particles (B) is small, the amount of particles is small even when localized at the bottom of the film, so that the characteristics of the particles (conductivity, high refractive index, low refractive index, improved adhesion to the substrate, etc.) can be sufficiently expressed. You may not be able to. When the content (W _PB ) of the metal oxide fine particles (B) is too large, it may be in a mixed state with the metal oxide fine particles (A) arranged at the top, so that a transparent coating having two or more functions of the present invention may not be obtained.

Matrix components

As the matrix component, a silicone (sol gel) matrix component, an organic resin matrix component, or the like can be used.

As a silicone matrix component, the hydrolyzed polycondensate of the organosilicon compound similar to the said Formula (2) can be used suitably. Among these, hydrolyzed polycondensates of 3,3,3-trifluoropropyltrimethoxysilane and methyl-3,3,3-trifluoropropyldimethoxysilane are suitable.

Moreover, as an organic resin matrix component, well-known thermosetting resin, a thermoplastic resin, an electron beam curing resin, etc. are mentioned as resin for coatings.

Specifically, the polyfunctional (meth) acrylic acid ester resin having a hydrophobic functional group is preferable. Examples of the hydrophobic organic resin matrix component include polyfunctional (meth) acrylic acid ester resins having hydrophobic functional groups such as vinyl groups, urethane groups, epoxy groups, (meth) acryloyl groups, and CF ₂ groups. The same thing can be mentioned.

As such resins, for example, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluorine resins, vinyl acetate resins, silicone rubbers, etc. And thermosetting resins such as thermoplastic resins, urethane resins, melamine resins, silicon resins, butyral resins, reactive silicone resins, phenol resins, epoxy resins, unsaturated polyester resins, thermosetting acrylic resins and ultraviolet curing acrylic resins. Moreover, 2 or more types of copolymers and modified bodies of these resin may be sufficient.

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

It is preferable that the matrix component used for this invention consists of a hydrophilic matrix component and a hydrophobic matrix component. It is suitable from the viewpoint of the dispersibility and the ubiquitous property of metal oxide fine particle (B) especially containing metal oxide fine particle (B).

When using a silicone matrix component, it is suitable from the viewpoint of affinity to use together with a hydrophilic silicone-based (sol-gel type) matrix component, and the hydrolysis polycondensation agent of the organosilicon compound represented by following formula (3) is used.

R _n -SiX _{4- n} (3)

(Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen, and n is an integer of 0.) )

Specifically, hydrolyzed polycondensates of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and methyltrimethoxysilane can be suitably used.

Moreover, as a hydrophilic organic resin matrix component, the polyfunctional (meth) acrylic acid ester resin which has hydrophilic functional groups, such as a hydroxyl group (OH group), an amino group, a carboxyl group, and a sulfone group, is mentioned, Specifically, the above-mentioned thing is mentioned.

The content ratio _{(W MA) / (W MB} ) having a solid content as the content of the hydrophilic matrix composition (W _MA) with a solid content as the content of the hydrophobic matrix components (W _MB) is preferably in the range of 0.01 to 1, and further 0.05 to 0.5 .

When (W _MA ) / (W _MB ) is small, the hydrophilic matrix forming component is small, and the metal oxide fine particles (A) (top) and the metal oxide fine particles (B) (bottom) are separated substantially in proximity to the hydrophobic matrix forming component. The effect becomes insufficient. Moreover, even if (W _MA ) / (W _MB ) is too large, the hydrophilic matrix forming component may become large, and the metal oxide fine particles (B) having a high surface charge amount may not be localized in the lower layer.

The content of the hydrophilic transparent matrix components in the coating film (W _MA) is preferably in the range of 10~99.8% by weight, and further 20~99.5% by weight. When the content (W _MA ) of the matrix component in the transparent film is small, the proportion of particles in the film becomes too large to substantially form a film in which metal oxide fine particles are uniformly dispersed throughout the film, thereby obtaining a film having two or more functions of the present invention. You may not lose.

Even if the content (W _MA ) of the hydrophilic matrix component in the transparent film is too large, the amount of the particles is small, so that the antireflection performance, antistatic performance, etc., due to the characteristics (low refractive index, conductivity, etc.) of the particles may be insufficient.

Although the film thickness of the transparent film of this invention changes with a use, it is preferable that it is usually the range of 30 nm-12 micrometers, Furthermore, 70 nm-10 micrometers. If two or more kinds of functions are provided in the first floor, this thickness is required.

In addition, when the film thickness of the transparent film is less than 30 nm, it is difficult to form a transparent film that is substantially divided into two layers. If the film thickness exceeds 12 μm, cracks are generated in the transparent film or curled on a substrate such as plastic. (Curvature or warpage) may occur.

Preferable embodiments of the transparent coating are as follows.

(1) When the upper part is a low refractive index or anti-glare film, and the lower part is a hard coating film, a high refractive index film, a conductive film, or the like, the film thickness of the antireflection film portion is in the range of 40 nm to 10 μm, and more preferably 60 nm to 8 μm. It is preferable.

In the case where the antireflection film is thin, the optical film thickness deviating from the Planel principle may be obtained and sufficient antireflection performance may not be obtained. Even if the film thickness of the antireflection film is too thick, curling may occur depending on the type of base, for example, in the case of a thin PET film due to shrinkage of the film.

In this case, the refractive index of the lower film is preferably in the range of 1.48 to 2.20, and the refractive index of the upper antireflection film is usually in the range of 1.45 or less.

At this time, the transparent film has low reflectivity and anti-glare property, and if the lower layer is a high refractive index film, it has a high anti-reflection performance. Also, if the lower layer contains hydrophobic metal oxide fine particles (B) and antimony pentoxide particles, it is charged with high hard coating performance. In the case of containing ATO or ITO particles, it has anti-static performance and heat shielding at the same time, and in the case of containing titanium oxide, it has ultraviolet absorbing performance.

(2) When used as a conductive film The film thickness of the conductive film portion is preferably in the range of 30 nm to 10 m and more preferably 60 nm to 8 m. When the thickness of the conductive film portion is less than 30 nm, the formation of another separated film having different functions is difficult, and sufficient conductive paths are not formed, which may result in insufficient conductivity.

When the film thickness of the conductive film exceeds 10 m, the film shrinks, so curling may occur in the case of a thin plastic film or the like.

It is preferable that the surface resistance value of the transparent film which has such a conductive film part is a range of 10 <^3> -10 <^13> Pa / square.

When the upper portion is a conductive film, except for the case of (1) above, the lower portion has hard coating property even when no particles are present.

In addition, when the lower part contains titanium oxide particles as the hydrophobic metal oxide fine particles (B), it has ultraviolet absorption performance, and when it contains low refractive index fine particles, it has low dielectric constant.

(3) When used as a high refractive index film, it is preferable that the film thickness of the high refractive index film portion is in the range of 40 nm to 10 m and more preferably 60 nm to 8 m.

When the film thickness of the high refractive index film portion is thin, it is difficult to form separate films having different functions, and in some cases, a layer having a desired refractive index may not be formed depending on the refractive index of the particles or the matrix having different functions. In addition, when the film thickness of the high refractive index film portion is thick, the film shrinks, so curling may occur in the case of a thin plastic film or the like.

It is preferable that the refractive index of the high refractive index film portion is usually in the range of 1.52 to 2.00. In the case where the upper portion is a high refractive index film, the lower portion has hard coating property even when no particles are present.

In addition, when the lower part contains ATO and ITO as the hydrophobic metal oxide fine particles (B), the lower part has conductivity, antistatic performance, and infrared shielding performance, while antimony performance and hard coating are included when antimony pentoxide and phosphorus doped tin oxide are included. In the case of containing low refractive index silica particles or hollow silica fine particles, it has high hard coating performance and low dielectric constant performance.

The transparent coating part base material of this invention can be manufactured by apply | coating the said coating film for transparent film formation on a base material, drying, and hardening. As a coating method, the paint is applied and dried on a substrate by well-known methods such as dipping, spraying, spina, roll coating, bar coating, gravure printing, and micro gravure printing. After the heat treatment, the ultraviolet curable resin can be formed by irradiating with ultraviolet light at about 400 mJ / cm 2 to cure it.

The transparent coating part substrate of the present invention may be provided with another coating different from the transparent coating between the substrate and the transparent coating and / or on the transparent coating. Other coatings may be a conventionally known hard coating film, high refractive index film, conductive film, low refractive film, anti-glare film, infrared shielding film, ultraviolet shielding film, a transparent film having a hard coating function of the present invention, a high refractive index transparent film, and conductive material. A transparent film or the like may be used.

(Example)

Hereinafter, although an Example demonstrates this invention, this invention is not limited by these Examples.

(Example 1)

Production of Transparent Film-forming Paint (A-1)

As the low refractive index component, a silica-based hollow fine particle dispersion sol (manufactured by Catalytic Co., Ltd .: Sluria 1420, an average particle diameter of 60 nm, a concentration of 20.5 wt%, a dispersion medium: isopropanol, and a particle refractive index of 1.30) was used. 10 g of perfluorooctylethyltriethoxysilane (100% of AY43-158E manufactured by Higashi Red Dow Corning) was mixed with 100 g of this sol, and 10 g of ultrapure water was added thereto, followed by stirring at 40 ° C. for 5 hours for surface treatment. A hollow particulate dispersion sol was obtained (solid content 19.3 wt%).

It was 8.3 microeq / g when the surface charge quantity of this surface-treated silica-type hollow fine particle dispersion sol was measured. 15.5 g of this surface-treated silica-based hollow fine particle dispersion sol and 30 g of hexaerythritol tripentaacrylate (Japan Kayaku Co., Ltd.) (KAYARAD DPHA) are dissolved with a photoinitiator (Irugacua 184, manufactured by Tiba Sprasha Co., Ltd.) and IPA. 0.42 g of solid content concentration 10%) and 54.08 g of a 1/1 (weight ratio) mixed solvent of isopropanol and methyl isobutyl kenone were sufficiently mixed to prepare a coating liquid (A-1) for forming a transparent film.

Transparency Film  Preparation of the base material (1)

The coating liquid (A-1) for forming a transparent coating part was applied to a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflectance 5.1%) by bar coating, and dried at 70 ° C. for 1 minute. A high pressure mercury lamp (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coating part substrate (1). At this time, the film thickness of the transparent film was 5 micrometers. A part of the transparent film was cut vertically in the vertical direction and the cross section was observed by a transmission electron microscope. As a result, silica-based hollow fine particles formed a 100 nm thick layer on the upper part, and the presence of particles was not confirmed only by the matrix on the lower part.

The surface resistance value, total light transmittance, haze, and the reflectance of the light of wavelength 550nm of the obtained transparent film part base material 1 were measured. The results are shown in Table 1.

The surface resistance was measured by a surface resistance meter (LORESTA manufactured by Samreung Petrochemical Co., Ltd.), and the total light transmittance and the haze were measured by a haze meter (NDH 2000 manufactured by Nippon Color Corporation). 55) respectively.

In addition, anti-glare property, adhesiveness, pencil hardness was evaluated by the following method and evaluation criteria and the results are shown in Table 1.

[Anti-glare]

Anti-reflective coating of the anti-reflective coating part substrate with hard coating function 1 Apply the back side of the substrate evenly with black spray, and visually check the degree of fluorescent light shining 2 m away from the fluorescent lamp of 30 W. Was evaluated. The results are shown in Table 1.

Fluorescent light is not visible at all: ◎

Fluorescent light slightly visible: ○

Fluorescent light is visible, but the outline is blurry: △

Fluorescent light is clearly visible: ×

[Adhesiveness]

On the surface of the anti-reflective coating substrate 1 to which the hard coating function was applied, 11 parallel scratches were made with a knife at intervals of 1 mm in width to form 100 grids, and then the cellophane tape was adhered thereto and then the cellophane tape was peeled off. Adhesiveness was evaluated by classifying the number of lattice | surfaces which remain | survived without peeling of a film | membrane in the following four steps. The results are shown in Table 1.

Number of remaining grids: ◎

Number of remaining grids 90-99: ○

Number of remaining grids 85 to 89: △

84 or less remaining grids: ×

[Pencil hardness]

It measured by the pencil hardness tester according to JIS-K-5400.

(Example 2)

Production of Transparent Coating Film (A-2)

As the low refractive index component, a silica-based hollow fine particle dispersion sol (manufactured by Catalytic Co., Ltd .: Sluria 1420, an average particle diameter of 60 nm, a concentration of 20.5 wt%, a dispersion medium: isopropanol, and a particle refractive index of 1.30) was used. 7.11 g of ethyl acetate (28.8% ethyl silicate 28 SiO ₂ component from Tama Chemical) was mixed with 100 g of this sol, 10 g of ultrapure water was added, and stirred at 40 ° C. for 5 hours to obtain a silica-based hollow particulate dispersion sol. (19.3 weight percent solids). It was 18.3 microeq / g when the surface charge quantity of this surface-treated silica-type hollow fine particle dispersion sol was measured. 15.5 g of this surface-treated silica-based hollow fine particle dispersion sol, pentaerythritol triacetate (CO-3: PE-3A), diethylaminoethyl methacrylate (Co., Ltd .: Light ester DE ) 3 g of a photoinitiator (Irugacua 184, manufactured by Tibasphariti Co., Ltd., dissolved in IPA, solid content concentration 10%) 0.42 g and 54.08 g of a 1/1 (weight ratio) mixed solvent of isopropanol and methyl isobutyl ketone It mixed and manufactured the coating liquid (A-2) for transparent film formation.

Transparency Film  Preparation of the base material (2)

The coating liquid (A-2) for transparent film formation was applied to a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflectance 5.1%) by bar coating, dried at 70 ° C. for 1 minute, and then A mercury lamp (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent film base substrate (2). At this time, the film thickness was 5 μm. A part of the transparent film was cut vertically in the vertical direction and the cross section was observed by a transmission electron microscope. As a result, silica-based hollow fine particles formed a 100 nm thick layer on the upper part, and the presence of particles was not confirmed only by the matrix on the lower part.

The surface resistance value, total light transmittance, haze, reflectance, anti-glare property, adhesiveness, and pencil hardness of the light having a wavelength of 550 nm of the obtained transparent coating part base material 2 were measured, and the result is shown in Table 1.

(Example 3)

Production of Transparent Coating Film (A-3)

As the low refractive index component, a silica-based hollow fine particle dispersion sol (manufactured by Catalytic Co., Ltd .: Sluria 1420-120, an average particle diameter of 120 nm, a concentration of 20.5 wt%, a dispersion medium: isopropanol, and a particle refractive index of 1.20) was used. 7.11 g of ethyl acetate (28.8% of ethyl silicate 28 SiO ₂ component) was mixed with 100 g of this sol, 10 g of ultrapure water was added, and stirred at 40 ° C. for 5 hours to obtain a silica-based hollow particulate dispersion sol. (19.3 weight percent solids). It was 15.3 microeq / g when the surface charge quantity of this surface-treated silica type microparticles | fine-particles dispersion sol was measured. 15.5 g of this surface-treated silica-based hollow particulate dispersion sol, 24 g of perfluoroethyl acrylate (FA-108), and diethylaminoethyl methacrylate (Co., Ltd .: Light) 0.42 g of photoinitiator (Irugacua 184, manufactured by Tibasphariti Co., Ltd., IPA, solid content concentration: 10%) in 3 g of ester DE) and 57.08 g of a 1/1 (weight ratio) mixed solvent of isopropanol and methyl isobutyl ketone The mixture was sufficiently mixed to prepare a transparent film-forming coating material (A-3).

Transparency Film  Preparation of the Substrate (3)

The coating film for forming a transparent film (A-3) was applied to a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflectance 5.1%) by bar coating, dried at 70 ° C. for 1 minute, and then A mercury lamp (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent film base substrate (3). At this time, the film thickness was 5 μm. A part of the transparent film was vertically cut vertically and the cross section was observed by a transmission electron microscope. As a result, the hollow hollow particles formed a 120 nm thick layer on the upper part, and the presence of the particles was not confirmed only by the matrix on the lower part.

The surface resistance value, total light transmittance, haze, reflectance, anti-glare property, adhesiveness, and pencil hardness of the light of wavelength 550 nm of the obtained transparent film part base material 3 were measured, and the result is shown in Table 1.

(Example 4)

Production of Transparent Film-forming Paint (A-4)

Antimony pentoxide microparticles | fine-particles dispersing sol (The Catalytic Co., Ltd. make: ELCOM V-4560, the average particle diameter of 20 nm, concentration 30.5 weight%, a dispersion medium: isopropanol, the particle refractive index 1.60) was used. To 100 g of this sol, 1.88 g of γ-methacrylooxypropyltrimethoxysilane (81.2% of KBM-503 SiO ₂ component manufactured by Shinwol Silicon Co., Ltd.) was mixed, 10 g of ultrapure water was added, and the mixture was stirred at 40 ° C. for 5 hours for surface treatment. One antimony pentoxide fine particle dispersion sol was obtained (solid content 28.6 wt%). It was 45.3 microeq / g when the surface charge quantity of this surface-treated antimony pentoxide microparticle dispersion sol was measured. 17.48 g of this surface-treated antimony pentoxide fine particle sol, 22.5 g of dihexaerythritol triacetate (DEP-6A), and an acrylate having a hydroxyl group (CongHong Chemical Co., Ltd .: MMH-40 propylene glycol mono Photoinitiator (Irugaqua 184, manufactured by Tivasphariti Co., Ltd., IPA dissolved in 6.25 g of methyl ether dispersed solid content 40%), 0.42 g of solid content concentration 10%) and 1/1 (weight ratio) of isopropanol and methyl isobutyl ketone 53.35 g of the mixed solvent were sufficiently mixed to prepare a transparent film-forming coating material (A-4).

Preparation of antireflection coating liquid (A-4R)

As the low refractive index component, a silica-based hollow fine particle dispersion sol (manufactured by Catalytic Co., Ltd .: Sluria 1420, an average particle diameter of 60 nm, a concentration of 20.5 wt%, a dispersion medium: isopropanol, and a particle refractive index of 1.30) was used. 33 g of a dispersion obtained by diluting this sol to 5% by weight of solid content with isopropanol, 1.54 g of ultraviolet curable resin (manufactured by Nippon Ink, Co., Ltd .: Unidyk 17-824-9, solid content of 78.9%), and photoinitiator (Tiba's spray) A coating solution for forming an anti-reflection film by sufficiently mixing 0.42 g of Irugaquaa 184 manufactured by T Co., IPA and a solid content concentration of 10%) and 65.46 g of a 1/1 (weight ratio) mixed solvent of isopropanol and butyl vertical solver (A -4R) was prepared.

Transparency Film  Preparation of the Substrate (4-1)

The transparent coating film (A-4) was applied to a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflectance 5.1%) with a bar coating, and dried at 70 ° C. for 1 minute, followed by high pressure mercury lamp. (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coating part base material (4-1). At this time, the film thickness was 5 μm. A part of the transparent film was vertically cut vertically and the cross section was observed with a transmission electron microscope. As a result, antimony pentoxide fine particles formed a 150 nm thick layer on the upper part, and the presence of the particles was not confirmed only by the matrix on the lower part.

The surface resistance value, total light transmittance, haze, reflectance, anti-glare property, adhesiveness, and pencil hardness of the light having a wavelength of 550 nm of the obtained transparent coating part base material 4-1 were measured, and the results are shown in Table 1.

Transparency Film  Preparation of the Substrate (4-2)

Apply the anti-reflection film-forming coating liquid (A-4R) on the transparent film base material 4-1 by bar coating, and dry at 70 ° C. for 1 minute, and then irradiate and cure the high-pressure mercury lamp (80 W / cm) for 1 minute. The transparent coating part base material (4-2) was produced. At this time, the film thickness of the antireflection film was 100 nm.

The surface resistance value, total light transmittance, haze, reflectance, anti-glare property, adhesiveness, and pencil hardness of the light having a wavelength of 550 nm of the obtained transparent coating part base material (4-2) were measured, and the results are shown in Table 1.

(Example 5)

Production of Transparent Film-forming Paint (A-5)

As the high refractive index particles, titania fine particle dispersion sol (manufactured by Catalytic Industries, Ltd .: OPTLAK 1137Z, average particle diameter 20 nm, concentration 30.5 wt%, dispersion medium: methanol, particle refractive index 2.10) was used. To 100 g of this sol, 1.86 g of γ-acrylooxypropyltrimethoxysilane (81.9% of KBM-503 SiO ₂ component manufactured by Shinwol Silicon Co., Ltd.) was mixed, 10 g of ultrapure water was added, and the mixture was stirred at 40 ° C. for 5 hours for surface treatment. Titania fine particle dispersion sol was obtained (solid content 28.6 weight%). It was 19.5 microeq / g when the surface charge quantity of this surface-treated titania fine particle dispersion sol was measured.

17.48 g of this surface-treated titania fine particle sol, 22.5 g of dihexaerythritol triacetate (DEP-6A), and an acrylate having a hydroxyl group (Dong-Gong Chemical Co., Ltd .: MMH-40 propylene glycol monomethyl 0.42 g of photoinitiator (Irugaqua 184, manufactured by Tibasphariti Co., Ltd., IPA, solid content concentration of 10%) and 1/1 (weight ratio) of isopropanol and methyl isobutyl ketone were mixed in 6.25 g of ether dispersed solid content 40%) 53.35 g of the solvent was sufficiently mixed to prepare a transparent film-forming coating material (A-5).

Transparency Film  Preparation of the Substrate (5-1)

A transparent coating film (A-5) was applied to a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflectance 5.1%) with a bar coating, and dried at 70 ° C. for 1 minute, followed by high pressure mercury lamp. (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coating part substrate (5-1). At this time, the film thickness was 5 μm. A part of the transparent film was vertically cut vertically and the cross section was observed by a transmission electron microscope. As a result, titania particles formed a layer of 80 nm in thickness on the upper part, and the presence of particles was not confirmed only in the matrix on the lower part.

The surface resistance value, total light transmittance, haze, reflectance, anti-glare property, adhesiveness, and pencil hardness of the light having a wavelength of 550 nm of the obtained transparent coating part base material 5-1 were measured, and the results are shown in Table 1.

Transparency Film  Preparation of the Substrate (5-2)

The anti-reflection film-forming coating liquid (A-4R) prepared in the same manner as in Example 4 was applied on the transparent coating part substrate 5-1 by bar coating, and dried at 70 ° C. for 1 minute, followed by a high-pressure mercury lamp (80 W). / cm) was irradiated for 1 minute and cured to prepare a transparent coating part substrate (5-2). At this time, the film thickness of the antireflection film was 100 nm.

The surface resistance value, total light transmittance, haze, reflectance, anti-glare property, adhesiveness, and pencil hardness of the light having a wavelength of 550 nm of the obtained transparent coating part base material 5-2 were measured, and the results are shown in Table 1.

(Example 6)

Production of Transparent Film-forming Paint (A-6)

As a low refractive index component, a silica-based hollow fine particle dispersion sol (manufactured by Catalytic Co., Ltd .: Sluria 1420, an average particle diameter of 60 nm, a concentration of 20.5 wt%, a dispersion medium: isopropanol, and a particle refractive index of 1.30) was used. 10 g of perfluorooctylethyltriethoxysilane (100% of AY43-158E manufactured by Higashi Red Dow Corning) was mixed with 100 g of this sol, and 10 g of ultrapure water was added, followed by stirring at 40 ° C. for 5 hours to obtain a silica-based hollow surface. A fine particle dispersion sol was obtained (solid content 19.3 wt%). It was 8.3 microeq / g when the surface charge quantity of this surface-treated silica-type hollow fine particle dispersion sol was measured. As the antistatic high refractive index component, ATO fine particle dispersing sol (manufactured by Catalyst Industries, Ltd .: ELCOM V-3501, average particle diameter 8 nm, concentration: 19.3 wt%, dispersion medium: ethanol, fine particle refractive index 1.75) was used. 100 g of this sol was mixed with 1.26 g of gamma -acrylooxypropyltrimethoxysilane (81.2% of KBM-5103 SiO ₂ component manufactured by Shinwol Silicon Co., Ltd.), 10 g of ultrapure water was added, and the mixture was stirred at 40 ° C. for 5 hours for surface treatment. ATO fine particle dispersion sol was obtained (solid content 19.3 weight%). It was 35.8 microeq / g when the surface charge quantity of this surface-treated ATO fine particle dispersion sol was measured. 15.5 g of this surface-treated silica-based hollow fine particle dispersion sol, 31.3 g of surface-treated ATO fine particle dispersion sol, and 27 g of hexaerythritol tripenta acrylate (Japan Kayaku Co., Ltd.) (KAYARAD DPHA) were used as a photoinitiator ) Irugaquaa 184, dissolved in IPA, solid concentration 10%) 0.35 g and 26.05 g of 1/1 (weight ratio) mixed solvent of isopropanol and methyl isobutyl ketone are sufficiently mixed to form a transparent film (A-6) Was prepared.

Transparency Film  Preparation of the Substrate 6

The transparent coating film (A-6) was applied to a TAC film (thickness 80 μm, refractive index 1.48, substrate transmittance 88.0%, haze 0.0%, reflectance 4.8%) by bar coating, dried at 70 ° C. for 1 minute, and then pressurized with a high pressure mercury lamp. (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coating part substrate (6). At this time, the film thickness was 5 μm. A part of the transparent film was cut vertically in the vertical direction and the cross section was observed by a transmission electron microscope. As a result, silica-based hollow fine particles formed a 100 nm thick layer on the top, and the ATO fine particles in the matrix as shown in FIG. As existed.

The surface resistance value, total light transmittance, haze of the obtained transparent film part base material 6, the reflectance, anti-glare property, adhesiveness, and pencil hardness of the light of wavelength 550nm were measured, and the result is shown in Table 1.

(Example 7)

Production of Transparent Coating Film (A-7)

As the low refractive index component, a silica-based hollow fine particle dispersion sol (manufactured by Catalytic Co., Ltd .: Sluria 1420, an average particle diameter of 60 nm, a concentration of 20.5 wt%, a dispersion medium: isopropanol, and a particle refractive index of 1.30) was used. 10 g of tridecyl methacrylate (light ester TD manufactured by Co., Ltd.) was mixed with 100 g of this sol, and stirred at 50 ° C. for 24 hours to obtain a silica-based hollow particulate dispersion sol (solid content 27.7 wt%). It was 5.3 microeq / g when the surface charge quantity of this surface-treated silica-type hollow fine particle dispersion sol was measured. An antimony pentoxide fine particle dispersion sol (catalytically manufactured by ELCOM V-4560, an average particle diameter of 20 nm, a concentration of 30.5% by weight, a dispersion medium: isopropanol, and a fine particle refractive index of 1.60) was used as an antistatic high refractive index component. 1.44 g (γ-glycidoxypropyltrimethoxysilane, 86.8% of AY43-026 SiO ₂ component manufactured by Higashi Red Dow Coating) was mixed with 100 g of an isol diluted to 20.5% with isopropanol, and 10 g of ultrapure water was added thereto and 40 ° C. The antimony pentoxide microparticles | fine-particles dispersion sol which surface-stirred and stirred for 5 hours was obtained (solid content 19.3 weight%). It was 35.3 microeq / g when the surface charge quantity of this surface-treated antimony pentoxide microparticle dispersion sol was measured.

10.8 g of this surface-treated silica-based hollow fine particle dispersion sol, 30 g of surface-treated ATO fine particle dispersion sol, and 27 g of hexaerythritol tripentacacrylate (Now Chemical Co., Ltd .: KAYARAD DPHA) were used as a photoinitiator (TIBAS SPARITY) ) Irugaquaa 184, dissolved in IPA, solid content concentration 10%) 0.35 g and 31.9 g of 1/1 (weight ratio) mixed solvent of isopropanol and methyl isobutyl ketone are sufficiently mixed to form a transparent film (A-7) Was prepared.

Transparency Film  Preparation of the Substrate 7

A transparent coating film (A-7) was applied to a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflectance 5.1%) by bar coating, and dried at 70 ° C. for 1 minute, followed by high pressure mercury lamp. (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coating part substrate (7). At this time, the film thickness was 5 μm. A part of the transparent film was cut vertically in the longitudinal direction and the cross section was observed by a transmission electron microscope. As a result, silica-based hollow particles formed a 100 nm thick layer on the upper side, and antimony pentoxide particles on the lower side as shown in FIG. It existed in a state.

The surface resistance value, total light transmittance, haze, reflectance, anti-glare property, adhesiveness, and pencil hardness of the light having a wavelength of 550 nm of the obtained transparent coating part substrate 7 were measured, and the results are shown in Table 1.

(Comparative Example 1)

Preparation of the transparent film-forming paint (R-1)

As the low refractive index component, a silica-based hollow fine particle dispersion sol (manufactured by Catalytic Co., Ltd .: Sluria 1420, an average particle diameter of 60 nm, a concentration of 20.5 wt%, a dispersion medium: isopropanol, and a particle refractive index of 1.30) was used. To 100 g of this sol, 32.69 g of vinylsilane (62.7% of KBE-1003 SiO ₂ component manufactured by Shinwol Chemical) was added, 10 g of ultrapure water was added, and stirred at 40 ° C. for 5 hours to obtain a silica-based hollow particulate dispersion sol subjected to surface treatment ( Solids 28.4%). As a result of measuring the surface charge amount of this surface-treated silica crab hollow particle dispersion sol, it was 3.3 microeq / g. 10.54 g of this surface-treated silica-based hollow fine particle dispersion sol, pentaerythritol triacetate (CO-3 Chemical Co., Ltd .: PE-3A), diethylaminoethyl methacrylate (Co., Ltd .: Light ester DE) ) 3 g of a photoinitiator (Tibasphariti Co., Ltd. Irugacua 184, dissolved in IPA, solid content concentration 10%) 0.42 g and 62.04 g of a 1/1 (weight ratio) mixed solvent of isopropanol and methyl isobutyl ketone It mixed and manufactured the coating film (R-1) for transparent film formation.

Transparency Film  Preparation of Substrate (R-1)

The transparent film-forming coating material (R-1) was applied to a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflectance 5.1%) by bar coating, and dried at 70 ° C. for 1 minute, followed by high pressure mercury lamp. (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coating part base material (R-1). At this time, the film thickness was 5 μm. A part of the transparent film was cut vertically in the longitudinal direction and the cross section was observed with a transmission electron microscope. As a result, the silica-based hollow fine particles existed in a uniform monodisperse form in the film. The surface resistance value, total light transmittance, haze, light transmittance of wavelength 550 nm, anti-glare property, adhesiveness, and pencil hardness of the obtained transparent film part base material (R-1) were measured, and the result is shown in Table 1.

(Comparative Example 2)

Production of Transparent Coating Film (R-2)

Antimony pentoxide microparticles | fine-particles dispersing sol (The Catalytic Co., Ltd. make: ELCOM V-4560, the average particle diameter of 20 nm, concentration 30.5 weight%, a dispersion medium: isopropanol, the particle refractive index 1.60) was used. To 100 g of this sol, 37.57 g of γ-methacrylooxypropyltrimethoxysilane (81.2% of KBM-503 SiO ₂ component manufactured by Shinwol Silicon Co., Ltd.) was mixed, 10 g of ultrapure water was added, and the mixture was stirred at 40 ° C. for 5 hours for surface treatment. One antimony pentoxide fine particle dispersion sol was obtained (solid content 42.1 wt%). It was 5.5 microeq / g when the surface charge quantity of this surface-treated antimony pentoxide microparticle dispersion sol was measured. 11.88 g of this surface-treated antimony pentoxide microparticles | fine-particles sol, 22.5 g of dihexaerythritol triacetate (DEP-6A), a acrylate which has a hydroxyl group (Dong-Sam Chemical Co., Ltd .: MMH-40 propylene glycol mono Photoinitiator (Irugaqua 184, manufactured by Tivasphariti Co., Ltd., IPA dissolved in 6.25 g of methyl ether dispersed solid content 40%), 0.42 g of solid content concentration 10%) and 1/1 (weight ratio) of isopropanol and methyl isobutyl ketone 58.95 g of a mixed solvent were sufficiently mixed to prepare a transparent film-forming coating material (R-2).

Transparency Film  Preparation of the Substrate (R-2-1)

The transparent film-forming paint (R-2) was applied to a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflectance 5.1%) by bar coating, dried at 70 ° C. for 1 minute, and then pressurized with a high pressure mercury lamp. (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coating part base material (R-2-1). At this time, the film thickness was 5 μm. A part of the transparent coating was cut vertically in the longitudinal direction and the cross section was observed with a transmission electron microscope. As a result, the antimony pentoxide fine particles existed in a uniform monodisperse form in the film.

The surface resistance value, total light transmittance, haze, light transmittance of wavelength 550 nm, anti-glare property, adhesiveness, and pencil hardness of the obtained transparent film part base material (R-2-1) were measured, and the result is shown in Table 1.

Transparency Film  Preparation of the Substrate (R-2-2)

The antireflection film-forming coating liquid (A-4R) prepared in the same manner as in Example 4 was applied to the transparent coating part base material (R-2-1) by bar coating, and dried at 70 ° C. for 1 minute, followed by high pressure mercury lamp ( 80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coating substrate (R-2-2). At this time, the film thickness was 100 nm.

The surface resistance value, total light transmittance, haze, light transmittance of wavelength 550nm, anti-glare property, adhesiveness, and pencil hardness of the obtained transparent film part base material (R-2-2) were measured, and the result is shown in Table 1.

(Comparative Example)

Anti-reflection Film  Preparation of the Substrate (R-3)

An antireflection film-forming coating liquid (A-4R) prepared in the same manner as in Example 4 was applied by bar coating to a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflectance 5.1%). After drying at 70 ° C. for 1 minute, a high-pressure mercury lamp (80 W / cm) was irradiated for 1 minute and cured to prepare an antireflection coating substrate (R-3). At this time, the film thickness was 100 nm. A part of the transparent coating was cut vertically in the longitudinal direction and the cross section was observed with a transmission electron microscope. As a result, the silica-based hollow fine particles were uniformly dispersed in the film.

The surface resistance value, total light transmittance, haze, light transmittance of wavelength 550 nm, anti-glare property, adhesiveness, and pencil hardness of the obtained anti-reflective coating part base material (R-3) were measured, and the result is shown in Table 1.

An effect of the present invention is to provide a transparent film-forming coating material and a transparent film portion base material capable of forming at least two layers having different functions separated up and down by one application. In addition, it is possible to significantly reduce the process for obtaining a transparent film in one coating step, and at the same time, to improve the yield and to provide a transparent film excellent in adhesion.

Claims (12)

(A) the surface is surface-treated with a polyfunctional acrylic acid ester resin with the organic silicon compound and / or a hydrophobic functional group represented by the following formula (1), and also the surface charge amount (Q _A) is in the range of 5~80 μeq / g Phosphorus metal oxide fine particles (A), R _n -SiX _{4- n} (1) Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen, and n is 0 to 3 Integer) (B) matrix formation comprising a hydrophobic matrix forming component composed of an organosilicon compound represented by the following formula (2) or a hydrolyzate thereof, a hydrolyzed polycondensate and / or a polyfunctional (meth) acrylic acid ester resin having a hydrophobic functional group Ingredients and R _{n '} -SiX _{4 - n'} (2) Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen, and n 'is 1 to 3 Is an integer of) (C) A transparent film-forming paint composed of a polar solvent, The concentration (C _PA ) of the metal oxide fine particles (A) as a solid content is in the range of 0.1 to 20% by weight, and the concentration (C _M ) as the solid content of the matrix forming component (C) is in the range of 1 to 50% by weight. Transparent film-forming paint The polyfunctional (meth) acrylic acid ester resin of claim 1, wherein the matrix forming component is an organosilicon compound represented by the following formula (3) together with a hydrophobic matrix, or a hydrolyzate, hydrolyzed polycondensate, or a hydrophilic functional group thereof. comprises a hydrophilic matrix-forming component consisting of a solid content concentration as a hydrophilic matrix forming component (C _MA) and the solid content concentration as the concentration ratio of the hydrophobic matrix forming component (C _MA) / _(MB C) of _(MB C) of 0.01 to 1 Paint for forming a transparent film, characterized in that the range SiX ₄ (3) (Wherein X is an alkoxy group, silanol group, halogen or hydrogen having 1 to 4 carbon atoms) The paint for forming a transparent film according to claim 1 or 2, wherein the average particle diameter of the metal oxide fine particles (A) is in a range of 5 to 500 nm. The surface charge amount of the metal oxide fine particles (B) according to any one of claims 1 to 3, further comprising metal oxide fine particles (B) having a surface charge amount (Q _B ) in a range of 25 to 100 μeq / g. The coating material for forming a transparent film, wherein the difference (Q _B )-(Q _A ) between (Q _B ) and the surface charge amount (Q _A ) of the metal oxide fine particles (A) is in a range of 20 to 95 μeq / g. The paint for forming a transparent film according to any one of claims 1 to 4, wherein the concentration (C _PB ) is in the range of 0.1 to 20% by weight as solid content of the metal oxide fine particles (B). The paint for forming a transparent film according to claim 4 or 5, wherein the average particle diameter of the metal oxide fine particles (B) is in a range of 5 to 500 nm. The said hydrophilic functional group is 1 or more types chosen from hydroxyl group, an amino group, a carboxyl group, a sulfone group, and a glycidyl group, The said hydrophobic functional group is a (meth) acryloyl group, an alkyl group, a phenyl group, and a urethane. group, a paint for forming a transparent coating, characterized in that at least one member selected from the group CF ₂ In the transparent coating part base material in which the transparent film was formed on the base material, The transparent film is composed of hydrophobic metal oxide fine particles (A) having a surface charge amount (Q _A ) in the range of 5 to 80 μeq / g and a matrix component, The metal oxide fine particles (A) form a layer on the transparent film and are localized, and the content (W _PA ) of the metal oxide fine particles (A) in the transparent film is in the range of 0.2 to 90% by weight, The content (W _M ) of the matrix component is in the range of 10 to 99.8 wt%, Wherein the matrix component is a hydrophobic matrix component selected from hydrolyzed polycondensates of the organosilicon compounds represented by the following formula (4) and / or polyfunctional (meth) acrylic acid ester resins having a hydrophobic functional group: R _n -SiX _{4- n} (4) (Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen, and n is 0 to 3). Is an integer of) The method of claim 8, wherein the matrix component is composed of a hydrophilic matrix component together with a hydrophobic matrix component, The hydrophilic matrix component is a polyfunctional (meth) acrylic acid ester resin having a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (3) and / or a hydrophilic functional group, Transparent film part base material characterized by the content ratio (W _MA ) / (W _MB ) of content (W _MA ) as a solid content of a hydrophilic matrix component, and content (W _MB ) as a solid content of a hydrophobic matrix component. SiX ₄ (3) (Wherein X is an alkoxy group, silanol group, halogen or hydrogen having 1 to 4 carbon atoms) The surface charge amount Q _{B of} the transparent film is in the range of 25 to 100 μeq / g, and the surface charge amount Q _B of the metal oxide fine particles ( _B ) and the metal oxide fine particles (A) according to claim 8 or 9. Further comprises metal oxide fine particles (B) having a difference (Q _B )-(Q _A ) of the surface charge amount Q _{A in} the range of 20 to 95 μeq / g, wherein the metal oxide fine particles (B) are formed on the substrate surface. The transparent coating part base material formed by forming a layer in and disperse | distributing between the layer which consists of said metal oxide fine particles (A), and the surface of a base material The average particle diameter of the said metal oxide fine particle (A) is the range of 5-500 nm, The average particle diameter of the said metal oxide fine particle (B) is 5-500 nm in any one of Claims 8-10. Transparent coating part substrate, characterized in that the range of The said hydrophilic functional group is at least 1 sort (s) chosen from a hydroxyl group, an amino group, a carboxyl group, and a sulfone group, The said hydrophobic functional group is a (meth) acryloyl group, an alkyl group, a phenyl group, a urethane. Transparent coating part substrate, characterized in that one or two or more selected from the group CF ₂

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