JP2008291174A - Coating material for forming transparent coating film and substrate with transparent film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating material for forming a transparent coating film, the material which can be used for forming a transparent coating film having two or more kinds of functions, for example, an antireflection performance, hard-coat function, antistatic performance and antiglare property, by applying once a single coating material. <P>SOLUTION: The coating material for forming a transparent coating film comprises (A-1) metal oxide fine particles surface-treated with an organic silicon compound and having a surface charge amount (Q<SB>A-1</SB>) of 20 to 100 μeq/g on the surface-treated fine particles, (B-1) a hydrophilic matrix-forming component, and (C) a polar solvent, and is characterized in that: the concentration (C<SB>PA-1</SB>) of the metal oxide fine particles as a solid content ranges from 0.1 to 20 wt.%; and the concentration (C<SB>MB-1</SB>) of the hydrophilic matrix-forming component (B-1) as a solid content ranges from 1 to 50 wt.%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention can be used for forming a transparent film having at least two or more functions, for example, antireflection performance, hard coat function, antistatic performance, antiglare property, etc., by applying one kind of paint once. The present invention relates to a transparent film-forming paint and a substrate with a transparent film formed using the paint.

  Conventionally, it has been known to form a hard coat film on the surface of a substrate in order to improve the scratch resistance of the substrate surface such as glass, plastic sheet, plastic lens, etc. An organic resin is used as such a hard coat film. A film or an inorganic film is formed on the surface of glass or plastic. Furthermore, it is practiced to further improve the scratch resistance by blending resin particles or inorganic particles such as silica in an organic resin film or an inorganic film.

In addition, in order to prevent reflection of the surface of a substrate such as glass, plastic sheet, plastic lens, etc., it is known to form an antireflection film on the surface. For example, by a coating method, a vapor deposition method, a CVD method, A film of a low refractive index substance such as fluororesin or magnesium fluoride is formed on the surface of a glass or plastic substrate, or a coating liquid containing low refractive index fine particles such as silica fine particles is applied to the substrate surface. A method of forming an antireflection coating is known (for example, see JP-A-7-133105 (Patent Document 1) and the like). At this time, in order to improve the antireflection performance, it is also known to form a high refractive index film containing fine particles of high refractive index under the antireflection coating.

  Further, in order to impart antistatic performance and electromagnetic wave shielding performance to the base material, a conductive film containing conductive oxide fine particles, metal fine particles and the like is also formed. For example, for the purpose of antistatic and antireflection of the surfaces of transparent substrates such as display panels such as cathode ray tubes, fluorescent display tubes, and liquid crystal display panels, transparent coatings having antistatic and antireflection functions are provided on these surfaces. Forming was done.

  In particular, in recent years, such various functional coatings are laminated and used. For example, a hard coat film is formed on a substrate, a conductive film or a high refractive index film is formed, and an antireflection film is formed.

Further, the inventors of the present application disclosed in Japanese Patent Application Laid-Open No. 2003-12965 (Patent Document 2) two kinds of fine particles having different average particle diameters and different conductive fine particles having a small particle size and low refractive index fine particles having a large particle size. It has been proposed that a conductive film excellent in antireflection performance can be formed by a single application by using a coating solution containing.
JP-A-7-133105 JP 2003-12965 A

  However, in the conventional method, each film consists of a step of applying a paint, drying, and curing as necessary. Therefore, when forming the multilayer film, many steps are required. Adhesion was insufficient, and there were problems with productivity and economy.

Moreover, in the thing of patent document 2, there may be a case where a fine particle layer cannot be formed in a form in which two kinds of fine particles are completely separated from each other, and thus antireflection performance and antistatic performance may be insufficient. Furthermore, the adhesion to a substrate such as plastic is low, and the strength of the film may be insufficient.

  As a result of intensive studies in view of such problems, the present inventors have used a transparent film-forming paint comprising a metal oxide particle surface-treated with a tetrafunctional organosilicon compound, a hydrophilic matrix-forming component, and a polar solvent. In the transparent film formed in this way, the present invention was completed by finding that the surface-treated metal oxide particles were layered on the transparent film without being uniformly dispersed in the transparent film. That is, the present invention has been completed by finding that it is possible to form a film having two or more functions by forming a film once.

The configuration of the present invention is as follows.
[1] (A-1) metal oxide fine particles that are surface-treated with an organosilicon compound, and the surface charge amount (Q _A-1 ) of the surface-treated fine particles is in the range of 20 to 100 μeq / g;
(B-1) consisting of a hydrophilic matrix-forming component and (C) a polar solvent,
The concentration (C _PA-1 ) as a solid content of the metal oxide fine particles (A-1) is in the range of 0.1 to 20% by weight,
Concentration (C _MB-1 ) as a solid content of the hydrophilic matrix forming component (B _-1 ) is 1 to 50% by weight
A transparent film-forming paint characterized by being in the range of

[2] The transparent film forming paint according to [1], wherein the organosilicon compound is an organosilicon compound represented by the following formula (1):
R _a Six _4-a (1)
(In the formula, X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, and hydrogen, and may be the same or different. R is unsubstituted or substituted having 1 to 10 carbon atoms. Hydrocarbon groups which may be the same or different from each other, a being an integer of 0 or 1)

[3] The surface-treated metal oxide fine particles (A-1) have a refractive index (n _A-1 ) of 1.15 to 1.40.
[1] or [2] transparent film forming paint in the range of

[4] The hydrophilic matrix forming component (B-1) is an organosilicon compound represented by the following formula (2) or a hydrolyzate, hydrolyzed polycondensate thereof, and / or a hydroxyl group, an amino group, a carboxyl [1]-[3] transparent film-forming paint, which is a polyfunctional (meth) acrylic ester resin having at least one hydrophilic functional group selected from a group and a sulfo group.
R _a Six _4-a (2)
(In the formula, X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, and hydrogen, and may be the same or different. R is unsubstituted or substituted having 1 to 10 carbon atoms. Hydrocarbon groups which may be the same or different from each other, a being an integer of 0 or 1)
[5] The transparent film-forming paint according to [1] to [4], wherein the surface-treated metal oxide fine particles (A-1) have an average particle diameter in the range of 5 to 500 nm.

[6] The matrix-forming component further includes a hydrophobic matrix-forming component (B-2), the concentration (C _MB-2 ) of the hydrophobic matrix-forming component as a solid content, and the (C _MB-1 ) The transparent film-forming paint of [1] to [5] in which the concentration ratio (C _MB-1 ) / (C _MB-2 ) is in the range of 0.005 to 1.

[7] The hydrophobic matrix-forming component (B-2) is an organosilicon compound represented by the following formula (3) or a hydrolyzate thereof, a hydrolyzed polycondensate, and / or a vinyl group, a urethane group, [1] to [6] transparent film-forming paint, which is a polyfunctional (meth) acrylate resin having at least one hydrophobic functional group selected from an epoxy group, a (meth) acryloyl group, and a CF ₂ group.
_{R n -SiX 4-n (3} )
(In the formula, 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: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3. However, when a in formula (2) is 1, n is 2 to 3)

[8] The paint, together with (A-1) metal oxide fine particles,
(A-2) A metal oxide fine particle which has been surface-treated with an organosilicon compound and has a surface charge amount (Q _A-2 ) in the range of 5 to 80 μeq / g, The surface charge of the metal oxide fine particles (A-2) whose surface refractive index (n _A-2 ) is higher than (n _A-1 ) and the surface-treated metal oxide fine particles (A-2) (Q _A-2 ) And (Q _A-1 ), (Q _A-1 ) − (Q _A-2 ) [1] to [7] for forming a transparent film, wherein the range is from 10 to 95 μeq / g.

[9] The paint for forming a transparent film according to [1] to [8], wherein the metal oxide fine particles (A-2) are surface-treated with an organosilicon compound represented by the following formula (4).
_{R n -SiX 4-n (4} )
(In the formula, 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: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3. However, when a in formula (1) is 1, n is 2 to 3))

[10] The concentration (C _PA-2 ) of the surface-treated metal oxide fine particles (A-2) as a solid content is 0
. The paint for forming a transparent film according to [1] to [9] in the range of 1 to 20% by weight.

[11] The paint for forming a transparent film according to [1] to [10], wherein the surface-treated metal oxide fine particles (A-2) have an average particle diameter in the range of 5 nm to 5 μm.

[12] A substrate with a transparent film in which a transparent film is formed on the substrate,
Transparent film
(i) consisting of metal oxide fine particles (A-1) surface-treated with an organosilicon compound having a surface charge (Q _A ) in the range of 20 to 100 μeq / g and a hydrophilic matrix component (B-1) ,
(ii) The surface-treated metal oxide particles (A-1) are unevenly distributed in the upper part of the transparent coating, and the content of the surface-treated metal oxide fine particles (A-1) in the transparent coating ( W _PA-1 ) is 0.2 to 90% by weight
The base material with a transparent film in which the content of the matrix component (W _M ) is in the range of 10 to 99.8% by weight.

[13] The matrix component further comprises a hydrophobic matrix component (B-2), the content (W _MB-1 ) of the hydrophilic matrix component (B-1) as a solid content and the hydrophobic matrix component The base material with a transparent coating according to [12], wherein the content ratio (W _MB-1 ) / (W _MB-2 ) to the content (W _MB-2 ) as a solid content is in the range of 0.005 to ₁ .

[14] The surface-treated metal oxide fine particles (A-2) further comprising surface-treated metal oxide fine particles (A-2) having a surface charge amount (Q _A-2 ) in the range of 5 to 80 μeq / g. The refractive index (n _A-2 ) of _A-2 ) is higher than the refractive index (n _A-1 ) of the surface-treated metal oxide fine particles (A-1), and the surface-treated metal oxide fine particles (A -2) is unevenly distributed in a layer on the substrate surface, or is dispersed between the surface-treated metal oxide fine particles (A-1) and the substrate surface [12] or [13] A substrate with a transparent coating.

[15] The substrate with a transparent coating according to [12] to [14], wherein the content of the surface-treated metal oxide fine particles (A-2) is in the range of 5 to 70% by weight.

[16] The surface-treated metal oxide fine particles (A-1) have an average particle size in the range of 5 to 500 nm, and the surface-treated metal oxide fine particles (A-2) have an average particle size of 5 nm. The base material with a transparent film of [12]-[15] in the range of ~ 5 μm.

[17] The refractive index (n _A-1 ) of the surface-treated metal oxide fine particles (A-1) and the refractive index (n _A-2 ) of the surface-treated metal oxide fine particles ( _A-2 ) [12] to [16], wherein the difference in refractive index from (n _A-2 ) − (n _A−1 ) is 0.20 or more.

  [18] The surface of the transparent film has irregularities, the average film thickness of the transparent film is in the range of 1 to 10 μm, the average height of convex portions (T convex) and the average height of concave portions (T (14) to [17] are substrates with a transparent coating, wherein the difference from (concave) is (T convex)-(T concave) is in the range of 30 to 1500 nm.

  ADVANTAGE OF THE INVENTION According to this invention, the coating material for transparent film formation and the base material with a transparent film which can form at least two layers from which the function separated into the upper and lower sides by one application | coating can be provided.

  Moreover, since a transparent film can be obtained by a single coating, the process can be greatly shortened and the yield is improved, and the obtained transparent film is excellent in adhesion.

Hereinafter, first, the transparent film-forming paint according to the present invention will be specifically described.
Transparent film forming paint The transparent film forming paint according to the present invention is
(A-1) metal oxide fine particles that have been surface-treated with an organosilicon compound and the surface-treated fine particles have a surface charge amount (Q _A-1 ) in the range of 20 to 100 μeq / g;
(B-1) consisting of a hydrophilic matrix-forming component and (C) a polar solvent,
The concentration (C _PA-1 ) as a solid content of the metal oxide fine particles (A-1) is in the range of 0.1 to 20% by weight,
Concentration (C _MB-1 ) as a solid content of the hydrophilic matrix forming component (B _-1 ) is 1 to 50% by weight
It is in the range.

Surface-treated metal oxide fine particles (A-1)
The surface-treated metal oxide fine particles (A-1) used in the present invention preferably have a surface charge amount (Q _A-1 ) of 20 to 100 μeq / g, more preferably 25 to 100 μeq / g.

When the surface charge amount is in the above range, the matrix-forming component has hydrophilicity, so that when the transparent film is formed, the surface-treated metal oxide fine particles (A-1) form a layer on the transparent film. For example, if the metal oxide fine particles (A-1) are particles having a low refractive index, a transparent film having antireflection performance can be formed by a single application.

When the surface charge amount (Q _A-1 ) is less than 25 μeq / g, the hydrophilicity of the metal oxide fine particles (A-1) is insufficient and the dispersibility in the hydrophilic matrix-forming component is reduced, and thus in the paint. The metal oxide fine particles (A-1) may aggregate, and a uniform layer of the metal oxide fine particles (A-1) may not be formed on the upper part of the film.

When the surface charge amount (Q _A-1 ) exceeds 100 μeq / g, the dispersibility in the hydrophilic matrix forming component is high, and the metal oxide fine particles (A-1) are highly dispersed in the paint, so In some cases, a uniform layer of metal oxide fine particles (A-1) may not be formed.

The method for measuring the surface charge amount described above uses a surface potential titrator (Mutek Inc. pcd-03),
The fine particle dispersion can be titrated with 0.001 N poly-diallyldimethylammonium chloride to determine the surface charge (μeq / g) per gram of particles.

The metal oxide particles (A-1) can be appropriately selected and used depending on the application. For example, the metal oxide fine particles used for the antireflection film usually have a refractive index of 1.45 or less, preferably 1.40 or less. metal oxide fine particles are used, specifically SiO _2, fine particles coated with metal oxides having a SiO ₂ or conductive thereto, having a cavity inside thereof.

Examples of the metal oxide fine particles used for the hard coat film include ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ , chain particles in which these particles are connected in a chain, Examples thereof include silica-based fine particles having a refractive index of 1.45 or less.

The metal oxide fine particles used for the high refractive index film are usually fine particles having a refractive index of 1.60 or more, more preferably 1.80 or more. Specifically, ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ , antimony-doped tin oxide, tin-doped indium oxide, tin oxide-doped phosphorus (P
TO) and the like.

The metal oxide fine particles used for the conductive film are usually Sb ₂ O ₅ , SnO ₂ , antimony-doped tin oxide, tin-doped indium oxide, tin oxide-doped phosphorus (PTO), or silica-based whose surface is coated with these conductive materials. Examples thereof include fine particles or silica-based fine particles having cavities therein.

  The transparent film-forming paint of the present invention is particularly useful for forming an antireflection film, and the metal oxide fine particles have a refractive index of 1.15 to 1.40, more preferably 1.15 to 1.35. Fine particles are used. As the metal oxide fine particles, silica-based fine particles having cavities therein disclosed in Japanese Patent Application Laid-Open No. 2001-233611 filed by the present applicant can be suitably used.

Such metal oxide fine particles (A-1) are surface-treated with an organosilicon compound. As the organosilicon compound, an organosilicon compound represented by the following formula (1) is preferable.
R _a Six _4-a (1)
(In the formula, X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, and hydrogen, and may be the same or different. R is unsubstituted or substituted having 1 to 10 carbon atoms. Hydrocarbon groups which may be the same or different from each other, a being an integer of 0 or 1)
Examples of the organosilicon compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, trimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, 3,3,3- Trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysila , Γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acryloxymethyltrimethoxysilane, γ- (Meth) acryloxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meta ) Acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropi Triethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, Hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, tri Examples include fluoropropyltrimethoxysilane.

The surface treatment of the metal oxide fine particles (A-1) is performed, for example, by adding a predetermined amount of the above-described organosilicon compound to the above-described alcohol dispersion of the metal oxide fine particles, adding water thereto, and if necessary, the organosilicon compound It can be carried out by hydrolyzing the organosilicon compound by adding an acid or alkali as a catalyst for hydrolysis of the above.

The amount ratio of the metal oxide fine particles (A-1) to the organosilicon compound (weight as the solid content of the organosilicon compound / weight of the metal oxide fine particles (A-1)) is the metal oxide fine particles (A-1) Depending on the average particle size, it is preferably in the range of 0.005 to 0.4, more preferably 0.01 to 0.2.

When the weight ratio is small, the hydrophilicity of the metal oxide fine particles (A-1) becomes insufficient, the dispersibility in the hydrophilic matrix-forming component is lowered, and the metal oxide fine particles (A-1) are contained in the paint. Aggregation may occur, and a uniform layer of metal oxide fine particles (A-1) may not be formed on the top of the film. Even if the weight ratio is too large, the hydrophilicity becomes too high, and the metal oxide fine particles (A-1) are highly dispersed in the paint, so a uniform layer of metal oxide fine particles (A-1) is formed on the upper part of the film. May not form.

If necessary, the surface-treated metal oxide fine particles (A-1) may be substituted with a desired organic solvent. Examples of the organic solvent include polar solvents described later.
When the metal oxide fine particles (A-1) are surface-treated with the above-mentioned organosilicon compound in the above-mentioned amount, they have a surface charge amount in the above-mentioned range, that is, have moderate hydrophilicity and agglomerate in the paint. It is possible to obtain a transparent film which is dispersed without any other material and arranged in layers on the transparent film.

The surface-treated metal oxide fine particles (A-1) have an average particle diameter of 5 to 500 nm, more preferably 10
It is preferable to be in the range of ˜100 nm (note that the average particle diameter of the metal oxide fine particles does not substantially change before and after the surface treatment).

When the average particle diameter of the metal oxide fine particles (A-1) is smaller than the above range, it is difficult to obtain itself, and when the average particle diameter is larger than the above range, the haze value of the transparent film to be obtained is In some cases, it cannot be used as an optical film.

The solid content concentration (C _PA-1 ) of the metal oxide fine particles (A-1) in the paint for forming a transparent film is 0.1 to 0.1.
It is preferably 20% by weight, more preferably in the range of 0.2 to 15% by weight. When (C _PA-1 ) is low, the amount of particles is small even when unevenly distributed on the top of the film, so the antireflection performance and antistatic performance due to the properties of the particles (low refractive index, conductivity, etc.) are insufficient. There is a case. Moreover, even if there is too much (C _PA-1 ), the ratio of the particles in the resulting film is too high, and the film is substantially uniformly dispersed throughout the entire area of the metal oxide fine particles surface-treated in the film. The film having two or more functions of the present invention may not be obtained.

Metal oxide fine particles (A-2)
The transparent film-forming paint of the present invention may further contain metal oxide fine particles (A-2) having a surface charge amount (Q _A-2 ) in the range of 5 to 80 μeq / g. Such metal oxide fine particles (A-2) are also surface-treated with an organosilicon compound.

As the metal oxide fine particles (A-2), particles having higher hydrophobicity than the metal oxide fine particles (A-1) and having a surface charge amount of 10 to 95 μeq / g are used.
When using such metal oxide fine particles (A-2),
In the metal oxide fine particles (A-2), the metal oxide fine particles (A-2) are surface-treated with an organosilicon compound represented by the following formula (4).
_{R n -SiX 4-n (4} )
(In the formula, 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: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3.

The compound represented by the formula (4) is more hydrophobic than the compound represented by the formula (1). When a in the formula (1) is 1, n is 2 to 3)
Specifically, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriexisilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyl Torie Toki Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxy Ethoxy) propyltrimethoxysilane, γ- (meth) acryloxymethyltrimethoxysilane, γ- (meth) acryloxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxy Ethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltri Ethoxysilane, butyltrimethoxysilane, isobutyltri Toxisilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, Perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (Aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysila , Trimethylsilanol, methyltrichlorosilane and the like. Among these, 3,3,3-trifluoropropyltrimethoxysilane and methyl-3,3,3-trifluoropropyldimethoxysilane are exemplified.

The surface treatment of the metal oxide fine particles (A-2) is performed, for example, by adding a predetermined amount of the above-described organosilicon compound to an alcohol dispersion of metal oxide fine particles, which will be described later, adding water thereto, and if necessary, an organosilicon compound It can be carried out by hydrolyzing the organosilicon compound by adding an acid or an alkali as a catalyst for hydrolysis.

The quantity ratio between the metal oxide fine particles (A-2) and the organosilicon compound (weight as the solid content of the organosilicon compound / weight of the high refractive index fine particles) depends on the average particle diameter of the metal oxide fine particles (A-2). However, it is preferably in the range of 0.005 to 0.4, more preferably 0.01 to 0.2.

  When the weight ratio is small, the hydrophobicity is insufficient, so that it is dispersed in the hydrophilic matrix-forming component without being dispersed in the hydrophobic matrix-forming component described later, and the metal oxide fine particles (A-1) and (A-2 ) And the metal oxide fine particles (A-1) and (A-2) in combination may be insufficiently separated.

If the weight ratio is too large, the hydrophobicity becomes too high (the surface charge amount becomes 5 μq / g or less) and may aggregate in the hydrophobic matrix forming component.
Subsequently, an organic solvent dispersion of the metal oxide fine particles (A-2) subjected to the surface treatment can be obtained by substituting with an organic solvent. As the organic solvent, a polar solvent described later is preferably used.

As the metal oxide fine particles (A-2), metal oxide fine particles different from the metal oxide fine particles used for the metal oxide fine particles (A-1) are selected and used.
Specifically, ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ used for the hard coat film are used.
SnO ₂ , chain particles in which these particles are linked in a chain, or silica-based fine particles having a refractive index of 1.45 or less, and the like, and a normal refractive index of 1.60 or more, Further, fine particles of 1.80 or more, specifically, ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ , antimony-doped tin oxide, tin-doped indium oxide, tin oxide-doped phosphorus (PTO) Etc.) Sb ₂ O ₅ , SnO ₂ used for conductive films, antimony-doped tin oxide, tin-doped indium oxide, tin oxide-doped phosphorus (PTO), or silica-based fine particles whose surface is coated with these conductive materials or inside Examples thereof include silica-based fine particles having cavities.

The surface charge amount (Q _A-2 ) of the metal oxide fine particles (A-2) is preferably in the range of 5 to 80 μeq / g, more preferably 7 to 70 μeq / g. Those having a small surface charge (Q _A-2 ) may agglomerate in the hydrophobic matrix-forming component and may not form a uniform layer below the membrane. If the surface charge amount (Q _A-2 ) is too large, the hydrophobicity is low and the hydrophilicity increases, so that it is dispersed in the hydrophilic matrix forming component, and the metal oxide fine particles (A-1 are not unevenly distributed in the lower part of the film. ) To be located at the upper part of the film, and the effect due to the characteristics of the metal oxide fine particles (A-1), for example, the antireflection performance due to the low refractive index characteristics may be insufficient.

The difference between the metal oxide fine particle surface charge amount of (A-1) (Q A -1) and the surface-treated metal oxide fine particle surface charge amount of (A-2) (Q A -2) (Q _A-1 )-(Q _A-2 ) is preferably in the range of 10 to 95 μeq / g, more preferably 15 to 85 μeq / g.

When (Q _A-1 )-(Q _A-2 ) is small, the difference in surface charge between the metal oxide fine particles (A-1) and the metal oxide fine particles (A-2) is small. May be insufficient, and a film having two or more functions which is the object of the present invention may not be obtained. When (Q _A-1 )-(Q _A-2 ) is too large, the metal oxide fine particles (A-1) are aggregated and the surface-treated metal oxide fine particles (A-2) are also aggregated to obtain. The film may be whitened or the adhesion and strength with the substrate may be insufficient.
Further, the refractive index (n _A-2 ) of the surface-treated metal oxide fine particles (A-2) is higher than the refractive index (n _A-1 ) of the surface-treated metal oxide fine particles (A-1). It is preferable that the refractive index difference (n _A−2 ) − (n _A−1 ) is 0.20 or more.

The average particle diameter of the metal oxide fine particles (A-2) is preferably in the range of 5 nm to 5 μm, more preferably 10 nm to 3 μm.
It is difficult to obtain a metal oxide fine particle (A-2) having a small average particle diameter. If it is too large, the height of the convex portion (T convex) and the height of the concave portion (described later) The difference between (T-concave) and (T-concave)-(T-concave) may exceed 1.5 μm, and sufficient anti-glare performance may not be obtained, and the scratch resistance of the transparent film may be a problem. There is.

The metal oxide fine particles (A-2) have a concentration (C _PA-2 ) in the range of 0.1 to 20% by weight, and further 0.2 to 15% by weight as a solid content in the paint for forming a transparent film. Preferably there is.
When (C _PA-2 ) is low, the amount of particles is small even if the metal oxide fine particles (A-2) are unevenly distributed in the lower part of the film, so reflection due to the characteristics of the particles (high refractive index, conductivity, etc.) The prevention performance improvement effect, the antistatic performance, etc. may be insufficient. If the amount of (C _PA-1 ) is large, the proportion of particles in the resulting film is too large and mixed with the metal oxide fine particles (A-1) or the metal oxide fine particles (A-2) In some cases, a film having two or more functions of the present invention cannot be obtained.

Matrix-forming component (B-1)
As the matrix forming component, a hydrophilic matrix forming component (B-1) is used.
The hydrophilic matrix-forming component is an organosilicon compound represented by the following formula (2), which is a silicone (sol-gel) matrix-forming component, or a hydrolyzate, hydrolyzed polycondensate or organic resin-based matrix-forming component. A polyfunctional (meth) acrylate resin having at least one hydrophilic functional group selected from a certain hydroxyl group, amino group, carboxyl group, and sulfo group is preferably used.
R _a Six _4-a (2)
(In the formula, X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, and hydrogen, and may be the same or different. R is unsubstituted or substituted having 1 to 10 carbon atoms. Hydrocarbon groups which may be the same or different from each other, a being an integer of 0 or 1)
Specifically, as the silicone-based (sol-gel-based) hydrophilic matrix-forming component, the above-described organosilicon compounds of the formula (1) and their hydrolysates and hydrolyzed polycondensates can be preferably used.

Specific examples of the organic resin-based hydrophilic matrix forming component (B-1) include, in addition to pentaerythritol triacrylate, diethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate. Crate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, methoxytri Ethylene glycol dimethacrylate, butoxydiethylene glycol methacrylate, triethylene glycol diacrylate, 1.6-he Sundiol diacrylate, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-acrylooxyethyl- 2-hydroxyethylphthalic acid, 2-methacryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, and mixtures thereof, or a copolymer of two or more of these resins And modified products.

The matrix-forming component used in the present invention may contain a hydrophobic matrix-forming component (B-2) together with the hydrophilic matrix-forming component (B-1).
As the hydrophobic matrix-forming component (B-2), an organosilicon compound represented by the following formula (3) or a hydrolyzate or hydrolyzed polycondensate of the silicone-based (sol-gel) matrix-forming component Used.
_{R n -SiX 4-n (3} )
(In the formula, 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: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen,
Hydrogen, n: an integer from 1 to 3. However, when a in formula (2) is 1, n is 2 to 3))
Specifically, an organosilicon compound represented by the formula (4), a hydrolyzate thereof, and a hydrolyzed polycondensate can be preferably used.

An organic resin-based hydrophobic matrix-forming component (B-2) can also be used, and vinyl groups,
Examples include polyfunctional (meth) acrylic acid ester resins having hydrophobic functional groups such as urethane groups, epoxy groups, (meth) acryloyl groups, and CF ₂ groups. Specifically, pentaerythritol tetraacrylate, trimethylol propane tri (Meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methylate, isodecyl methylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate Relate, urethane acrylate and the like and mixtures thereof.

When the hydrophobic matrix-forming component (B-2) is used in combination with the hydrophilic matrix-forming component (B-1), the hydrophilic matrix-forming component (B-1) forms an upper layer, and the hydrophobic matrix-forming component ( B-2) forms a lower layer, and correspondingly, the metal oxide fine particles (A-1) are unevenly distributed in the upper surface layer, and the metal oxide fine particles (A-2) are unevenly distributed in the lower portion of the lower layer, It becomes easy to obtain a film divided into two layers.

The concentration of the matrix-forming component is preferably in the range of 1 to 30% by weight, preferably 15 to 85% by weight in the coating solution in terms of solid content.
When the hydrophobic matrix-forming component is included, the concentration of the hydrophilic matrix-forming component (B-1) as the solid content (C _MB-1 ) and the concentration of the hydrophobic matrix-forming component as the solid content (C _MB-2 )) (C _MB-1 ) / (C _MB-2 ) is preferably in the range of 0.005 to 1, more preferably 0.01 to 0.5.

Those having a small concentration ratio (C _MB-1 ) / (C _MB-2 ) have few hydrophilic matrix forming components and are substantially close to only hydrophobic matrix forming components, so that the metal oxide fine particles (A-1) The effect of separating (upper part) and metal oxide fine particles (A-2) (lower part) becomes insufficient. The concentration ratio (
Even if C _MB-1 ) / (C _MB-2 ) is too large, the surface-treated metal oxide fine particles (A-1) having a large hydrophilic matrix-forming component and a high surface charge amount are present in the upper layer (hydrophilic matrix component). ) May not be unevenly distributed at the top.
Polar solvent The polar solvent used in the present invention can dissolve or disperse the matrix-forming component and the polymerization initiator for matrix curing, and uniformly disperse the metal oxide fine particles (A-1) and metal oxide fine particles (A-2). A conventionally known solvent that can be dispersed can be used. In the present invention, it is preferable to use a mixture of two or more polar solvents having different boiling points.

In the present invention, a mixed solvent of the polar solvent (A-1) having a boiling point of 50 to 100 ° C. and the polar solvent (A-2) having a boiling point of more than 100 ° C. to 200 ° C. is desirable. The proportion of the polar solvent (A-1) in the solvent is preferably in the range of 50 to 90% by weight, and the proportion of the polar solvent (A-2) is preferably in the range of 10 to 50% by weight.

The polar solvent may be either hydrophilic or hydrophobic.
Polar solvents (A-1) and hydrophilic solvents include water; alcohols such as methanol, ethanol, propanol and 2-propanol (IPA), and hydrophobic solvents include methyl acetate, ethyl acetate and isopropyl acetate Esters such as; ketones such as acetone and methyl ethyl ketone; and toluene. These may be used singly or in combination of two or more.

Polar solvents (A-2) and hydrophilic solvents include butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol and the like; glycols such as ethylene glycol and hexylene glycol; diethyl ether, ethylene glycol monomethyl Ethers such as 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, and propylene glycol monoethyl ether, and hydrophobic Solvents include propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoacetate Esters such as cibutyl, 2-ethylbutyl acetate, cyclohexyl acetate, and ethylene glycol acetate; ketones such as methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, and diisobutyl ketone . These may be used singly or in combination of two or more.

When the ratio of the polar solvent (A-1) in the mixed solvent is too large, the coating film is dried too quickly, and the transparent film may not become dense, and the hardness and scratch resistance may be insufficient. If the proportion of (A-1) is too small, naturally the polar solvent (A-2) increases, so the drying of the coating film slows down, resulting in poor curing due to residual solvent, and insufficient hardness and scratch resistance. It may become.
A more desirable ratio of the polar solvent (A-2) in the mixed solvent is in the range of 20 to 40% by weight.

The ratio of the solvent in the coating for forming a transparent film is preferably in the range of about 50 to 99% by weight, more preferably 60 to 98% by weight.
The polar solvent (A-2) may be a mixture of a hydrophilic solvent and a hydrophobic solvent, but the solvent having the highest boiling point is preferably a hydrophilic solvent.

When the solvent having the highest boiling point is hydrophilic, both the hydrophilic resin and the hydrophilic particles can be easily and unevenly distributed on the upper part of the transparent film.
At this time, the ratio of the hydrophobic solvent / hydrophilic solvent in the polar solvent (A-2) is preferably in the range of 0 to 0.5.

A coating for forming a transparent film containing the above metal oxide fine particles (A-1), (A-2), matrix forming components (B-1), (B-2) and a polar solvent (C) Transparent by applying to a substrate by a known method such as a method, a spinner method, a roll coating method, a bar coating method, a gravure printing method, a micro gravure printing method, drying, and curing by an ordinary method such as ultraviolet irradiation or heat treatment. A film can be formed.

In addition, the preparation method of a coating material is not restrict | limited in particular, What is necessary is just to mix each component by a well-known method without a restriction | limiting in particular.
A substrate with a transparent coating The substrate with a transparent coating according to the present invention is a substrate with a transparent coating in which a transparent coating is formed on the substrate,
Transparent film
(i) consisting of metal oxide fine particles (A-1) surface-treated with an organosilicon compound having a surface charge (Q _A ) in the range of 20 to 100 μeq / g and a hydrophilic matrix component (B-1) ,
(ii) The surface-treated metal oxide particles (A-1) are unevenly distributed in the upper part of the transparent coating, and the content of the surface-treated metal oxide fine particles (A-1) in the transparent coating ( W _PA-1 ) is 0.2 to 90% by weight
The matrix component content (W _M ) is in the range of 10 to 99.8% by weight.

Base Material As the base material used in the present invention, conventionally known materials 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.

Surface-treated metal oxide fine particles (A-1)
As the surface-treated metal oxide fine particles (A-1), those described above are used.
The content (W _PA-1 ) of the metal oxide fine particles (A-1) in the transparent film is preferably in the range of 0.2 to 90% by weight, more preferably 0.5 to 80% by weight. When the content (W _PA-1 ) is small, the amount of particles is small even when unevenly distributed on the upper part of the film, so that the antireflective performance based on the characteristics of the particles such as low refractive index, high refractive index, and conductivity, Functions such as antistatic performance may not be fully developed. When the content (W _PA-1 ) is too large, the metal oxide fine particles (A-1) are substantially present over the entire region, and the transparent film having two or more functions of the present invention is not obtained. Adhesiveness may be insufficient.

In such a transparent film, the surface-treated metal oxide fine particles (A-1) are unevenly distributed in a layer on the upper part in the transparent film. Such a state is schematically shown in FIG.
By selecting the metal oxide fine particles (A-1) and the hydrophilic matrix, an antireflection function or an antistatic function can be imparted to the upper layer. Further, in order to impart a hard coat function to the lower layer, a hydrophobic matrix may be included.

Surface-treated metal oxide fine particles (A-2)
The transparent film of the substrate with a transparent film of the present invention may further contain the metal oxide fine particles (A-2). The metal oxide fine particles (A-2) are unevenly distributed in a layer on the substrate surface (lower part in the transparent coating), or between the layer made of the metal oxide fine particles (A-1) and the substrate surface Are distributed.

Such schematic diagrams are shown in FIGS.
2 and 3 are schematic views of a layer of metal oxide fine particles (A-2) formed in the lower part of the transparent film. FIG. 2 shows metal oxide fine particles (A-1) and (A- FIG. 3 shows the metal oxide fine particles (A-1) and (A-2) separated from each other, and the layers are composed of a matrix. Figures 2 and 3 show that the thickness of each layer and the thickness of the intermediate matrix layer can be adjusted by adjusting the thickness of the transparent coating and the amount of metal oxide fine particles (A-1) and (A-2). It becomes.

In FIG. 4, the metal oxide fine particles (A-2) are dispersed without forming a layer. In order to achieve such a configuration, the metal oxide fine particles (A-2) that have been surface-treated so as to have a surface charge amount that is highly dispersed in the hydrophobic matrix-forming component may be used so as not to be excessive.

5-7, the metal oxide fine particles (A-1) are low refractive index particles, the metal oxide fine particles (A-2) are high refractive index particles (large particles), and (A- Concavities and convexities derived from 2) are formed.

The total amount of the metal oxide fine particles (A-2) in the transparent film and (A-1) is preferably in the range of 0.2 to 90% by weight, more preferably 0.5 to 80% by weight. Further, the content (W _PA-2 ) of the metal oxide fine particles (A-2) is preferably in the range of 0.1 to 70% by weight, more preferably 0.2 to 50% by weight as the solid content. When (W _PA-2 ) is low, the amount of particles is small even when unevenly distributed in the lower layer of the film, so the properties of the particles (conductivity, high refractive index, low refractive index, improved adhesion to the substrate, etc.) It may not be fully expressed. Moreover, when it is going to obtain the transparent film which has anti-glare property using the particle | grains with a large average particle diameter mentioned later, the unevenness | corrugation on the surface of a transparent film may become inadequate, and anti-glare performance may become inadequate.

When the content of the surface-treated metal oxide fine particles (A-2) exceeds 70% by weight as a solid content, the film thickness of the transparent film may be uneven or the scratch resistance may be insufficient.
Moreover, it may be in a state of being mixed with the surface-treated metal oxide fine particles (A-1) arranged in the upper portion, and the transparent film having two or more functions of the present invention may not be obtained.
Matrix component As the matrix component, a hydrophilic matrix component (B-1) is used.
Hydrophilic matrix components include hydrolytic polycondensates of organosilicon compounds represented by the following formula (3) that are silicone (sol-gel) matrix forming components or hydroxyl groups, amino groups, and carboxyl groups that are organic resin matrix components. Polyfunctional (meth) acrylic acid ester resins having one or more hydrophilic functional groups selected from sulfo groups are preferably used.
R _a Six _4-a (2)
(In the formula, X, R and a are as described above.)
Specifically, hydrolysis polycondensates of those exemplified as the hydrophilic silicone-based (sol-gel) matrix-forming component are preferable. Also. It is also possible to use polymers, copolymers, and modified products of the hydrophilic organic resin matrix forming component described above.

The matrix component used in the present invention may further contain a hydrophobic matrix component (B-2) in addition to the hydrophilic matrix component.
As the hydrophobic matrix component, a silicone (sol-gel) matrix component which is a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (3) is used.
_{R n -SiX 4-n (3} )
(Wherein R, X and n are as described above.)
Specifically, hydrolysis polycondensates of those exemplified as the hydrophobic matrix-forming component can be mentioned.

Furthermore, a hydrophobic organic resin matrix component can also be used, and specific examples thereof include the polymers exemplified as the hydrophobic organic resin matrix forming component described above.
When the hydrophobic matrix component is used in combination with the hydrophilic matrix component, the hydrophilic matrix component forms the upper layer, and the hydrophobic matrix component forms the lower layer. Correspondingly, the metal oxide fine particles (A-1) Is unevenly distributed in the upper surface layer, the metal oxide fine particles (A-2) are unevenly distributed in the lower part of the lower layer, and the metal oxide fine particles (A-1) and the metal oxide fine particles (A-2) are easily separated. It becomes easy to obtain a film divided into two layers. In addition, when using an organic resin matrix as a matrix component, after forming a transparent film using a matrix formation component, it is good also as a polymer by a heating and hardening process.

The ratio of the content of the content of the solid content of the hydrophilic matrix components in the transparent coating (W _MB-1) and the content of the solid content of the hydrophobic matrix components _{(W MB-2) (W} MB-1 ) / (W _MB-2 ) is preferably in the range of 0.01 to 1, more preferably 0.05 to 0.5.

When the amount of (W _MB-1 ) / (W _MB-2 ) is too small, the hydrophilic matrix component is small, and it is substantially close to only the hydrophobic matrix component, and the metal oxide fine particles (A-1) (upper part) And the metal oxide fine particles (A-2) (lower part) are not sufficiently separated.

If the (W _MB-1 ) / (W _MB-2 ) is too large, the surface-treated metal oxide fine particles (A-1) having a large amount of hydrophilic matrix components and a high surface charge amount are formed in the upper layer (hydrophilic matrix components). ) May not be unevenly distributed at the top.

The total amount of the matrix component in the transparent coating (W _M) is 10 to 99.8 wt%, more preferably in the range of 20 to 99.5 wt% (the total amount of the metal oxide fine particles Does not exceed 100% by weight). When the content of the matrix component is small, the ratio of the particles in the film is too large, and the film is substantially uniformly dispersed throughout the film with the metal oxide fine particles, and the two or more functions of the present invention are achieved. In some cases, a film having such a property cannot be obtained. If there are too many matrix components in the transparent coating, the amount of particles is so small that the antireflection performance and antistatic performance due to the properties (low refractive index, conductivity, etc.) of the particles may be insufficient.

The film thickness of the transparent coating varies depending on the application, but is preferably in the range of approximately 30 nm to 12 μm, and more preferably 70 nm to 10 μm.
If the film thickness is too thin, it is difficult to form a transparent film that is substantially separated into two layers. If the film thickness is too thick, cracks may occur in the transparent film, or curling may occur on plastic substrates. (Curvature or warping) may occur.

In the present invention, a single coating liquid can impart a plurality of functions to the transparent film.
Depending on the configuration of the transparent film, the film thickness may be adjusted as follows, for example.
Case (1)
When the upper part is an antireflection film or antiglare film having a low refractive index and the lower part is a hard coat film, a high refractive index film, a conductive film, etc., the film thickness of the antireflection film part is 40 nm to 10 μm, It is preferable that it exists in the range of 60 nm-8 micrometers. If the antireflection film is thin, the optical film thickness deviates from the Fresnel principle, and sufficient antireflection performance may not be obtained. If the antireflection film is too thick, curling may occur in the case of a thin PET film, for example, depending on the type of substrate due to film shrinkage.

  At this time, the refractive index of the lower part of the film is preferably in the range of about 1.48 to 2.20, and the refractive index of the upper antireflection film part is preferably in the range of about 1.45 or less. What is necessary is just to select a metal oxide particle and a matrix so that it may become.

In addition, the transparent film has low reflectivity and antiglare properties, and has high antireflection performance if the lower layer is a high refractive index film, and the metal oxide fine particles (A-2) whose lower layer is surface-treated When antimony pentoxide fine particles are included, it has high hard coat performance and antistatic performance, and ATO
When it contains ITO particles, it has heat ray shielding performance as well as antistatic performance, and when it contains titanium oxide, it has ultraviolet absorption performance.
Case (2)
When the entire transparent coating is used as a conductive film, the thickness of the conductive film portion is preferably in the range of 30 nm to 10 μm, and more preferably in the range of 60 nm to 8 μm. If the film thickness of the conductive film portion is thin, it is difficult to form other films having different functions, and the conductivity may be insufficient because a sufficient conductive path is not formed. If the conductive film is too thick, the shrinkage of the film increases, and curling may occur when the substrate is a thin plastic film or the like.

The surface resistance value of the transparent film having such a conductive film portion is preferably in the range of 10 ³ to 10 ¹³ Ω / □.
When the upper part is a conductive film, the metal oxide fine particles (A-2) having conductivity are used.
The lower part has a hard coat property even when no particles are present.

In addition, when titanium oxide particles are included as the surface-treated metal oxide fine particles (A-2), they have ultraviolet absorption performance, or when low refractive index fine particles are included, they have low dielectric constant characteristics. Yes.
Case (3)
When a transparent film is used as the high refractive index film, the film thickness of the high refractive index film portion is preferably in the range of 40 nm to 10 μm, and more preferably in the range of 60 nm to 8 μm.
When the film thickness of the high refractive index film portion is less than 40 nm, it is difficult to form other films having different functions, and depending on the refractive index of particles or matrices having other functions, a desired refractive index may be obtained. In some cases, a layer having the same cannot be formed.
When the film thickness of the high refractive index film portion exceeds 10 μm, the film shrinks greatly, and curling may occur in the case of a thin plastic film or the like.

The refractive index of the high refractive index film portion is preferably in the range of approximately 1.52 to 2.00.
When the upper part is a high refractive index film, except for the cases (1) and (2), the lower part has a hard coat property even when no particles are present.

  In addition, when ATO, ITO is included as the surface-treated metal oxide fine particles (A-2), it has conductivity, antistatic performance, infrared shielding performance, and contains antimony pentoxide and phosphorus-doped tin oxide. Has antistatic performance and hard coat performance, and when it contains low refractive index silica particles or hollow silica fine particles, it has high hard coat performance and low dielectric constant performance.

  Cases (1), (2), and (3) are cases where the film thickness of the transparent film is uniform. In the substrate with a transparent film of the present invention, the surface of the transparent film has irregularities, and the average of the transparent film The film thickness is in the range of 1 to 10 μm, and the difference (T convex) − (T concave) between the average height of convex parts (T convex) and the average height of concave parts (T concave) is 30 to 1500 nm. It is also suitable as a substrate with a transparent film having an antiglare property, characterized by being in the range.

In the case of a substrate with a transparent coating having antiglare performance, the average particle diameter of the surface-treated metal oxide fine particles (A-2) is preferably in the range of 0.5 to 5 μm, more preferably 1 to 3 μm.
When the average particle diameter of the surface-treated metal oxide fine particles (A-2) is less than 0.5 μm, the difference between the height of the convex portion (T convex) and the height of the concave portion (T concave) of the transparent coating (T convex)-(T concave) may be less than 30 nm, and sufficient anti-glare performance may not be obtained.

When the average particle diameter of the surface-treated metal oxide fine particles (A-2) exceeds 5 μm, the difference between the height (T convex) and the height (T concave) of the convex portion of the transparent coating (T convex) )-(T-concave) may exceed 1.5 μm. In this case, sufficient antiglare performance may not be obtained. In addition, the scratch resistance of the transparent coating may be a problem.

A more preferable range of the difference (T convex) − (T concave) between the average height of convex portions (T convex) and the average height of concave portions (T concave) of the transparent coating is 50 to 1000 nm.
The average film thickness of the transparent coating is preferably in the range of 1 to 10 μm, more preferably 2 to 8 μm. Here, the average film thickness refers to the average value of the average height of convex portions (T convex) and the average height of concave portions (T concave) of the transparent coating. If the transparent film is thin, it is difficult to form a transparent film having two layers and having irregularities, which will be described later. (Curvature or warping) may occur.
Further, the difference (T convex) − (T concave) between the average height of convex portions (T convex) and the average height of concave portions (T concave) of the transparent coating is in the range of 30 to 1500 nm, and further 50 to 1000 nm. Preferably there is.
If (T-convex)-(T-concave) is too small, sufficient antiglare properties may not be obtained. If it is too large, the surface scattering of light may appear large and whitish.

Further, the thickness of the metal oxide fine particles (A-1) unevenly distributed on the upper part of the transparent film is approximately 10 to 10 mm.
It is preferably in the range of 500 nm, more preferably 20 to 300 nm, particularly 50 to 200 nm. When the thickness of the (A-1) layer is small, the antireflection performance may be insufficient. (A-1) Even if the thickness of the layer is too thick, the thickness may deviate from the Fresnel principle. There is a taste.

The base material with a transparent film according to the present invention can be produced by applying the above-described coating material for forming a transparent film onto a base material, drying and curing.
Specifically, the transparent film-forming paint is applied to the substrate by a known method such as dipping, spraying, spinner, roll coating, bar coating, slit coater printing, gravure printing, or micro gravure printing. A transparent film can be formed by applying, drying, and curing by an ordinary method such as ultraviolet irradiation or heat treatment. When manufacturing a substrate with a transparent coating having antiglare properties, a roll coating method, a slit coater printing method, a gravure printing method, and a micro gravure printing method are recommended.

Furthermore, the base material with a transparent film of the present invention may be provided with another film different from the transparent film between the base material and the transparent film and / or on the transparent film. The other coating may be a conventionally known hard coat film, high refractive index film, conductive film, low refractive index film, anti-glare film, infrared shielding film, ultraviolet shielding film, and the hard coating function according to the present invention. May be a transparent film having a high refractive index, a transparent film having a high refractive index, a transparent film having conductivity, and the like.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

[Example 1]
Preparation of paint for forming transparent film (A-1) Silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5% by weight, dispersion medium as low refractive index component : Isopropanol (particle refractive index: 1.30). The sol 100g was mixed with 7.11 g of normal ethyl silicate (manufactured by Tama Chemical Co., Ltd .: ethyl silicate 28, SiO ₂ component 28.8% by weight), 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 5 hours for surface treatment. A silica-based hollow fine particle-dispersed sol was obtained (solid content concentration: 19.3% by weight). The surface charge amount of this surface-treated silica-based hollow fine particle dispersed sol was measured and found to be 25.3 μeq / g. 14.3 g of this surface-treated silica-based hollow fine particle-dispersed sol, 3 g of a hydrophilic resin having a hydroxyl group, 2-hydroxy3-acryloyloxypropyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester G-201P), and hydrophobicity Of resin dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD DPHA), 2.3 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd.) and 100 g of solvent isopropanol, 10 g of methyl isobutyl ketone, A coating solution (A-1) for forming a transparent film was prepared by thoroughly mixing 50 g of propylene glycol monomethyl ether.

Preparation of substrate with transparent film (1) Coating liquid (A-1) for forming a transparent film was prepared as a PET film (Toray Industries, Inc .: Lumirror A-80: thickness 100 μm, refractive index 1.65, substrate transmittance. 88.0%, Haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then cured by irradiation with a high-pressure mercury lamp (80 W / cm) for 1 minute to be transparent A coated substrate (1) was prepared. The film thickness of the transparent coating at this time was 5 μm. A portion of the transparent coating was cut perpendicular to the vertical direction, and the cross-section was observed with a transmission electron microscope. Was not recognized.

The surface resistance value, total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate (1) with a transparent coating were measured, and the results are shown in Table 1.
The total light transmittance and haze were measured with a haze meter (Nippon Denshoku Co., Ltd .: NDH2000), and the reflectance was measured with a spectrophotometer (Nippon Bunko Co., Ltd .: Ubest-55).

Moreover, anti-glare property, adhesiveness, and pencil hardness were evaluated by the following methods and evaluation criteria, and the results are shown in the table.
Anti-glare base material with anti-glare coating with anti-glare function (1) The anti-glare property of the base material is evenly applied with black spray on the back side of the base material. The antiglare property was evaluated. The results are shown in Table 1.

I can't see any fluorescent lights: ◎
Fluorescent light is slightly visible: ○
Fluorescent lamp is visible but outline is blurred: △
Fluorescent light is clearly visible: ×
1 on the surface of the substrate with anti-reflection coating with adhesive hard coat function (1) at intervals of 1 mm in length and width with a knife
One parallel scratch was made to make 100 squares, cellophane tape was adhered to this, and when the cellophane tape was peeled off, the number of squares remaining after the coating was not peeled The adhesion was evaluated by classifying into 4 stages. The results are shown in Table 1.

Number of remaining squares: ◎
Number of remaining squares 90-99: ○
Number of remaining squares: 85 to 89: Δ
Number of remaining squares: 84 or less: ×
Pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.
[Example 2]
Preparation of paint for forming transparent film (A-2) As conductive component, antimony pentoxide fine particle dispersed sol (manufactured by Catalyst Chemical Industry Co., Ltd .: ELCOM V-
4560, an average particle size of 20 nm, a concentration of 30.5% by weight, a dispersion medium: isopropanol, a particle refractive index of 1.60). 100 g of this sol was mixed with 3.76 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicon Co., Ltd .: KBM-503, SiO ₂ component 81.9% by weight), and 10 g of ultrapure water was added to the mixture at 50 ° C. To obtain an antimony pentoxide fine particle-dispersed sol which was stirred for 15 hours and surface-treated (solid content concentration: 29.5% by weight). The surface charge amount of the surface-treated antimony pentoxide fine particle-dispersed sol was measured and found to be 9.8 μeq / g. 84.4 g of this surface-treated antimony pentoxide fine particle sol, 14.3 g of silica-based hollow fine particle dispersed sol prepared in the same manner as in Example 1, and hydrophilic resin 2-hydroxy-3-acryloyloxypropyl methacrylate having hydroxyl groups (Kyoeisha Chemical Co., Ltd .: Light Ester G-201P) 3 g and hydrophobic resin dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) Irgacure 184) 2.3 g, solvent isopropanol 9.1 g, methyl isobutyl ketone 10 g and propylene glycol monomethyl ether 50 g were sufficiently mixed to prepare a coating solution (A-2) for forming a transparent film.
Preparation of substrate with transparent film (2) Transparent film-forming coating material ( A-2) was obtained from a PET film (Toray Industries, Inc .: Lumirror A-80, thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0%, haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was cured by irradiation for 1 minute to prepare a substrate (2) with a transparent coating. The film thickness at this time was 5 μm. A part of the transparent film was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. Silica-based hollow fine particles formed a layer with a thickness of 100 nm at the top, and the presence of antimony pentoxide fine particles at the bottom. Was recognized.

Table 1 shows the results obtained by measuring the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion, and pencil hardness of the obtained substrate (2) with a transparent coating.
[Example 3]
Preparation of coating film for forming transparent film (A-3) Titania fine particle dispersed sol (manufactured by Catalytic Chemical Industry Co., Ltd .: OPTLAK 1137Z average particle diameter 20 nm, concentration 30.5% by weight, dispersion medium: methanol Particle refraction The rate 2.10) was used. 100 g of this sol was mixed with 7.45 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicon Co., Ltd .: KBM-5103, SiO ₂ component 81.9 wt%), and 10 g of ultrapure water was added to the mixture at 50 ° C. To obtain a titania fine particle dispersed sol which was stirred for 5 hours and surface-treated (solid content concentration: 31.2 wt%). The surface charge amount of the surface-treated titania fine particle-dispersed sol was measured and found to be 8.2 μeq / g.

86.3 g of this surface-treated titania fine particle gel, 14.3 g of silica-based hollow fine particle dispersed sol prepared in the same manner as in Example 1, and a hydrophilic acrylate resin having a hydroxyl group (manufactured by Kyoeisha Chemical Co., Ltd .: MMH-40) 3.8 g of propylene glycol monomethyl ether dispersion, solid content concentration: 40% by weight) and 28.5 g of hydrophobic resin dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD DPHA) A coating for transparent film formation (A- 3) was prepared.
Preparation of substrate with transparent coating (3) A coating for forming a transparent coating (A-3) was prepared from PET film (Toray Industries, Inc .: Lumirror A-80: thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0%, haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was irradiated and cured for 1 minute to prepare a substrate (3) with a transparent coating. The film thickness at this time was 5 μm. A part of the transparent coating was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. As a result, silica-based hollow fine particles formed a layer with a thickness of 100 nm in the upper part, and the presence of titania fine particles was observed in the lower part. It was.

Table 1 shows the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion, and pencil hardness of the obtained substrate (3) with a transparent coating.
[Example 4]
Preparation of paint for forming transparent film (A-4) ATO fine particle dispersed sol (manufactured by Catalyst Chemical Industries, Ltd .: ELCOM V-3) as an antistatic high refractive index component
501; average particle diameter 8 nm; concentration 20.5 wt%; dispersion medium: ethanol particle refractive index 1.75). To 100 g of this sol, 5.05 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicon Co., Ltd .: KBM-503, SiO ₂ component 81.9 wt%) was added, and 10 g of ultrapure water was added and 50 ° C. The surface-treated ATO fine particle-dispersed sol was obtained (solid content concentration: 21.4% by weight). The surface charge amount of this surface-treated ATO fine particle-dispersed sol was measured and found to be 7.78 μeq / g. 100 g of this surface-treated ATO fine particle dispersed sol, 14.3 g of silica-based hollow fine particle dispersed sol prepared in the same manner as in Example 1, and a hydrophilic resin 2-hydroxyethyl acrylate having a hydroxyl group (Kyoeisha Chemical Co., Ltd .: Light Ester) 3 g of HOP-A) and 27 g of hydrophobic resin dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA), 2.3 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) and solvent isopropanol 23.4 g and ethylene glycol monobutyl ether 20 g were sufficiently mixed to prepare a coating solution (A-4) for forming a transparent film.
Preparation of substrate with transparent film (4) Paint for transparent film formation (A-4) was obtained from PET film (Toray Industries, Inc .: Lumirror A-80, thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0%, haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was cured by irradiation for 1 minute to prepare a substrate (4) with a transparent coating. The film thickness at this time was 3 μm. When a part of the transparent coating was cut perpendicularly in the vertical direction and the cross section was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer with a thickness of 100 nm in the upper part, and the presence of ATO particles was observed in the lower part. It was.

Table 1 shows the results obtained by measuring the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion, and pencil hardness of the obtained substrate with transparent coating (4).
[Example 5]
Preparation of paint for forming transparent film (A-6) Silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium) : Isopropanol (particle refractive index: 1.30). 100 g of this sol was mixed with 4.02 g of methyl silicate (manufactured by Tama Chemical Co., Ltd .: methyl silicate 51, SiO ₂ component 51.0 wt%), 10 g of ultrapure water was added, and the mixture was stirred at 40 ° C. for 5 hours for surface treatment. A silica-based hollow fine particle-dispersed sol was obtained (solid content concentration: 19.8% by weight). The surface charge amount of the surface-treated silica-based hollow fine particle-dispersed sol was measured and found to be 28.0 μeq / g. ATO fine particle dispersion sol (manufactured by Catalytic Chemical Industry Co., Ltd .: ELCOM V-3501, average particle diameter 8 nm, concentration 20.5 wt%, dispersion medium: ethanol, particle refractive index 1.75) as an antistatic high refractive index component Using. 100 g of this sol was mixed with 2.50 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicon Co., Ltd .: KBM-5103, SiO ₂ component 81.2% by weight), and 10 g of ultrapure water was added to the mixture at 50 ° C. The surface-treated ATO fine particle-dispersed sol was obtained (solid content concentration: 20.0% by weight). The surface charge amount of this surface-treated ATO fine particle dispersed gel was measured and found to be 9.9 μeq / g. The surface-treated silica-based hollow fine particle dispersion sol 14 g, the surface-treated ATO fine particle dispersion sol 100 g, a hydrophilic resin 2-hydroxyethyl acrylate having a hydroxyl group (manufactured by Kyoeisha Chemical Co., Ltd .: Light Ester HOP-A) and hydrophobic Resin resin hexaerythritol tripentaacrylate (made by Nippon Kayaku Co., Ltd .: KAYARAD DPHA), photoinitiator (Irgacure 184 made by Ciba Specialty Co., Ltd.) 2.3 g and isopropanol 23.7 g and ethylene glycol mono A transparent coating film-forming paint (A-5) was prepared by thoroughly mixing 30 g of butyl ether.
Preparation of substrate with transparent film (5) Paint for transparent film formation (A-5) was obtained from PET film (Toray Industries, Inc .: Lumirror A-80, thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0%, haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was irradiated for 1 minute and cured to prepare a substrate (5) with a transparent coating. The film thickness at this time was 3 μm. When a part of the transparent coating was cut perpendicularly in the vertical direction and the cross section was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer with a thickness of 100 nm in the upper part, and the presence of ATO particles was observed in the lower part. It was.

Table 1 shows the results obtained by measuring the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion, and pencil hardness of the obtained substrate (5) with a transparent coating.
[Example 6]
Preparation of paint for forming transparent film (A-6) Titanium oxide particles (Catalyst Chemical Industries, Ltd .: titanium microbead, average particle diameter 0.5 μm, particle refractive index 2.40) were used as high refractive index components. . 20.5 g of this titanium oxide particle was put into 79.5 g of ethyl alcohol, and 3.75 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, SiO ₂ component 81.9% by weight) ), 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated titanium oxide particle dispersion (solid content concentration: 20.7 wt%). The surface charge amount of this surface-treated titanium oxide particle dispersion was measured and found to be 10.2 μeq / g. 30 g of this surface-treated titanium oxide particle dispersion liquid, 7.7 g of a silica-based hollow fine particle dispersion sol prepared in the same manner as in Example 1, and a hydrophilic resin 2-hydroxy-3acryloyloxypropyl methacrylate having a hydroxyl group (Kyoeisha) 2.7 g of Chemical Co., Ltd .: Light Ester G-201P) and 24.3 g of hydrophobic resin hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) ) Irgacure 184) 1.6 g and 13.2 g of isopropanol as a solvent, 2.7 g of methyl isobutyl ketone, and 10 g of propylene glycol monomethyl ether were sufficiently mixed to prepare a paint (A-6) for forming a transparent film. .
Preparation of substrate with transparent film (6) Paint (A-6) for forming a transparent film was made of PET film (Toray Industries, Inc .: Lumirror A-80, thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0% Haze 2.0% reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) Was cured by irradiation for 1 minute to prepare a substrate (6) with a transparent coating. When a part of the transparent coating was cut perpendicularly in the vertical direction and the cross section was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer of 100 nm in thickness on the top and the presence of titanium oxide particles on the bottom. Admitted.

Table 1 shows the results obtained by measuring the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion, and pencil hardness of the obtained substrate with transparent coating (6).
[Example 7]
Preparation of coating film for forming transparent film (A-7) Titanium oxide particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: titanium microbead, average particle diameter 3.0 μm, particle refractive index 2.40) were used as high refractive index components. . 20.5 g of this titanium oxide particle was put into 79.5 g of ethyl alcohol, and 3.75 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, SiO ₂ component 81.9% by weight) ), 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated titanium oxide particle dispersion (solid content concentration: 20.7 wt%). The surface charge amount of the surface-treated titanium oxide particle dispersion was measured and found to be 9.2 μeq / g. 30 g of this surface-treated titanium oxide particle dispersion, 7.7 g of a silica-based hollow fine particle dispersion sol prepared in the same manner as in Example 1, and a hydrophilic resin diethylaminoethyl methacrylate having an amino group (Kyoeisha Chemical Co., Ltd .: Wright) 2.7 g of ester DE) and 24.3 g of hydrophobic resin pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate PE-4A) and photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184) 1 .6 g and 13.2 g of isopropanol as a solvent, 2.7 g of methyl isobutyl ketone, and 10 g of propylene glycol monomethyl ether were sufficiently mixed to prepare a transparent film-forming paint (A-7).
Preparation of substrate with transparent coating (7) A coating for forming a transparent coating (A-7) was made from a PET film (Toray Industries, Inc .: Lumirror A-80: thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0%, Haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was irradiated and cured for 1 minute to prepare a substrate (7) with a transparent coating. When a part of the transparent coating was cut perpendicularly in the vertical direction and the cross section was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer of 100 nm in thickness on the top and the presence of titanium oxide particles on the bottom. Admitted.

Table 1 shows the results obtained by measuring the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion, and pencil hardness of the obtained substrate with transparent film (7).
[Example 8]
Preparation of transparent film-forming coating material (A-8) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Thruria 1420, average particle diameter 100 nm, concentration 20.5% by weight, dispersion medium : Isopropanol particle refractive index 1.20). To 100 g of this sol, 7.11 g of ethyl orthosilicate (Tama Chemical (
Co., Ltd .: ethyl silicate 28, SiO ₂ component 28.8% by weight), 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 5 hours to obtain a silica-based hollow fine particle dispersed sol (solid content concentration). : 19.3% by weight). The surface charge amount of the surface-treated silica-based hollow fine particle dispersed sol was measured and found to be 30.0 μeq / g. 14.3 g of this surface-treated silica-based hollow fine particle dispersed sol, 84.4 g of antimony pentoxide fine particle sol prepared in the same manner as in Example 2 (solid content concentration: 29.5 wt%), and a hydrophilic resin having a hydroxyl group 2 g of 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester HO) and 27 g of hydrophobic resin dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) and photoinitiator (Ciba Specialty) Co., Ltd .: Irgacure 184) 2.3 g, solvent isopropanol 9.1 g, methyl isobutyl ketone 10 g, and propylene glycol monomethyl ether 50 g were sufficiently mixed to prepare a coating solution (A-8) for forming a transparent film. .
Preparation of substrate with transparent film (8) Paint for transparent film formation (A-8) was obtained from PET film (Toray Industries, Inc .: Lumirror A-80: thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0% Haze 2.0% reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) Was cured by irradiation for 1 minute to prepare a substrate (8) with a transparent coating. The film thickness at this time was 5 μm. A part of the transparent film was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. Silica-based hollow fine particles formed a layer with a thickness of 100 nm at the top, and the presence of antimony pentoxide fine particles at the bottom. Was recognized.

Table 1 shows the results obtained by measuring the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion, and pencil hardness of the obtained substrate with transparent coating (8).
[Example 9]
Preparation of paint for forming transparent film (A-9) 7.7 g of surface-treated silica-based hollow fine particle dispersion sol prepared in the same manner as in Example 8 and surface-treated titanium oxide particle dispersion prepared in the same manner as in Example 7 30 g of a liquid and 2.7 g of a hydrophilic resin having a hydroxyl group, 2-hydroxy-3acryloyloxypropyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Ester G-201P) and a hydrophobic resin hexaerythritol tripentaacrylate (Japan) 24.3 g of Kayaku Co., Ltd .: KAYARAD DPHA, 1.6 g of photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184), 13.2 g of isopropanol as a solvent, and 12.7 g of ethylene glycol monobutyl ether Were sufficiently mixed to prepare a transparent film-forming paint (A-9).
Preparation of substrate with transparent film (9) Paint (A-9) for forming a transparent film was made of PET film (Toray Industries, Inc .: Lumirror A-80: thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0% Haze 2.0% reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) Was cured by irradiation for 1 minute to prepare a substrate (9) with a transparent coating. When a part of the transparent coating was cut perpendicularly in the vertical direction and the cross section was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer of 100 nm in thickness on the top and the presence of titanium oxide particles on the bottom. Admitted.

Table 1 shows the results obtained by measuring the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion and pencil hardness of the obtained substrate (9) with a transparent coating.
[Comparative Example 1]
Preparation of Transparent Film Forming Paint (R-1) 14.3 g of silica-based hollow fine particle dispersion sol prepared in the same manner as in Example 1, and hydrophobic resin dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 2.3 g of photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184), 90 g of solvent isopropanol, and 70 g of methyl isobutyl ketone were sufficiently mixed to form a coating solution for forming a transparent film (R- 1) was prepared.

Preparation of substrate with transparent coating (R-1) A coating solution (R-1) for forming a transparent coating was obtained from a PET film (Toray Industries, Inc .: Lumirror A-80: thickness 100 μm, refractive index 1.65, substrate. (Transmissivity 88.0%, Haze 2.0%, Reflectance 5.1%) applied with a bar coater, dried at 70 ° C for 1 minute, and then cured by irradiation with a high-pressure mercury lamp (80 W / cm) for 1 minute. Thus, a substrate (1) with a transparent coating was prepared. The film thickness of the transparent coating at this time was 5 μm. A part of the transparent film was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. Admitted.

The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate with transparent coating (R-1) were measured, and the results are shown in Table 1.
[Comparative Example 2]
Preparation of paint for forming transparent film (R-2) Silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5% by weight, dispersion medium as low refractive index component : Isopropanol, particle refractive index 1.30). The surface charge amount of the silica-based hollow fine particle dispersed sol was measured and found to be 39.0 μeq / g.

As a conductive component, antimony pentoxide fine particle dispersion sol (manufactured by Catalyst Chemical Industry Co., Ltd .: ELCOM V-
4560, an average particle size of 20 nm, a concentration of 30.5% by weight, a dispersion medium: isopropanol, a particle refractive index of 1.60). The surface charge amount of the antimony pentoxide fine particle-dispersed sol was measured and found to be 38.0 μeq / g.

84 g of this antimony pentoxide fine particle sol, 14 g of silica-based hollow fine particle dispersion sol, 3 g of hydrophilic resin 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester HO) having a hydroxyl group and hydrophobic resin dipentaerythritol hexa 27 g of acrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA), 2.3 g of photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184), 9.1 g of solvent isopropanol, and 60 g of methyl isobutyl ketone are sufficiently mixed. Thus, a coating solution (R-2) for forming a transparent film was prepared.
Preparation of substrate with transparent film (R-2) Paint (R-2) for forming a transparent film was obtained from PET film (Toray Industries, Inc .: Lumirror A-80: Thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0% Haze 2.0% reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) Was cured by irradiation for 1 minute to prepare a substrate with transparent coating (R-2). The film thickness at this time was 5 μm. A part of the transparent film was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. Silica hollow fine particles and antimony pentoxide fine particles were dispersed throughout the film. Existence was observed in a state where hollow fine particles and antimony pentoxide fine particles were mixed.

Table 1 shows the results obtained by measuring the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion, and pencil hardness of the obtained transparent film-coated substrate (R-2).
[Comparative Example 3]
Preparation of Transparent Film Forming Paint (R-3) Titanium oxide particles (Catalyst Chemical Industries, Ltd .: Titanium microbead, average particle size 3.0 μm, particle refractive index 2.40) were used as high refractive index components. . 20.5 g of the titanium oxide particles are put in 79.5 g of ethyl alcohol, 7.11 g of normal ethyl silicate (ethyl silicate 28 SiO ₂ component 28.8% manufactured by Tama Chemical) is mixed, and 10 g of ultrapure water is added. A silica-based hollow fine particle-dispersed sol which was stirred for 5 hours at 50 ° C. and surface-treated was obtained (solid content concentration: 19.3% by weight).

The surface charge amount of this surface-treated titanium oxide particle dispersion was measured and found to be 32.0 μeq.
/ G. 30 g of this surface-treated titanium oxide particle dispersion and a silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Thruria 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium) : Isopropanol, particle refractive index 1.30, surface charge 39.0 μeq / g) 7.7 g and a hydrophilic resin 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester HO) 2 .7 g and a hydrophobic resin hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 24.3 g, photoinitiator (manufactured by Ciba Specialty Ltd .: Irgacure 184) and isopropano as a solvent -A coating (R-3) for forming a transparent film was prepared by thoroughly mixing 13.2 g of styrene and 12.7 g of ethylene glycol monobutyl ether.
Preparation of substrate with transparent coating (R-3) A coating for forming transparent coating (R-3) was obtained from PET film (Toray Industries, Inc .: Lumirror A-80: thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0%, haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was irradiated and cured for 1 minute to prepare a substrate with a transparent coating (R-3). When a part of the transparent coating was cut perpendicularly in the vertical direction and the cross section was observed with a transmission electron microscope, silica-based hollow fine particles and titanium oxide particles were dispersed throughout the film. Existence was observed in a state where fine particles and titanium oxide particles were mixed.

Table 1 shows the results obtained by measuring the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion and pencil hardness of the obtained substrate with transparent coating (R-3).
[Comparative Example 4]
Preparation of Transparent Film Forming Paint (R-3) Silica-based hollow fine particle dispersion sol 14.3 prepared in the same manner as in Example 1, and 84.4 g of antimony pentoxide fine particle sol prepared in the same manner as in Example 2 30 g of hydrophobic resin dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 2.3 g of photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184) and 29.1 g of solvent isopropanol, methyl isobutyl ketone A coating solution (R-4) for forming a transparent film was prepared by sufficiently mixing 40 g.
Preparation of substrate with transparent coating (R-4) A coating for transparent coating formation (R-4) was prepared from PET film (Toray Industries, Inc .: Lumirror A-80: thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0%, haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coated substrate (R-4). A part of the transparent film was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. Silica hollow fine particles and antimony pentoxide fine particles were dispersed throughout the film. Existence was observed in a state where hollow fine particles and antimony pentoxide fine particles were mixed.

Table 1 shows the results obtained by measuring the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, antiglare property, adhesion, and pencil hardness of the obtained substrate with transparent coating (R-4).
[Comparative Example 5]
Preparation of Transparent Film Forming Coating Material (R-5) 143 g of silica-based hollow fine particle dispersion sol prepared in the same manner as in Example 1, and hydrophilic resin 2-hydroxyethyl methacrylate having a hydroxyl group (Kyoeisha Chemical Co., Ltd .: 2.7 g of light ester HO and 27.3 g of hydrophobic resin dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 1.8 g of photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184) Then, 90 g of a solvent isopropanol and 50 g of methyl isobutyl ketone were sufficiently mixed to prepare a coating solution (R-1) for forming a transparent film.

Preparation of substrate with transparent coating (R-5) A coating solution (R-5) for forming a transparent coating was prepared from a PET film (Toray Industries, Inc .: Lumirror A-80: thickness 100 μm, refractive index 1.65, substrate. (Transmissivity 88.0%, Haze 2.0%, Reflectance 5.1%) applied with a bar coater, dried at 70 ° C for 1 minute, and then cured by irradiation with a high-pressure mercury lamp (80 W / cm) for 1 minute. Thus, a substrate (1) with a transparent coating was prepared. The film thickness of the transparent coating at this time was 5 μm. A part of the transparent film was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. Admitted.

Surface resistance value, total light transmittance, haze, wavelength 550 nm of the obtained substrate with transparent coating (R-5)
The reflectance of the light beam was measured, and the results are shown in Table 1.
[Comparative Example 6]
Preparation of paint for forming transparent film (R-6) 72 g of silica-based hollow fine particle dispersion sol prepared in the same manner as in Example 1, 72 g of antimony pentoxide fine particle sol prepared in the same manner as in Example 2, and a hydroxyl group Photoinitiator to 2.7 g of hydrophilic resin 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester HO) and 30 g of hydrophobic resin dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) (Ciba Specialty Co., Ltd .: Irgacure 184) 2.3 g, solvent isopropanol 29 g, and methyl isobutyl ketone 40 g were sufficiently mixed to prepare a coating solution (R-6) for forming a transparent film.
Preparation of substrate with transparent coating (R-6) A coating for transparent coating (R-6) was prepared from PET film (Toray Industries, Inc .: Lumirror A-80: thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0%, haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was cured by irradiation for 1 minute to prepare a transparent coated substrate (R-6). The film thickness at this time was 5 μm. A part of the transparent film was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. Silica hollow fine particles and antimony pentoxide fine particles were dispersed throughout the film. Existence was observed in a state where hollow fine particles and antimony pentoxide fine particles were mixed.

Surface resistance value, total light transmittance, haze, wavelength 550 nm of the obtained substrate with transparent coating (R-6)
The light reflectance, antiglare property, adhesion and pencil hardness were measured and the results are shown in Table 1.
[Comparative Example 7]
Preparation of transparent film-forming coating material (R-7) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium : Isopropanol particle refractive index 1.30). 100 g of this sol was mixed with 10 g of perfluorooctylethyltriethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: AY43-158E, 26.6% by weight of SiO ₂ component), 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 15 hours. Thus, a silica-based hollow fine particle-dispersed sol surface-treated was obtained (solid content concentration: 19.3% by weight). The surface charge amount of this surface-treated silica-based hollow fine particle dispersed sol was measured and found to be 8.3 μeq / g. 14.3 g of this surface-treated silica-based hollow fine particle dispersed sol, 3 g of hydrophilic resin 2-hydroxy-3-acryloyloxypropyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester G-201P) having a hydroxyl group, and hydrophobicity Resin dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 54 g, photoinitiator (Ciba Specialty Co., Ltd .: Irgacure 184) 2.3 g, solvent isopropanol 100 g, methyl isobutyl ketone 10 g Then, 50 g of propylene glycol monomethyl ether was thoroughly mixed to prepare a coating solution for forming a transparent film (R-7).
Preparation of substrate with transparent coating (R-7) A coating for forming transparent coating (R-7) was prepared from PET film (Toray Industries, Inc .: Lumirror A-80: Thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0%, Haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coated substrate (R-7). The film thickness at this time was 5 μm. When a part of the transparent coating was cut perpendicular to the vertical direction and the cross section was observed with a transmission electron microscope, silica-based hollow fine particles were dispersed throughout the film, and the presence of more silica-based hollow fine particles was observed in the lower part. It was.

Surface resistance value, total light transmittance, haze, wavelength of 550 nm of the obtained substrate with transparent coating (R-7)
The light reflectance, antiglare property, adhesion and pencil hardness were measured and the results are shown in Table 1.
[Comparative Example 8]
Preparation of transparent film-forming coating material (R-7) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium : Isopropanol (particle refractive index: 1.30). Silica solution 20g (manufactured by Catalyst Kasei Kogyo Co., Ltd .: SiO ₂ component 4.0%) was added to 100 g of this sol and stirred for 15 hours at 50 ° C. to obtain a silica-based hollow fine particle dispersed sol (solid content). 17.8%). The surface charge amount of this surface-treated silica-based hollow fine particle dispersed sol was measured and found to be 102 μeq / g. 14.3 g of this surface-treated silica-based hollow fine particle dispersed sol, 3 g of hydrophilic resin 2-hydroxy-3-acryloyloxypropyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester G-201P) having a hydroxyl group, and hydrophobicity Resin dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 54 g, photoinitiator (Ciba Specialty Co., Ltd .: Irgacure 184) 2.3 g, solvent isopropanol 100 g, methyl isobutyl ketone 10 g Then, 50 g of propylene glycol monomethyl ether was thoroughly mixed to prepare a coating solution for forming a transparent film (R-8).
Preparation of substrate with transparent coating (R-8) A coating for forming transparent coating (R-8) was prepared from PET film (Toray Industries, Inc .: Lumirror A-80: thickness 1
00 μm, refractive index 1.65, base material transmittance 88.0%, Haze 2.0%, reflectance 5.1%), coated with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was irradiated for 1 minute and cured to prepare a transparent coated substrate (R-7). The film thickness at this time was 5 μm. A part of the transparent film was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. Silica hollow particles were dispersed throughout the film, and the presence of locally agglomerated silica hollow particles was observed. It was.

Surface resistance value, total light transmittance, haze, wavelength of 550 nm of the obtained substrate with transparent coating (R-8)
The light reflectance, antiglare property, adhesion and pencil hardness were measured and the results are shown in Table 1.

The schematic diagram of the cross section of the transparent film which concerns on this invention is shown. The schematic diagram of the cross section of the transparent film which concerns on this invention is shown. The schematic diagram of the cross section of the transparent film which concerns on this invention is shown. The schematic diagram of the cross section of the transparent film which concerns on this invention is shown. The schematic diagram of the cross section of the transparent film which concerns on this invention is shown. The schematic diagram of the cross section of the transparent film which concerns on this invention is shown. The schematic diagram of the cross section of the transparent film which concerns on this invention is shown.

Claims (18)

(A-1) metal oxide fine particles that have been surface-treated with an organosilicon compound and the surface-treated fine particles have a surface charge amount (Q _A-1 ) in the range of 20 to 100 μeq / g;
(B-1) consisting of a hydrophilic matrix-forming component and (C) a polar solvent,
The concentration (C _PA-1 ) as a solid content of the metal oxide fine particles (A-1) is in the range of 0.1 to 20% by weight,
Concentration (C _MB-1 ) as a solid content of the hydrophilic matrix forming component (B _-1 ) is 1 to 50% by weight
A transparent film-forming paint characterized by being in the range of 2. The transparent film-forming paint according to claim 1, wherein the organosilicon compound is an organosilicon compound represented by the following formula (1).
R _a Six _4-a (1)
(In the formula, X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, and hydrogen, and may be the same or different. R is unsubstituted or substituted having 1 to 10 carbon atoms. Hydrocarbon groups which may be the same or different from each other, a being an integer of 0 or 1) The transparent film according to claim 1 or 2, wherein the surface-treated metal oxide fine particles (A-1) have a refractive index (n _A-1 ) in the range of 1.15 to 1.40. Forming paint. The hydrophilic matrix forming component (B-1) is an organosilicon compound represented by the following formula (2) or a hydrolyzate, hydrolyzed polycondensate thereof, and / or a hydroxyl group, an amino group, a carboxyl group, a sulfo group. The transparent film-forming paint according to any one of claims 1 to 3, which is a polyfunctional (meth) acrylic acid ester resin having at least one hydrophilic functional group selected from a group.
R _a Six _4-a (2)
(In the formula, X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, and hydrogen, and may be the same or different. R is unsubstituted or substituted having 1 to 10 carbon atoms. Hydrocarbon groups which may be the same or different from each other, a being an integer of 0 or 1) 5. The transparent film-forming paint according to claim 1, wherein the surface-treated metal oxide fine particles (A-1) have an average particle diameter in the range of 5 to 500 nm. As the matrix-forming component, further comprising a hydrophobic matrix-forming component (B-2),
The concentration ratio (C _MB-1 ) / (C _MB-2 ) between the concentration (C _MB-2 ) of the hydrophobic matrix-forming component as a solid content and the above (C _MB-1 ) is 0.005 to 1 It is in a range, The transparent film formation coating material in any one of Claims 1-5 characterized by the above-mentioned. The hydrophobic matrix forming component (B-2) is an organosilicon compound represented by the following formula (3) or a hydrolyzate thereof, a hydrolyzed polycondensate, and / or a vinyl group, a urethane group, an epoxy group, (meth) acryloyl group, a transparent according to claim 1, characterized in that the polyfunctional (meth) acrylic acid ester resin having one or more hydrophobic functional group selected from CF ₂ group Film-forming paint.
_{R n -SiX 4-n (3} )
(In the formula, 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: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3. However, when a in formula (2) is 1, n is 2 to 3)) The paint, together with (A-1) metal oxide fine particles,
(A-2) Surface charge of the surface treated particles (Q _A
-2 ) is a metal oxide fine particle in the range of 5 to 80 μeq / g, and the refractive index (n _A-2 ) of the metal oxide fine particle (A-2) is higher than (n _A-1 ), The difference (Q _A-1 ) − (Q _A-2 ) between the surface charge amount (Q _A-2 ) and (Q _A-1 ) of the surface-treated metal oxide fine particles ( _A-2 ) is 10 to 95 μeq. The paint for forming a transparent film according to any one of claims 1 to 7, which is in a range of / g. The paint for forming a transparent film according to any one of claims 1 to 8, wherein the metal oxide fine particles (A-2) are surface-treated with an organosilicon compound represented by the following formula (4): .
_{R n -SiX 4-n (4} )
(In the formula, 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: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3. However, when a in formula (1) is 1, n is 2 to 3)) The concentration (C _PA-2 ) as a solid content of the surface-treated metal oxide fine particles (A _-2 ) is 0.1.
The paint for forming a transparent film according to claim 1, wherein the paint is in a range of ˜20 wt%. 11. The coating material for forming a transparent film according to claim 1, wherein the surface-treated metal oxide fine particles (A-2) have an average particle diameter in the range of 5 nm to 5 [mu] m. A substrate with a transparent coating in which a transparent coating is formed on the substrate,
Transparent film
(i) consisting of metal oxide fine particles (A-1) surface-treated with an organosilicon compound having a surface charge (Q _A ) in the range of 20 to 100 μeq / g and a hydrophilic matrix component (B-1) ,
(ii) The surface-treated metal oxide particles (A-1) are unevenly distributed in the upper part of the transparent coating, and the content of the surface-treated metal oxide fine particles (A-1) in the transparent coating ( W _PA-1 ) is 0.2 to 90% by weight
A substrate with a transparent coating, wherein the matrix component content (W _M ) is in the range of 10 to 99.8% by weight. The matrix component further comprises a hydrophobic matrix component (B-2), and the content (W _MB-1 ) of the hydrophilic matrix component (B-1) as a solid content and the solid content of the hydrophobic matrix component the ratio of the content of the content _{(W MB-2) (W} MB-1) / (W MB-2) is transparent according to claim 12, characterized in that in the range of 0.005 Base material with coating. Furthermore, the surface-treated metal oxide fine particles (A-2) comprising surface-treated metal oxide fine particles (A-2) having a surface charge amount (Q _A-2 ) in the range of 5 to 80 μeq / g. ) Refractive index (n _A-2 )
Is higher than the refractive index (n _A-1 ) of the surface-treated metal oxide fine particles (A-1), and the surface-treated metal oxide fine particles (A-2) form a layer on the substrate surface. 14. The transparent film-coated base according to claim 12 or 13, wherein the transparent film-coated base is unevenly distributed or dispersed between the surface-treated metal oxide fine particles (A-1) and the substrate surface. Wood. 15. The substrate with a transparent coating according to claim 12, wherein the content of the surface-treated metal oxide fine particles (A-2) is in the range of 5 to 70% by weight. The average particle diameter of the surface-treated metal oxide fine particles (A-1) is in the range of 5 to 500 nm, and the average particle diameter of the surface-treated metal oxide fine particles (A-2) is 5 nm to 5 μm. It is in a range, The base material with a transparent film in any one of Claims 12-15 characterized by the above-mentioned. Refraction of the surface-treated metal oxide fine particles refractive index of (A-1) the refractive index of the (n _A-1) and the surface-treated metal oxide fine particles _{(A-2) (n A} -2) The base material with a transparent film according to any one of claims 12 to 16, wherein the rate difference (n _A-2 )-(n _A-1 ) is 0.20 or more.   The surface of the transparent coating has irregularities, the average film thickness of the transparent coating is in the range of 1 to 10 μm, the average height of convex portions (T convex) and the average height of concave portions (T concave) The substrate with a transparent coating according to claim 14, wherein the difference (T convex) − (T concave) is in the range of 30 to 1500 nm.

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