JP2012025793A - Transparent film-forming coating liquid and substrate with transparent film - Google Patents

Abstract

[PROBLEMS] To form a substrate with a transparent coating that has high conductivity even with a small amount of conductive inorganic oxide fine particles, has high transparency, suppresses coloring and interference fringes, and is excellent in economy. A coating solution for forming a transparent film is provided.
SOLUTION: Conductive inorganic oxide fine particles surface-treated with an organosilicon compound represented by the following formula (1) are non-aggregated and highly dispersed, and the concentration as a solid content is 0.01 to 6 mass. The coating for forming a transparent film, which contains ketones as a dispersion medium, has a total solid concentration of 1 to 60% by mass, and a matrix-forming component has a concentration of 0.1 to 59.4% by mass. liquid. R _n —SiX _4-n (1) (wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: carbon (Alkoxy group of formulas 1 to 4, hydroxyl group, halogen, hydrogen, n: integer of 0 to 3)
[Selection] Figure 1

Description

  In the present invention, the surface-treated conductive inorganic oxide fine particles have a chain structure in the transparent film and are highly dispersed. Therefore, even if the amount of the conductive inorganic oxide fine particles is small, high conductivity is obtained. It has high transparency, coloring and interference fringes are suppressed, and the coating liquid for forming a transparent film and the substrate with a transparent film are excellent in economy.

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

Further, when used in a display device or the like, in order to prevent electrostatic adhesion of dust, dust and the like in addition to hard coat properties, conductivity is imparted to a transparent film to prevent charging.
In order to impart such conductivity, it is known to incorporate conductive oxide particles.

  As the conductive oxide particles, tin oxide, Sb, F or P-doped tin oxide, indium oxide, Sn or F-doped indium oxide, antimony pentoxide, low-order titanium oxide, and the like are known. (Patent Document 1: JP 2002-79616 A)

  The applicant of the present application is a substrate with a transparent antistatic film containing antimony pentoxide fine particles having a pyrochlore structure (Patent Document 2: JP-A-2001-72929), as a substrate with a film containing conductive oxide particles, Substrate with hard coat film containing antimony oxide fine particles (Patent Document 3: Japanese Patent Application Laid-Open No. 2004-50810), and substrate with hard coat film containing chain antimony pentoxide fine particles (Patent Document 4: Japanese Patent Application Laid-Open No. 2005-139026) In addition, a substrate with a transparent conductive film containing chain-shaped conductive fine particles (ATO and other various types) in which conductive fine particles are connected by a hydrolyzate of an organosilicon compound (Patent Document) 5: Japanese Patent Laid-Open No. 2006-339113).

JP 2002-79616 A JP 2001-72929 A JP 2004-50810 A JP 2005-139026 A JP 2006-339113 A

  However, in the case of a conventional coated substrate using conductive oxide particles, for example, when antimony pentoxide fine particles are used, the transparency is excellent but the antistatic performance is insufficient. For this reason, when the content of the antimony pentoxide fine particles is increased, there is a problem that interference fringes are generated or the economy is lowered.

  Further, when P-doped tin oxide (PTO) is used, the antistatic performance is improved as compared with the case where antimony pentoxide fine particles are used, but transparency is insufficient, and Sb-doped tin oxide (ATO) is used. However, although the antistatic performance is further improved, the transparency may be lowered or the color may be colored to lower the transmittance. Further, when Sn-doped indium oxide (ITO) is used, the antistatic performance is further improved, but there is a problem in transparency and colorability.

  It has been known that the conductivity of tin oxide and indium oxide is improved by doping with a doping agent as described above. However, although P-doped tin oxide fine particles (PTO), Sn-doped indium oxide fine particles (ITO), and Sb-doped tin oxide fine particles (ATO) have high conductivity, there is a problem that transparency is lowered or coloring is caused. Depending on the refractive index of the matrix component, interference fringes may occur, and if the content is decreased to suppress coloring, the antistatic performance may be insufficient.

  Therefore, in order to improve the conductivity, as disclosed in Patent Document 4, by connecting the fine particles in a chain and reducing the grain boundary resistance, sufficient charge can be obtained even if the amount of the particles themselves is reduced. It was difficult to maintain the prevention performance and obtain a transparent coating without coloring and interference fringes.

  Furthermore, conventionally, when both hard coat performance and antistatic performance are required, a separate antistatic layer has been formed on the hardcoat layer. A coating solution capable of forming a transparent film having performance and a substrate with a transparent film are desired.

  As a result of intensive studies in view of such problems, the present inventors have found that when a dispersion medium of ketones and, for example, an ethylene oxide-modified acrylic resin is used as a matrix-forming component, surface-treated conductive inorganic oxide particles are obtained. A transparent coating that exists in the form of chain particles highly dispersed in a transparent coating, has high conductivity even when used in a small amount, has high transparency, and suppresses coloring and interference fringes and has excellent hard coat properties. As a result, the present invention was completed.

[1] A conductive inorganic oxide fine particle, a matrix-forming component, and a dispersion medium, the conductive inorganic oxide fine particle is surface-treated with an organosilicon compound represented by the following formula (1), and the dispersion medium is a ketone The concentration of the total solid content is in the range of 1 to 60% by mass, the surface-treated conductive inorganic oxide fine particles are non-agglomerated and highly dispersed, and the concentration as a solid content is 0.01 The concentration of the matrix-forming component as a solid content is in the range of 0.1 to 59.4% by mass, and the conductive inorganic oxide fine particles have a chain structure in the obtained transparent film. A coating liquid for forming a transparent film that can be formed.
_{R n -SiX 4-n (1} )
(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 0 to 3)

[2] The transparent coating film according to [1], wherein the conductive inorganic oxide fine particles are Sb-doped tin oxide (ATO) fine particles and / or P-doped tin oxide (PTO) fine particles, and the average particle diameter is in the range of 5 to 10 nm. Coating liquid for forming.

[3] The transparent coating film according to [1] or [2], wherein the conductive inorganic oxide fine particles are chain conductive inorganic oxide fine particles in which three or more primary particles of the conductive inorganic oxide fine particles are connected in a chain shape Coating liquid for forming.
[4] The coating liquid for forming a transparent film according to [1] to [3], wherein the matrix-forming component is an alkylene oxide-modified acrylic resin (A).

[5] The coating solution for forming a transparent film according to [4], wherein the alkylene oxide-modified acrylic resin (A) is an ethylene oxide-modified acrylic resin.
[6] In addition to the alkylene oxide modified acrylic resin (A), the matrix-forming component further includes a non-modified acrylic resin (B), and the non-modified acrylic resin (B) and the alkylene oxide modified acrylic resin (A) The coating liquid for forming a transparent film according to [1] to [5], wherein the weight ratio ((B) :( A)) as a solid content is in the range of 5:95 to 50:50.

[7] A ketone selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, acetylacetone, and acetoacetate The coating liquid for forming a transparent film according to [1] to [6] as described above.
[8] The coating solution for forming a transparent film according to [7], wherein the ketone of the dispersion medium is acetone and / or methyl ethyl ketone.

[9] including a substrate and a transparent coating formed on the substrate surface,
The transparent coating contains conductive inorganic oxide fine particles and a matrix component, and the conductive inorganic oxide fine particles are surface-treated with an organosilicon compound represented by the following formula (1), the conductive inorganic oxide fine particles Constitutes a chain structure in the transparent film and is highly dispersed,
The content of the conductive inorganic oxide fine particles in the transparent film is in the range of 1 to 12% by mass,
The surface resistance value of the transparent coating is in the range of 10 ⁸ to 10 ¹¹ Ω / □, the haze is 0.3% or less, the total light transmittance is 90% or more,
A substrate with a transparent coating, wherein the difference between the refractive index (N _S ) of the substrate and the refractive index (N _H ) of the transparent coating is 0.02 or less.
_{R n -SiX 4-n (1} )
(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 0 to 3)

[10] The conductive inorganic oxide fine particles are Sb-doped tin oxide (ATO) fine particles and / or P-doped tin oxide (PTO) fine particles, and the average particle diameter of primary particles constituting the chain structure is 5 to 10 nm. The substrate with a transparent coating according to [9], which is in the range and the number of connections is 3 or more.

[11] The coating liquid for forming a transparent film according to [9] or [10], wherein the matrix component is an alkylene oxide-modified acrylic resin (A).
[12] The substrate with a transparent coating according to [11], wherein the alkoxy-modified acrylic resin (A) is an ethylene oxide-modified acrylic resin.

[13] The matrix component further contains a non-modified acrylic resin (B), and a weight ratio ((B) :( B) :( N) is a solid content of the non-modified acrylic resin (B) and the alkoxy-modified acrylic resin (A). A substrate having a transparent coating according to [9] to [12], wherein A)) is in the range of 5:95 to 50:50.
[14] The substrate with a transparent coating according to [9] to [13], wherein the thickness of the transparent coating is in the range of 1 to 20 μm.

[15] The substrate with a transparent coating according to [9] to [14], wherein the substrate is triacetylcellulose.
[16] The substrate with a transparent coating according to [9] to [15], wherein the transparent coating is obtained by using the coating liquid for forming a transparent coating according to any one of claims 1 to 8.

  According to the present invention, even if the blending amount of the conductive inorganic oxide fine particles is small, it has high conductive performance, excellent transparency, no coloring and interference fringes, excellent antistatic performance, and It is possible to provide a coating solution for forming a transparent film and a substrate with a transparent coating, which are used for forming a substrate with a transparent coating that is excellent in adhesion, scratch resistance, scratch strength, pencil hardness, and the like, and is excellent in economy.

  The reason for this is not clear, but because a specific solvent and matrix-forming component are used, the monodisperse particles in the coating solution constitute chain particles in the transparent coating, and when chain particles are used. It is considered that the chain particles are highly dispersed without agglomeration, the antistatic performance is improved, and the adhesion to the base material, scratch resistance, scratch strength, and pencil hardness are increased.

2 is a scanning electron micrograph showing a dispersion state of particles of Example 1. FIG. 4 is a scanning electron micrograph showing the dispersion state of particles of Comparative Example 1.

First, the coating liquid for forming a transparent film according to the present invention will be described.
Transparent Film Forming Coating Liquid The transparent film forming coating liquid according to the present invention contains conductive inorganic oxide fine particles, a matrix forming component, and a dispersion medium.

Conductive inorganic oxide fine particles As the conductive inorganic oxide fine particles used in the present invention, conventionally known inorganic oxide fine particles having conductivity can be used, but oxidation with tin oxide, Sb, F or P doped is also possible. It is preferably at least one selected from the group consisting of tin, indium oxide, Sn or F-doped indium oxide, and antimony oxide. When such conductive inorganic oxide fine particles are used, a transparent film having antistatic performance can be obtained.

  Among them, Sb-doped tin oxide (ATO) fine particles and P-doped tin oxide (PTO) fine particles have high conductivity, so that the amount of conductive inorganic oxide fine particles used can be reduced and coloring is suppressed. Therefore, a transparent coated substrate with excellent transparency can be obtained even when a thick film is formed.

  The conductive inorganic oxide fine particles in the coating solution may be primary particles or chain particles (secondary particles) linked in advance in a chain. Even if dispersed in the primary particles in the coating liquid, the coating liquid of the present invention uses a specific solvent and a matrix component, and therefore, when the transparent film is formed, they are linked to form chain particles.

The average particle diameter of the conductive inorganic oxide fine particles (primary particles) is preferably in the range of 5 to 10 nm, more preferably 5 to 8 nm.
If the average particle size of the conductive inorganic oxide fine particles (primary particles) is small, the crystal structure may not be sufficiently developed, and in addition, there is a tendency to form aggregated particles, and the effect of improving the conductivity is not good. May be sufficient. Further, when aggregated, the transparency may be lowered or the haze may be increased. Even if the average particle size of the conductive inorganic oxide fine particles (primary particles) is too large, there is little tendency to form a chain in the transparent film, and even if the chain is formed, it is difficult to form a conductive path effectively. The effect of improving the property may be insufficient.

The “primary particles” in the present invention are monodispersed inorganic oxide fine particles. The chain particle means a particle in which three or more primary particles are connected.
The average particle diameter of the conductive inorganic oxide fine particles (primary particles) is obtained by measuring a transmission electron micrograph (TEM), measuring the particle diameter of 100 particles, and obtaining the average value.

The refractive index of the conductive inorganic oxide fine particles (primary particles) used in the present invention was measured by the following method using Series A and AA made by CARGILL as the standard refractive liquid.
(1) The conductive inorganic oxide fine particle dispersion is taken in an evaporator and the dispersion medium is evaporated.
(2) This is dried at 80 ° C. for 12 hours to obtain a powder.
(3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.
(4) The operation of (3) above is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is set as the refractive index of the conductive inorganic oxide fine particles.

The number of connected conductive inorganic oxide fine particles (primary particles) in the chain conductive inorganic oxide fine particles used in the present invention is preferably 3 or more, more preferably 5, particularly 10 or more.

  If the number of conductive inorganic oxide fine particles (primary particles) connected is small, the effect of improving the conductivity cannot be obtained sufficiently. For this reason, in order to obtain the desired conductivity, the amount of the conductive inorganic oxide fine particles used must be reduced. Since it cannot be reduced, the coloring suppression effect may be insufficient.

The chain-like conductive inorganic oxide fine particles (secondary particles) chained in advance can be produced according to the method disclosed in Patent Document 4.
For the conductive inorganic oxide fine particles (secondary particles), the transmission electron micrograph (TEM) of the conductive inorganic oxide fine particles (secondary particles) is measured, the particle diameter is measured for 100 primary particles, The average number is obtained, and the number of connections is determined by determining the number of connections of 50 only for the chain particles connected by the primary particles, and the number of connections is obtained as the average value.

It is preferable that the density | concentration of the electroconductive inorganic oxide microparticles | fine-particles in the coating liquid for transparent film formation exists in the range of 0.01-6 mass% as solid content, Furthermore, 0.02-4.8 mass%.
If the concentration of the conductive inorganic oxide fine particles in the coating liquid for forming a transparent film is small, the conductive performance may be insufficient, and the resulting antistatic performance of the substrate with a transparent film may be insufficient. In addition, even if there are too many conductive inorganic oxide fine particles, coloring of the obtained transparent film becomes remarkable, and the transmittance decreases or the refractive index of the transparent film increases. May cause streaks.

Such conductive inorganic oxide fine particles are surface-treated with an organosilicon compound represented by the following formula (1).
_{R n -SiX 4-n (1} )
(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 0 to 3)

Examples of the organosilicon compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane. , Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3- Trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) Acryloxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltrioxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane, γ- ( (Meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyl Trimethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyl Triethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyl Triethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyl Methyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane and the like and mixtures thereof Is mentioned.

  In particular, when the surface treatment is performed with the organic silicon compound of n = 0 in the formula (1), the conductive inorganic oxide fine particles (primary particles) are obtained when the conductive inorganic oxide fine particles (primary particles) are used. There is a tendency for the chained particles to become highly dispersed during the formation of the transparent film, and when the conductive inorganic oxide fine particles (secondary particles) that have been chained in advance are used, they are chained during the formation of the transparent film. Particles tend to be highly dispersed.

The surface treatment of the conductive inorganic oxide fine particles (primary particles) is performed, for example, by adding a predetermined amount of the organosilicon compound to an alcohol dispersion of the conductive inorganic oxide fine particles (primary particles), adding water thereto, and if necessary Then, acid or alkali is added as a catalyst for hydrolysis of the organosilicon compound to hydrolyze the organosilicon compound. The amount of the organosilicon compound used at this time depends on the size of the conductive inorganic oxide fine particles (primary particles), but the conductive inorganic oxide fine particles (primary particles) as R _n -SiO _{(4-n) / 2.} Is preferably in the range of 2 to 30% by mass, more preferably 3 to 10% by mass.

  As described above, when the surface treatment is performed with the organosilicon compound, the dispersion is uniformly highly dispersed in the coating liquid for forming the transparent film and the stability is improved, and the chained particles are highly dispersed in the transparent film. In addition, the use of a small amount of conductive inorganic oxide fine particles can provide a transparent film having high conductivity and excellent transparency, transmittance, hardness and the like.

  As for the surface treatment of the chain conductive inorganic oxide fine particles (secondary particles), the organosilicon compound represented by the above formula (1) is hydrolyzed during the production process of the chain conductive inorganic oxide fine particles. It is used and surface-treated with the connection of conductive inorganic oxide fine particles (primary particles).

Matrix-forming component As the matrix-forming component, an alkylene oxide-modified acrylic resin (A) is preferably used.

Examples of the alkylene oxide-modified acrylic resin (A) include ethylene oxide-modified acrylic resin and propylene oxide-modified acrylic resin.
When such an alkylene oxide-modified acrylic resin (A) is used, when the dispersion medium described later is a ketone-based dispersion medium, the surface-treated conductive inorganic oxide fine particles (primary particles) are used. In addition, a transparent film having a chain structure and high dispersion in the obtained transparent film and having excellent conductivity can be obtained even if the amount of conductive inorganic oxide fine particles used is small. In particular, ethylene oxide-modified acrylic resin is excellent in these respects. In addition, a matrix formation component says the thing before the polymerization reaction of such an acrylic resin.

  In the present invention, it is preferable to include an unmodified acrylic resin (B) in addition to the alkylene oxide-modified acrylic resin (A). Thus, the strength, hardness, and scratch resistance of the transparent film obtained by using the unmodified acrylic resin (B) can be improved.

  Non-modified acrylic resins (B) include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, Methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-he, sundiol dimethacrylate, perfluorooctylethyl Methacrylate, trifluoroethyl methacrylate, urethane acrylate, etc. and mixtures thereof

  When the non-modified acrylic resin (B) is contained, the weight ratio ((B) :( A)) as a solid content of the non-modified acrylic resin (B) and the alkylene oxide-modified acrylic resin (A) is 0: It is preferably in the range of 95-50: 50, more preferably 5: 95-40: 60.

  If the amount of the non-modified acrylic resin (B) is small, the effect of using the non-modified acrylic resin (B), that is, the effect of improving the strength, hardness and scratch resistance of the resulting transparent film is insufficient, The conductive inorganic oxide fine particles are less likely to be chained, and the conductive inorganic oxide fine particles or the conductive inorganic oxide fine particles may not be sufficiently effective in improving the conductivity with a small amount of use. .

The concentration of the matrix-forming component in the coating solution for forming a transparent film is preferably in the range of 0.1 to 59.4% by mass, more preferably 0.2 to 47.8% by mass as the solid content.
When the concentration of the matrix forming component in the coating liquid for forming the transparent coating is low, the conductive inorganic oxide fine particles are less likely to be chained, and there are few conductive inorganic oxide fine particles or conductive inorganic oxide fine particles. There may be a case where the effect of improving the conductivity is not sufficiently obtained by the amount used. In addition, since the matrix-forming component is reduced, the scratch resistance and adhesion with the substrate of the transparent film obtained may be insufficient.

  Even if there are too many matrix forming components in the coating solution for forming a transparent coating, the conductive inorganic oxide fine particles are reduced, resulting in insufficient conductivity, and the resulting antistatic performance of the substrate with the transparent coating is insufficient. In addition, the scratch resistance and the adhesion to the substrate may be insufficient.

Dispersion medium As the dispersion medium used in the present invention, ketones are preferably used.
Specifically, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, acetylacetone, acetoacetate, and mixed dispersion media thereof Can be mentioned.

Of these, acetone, methyl ethyl ketone, and mixtures thereof are particularly preferable.
The dispersion medium may contain a dispersion medium other than ketones. Examples of the dispersion medium other than ketones include methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydro. Alcohols such as furfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; esters such as methyl acetate, ethyl acetate, butyl acetate; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Butyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl Ethers, ethers such as pull-propylene glycol monoethyl ether; toluene, xylene and the like and mixtures thereof.

  When these mixed dispersion media are used in combination with the alkoxy-modified acrylic resin (A), when the conductive oxide fine particles (primary particles) are used, the conductive oxide fine particles (primary particles) are formed during the formation of the transparent film. There is a tendency to chain-like, and the chain-like conductive oxide fine particles are highly dispersed without agglomerating with each other. Therefore, the conductivity is improved, and even if a small amount of the conductive oxide fine particles is used, the conductivity, transparency, A transparent film having excellent transmittance and hardness and suppressed interference fringes can be obtained.

  The proportion of ketones in the dispersion medium is preferably 30% by mass or more, and more preferably 40% by mass or more. If the proportion of ketones is small, the conductive oxide fine particles may not be chained during the formation of the transparent film, and the chain conductive oxide fine particles may aggregate together, and the chained conductive in the transparent film. In some cases, a transparent film in which the fine oxide particles are highly dispersed cannot be obtained. Also, when the substrate is TAC, if the ketones are included in the coating solution, the surface of the TAC swells or dissolves and interpenetrates with the transparent coating component, and the optical interface at the boundary becomes unclear. However, if the proportion of ketones is small, the effect of suppressing such interference fringes may not be obtained.

In addition, when the above-described dispersion medium is used, when a TAC film is used as the substrate, a transparent film with particularly suppressed interference fringes can be obtained.
It is preferable that the density | concentration of the coating liquid for transparent film formation exists in the range of 1-60 mass% as a total solid, and also 2-40 mass%.

  If the total solid content concentration of the coating liquid for forming a transparent film is too low, the conductive oxide fine particles do not tend to be chained, and the effect of improving the conductivity may not be obtained. In some cases, it is difficult to obtain a transparent conductive film, and when repeated application and drying are repeated, there is a problem that the strength of the film is lowered or the economy is lowered.

  Even if the total solid content is too high, the viscosity of the coating solution increases, the coating property decreases, or the conductive oxide fine particles are chained or the chained conductive oxide fine particles are aggregated. In some cases, sufficient conductivity may not be obtained, and the haze of the obtained transparent film may be increased or the scratch resistance may be insufficient.

By applying such a coating solution to the above-mentioned substrate by a known method such as a dipping method, a spray method, a spinner method, a gravure coating method, a roll coating method, drying, and curing by heat treatment, ultraviolet irradiation, etc. A transparent film can be formed. The matrix-forming component is polymerized and cured by this heating or ultraviolet irradiation.
Below, the base material with a transparent film which concerns on this invention is demonstrated.

Substrate with Transparent Film The substrate with a transparent film according to the present invention includes a substrate and a transparent film formed on the surface of the substrate.

The base material used for the substrate present invention may be used conventionally known glass, polycarbonate, acrylic resin, polyethylene terephthalate (PET), plastic sheets such as triacetyl cellulose (TAC), a plastic film, a plastic panel or the like .

  Of these, TAC, polycarbonate, an acrylic resin base material and the like are preferably used. In particular, TAC uses ketones as the dispersion medium of the coating liquid for forming a transparent film of the present invention, so that the TAC base material swells or dissolves, and the TAC and the transparent film component enter each other to blur the optical interface at the boundary. This is preferable because the interference fringes can be suppressed, or because the refractive index has an inclination.

The refractive index (N _s ) of the substrate used in the present invention is preferably 1.49 to 1.59, more preferably 1.49 to 1.56, and particularly preferably 1.49 to 1.52.
When the refractive index (N _S ) of the substrate is not within the above range, it is difficult to adjust the refractive index of the transparent film, and the difference in refractive index from the refractive index (N _S ) of the substrate is 0.2 or less. In some cases, interference fringes cannot be suppressed.

Transparent coating The transparent coating contains conductive inorganic oxide fine particles and a matrix component.
In the conductive inorganic oxide fine particle transparent coating, the surface-treated conductive inorganic oxide fine particles used in the coating solution have a chain structure and are highly dispersed.

  In addition, the above-mentioned chain conductive inorganic oxide fine particles are connected to the primary particles in the coating solution connected in the film forming process, the particles connected in advance, and the particles connected in advance or the primary particles. Say things.

  Here, “high dispersion” varies depending on the content of the conductive inorganic oxide fine particles, but the conductive oxide fine particles are chained, the chained conductive oxide fine particles are entangled with each other, It means that the chain structure is highly dispersed so that the chain structure can be visually recognized in the transparent film without being agglomerated and unevenly distributed. In addition, the chain particles may be further connected.

The number of connections of the conductive inorganic oxide fine particles in the transparent film is usually 3 or more, more preferably 5, particularly 10 or more.
When the number of chain conductive inorganic oxide fine particles connected is small, the effect of improving conductivity may not be sufficiently obtained. When chain particles are used in advance, the number of connections may be further increased, or monodisperse particles and chain particles may be connected.

  Although it is not clear why the chained conductive oxide fine particles are highly dispersed in the transparent film of the present invention, as described above, the concentration of the specific dispersion medium, the specific resin, and the coating solution used in the present invention Is considered to have contributed.

Moreover, content of the electroconductive inorganic oxide fine particle in a transparent film is 1-12 mass% as solid content, Preferably it exists in the range of 1-10 mass%.
If the conductive inorganic oxide fine particles in the transparent film are too small, the conductivity may be insufficient even if the chained conductive fine particles are highly dispersed. Even if there are too many conductive inorganic oxide fine particles, the conductivity is improved, but coloring derived from inorganic oxides such as ATO and PTO is recognized, and the total light transmittance becomes insufficient, or the refractive index. The interference fringes may occur depending on the substrate.

Matrix component The matrix component corresponds to a resin obtained by curing the above-described alkylene oxide-modified acrylic resin (A). Further, an unmodified acrylic resin (B) may be included together with the alkylene oxide-modified acrylic resin (A).
When the non-modified acrylic resin (B) and the alkoxy-modified acrylic resin (A) are used in combination, the weight ratio ((B) :( A)) is 0:95 to 50:50, as in the matrix forming component. Furthermore, it is preferable to be in the range of 5:95 to 40:60.

The content of the matrix component in the transparent coating is preferably in the range of 88 to 99% by mass, more preferably 90 to 99% by mass as the solid content.
When there are few matrix components in a transparent film, the said electroconductive inorganic oxide fine particle will increase relatively, and the problem of coloring may arise. Even if there are too many matrix components in the transparent coating, the conductive inorganic oxide fine particles are reduced, so that the conductivity is insufficient and the antistatic performance may be insufficient.

The difference between the refractive index (N _S ) of the substrate and the refractive index (N _H ) of the transparent coating is 0.02 or less, preferably 0.01 or less.
When the refractive index difference exceeds 0.02, clear interference fringes are generated, which may cause a problem in appearance, and when used in a display device, the visibility of an image may be lowered.

In the present invention, the refractive index (N _H ) of the transparent coating is preferably 1.49 to 1.59, more preferably 1.49 to 1.56, and particularly preferably 1.49 to 1.52.
When the refractive index (N _H ) of the transparent coating is not within the above range, the refractive index difference from the refractive index (N _S ) of the substrate to be used may be larger than 0.02, which may cause interference fringes. .

The surface resistance value of the transparent coating is in the range of 10 ⁸ to 10 ¹¹ Ω / □, preferably 10 ⁸ to 10 ¹⁰ Ω / □.
When the surface resistance value of the transparent coating is too low, the content of the conductive inorganic oxide fine particles needs to be 12% by mass or more, and in this case, a coloring problem may occur.

If the surface resistance value of the transparent coating is too large, the antistatic performance may be insufficient.
The haze of the transparent coating is 0.3% or less, preferably 0.2% or less. Those having a high haze have insufficient transparency, and desired optical characteristics such as contrast and visibility may not be obtained.

The total light transmittance of the transparent coating is 90% or more, preferably 92% or more.
If the total light transmittance is low, the desired optical characteristics cannot be obtained, and if the total light transmittance is low due to coloring, the design and design of the optical member may be adversely affected.

The film thickness of the transparent coating is preferably in the range of 1 to 20 μm, more preferably 4 to 15 μm.
If the film thickness of the transparent film is too thin, sufficient hardness and scratch resistance may not be obtained. Even if the film thickness of the transparent film is too thick, coloring is promoted because of the thick film, and the transmittance is low. It may be insufficient.

  In the present invention, a transparent film having a refractive index lower than that of the transparent film can be formed on the transparent film as an antireflection film. As the antireflection film, a conventionally known antireflection film can be formed. For example, the antireflection film forming coating solution and antireflection film disclosed in JP-A-2006-339113 filed by the applicant of the present application are suitable. Can be used.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.

[Example 1]
Preparation of chain conductive inorganic oxide particle (1) dispersion A mixed solution in which 130 g of potassium stannate and 30 g of potassium antimonyl tartrate were dissolved in 400 g of pure water was prepared. This prepared solution was dissolved in 1.0 g of ammonium nitrate under stirring at 60 ° C. over 12 hours, and added to 1000 g of pure water adjusted to pH 10.5 using potassium hydroxide for hydrolysis. At this time, a 10% nitric acid solution was simultaneously added so as to keep the pH at 10.5. The generated precipitate was washed by filtration and then dispersed again in water to prepare a metal oxide precursor hydroxide dispersion having a solid content concentration of 20% by mass.

  This dispersion was spray-dried at a temperature of 100 ° C. to prepare a metal oxide precursor hydroxide powder. This powder was heat-treated at 550 ° C. for 2 hours in an air atmosphere to obtain Sb-doped tin oxide (ATO) powder.

60 g of this powder was dispersed in 140 g of an aqueous potassium hydroxide solution having a concentration of 4.3% by mass, and the dispersion was pulverized with a sand mill for 3 hours while maintaining the dispersion at 30 ° C. to prepare a sol.
Next, pure water was added to the sol to dilute to a concentration of 8% by mass. The sol had a pH of 5.2. Subsequently, this sol was treated with an anion exchange resin (manufactured by Mitsubishi Chemical Corporation; Diaion SANUPC) to adjust the pH to 5.5. Next, hydrothermal treatment was performed at 200 ° C. for 24 hours. Subsequently, after treatment with anion exchange resin (Mitsubishi Chemical Corporation; Diaion SANUPC), treatment with cation exchange resin (Mitsubishi Chemical Corporation; Diaion SK1BH), pH 2.7, concentration 8 mass % Sol was obtained. This was concentrated with an ultrafiltration membrane to prepare a conductive inorganic oxide fine particle (1) dispersion composed of Sb-doped tin oxide particles having a solid content of 20% by mass. The average particle diameter of the conductive inorganic oxide fine particles (1) was 8 nm.

Next, 100 g of the conductive inorganic oxide fine particle (1) dispersion having a concentration of 20% by mass was adjusted to 25 ° C., and tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: normal ethyl silicate, SiO ₂ concentration of 28.8% by mass). After adding 5.2 g in 3 minutes, the mixture was stirred for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, the temperature was raised to 50 ° C. over 30 minutes, and a heat treatment was performed for 15 hours. The solid content concentration at this time was 10% by mass.

  Subsequently, water and ethanol as a dispersion medium are replaced with ethanol in an ultrafiltration membrane, and then the chain conductive inorganic oxide fine particles are chain-formed and surface-treated with an organic silicon compound having a solid content concentration of 20% by mass. (1) A dispersion was prepared. The average number of connected primary particles constituting the chain conductive inorganic oxide fine particles (1) was 10. The chain conductive inorganic oxide fine particles (1) had a refractive index of 1.75.

Preparation of coating liquid for forming transparent film (1) 100 g of surface-treated chain conductive inorganic oxide fine particles (1) dispersion having a solid content concentration of 20% by mass and ethylene oxide-modified acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate TMP-3EO-A, resin concentration 100% by mass) 480 g, photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184) 38.4 g and acetone solvent 658 g and methyl ethyl ketone 160 g were mixed well. A coating liquid (1) for forming a transparent film having a solid content concentration of 40% by mass was prepared.

Preparation of substrate with transparent film (1) Coating liquid for forming a transparent film (1) was placed on a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1.5). After coating by the coater method (bar # 10) and drying at 80 ° C. for 120 seconds, a substrate (1) with a transparent coating was prepared by irradiating with 300 mJ / cm ² of ultraviolet rays and curing. The film thickness of the transparent coating was 5 μm.

  Table 1 shows the total light transmittance, haze, film refractive index, surface resistance, adhesion, pencil hardness, coloring, interference fringes, chain particle dispersion state and scratch resistance of this substrate with transparent coating (1). Show. The total light transmittance and haze were measured by a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the reflectance was measured by a spectrophotometer (JASCO Corporation, Ubest-55). The surface resistance value was measured with a surface resistance meter (manufactured by Mitsubishi Chemical Corporation: Hiresta).

The uncoated TAC film had a total light transmittance of 93.2%, a haze of 0.2%, and a reflectance of light having a wavelength of 550 nm of 6.0%.
Further, adhesion, pencil hardness, coloring, interference fringes, dispersion state of chain particles, and scratch resistance were evaluated by the following methods and evaluation criteria, and the results are shown in the table. Moreover, the scanning electron micrograph at the time of evaluating the dispersion state of the chain particles is shown in FIG.

The coating liquid for forming a transparent film with refractive index (1) is applied onto a silicone wafer, dried and cured to form a transparent film, and the refractive index of the transparent film is measured with an ellipsometer (EMS-1 manufactured by ULVAC). did.

The substrate with colored transparent coating (1) was irradiated with light from a fluorescent lamp and visually observed for the presence or absence of coloring. The results are shown in Table 1.
Evaluation criteria:
Colorless and transparent, no coloration is recognized: ◎
Very thin and slightly colored: ◯
Lightly colored: △
Dark coloring is recognized: ×

Adhesive transparent film-coated substrate (1) The surface of the substrate (1) with a knife is made 11 parallel scratches at intervals of 1 mm in length and width to make 100 squares, cellophane tape is adhered to this, then cellophane tape is attached. Adhesion was evaluated by classifying the number of squares that remained without peeling off when the film was peeled into the following four 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: ×

Measurement of Scratch Resistance Using # 0000 steel wool, sliding 50 times at a load of 500 g / cm 2, visually observing the surface of the film and evaluating according to the following criteria, the results are shown in Table 1.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×

The light of the fluorescent lamp was reflected on the surface of the transparent coating in a state where the background of the substrate with the interference fringe transparent coating (1) was black, and the occurrence of a rainbow pattern due to light interference was visually observed and evaluated according to the following criteria.
No rainbow pattern is recognized: ◎
A slight rainbow pattern is recognized: ○
A rainbow pattern is clearly recognized: △
Rainbow pattern is clearly recognized: ×

Dispersion state of chain particles Transmission electron micrographs of the cross section of the transparent coating were taken, the dispersion state of the chain conductive inorganic oxide fine particles was observed, and evaluated according to the following criteria.
Chain particles are dispersed at almost equal intervals without being entangled with each other: ◎
Chain particles are partially entangled, but are distributed at almost equal intervals: ○
Most of the chain particles are entangled and non-uniformly distributed: △
The monodisperse particles are monodispersed or agglomerated without being chained, or the chain particles are agglomerated and dispersed non-uniformly: ×

[Example 2]
Preparation of coating liquid for forming transparent film (2) 100 g of surface-treated conductive inorganic oxide fine particle (1) dispersion prepared in the same manner as in Example 1 and ethylene oxide-modified acrylic resin (Daicel Cytec Co., Ltd.) Manufactured by: EBECRYL40, resin concentration 100% by mass) 384 g, dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) 96 g as non-modified acrylic resin, photoinitiator ( Ciba Specialty Co., Ltd .: Irgacure 184) 38.4 g, acetone as a ketone solvent, 568 g, and methyl ethyl ketone 160 g were sufficiently mixed to prepare a coating solution (2) for forming a transparent film having a solid concentration of 40% by mass.

Preparation of substrate with transparent film (2) A substrate with transparent film (2) was prepared in the same manner as in Example 1, except that the coating liquid for forming a transparent film (2) was used. The film thickness of the transparent coating was 5 μm.
Total light transmittance, haze, film refractive index, surface resistance, adhesion, pencil hardness, coloring, interference fringes, chain particle dispersion state, and scratch resistance of the obtained substrate with transparent coating (2) Is shown in the table.

[Example 3]
Preparation of coating liquid for forming transparent film (3) 100 g of the surface-treated chain conductive inorganic oxide fine particle (1) dispersion prepared in the same manner as in Example 1 and ethylene oxide-modified acrylic resin (Shin Nakamura Chemical Co., Ltd.) ): NK ester ATM-4E, resin concentration 100% by mass) 288 g, non-modified acrylic resin (Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) 192 g with photoinitiator (Ciba Specialty) Co., Ltd. Irgacure 184) 38.4 g and 568 g of acetone as a ketone solvent and 160 g of methyl ethyl ketone were sufficiently mixed to prepare a coating solution (3) for forming a transparent film having a solid content concentration of 40% by mass.

Preparation of substrate with transparent film (3) A substrate with transparent film (3) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (3) was used. The film thickness of the transparent coating was 5 μm.
The total light transmittance, haze, film refractive index, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate (3) with a transparent film are shown in the table.

[Example 4]
Preparation of coating liquid for forming transparent film (4) 50 g of the surface-treated chain conductive inorganic oxide fine particle (1) dispersion prepared in the same manner as in Example 1 and ethylene oxide-modified acrylic resin (Shin Nakamura Chemical Co., Ltd.) ): NK ester ATM-4E, resin concentration 100% by mass) 294 g, non-modified acrylic resin (Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) 196 g with photoinitiator (Ciba Specialty) Co., Ltd. Irgacure 184) 39.2 g and 600 g of acetone as a ketone solvent and 169 g of methyl ethyl ketone were sufficiently mixed to prepare a coating solution (4) for forming a transparent film having a solid content concentration of 40% by mass.

Preparation of substrate with transparent film (4) A substrate with transparent film (4) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (4) was used. The film thickness of the transparent coating was 5 μm.
The total light transmittance, haze, film refractive index, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate (4) with a transparent film are shown in the table.

[Example 5]
Preparation of coating liquid for forming transparent film (5) 100 g of surface-treated conductive inorganic oxide fine particle (1) dispersion prepared in the same manner as in Example 1 and ethylene oxide-modified acrylic resin (Shin Nakamura Chemical Co., Ltd.) ): NK ester ATM-4E, resin concentration 100% by mass) 108 g, non-modified acrylic resin (Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) 72 g photoinitiator (Ciba Specialty) A coating solution (5) for forming a transparent film having a solid concentration of 40% by mass was prepared by sufficiently mixing 14.4 g of Irgacure 184) and 188 g of acetone as a ketone solvent and 53 g of methyl ethyl ketone.

Preparation of substrate with transparent film (5) A substrate with transparent film (5) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (5) was used. The film thickness of the transparent coating was 5 μm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, coloring, interference fringes, chain particle dispersion state, and scratch resistance of the obtained substrate with transparent coating (5) are represented. Shown in

[Example 6]
Preparation of coating liquid for forming transparent film (6) In Example 3, as an alkylene oxide-modified acrylic resin, a propylene oxide-modified acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester ATM-4P, resin concentration 100% by mass) ) A coating solution for forming a transparent film (6) was prepared in the same manner except that 288 g was used.

Preparation of substrate with transparent film (6) A substrate with transparent film (6) was prepared in the same manner as in Example 1, except that the coating liquid for forming a transparent film (6) was used. The film thickness of the transparent coating was 5 μm.
The total light transmittance, haze, film refractive index, adhesion, pencil hardness, coloring, interference fringes, chain particle dispersion state, and scratch resistance of the obtained substrate with transparent film (6) are shown in the table.

[Example 7]
Preparation of coating liquid for forming transparent film (7) 100 g of surface-treated chain conductive inorganic oxide fine particles (1) having a solid content of 20% by mass prepared in the same manner as in Example 1 and ethylene oxide-modified acrylic Resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester ATM-4E, resin concentration 100% by mass) 288 g, non-modified acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) 192 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd.) and 568 g of acetone as a ketone solvent and 160 g of methyl isobutyl ketone were mixed thoroughly to form a coating solution for forming a transparent film having a solid content of 40% by mass. (7) was prepared.

Preparation of substrate with transparent film (7) A substrate with transparent film (7) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (7) was used. The film thickness of the transparent coating was 5 μm.
The total light transmittance, haze, film refractive index, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate with transparent film (7) are shown in the table.

[Example 8] (changed to PTO particles in Example 3, particles: resin = 10: 90)
Preparation of dispersion of chain conductive inorganic oxide particles (3) 150 g of potassium stannate was dissolved in 430 g of pure water to prepare a solution. This solution was added to a solution prepared by adding 800 g of pure water under stirring at 60 ° C., 1.3 g of ammonium nitrate, and an aqueous potassium hydroxide solution to a pH of 10.0 for 12 hours, and then hydrolyzed. At this time, an aqueous nitric acid solution having a concentration of 10% by mass was simultaneously added so as to keep the pH at 10.0. The produced precipitate was filtered and washed, and then dispersed again in water to prepare 200 g of a tin hydroxide dispersion having a solid concentration of 20% by mass.

After adding 3.2 g of 85% by weight phosphoric acid aqueous solution to this dispersion and stirring for 30 minutes, it was spray-dried at a temperature of 100 ° C. to prepare a hydroxide powder of a phosphorus-doped tin oxide precursor. This powder was heat-treated at 650 ° C. for 2 hours in an air atmosphere to obtain phosphorus-doped tin oxide powder.
60 g of this powder was dispersed in 140 g of an aqueous potassium hydroxide solution having a concentration of 4.3% by mass, and the dispersion was pulverized with a sand mill for 3 hours while maintaining the dispersion at 30 ° C. to prepare a sol.

Next, this sol was dealkalized with an ion exchange resin until the pH became 3.3, and pure water was added to prepare a conductive fine particle (3) dispersion composed of phosphorus-doped tin oxide fine particles having a concentration of 20% by mass.
The pH of the conductive inorganic oxide fine particle (3) dispersion was 3.6. The average particle diameter of the conductive inorganic oxide fine particles (3) was 8 nm.

Next, 100 g of a conductive inorganic oxide fine particle (3) dispersion having a concentration of 20% by mass was adjusted to 25 ° C. and tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: normal ethyl silicate, SiO ₂ concentration of 28.8% by mass). After adding 3.5 g in 3 minutes, the mixture was stirred for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, the temperature was raised to 60 ° C. over 30 minutes, and a heat treatment was performed for 12 hours. The solid content concentration at this time was 10% by mass.

  Next, water and ethanol as a dispersion medium are solvent-substituted with ethanol in an ultrafiltration membrane, and the chain-like conductive inorganic oxide fine particles are chain-formed and surface-treated with an organic silicon compound having a solid concentration of 20% by mass. (3) A dispersion was prepared. The average number of connected primary particles constituting the chain conductive inorganic oxide fine particles (3) was 5. The refractive index of the chain-like conductive inorganic oxide fine particles (3) was 1.74.

Preparation of coating liquid for forming transparent film (8) Surface-treated chain-like conductive inorganic oxide fine particle (3) dispersion of 20% by mass solid content and ethylene oxide-modified acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd.) : NK ester ATM-4E, resin concentration 100 mass%) 108 g, non-modified acrylic resin (Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100 mass%) 72 g photoinitiator (Ciba Specialty Co., Ltd.) ) Irgacure 184) 14.4 g and 188 g of acetone as a ketone solvent and 53 g of methyl ethyl ketone were sufficiently mixed to prepare a coating solution (7) for forming a transparent film having a solid concentration of 40% by mass.

Preparation of substrate with transparent film (8) A substrate with transparent film (8) was prepared in the same manner as in Example 1, except that the coating liquid for forming a transparent film (8) was used. The film thickness of the transparent coating was 5 μm.
The total light transmittance, haze, film refractive index, adhesion, pencil hardness, coloring, interference fringes, chain particle dispersion state, and scratch resistance of the obtained substrate (8) with a transparent film are shown in the table.

[Example 9]
Preparation of substrate with transparent film (9) A coating liquid for forming a transparent film (3) prepared in the same manner as in Example 3 was prepared by using a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, Applying to the refractive index: 1.5) by the bar coater method (bar # 4), drying at 80 ° C. for 120 seconds, curing by irradiating with 300 mJ / cm ² ultraviolet rays (9) Was prepared. The film thickness of the transparent coating was 2 μm.
The total light transmittance, haze, film refractive index, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate with transparent coating (9) are shown in the table.

[Example 10]
Preparation of substrate with transparent film (10) A coating liquid for forming a transparent film (3) prepared in the same manner as in Example 3, was prepared by using a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, Applying to the refractive index: 1.5) by the bar coater method (bar # 20), drying at 80 ° C. for 120 seconds, curing by irradiating with 300 mJ / cm ² of ultraviolet rays (10) Was prepared. The film thickness of the transparent coating was 10 μm.
The table below shows the total light transmittance, haze, refractive index of the coating, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate with transparent coating (10).

[Example 11]
Preparation of coating liquid (1) for forming an antireflection transparent coating (1) Silica-based fine particle dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Thruria 4320, particle refractive index = 1.30, solid content concentration 20% by mass, dispersion medium = methyl Isobutyl ketone) (6.5 g) was diluted with 5.9 g of methyl isobutyl ketone and then diluted with 1.03 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: DPE-6A, solid content concentration 100 mass%). Reactive silicone oil for hydrated material (Shin-Etsu Chemical Co., Ltd .; X-22-174DX, solid content concentration: 100% by mass) and 1.6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; Light acrylate) 1.6HX-A) 0.09 g and a photopolymerization initiator (Ciba Japan Co., Ltd.): Irgacure 184: dissolved in IPA at a solid content concentration of 10% by mass) 0.76 g, 70.66 g of isopropyl alcohol, and 15.00 g of isopropyl glycol were mixed to prepare a coating solution (1) for forming an antireflection transparent film having a solid content concentration of 2.5% by mass.

Preparation of substrate with transparent coating (11) A substrate with transparent coating (3) was prepared in the same manner as in Example 3. Then, a coating solution for forming a transparent coating for antireflection (1) was applied to the bar coater method (bar # After coating at 3) and drying at 80 ° C. for 120 seconds, a substrate with a transparent coating (11) provided with an antireflection film was prepared by irradiating with an ultraviolet ray of 600 mJ / cm _{2 in} an N ₂ atmosphere and curing. At this time, the film thickness of the antireflection transparent coating was 100 nm.
It represents the total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, scratch resistance of the obtained substrate with transparent coating (11). Shown in

[Example 12]
Conductive inorganic oxide particles (12) dispersed concentration of 20 mass% of conductive prepared in the same manner as in Preparation Example 1 of liquid inorganic oxide fine particles (1) the dispersion 100g was adjusted to 25 ° C., tetraethoxysilane ( After adding 4.9 g of Tama Chemical Co., Ltd. product: normal ethyl silicate, SiO ₂ concentration 28.8 mass%) in 3 minutes, the mixture was stirred for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, the temperature was raised to 50 ° C. over 30 minutes, and a heat treatment was performed for 20 hours. The solid content concentration at this time was 15% by mass.

  Next, the conductive inorganic oxide fine particle (12) dispersion obtained by subjecting the dispersion medium water and ethanol to solvent substitution with an ultrafiltration membrane and surface-treated with an organic silicon compound having a solid content of 20% by mass was obtained. Prepared. The average particle diameter of the conductive inorganic oxide fine particles (12) was 8 nm. The refractive index of the conductive inorganic oxide fine particles (11) was 1.74.

Preparation of Transparent Film Forming Coating Liquid (12) In Example 3, except that 100 g of the conductive inorganic oxide fine particle (12) dispersion liquid surface-treated with an organosilicon compound having a solid concentration of 15% by mass was used. A coating liquid (12) for forming a transparent film having a solid content concentration of 40% by mass was prepared.

Preparation of substrate with transparent film (12) A substrate with transparent film (12) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (12) was used. The film thickness of the transparent coating was 5 μm.

  The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, coloring, interference fringes, chain particle dispersion state, and scratch resistance of the obtained substrate with transparent coating (12) are represented. Shown in The chain conductive inorganic oxide fine particles in the transparent film had an average particle diameter of 8 nm and a connection number of 3.

[Comparative Example 1]
Preparation of coating liquid for forming transparent film (R1) 100 g of surface treated chain-like conductive inorganic oxide fine particle (1) dispersion prepared in the same manner as in Example 1 and urethane acrylate UV curable resin (manufactured by DIC Corporation): Unidic 17-824-9, solid content concentration 77 mass%) 623 g, 430 g of acetone as a ketone solvent, 121 g of methyl ethyl ketone are sufficiently mixed to form a coating solution for forming a transparent film (R1) with a solid content concentration of 40 mass% Was prepared.

Preparation of substrate with transparent film (R1) In Example 1, the coating liquid for transparent film formation (R1) was prepared by using a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1). A substrate with a transparent coating (R1) was prepared in the same manner except that the coating was applied to 5) by the bar coater method (bar # 10). The film thickness of the transparent coating was 5 μm.

  The table shows the total light transmittance, haze, refractive index of the coating, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate with transparent coating (R1). Moreover, the scanning electron micrograph at the time of evaluating the dispersion state of a chain particle was shown in FIG. The particles were agglomerated as shown in FIG.

[Comparative Example 2]
Preparation of coating liquid for forming transparent film (R2) 100 g of surface-treated chain-like conductive inorganic oxide fine particle (R1) dispersion prepared in the same manner as Comparative Example 1 and ethylene oxide-modified acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd.) : 288 g of light acrylate TMP-3EO-A, resin concentration 100% by mass), 192 g of non-modified acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) and photoinitiator (Ciba Specialty) Co., Ltd .: Irgacure 184) 38.4 g, isopropyl alcohol 568 g, and toluene 160 g were sufficiently mixed to prepare a coating solution (2) for forming a transparent film having a solid concentration of 40% by mass.

Preparation of substrate with transparent film (R2) In Example 1, the coating liquid for transparent film formation (R2) was prepared by using a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1). A substrate with a transparent coating (R2) was prepared in the same manner except that the coating was applied to 5) by the bar coater method (bar # 20). The film thickness of the transparent coating was 10 μm.
The total light transmittance, haze, film refractive index, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate with transparent coating (R2) are shown in the table.

[Comparative Example 3]
Preparation of coating liquid for forming transparent film (R3) 100 g of the surface-treated conductive inorganic oxide fine particle (R1) dispersion prepared in the same manner as in Comparative Example 1 and UV curable resin diethylene glycol diglycidyl ether diacrylate having an OH group (Shin Nakamura Chemical Co., Ltd .: NK Oligo EA-5821) 480g, 38.4g of photoinitiator (Ibusacure 184, Ciba Specialty Co., Ltd.) and isopropyl alcohol 568g, ethyl cellosolve 160g was mixed well. A coating solution (R3) for forming a transparent film having a solid content concentration of 40% by mass was prepared.

Preparation of transparent film-coated substrate (R3) In Comparative Example 1, the transparent film-forming coating solution (R3) was prepared using a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1). A substrate with a transparent coating (R3) was prepared in the same manner except that the coating was performed by the bar coater method (bar # 10). The film thickness of the transparent coating was 5 μm.
The table shows the total light transmittance, haze, refractive index of the coating, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate with transparent coating (R3).

[Comparative Example 4]
Preparation of coating liquid for forming transparent film (R4) 10 g of the surface-treated conductive inorganic oxide fine particle (1) dispersion prepared in the same manner as in Example 1 and ethylene oxide-modified acrylic resin (Shin Nakamura Chemical Co., Ltd.) ): NK ester ATM-4E, resin concentration 100% by mass) 229 g, non-modified acrylic resin (Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) 159 g and photoinitiator (Ciba Specialty) Co., Ltd. Irgacure 184) 31.8 g and 499 g of acetone as a ketone solvent and 141 g of methyl ethyl ketone were sufficiently mixed to prepare a coating solution (R4) for forming a transparent film having a solid concentration of 40% by mass.

Preparation of substrate with transparent film (R4) In Example 1, the coating liquid for transparent film formation (R4) was prepared by using a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1). A substrate with a transparent coating (R4) was prepared in the same manner except that the coating was applied to 5) by the bar coater method (bar # 10). The film thickness of the transparent coating was 5 μm.
The total light transmittance, haze, film refractive index, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained transparent coated substrate (R4) are shown in the table.

[Comparative Example 5]
Preparation of coating liquid for forming transparent film (R5) 100 g of surface-treated chain-like conductive inorganic oxide fine particle (1) dispersion prepared in the same manner as in Example 1 and ethylene oxide-modified acrylic resin (Shin Nakamura Chemical Co., Ltd.) ) Made: NK ester ATM-4E, resin concentration 100 mass%) 48 g, non-modified acrylic resin (Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100 mass%) 32 g photoinitiator (Ciba Specialty) A coating solution (R5) for forming a transparent film having a solid content of 40% by mass was prepared by thoroughly mixing 6.4 g of Irgacure 184) and 62 g of acetone as a ketone solvent and 18 g of methyl ethyl ketone.

Preparation of substrate with transparent film (R5) In Example 1, the coating liquid for transparent film formation (R5) was prepared by using a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1). A substrate with a transparent coating (R5) was prepared in the same manner except that the coating was applied to 5) by the bar coater method (bar # 10). The film thickness of the transparent coating was 5 μm.
The table below shows the total light transmittance, haze, refractive index of the coating, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate with transparent coating (R5).

[Comparative Example 6]
Preparation of conductive inorganic oxide particle (R1) dispersion A mixed solution of 130 g of potassium stannate and 30 g of potassium antimonyl tartrate in 400 g of pure water was prepared. This prepared solution was added to 1000 g of pure water in which 1.0 g of ammonium nitrate and 12 g of 15% ammonia water were dissolved at 60 ° C. over 12 hours for hydrolysis. At this time, a 10% nitric acid solution was simultaneously added so as to keep the pH at 8.8. The generated precipitate was washed by filtration and then dispersed again in water to prepare a metal oxide precursor hydroxide dispersion having a solid content concentration of 20% by mass.

  This dispersion was spray-dried at a temperature of 100 ° C. to prepare a metal oxide precursor hydroxide powder. This powder was heat-treated at 550 ° C. for 2 hours in an air atmosphere to obtain Sb-doped tin oxide (ATO) powder. 60 g of this powder was dispersed in 140 g of an aqueous potassium hydroxide solution having a concentration of 4.3% by mass, and the dispersion was pulverized with a sand mill for 3 hours while maintaining the dispersion at 30 ° C. to prepare a sol.

  Next, this sol is subjected to dealkalization treatment with an ion exchange resin until the pH becomes 3.0, and conductive inorganic oxide fine particles (1) dispersion comprising Sb-doped tin oxide fine particles having a concentration of 20% by mass. Was prepared. The pH of this conductive inorganic oxide fine particle (1) dispersion was 3.2. The average particle diameter of the conductive inorganic oxide fine particles (R1) was 20 nm.

Next, 100 g of the conductive inorganic oxide fine particle (1) dispersion having a concentration of 20% by mass was adjusted to 25 ° C., and tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: normal ethyl silicate, SiO ₂ concentration of 28.8% by mass). After adding 4.9 g in 3 minutes, the mixture was stirred for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, the temperature was raised to 50 ° C. over 30 minutes, and a heat treatment was performed for 15 hours. The solid content concentration at this time was 15% by mass.

  Subsequently, the dispersion medium water and ethanol were replaced with ethanol in an ultrafiltration membrane, and the resulting solution was concentrated to a conductive inorganic oxide that was chained and surface-treated with an organic silicon compound having a solid content of 20% by mass. A fine particle (R1) dispersion was prepared. No chain connection was observed in the conductive inorganic oxide fine particles (R1). The refractive index of the conductive inorganic oxide fine particles (R1) was 1.74.

Preparation of coating liquid for forming transparent film (R6) 100 g of surface-treated conductive inorganic oxide fine particle (R1) dispersion with a solid content concentration of 20% by mass and ethylene oxide-modified acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Ester ATM-4E, resin concentration 100% by mass) 48 g, non-modified acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) 32 g photoinitiator (Ciba Specialty Co., Ltd.) Irgacure 184) 6.4 g, 62 g of acetone as a ketone solvent, and 18 g of methyl ethyl ketone were sufficiently mixed to prepare a coating solution (R6) for forming a transparent film having a solid concentration of 40% by mass.

Preparation of substrate with transparent film (R6) In Example 1, the coating liquid for transparent film formation (R6) was prepared by using a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1). A substrate with a transparent coating (R6) was prepared in the same manner except that the coating was applied by .5) by the bar coater method (bar # 10). The film thickness of the transparent coating was 5 μm. The table shows the total light transmittance, haze, refractive index of the coating, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate with transparent coating (R6).

[Comparative Example 7]
Preparation of chain conductive inorganic oxide particle (R2) dispersion Antimony trioxide (manufactured by Sumitomo Mine Co., Ltd.) in a solution of 25 g of caustic potash (manufactured by Asahi Glass Co., Ltd .: purity 85 mass%) in 800 g of pure water 50 g of KN, purity 98.5% by mass) was suspended. This suspension was heated to 95 ° C., and then added in 9 hours of an aqueous solution obtained by diluting 15 g of hydrogen peroxide (produced by Hayashi Junyaku Co., Ltd .: special grade, concentration 35% by mass) with 50 g of pure water, Antimony was dissolved and then aged for 11 hours. Next, after cooling, 800 g is taken from the obtained solution, and after diluting this solution with 4800 g of pure water, the pH is adjusted to 3.5 with a cation exchange resin (Mitsubishi Chemical Corporation: pk-216). Treated and deionized. The solution obtained by deionization was aged at 70 ° C. for 10 hours, and then concentrated with an ultrafiltration membrane to prepare a conductive fine particle dispersion composed of antimony pentoxide having a solid concentration of 14% by mass. The pH of this conductive fine particle dispersion was 4.0, and the average particle size of the conductive fine particles was 20 nm.

Next, 100 g of the conductive fine particle dispersion was adjusted to 25 ° C., and 2.5 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: normal ethyl silicate, SiO ₂ concentration 28.8 mass%) was added in 3 minutes. Stirring was performed for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, the temperature was raised to 50 ° C. over 30 minutes, and a heat treatment was performed for 19 hours. The solid content concentration at this time was 7% by mass.

  Subsequently, water and ethanol as a dispersion medium are solvent-substituted with ethanol in an ultrafiltration membrane, and are concentrated to a chain-conducting inorganic material that has been chained and surface-treated with an organic silicon compound having a solid concentration of 20% by mass. An oxide fine particle (R2) dispersion was prepared. The average number of connected primary particles constituting the chain conductive inorganic oxide fine particles (R2) was 5. The refractive index of the chain-like conductive inorganic oxide fine particles (R2) was 1.65.

Preparation of coating liquid for forming transparent film (R7) 100 g of surface-treated conductive inorganic oxide fine particle (R2) dispersion with a solid content of 20% by mass and ethylene oxide-modified acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd.) : NK ester ATM-4E, resin concentration 100% by mass) 288 g, non-modified acrylic resin (Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) 192 g and photoinitiator (Ciba Specialty Co., Ltd.) ) Irgacure 184) 38.4 g and 568 g of acetone as a ketone solvent and 160 g of methyl ethyl ketone were sufficiently mixed to prepare a coating solution (R7) for forming a transparent film having a solid content of 40% by mass.

Preparation of substrate with transparent film (R7) In Example 1, the coating liquid for transparent film formation (R7) was prepared using a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1). A substrate with a transparent coating (R7) was prepared in the same manner except that the coating was applied to 5) by the bar coater method (bar # 10). The film thickness of the transparent coating was 5 μm.
The table shows the total light transmittance, haze, refractive index of the coating, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, and scratch resistance of the obtained substrate with transparent coating (R7).

[Comparative Example 8]
Preparation of chain conductive inorganic oxide particle (R3) dispersion 100 g of 20 wt% conductive inorganic oxide fine particle (1) dispersion prepared in the same manner as in Example 1 was adjusted to 25 ° C. After adding 6.9 g of silane (manufactured by Tama Chemical Co., Ltd .: normal ethyl silicate, SiO ₂ concentration 28.8 mass%) in 3 minutes, the mixture was stirred for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, the temperature was raised to 50 ° C. over 30 minutes, and a heat treatment was performed for 15 hours. The solid content concentration at this time was 15% by mass.

  Subsequently, water and ethanol as a dispersion medium are solvent-substituted with ethanol in an ultrafiltration membrane, and are concentrated to a chain-conducting inorganic material that has been chained and surface-treated with an organic silicon compound having a solid concentration of 20% by mass. An oxide fine particle (R3) dispersion was prepared. The primary particles constituting the chain conductive inorganic oxide fine particles (R3) were partially connected, but were almost monodispersed. The chain conductive inorganic oxide fine particles (R3) had a refractive index of 1.73.

Preparation of coating liquid for forming transparent film (R8) 100 g of surface treated chain-like conductive inorganic oxide fine particle (R3) dispersion having a solid content concentration of 20% by mass and an ultraviolet curable resin (manufactured by DIC Corporation: Unidic 17-824) -9, solid content concentration 77 mass%) 623 g, 430 g of acetone as a ketone solvent, and 121 g of methyl ethyl ketone were sufficiently mixed to prepare a coating solution (R8) for forming a transparent film having a solid content concentration of 40 mass%.

Preparation of substrate with transparent film (R8) In Example 1, the coating liquid for transparent film formation (R8) was prepared by using a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1). A substrate with a transparent coating (R8) was prepared in the same manner except that the coating was applied by the bar coater method (bar # 10). The film thickness of the transparent coating was 5 μm.

  Shows the total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, coloring, interference fringes, dispersed state of chain particles, scratch resistance of the obtained substrate with transparent coating (R9) Shown in

Claims (16)

Conductive inorganic oxide fine particles, a matrix-forming component, and a dispersion medium, the conductive inorganic oxide fine particles are surface-treated with an organosilicon compound represented by the following formula (1), and the dispersion medium contains ketones The concentration of the total solid content is in the range of 1 to 60% by mass, the surface-treated conductive inorganic oxide fine particles are non-agglomerated and highly dispersed, and the concentration as a solid content is 0.01 to 6% by mass. %, The concentration of the matrix-forming component as a solid content is in the range of 0.1 to 59.4 mass%, and the conductive inorganic oxide fine particles can form a chain structure in the obtained transparent film. A coating liquid for forming a transparent film, characterized in that it is a liquid.
_{R n -SiX 4-n (1} )
(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 0 to 3)   The conductive inorganic oxide fine particles are Sb-doped tin oxide (ATO) fine particles and / or P-doped tin oxide (PTO) fine particles, and the average particle diameter is in the range of 5 to 10 nm. The coating liquid for transparent film formation of description.   3. The conductive inorganic oxide fine particles are chain conductive inorganic oxide fine particles in which three or more primary particles of the conductive inorganic oxide fine particles are connected in a chain. Coating liquid for forming a transparent film.   The coating liquid for forming a transparent film according to any one of claims 1 to 3, wherein the matrix-forming component is an alkylene oxide-modified acrylic resin (A).   The coating liquid for forming a transparent film according to claim 4, wherein the alkylene oxide-modified acrylic resin (A) is an ethylene oxide-modified acrylic resin.   In addition to the alkylene oxide-modified acrylic resin (A), the matrix-forming component further contains a non-modified acrylic resin (B), and the solid content of the non-modified acrylic resin (B) and the alkylene oxide-modified acrylic resin (A) The coating liquid for forming a transparent film according to claim 1, wherein the weight ratio ((B) :( A)) is in the range of 5:95 to 50:50.   The dispersion medium has at least one ketone selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, acetylacetone, and acetoacetate. The coating liquid for forming a transparent film according to any one of claims 1 to 6.   The coating liquid for forming a transparent film according to claim 7, wherein the ketone of the dispersion medium is acetone and / or methyl ethyl ketone. Including a substrate and a transparent coating formed on the substrate surface;
The transparent coating contains conductive inorganic oxide fine particles and a matrix component, and the conductive inorganic oxide fine particles are surface-treated with an organosilicon compound represented by the following formula (1), the conductive inorganic oxide fine particles Constitutes a chain structure in the transparent film and is highly dispersed,
The content of the conductive inorganic oxide fine particles in the transparent film is in the range of 1 to 12% by mass,
The surface resistance value of the transparent coating is in the range of 10 ⁸ to 10 ¹¹ Ω / □, the haze is 0.3% or less, the total light transmittance is 90% or more,
A substrate with a transparent coating, wherein the difference between the refractive index (N _S ) of the substrate and the refractive index (N _H ) of the transparent coating is 0.02 or less.
_{R n -SiX 4-n (1} )
(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 0 to 3) The conductive inorganic oxide fine particles are Sb-doped tin oxide (ATO) fine particles and / or P-doped tin oxide (PTO) fine particles,
The base material with a transparent film according to claim 9, wherein the primary particles constituting the chain structure have an average particle diameter in the range of 5 to 10 nm and the number of connections is 3 or more.   The coating liquid for forming a transparent film according to claim 9 or 10, wherein the matrix component is an alkylene oxide-modified acrylic resin (A).   The substrate with a transparent coating according to claim 11, wherein the alkoxy-modified acrylic resin (A) is an ethylene oxide-modified acrylic resin.   The matrix component further contains a non-modified acrylic resin (B), and a weight ratio ((B) :( A)) as a solid content of the non-modified acrylic resin (B) and the alkoxy-modified acrylic resin (A). Is in the range of 0:95 to 50:50, The substrate with a transparent coating film according to any one of claims 9 to 12.   The substrate with a transparent coating according to any one of claims 9 to 13, wherein the thickness of the transparent coating is in the range of 1 to 20 µm.   The substrate with a transparent coating according to any one of claims 9 to 14, wherein the substrate is triacetylcellulose.   The said transparent film is obtained using the coating liquid for transparent film formation in any one of Claims 1-8, The any one of Claims 9-15 characterized by the above-mentioned. Base material with transparent coating.