KR20120010141A - Coating solution for forming transparent film and substrate coated by transparent film - Google Patents

Abstract

PURPOSE: A coating solution for forming a transparent film is provided to have high conductivity in spite of the low content of conductive inorganic oxide particles, to have high transparency, and to restrain yellowing and interference fringes. CONSTITUTION: A coating solution for forming a transparent film comprises conductive inorganic oxide particles, a matrix-forming component, and a dispersing medium. The conductive inorganic oxide particles are surfaced treated by an organosilicon compound in chemical formula 1: R_n-SiX_(4-n). The dispersing medium comprises ketones. The total solid content is 1-60 weight%. The surface treated conductive inorganic oxide particle has non-condensed highly dispersed form. The concentration of the conductive inorganic oxide particle as solid phase is 0.1-59.4 weight%. The conductive inorganic oxide in the transparent film particle forms chain-like structure.

Description

Coating solution for forming transparent film and substrate {Coating solution for forming transparent film and substrate coated by transparent film}

The present invention has a high conductivity even when the surface-treated conductive inorganic oxide fine particles have a chain-like structure in the transparent coating and are highly dispersed therefor, so that the amount of the conductive inorganic oxide fine particles is low, and also has high transparency, suppressed coloring and interference fringes, and economical efficiency. This excellent coating liquid for transparent film formation and a transparent film part base material are related.

Background Art It is known to form a transparent coating having a hard coating function on the surface of a substrate in order to improve scratch resistance of the surface of the substrate such as glass, plastic sheet, plastic lens, or the like. As such a transparent film, forming an organic resin film or an inorganic film on the surface of glass, plastics, etc. is performed. Moreover, in order to mix | blend inorganic particle, such as resin particle or a silica, in an organic resin film or an inorganic film, improving scratch resistance is performed further.

On the other hand, in the case of use in a display device or the like, in addition to hard coating performance, in order to prevent electrostatic adhesion of dust particles, an attempt has been made to prevent electrostatic charge by applying a conductive film to a transparent film. In order to provide such electroconductivity, it is known to mix | blend electroconductive oxide particle.

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 titanium oxide, and the like are known (Patent Document 1: Japanese Patent Laid-Open No. 2002-79616). report).

Applicant of the present invention is a transparent antistatic film portion substrate containing antimony pentoxide fine particles having a Pyrochlore structure as a coating portion substrate containing conductive oxide fine particles (Patent Document 2: Japanese Patent Laid-Open No. 2001-72929), Hard coating membrane part base material containing antimony pentoxide microparticles | fine-particles (patent document 3: Unexamined-Japanese-Patent No. 2004-50810) Moreover, hard coat membrane part base material containing chain-shaped antimony pentoxide microparticles | fine-particles (patent document 4: Unexamined-Japanese-Patent No. 2005-139026) It is also proposed in the transparent conductive coating part base material (patent document 5: Unexamined-Japanese-Patent No. 2006-339113) etc. which were proposed, etc., and also the chain | strand-shaped electroconductive fine particles (ATO etc.) which connected electroconductive fine particles with the hydrolyzate of an inorganic silicon compound. have.

Patent Document 1: Japanese Patent Publication No. 2002-79616 Patent Document 2: Japanese Patent Application Laid-Open No. 2001-72929 Patent Document 3: Japanese Patent Publication No. 2004-50810 Patent Document 4: Japanese Patent Application Laid-Open No. 2005-139026 Patent Document 5: Japanese Patent Application Laid-Open No. 2006-339113

For example, when antimony pentoxide microparticles | fine-particles were used for the coating part base material which used the conventional electroconductive oxide microparticles | fine-particles, transparency became excellent but electroconductivity fell and the antistatic performance was inadequate. For this purpose, even if the content of the antimony pentoxide fine particles is increased, interference fringes are generated and economical efficiency is deteriorated.

In addition, when P-doped tin oxide (PTO) is used, the antistatic performance is improved even though the anti-static performance is improved compared to the case where the antimony pentoxide fine particles are used, and even when Sb-doped tin oxide (ATO) is used, the antistatic performance is further improved. Even if it is, transparency may fall and the colored transmittance may fall. In addition, even when Sn-doped indium oxide (ITO) was used, there was a problem in the transparency colorability even if the antistatic performance was improved.

In tin oxide and indium oxide, it is known that electroconductivity improves by doping using a dopant as mentioned above. However, P-doped tin oxide fine particles (PTO), Sn-doped indium oxide fine particles (ITO), and Sb-doped tin oxide fine particles (ATO) have a problem in coloring due to reduced transparency even though the conductivity is improved. In some cases, interference fringes may be produced, so that the content must be reduced in order to suppress coloring and the antistatic performance is insufficient.

Therefore, in order to improve the conductivity, as described in Patent Literature 4, the fine particles are connected in a chain to minimize grain boundary resistance, thereby obtaining a transparent film having sufficient antistatic performance even when the amount of the particles themselves is reduced and having no colored interference pattern. It was difficult.

In addition, in the case where both the conventional hard coating performance and antistatic performance are desired, a separate antistatic layer should be formed on the hard coating layer. There is a need for a coating liquid and a transparent coating part substrate capable of forming a transparent coating having a hard coating performance and an antistatic performance with a single coating.

The present inventors earnestly examined in view of such a problem, and as a result, the conductive inorganic oxide fine particles surface-treated using, for example, ethylene oxide-modified acrylic resin as the dispersion medium of the ketones and the matrix-forming component are highly dispersed in the transparent film to form chain particles. The present invention has been found to obtain a transparent coating having a high conductivity even when used in small amounts when formed and having excellent transparency, and excellent hard coating performance in which coloring and interference fringes are suppressed.

[1] A coating film for forming a transparent film containing conductive inorganic oxide fine particles, a matrix forming component and a dispersion medium, wherein the conductive inorganic oxide fine particles are surface treated with an organosilicon compound represented by the following formula (1), and the dispersion medium is a ketone. Containing, the total inorganic content in the range of 1 to 60% by mass and the surface-treated conductive inorganic oxide fine particles in the non-agglomerated high dispersion form and the solids of the conductive inorganic oxide fine particles in the concentration range of 0.1 to 59.4 mass%, the obtained transparent A coating liquid for forming a transparent film, wherein the conductive inorganic oxide fine particles form a chain structure in the film.

R _n -SiX _4-n (1)

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

[2] 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 transparent film formation of [1] having an average particle diameter in the range of 5-10 nm. Coating liquid.

[3] The coating liquid for forming a transparent film according to [1] or [2], wherein the conductive inorganic oxide fine particles are chain conductive inorganic oxide fine particles in which primary particles of the conductive inorganic oxide fine particles are chained in three or more chains.

[4] The coating liquid for forming a transparent film of [1] to [3], wherein the matrix forming component is an alkylene oxide modified acrylic resin (A).

[5] The coating liquid for forming a transparent film of [4], wherein the alkylene oxide modified acrylic resin (A) is an ethylene oxide modified acrylic resin.

[6] The matrix forming component includes an alkylene oxide modified acrylic resin (A) and an unmodified acrylic resin (B), and the weight ratio as a solid content of the unmodified acrylic resin (B) and the alkylene oxide modified acrylic resin (A). Coating liquid for transparent film formation of [1]-[5] whose ((B) :( A)) is the range of 5: 95-50: 50.

[7] The ketones of the dispersion medium are acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone and acetylacetone The coating liquid for transparent film formation of [1]-[6] which is 1 or more types chosen from acet acetate ester.

[8] The coating liquid for forming a transparent film of [7], wherein the ketones of the dispersion medium are acetone and / or methyl ethyl ketone.

[9] A transparent film base material consisting of a transparent film formed on a surface of a device material and a base material, wherein the transparent film contains conductive inorganic oxide fine particles and a matrix component, and the conductive inorganic oxide fine particles are organically represented by the following formula (1). Surface-treated with a silicon compound, the conductive inorganic oxide fine particles formed a chain structure in a transparent coating and is highly dispersed

The content of the conductive inorganic oxide fine particles in the transparent coating is in the range of 1 to 12 mass%,

The surface resistance value of the transparent coating film is 10 ^8? 10 ¹¹ Ω / □ in the range of the haze is more than 0.3% and the light transmittance is 90% or more,

The transparent film part base material whose difference between the refractive index N _S of a base material and the refractive index N _H of the said transparent film is 0.02 or less.

R _n -SiX _4-n (1)

(Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, the same as or different from each other, X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, hydrogen, n is 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 the primary particles forming the chain structure is in the range of 5 to 10 nm. The transparent coating part base material of [9] whose connection number is three or more.

[11] The transparent coating part base material of [9] or [10], wherein the matrix component is an alkylene oxide modified acrylic resin (A).

[12] The transparent coating part base material of [11], wherein the alkoxy-modified acrylic resin (A) is an ethylene oxide-modified acrylic resin.

[13] The matrix component contains an unmodified acrylic resin (B), and the weight ratio ((B): (A)) as a solid content of the unmodified acrylic resin (B) and the alkoxy modified acrylic resin (A) is 5:95? The transparent film | membrane base material of [9]-[12] which is the range of 50:50.

[14] The transparent coating part base material of [9] to [13], wherein the transparent film has a film thickness in the range of 1 to 20 µm.

[15] The transparent coating part substrate of [9] to [14], wherein the substrate is triacetyl cellulose.

[16] The transparent film base material according to [9] to [15], wherein the transparent film is obtained by using a coating liquid for forming a transparent film according to claims 1 to 8.

According to the present invention, even when the amount of the conductive inorganic oxide fine particles is small, it has high conductivity, excellent transparency, no coloring interference pattern, excellent antistatic performance, good scratch resistance, scratch strength, pencil hardness, etc. The coating liquid for transparent film formation and the transparent film part base material which are used for formation of the transparent film part base material excellent also in economic efficiency can be provided.

Although the reason is not clear, since a specific solvent and a matrix-forming component are used, when the monodisperse particles constitute the chain particles in the transparent coating and the chain particles are used in the coating liquid, the chain particles do not aggregate and are highly dispersed. It is judged that it will be in a state and antistatic performance will improve and adhesiveness scratch resistance scratch strength pencil hardness with a base material will be improved.

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

First, the coating liquid for transparent film formation which concerns on this invention is demonstrated.

Coating liquid for transparent film formation

The coating liquid for transparent film formation which concerns on this invention contains electroconductive inorganic oxide microparticles | fine-particles, a matrix formation 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 tin oxide doped with tin, Sb, F or P, indium oxide doped with indium, Sn or F, and antimony oxide doped. It is preferable that it is 1 or more types chosen from. By using such conductive inorganic oxide fine particles, a transparent film having antistatic performance can be obtained.

Among them, the Sb-doped tin oxide (ATO) fine particles and the P-doped tin oxide (PTO) fine particles have high conductivity, so that the amount of the conductive inorganic oxide fine particles can be minimized, further suppressing coloring and forming a thick film. A transparent coating part base material excellent in transparency can be obtained.

In the coating liquid, the conductive inorganic oxide fine particles may be primary particles or chain particles (secondary particles) already connected in a chain form. In the coating liquid, even if the primary particles are dispersed, the specific solvent and the matrix component are used as the coating liquid of the present invention, so that the particles are connected to form the chain particles when the transparent film is formed.

The average particle diameter of the conductive inorganic oxide fine particles (primary particles) is preferably in the range of 5 to 10 nm, preferably in the range of 5 to 8 nm.

If the average particle diameter of the conductive inorganic oxide fine particles (primary particles) is small, the crystal structure may not sufficiently develop, and there is a tendency to form aggregated particles, and the effect of improving conductivity may be insufficient. Moreover, when it aggregates, transparency may fall or a haze may increase. Even if the average particle diameter of the conductive inorganic oxide fine particles (primary particles) is too large, the tendency to form a chain in the transparent coating is small, and the conductive path may not be effectively formed even if the chain is formed, so that the effect of improving conductivity may be insufficient.

In addition, in this invention, a "primary particle" means the monodisperse inorganic oxide fine particle. In addition, a chain particle means that the said primary particle connected three or more.

The average particle diameter of electroconductive inorganic oxide microparticles | fine-particles (primary particle) is measured through a transmission electron micrograph (TEM), and a particle size is measured about 100 particle | grains, and is calculated | required as the average value.

In addition, the measuring method of the refractive index of the electroconductive inorganic oxide microparticles | fine-particles (primary particle) used by this invention is measured by the following method using SeriesA and AA made from CARGILL as a standard refractive solution.

(1) The dispersion medium is evaporated from the conductive inorganic oxide fine particle dispersion through an evaporator.

(2) This is dried at 80 ° C. for 12 hours to obtain a powder.

(3) 2,3 drops of the standard refractive solution of known refractive index are dropped on a glass plate, and the powder is mixed thereon.

(4) The refractive index of the standard refractive solution when the mixed solution becomes transparent by performing the operations of (3) above with several standard refractive solutions is set to the refractive index of the conductive inorganic oxide fine particles.

In the chain | strand-shaped electroconductive inorganic oxide microparticles | fine-particles used by this invention, it is preferable that the connection number of electroconductive inorganic oxide microparticles | fine-particles (primary particle) is 3 or more, 5 or more, especially 10 or more.

If the number of the conductive inorganic oxide fine particles (primary particles) is small, the effect of improving the conductivity is not sufficiently obtained. Therefore, the amount of the conductive inorganic oxide fine particles cannot be reduced in order to obtain desired conductivity, so that the color suppression effect may be insufficient.

The chain-shaped chain | strand-shaped conductive inorganic oxide microparticles | fine-particles (secondary particle) can be manufactured previously based on the method disclosed by patent document 4. As shown in FIG.

The conductive inorganic oxide fine particles (secondary particles) were measured by transmission electron micrograph (TEM) of the conductive inorganic oxide fine particles (secondary particles), and the particle diameters of 100 primary particles were measured and obtained as the average value thereof. The number of connections is calculated only for the chain-shaped particles to which is connected, and the number of connections is calculated as the average value.

The concentration of the conductive inorganic oxide fine particles in the coating liquid for forming a transparent film is preferably in the range of 0.016% mass, preferably 0.02 to 4.8 mass% as solid content.

When the concentration of the conductive inorganic oxide fine particles in the coating film for forming a transparent film is low, the electroconductive performance may be insufficient, and thus the antistatic performance of the transparent coating part base material obtained may be insufficient. Moreover, even if there are too many electroconductive inorganic oxide microparticles | fine-particles, the coloring of the obtained transparent film becomes remarkable and the transmittance | permeability falls or the refractive index of a transparent film becomes high, and an interference fringe may arise depending on the refractive index of a base material.

These conductive inorganic oxide fine particles were surface treated with the organosilicon compound shown in the following formula (1).

R _n -SiX _4-n (1)

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

Examples of the organosilicon compound represented by formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and diphenyl Dimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris ( β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acryloxymethyltri Methoxysilane, γ- (meth) acryloxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxy Propyltrimethoxysilane, γ- (meth) acryloxyoxytrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth_acryloxypropyltriethoxysilane, butyltrimethoxy Silane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, Decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluoro Rhoctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane , N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilol, methyltrichlorosilane and the like, and And mixtures thereof.

Especially, when surface-treating with n = 0 organosilicon compound in said Formula (1), when electroconductive inorganic oxide microparticles | fine-particles (primary particle) are used, electroconductive inorganic oxide microparticles | fine-particles (primary particle) will be chain-shaped at the time of transparent film formation, At the same time, the chain-shaped particles tend to be highly dispersed, and in the case where the chain-shaped conductive inorganic oxide fine particles (secondary particles) are used, the chain-shaped particles tend to be highly dispersed at the time of forming the transparent film.

For the surface treatment of the conductive inorganic oxide fine particles (primary particles), for example, a predetermined amount of the organosilicon compound is added to an alcohol dispersion of the conductive inorganic oxide fine particles (primary particles), and water is added thereto, whereby the valence of the organosilicon compound is added as necessary. As the decomposition catalyst, an acid or an alkali is added to hydrolyze the organosilicon compound. In this case, the amount of the organosilicon compound used is R _n -SiO _{(4-n) / 2} rather than the size of the conductive inorganic oxide fine particles (primary particles), and is approximately 2 to 30% by mass of the conductive inorganic oxide fine particles (primary particles), preferably It is preferable to exist in the range of 3-10 mass%.

When surface-treated with an organosilicon compound, it is uniformly highly dispersed in the coating liquid for forming a transparent film and at the same time, stability is improved, and chain-shaped particles are highly dispersed in the transparent film, and the use of a small amount of conductive inorganic oxide fine particles A transparent coating having high conductivity and excellent transparency, transmittance, hardness, and the like can be obtained.

In addition, about the surface treatment of chain-shaped conductive inorganic oxide microparticles | fine-particles (secondary particle), the organosilicon compound shown by said Formula (1) is hydrolyzed and used in the manufacturing process of chain | strand-shaped conductive inorganic oxide microparticles | fine-particles, and conductive inorganic oxide microparticles | fine-particles (primary Surface) with the connection of particles).

Matrix forming components

As a matrix formation component, alkylene oxide modified acrylic resin (A) is used suitably.

As alkylene oxide modified acrylic resin (A), ethylene oxide modified acrylic resin, propylene oxide modified acrylic resin, etc. are mentioned.

When such an alkylene oxide-modified acrylic resin (A) is used, when the dispersion medium described later is a ketone-based dispersion medium, even when the surface-treated conductive inorganic oxide fine particles (primary particles) are used, a chain structure is obtained in the transparent film obtained. At the same time, it is highly dispersed, and a transparent film having excellent conductivity at least in the amount of the conductive inorganic oxide fine particles can be obtained. In particular, ethylene oxide modified acrylic resin is excellent in this respect. In addition, a matrix formation component says the thing before the polymerization reaction of such an acrylic resin.

In this invention, it is preferable to add an unmodified acrylic resin (B) to the said alkylene oxide modified acrylic resin (A). Thus, the intensity | strength, hardness, and abrasion resistance of the transparent film obtained by using an unmodified acrylic resin (B) can be improved.

Examples of the non-modified acrylic resin (B) are pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, ditrimethyllopropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, and methyl methacrylate. Acrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6 Hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, urethane acrylate and the like and mixtures thereof.

When non-modified acrylic resin (B) is included, the weight ratio ((B) :( A)) is 0:95 to 50:50 as a solid content of the unmodified acrylic resin (B) and the alkylene oxide modified acrylic resin (A). Preferably, it exists in the range of 5: 95-40: 60.

When there is little unmodified acrylic resin (B), the effect of using an unmodified acrylic resin (B), ie, the effect of improving the strength, hardness, and abrasion resistance of the obtained transparent film, becomes inadequate, and even if too many, the conductive inorganic oxide fine particles form a chain. The tendency to become small becomes small, and the effect which improves electroconductivity may not fully be acquired by the small usage amount of electroconductive inorganic oxide fine particles or electroconductive inorganic oxide fine particles.

The concentration of the matrix forming component in the coating liquid for forming a transparent film is preferably 0.1 to 59.4 mass%, preferably 0.2 to 47.8 mass%, as a solid content.

When the concentration of the matrix-forming component in the coating liquid for forming a transparent film is small, the tendency for the conductive inorganic oxide fine particles to be chain-shaped becomes small, and the effect of improving the conductivity is sufficiently achieved with a small amount of the conductive inorganic oxide fine particles or the conductive inorganic oxide fine particles. You may not get it. Moreover, the scratch resistance of the transparent film obtained by decreasing the matrix formation component and the lubricity with a base material may become inadequate.

Even if there are too many matrix forming components in the coating liquid for forming a transparent film, the conductive inorganic oxide fine particles are reduced, so that the conductivity is insufficient, and the antistatic performance of the obtained transparent film base material may be insufficient, and also scratch resistance and adhesion to the substrate. This may become insufficient.

Dispersion

Ketones are used suitably as a dispersion medium used for this invention.

Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanol, methylcyclohexanol, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, acetylacetone, acetic acid ester, etc. Ketones and mixtures thereof.

Among them, acetone, methyl ethyl ketone and mixtures thereof are particularly preferable.

The dispersion medium may contain a dispersion medium other than ketones, and examples of the dispersion medium other than ketones include methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, and ethylene. Alcohols such as glycol, hexylene glycol and isopropylene glycol; Esters such as methyl acetate, ethyl acetate and butyl acetate; Diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethyl glycol monomethyl ether, diethylene glycol monoethylene ether, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether; Toluene, xylene and the like and mixtures thereof.

When such a mixed dispersion medium is used together with the alkoxy-modified acrylic resin (A), when the conductive oxide fine particles (primary particles) are used, the conductive oxide fine particles (primary particles) tend to be chain-shaped at the time of forming the transparent film, and also the chain conductivity It is possible to obtain a transparent film having excellent conductivity, transparency, transmittance, and hardness, and suppressing interference fringes, even when a small amount of conductive oxide particles is used, because oxide fine particles are highly dispersed without agglomeration with each other.

The ratio of ketones in the dispersion medium is 30 mass% or more, preferably 40 mass% or more. When the ratio of ketones is small, the conductive oxide fine particles may not be chain-shaped at the time of the transparent coating, and the chain conductive oxide fine particles may agglomerate with each other, and a transparent film obtained by highly dispersing the chain-shaped conductive oxide fine particles in the transparent coating is obtained. There may not be. In the case where the base material is TAC, if ketones are included in the coating liquid, interference patterns may be suppressed because the surface of the TAC swells or dissolves and enters the transparent coating component and the interface becomes unclear. If the ratio is small, the effect of suppressing such interference fringe may not be obtained.

In addition, when the above-described dispersion medium is used, in the case where a TAC film is used as the substrate, a transparent film in which interference fringes are suppressed can be obtained.

It is preferable that the density | concentration of the coating liquid for transparent film formation is 1-60 mass% as a total solid, Preferably it exists in the range of 2-40 mass%.

When the total solid concentration of the coating liquid for forming a transparent film is too low, the conductive oxide fine particles may not tend to be chain-shaped, so that the effect of improving conductivity may not be obtained, and to obtain a transparent conductive film of a thick film by one application may be obtained. It may be difficult, and there is a problem that the strength of the film is lowered or the economic efficiency is lowered if the repeated coating and drying are repeated.

In addition, even if the total solid concentration is too high, the viscosity of the coating liquid may be high and the coating property may be deteriorated, or the conductive oxide fine particles may tend to aggregate the chain-shaped particles or the chain-shaped conductive oxide fine particles, and sufficient conductivity may not be obtained. The haze of the obtained transparent film may become high or scratch resistance may become inadequate.

Such a coating liquid can be formed by coating, drying, heat treatment, ultraviolet light, or the like on the base material by a known method such as dipping method, spray method, spina method, gravure coating method or roll coating method to form a transparent film. have. The matrix forming component is polymerized and cured by such heating and ultraviolet irradiation.

Next, the transparent film base material which concerns on this invention is demonstrated.

Transparent film base material

The transparent coating part base material which concerns on this invention contains a base material and the transparent film formed in the surface of a base material.

materials

As a base material used for this invention, plastic panels, such as plastic sheet, plastic film, etc. which are conventionally well-known glass, polycarbonate, an acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC), etc. can be used.

Especially, TAC, a polycarbonate, an acrylic resin base material etc. are used suitably. In particular, in order to use ketones in the dispersion medium of the coating liquid for forming a transparent film of the present invention, the TAC swells or dissolves the TAC base material so that the TAC and the transparent film component enter each other, resulting in an unclear optical interface or inclination of the refractive index. It is preferable because the interference fringes can be suppressed because they have a.

The refractive index N _S of the base material used for this invention is 1.49-1.59, Preferably it is 1.49-1.65, It is preferable to exist in the range of 1.49-1.52 especially.

If the refractive index N _S of the substrate is not in the above range, it may be difficult to control the refractive index of the transparent film, and the difference in refractive index with the refractive index N _S of the substrate may not be 0.2 or less, and the interference fringe may not be suppressed. .

Transparent film

The transparent film contains a matrix component as conductive inorganic oxide fine particles.

Conductive inorganic oxide fine particles

In the transparent coating, the surface-treated conductive inorganic oxide fine particles used in the coating liquid take a chain structure and are highly dispersed.

In addition, the said chain | strand electroconductive inorganic oxide microparticles | fine-particles mean that the said primary particle in the coating liquid was connected in the film formation process, the particle which was already connected, and the particle | grains which were already connected, or connected with primary particle.

Here, the term "high dispersion" also varies depending on the content of the conductive inorganic oxide fine particles, but the chain-like structure in the transparent coating without the particles having the chain-shaped conductive oxide particles and the chain-shaped conductive oxide fine particles interlocked or agglomerated and localized. This means that it is in a highly dispersed state so that it can be seen with the naked eye. In addition, the chain particles may be further connected.

The number of connections of the conductive inorganic oxide fine particles in the transparent coating is usually 3 or more, preferably 5 or more, particularly 10 or more.

When the number of chain-shaped conductive inorganic oxide fine particles is small, the effect of improving the conductivity cannot be sufficiently obtained. In addition, when chain particles are used in advance, the number of connections increases, or the monodisperse particles and the chain particles may be connected.

Although it is not clear why the chain-shaped electroconductive oxide fine particles disperse | distribute in the transparent film of this invention, it can be considered that the density | concentration of the specific dispersion medium, specific resin, and the said coating liquid used for this invention contributed as mentioned above.

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%.

When there are too few electroconductive inorganic oxide microparticles | fine-particles in a transparent film, even if the said chain-shaped electroconductive fine particles are highly dispersed, electroconductivity may become inadequate. Even if there are too many conductive inorganic oxide fine particles, electroconductivity improves, but coloring derived from inorganic oxides, such as ATO and PTO, is confirmed, the total light transmittance becomes inadequate, or refractive index becomes high, and an interference fringe may arise depending on a base material.

Matrix components

As a matrix component, resin in which said alkylene oxide modified acrylic resin (A) was hardened is preferable. Moreover, a non-modified acrylic resin (B) may be included with such alkylene oxide modified acrylic resin (A).

When using unmodified acrylic resin (B) and alkoxy modified acrylic resin (A) together, the weight ratio ((B) :( A)) is 0: 95-50: 50 like the said matrix formation component, Preferably, It is preferable to exist in the range of 5: 95-40: 60.

Content of the matrix component in a transparent film is 88-99 mass% as solid content, Preferably it exists in the range of 90-99 mass%.

When there is little matrix component in a transparent film, the said electroconductive inorganic oxide microparticles | fine-particles will become relatively large and a problem of coloring may arise. Even if there are too many matrix components in a transparent film, electroconductivity may become inadequate and antistatic performance may become inadequate because there are few electroconductive inorganic oxide fine particles.

The difference between the refractive index N _S of the substrate and the refractive index N _H of the electrically transparent film is 0.02 or less, preferably 0.01 or less.

If the difference in refractive index is more than 0.02, a sharp interference fringe may cause a problem in appearance, or the clarity of an image may be degraded when used in a display device.

In the present invention, the refractive index (N _H ) of the transparent coating is preferably in the range of 1.49 to 1.59, preferably 1.49 to 1.56, particularly 1.49 to 1.52.

When the refractive index N _H of a transparent film is not in the said range, the difference in refractive index with the refractive index N _S of the base material used may be larger than 0.02, and an interference fringe may be produced.

A surface resistance of the transparent film 10 is ^8? Is the 10 ¹¹ Ω / □, preferably 10 ^8? 10 in the ¹⁰ Ω / □ range.

When the surface resistance of a transparent film is too low, it is necessary to make content of the said electroconductive inorganic oxide fine particle 12 mass% or more, and a coloring problem may arise in this case.

If the surface resistance of a transparent film is too large, antistatic performance may become inadequate.

The haze of a transparent film is 0.3% or less, Preferably it is 0.2% or less. High haze may result in insufficient transparency and inability to obtain desired optical properties such as contrast and clarity.

Moreover, the total light transmittance of a transparent film is 90% or more, Preferably it is 92% or more.

When the total light transmittance is low, not only the desired optical characteristics cannot be obtained, but when the colored light is low, the design and design of the optical member may be adversely affected.

The film thickness of a transparent film is 1-20 micrometers, It is preferable to exist in the range of 4-15 micrometers preferably.

If the film thickness of the transparent film is too thin, sufficient hardness and scratch resistance may not be obtained, and even if the film thickness of the transparent film is too thick, the film is thick, so that coloring may be promoted or the transmittance may be insufficient.

In the present invention, a transparent film having a refractive index lower than the refractive index 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 coating liquid for antireflection film formation and the antireflection film disclosed in Japanese Patent Application Laid-Open No. 2006-339113 by the applicant of the present applicant can be suitably used.

EXAMPLE

The present invention will be described in more detail with reference to the following Examples, but the present invention is not limited to these Examples.

Example 1

Production of Chain Conductive Inorganic Oxide Fine Particles (1)

A mixed solution was prepared in which 130 g of potassium stannate and 30 g of antimonyl potassium stannate were dissolved in 400 g of pure water. 1.0 g of ammonium nitrate was dissolved in this solution over 60 hours at 60 ° C. under stirring, and then added to 1000 g of pure water prepared at pH 10.5 using potassium hydroxide for hydrolysis. At this time a 10% acetic acid solution was added to the copper to maintain a pH of 10.5. The resulting precipitate was isolated by filtration, washed, and then dispersed in water to prepare a metal oxide precursor hydroxide dispersion having a solid concentration of 20% by mass.

This dispersion was spray dried at a temperature of 100 ° C. to prepare a metal oxide precursor hydroxide powder.

Sb-doped tin oxide (ATO) powder was obtained by heat-processing this powder at 550 degreeC for 2 hours in air atmosphere.

60 g of this powder was dispersed in 140 g of a 4.3% by mass aqueous potassium hydroxide solution, and pulverized with a sand mill for 3 hours while maintaining the dispersion at 30 ° C.

Pure water was then added to this sol and diluted to 8 mass% in concentration. The pH of this sol was 5.2. Subsequently, this sol was processed by anion exchange resin (made by Mitsubishi Chemical Corporation; diamond ion SANUPC), and it was set to pH 5.5. Next, water heat treatment was performed at 200 ° C. for 24 hours. Subsequently, the mixture was treated with an anion exchange resin (manufactured by Mitsubishi Chemical Corporation; diamond ion SANUPC) and then treated with a cation exchange resin (manufactured by Mitsubishi Chemical Corporation; diamond ion SK1BH) to obtain a sol having a pH of 2.7 and a concentration of 8 mass%. It was. This was concentrated in an ultrafiltration membrane to prepare a conductive inorganic oxide fine particle (1) dispersion prepared from Sb-doped tin oxide particles having a solid concentration 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 particles (1) dispersion liquid having a concentration of 20% by mass was adjusted to 25 ° C, and 5.2g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd.: ethyl silicate and SiO ₂ concentration 28.8% by mass) was obtained. After adding about 3 minutes, it stirred for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, and the temperature was increased at 50 ° C. for about 30 minutes, and the superheat treatment was performed for 15 hours. Solid content concentration at this time was 10 mass%.

Subsequently, in the ultrafiltration membrane, water and ethanol of the dispersion medium were solvent-substituted in ethanol to prepare a chain-conductive inorganic oxide fine particle (1) dispersion liquid chain-shaped and surface-treated with an organosilicon compound having a solid concentration of 20% by mass. The average connection number of the primary particle which comprises the chain | strand electroconductive inorganic oxide fine particle 1 was ten pieces. In addition, the refractive index of the chain-shaped conductive inorganic oxide fine particles 1 was 1.75.

Preparation of the coating liquid 1 for transparent film formation

100 g of chain-shaped conductive inorganic oxide fine particles (1) dispersion liquid and surface treatment of solid content concentration 20 mass% and ethylene oxide modified acrylic resin (manufactured by Kogyo Chemical Co., Ltd.): Light acrylate TMP-3EO-A, resin concentration 100 mass% ) 480 g of 38.4 g of a photoinitiator (Ciba Special Co., Ltd. make: Irgacure 184) and 658 g of acetone and 160 g of methyl ethyl ketone as a ketone solvent are sufficiently mixed to form a transparent film having a solid concentration of 40% by mass. The coating liquid 1 was prepared.

Preparation of the transparent film base material (1)

The coating liquid 1 for transparent film formation was apply | coated to TAC film (Fanak Co., Ltd. make: FT-PB80UL-M, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (bar 10), and it is 120 at 80 degreeC. After drying for a second, 300 mJ / cm ² of ultraviolet light was irradiated and cured to prepare a transparent film base material (1). The film thickness of the transparent film was 5 micrometers.

The total light transmittance, the haze, the refractive index of the film, the surface resistance value, the adhesion, the pencil hardness, the coloring, the interference fringe, the dispersion state of the chain-shaped particles, and the scratch resistance of the transparent coating part base material 1 are shown in the table. The total light transmittance and the haze were measured by a haze meter (manufactured by Suga Tester Co., Ltd.) and the reflectance was measured by a spectrophotometer (Japanese spectrometer, Ubest-55). The surface resistance value was measured by the surface ohmmeter (Mitsubishi Chemical Corporation make: Highstar).

In addition, the uncoated TAC film had a total light transmittance of 93.2%, a haze of 0.2%, and a reflectance of the light having a wavelength of 550 nm of 6.0%.

Moreover, adhesiveness, pencil hardness, coloring, interference fringe, dispersion | distribution state, and abrasion resistance of chain-shaped particle were evaluated by the following method and evaluation criteria, and the result was shown in the table | surface. In addition, the scanning electron microscope photograph at the time of evaluating the dispersion state of chain form particle | grains is shown in FIG.

Refractive index

The coating liquid 1 for transparent film formation was apply | coated, dried, and hardened | cured on a silicon wafer, the transparent film was formed, and the refractive index of the transparent film was measured with the lipsomator (EMS1 made from ULVAC).

coloring

Fluorescent lamp light was applied to the transparent coating part base material 1, and the presence or absence of coloring by transmission was visually observed. The results are shown in Table 1.

Evaluation standard:

Colorless and transparent, no coloring at all confirmed ： ◎

Ultra-thin coloring is confirmed slightly ○

Thin coloring is confirmed ： △

Dark coloring is confirmed ： ×

Adhesion

When 11 parallel wounds are made on the surface of the transparent film base material 1 with a knife at an interval of 1 mm in width, 100 cells are made, and the tape is vertically bonded thereto, and then the tape is vertically peeled off. The number of cells remaining without peeling of the coating was classified into the following four steps to evaluate the adhesion. The results are shown in Table 1.

The number of remaining spaces ： ◎

The number of remaining spaces 90-99 ： ○

85 to 89 spaces remaining ： △

The number of remaining spaces 84 or less ： ×

Measurement of scratch resistance

The surface of the membrane was visually observed by sliding 50 times with a load of 500 g / cm ² using a # 0000 steel cotton, and the results were shown in Table 1 below.

Evaluation standard:

The root wound was not confirmed ： ◎

A few wounds are confirmed in root 조 ○

A lot of wounds were confirmed by root ： △

The face is cut entirely: ×

Interference pattern

Fluorescent lamp light was reflected on the surface of the transparent film in the state where the transparent film base material 1 was made black, and the occurrence of rainbow shape by the interference of light was visually observed and evaluated according to the following criteria.

Rainbow pattern is not confirmed at all

Slightly confirmed rainbow shape ： ○

Rainbow shape is clearly identified ： △

The rainbow shape is clearly confirmed ： ×

Dispersion State of Chain Particles

The transmission electron microscope photograph of the cross section of the transparent film | membrane was image | photographed, the dispersion state of chain-shaped electroconductive inorganic oxide fine particle was observed, and the following references | standards evaluated.

Chain particles disperse at approximately equal intervals without intermingling each other.

Particles in the chain are entangled, but are generally dispersed at equal intervals.

Most of the chain particles entangle and disperse unevenly ： △

Monodisperse particles disperse or disperse monodisperse or aggregate without chaining, or disperse and disperse heterogeneously:

Example 2

Preparation of the coating liquid 2 for transparent film formation

100 g of surface-treated chain-shaped conductive inorganic oxide fine particles (1) dispersion liquid prepared in the same manner as in Example 1, and 384 g of an ethylene oxide-modified acrylic resin (Diecel-Cytec Co., Ltd. product: EBECRYL40, resin concentration 100 mass%), As an unmodified acrylic resin, it is a photoinitiator (Ciba Specialty Co., Ltd. product: Irgacure 184 to 96 g of dipentaerythritol hexaacrylate (the public corporation chemical company make: Light acrylate DPE-6A, resin concentration 100 mass%) ) 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 (2) for forming a transparent film having a solid concentration of 40% by mass.

Preparation of the transparent coating part base material 2

A transparent coating part base material 2 was produced in the same manner as in Example 1 except that the coating liquid for forming a transparent film was used. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, film refractive index, surface resistance value, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material 2 are shown in a table.

EXAMPLE 3

Preparation of the coating liquid 3 for transparent film formation

100 g of surface-treated chain-shaped conductive inorganic oxide fine particles (1) dispersion liquid 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, 38.4 g of photoinitiators (Irgacure 184 made from Tiba Specialty Co., Ltd.) and ketone to 192 g of unmodified acrylic resin (Co., Ltd. company make: Light acrylate DPE-6A, resin concentration 100 mass%) 568 g of acetone and 160 g of methyl ethyl ketone were sufficiently mixed as a system solvent to prepare a coating liquid (3) for forming a transparent film having a solid content concentration of 40% by mass.

Preparation of the transparent film base material 3

The transparent coating part base material 3 was produced similarly except having used the coating liquid 3 for transparent film formation in Example 1. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, the haze, the refractive index of the film, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain-shaped particles, and scratch resistance of the obtained transparent coating part base material 3 are shown in a table.

EXAMPLE 4

Preparation of the coating liquid 4 for transparent film formation

50 g of surface-treated chain-shaped conductive inorganic oxide fine particles (1) dispersion liquid and ethylene oxide modified acrylic resin (Shin-Nakamura Chemical Co., Ltd. make: NK ester ATM-4E, resin concentration 100 mass%) prepared similarly to Example 1 39.2 g of a photoinitiator (Irgacure 184 by Tiba Specialty Co., Ltd.) to 196 g of 294 g of unmodified acrylic resin (manufactured by Kogyo Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) and ketone 600 g of acetone and 169 g of methyl ethyl ketone were sufficiently mixed as the system solvent to prepare a coating liquid 4 for forming a transparent film having a solid content concentration of 40% by mass.

Preparation of the transparent coating part base material 4

The transparent coating part base material 4 was produced similarly except having used the coating liquid 4 for transparent film formation in Example 1. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, film refractive index, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material 4 are shown in a table.

EXAMPLE 5

Preparation of the coating liquid 5 for transparent film formation

100 g of surface-treated chain-shaped conductive inorganic oxide fine particles (1) dispersion liquid 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 mass% ) 14.4 g of a photoinitiator (Irgacure 184 manufactured by Tiba Specialty Co., Ltd.) to 72 g of 108 g, unmodified acrylic resin (manufactured by Kogyo Chemical Co., Ltd.) As a ketone solvent, 188 g of acetone and 53 g of methyl ethyl ketone were sufficiently mixed to prepare a coating liquid 5 for forming a transparent film having a solid content concentration of 40% by mass.

Preparation of the transparent coating part base material 5

The transparent coating part base material 5 was produced similarly except having used the coating liquid 5 for transparent film formation in Example 1. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, reflectance, refractive index of the film, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain-shaped particles, and scratch resistance of the obtained transparent coating part base material 5 are shown in a table.

EXAMPLE 6

Preparation of the coating liquid 6 for transparent film formation

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

Preparation of the transparent film base material 6

The transparent coating part base material 6 was produced similarly except having used the coating liquid 6 for transparent film formation in Example 1. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, refractive index of the film, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material 6 are shown in a table.

Example 7

Preparation of the coating liquid 7 for transparent film formation

100 g of the chain-conductive inorganic oxide fine particle (1) dispersion liquid which surface-treated at 20 mass% of solid content concentration similarly to Example 1, and ethylene oxide modified acrylic resin (Shin-Nakamura Chemical Co., Ltd. make: NK ester ATM-4E) Into 288 g of resin concentration 100 mass%), unmodified acrylic resin (the public corporation chemical company make: light acrylate DPE-6A, resin concentration 100 mass%) photoinitiator (Tibaspecity Co., Ltd. product) Irgacure 184) 38.4 g of acetone as a ketone solvent and 160 g of methyl ISO butyl ketone were sufficiently mixed to prepare a coating liquid 7 for forming a transparent film having a solid content of 40% by mass.

Preparation of the transparent film base material 7

A transparent coating part base material 7 was produced in the same manner as in Example 1 except that the coating liquid 7 for forming a transparent film was used. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, refractive index, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material 7 are shown in a table.

[Example 8] (change to PTO particles in Example 3, particles: resin = 10:90)

Preparation of Chain Conductive Inorganic Oxide Particles (3) Dispersion

A solution was prepared by dissolving 150 g of potassium stannate in 430 g of pure water. The solution was hydrolyzed for 12 hours by adding 800 g of pure water, 1.3 g of ammonium nitrate, and an aqueous potassium hydroxide solution at 60 ° C. under stirring, to a solution prepared at pH 10.0. At this time, an aqueous solution of acetic acid having a concentration of 10% by mass was added simultaneously to maintain the pH at 10.0. The resulting precipitate was separated by filtration, washed, and then dispersed in water to prepare 200 g of a tin hydroxide dispersion having a solid content of 20% by mass.

3.2 g of an aqueous solution of phosphoric acid at a concentration of 85% by mass was added to the dispersion, followed by stirring for 30 minutes, followed by spray drying at a temperature of 100 ° C to prepare a hydroxide powder of a phosphorus-doped tin oxide precursor. Phosphorus-doped tin oxide powder was obtained by heat-processing this powder at 650 degreeC for 2 hours in air atmosphere.

60 g of this powder was dispersed in 140 g of potassium hydroxide aqueous solution having a concentration of 4.3% by mass, and ground in a sand mill for 3 hours while maintaining the dispersion at 30 ° C to prepare a sol.

This sol was then de-alkali treated with an ion exchange resin until the pH reached 3.3 and pure water was added to prepare a conductive fine particle (3) dispersion formed from phosphorus doped tin oxide fine particles having a concentration of 20% by mass.

PH of this electroconductive inorganic oxide fine particle (3) dispersion liquid was 3.6. Moreover, the average particle diameter of the electroconductive inorganic oxide fine particle 3 was 8 nm.

Next, 100 g of the conductive inorganic oxide fine particle (3) dispersion liquid having a concentration of 20% by mass was adjusted at 25 ° C to adjust 3.5 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: ethyl silicate and SiO ₂ concentration 28.8% by mass). After adding about 3 minutes, it stirred for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, and the temperature was increased at 60 ° C. for about 30 minutes and subjected to overheating for 12 hours. Solid content concentration at this time was 10 mass%.

Subsequently, water and ethanol of the dispersion medium were solvent-substituted with ethanol in an ultrafiltration membrane to prepare a chain conductive inorganic oxide fine particle (3) dispersion liquid which was chain-formed and surface treated with an organosilicon compound having a solid content of 20% by mass. The average connection number of the primary particle which comprises the chain | strand electroconductive inorganic oxide microparticles | fine-particles 3 was five pieces. Further, the refractive index of the chain conductive inorganic oxide fine particles 3 was 1.74.

Preparation of the coating liquid 8 for transparent film formation

100 g of surface-treated chain-shaped conductive inorganic oxide fine particles (3) dispersion liquid and ethylene oxide modified acrylic resin (made by Shin-Nakamura Chemical Co., Ltd .: NK ester ATM-4E, resin concentration 100 mass%) of 20 mass% of solid content concentration: 108 g 14.4 g of a photoinitiator (Ilgacure 184 manufactured by Tiba Specialty Co., Ltd.) and a ketone solvent in 72 g of an unmodified acrylic resin (manufactured by Kogyo Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100% by mass) As a result, 188 g of acetone and 53 g of methyl ethyl ketone were sufficiently mixed to prepare a coating liquid 7 for forming a transparent film having a solid content concentration of 40% by mass.

Preparation of the transparent film base material 8

A transparent coating part base material 8 was produced in the same manner as in Example 1 except that the coating liquid 8 for forming a transparent film was used. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, refractive index of the film, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material 8 are shown in a table.

EXAMPLE 9

Preparation of the transparent film base material 9

The coating liquid 3 for transparent film formation manufactured similarly to Example 3 was apply | coated to the TAC film (Panak Co., Ltd. product: FTPB80ULM, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (bar 4). After drying at 80 ° C. for 120 seconds, a 300 mJ / cm ² ultraviolet ray was irradiated and cured to prepare a transparent coating part substrate (9). The film thickness of the transparent film was 2 micrometers.

The total light transmittance, haze, refractive index, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles and scratch resistance of the obtained transparent coating part base material 9 are shown in the table.

Example 10

Manufacture of the transparent film base material 10

The coating liquid 3 for transparent film formation manufactured similarly to Example 3 was apply | coated to the TAC film (Panak Co., Ltd. product: FTPB80ULM, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (barbar 20). After drying at 80 ° C. for 120 seconds, a 300 mJ / cm ² ultraviolet ray was irradiated and cured to prepare a transparent coating part substrate 10. The film thickness of the transparent film was 10 micrometers.

The total light transmittance, haze, film refractive index, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material 10 are shown in a table.

EXAMPLE 11

Preparation of the coating liquid 1 for antireflection transparent film formation

5.9 g of methyl isobutyl ketone was added to and diluted with 6.5 g of a silica-based fine particle dispersion (Swiria Catalytic Co., Ltd. product: Surea 4320, particle refractive index = 1.30, solid concentration 20 mass%, dispersion medium = methyl ISO butyl ketone), and then diluted. 1.03 g of dipentaerythritol hexaacrylate (the public corporation chemical company make: DPE-6A, solid content concentration 100 mass%) and reactive silicone oil (Shinwol Chemical Co., Ltd .; X-22-174DX,) for water-repellent materials Solid content concentration 100 mass%) 0.08 g and 1.6-hexanediol diacrylate (manufactured by Kogyo Chemical Co., Ltd .; light acrylate 1.6HXA) 0.09 g and photopolymerization initiator (Chiba Japan Co., Ltd.) agent: Irgacure 184: In IPA 0.76 g of isopropyl alcohol, 70.66 g of isopropyl glycol, and 15.00 g of isopropyl glycol were mixed to prepare a coating liquid (1) for antireflection transparent film formation having a solid content of 2.5% by mass.

Manufacture of the transparent coating part base material 11

A transparent coating part base material 3 was prepared in the same manner as in Example 3, and then the coating liquid 1 for antireflection transparent film formation was applied by a bar coater method (bar 3) and dried at 80 ° C. for 120 seconds. A transparent coating part base material 11 was prepared by irradiating and curing 600 mJ / cm ² ultraviolet rays under an N ₂ atmosphere to form an antireflection film. At this time, the film thickness of the antireflection coating was 100 nm.

The total light transmittance, haze, reflectance, refractive index of the film, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material 11 are shown in a table.

Example 12

Preparation of Conductive Inorganic Oxide Particles 12 Dispersion

100 g of the conductive inorganic oxide fine particles (1) dispersion liquid having a concentration of 20% by mass prepared in the same manner as in Example 1 was adjusted to 25 ° C, and tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: ethyl silicate and SiO ₂ concentration of 28.8 mass) was used. %) 4.9 g was added for about 3 minutes, and then stirred for 30 minutes. After that, 100 g of ethanol was added over 1 minute, and the temperature was increased at 50 ° C. for 30 minutes, and the superheat treatment was performed for 20 hours. Solid content concentration at this time was 15 mass%.

Subsequently, the dispersion of the conductive inorganic oxide fine particles (12) prepared by surface-treating the organic silicon compound having a solid content of 20% by mass by solvent-substituting water and ethanol of the dispersion medium in the ultrafiltration membrane. The average particle diameter of the conductive inorganic oxide fine particles 12 was 8 nm. In addition, the refractive index of the conductive inorganic oxide fine particles 11 was 1.74.

Preparation of the coating liquid 12 for transparent film formation

In Example 3, the coating liquid 12 for transparent film formation of 40 mass% of solid content concentration was similarly used except having used 100 g of the conductive inorganic oxide fine particles 12 dispersion surface-treated with the organosilicon compound of 15 mass% of solid content concentration. Prepared.

Preparation of the transparent coating part base material 12

A transparent coating part base material 12 was produced in the same manner as in Example 1 except that the coating liquid 12 for forming a transparent film was used. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, reflectance, refractive index of the film, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain-shaped particles, and scratch resistance of the obtained transparent coating part base material 12 are shown in a table. The chain-shaped 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 (R1) for transparent film formation

100 g of surface-treated chain-shaped conductive inorganic oxide fine particles (1) dispersion liquid prepared in the same manner as in Example 1, and urethane acrylate-based ultraviolet curable resin (DIC Co., Ltd. product: Unidiq 17-824-9, solid content concentration 77% by mass) ) 623 g, 430 g of acetone and 121 g of methyl ethyl ketone were sufficiently mixed as a ketone solvent to prepare a coating liquid (R1) for forming a transparent film having a solid content concentration of 40% by mass.

Preparation of transparent film base material (R1)

In Example 1, the coating liquid R1 for transparent film formation was apply | coated to a TAC film (Fanak Co., Ltd. make: FT-PB80UL-M, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (bar 10). A transparent coating part base material R1 was similarly manufactured except having done this. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, film refractive index, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material (R1) are shown in a table. In addition, the scanning electron micrograph when the dispersion | distribution state of a chain particle was evaluated is shown in FIG. 2. As shown in FIG. 2, the particle | grains were aggregated.

[Comparative example 2]

Preparation of coating liquid (R2) for transparent film formation

288 g of surface-treated chain-shaped conductive inorganic oxide fine particles (R1) dispersion liquid and ethylene oxide modified acrylic resin (manufactured by Kogyo Chemical Co., Ltd .: light acrylate TMP3EOA, resin concentration 100 mass%) prepared in the same manner as in Comparative Example 1 38.4 g and isopropyl alcohol 568 to a photoinitiator (Tiba Specialty Co., Ltd. make: Irgacure 184) to 192 g of unmodified acrylic resin (Co., Ltd. make: Light acrylate DPE6A, resin concentration 100 mass%). g and toluene 160g were fully mixed, and the coating liquid 2 for transparent film formation of 40 mass% of solid content concentration was manufactured.

Preparation of transparent film base material (R2)

In Example 1, the coating liquid R2 for transparent film formation was apply | coated to TAC film (Fanak Co., Ltd. product: FT-PB80UL-M, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (bar 20). A transparent coating part base material R2 was similarly manufactured except having done this. The film thickness of the transparent film was 10 micrometers.

The total light transmittance, haze, film refractive index, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material (R2) are shown in a table.

[Comparative Example 3]

Preparation of coating liquid (R3) for transparent film formation

UV curable resin diethylene glycol diglycidyl ether diacrylate (Shin-Nakamura Chemical Co., Ltd. product) which has 100 g of surface-treated chain | strand-shaped conductive inorganic oxide fine particle (R1) dispersion liquids, and OH group which were manufactured similarly to the comparative example 1: To 480 g of NK oligo EA5821), 38.4 g of a photoinitiator (Irgacure 184 manufactured by Tiba Specialty Co., Ltd.) and 568 g of isopropyl alcohol and 160 g of ethyl cellosolve are sufficiently mixed to form a transparent film having a solid concentration of 40% by mass. A coating liquid (R3) was prepared.

Preparation of transparent film base material (R3)

In the comparative example 1, the coating liquid R3 for transparent film formation was apply | coated to TAC film (Fanak Co., Ltd. make: FT-PB80UL-M, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (bar 10). A transparent coating part base material (R3) was similarly manufactured except having done this. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, film refractive index, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material (R3) are shown in the table.

[Comparative example 4]

Preparation of coating liquid (R4) for transparent film formation

229 g of surface-treated chain-shaped conductive inorganic oxide fine particles (1) dispersion liquid prepared in the same manner as in Example 1 and ethylene oxide-modified acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester ATM4E, resin concentration 100% by mass) To 159 g of an unmodified acrylic resin (manufactured by Kogyo Chemical Co., Ltd .: Light acrylate DPE6A, resin concentration 100% by mass), 31.8 g of a photoinitiator (Tiba Specialty Co., Ltd. Irgacure 184) and acetone as a ketone solvent 499 g of ethylene and 141 g of methyl ethyl ketone were sufficiently mixed to prepare a coating solution (R4) for forming a transparent film having a solid content concentration of 40% by mass.

Preparation of transparent film base material (R4)

In Example 1, the coating liquid R4 for transparent film formation was apply | coated to a TAC film (Panak Co., Ltd. product: FT-PB80UL-M, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (bar 10). A transparent coating part base material R4 was similarly manufactured except having done this. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, film refractive index, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material (R4) are shown in a table.

[Comparative Example 5]

Preparation of coating liquid (R5) for transparent film formation

100 g of surface-treated chain-shaped conductive inorganic oxide fine particles (1) dispersion liquid 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) 6.4 g of photoinitiator (Irgacure 184 made from Tiba Specialty Co., Ltd.) and ketone to 32 g of 48 g, unmodified acrylic resin (manufactured by Kogyo Chemical Co., Ltd .: light acrylate DPE-6A, resin concentration 100 mass%) 62 g of acetone and 18 g of methyl ethyl ketone were sufficiently mixed as a system solvent to prepare a coating liquid (R5) for forming a transparent film having a solid content concentration of 40% by mass.

Preparation of transparent film base material (R5)

In Example 1, the coating liquid R5 for transparent film formation was apply | coated to TAC film (Fanak Co., Ltd. make: FT-PB80UL-M, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (bar 10). A transparent coating part base material R5 was similarly manufactured except having done this. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, the haze, the refractive index, the adhesiveness, the pencil hardness, the coloring, the interference fringe, the dispersion state of the chain-shaped particles, and the scratch resistance of the obtained transparent coating part base material R5 are shown in the table.

[Comparative Example 6]

Preparation of Conductive Inorganic Oxide Particle (R1) Dispersion

A mixed solution was prepared in which 130 g of potassium stannate and 30 g of antimonyl potassium stannate were dissolved in 400 g of pure water. The prepared solution was added to 1000 g of pure water in which 1.0 g of ammonium nitrate and 12 g of 15% aqueous ammonia were dissolved at 60 ° C under stirring for 12 hours, followed by hydrolysis. At this time 10% acetic acid solution was added simultaneously to maintain pH 8.8. The resulting precipitate was isolated by filtration, washed, and then dispersed in water to prepare a metal oxide precursor hydroxide dispersion having a solid 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-processed at 550 degreeC for 2 hours in air atmosphere, and Sb doped tin oxide (ATO) powder was obtained. 60 g of this powder was dispersed in 140 g of a 4.3% by mass aqueous potassium hydroxide solution, and pulverized with a sand mill for 3 hours while maintaining the dispersion at 30 ° C.

Next, the sol was subjected to de-alkali treatment with an ion exchange resin until the pH reached 3.0 to prepare a conductive inorganic oxide fine particle (1) dispersion liquid containing 20 mass% of Sb-doped tin oxide fine particles. PH of this electroconductive inorganic oxide fine particle (1) dispersion liquid was 3.2. Moreover, the average particle diameter of electroconductive inorganic oxide fine particle (R1) was 20 nm.

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

Subsequently, water and ethanol of the dispersion medium in the ultrafiltration membrane were concentrated at the same time as solvent substitution with ethanol to prepare a conductive inorganic oxide fine particle (R1) dispersion liquid which was chain-phased and surface treated with an organosilicon compound having a solid content of 20% by mass. No chained connection was found in the conductive inorganic oxide fine particles (R1). The refractive index of the conductive inorganic oxide fine particles (R1) was 1.74.

Preparation of the coating liquid R6 for transparent film formation

100 g of surface-treated conductive inorganic oxide fine particles (R1) dispersion liquid and ethylene oxide modified acrylic resin (made by Shin-Nakamura Chemical Co., Ltd .: NK ester ATM-4E, resin concentration 100 mass%) of 20 mass% of solid content concentration, ratio, ratio To 32 g of modified acrylic resin (manufactured by Kogyo Chemical Co., Ltd .: light acrylate DPE6A, resin concentration 100% by mass), 6.4 g of a photoinitiator (Tiba Specialty Co., Ltd. Irgacure 184) and acetone as a ketone solvent were 62 g and 18 g of methyl ethyl ketone were sufficiently mixed to prepare a coating film for forming a transparent film (R6) having a solid content concentration of 40% by mass.

Production of Transparent Film Substrate R6

In Example 1, the coating liquid R6 for transparent film formation was apply | coated to TAC film (Fanak Co., Ltd. product: FT-PB80UL-M, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (bar 10). A transparent coating part base material R5 was similarly manufactured except having done this. The film thickness of the transparent film was 5 micrometers. The total light transmittance, haze, film refractive index, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material R6 are shown in the table.

Comparative Example 7

Preparation of Chain Conductive Inorganic Oxide Particles (R2) Dispersion

50 g of antimony trioxide (Sumitomo mine Co., Ltd. product: KN, purity 98.5 mass%) was suspended in the solution which melt | dissolved 25 g of potassium hydroxide (Asahi Glass Co., Ltd. make: purity 85 mass%) in 800 g of pure water. The suspension was heated at 95 ° C., and then 15 g of hydrogen peroxide (Lim Pharm Co., Ltd., Limited, concentration: 35 mass%) was added to an aqueous solution diluted with 50 g of pure water for about 9 hours, followed by antimony trioxide. Was dissolved and aged for 11 hours thereafter. Subsequently, 800 g was taken from the solution obtained after cooling, and this solution was diluted with 4800 g of pure water, and then treated with a cation exchange resin (Mitsubishi Chemical Co., Ltd .: pk-216) until the pH became 3.5, thereby deionizing. Was carried out. The solution obtained by deionization was aged for 10 hours at a temperature of 70 ° C., and then concentrated by an ultrafiltration membrane to prepare a conductive fine particle dispersion formed from antimony pentoxide having a solid content of 14% by mass. The pH of this electroconductive fine particle dispersion was 4.0 nm in average particle diameter of 4.0 electroconductive fine particles.

Subsequently, 100 g of the conductive fine particle dispersion was adjusted to 25 ° C., and 2.5 g of tetraethoxysilane (Chemical Co., Ltd. product: ethyl regular acid, SiO ₂ concentration 28.8 mass%) was added for about 3 minutes, followed by stirring for 30 minutes. It was. Then, 100 g of ethanol was added over 1 minute, and the temperature was increased to 50 ° C. for 30 minutes, and the superheat treatment was performed for 19 hours. Solid content concentration at this time was 7 mass%.

Subsequently, water and ethanol of the dispersion medium were solvent-substituted with ethanol in an ultrafiltration membrane, and concentrated at the same time to prepare a chain-conductive inorganic oxide fine particle (R2) dispersion liquid which was chained and surface treated with an organosilicon compound having a solid content of 20% by mass. It was. The average connection number of the primary particle which comprises chain | strand-shaped electroconductive inorganic oxide fine particle (R2) was five pieces. In addition, the refractive index of the chain-shaped conductive inorganic oxide fine particles (R2) was 1.65.

Preparation of coating liquid (R7) for transparent film formation

100 g of surface-treated electroconductive inorganic oxide fine particles (R2) dispersion liquid of 20 mass% of solid content concentration, and ethylene oxide modified acrylic resin (Shin-Nakamura Chemical Co., Ltd. make: NK ester ATM-4E, resin concentration 100 mass%) 288 g, 38.4 g of a photoinitiator (Ilgacua 184 manufactured by Tiba Specialty Co., Ltd.) and a ketone solvent in 192 g of an unmodified acrylic resin (manufactured by Kogyo Chemical Co., Ltd .: 100 mass% of light acrylate DPE-6A resin concentration) 568 g of acetone and 160 g of methyl ethyl ketone were sufficiently mixed to prepare a coating liquid (R7) for forming a transparent film having a solid content concentration of 40% by mass.

Preparation of transparent film base material (R7)

In Example 1, the coating liquid R7 for transparent film formation was apply | coated to TAC film (Panak Co., Ltd. product: FT-PB80UL-M, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (bar 10). A transparent coating part base material R7 was similarly manufactured except having done this. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, film refractive index, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain particles, and scratch resistance of the obtained transparent coating part base material R7 are shown in the table.

[Comparative Example 8]

Preparation of Chain Conductive Inorganic Oxide Particles (R3) Dispersion

100 g of the conductive inorganic oxide fine particles (1) dispersion liquid having a concentration of 20 mass% prepared in the same manner as in Example 1 was adjusted to 25 ° C, and tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: ethyl silicate and SiO ₂ concentration 28.8 mass) %) After adding 6.9 g for about 3 minutes, stirring was performed for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, and the temperature was increased at 50 ° C. for about 30 minutes and superheated for 15 hours. Solid content concentration at this time was 15 mass%.

Subsequently, water and ethanol of the dispersion medium were concentrated on the ultrafiltration membrane at the same time as solvent substitution with ethanol to prepare a chain-conductive inorganic oxide fine particle (R3) dispersion liquid which was chainified and surface-treated with an organosilicon compound having a solid content of 20% by mass. Although the primary particle | grains which comprise chain | strand-shaped electroconductive inorganic oxide fine particle (R3) confirmed some connection, it was almost monodisperse. In addition, the refractive index of the chain-shaped conductive inorganic oxide fine particles (R3) was 1.73.

Preparation of coating liquid (R8) for transparent film formation

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

Preparation of transparent film base material (R8)

In Example 1, the coating liquid R8 for transparent film formation was apply | coated to TAC film (Fanak Co., Ltd. make: FT-PB80UL-M, thickness: 80 micrometers, refractive index: 1.5) by the bar coater method (bar 10). A transparent coating part base material R8 was similarly manufactured except having done this. The film thickness of the transparent film was 5 micrometers.

The total light transmittance, haze, reflectance, refractive index of the film, adhesiveness, pencil hardness, coloring, interference fringe, dispersion state of chain-shaped particles, and scratch resistance of the obtained transparent coating part base material (R9) are shown in the table.

Claims (16)

In the coating film for forming a transparent film containing 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 and is entirely The conductive inorganic oxide fine particles having a solid content in the range of 1 to 60% by mass and the surface-treated conductive inorganic oxide fine particles are in the non-agglomerated, highly dispersed form, and the solid content of the conductive inorganic oxide fine particles has a concentration in the range of 0.1 to 59.4% by mass and is conductive in the obtained transparent film. An inorganic oxide fine particle forms a chain structure, The coating liquid for transparent film formation characterized by the above-mentioned.

R _n -SiX _4-n (1)

(Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, the same as or different from each other, X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, hydrogen, n is an integer of 0 to 3) .)
The transparent inorganic film of claim 1, wherein the conductive inorganic oxide fine particles are Sb-doped tin oxide (ATO) particles and / or P-doped tin oxide (PTO) particles, and have an average particle diameter in a range of 5 to 10 nm. Coating liquid for formation.
The coating liquid for forming a transparent film according to claim 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 chained.
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.
The matrix-forming component according to any one of claims 1 to 5, wherein the matrix forming component comprises an alkylene oxide modified acrylic resin (A) and an unmodified acrylic resin (B), and includes an unmodified acrylic resin (B) and an alkylene. The weight ratio ((B) :( A)) as solid content with oxide modified acrylic resin (A) is the range of 5: 95-50: 50 The coating liquid for transparent film formation.
The ketone of the dispersion medium is acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methyl pentyl ketone according to any one of claims 1 to 6. And at least one selected from diisobutyl ketone, isophorone, acetylacetone, and acetic acid ester.
8. The coating liquid for forming a transparent film according to claim 7, wherein the ketones of the dispersion medium are acetone and / or methyl ethyl ketone.
In the transparent coating part base material which consists of a base material and the transparent film formed in the surface of the base material, the said transparent film contains electroconductive inorganic oxide fine particle and a matrix component, and electroconductive inorganic oxide fine particle is surfaced with the organosilicon compound represented by following formula (1). The conductive inorganic oxide fine particles are processed and manufactured to form a chain structure in a transparent film and to be highly dispersed.
The content of the conductive inorganic oxide fine particles in the transparent coating is in the range of 1 to 12 mass%,
The surface resistance value of the transparent coating film is 10 ^8? 10 ¹¹ Ω / □ in the range of the haze is more than 0.3% and the light transmittance is 90% or more,
The transparent film part base material whose difference between the refractive index N _S of a base material and the refractive index N _H of the said transparent film is 0.02 or less.
R _n -SiX _4-n (1)
(Wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, the same as or different from each other, X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, hydrogen, n is an integer of 0 to 3) .)
10. The method of claim 9, wherein the conductive inorganic oxide fine particles are Sb doped tin oxide (ATO) fine particles and / or P-doped tin oxide (PTO) fine particles, the average particle diameter of the primary particles forming a chain structure is 5-10. A transparent coating part base material having a range of nm and a connecting number of 3 or more.
The transparent coating part base material according to claim 9 or 10, wherein the matrix component is an alkylene oxide modified acrylic resin (A).
The transparent coating part base material according to claim 11, wherein the alkoxy-modified acrylic resin (A) is an ethylene oxide-modified acrylic resin.
The said matrix component contains an unmodified acrylic resin (B), The weight ratio as solid content of an unmodified acrylic resin (B) and an alkoxy modified acrylic resin (A) (14). ): (A)) is a transparent film base material, characterized in that the range of 5: 95-50: 50.
The transparent film base material according to any one of claims 9 to 13, wherein the film thickness of the transparent film is in a range of 1 to 20 µm.
The transparent coating part base material according to any one of claims 9 to 14, wherein the base material is triacetyl cellulose.
The transparent film base material according to any one of claims 9 to 15, wherein the transparent film is obtained by using the coating liquid for forming a transparent film according to any one of claims 1 to 8. .

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