KR0124138B1 - Coating solution for formation of coating and use thereof - Google Patents

Abstract

The present invention relates to the use of the coating liquid for such things as a coating liquid for film formation and a display panel. The coating solution is composed of at least one substrate and particulate inorganic compound selected from a partial hydrolyzate of acetylacetonato chelate, a hydrolyzate of alkoxysilane and a partial hydrolyzate of metal alkoxide, and the ions per 100 g of all solid contents contained in the coating solution. It is characterized by a concentration of 10 mmol or less. The coated substrate obtained from the coating solution is excellent in electrical, optical and mechanical properties.

Description

Coating solution for forming film and method for preparing same

1 is a bar chart used to measure resolution.

2 shows the apparatus used to measure the resolution.

The present invention relates to a coating liquid capable of forming a film having excellent antireflection and antistatic effect, a method for manufacturing the same, and a substrate coated by laminating a film formed of one or two coating liquids on a substrate in a single layer or multiple layers. will be. More specifically, the present invention relates to one or two coating liquids capable of forming a film containing fine particles of an inorganic compound in a monodisperse state, a method for producing the same, and a coated substrate on which the film is formed on a substrate. will be. Furthermore, the present invention provides a coating liquid which is excellent in adhesion to a substrate and excellent in smoothness of the surface of the film, and can form a transparent conductive film having excellent durability against water and alkaline resistant materials. A coating substrate and a display unit in which said film is formed on a board | substrate.

In general, a coating liquid for forming a film composed of inorganic particles and a matrix is used to form a film on the surface of a substrate such as a glass plate or a plastic plate to add various functions such as antireflection and antistatic properties. come.

For example, a transparent film having antireflection and antistatic properties may be formed on surfaces of cathode ray, display panel, fluorescent display panel, plasma display device, liquid crystal display device, etc. to prevent reflection of external light and electrostatic charge. The method of forming and the coating liquid used to form the transparent coating are already known (see Japanese Patent Laid-Open Nos. 15445/1989, 298301/1989 and 78946/1991).

Japanese Laid-Open Patent No. 193971/1998 discloses a coating liquid for forming a conductive film composed of a conductive particle such as tin oxide or indium oxide and a colorant consisting of an organosilicon compound such as alkoxysilane. It is described.

In Japanese Patent Laid-Open Publication No. 554613/1989 and WO 89/03114 and WO 90/02157, the present applicants have applied a coating liquid for forming a conductive coating with a conductive material: alkoxysilane and acetylacetonato chelate. A coating solution in the form of a mixture of a product obtained by partially hydrolyzing, for example, a mixed solvent consisting of water and an organic solvent, of a substrate consisting of bis (acetylacetonato) dialkoxyzirconium, is also proposed. A substrate coated with a conductive coating obtained from a coating solution is proposed.

However, in forming a film on a substrate using the above-mentioned conventional coating liquid used to form a film containing the fine particles of the inorganic compound, no matter how the fine particles of the inorganic compound exist in the coating liquid in a monodisperse state, During the formation process, the fine particles of some inorganic compounds aggregate to obtain a desired film in which the fine particles of the inorganic compound exist in the monomolecular state.

The film in which the fine particles of some inorganic compounds are aggregated not only has poor mechanical properties such as antireflection, antistatic and anti-friction resistance, but also partially agglomerated particles appear in the form of spots. Iii) is more likely to occur, and furthermore, there is a drawback that stains due to fingerprints or the like are more likely to occur than the film in which the fine particles of the inorganic compound exist in a monodisperse state.

Under the above circumstances, the present inventors have no fear of agglomeration of the inorganic compound particles which are likely to occur in the coating liquid consisting of the fine particles of the inorganic compound, and the inventors are concerned about the aggregation of the inorganic compound particles which are likely to occur during the process of forming a film from the coating liquid. Extensive and thorough research has been conducted to provide a coating solution without concern. Furthermore, the present inventors have studied extensively and thoroughly for the purpose of providing a coated substrate in which the fine particles of the inorganic compound are present in the terminal state. As a result, the inventors have found that a small amount of cations and anions present in the coating liquid act as an important factor in the aggregation of the fine particles of the inorganic compound, which occurs in the coating liquid and during the process of forming the film.

As described above, the inventors' analysis of conventional coating liquids shows that some coating liquids are generally added because alkali metals are generally added to stabilize the particles in dispersions of fine particles of inorganic compounds, such as colloidal solutions of inorganic compounds. Ions such as sodium ions (Na +) are contained in the dispersion of the fine particles of the inorganic compound. Furthermore, since acid or ammonia water is used to prepare a product obtained by partial hydrolysis of acetylacetonato chelate and alkoxysilane or metal alkoxide, which are used as substrates in the coating liquid for coating, as a result, alkali metals, ammonium and various Cations such as polyvalent metal ions: inorganic anions such as halogen ions, sulfate ions, nitrate ions and phosphate ions and / or organic anions such as formic acid and acetic acid are present in the reaction solution containing the substrate. Thus, most coating solutions made from by-products and / or substrate solutions of fine particles of inorganic compounds contain ions at concentrations of several tens of millimoles or more per 100 g of the total solid content contained in the coating solution. The dispersion state of the inorganic compound fine particles in the coating liquid containing such high concentration of ions cannot necessarily be good, and the inorganic compound fine particles in the monodisperse state in each coating liquid tend to gradually aggregate after the coating liquid is made. Moreover, aggregation of some inorganic compound fine particles is also observed in a film formed on a substrate coated with a conventional coating liquid containing such high concentrations of ions. The coating made of the coating liquid may become cloudy when the film thickness becomes nonuniform due to aggregation of the inorganic compound fine particles.

The inventors have found that if the concentration of the cations and anions contained in the coating solution for coating formation is below a certain level, the dispersion state of the inorganic compound fine particles in the coating solution becomes good, as well as the inorganic in the coating film formed from such coating solution. It has been found that the monodisperse state of the compound fine particles can be maintained well. The present invention has been completed based on this finding.

The present invention is to overcome the above-mentioned drawbacks of the prior art, and therefore an object of the present invention is to provide a film containing inorganic compound fine particles in a monodisperse state on substrates such as glass substrates, plastic substrates, metal substrates and ceramic substrates. It is to provide a coating liquid that can be formed. Another object of the present invention is to provide a method for preparing the coating solution.

It is still another object of the present invention to provide a coated substrate having the above coating on the substrate, and particularly excellent in antireflection and antistatic properties.

It is still another object of the present invention to provide a coating liquid comprising conductive particles having a specific particle size distribution and partial hydrolyzate of an alkoxysilane having a specific molecular weight distribution: excellent adhesion to a substrate, uniform coating surface and durability A coating substrate obtained by coating the above-described coating liquid capable of forming an excellent coating on a transparent substrate such as a glass plate or a plastic plate. The manufacturing method of the above-described coating substrate: and a display device including the coating film.

The coating solution for forming a film according to the present invention comprises at least one substrate selected from the group consisting of inorganic compound microparticles: partial hydrolyzate of acetylacetonato chelate, partial hydrolyzate of alkoxysilane and partial hydrolyzate of metal alkoxide. And / or dispersed or dissolved in an organic solvent.

The coating solution contains ions at a concentration of 10 mmol or less per 100 g of all solid contents contained in the coating solution.

The inorganic compound fine particles that can be used in the coating liquid for forming a film according to the present invention are preferably conductive particles having the following particle composition:

(a) the average particle size is 50 mm or less,

(b) 5% by weight of particles each having a particle size of 60 nm or less,

(c) 5% by weight of particles each having a particle size of 10 nm or less,

(d) The particles each having a particle size of 100 nm or more are 15% by weight or less.

And the substrate usable in the present invention is preferably a partial hydrolyzate of an alkoxysilane having the molecular weight configuration as follows:

(1) the average molecular weight is 1,500 to 10,000,

(2) 50 wt% or less of polymer having molecular weight of 3,000 or less,

(3) The polymer having a molecular weight of 10,000 or more is 20% by weight or less.

The coating solution is 10 mmol per 100 g of all the solid contents of all the solid content of the coating liquid by any one of the dispersion of the inorganic compound fine particles, the substrate solution and the coating solution made by mixing them through a cation and / or anion removal process It can manufacture by making it become the following.

According to another aspect of the present invention, a coated substrate is composed of a substrate and a film laminated in a single layer or multiple layers formed by coating the coating solution thereon.

The coated substrate can be prepared by coating a coating liquid for film formation on the substrate to form an uncured coating, and curing the uncured coating by heating.

A display device according to another aspect of the present invention includes a display panel having a transparent conductive film formed by applying the above-described coating liquid for film formation on its outer surface.

The coated substrates having a film formed on the substrate such as the display device and the lens are not only excellent in antireflection and antistatic effect, but also excellent in adhesion to the substrate and excellent in durability.

Hereinafter, the coating liquid for forming a film according to the present invention, a manufacturing method thereof, and a coated substrate will be described in more detail.

Coating liquid for film formation

First, the coating liquid according to the present invention will be described.

The coating liquid of the present invention contains the inorganic compound fine particles and the substrate in the form of being dispersed or dissolved in water and / or an organic solvent.

Examples of the inorganic compound fine particles dispersed in the coating liquid of the present invention include fine silicon dioxide, titanium oxide (including partially reduced titanium oxide), zirconium oxide, aluminum oxide, cerium oxide, iron oxide, tungsten oxide, tin oxide and oxidation Fine particles of an inorganic oxide such as antimony and fine particles of fluoride such as fine magnesium fluoride, potassium fluoride and calcium fluoride.

Moreover, in the present invention, mixing factors composed of many of the above-described inorganic compounds or mixtures of the above-mentioned particles can be used as the inorganic compound fine particles.

In the present invention, depending on the function given on the surface of the substrate, the size and shape of the inorganic compound fine particles to be dispersed in the coating liquid can be selected and one or more inorganic compound fine particles can be added to the coating liquid.

For example, by coating a coating liquid containing silicon dioxide fine particles as the inorganic compound fine particles, an elaborate but uneven coating can be formed, thereby reducing reflection on the substrate surface due to fine non-flatness. On the other hand, as the inorganic compound fine particles, a conductive coating is formed by coating a substrate with a coating liquid containing conductive inorganic oxide fine particles selected from tin oxide added with a small amount of antimony or fluorine, indium oxide added with a small amount of tin (ITO), and antimony oxide. Can be formed.

The refractive index of the film formed on the substrate can be adjusted by selecting the form in which the inorganic compound fine particles contained in the coating liquid or a plurality of inorganic compound fine particles are blended. For example, a film having high refractive index and high transparency can be obtained by using titanium oxide, cerium oxide, iron oxide, or the like as the inorganic compound fine particles. On the other hand, a film having a low refractive index and a low surface reflectance can be obtained by using magnesium fluoride, calcium fluoride, or the like as the inorganic compound fine particles.

In addition, the film having a low surface reflectance is a porous particulate oxide prepared by treating the particulate oxide with an acid to filter out the non-silica metal component, as disclosed in Japanese Patent Application No. 91650/1992 filed previously by the present applicant. Can be obtained using the inorganic compound fine particles.

It is preferable that average particle size is 3-300 nm as a fine particle inorganic compound used for this invention. When the film should be flat and firm, and the particulate inorganic compound is crystalline or amorphous conductive particulate inorganic oxide, it is preferable to use an average particle size in the range of 3 to 100 mn. When using inorganic compound microparticles | fine-particles in order to provide antireflective property to a board | substrate surface, it is preferable to use the thing in which the average size of particle | grains exists in the range of 40-300 nm. Furthermore, the inorganic compound fine particles having a uniform particle size variation coefficient ((standard deviation / average particle size) × 100] of 30% or less, preferably 20% or less, and more preferably 10% or less are uniformly dispersed. good.

The coating solution of the present invention contains at least one substrate selected from products obtained by partial hydrolysis of acetylacetonato chelate, alkoxysilane and metal alkoxide.

The partial hydrolyzate of acetylacetonato chelate, used as a substrate in the present invention, is a chelating compound having an acetylacetone ligand and is a concentrate of the compound represented by the following general formula (1):

Wherein a + b is 2-4: a is 0-3: b is 1-4: R is -C _n H _2n (n is 3-4): X is -CH ₃ , -OCH ₃ , -C ₂ H ₅ or -OC ₂ H ₅ : M ₁ is a periodic table of Groups IB, IIA and B, IIIA and B, IVA and B, VA and B, VIA, VIA and VI It is an element or vanidyl group (VO). Preferred combinations of binary elements and vanidyl groups and a, b are shown in Table 1 below.

Examples of acetylacetonato chelate compounds include dibutoxybis (acetylacetonato) zirconium, tributoxy mono (acetylacetonato) zirconium, and bis (acetylacetonato) lead. (bis (acetylacetonato) lead), tris (acetylacetonato) iron, dibutoxybis (acetylacetonato) hafnium, mono (acetylacetonato) tributoxyhafnium (mono (acetylacetonato) tributoxyhafnium).

Partial hydrolysates of alkoxysilanes can be obtained from all alkoxysilanes which are hydrolyzable. However, in the present invention, preferred partial hydrolyzates are those obtained from alkoxysilanes represented by the following general formula.

R nSi (OR )

General Formula R And R Are an aryl group, an acrylic group, a vinyl group, an alkyl group having 1 to 8 carbon atoms, and a general formula -CHOCmH (m is an integer between 1 and 4, n is 0 to 3). And an substituent selected from the substituents represented by (integer between).

Examples of the alkoxysilane represented by the above general formula include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraoctoxysilane, methyltrimethoxysilane and methyltriethoxysilane , Dimethyldimethoxysilane, methyltributoxysilane, octyltriethoxysilane, phenyltrimethoxysilane, and vinyltrimethoxysilane.

Partial hydrolysates of metal alkoxides can also be used as substrates. The partial hydrolyzate of the metal alkoxide is a concentrate of the compound represented by the following general formula.

M (OR)

In the above formula, M Represents a metal atom: R represents an alkyl group or -CHO (m is an integer between 3 and 10) and n is M An integer corresponding to the valence of.

The concentrates selected from these can be used alone or in combination. M in the formula Is not particularly limited as long as it is a metal atom. However, preferably, beryllium (Be), aluminum (Al), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), nickel (Ni), zinc (Zn) , Gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), indium (In), tin (Sn), antimony (Sb) It is preferable to select from the group consisting of tellurium (Te), hafnium (Hf), tantalum (Ta), cerium (Ce) and copper (Cu).

Examples of hydrolyzable metal alkoxides are tetrabutoxyzirconium, tetraoctyloxytitanium and diisopropoxy-dioctyloxytitanium.

The partial hydrolyzate of the acetylacetonato chelate compound, the alkoxysilane and the metal alkoxide may be prepared by conventional methods, for example, at least one compound selected from hydrolyzable acetyl acetonato chelate compounds, alkoxysilanes and metal alkoxides. After mixing with an alcohol such as methanol or ethanol, it can be obtained by adding water and acid or alkali to the mixture. In the preparation of the partial hydrolyzate by the above method, the partial hydrolyzate adjusted to an average molecular weight of about 1,500 to 10,000, preferably 2,000 to 7,000 (in terms of polystyrene) can obtain a film having a uniform thickness. It is preferable at the point.

The appropriate mixing ratio of the particulate inorganic compound (F) to the substrate (M) to be mixed together to prepare the coding liquid of the present invention depends on the physical properties and conditions to be applied to the coating formed from the coating liquid, but is not particularly limited. However, in terms of oxides of the respective components, the F / M is preferably between 0.05 and 7 by weight ratio.

In particular, it is formed from a coating liquid containing a particulate inorganic compound (F) and a substrate (M) such as particulate silica having an average particle size of 40 to 300 nm, preferably 80 to 200 nm so that the F / M is 1 to 5 by weight. The film is excellent in antireflection, and excellent in corrosion resistance unless it is cloudy. Color cathode-rays without color shading on the display image can be obtained by forming the above-described coating on the surface of the face plate of the color cathode ray tube as an antireflective film.

Moreover, a coating excellent in both conductivity and antireflection can be formed from a coating liquid containing both a substrate and the above-mentioned particulate silicon dioxide and particulate conductive inorganic oxide. In addition, the coating having excellent conductivity and antireflection can be formed by first coating a substrate with a coating liquid containing particulate inorganic oxide and a substrate to form a conductive coating on the substrate, and then coating a coating liquid containing particulate silicon dioxide and a substrate thereon. It can be formed by forming an antireflective film on the conductive film.

In the present invention, transparent conductive particles having a particle size distribution as follows:

(a) the average particle size is 50 nm or less, preferably 5 to 30 nm,

(b) particles having a particle size of 60 nm or less, respectively, of at least 60% by weight, preferably at least 80% by weight,

(c) particles having a particle size of 10 nm or less, respectively, of at least 5% by weight, preferably at least 20% by weight,

(d) The particles each having a particle size of 10 nm or more are 15% by weight or less, preferably 5% by weight or less.

Containing as a particulate inorganic compound,

Partial hydrolysates of alkoxysilanes having the molecular weight distribution as follows:

(1) the average molecular weight is 1,500 to 10,000, preferably 2,500 to 7,500,

(2) the polymer having a molecular weight of 3,000 or less is 50% by weight or less, preferably 20% by weight or less,

(3) The polymer having a molecular weight of 10,000 or more is 20% by weight or less, preferably 10% by weight or less.

By coating the coating liquid containing all substrates, a coating having excellent conductivity as well as adhesion to the substrate and durability can be obtained. In forming said film, it is preferable that the weight ratio of F [particulate inorganic compound (conductive particle)] / M (substrate) is 0.5-5.

In the coating liquid of the present invention, water or an organic solvent is used as the dispersion medium.

The organic solvent is selected from among those capable of completely dissolving or dispersing the particulate inorganic compound and the substrate. Examples of such organic solvents include alcohols such as methanol, ethanol propanol and butanol: ethylene glycol ethers such as methyl cellosolve and ethyl cellosolve: glycols such as ethylene glycol and propylene glycol. Esters such as methyl acetate, ethyl acetate and methyl lactate; ketones such as acetone and methyl ethyl ketone; and ethers such as butyl ether and tetra hydrofuran.

In the coating liquid of the present invention, the total concentration of the particulate inorganic compound and the substrate is preferably 0.1 to 30% by weight, particularly 0.5 to 20% by weight.

Moreover, in the coating liquid of the present invention, the total concentration of cations such as alkali metal ions, ammonium ions and polyvalent metal ions contained in the coating liquid: inorganic anions such as inorganic acids: and organic anions such as formic acid and acetic acid is determined by the total concentration of the coating liquid. It is a requirement to be less than 10 mmol for 100 g of solid content.

When the ion concentration of the coating liquid is reduced to 10 mmol or less with respect to 100 g of all the solid contents contained in the coating liquid, it is possible to obtain a coating liquid which is excellent in the dispersion state of the particulate inorganic compound contained in the coating liquid and practically does not aggregate any particles. . The monodisperse state of the particulate inorganic compound contained in this coating liquid is maintained even during the process of forming the film. As a result, a film containing the particulate inorganic compound in a monodisperse state can be formed on the substrate surface. That is, no agglomeration of particles is observed in the coating obtained by coating the substrate with a coating solution containing ions at a concentration of 10 mmol or less with respect to 100 g of all the solid contents contained in the coating solution. A film without problems such as nonuniform film thickness can be formed on the substrate.

The reason why the fine particles and the inorganic compound are kept in the monodisperse state in the coating liquid of the present invention is that the extremely low ion concentration in the coating liquid increases the Debye length of the particle surface, thereby increasing the mutual repulsive force between the particles, thereby causing the particles to have a desired dispersion state. It is assumed that this can be maintained.

As used herein, the term 'concentration of the coating liquid of the present invention' refers to cations such as ammonium ions, alkali metal ions and polyvalent metal ions contained in the coating liquid: inorganic anions such as halogen anions and inorganic anions: and formic acid ions. It means the total concentration of organic anions such as acetate anion.

As used herein, the term ions present in the coating solution means not only present in isolated form in the solvent of the coating solution, but also all the ions adsorbed or attached to the particulate inorganic compound and the substrate.

In the present invention, the ion concentration is measured and calculated by the following method.

First, the weight of the solid content obtained by drying a coating liquid at the temperature of about 100-110 degreeC is measured.

Thus, the total weight of the solid contents contained in the coating liquid is obtained.

The solid contents are completely dissolved in acid or the like. The amount of alkali metal and alkaline earth metal ions contained in the solution is measured by atomic absorption spectrometry, and the amount of other metal ions is measured by emission spectral analysis (ICP). Separately, the coating solution is analyzed directly by potentiometric titration to determine the amount of ammonium ions and anions.

From the total amount of solid contents and ions determined as described above, the concentration of ions relative to 100 g of the solid contents is calculated.

Manufacturing method of coating liquid for film formation

Hereinafter, a method for producing a coating liquid according to the present invention will be described.

The preliminary solution for the coating liquid of the present invention is generally prepared by dispersing or dissolving a predetermined amount of the particulate inorganic compound and the substrate in an organic solvent such as distilled water or alcohol, and a mixed solvent thereof. In this process, the preliminary solution may be prepared by dissolving the particulate inorganic compound and the hydrolyzable compound, which is a precursor of the substrate, in a solvent and mixing the mixture, followed by partially hydrolyzing the hydrolyzable material.

After preparing the preliminary solution, or at an appropriate stage in the preparation of the preliminary solution, the deionization reaction is carried out so that the resulting ion concentration of the coating solution is 10 mmol or less for 100 g of all the solid contents contained in the coating solution. .

The particulate inorganic compound to be added to the coating liquid may be in powder form or in the form of a sol dispersed in a solvent such as water.

When dispersing the powder, the particulate inorganic compound is mixed with the substrate and uniformly dispersed using a sand mill or the like. Alternatively, the coating liquid can be prepared by uniformly dispersing the particulate inorganic compound in a dispersion medium such as water, and then mixing the obtained dispersion with a substrate. In this case, both the dispersion and the substrate of the particulate inorganic compound can first be deionized.

The above-mentioned conductive particles having a specific average particle size and particle size distribution are ground using appropriate means and / or classifying conventional conductive particles until the average particle size and its particle size distribution fall within the above-mentioned specific ranges. You can get it by

Grinding and / or classification to control the average particle size and particle size distribution of the conductive particles can be performed on their powder or sol state. Said grinding and / or classification can be carried out before or after the preparation in the coating liquid for film formation.

Partial hydrolysates of the above-mentioned alkoxysilanes having a particular average molecular weight and molecular weight distribution can be obtained by a method of hydrolyzing the alkoxysilane in a mixed solution of water and alcohol, for example, in the presence of an acid such as nitric acid, hydrochloric acid or acetic acid. have.

It is preferable to perform hydrolysis of said alkoxysilane on condition of the following.

Acid / silicon dioxide (SiO) = 0.001 ~ 0.05 (wt / wt)

Water / silicon dioxide (SiO) = 4 ~ 16 (mol / mol)

Here, silicon dioxide means the quantity of the alkoxysilane converted into silicon dioxide. Coatings prepared by deionizing the sol of the substrate solution and the particulate inorganic compound such that the ionic concentration for 100 g of all solid contents is 10 mmol or less generally do not require any further deionization reaction.

However, if the ion concentration of the prepared coating liquid exceeds 10 mmol for 100 g of all solid contents contained in the coating liquid, the coating liquid is deionized to reduce the ion concentration to 10 mmol or less for 100 g of all solid compounds.

The deionization method is not particularly limited as long as the resultant ion concentration of the coating liquid for forming a film is 10 mmol or less with respect to 100 g of all the solid contents contained in the coating liquid. However, preferred deionization methods include a method and a dispersion and / or a solution of contacting a cation exchange resin and / or an anion exchange resin with a dispersion and / or substrate solution of a particulate inorganic compound as a precursor for a coating solution or a coating solution prepared therefrom. Or filtering the coating liquid with an ultrafiltration membrane.

The above method of contacting the cation and / or anion exchange resin can be carried out by passing the dispersion and / or solution or coating liquid through at least one time through a column filled with a cation or anion exchange resin or a mixed resin thereof. Alternatively, the cation and / or anion exchange resin may be added to the dispersion and / or the solution or the coating solution, followed by stirring for a suitable time.

Coated substrate

Now, the coating substrate of this invention is demonstrated.

The coated substrate of the present invention is composed of a substrate such as a plate or film made of organic, plastic, metal, ceramic, or the like, and a film formed of the above-described coating liquid coated thereon.

The above-mentioned coating is a single-layer coating formed of a coating liquid composed of at least one particulate inorganic compound and a substrate, or a particulate inorganic which can impart a function different from the function imparted by the coating of the single-layer and the particulate inorganic compound and the substrate. It may be a linate coating (multilayer coating) formed by laminating another coating formed of a coating liquid containing a compound on the coating. These coatings may each be coated on a protective coating having various functions.

The coating on the top has characteristics such as rolling property, high refractive index or low refractive index, and antireflective effect, depending on the type of the particulate inorganic compound contained in the coating and the ratio of the particulate inorganic compound to the substrate.

As can be seen from the foregoing, the coated substrates of the present invention include a substrate having a conductive coating, a coating substrate having a desired reflectance, a substrate having antireflection, and a coating substrate excellent in both conductivity and antireflection.

Among the substrates described above, the preferred surface resistivity of the coating with the conductive coating is 10 per unit area. To 10 And a preferred example thereof is a face plate of a cathode ray tube having a transparent conductive film on its outer surface and a platen glass of a copier having a transparent conductive film on the surface which comes into contact with the original.

For a substrate having an antireflective coating, it is preferable to manufacture it so that the reflectance does not exceed 1%. A preferable example thereof is a lens having a transparent antireflective coating formed on the inner and outer surfaces, or a face plate of a cathode ray tube. It includes a transparent substrate.

An example of such an antireflective coating is a laminate formed by arranging a film having a fine surface and a smooth surface, a film containing a transparent substrate and particles having a refractive index lower than that of the substrate, a film having a high refractive index and a film having a low refractive index thereon. It contains a film.

The coated substrate of the present invention is used as a laminate consisting of a substrate coated with a conventional functional coating such as glass on which a NESA film is formed and a coating formed of the coating liquid of the present invention laminated on the coating.

The coating of the coating substrate of the present invention may contain a small amount of dyes and pigments. In such a coated substrate, the coating absorbs light having a specific wavelength depending on the dye or dye contained in the coating, and as a result, for example, the relative ratio on the cathode ray tube made of the coating substrate can be improved. Can be.

In the present invention, as the particulate inorganic compound, the transparent conductive film made of the above-mentioned coating liquid, which consists of conductive particles having a specific average particle size and particle size distribution, and a substrate having a specific average molecular weight and molecular weight distribution, It is a flat and dense film without surface nonuniformity due to agglomeration and no gaps (pores or small gaps) between particles.

The term flatness as used herein means not only no surface irregularities and roughness, but also denseness without gaps between particles.

Therefore, the above-mentioned substrate having a transparent conductive film not only has excellent optical properties and hardness, such as transparency and dull turbidity, but also improves durability against atmospheric acids, alkalis, high temperature and moisture, Adhesion is improved and also has excellent stain resistance. As used herein, the term "pollution resistance" refers to the characteristics of a film such that the surface of the film is not contaminated and, if contaminated, can be easily removed.

Transparent conductive substrates are 103 to 1010 per unit area It has a surface resistivity of 1, and has a dull turbidity of 1% or less, and can be obtained by forming a transparent protective film on an optionally transparent conductive film after forming the transparent conductive film on the surface of the substrate.

Furthermore, by performing nonglare treatment, which will be described later during the film formation process, a transparent conductive substrate can be obtained, which shows glossiness of 40 to 90% and surface resistivity as in the case of non-fluorescence treatment. Can be.

As for the thickness of the coating substrate which concerns on this invention, 0.05-0.7 micrometer is preferable.

The coated substrate of the present invention is first coated with the above-described coating liquid on the surface of a substrate such as glass or plastic by a method such as deposition, spinner, sprayer, roll coater, rotoprinting, or the like. Thereafter, the coating liquid formed on the surface of the substrate is dried at a temperature of room temperature ˜90 ° C., and finally, the dried layer may be obtained by heating and curing at a temperature of 100 ° C. or more.

Furthermore, in the present invention, a coated substrate having the above-described effects of the present invention can be produced by the following method.

As described above, after the drying step after the coating step or during the drying step, the uncured film is exposed to a gas phase capable of irradiating electromagnetic waves having a wavelength shorter than visible light or promoting a curing reaction.

Examples of electromagnetic waves used to irradiate uncured coatings prior to heating include ultraviolet radiation, electron beams, X-rays and gamma rays. Actual ultraviolet irradiation is preferred. For example, the uncured coating has a maximum luminous intensity at about 250 nm and 360 nm as an ultraviolet irradiation source, and has an energy flux of 100 mJ / m emitted from a mercury lamp having a luminous intensity of 10 mW / cm 2 or more, preferably 100 mW / cm 2 or more. Irradiation is carried out using ultraviolet light of at least 2 cm 2, preferably at least 1000 mJ / cm 2.

Examples of gases that can accelerate the curing reaction of uncured coatings prior to heating are ammonia and ozone.

For example, the treatment for promoting hardening of the film is performed for 1 to 60 minutes on an uncured film on an active gas having a gas concentration of 100 to 10,000 ppm, preferably 1000 to 10,000 ppm, as described above. By exposing.

The above treatments for promoting curing accelerate the evaporation of the solvent and the water remaining in the coating as well as the polymerization of the substrate. As a result, thermal curing conditions such as heating temperature or time applied in subsequent heating steps can be alleviated.

In the present invention, the non-fluorescent transparent coated substrate coated with coatings having a large number of fine protrusions and depressions on the surface maintains the above temperature range after first preheating the surface of the substrate such as glass or plastic to a temperature of about 40 to 90 ° C. It can be obtained by spraying the coating liquid onto the preheated surface, followed by heating and curing the coating. When the transparent coated substrate is produced by the above-described procedure, the apparent surface flatness of the coating is somewhat weakened, but there is no change in the antifouling properties and durability of the coated substrate.

The above process for promoting hardening may be carried out prior to heat treatment hardening.

The transparent protective film that can be formed on the film prepared by the above process can be successfully formed by performing the same application, drying and heating process as the process of manufacturing the film. The above treatment process for promoting hardening and / or treatment for imparting non-fluorescence on the surface of the coating may be carried out during the process of forming a transparent protective coating.

The coating liquid used to form the transparent protective coating is preferably composed of only the above-mentioned substrate used in the present invention or, together with the substrate, of a particulate inorganic compound suitable for adding a desired function to the coated substrate.

The preferable thickness of the above-mentioned transparent protective film is about 0.5 micrometer or less.

Display unit having a transparent conductive coating substrate

The display device of the present invention comprises a cathode-ray tube (CRT), a fluorescent character display tube (FIP), a plasma display (PDP) and a liquid crystal display (LCD); Likewise, it is a device capable of displaying an image electrically and includes a display panel on which a transparent conductive film is coated on its outer surface. That is, the display device of the present invention is a transparent conductive coating substrate and includes a display panel having a transparent conductive film.

The transparent conductive film can be made by coating the coating liquid, which can form a transparent conductive film, among the various types of coating liquids of the present invention.

The display panel thus obtained has a transparent conductive film and is excellent in conductivity, flatness, durability, adhesion between the film and the substrate, and stain resistance. The resolving power of an image output through this display panel having a transparent conductive film can be maintained at a high level.

Incidentally, all display panels with a transparent conductive film used in the present invention have a surface resistance value between 103 and 1010 mW / cm 3 per unit area. In the case of the non-fluorescent coating, the film exhibits a dull turbidity of 1% or less and a resolution of 70 bar / cm or more.

Here, the resolution is measured by the following method.

As shown in FIG. 1, bar chart 1, which engraved the number of bars 2 per centimeter, was pasted on one side of the test display panel where the film was not formed. The surface on which the above bar chart was pasted on the test apparatus 4 shown in the figure was installed so as to be located inside the test apparatus 4. In the test apparatus 4 whose inner wall is white, two fluorescent lamps 20W are arranged in the transverse direction with a distance of 30 cm at a distance of 50 cm from the position of the test display panel. In this case, the bar chart used is continuously changed from bars with a small number per centimeter to bars with a larger number per centimeter, with the highest number of bars per centimeter in the bar chart that can be confirmed by visual observation being taken with resolution. Is brought in.

In the display device of the present invention, the light reflectance of the display panel, together with the conductive particles, is transparent to contain particulate compounds such as titanium oxide and zirconium oxide particles to control the refractive index at the outer surface of the display panel and further form a protective film. It can be reduced to less than 1% by forming a conductive film and by forming a protective film containing particulate compounds such as magnesium fluoride (MgF 2) and calcium fluoride (CaF 2) particles to control the refractive index on the surface of the transparent conductive film. have. That is, by reducing the light reflectance on the surface of the display screen, an image appearing on the display panel can be more easily observed.

Therefore, in the display device of the present invention, for example, by forming a special protective film on the conductive film of the display panel, various advantages can be obtained such that the display screen light reflectance is reduced.

According to the present invention, the film containing the particulate inorganic compound in a monodisperse state can be produced by coating a coating liquid composed of the particulate inorganic compound and the substrate on a substrate such as glass, plastic, metal, ceramic, or the like. Furthermore, by varying the type of particulate inorganic compound contained in the coating liquid and the ratio of the particulate inorganic compound to the substrate used, the film has a dull turbidity and enhanced transparency, abrasion resistance, and adhesion of the film to the substrate. The coating can have various functions such as conductivity and / or antireflection and the desired refractive index. In addition, by coating the coating liquid according to the present invention, the particulate inorganic compound in the coating can be maintained in a monodisperse state, a flat film having a uniform thickness can be obtained, and even if the amount of the particulate inorganic compound contained in the coating liquid is reduced. It is possible to produce a film having functions such as conductivity and antireflection that is comparable to that of a film made of a conventional coating liquid.

In addition, all the films formed on the substrate in the above-described manner are extremely dense because there are little or no gaps or small pores between the particles, and therefore are excellent in chemical resistance and heat resistance, and are prevented from staining by the back of the hand. Also excellent in safety, the amount of stains on the back of the hand is extremely small.

The above coating liquid capable of forming a film having excellent properties can be easily and clearly prepared by the process of preparing the coating liquid according to the present invention.

In the manufacturing process of the coated substrate according to the present invention, thermally by performing a treatment process for promoting hardening, such as irradiating the film with a wavelength shorter than visible light in the uncured state or exposing it onto a specific gas before heating. Curing conditions can be relaxed.

The coated substrate of the present invention is suitable for use as a display panel such as a cathode ray tube, a liquid crystal display device, a camera lens, etc., by forming the above-described film having excellent properties on the substrate.

The display device of the present invention maintains an antistatic effect and an electromagnetic shielding effect on a display screen for a long time even in a bad environment by providing the display device with the display panel coated with a transparent conductive film having excellent performance on its surface. Can be. Therefore, dirt and dust accumulate less on the display screen, and the integrated circuit IC is not damaged or its function is deteriorated for a long time.

In addition, since the resolution of the display image observed through the display panel on which the transparent conductive film is formed can be maintained at a high level, the display device of the present invention can guarantee a clean image.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.

[Examples 1-8 and Comparative Example 1]

A. Preparation of Substrate Solutions M1 to M5

As shown in Table 2, the substrate solutions M1 to M5 having various average molecular weights, solid contents, and ion concentrations were used as precursors, ethyl silicate 28 (SiO ₂ : 28 wt%), ethyl silicate 40 (SiO ₂ : 40 wt%). , Dibutoxybis (acetylacetonato) zirconium (Zr (AA) ₂ (OBu) ₂ : ZrO ₂ : 10% by weight), and titanium tetraisopropoxide (Ti (OC ₃ H ₇ ) ₄ : TiO ₂ : 10 % By weight) was hydrolyzed in a mixed solvent consisting of distilled water, ethanol and 35% hydrochloric acid and optionally deionized.

The deionization treatment was performed by mixing and stirring each substrate solution with an amphoteric ion exchange resin (Diaion SMNUPB manufactured by Mitsubishi Chemical Corporation), and then removing the ion exchange resin from the substrate solution.

*: (mmol / solid content 100g)

B. Preparation of inorganic compound colloidal solution (sol) F1 ~ F8

(1) Preparation of an Antibon-doped (small amount) conductive tin oxide colloidal solution F1

333 g of potassium stannate and 69.5 g of tartar emetic potassium (tartar emetic) were dissolved in 1019 g of distilled water to obtain an aqueous solution of potassium stannate and potassium antimonyl tartarate.

The whole of this aqueous solution was combined with 1876 g of distilled water, and the concentrated nitric acid solution was added and heated at 50 ° C. for 12 hours while adjusting the pH of the mixture to 10. In this way, the tin oxide hydrate containing an antibone was obtained.

The tin oxide hydrate containing the antibones was separated from the reaction mixture by ultrafiltration.

The filtered solid was washed with distilled water and then heated in an atmosphere of 550 ° C. to obtain a tin oxide powder doped with a conductive anti-bone.

400 g of the conductive anti-bone doped tin oxide was added 1600 g of an aqueous solution containing 40 g of potassium hydroxide, and ground in a sand mill at 30 ° C. for 5 hours to obtain a tin oxide colloidal solution doped with the conductive anti-bone.

The obtained solution was subjected to deionization in the same manner as the deionization treatment of the substrate solution described above to obtain a tin oxide colloidal solution doped with a conductive anti-bone having an average particle size, solid content, and ion concentration shown in Table 3.

(2) Preparation of silicon dioxide colloidal solution (F2)

Silicon dioxide colloidal solution (SI-200P manufactured by Catalyss Chemicals Industrial Co., Ltd.) was heated in an autoclave at 200 ° C. for 3 hours and treated with an amphoteric ion exchange resin. Silicon dioxide colloidal solution having an average particle size, solid content, and ion concentration indicated in Table 3 was obtained.

(3) Preparation of titanium oxide colloidal solution (F3)

Titanium oxide colloidal solution (PW-1010 manufactured by Catalysts Chemicals, Inc.) was treated with the amphoteric ion exchange resin described above. A titanium oxide colloidal solution having an average particle size, solid content, and ion concentration as indicated in Table 3 was obtained.

(4) Preparation of magnesium fluoride colloidal solution (F4)

An aqueous solution obtained by dissolving 508.3 g of magnesium chloride hexahydrate in 12500 g of distilled water and an aqueous solution obtained by dissolving 470.7 g of potassium fluoride dihydrate in 12500 g of distilled water were simultaneously added to 25000 g of distilled water over 6 hours. Thus, magnesium fluoride colloidal solution was obtained. This magnesium fluoride colloidal solution was aged at 90 ° C. for 2 hours and treated with the amphoteric ion exchange resin described above. This gave a magnesium fluoride colloidal solution having the average particle size, solids content, and ion concentration shown in Table 3.

(5) Preparation of silicon dioxide colloidal solution (F5)

Silicon dioxide colloidal solution (SI-45P manufactured by Catalyss Chemicals Industrial Co., Ltd.) was treated with an amphoteric ion exchange resin. Thus, silicon dioxide colloidal solution (F5) having an average particle size, solid content, and ion concentration indicated in Table 3 was obtained.

(6) Preparation of silicon dioxide-aluminum oxide colloidal solution (F6)

A mixture (pH 10.5) of 20 g of silicon dioxide colloidal solution containing 20 wt% of silicon dioxide having an average particle size of 5 nm and 380 g of distilled water was heated to 80 ° C. Subsequently, 1800 g of water-soluble sodium silicate containing 1.5% by weight of silicon dioxide and 1800 g of water-soluble sodium aluminate containing 0.5% by weight of aluminum oxide were simultaneously added to the mixture. The temperature of the reaction mixture was maintained at 80 ° C. while adding the above aqueous solution. After mixing was completed, the reaction mixture was cooled to room temperature, and a colloidal solution of silicon dioxide-aluminum oxide having an average particle size of 20 nm and a mole ratio of silicon dioxide / aluminum oxide of 5.1 was obtained. This colloidal solution was treated with cation exchange resin, and the pH of the colloidal solution was adjusted to 8. Ten liters of a 0.1% aqueous acetic acid solution was gradually added to 2 kg of the above solution to partially filter out aluminum from the silicon dioxide-aluminum oxide particles. Distilled water was added to the colloidal solution thus obtained, and aluminum dissolved in the colloidal solution was separated by ultrafiltration. Thus, a colloidal solution of silicon dioxide-aluminum oxide having a SiO / AlO molar ratio of 50 was obtained. This colloidal solution was heated in an autoclave at 200 ° C. for 3 hours and deionized in the same manner as the deionization treatment of the substrate solution described above. The colloidal solution (F6) of silicon dioxide-aluminum oxide having the average particle size, solid content, and ion concentration shown in Table 3 thus obtained was obtained.

(7) Preparation of silicon dioxide-aluminum oxide colloidal solution (F7)

1800 g of water-soluble sodium silicate containing 1.5% by weight of silicon dioxide and 1800 g of water-soluble sodium aluminate containing 1.4% by weight of aluminum oxide were simultaneously added to 400 g of 0.1% sodium hydroxide aqueous solution heated to 80 ° C. The temperature of the reaction mixture was maintained at 80 ° C. while adding the above aqueous solution. After mixing was completed, the reaction mixture was cooled to room temperature, and a colloidal solution of silicon dioxide-aluminum oxide having an average particle size of 80 nm and a mole ratio of silicon dioxide / aluminum oxide of 0.6 was obtained. This colloidal solution was treated with cation exchange resin and the pH of the colloidal solution was adjusted to 10.5. 300 g of the silicic acid solution containing 2% by weight of silicon dioxide was added to 1.5 kg of the colloidal solution described above for 6 hours, and the surface treatment of the silicon dioxide-aluminum oxide oxide particles in the colloidal solution while maintaining the temperature of the colloidal solution at 80 ° C. Affects. Followed by 30 N aqueous hydrochloric acid solution 30 Was gradually added to the above solution to partially filter aluminum from the silicon dioxide-aluminum oxide particles. Distilled water was added to the colloidal solution thus obtained, and aluminum dissolved in the colloidal solution was separated by ultrafiltration. In this way, a colloidal solution of silicon dioxide-aluminum oxide having a SiO ₂ / Al ₂ O ₃ molar ratio of 30 was obtained. This colloidal solution was heated in an autoclave at 200 ° C. for 3 hours and deionized in the same manner as the deionization treatment of the substrate solution described above. Thus obtained silicon dioxide-aluminum oxide oxide colloidal solution (F7) having the average particle size, solid content, and ion concentration shown in Table 3 was obtained.

(8) Preparation of colloidal solution (F8) in which pigment was dispersed

The dispersion obtained by dispersing 100 g of titanium black (manufactured by Ishihara Sangyo Co., Ltd.) and 30 g of silicon dioxide colloidal solution (SI-30 manufactured by Catalyss Chemical Co., Ltd.) in 300 g of distilled water was ground in a sand mill for 3 hours. The dispersion thus obtained was diluted with distilled water to 5% by weight of solids, treated with an amphoteric ion exchange resin, and filtered through an ultrafiltration membrane. Thus obtained pigment dispersed colloidal solution having the average particle size, solid content, and ion concentration shown in Table 3 was obtained.

C. Preparation of Coating Liquid

The substrate solutions M1 to M5 and the inorganic compound colloidal solutions F1 to F8 were mixed together at various ratios, and diluted with various diluents to prepare a coating solution for forming a film having various solid contents. F / M ratios and ion concentrations are shown in Table 4.

[Examples 9-16 and Comparative Example 2]

I. Fabrication of Cover Substrate

As shown in Table 5, the coated substrate was prepared by forming a single or double transparent coating on the surface of the glass plate used as the substrate using the coating liquids prepared in Examples 1-8 and Comparative Example 1.

Formation of the coating layer was carried out as follows.

(1) Coating Method: Spinner

The spinner's rotational frequency when forming the second layer of Example 18 was 100 rpm.

1st layer (on substrate): 100 rpm, 60 sec

Second layer (upper layer): 200rpm, 60sec

(2) Coating temperature: room temperature

(3) Heating condition: 160 ℃, 30 minutes

II. Evaluation of Cover Substrate

The following evaluation was performed about each of the coated substrates produced above.

(a) Nonuniformity of film thickness, point defect

For each of the coated substrates, the degree of non-uniformity of the film thickness and the point bonding were visually inspected during the surface change using an illuminator for visual inspection.

(b) haze

The turbidity of the surface of each film of the coated substrate was measured using a haze computer (manufactured by Sugar Shigenki Co., Ltd.).

(c) reflectivity

The reflectance at the time of tilting 5 degrees of light of 550 nm wavelength on the film surface of each coated substrate was measured using the visible region or the ultraviolet spectrometer.

(d) sheet resistance

The sheet resistance of each film of the coated substrate was measured using a sheet resistance meter.

(e) film strength

An office eraser was placed on the surface of each coating of the coated substrate and rubbed 200 times at a load of 11 g. The coating was then visually inspected for peeling or not peeling off.

(f) boiling resistance

Each coated substrate was immersed in boiling water for 30 minutes and then visually inspected to see if the coating was peeled off or not.

Examples 17 and 18

A substrate was prepared in the same manner as in Example 9 except that a 14-inch cathode ray tube plate was used as a substrate and the conditions for forming the film were as follows.

(1) Coating Method: Spinner 200rpm, 60sec

(2) Coating temperature: room temperature

(3) Heating condition: 160 ℃, 30 minutes

The results are shown in Table 5.

* A coating solution for forming a protective film, in which 100 g of the substrate M1 solution is diluted in 900 g of ethanol.

Examples 19 to 26 and Comparative Examples 3 and 4

D. Preparation of M-M Substrate Solution

Ethyl silicate 28 (28 wt% SiO) or ethyl silicate 40 (40 wt% SiO) was added to the mixed solvent of organic solvent, distilled water and acid and hydrolyzed under the conditions shown in Table 6. In this way, substrate solutions M6 to M12 were obtained. Deionization treatment was performed in the same manner as in preparing the substrate solutions M1 to M5.

E. Preparation of Tin Oxide Colloidal Solutions F9 to F13 Doped with Conductive Antimony

(1) Tin oxide colloidal solution F9 doped with conductive antimony was prepared in the same manner as described above with the tin oxide colloidal solution F1 doped with conductive antimony, and was prepared in the same manner as described above. Has a particle size distribution.

(2) Tin oxide colloidal solution F10 doped with conductive antimony was prepared in the same manner as in (1) above except that the pH was adjusted to 8.5 when tin oxide hydrate was prepared.

(3) Tin oxide F11 doped with conductive antimony was prepared in the same manner as in (2), and the obtained dispersion of tin oxide hydrate was filtered through ultrafiltration and washed, and 300 g of 5% aqueous hydrogen peroxide (HO) solution was added. The mixture was added and heated at 100 ° C. for 30 minutes and then transferred to an autoclave and heated to 300 ° C. for 2 hours.

(4) The same method as in (1) above, except that the tin oxide colloidal solution F12 doped with conductive antimony was ground in a sand mill for 3 hours and separated in a centrifuge (5000 rpm, 1 hour). It was prepared by.

(5) A tin oxide colloidal solution F13 doped with conductive antimony was prepared in the same manner as in (1) above except that an aqueous potassium hydroxide solution in milling in a sand mill containing 10 g of potassium hydroxide was used.

F. Preparation of Coating Liquid for Forming Transparent Conductive Film

The substrate solution M6 to M12: the tin oxide colloidal solution F9 to F13 doped with the above-described conductive anti-bone: and the mixed solvent (diluent) of the organic solvent and / or distilled water were mixed together, and then acid was added to adjust the pH. The coating liquid for forming the transparent conductive film shown in Table 8 was obtained.

*: (Rhodamine 6G: 006% by weight)

**: Dibutoxybis (acetylacetonato) zirconium (10g)

[Examples 27-34 and Comparative Examples 6-8]

Manufacturing of Display Panels with Transparent Conductive Coatings

Each of the coating liquids obtained in Examples 19 to 26 and Comparative Examples 3 to 5 as shown in Table 8 was not preheated at a predetermined temperature or not, and under the conditions shown in Table 9, a transparent conductive film was coated. By obtaining a display panel, it can apply to the display element (14 inches) for cathode ray tubes.

Coating conditions and processing conditions for rapid processing are as follows.

Injection: Injector of Spraying System Co.

1A nozzle, air pressure of 1.5㎏ / ㎠, feed rate of 20ml / min, feed for 1 minute

Spinner: 100rpm, 30sec

UV irradiation: mercury lamp, 500mW / ㎠ 6000mj

Ammonia treatment: 5 minutes at 1000 ppm NH boil atmosphere

Evaluation of Transparent Conductive Coated Display Panel

The prepared transparent conductive film was coated, and each of the display panels was evaluated by the following evaluation method. The results are shown in Table 10.

*: UV treatment after drying and after applying protective solution

**: dried and separated by ammonia gas

Haze; It carried out in the same manner as in Examples 9-18.

Glossiness; It carried out by JISK7105-81. (Measurement angle: 6 °)

Sheet resistance; It carried out in the same manner as in Examples 9-18.

Membrane strength; Put the four-thread eraser on the membrane and reciprocate 200 times with 1kg of Xiamen. Glossiness difference before and after friction G) and the surface resistance ratio before and after friction are determined.

Boiling resistance; Compare the glossiness and sheet resistance of the coated panels after soaking in boiling water for 30 to 60 minutes and before soaking.

Stain resistance; Draw a line down 1kg with a pencil with a pencil strength of 6B-9H. Gently wipe the pencil marks with a gauge immersed in ethanol. After 10 wipes, use the pencil strength of the visible marks as a measure of contamination resistance.

Resolution (resolution): It evaluates by the method mentioned above.

As is apparent from Table 10, the transparent conductive coating film formed from the coating solution according to the present invention showed little change in glossiness and sheet resistance even after the film strength and sheet resistance test. In addition, they were also excellent in pollution resistance. On the other hand, the display panel having a small average molecular weight showed a sheet resistance of about 5Ｘ1111kPa per unit area.

The reason why the insulating layer is formed on the non-valued portion of the conductive particles is due to the phenomenon that the components having the low molecular weight of the substrate bind on the surface of the conductive particles. However, in the present invention, such a phenomenon did not occur, and a film showing a very stable sheet resistance could be obtained.

Claims (11)

In the coating liquid for film formation, the coating liquid is a particulate inorganic compound composed of the following particle structure, (a) the average particle size is 50 mm or less, (b) 6% by weight of particles each having a particle size of 60 nm or less, (c) 5% by weight of particles each having a particle size of 10 nm or less, (d) The particles each having a particle size of 100 nm or more are 15% by weight or less. As the substrate, a partial hydrolyzate of an alkoxysilane having the following molecular weight composition, (1) the average molecular weight is 1,500 to 10,000, (2) 50 wt% or less of polymer having molecular weight of 3,000 or less, (3) The polymer having a molecular weight of 10,000 or more is 20% by weight or less. It is contained in the form of dispersed or dissolved in water and / or organic solvent, and 100mmo per 100g of all solid contents contained in the coating liquid A coating liquid for forming a film, characterized by containing ions at a concentration of (pre-mol) below. A coating liquid prepared by dispersing a dispersion of a particulate inorganic compound, a substrate solution, or a mixture thereof has a concentration of 10 mmo per 100 g of all the solid contents contained in the coating liquid. A process for producing a coating liquid for forming a film according to claim 1, wherein the process for removing cations and / or anions is carried out so as to be below. A coating substrate comprising a substrate and a coating formed by coating a coating liquid according to claim 1 on a substrate. The coating liquid of Claim 1 is apply | coated to the surface of a board | substrate, and an unhardened film is formed, The said uncured film formed in the board | substrate was irradiated and heated the electromagnetic wave whose wavelength is shorter than a visible light, The coating substrate is characterized by the above-mentioned. Method for producing a coated substrate. The coating liquid of Claim 1 was apply | coated to the surface of a board | substrate, an uncured film was formed, and the said uncured film formed in the board | substrate was exposed and heated on the gas phase which can accelerate | stimulate a hardening effect, and a coating substrate was manufactured. The manufacturing method of the coating substrate characterized by the above-mentioned. A display device comprising a display panel coated with a transparent conductive film formed of the coating liquid according to claim 1 on an outer surface thereof. The display device according to claim 6, further comprising a display panel coated with a transparent protective film on the transparent conductive film on the surface. The display device according to claim 6 or 7, wherein the display panel coated with the transparent conductive film has a surface resistivity of 10 ³ to ^{10 10} GPa per unit area, a turbidity of 1%, and a resolution of 70 bars / cm or more. . Claim 6 according to any one of claims 7, wherein the transparent conductive film surface resistivity of ^{10 3} ~10 10 Ω per unit of the display panel is coated with, a glossiness of 40 to 90%, characterized in that the resolution is at least 60bars / cm Display device. The display panel according to claim 7, wherein the display panel having the transparent conductive film and the transparent protective film has a surface resistivity of 10 ³ to ¹⁰ 10 GPa per unit surface, glossiness of 40 to 90%, reflectance of 1% or less, and resolution. Display device characterized in that more than 60bars / cm. The coating liquid for forming a film according to claim 1, further comprising a partial hydrolyzate of acetylacetonato chelate or a partial hydrolyzate of a metal alkoxide having an average molecular weight of 1,500 to 10,000 as a substrate.