JP2001187864A - Transparent coating film-forming coating fluid, substrate with transparent coating film and display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating fluid capable of forming transparent coating films having excellent performances such as antioxidant action, rust prevention, chemical resistance, mar resistance, weatherability, prevention of reflection and the like. SOLUTION: The transparent coating film-forming coating fluid comprises an inorganic oxide precursor and an organosilicon compound represented by formula (1) [wherein R1 and R2 are each an alkyl group, a halogenated alkyl group, an aryl group or the like; R3 to R6 are each an alkoxy group, an alkyl group, a halogenated alkyl group, an aryl group or the like; X is -(CH2)n-, -(Ph)- (wherein Ph is a benzene ring), -(CH2)n-(Ph)-, -(CH2)n-(Ph)-(CH2)n-, -(S)m- OR -(CH2)n-(S)m-(CH2)n-; m is an integer of 1-30; and n is an integer of 1-30] or a hydrolyzate condensation polymerizate of the organosilicon compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating solution for forming a transparent film,
Regarding a transparent coated substrate and a display device provided with the substrate,
More specifically, it is formed on a transparent coating with excellent stability of coating liquid, excellent adhesion, film strength, antireflection performance, chemical resistance, etc., and a coating composed of a transparent conductive fine particle layer formed on a substrate. If you do, antistatic performance, electromagnetic shielding performance,
The present invention relates to a display device having a substrate with a transparent coating having excellent anti-reflection performance and excellent durability and chemical resistance, and a front plate composed of the substrate.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a coating for the purpose of oxidation prevention, rust prevention, chemical resistance, etc., and a coating for the purpose of abrasion resistance, weather resistance, ultraviolet shielding, antireflection, etc. have been made of a metal substrate,
It was performed on an optical lens substrate or the like. Also, for the purpose of antistatic and antireflection of the surface of a transparent substrate such as a display panel such as a cathode ray tube, a fluorescent display tube, and a liquid crystal display panel, a transparent film having an antistatic function and an antireflection function is formed on these surfaces. That is being done.

[0003] The effect of electromagnetic waves emitted from a cathode ray tube or the like on the human body has recently been considered a problem, and in addition to the conventional antistatic and antireflective effects, the electromagnetic waves and the electromagnetic waves are formed with the emission of the electromagnetic waves. It is desired to shield electromagnetic fields. One way to shield the like these waves, there is a method of forming a conductive coating film for electromagnetic wave shielding on a surface of the display panel, such as a cathode ray tube, the conductive coating of such electromagnetic shielding 10 ² - It is necessary to have a low surface resistance such as 10 ⁴ Ω / □.

As one method of forming a conductive film having such a low surface resistance, a coating film containing fine metal particles is formed on the surface of a substrate using a coating liquid for forming a conductive film containing fine metal particles such as Ag. There is a way to do that. In this method, as a coating liquid for forming a metal fine particle-containing film, a liquid in which colloidal metal fine particles are dispersed in a polar solvent is used. However, in a transparent conductive film containing fine metal particles such as Ag, the metal may be oxidized, particles may grow due to ionization, and in some cases, corrosion may occur. And the display device lacks reliability.

Further, a transparent coating having a lower refractive index than that of the conductive coating is further provided on such a conductive coating to prevent reflection and protect the conductive coating. A coating solution for forming a transparent film sometimes lacks stability and sometimes lacks manufacturing reliability (reproducibility). For this reason, a transparent coating formed using a conventional coating liquid for forming a transparent coating lacks transparency and adhesiveness, and particularly has resistance to oxidation or corrosive substances of the underlying metal (fine particles), ie, durability, and chemical resistance. Was insufficient.

[0006]

An object of the present invention is to provide a coating solution capable of forming a transparent film having excellent properties such as antioxidation, rust prevention, chemical resistance, abrasion resistance, weather resistance and antireflection. I have. In addition, the present invention is excellent in antistatic properties, antireflection properties and electromagnetic shielding properties, as well as adhesion to a substrate,
It is an object of the present invention to provide a substrate with a transparent film on which a transparent film excellent in chemical resistance and the like and excellent in appearance is formed, and a display device provided with the substrate.

[0007]

The coating solution for forming a transparent film according to the present invention comprises:
It is characterized by containing an inorganic oxide precursor and an organosilicon compound represented by the following formula (1) or a hydrolyzed condensation polymer of the organosilicon compound.

[0008]

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(Wherein, R ¹ and R ² may be the same or different from each other, and include an alkyl group, a halogenated alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkenyl group, a hydrogen atom or R ^{3 to} R ⁶ may be the same or different and each represents an alkoxy group, an alkyl group, a halogenated alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkenyl group, a hydrogen atom, Or a halogen atom.

X is-(CH ₂ ) _n -,-(Ph)-(Ph is a benzene ring),-(CH ₂ ) _n- (Ph)-,-(CH ₂ ) _n- (Ph)-( CH ₂ ) _n -,-(S) _m- ,
-(CH ₂ ) _n- (S) _m- (CH ₂ ) _n- , where m is an integer of 1 to 30,
Represents an integer of 1 to 30. The inorganic oxide precursor is at least one selected from a silicon compound (excluding the organosilicon compound represented by the formula (1)), a titanium compound, a zirconium compound, an antimony compound, and a hydrolyzate thereof. Is preferred. In particular, a hydrolyzed polycondensate of the organosilicon compound represented by the formula (2) or a silicic acid polycondensate obtained by removing alkali from an aqueous alkali metal silicate solution is preferable.

R_aSi (OR ')_4-a ... (2) (wherein R is a vinyl group, an aryl group, an acryl group,
An alkyl group of the formulas 1 to 8, a hydrogen atom or a halogen atom
Yes, R 'is vinyl group, aryl group, acryl group, charcoal
An alkyl group of the formulas 1 to 8, -C_TwoH_FourOC_nH_{2n + 1}(N = 1
To 4) or a hydrogen atom, and a is an integer of 0 to 3
You. In such a coating liquid for forming a transparent film according to the present invention,
Organosilicon represented by formula (1) together with organic oxide precursor
A compound or a hydrolyzed condensation polymer of the organosilicon compound.
Contains. The organosilicon compound represented by the formula (1)
If included, the three-dimensional network structure of the formed coating
For example, in the case of a silicon compound, the polysiloxane structure [-S
i-O-Si-O-]_n)), [-Si-X-Si-O
−]_nCan be introduced. Such [-Si-X-Si-O
−]_nIs, for example,-(CH_Two)_nIn case of-, hydrophobicity is given
And-(S)_mIn case of-, excellent affinity with metal
It has excellent chemical resistance,
Also (-CH_Two)_n-,-(S) _m−), Elastic coupling flexibility
Rich in Therefore, the organosiliconization represented by the formula (1)
Compound or a hydrolyzed condensation polymer of the organosilicon compound.
When using a coating solution, it is dense, rich in elasticity and strong
Can also form an excellent coating.

The substrate with a transparent coating according to the present invention comprises:
And a transparent film formed on the surface of the base material, wherein the transparent film is obtained by applying the coating liquid for forming a transparent film and drying. Further, the substrate with a transparent coating according to the present invention comprises a substrate, a transparent conductive fine particle layer formed on the surface of the substrate, and a transparent coating formed on the surface of the transparent conductive fine particle layer, wherein the transparent The coating is characterized by being obtained by applying the coating liquid for forming a transparent coating and drying.

[0013] A display device according to the present invention is characterized in that it has a front plate made of the base material with a transparent coating, and a transparent coating is formed on the outer surface of the front plate.

[Detailed Description of the Invention]

[0015]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. Transparent film-forming coating liquid is first described organosilicon compounds used in the present invention. The coating solution for forming a transparent film according to the present invention is characterized by containing an inorganic oxide precursor (matrix forming component) and an organosilicon compound or a hydrolyzed polycondensate of the organosilicon compound.

[Organosilicon Compound] In the present invention, an organosilicon compound represented by the following formula (1) or a hydrolyzed polycondensate of the organosilicon compound is used as the organosilicon compound.

[0017]

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(Wherein R ¹ and R ² may be the same or different from each other, and include an alkyl group, a halogenated alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkenyl group, a hydrogen atom or R ^{3 to} R ⁶ may be the same or different and each represents an alkoxy group, an alkyl group, a halogenated alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkenyl group, a hydrogen atom, Or a halogen atom.

X is-(CH ₂ ) _n -,-(Ph)-(Ph represents a benzene ring),-(CH ₂ ) _n- (Ph)-,-(CH ₂ ) _n- (Ph) -(CH ₂ ) _n -,-
(S) _m -,-(CH ₂ ) _n- (S) _m- (CH ₂ ) _n- , where m is an integer of 1 to 30, and n is an integer of 1 to 30. m represents an integer of 1 to 30. n represents an integer of 1 to 30, preferably 1 to 16.

As such an organosilicon compound, an organosilicon compound that can be dissolved or dispersed in water or an organic solvent is used. Further, two or more organic silicon compounds may be used in combination. Examples of such organosilicon compounds include bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) propane, bis (trimethoxysilyl) butane, (trimethoxysilyl) pentane, bis (trimethoxysilyl) hexane, and bis (trimethoxysilyl) pentane. (Trimethoxysilyl)
Heptane, bis (trimethoxysilyl) octane, bis
(Trimethoxysilyl) nonane, bis (trimethoxysilyl) decane, bis (trimethoxysilyl) dodecane, bis
(Trimethoxysilyl) heptadecane, bis (trimethoxysilyl) octadecane, bis (triethoxysilyl) hexane, bis (tripropoxysilyl) hexane, bis
(Tri-n-butoxysilyl) hexane, bis (tri-i-butoxysilyl) hexane, bis (allyldimethoxysilyl) hexane, bis (vinyldimethoxysilyl) hexane, bis
(Acrylic dimethoxysilyl) hexane, bis (trifluoropropyldimethoxysilyl) hexane,

[0021]

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And organic hydrolysates thereof. In particular, a hydrolyzate of the exemplified compound is preferable, and a hydrolyzate having a molecular weight in terms of polyethylene of 500 to 100,000, particularly preferably 1,000 to 20,000 is preferable. When the organosilicon compound represented by the formula (1) and a hydrolyzate thereof are used, the organosilicon compound is hydrolyzed at the time of forming a transparent film, and the hydrolyzate is combined with the inorganic oxide precursor to form a film. At this time, since the alkoxy groups present at both ends of the organosilicon compound are bonded to the inorganic oxide precursor, a dense and elastic film having excellent strength can be obtained.

The reason why a dense and elastic film can be obtained by using the organosilicon compound having two Si atoms in the molecule as in the present invention is not clear, but the organic silicon compound having two Si atoms in the molecule is not clear. When a silicon compound is used, [-Si-X-Si
—O—] A group represented by _n is introduced. This [-Si-X
Since -Si-O-] _n has a high affinity for metals and is rich in elasticity, it is presumed that it is possible to form a film that is dense, rich in elasticity, and excellent in strength. In addition, in the organosilicon compound represented by the formula (1) and the hydrolyzate thereof, the alkoxy groups at both ends are bonded to the inorganic oxide precursor, so that holes and micropores are not easily generated in the coating.

On the other hand, in an organosilicon compound having only one Si in a molecule, when an alkyl group is directly bonded to a Si atom like an alkylalkoxysilane, the alkyl group becomes an inorganic oxide precursor. Since they are not bonded, they may be decomposed by the heat treatment at the time of forming the film, and holes or micropores may be generated in the film. In addition, when an organosilicon compound having two Si atoms in a molecule is used as in the present invention, the hydrolyzate is converted into a Si—C bond, a Si—O—Si
Since both have a bond, the resulting film is thermally stable (excellent in heat resistance) and alkali resistant,
It is excellent in chemical resistance such as acid resistance, and has high hydrophobicity or high affinity with metal due to having -X- group, so it has water resistance, durability and chemical resistance. It also has excellent properties as a protective film for the purpose of performance and the like.

When the —X— group is a — (CH ₂ ) _n — group, the resulting coating has a low refractive index, and the effect of antireflection performance can be obtained. Such an organosilicon compound and / or a hydrolyzate thereof is preferably contained in the coating solution for forming a transparent film in a range of 0.1 to 20% by weight in terms of solid content.

When the amount of the organosilicon compound and / or the hydrolyzate thereof is less than 0.1% by weight, the amount of the organosilicon compound and / or the hydrolyzate thereof in the coating solution is too small. Effects such as chemical resistance are insufficient, and effects such as improving the stability of the coating solution and improving the flatness of the coating surface may not be obtained. If the content exceeds 20% by weight, cracks may occur in the obtained coating. In some cases, the effect as the protective film may be reduced.

Further, the organosilicon compound and / or the hydrolyzate thereof is contained in the formed transparent film in an amount of 1 to 60.
It is preferably contained in the range of weight%. When the proportion in the transparent coating is less than 1% by weight, the effect of the present invention described above becomes insufficient because the amount of the organosilicon compound and / or the hydrolyzate thereof is small. Since the amount of the precursor is reduced, the adhesion to the lower substrate may be reduced.

[Inorganic Oxide Precursor] As the inorganic oxide precursor (also referred to as a matrix-forming component), when a transparent film is formed, the resulting film has transparency and is refracted from the substrate. There is no particular limitation as long as the ratio is low and the film has antireflection performance. In the present invention, as the inorganic oxide precursor, silica, titania, a precursor of an inorganic oxide such as zirconia, or a precursor of a composite oxide thereof, an organosilicon compound represented by the above formula (1) Excluding silicon compounds, titanium compounds, zirconium compounds, antimony compounds or hydrolysates and polycondensates thereof are preferably used. Further, the inorganic oxide precursor may be a silica sol, a titania sol, a zirconia sol, or an antimony sol.

Among these inorganic oxide precursors, silicon compounds are desirable. The silicon compound has the following general formula
Hydrolysis and polycondensate of alkoxysilane represented by (2), or a silicic acid solution obtained by dealkalization of an alkali metal silicate aqueous solution is preferable, and particularly, hydrolysis of alkoxysilane represented by formula (2). Decomposition / polycondensation products are more preferred.

R _a Si (OR ′) _4-a (2) (wherein R is a vinyl group, an aryl group, an acryl group, an alkyl group having 1 to 8 carbon atoms, a hydrogen atom or a halogen atom, vinyl group, an aryl group, an acrylic group, an alkyl group of carbon-based number _{1~8, -C 2 H 4 OC n} H 2n + 1 (n = 1
To 4) or a hydrogen atom, and a is an integer of 0 to 3. Examples of such alkoxylans include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraoctylsilane,
Examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltriisopropoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and the like.

The transparent coating formed from the coating liquid for forming a transparent coating containing such a silicon compound as an inorganic oxide precursor has a low refractive index in the range of 1.25 to 1.50. . Moreover, the substrate with a transparent film on which the transparent film is formed has excellent antireflection properties. The inorganic oxide precursor is contained in the coating liquid for forming a transparent film in an amount of 0.1 to 0.1 in terms of oxide.
It is desirable that it be contained at a concentration of 10% by weight, preferably 0.5 to 2.0% by weight.

If the amount of the inorganic oxide precursor contained in the coating solution for forming a transparent film is less than 0.1% by weight, the amount of the inorganic oxide precursor is too small, so that the film thickness when the film is formed is thin. And the antireflection performance of the coating may decrease.
If the amount of the inorganic oxide precursor contained in the coating liquid for forming a transparent coating is less than 0.1% by weight, a coating having a sufficient film thickness may not be obtained by one coating, and the coating is repeated. Even if it is performed, it is often difficult to form a film having a uniform thickness. Further, the chemical resistance of the coated substrate may be poor.

If the concentration of the inorganic oxide precursor contained in the coating solution for forming a transparent film exceeds 10% by weight, cracks may occur in the obtained film or the strength of the film may be reduced. If the concentration of the inorganic oxide precursor contained in the coating liquid for forming a transparent coating exceeds 10% by weight, the thickness of the coating may be too large and the antireflection performance may be insufficient. The quantitative ratio of the inorganic oxide precursor to the organosilicon compound represented by the formula (1) (inorganic oxide precursor / organic silicon compound oxide represented by the formula (1)) is 0. 005 to 4, preferably 0.02 to 2. In addition,
The weight ratio of the inorganic oxide precursor is calculated as oxide, and the ratio of the organic silicon compound is calculated as SiO _3/2 X _1/2 .

[Preparation of Coating Solution for Forming Transparent Film] The coating solution for forming a transparent film according to the present invention is prepared by dispersing an organosilicon compound represented by the above formula (1) and an inorganic oxide precursor in a solvent. It is dissolved. The solvent is not particularly limited as long as it is evaporable, and water; alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol and hexylene glycol; Esters such as methyl acetate and ethyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and glycol ether; acetone, methyl ethyl ketone ,
Ketones such as acetylacetone and acetoacetate are exemplified.

Such a coating liquid for forming a transparent film according to the present invention is prepared by preparing an inorganic oxide precursor dispersion and adding the organic oxide represented by the above formula (1) to the inorganic oxide precursor dispersion. It is prepared by mixing a silicon compound. The inorganic oxide precursor dispersion is, for example, a silicon compound (formula
(1) excluding an organosilicon compound), a titanium compound, a zirconium compound, and an antimony compound in water and / or an organic solvent in the presence of an acid catalyst or a base catalyst. You.

For example, an inorganic oxide precursor of the formula (2)
When a hydrolysis / polycondensate of an alkoxysilane represented by is used, the alkoxysilane is hydrolyzed in a water-alcohol mixed solvent in the presence of an acid catalyst to form a hydrolysis / polycondensate of the alkoxysilane. Prepare an inorganic oxide precursor dispersion, the above inorganic oxide precursor dispersion to the above formula
By mixing the organosilicon compound represented by (1), the coating liquid for forming a transparent film of the present invention can be obtained.

The coating liquid for forming a transparent film used in the present invention contains, in addition to the above components, fine particles made of a material having a low refractive index such as magnesium fluoride, and does not impair the transparency and antireflection performance of the transparent film. A small amount of conductive fine particles and / or additives such as dyes or pigments may be contained. First Transparent Coated Substrate The first transparent coated substrate according to the present invention has a substrate and a transparent film formed on the surface of the substrate. This transparent film is formed by applying and drying the above-mentioned coating solution for forming a transparent film on the surface of the substrate.

Examples of the substrate include substrates made of metal, glass, plastic, ceramic, and the like, and substrates with an electrode film formed by forming an electrode film or the like on these substrates. The transparent film is formed by applying the above-mentioned coating solution for forming a transparent film, and the application method is not particularly limited, and a known wet method such as a dipping method, a spinner method, a spray method, a roll coater method, and a flexographic printing method is used. A thin film forming method can be adopted.

The thickness of the transparent film to be formed is appropriately selected depending on the purpose of forming the film, and is 30 to 300 nm.
Preferably, it is in the range of 80 to 200 nm. When the film thickness is in such a range, excellent chemical resistance and excellent antireflection properties are exhibited. If the thickness of the transparent coating is less than 30 nm, the chemical resistance and antireflection performance may be poor.

When the thickness of the transparent film exceeds 300 nm,
The strength of the film may be reduced, and the film may be too thick and the antireflection performance may be insufficient. After the application of the coating liquid for forming a transparent film, drying is usually performed, but the drying temperature is not particularly limited as long as the solvent evaporates. Further, the coating formed on the surface of the base material may be subjected to a curing treatment. The curing treatment may be performed by heating at 150 ° C. or more during drying, or for another 1 hour after drying.
Examples of such treatment include heating at 50 ° C. or higher, irradiating the coating with electromagnetic waves such as ultraviolet rays, electron beams, X-rays, and γ-rays having a wavelength shorter than that of visible light, or exposing the film to an active gas atmosphere such as ammonia. Can be By such a curing treatment, the curing of the film-forming components (the organosilicon compound (including the hydrolyzate) and the inorganic oxide precursor represented by the formula (1)) is accelerated, and the hardness of the obtained transparent film is increased. Get higher.

When the coating liquid for forming a transparent film according to the present invention is applied by spraying while maintaining the temperature of the substrate at about 40 to 90 ° C., a transparent film having ring-shaped irregularities is formed. It is formed. As a result, an antiglare substrate with a transparent coating with little glare can be obtained. It is preferable that the refractive index of the formed transparent film is lower than the refractive index of the substrate. The difference between the refractive index of the substrate and the transparent film is 0.3 or more,
Preferably, it is 0.6 or more. If the difference in refractive index is less than 0.3, the antireflection performance will be insufficient.

Second Transparent Coated Substrate In the second transparent coated substrate according to the present invention,
A substrate having a functional film formed on the substrate is used.
Examples of the functional coating include an ultraviolet shielding coating, an antistatic coating, and an electromagnetic shielding coating formed on a substrate such as a glass or plastic substrate.

In the present invention, antistatic,
A substrate with a transparent conductive coating comprising a layer of transparent conductive fine particles having an electromagnetic wave shielding function is preferred. Such a transparent conductive fine particle layer is formed using the following coating liquid for forming a transparent conductive film. Coating solution for forming transparent conductive fine particle layer The coating solution for forming the transparent conductive fine particle layer used in the present invention comprises metal fine particles and a polar solvent.

The “metal fine particles” used in the present invention include:
Conventionally known metal fine particles can be used, and may be single component metal fine particles or composite metal fine particles containing two or more metal components. The two or more kinds of metals constituting the composite metal fine particles may be an alloy in a solid solution state, a eutectic body not in a solid solution state, or an alloy and a eutectic may coexist. Since such composite metal fine particles suppress metal oxidation and ionization, particle growth and the like of the composite metal fine particles are suppressed, the corrosion resistance of the composite metal fine particles is high, and the conductivity and the decrease in light transmittance are small. It has excellent reliability.

As such metal fine particles, Au, Ag,
Pd, Pt, Rh, Ru, Cu, Fe, Ni, Co, Sn, Ti, In, Al, T
Fine particles of a metal selected from metals such as a and Sb. Further, as the composite metal fine particles, Au, Ag, Pd, Pt,
Composite metal fine particles composed of at least two or more metals selected from metals such as Rh, Ru, Cu, Fe, Ni, Co, Sn, Ti, In, Al, Ta, and Sb. Preferred combinations of two or more metals are Au-Cu, Ag-Pt, Ag-Pd, Au-P
d, Au-Rh, Pt-Pd, Pt-Rh, Fe-Ni, Ni-Pd, Fe-Co,
Cu-Co, Ru-Ag, Au-Cu-Ag, Ag-Cu-Pt, Ag-Cu-P
d, Ag-Au-Pd, Au-Rh-Pd, Ag-Pt-Pd, Ag-Pt-Rh,
Fe-Ni-Pd, Fe-Co-Pd, Cu-Co-Pd and the like.

Further, Au, Ag, Pd, Pt, Rh, Cu, Co, Sn,
When metal fine particles made of a metal such as In or Ta are used, a part thereof may be in an oxidized state or may contain an oxide of the metal. Further, P and B atoms may be contained by bonding. Such a metal fine particle can be obtained, for example, by the following known method (JP-A-10-188681).
Gazette).

(I) A method of reducing one metal salt or two or more metal salts simultaneously or separately in a mixed solvent of alcohol and water. At this time, a reducing agent may be added as needed. Examples of the reducing agent include ferrous sulfate, trisodium citrate, tartaric acid, sodium borohydride, sodium hypophosphite and the like. Moreover, you may heat-process in a pressure vessel at the temperature of about 100 degreeC or more. (ii) In a dispersion of single component metal fine particles or alloy fine particles,
A method in which fine particles or ions of a metal having a higher standard hydrogen electrode potential than metal fine particles or alloy fine particles are present to precipitate a metal having a higher standard hydrogen electrode potential on fine metal particles or / and alloy fine particles. At this time, a metal having a higher standard hydrogen electrode potential may be deposited on the obtained composite metal fine particles.

It is preferable that such a metal having the highest standard hydrogen electrode potential be present in a large amount in the surface layer of the composite metal fine particles. As described above, when the metal having the highest standard hydrogen electrode potential exists in a large amount in the surface layer of the composite metal fine particles,
Oxidation and ionization of the composite metal fine particles are suppressed, and particle growth due to ion migration or the like can be suppressed. Furthermore, since such composite metal fine particles have high corrosion resistance, it is possible to suppress a decrease in conductivity and light transmittance.

The average particle diameter of such metal fine particles is 1 to
It is desirably in the range of 200 nm, preferably 2 to 70 nm. When the average particle size of the metal fine particles exceeds 200 nm,
The absorption of light by the metal increases, the light transmittance of the particle layer decreases, and the haze increases. For this reason, when the coated substrate is used, for example, as a front plate of a cathode ray tube, the resolution of a displayed image may be reduced. Further, when the average particle diameter of the metal fine particles is less than 1 nm, the surface resistance of the particle layer rapidly increases, so that a film having a resistance value low enough to achieve the object of the present invention may not be obtained. is there.

The polar solvent used in the coating solution for forming the transparent conductive fine particle layer includes water; methanol, ethanol, propanol, butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol and the like. Alcohols; esters such as methyl acetate and ethyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
Examples include ketones such as acetone, methyl ethyl ketone, acetylacetone, and acetoacetate. These may be used alone or as a mixture of two or more.

The coating liquid for forming a layer of transparent conductive fine particles used in the present invention contains metal fine particles in an amount of 0.05 to 5% by weight, preferably 0.1 to 2% by weight. Is desirable. When the amount of the metal fine particles in the coating liquid for forming the transparent conductive fine particle layer is less than 0.05% by weight, the resulting coating film is too thin, so that sufficient conductivity may not be obtained.

When the content of the metal fine particles exceeds 5% by weight, the film thickness is increased, the light transmittance is reduced, the transparency is deteriorated, and the appearance is also deteriorated. Such a coating liquid for forming a transparent conductive fine particle layer may contain conductive fine particles other than the metal fine particles. As the conductive fine particles other than the metal fine particles, known transparent conductive inorganic oxide fine particles or fine carbon particles can be used.

Examples of the transparent conductive inorganic oxide fine particles include tin oxide, tin oxide doped with Sb, F or P, indium oxide, indium oxide doped with Sn or F, antimony oxide, and lower titanium oxide. Is mentioned. The average particle size of these conductive fine particles is
It is preferably in the range of 1 to 200 nm, preferably 2 to 150 nm.

The conductive fine particles may be contained in an amount of 4 parts by weight or less per 1 part by weight of the metal fine particles. When the amount of the conductive fine particles is more than 4 parts by weight, the conductivity is lowered and the electromagnetic wave shielding effect may be lowered, which is not preferable. When such a conductive fine particle is contained, a transparent conductive fine particle layer having more excellent transparency can be formed as compared with the case where the transparent conductive fine particle layer is formed only of the metal fine particles. Further, by containing the conductive fine particles, a substrate with a transparent conductive film can be manufactured at low cost.

Further, a dye, a pigment, and the like may be added to the coating liquid for forming the transparent conductive fine particle layer so that the visible light transmittance is constant in a wide wavelength range of visible light. The solid content concentration in the coating liquid for forming the transparent conductive fine particle layer used in the present invention (the total amount of conductive fine particles other than metal fine particles and metal fine particles added as needed, dyes, pigments and other additives) is 15% by weight or less from the viewpoints of fluidity of the liquid and dispersibility of particulate components such as metal fine particles in the coating liquid,
Preferably, it is 0.15 to 5% by weight.

The coating liquid for forming a transparent conductive fine particle layer used in the present invention may contain a binder-forming component that acts as a binder for the conductive fine particles after the formation of the conductive fine particle layer. As such a binder forming component,
Conventionally known ones can be used, but in the present invention, those composed of one or more oxide precursors selected from silica, silica-based composite oxides, zirconia, and antimony oxide are preferable, and in particular, alkoxy A hydrolyzed polycondensate of an organosilicon compound such as silane or a silicic acid polycondensate obtained by dealkalization of an aqueous alkali metal silicate solution is preferably used. In addition, a resin for paint or the like can be used. Such a binder-forming component is contained as an oxide or a resin in an amount of 0.01 to 0.5 part by weight, preferably 0.03 to 0.3 part by weight, per 1 part by weight of the metal fine particles. Just do it. As the binder-forming component, an inorganic oxide precursor used in the coating liquid for forming a transparent film described above may be used, or an organic silicon compound or a general organic silicon compound represented by the formula (1) may be used. Hydrolysis polycondensates may be used.

Further, such a coating liquid for forming a transparent conductive film may contain an organic stabilizer in order to improve the dispersibility of metal fine particles. Specific examples of such organic stabilizers include gelatin, polyvinyl alcohol, polyvinylpyrrolidone, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and citric acid. Polycarboxylic acids and salts thereof, such as sulfonates, organic sulfonates, etc.
Phosphates, organic phosphates, heterocyclic compounds, and mixtures thereof are exemplified.

Such an organic stabilizer varies depending on the type of the organic stabilizer, the particle size of the metal fine particles, etc., but is preferably 0.005 to 0.5 part by weight, more preferably 1 part by weight of the metal fine particles. It may be contained in an amount of 0.01 to 0.2 parts by weight. When the amount of the organic stabilizer is less than 0.005 parts by weight, sufficient dispersibility cannot be obtained. When the amount is more than 0.5 parts by weight, conductivity may be inhibited.

Further, the coating solution for forming the transparent conductive fine particle layer used in the present invention includes alkali metal ions, ammonium ions, polyvalent metal ions, inorganic anions such as mineral acids, acetic acid, formic acid, etc., which are present in the coating solution. It is desirable that the total amount of ion concentration released from the particles of the organic anion is not more than 10 mmol per 100 g of solids in the coating solution. In particular, inorganic anions such as mineral acids
Since the stability and dispersibility of the metal fine particles are impaired, the lower the amount contained in the coating solution, the better. When the ion concentration is low, the dispersed state of the particulate components, particularly the conductive fine particles, contained in the coating liquid for forming the transparent conductive fine particle layer becomes good, and a coating liquid containing almost no aggregated particles can be obtained. The monodispersed state of the particulate components in the coating liquid is maintained during the formation of the transparent conductive fine particle layer. For this reason, when the transparent conductive fine particle layer is formed from the coating liquid for forming the transparent conductive fine particle layer having a low ion concentration, no aggregated particles are observed in the fine particle layer.

In the transparent conductive fine particle layer formed from the coating solution having a low ion concentration as described above, conductive fine particles such as metal fine particles can be well dispersed and arranged. As compared with the case where the conductive fine particles are aggregated, it is possible to provide a transparent conductive fine particle layer having less conductive fine particles and the same conductivity. Further, it is possible to form a transparent conductive fine particle layer having no point defects and uneven thickness, which is considered to be caused by aggregation of the granular components, on the base material.

The deionizing method for obtaining a coating solution having a low ion concentration as described above may be a method in which the ion concentration finally contained in the coating solution falls within the above range. Although there is no particular limitation on the method of deionization, a dispersion of the particulate component used as a raw material of the coating liquid, or a coating liquid prepared from the dispersion may be used as a cation exchange resin and / or an anion exchange resin. And a method of washing these liquids using an ultrafiltration membrane.

[Formation of Transparent Conductive Fine Particle Layer] The transparent conductive fine particle layer is formed by applying the above-mentioned coating solution for forming a transparent conductive fine particle layer on a base material, drying and applying the transparent conductive fine particle layer. Form on the material. Specifically, for example, after applying the coating liquid for forming the transparent conductive fine particle layer on a substrate by a method such as dipping method, spinner method, spray method, roll coater method, flexographic printing method, and the like, and then at room temperature to about Dry at a temperature in the range of 90 ° C.

When the above-mentioned binder forming component is contained in the coating liquid for forming the transparent conductive fine particle layer,
A curing treatment of the binder forming component may be performed. Examples of the curing treatment include the following methods. Heat curing The dried coating film is heated to cure the binder-forming component. The heat treatment temperature at this time is desirably 100 ° C. or higher, preferably 150 to 300 ° C. 100
If the temperature is lower than ℃, the inorganic oxide precursor may not be sufficiently cured. Although the upper limit of the heat treatment temperature varies depending on the type of the base material, the upper limit may be lower than the transition point of the base material.

Electromagnetic Wave Curing After the coating step or the drying step, or during the drying step, the coating film is irradiated with an electromagnetic wave having a shorter wavelength than visible light to cure the binder-forming component. Ultraviolet rays, electron beams, X-rays, γ-rays, and the like are used as the electromagnetic waves to be applied to accelerate the curing of such an inorganic oxide precursor, depending on the type of the inorganic oxide precursor. For example, to promote the curing of the ultraviolet curable inorganic oxide precursor, for example,
A high-pressure mercury lamp having an emission intensity of about 250 nm and 360 nm and a light intensity of 10 mW / m ² or more is used as an ultraviolet light source, and is irradiated with an ultraviolet ray having an energy amount of 100 mJ / cm ² or more.

Gas Curing After the coating step or the drying step, or during the drying step, the inorganic oxide precursor is cured by exposing the coating film to a gas atmosphere that promotes the curing reaction of the inorganic oxide precursor. Among the inorganic oxide precursors, there is an inorganic oxide precursor whose curing is promoted by an active gas such as ammonia, and a transparent conductive fine particle layer containing such an inorganic oxide precursor has a gas concentration of 100 to 100,000 ppm. The curing of the inorganic oxide precursor can be greatly promoted by performing the treatment for 1 to 60 minutes in a curing accelerating gas atmosphere of preferably 1000 to 10000 ppm.

The thickness of the transparent conductive fine particle layer formed by the above-described method is preferably in the range of about 20 to 200 nm. A substrate can be obtained. Display device The substrate with a transparent conductive film according to the present invention has a surface resistance in the range of 10 ² to 10 ⁴ Ω / □ required for electromagnetic shielding, and has sufficient reflection in the visible light region and the near infrared region. The substrate with a transparent conductive film having the prevention performance is suitably used as a front plate of a display device.

The display device according to the present invention comprises a cathode ray tube (C
RT), a fluorescent display tube (FIP), a plasma display (PDP), a display for liquid crystal display (LCD), etc., for electrically displaying images. Equipped with a front plate.
When a display device having a conventional front panel is operated, an image is displayed on the front panel, and at the same time, an electromagnetic wave is emitted from the front panel, and this electromagnetic wave affects a human body of an observer. In the device, since the front plate is formed of a substrate with a transparent conductive film having a surface resistance of 10 ² to 10 ⁴ Ω / □, such an electromagnetic wave and an electromagnetic field generated by the emission of the electromagnetic wave are effectively prevented. Can be shielded.

Further, if reflected light is generated on the front panel of the display device, the reflected light makes it difficult to view a displayed image. However, in the display device according to the present invention, the front panel is sufficient in the visible light region and the near infrared region. Since it is composed of a transparent conductive film having antireflection performance and a substrate with a transparent film, such reflected light can be effectively prevented. Further, the front plate of the cathode ray tube is composed of the substrate with a transparent conductive film according to the present invention, and among these transparent conductive films, a transparent conductive fine particle layer and a small amount of the transparent conductive fine particle layer are formed on at least one of the transparent films formed thereon. When these dyes or pigments are contained, each of these dyes or pigments absorbs light having a unique wavelength, thereby improving the contrast of a display image projected from a CRT.

Further, since the front plate of the cathode ray tube is composed of a substrate with a transparent coating formed from the coating liquid for forming a transparent coating according to the present invention, it has excellent antireflection performance and chemical resistance, so that it is visible. A clear display image can be obtained without scattering of light, and excellent display performance can be maintained for a long time. Further, since the conductivity can be maintained for a long period of time, the antistatic performance and the electromagnetic wave shielding performance do not decrease.

[0070]

According to the present invention, it is possible to obtain a coating liquid for forming a transparent film capable of forming a transparent film excellent in antireflection property, antioxidation property, rust prevention property, durability, chemical resistance and the like. . ADVANTAGE OF THE INVENTION According to this invention, the base material with a transparent coating in which the transparent coating which was excellent in adhesiveness and film strength, especially excellent in durability and chemical resistance was formed can be obtained.

Further, the display device according to the present invention is excellent in anti-reflection performance and chemical resistance, can obtain a clear display image without scattering of visible light, and maintains excellent display performance for a long period of time. Can be. In addition, antistatic performance, since conductivity can be maintained for a long time,
Electromagnetic wave shielding performance does not decrease.

[0072]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0073]

[Production Examples] a) Preparation of Conductive Fine Particle Dispersion Table 1 shows the compositions of the metal fine particles (P-1 to P-4) used in the present Examples and Comparative Examples. Table 2 shows the composition of S-4). Dispersions (S-1, S-4) of metal fine particles (P-1, P-4) were prepared by the following method.

To 100 g of pure water, trisodium citrate was added in advance so as to be 0.01 part by weight per 1 part by weight of metal fine particles, and the concentration became 10% by weight in terms of metal. An aqueous solution of silver nitrate and palladium nitrate was added so as to obtain a ratio, and an aqueous solution of ferrous sulfate in an equimolar number to the total mole number of silver nitrate and palladium nitrate was added. The mixture was stirred for 1 hour under a nitrogen atmosphere to disperse the metal fine particles. A liquid was obtained. The obtained dispersion was washed with water using a centrifuge to remove impurities, redispersed in water, mixed with a solvent (1-ethoxy-2-propanol) shown in Table 1, and dried with a rotary evaporator. Was removed and the mixture was concentrated to prepare metal fine particle dispersions (S-1) and (S-4) having a solid content concentration shown in Table 1.

Dispersions of metal fine particles (P-2, P-3) (S-2, S-
3) The solution was prepared by the following method. To 100 g of pure water, trisodium citrate was added in advance in an amount of 0.1 part by weight per 1 part by weight of metal fine particles, and the metal salt of the metal species shown in Table 1 was adjusted to a concentration of 1% by weight in terms of metal. An aqueous solution (aqueous chloroauric acid solution, ruthenium chloride aqueous solution) is added and dissolved, and a 5% by weight aqueous solution of sodium borohydride having a concentration equal to the total number of moles of the dissolved metal salts is added, and a dispersion of fine metal particles is added. Was prepared, and the dispersion was washed with an ultrafiltration apparatus and then concentrated. The dispersion liquid of the obtained metal fine particles (P-2, P-3) was mixed with a solvent (1-ethoxy) shown in Table 1.
-2-propanol, isobutanol)
Water was removed using a rotary evaporator and the mixture was concentrated to prepare metal fine particle dispersions (S-2, S-3) having a solid content concentration shown in Table 1.

The particle size of the fine particles was measured using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.). b) Preparation of Inorganic Oxide Precursor Dispersion (M) A mixed solution of 50 g of ethyl orthosilicate (TEOS, equivalent to 28% by weight in terms of SiO ₂ ), 194.6 g of ethanol, 1.4 g of concentrated nitric acid and 34 g of pure water was prepared. Stir at room temperature for 5 hours.
Liquid containing inorganic oxide precursor having SiO ₂ concentration of 5% by weight
(M) was prepared.

[0077]

[Table 1]

C) Preparation of a Coating Solution for Forming a Transparent Conductive Film The above-mentioned metal fine particle dispersions (S-1) to (S-4), a solution (M) containing the above-mentioned inorganic oxide precursor, ethanol and isopropyl alcohol , T-butanol, 1-ethoxy-2-propanol and a coating solution for forming a transparent conductive film shown in Table 2 (CS-1)
~ (CS-4) was prepared.

[0079]

[Table 2]

[0080]

Example 1 Bis (trimethoxysilyl) hexane
Preparation of digest ( organosilicon compound) 52.5 g of bis (trimethoxysilyl) hexane was dissolved in 300 g of ethanol, and 3 g of concentrated nitric acid and 3 g of pure water were added thereto. _{Polycondensation} was performed to prepare a dispersion of a hydrolyzate of bis (trimethoxysilyl) hexane having a concentration of 5% by weight in terms of SiO _3/2 X _1/2 . The bis (trimethoxysilyl) hexane hydrolyzate had a molecular weight in terms of polyethylene of 2,000.

Preparation of Transparent Film Forming Coating Solution (B-1) Ethanol / butanol / diacetone alcohol / isopropyl alcohol (weight ratio: 2: 1: 1: 5) was added to the inorganic oxide precursor dispersion (M). ), And the ethanol dispersion of the bis (trimethoxysilyl) hexane hydrolyzate is added so that the weight ratio of the organosilicon compound to the inorganic oxide precursor becomes the concentration shown in Table 3. ,
A coating solution (B-1) for forming a transparent film having a solid content of 1% by weight in the coating solution was prepared.

Preparation of Substrate with Transparent Coating A transparent glass plate with an ITO (tin-doped indium oxide) film was used as a substrate, and the surface was maintained at 40 ° C.
The coating liquid for forming a transparent film (B-1) was applied under the conditions of 100 rpm and 90 seconds by a spinner method so that the film thickness of the transparent film was 100
It was applied and dried so as to have a thickness of nm, and baked at 160 ° C. for 30 minutes to obtain a substrate with a transparent coating.

Panel glass with transparent coating (transparent conductive coating)
Preparation of the transparent conductive film-forming coating solution (CS-1) under the conditions of 100 rpm and 90 seconds by the spinner method while maintaining the surface of the CRT panel glass (14 ″) at 40 ° C. The conductive film was applied to a thickness of 20 nm and dried, and then the transparent conductive fine particle layer thus formed was similarly coated with a spinner method at 100 rpm for 90 seconds at 90 rpm. The coating liquid (B-1) for coating formation was applied and dried so that the thickness of each transparent coating was 80 nm, and baked at 160 ° C. for 30 minutes to obtain a panel glass with a transparent coating.

The haze of the resulting substrate with a transparent coating and the panel glass with a transparent coating was measured with a haze computer (3000A, manufactured by Nippon Denshoku Co., Ltd.). The reflectivity was measured using a reflectometer (MCPD-2000, manufactured by Otsuka Electronics Co., Ltd.), and the reflectance at the wavelength having the lowest reflectance in the wavelength range of 400 to 700 nm was used. The surface resistance of the panel glass with a transparent coating was measured with a surface resistance meter (LORESTA, manufactured by Mitsubishi Yuka Co., Ltd.).

The following chemical resistance evaluations were carried out on the transparent-coated substrate and the transparent-coated panel glass obtained above. Table 4 shows the results. Evaluation of chemical resistance (1) The substrate with a transparent film was immersed in a 5% by weight aqueous hydrochloric acid solution for 10 hours, and the reflectance, haze, and surface resistance (only the panel glass with a transparent film) were measured by the above-described methods. .

Evaluation of chemical resistance (2) The substrate with a transparent film was immersed in a 5% by weight aqueous solution of hydrochloric acid for 200 hours, and the surface resistance (only panel glass with a transparent film), the reflectance, and the haze were measured in the same manner as described above. It was measured.

[0087]

Example 2 and Example 3 A coating solution for forming a transparent film (B-
Preparation of 2) and (B-3) In the same manner as in Example 1, the inorganic oxide precursor dispersion liquid (M)
To ethanol / butanol / diacetone alcohol /
Isopropyl alcohol (2: 1: 1: 5 weight mixing ratio)
, And then the ethanol dispersion of the bis (trimethoxysilyl) hexane hydrolyzate was added so that the weight ratio of the organosilicon compound to the inorganic oxide precursor became the concentration shown in Table 3 and applied. The concentration of solids in the liquid is 1% by weight
Were prepared (B-2) and (B-3).

Using the obtained coating solution for forming a transparent film,
A substrate with a transparent coating and a panel glass with a transparent coating were prepared in the same manner as in Example 1, and the surface resistance, reflectance, haze, and chemical resistance (1) and (2) were evaluated in the same manner as in Example 1. Was. Table 4 shows the results.

[0089]

Example 4 Preparation of a Coating Solution (B-4) for Forming a Transparent Film The inorganic oxide precursor dispersion (M) was mixed with ethanol / butanol / diacetone alcohol / isopropyl alcohol (weight ratio: 2: 1: 1: Add the mixed solvent of 5) and add bis
An ethanol dispersion of (trimethoxysilyl) hexane (concentration: 5% by weight) was added such that the weight ratio of the organosilicon compound to the inorganic oxide precursor became the concentration shown in Table 3, and the solid content in the coating solution was added. (Bis (trimethoxysilyl) hexane, inorganic oxide precursor, bis (trimethoxysilyl) hexane, converted to SiO _3/2 X _1/2 ) 1% by weight of a coating solution for forming a transparent film (B -4) was prepared. The solid content concentration of this bis (trimethoxysilyl) hexane was converted to the solid content after hydrolysis.

Using the obtained coating solution for forming a transparent film,
A substrate with a transparent coating and a panel glass with a transparent coating were prepared in the same manner as in Example 1, and the surface resistance, reflectance, haze, and chemical resistance (1) and (2) were evaluated in the same manner as in Example 1. Was. Table 4 shows the results.

[0091]

Example 5 Bis (triethoxysilyl) ethane hydrolysis
Preparation of bis solution was (triethoxysilyl) ethane 74.2g was dissolved in ethanol 300 g, concentrated nitric acid 3g and pure water 3g addition, and stirred for 5 hours at room temperature, SiO _3/2 X _1/2 A hydrolyzate of bis (triethoxysilyl) ethane having a concentration of 5% by weight in terms of was prepared. The molecular weight in terms of polyethylene was 1500.

Preparation of Transparent Film Forming Coating Solution (B-5) The above inorganic oxide precursor dispersion (M) was mixed with ethanol / butanol / diacetone alcohol / isopropyl alcohol (weight ratio: 2: 1: 1: 5). ), And the ethanol dispersion of the bis (triethoxysilyl) ethane hydrolyzate is added so that the weight ratio of the organosilicon compound to the inorganic oxide precursor becomes the concentration shown in Table 4, A coating solution for forming a transparent film having a solid content of 1% by weight in the coating solution
(B-5) was prepared.

Production of Substrate with Transparent Coating The same transparent glass plate with an ITO (tin-doped indium oxide) film as in Example 1 was used, and the surface was maintained at 40 ° C. by spinner at 100 rpm for 90 seconds. The coating liquid for forming a transparent film (B-5) was applied to the transparent film having a thickness of 1
It was applied and dried to a thickness of 00 nm, and baked at 160 ° C. for 30 minutes to obtain a substrate with a transparent coating.

Production of Panel Glass with Transparent Coating While holding the surface of the same CRT panel glass (14 ″) as in Example 1 at 40 ° C., the spinner method was applied at 100 rpm.
Under the condition of 90 seconds, the coating liquid for forming the transparent conductive film (CS-2)
Was applied so that the film thickness of each transparent conductive film became 20 nm, and dried.

Next, 100 μm is formed on each of the thus formed transparent conductive fine particle layers by the spinner method in the same manner.
The coating solution for forming a transparent film (B-5) is applied and dried under the conditions of rpm and 90 seconds so that the film thickness of the transparent film becomes 80 nm, and baked at 160 ° C. for 30 minutes to form a substrate having a transparent conductive film. Wood was obtained. The obtained substrate with a transparent coating and panel glass with a transparent coating were evaluated for surface resistance, reflectance, haze, and chemical resistance (1) and (2) in the same manner as in Example 1.

Table 4 shows the results.

[0097]

Example 6 1,4-bis (trimethoxysilylethyl) benzene
Preparation of benzene hydrolyzate 1,4-bis (trimethoxysilylethyl) benzene 53.
9 g was dissolved in ethanol 300 g, and concentrated nitric acid 3 g
And 3 g of pure water, and the mixture was stirred at room temperature for 5 hours.
A hydrolyzate of 1,4-bis (trimethoxysilylethyl) benzene having a concentration of 5% by weight in terms of _3/2 X _1/2 was prepared.
The molecular weight in terms of polyethylene was 1,700.

Preparation of Transparent Film Forming Coating Solution (B-6) The above inorganic oxide precursor dispersion (M) was mixed with ethanol / butanol / diacetone alcohol / isopropyl alcohol (weight ratio: 2: 1: 1: 5). ), And the ethanol dispersion of the 1,4-bis (trimethoxysilylethyl) benzene hydrolyzate is added so that the weight ratio of the organosilicon compound to the inorganic oxide precursor becomes the concentration shown in Table 4. To prepare a coating solution (B-6) for forming a transparent film having a solid content of 1% by weight in the coating solution.

Production of a Substrate with a Transparent Coating The same transparent glass plate with an ITO (tin-doped indium oxide) film as in Example 1 was used, and the surface was maintained at 40 ° C. by the spinner method at 100 rpm for 90 seconds. The coating liquid for forming a transparent film (B-6) was applied to the transparent film having a thickness of 1
It was applied and dried to a thickness of 00 nm, and baked at 160 ° C. for 30 minutes to obtain a substrate with a transparent coating.

Production of Panel Glass with Transparent Coating While holding the surface of the same CRT panel glass (14 ″) as in Example 1 at 40 ° C., spinning at 100 rpm.
Under the condition of 90 seconds, the transparent conductive film forming coating solution (CS-3)
Was applied so that the film thickness of each transparent conductive film became 20 nm, and dried.

Next, the transparent conductive fine particle layers thus formed are similarly coated with a spinner method to form 100 μm.
The coating liquid for forming a transparent film (B-6) is applied and dried under the conditions of rpm and 90 seconds so that the film thickness of the transparent film becomes 80 nm, and baked at 160 ° C. for 30 minutes to form a substrate having a transparent conductive film. Wood was obtained. The obtained substrate with a transparent coating and panel glass with a transparent coating were evaluated for surface resistance, reflectance, haze, and chemical resistance (1) and (2) in the same manner as in Example 1.

Table 4 shows the results.

[0103]

Example 7 Bis [3- (triethoxysilyl) propyl] te
Preparation of Trasulfide Hydrolyzate 58.2 g of bis [3- (triethoxysilyl) propyl] tetrasulfide was dissolved in 300 g of ethanol, 3 g of concentrated nitric acid and 3 g of pure water were added, and the mixture was stirred at room temperature for 5 hours. ,
A hydrolyzate of bis [3- (triethoxysilyl) propyl] tetrasulfide having a concentration of 5% by weight in terms of SiO _3/2 X _1/2 was prepared. The molecular weight of the hydrolyzate in terms of polyethylene was 1,800.

Preparation of Coating Solution (B-7) for Forming Transparent Film The above-mentioned inorganic oxide precursor dispersion (M) was mixed with ethanol / butanol / diacetone alcohol / isopropyl alcohol (weight ratio: 2: 1: 1: 5). ), And the above-mentioned ethanol dispersion of bis [3- (triethoxysilyl) propyl] tetrasulfide hydrolyzate was mixed with an organosilicon compound and an inorganic oxide precursor at a concentration shown in Table 4 by weight ratio. As a result, a coating solution (B-7) for forming a transparent film having a solid content of 1% by weight in the coating solution was prepared.

Production of a Substrate with a Transparent Coating The same transparent glass plate with an ITO (tin-doped indium oxide) film as in Example 1 was used, and the surface was maintained at 40 ° C. by the spinner method at 100 rpm for 90 seconds. The coating liquid for forming a transparent coating (B-7) was applied to each of the transparent coatings having a thickness of 1
It was applied and dried to a thickness of 00 nm, and baked at 160 ° C. for 30 minutes to obtain a substrate with a transparent coating.

Production of Panel Glass with Transparent Coating While keeping the surface of the same CRT panel glass (14 ″) as in Example 1 at 40 ° C., spinner method was applied at 100 rpm.
90 seconds above the transparent conductive film forming coating solution (CS-4)
Was applied so that the film thickness of each transparent conductive film became 20 nm, and dried.

Next, the transparent conductive fine particle layers thus formed are similarly coated with the spinner method to form 100 μm.
The coating liquid for forming a transparent film (B-7) was applied and dried under the conditions of rpm and 90 seconds so that the thickness of the transparent film became 80 nm, and baked at 160 ° C. for 30 minutes to obtain a panel glass with a transparent film. Produced. The obtained substrate with a transparent coating and panel glass with a transparent coating were evaluated for surface resistance, reflectance, haze, and chemical resistance (1) and (2) in the same manner as in Example 1.

Table 4 shows the results.

[0109]

Comparative Example 1 Preparation of Coating Solution (B-8) for Forming Transparent Film The solution ( M) containing the inorganic oxide precursor was added to ethanol / butanol / diacetone alcohol / isopropyl alcohol (2: 1: 1: 5). (Mixing ratio by weight) and a coating solution (B-
8) was prepared.

A substrate with a transparent film and a panel glass with a transparent film were prepared in the same manner as in Example 1 except that the obtained coating solution for forming a transparent film (B-8) was used. The obtained panel glass with a transparent coating was evaluated for surface resistance, reflectance, haze, and chemical resistance (1) and (2) in the same manner as in Example 1. Table 4 shows the results.

[0111]

[Table 3]

[0112]

[Table 4]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshiro Komatsu 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka F-term (in reference) inside the Wakamatsu plant 4C045 CB06 EA43 EB01 EB43 EC02 4J038 DL021 DL031 DL101 HA216 JC31 JC32 JC38 5G435 AA01 AA09 AA13 AA16 GG33 HH02 HH03 HH05 KK07

Claims (6)

[Claims] 1. A coating solution for forming a transparent film, comprising: an inorganic oxide precursor; and an organosilicon compound represented by the following formula (1) or a hydrolysis-condensation polymer of the organosilicon compound. Embedded image (Wherein R ¹ and R ² may be the same or different from each other, and include an alkyl group, a halogenated alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkenyl group, a hydrogen atom or a halogen atom. Shown: R ³
To R ⁶ may be the same or different and represent an alkoxy group, an alkyl group, a halogenated alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkenyl group, a hydrogen atom or a halogen atom. X
Is-(CH ₂ ) _n -,-(Ph)-(Ph is a benzene ring),-(CH ₂ ) _n- (P
h)-,-(CH ₂ ) _n- (Ph)-(CH ₂ ) _n -,-(S) _m -,-(CH ₂ ) _n- (S) _m- (C
H _{2) n} - indicates, m is an integer from 1 to 30, n is an integer of 1 to 30. ) 2. The inorganic oxide precursor is selected from the group consisting of a silicon compound (excluding the organosilicon compound represented by the formula (1)), a titanium compound, a zirconium compound, an antimony compound and a hydrolyzate thereof. The coating liquid for forming a transparent film according to claim 1, wherein the coating liquid is at least one of the following. 3. The polycondensate of an inorganic silicon obtained by hydrolyzing a polycondensate of an organosilicon compound represented by the formula (2) or an alkali metal silicate aqueous solution, wherein the inorganic oxide precursor is: The coating liquid for forming a transparent film according to claim 1 or 2, wherein R _a Si (OR ′) _4-a (2) (wherein R is a vinyl group, an aryl group, an acryl group, an alkyl group having 1 to 8 carbon atoms, a hydrogen atom or a halogen atom, and R ′ is a vinyl group. group, aryl group, acrylic group, alkyl group of carbon-based number _{1~8, -C 2 H 4 OC n} H 2n + 1 (n = 1
To 4) or a hydrogen atom, and a is an integer of 0 to 3. ) 4. A transparent film formed on a surface of the substrate, wherein the transparent film is formed by applying the coating liquid for forming a transparent film according to claim 1 and drying the transparent film. A substrate provided with a transparent coating, characterized by being obtained by the above method. 5. A transparent film formed of a substrate, a transparent conductive fine particle layer formed on the surface of the substrate, and a transparent film formed on the surface of the transparent conductive fine particle layer, wherein the transparent film is 3. A substrate with a transparent coating, which is obtained by applying the coating liquid for forming a transparent coating according to any one of 3 and drying. 6. A display device comprising a front plate made of the substrate with a transparent coating according to claim 4 or 5, wherein a transparent coating is formed on an outer surface of the front plate.