JP2002079616A - Transparent film-applied base material, coating solution for forming transparent film and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent film-applied base material having a transparent film, which has a low refractive index, low shrinkability and hydrophobicity and is excellent in the adhesion with a transparent conductive layer (transparent conductive film) or a base material, film strength, water resistance, chemical resistances or the like, formed thereto. SOLUTION: The transparent film-applied base material consists of the base material and the transparent film provided on the surface of the base material, and the transparent film contains (i) a matrix containing a fluorine substituted alkyl group-containing silicone component and (ii) inorganic compound particles having outer shell layers and made porous or hollow internally, and a porous or hollow state is held in the transparent film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate with a transparent film, a coating solution for forming a transparent film, and a display device provided with the substrate with a transparent film, and more particularly to an antireflection property, an antistatic property, and an electromagnetic wave shielding. A substrate with a transparent film on which a transparent film having excellent durability, water resistance, chemical resistance, and film strength, particularly excellent film scratch strength, is formed, and a film formation suitable for forming the transparent film. The present invention relates to a display device having a front plate composed of a coating solution for use and a substrate with a transparent film.

[0002]

BACKGROUND OF THE INVENTION Hitherto, it has been known to form an anti-reflection film on the surface of a substrate such as glass or plastic sheet in order to prevent reflection on the surface. For example, a coating of a material having a low refractive index such as magnesium fluoride is formed on the surface of glass or plastic by a vapor deposition method, a CVD method, or the like. However, these methods are costly.

There is also known a method in which a coating liquid containing fine silica particles is applied to a glass surface to form an antireflection coating having fine and uniform irregularities due to fine silica particles.
However, this method utilizes the fact that the regular reflection is reduced due to irregular reflection of light on the uneven surface formed by the silica fine particles, or uses an air layer generated in the fine particle gap to prevent reflection. In addition, it is difficult to fix the particles on the surface of the base material or to form a monolayer film, and it is not easy to control the reflectance of the surface.

For this reason, the applicant of the present application has reported that a transparent coating comprising low-refractive-index composite oxide fine particles in which the surfaces of porous fine particles are coated with silica and a silica-based coating-forming matrix has low reflectance and low-reflection glass. It can be used as a component of the surface coating of a low-reflection substrate such as a low-reflection sheet or film (Japanese Patent Laid-Open No. 7-13310).
No. 5). Furthermore, JP-A-10-40834 discloses that a layer containing SiO ₂ as a main component and containing silicones and / or ZrO ₂ is provided directly above a conductive layer made of conductive fine particles such as ultrafine particles of silver or a silver compound. Disclosed is a provided cathode ray tube, and a layer containing SiO ₂ as a main component and containing silicones and / or ZrO ₂ is a coating layer containing SiO ₂ as a main component and alkoxysilane or the like directly on the conductive fine particle layer. Are formed, and the upper and lower coating layers are simultaneously formed by firing. And JP-A-10-
Japanese Patent No. 40834 discloses that by using an alkoxysilane derivative having a fluoroalkyl group, a high-brightness and low surface resistance effective for preventing AEF, as well as an improvement in the water resistance and chemical resistance of the film and an anti-reflection film are provided. A cathode ray tube is disclosed.

However, such a transparent film does not always have sufficient abrasion, and the surface is easily scratched.
As a result, there has been a problem that the transparency and the antireflection property of the coated substrate are reduced. In the case of a transparent substrate used for a display panel such as a cathode ray tube, a fluorescent display tube, and a liquid crystal display panel, a coating having an antistatic function is formed on the surface of the substrate for the purpose of preventing the surface of the transparent substrate from being charged. It has also been known that a transparent film is formed on the surface of the antistatic film.

For example, as a film having an antistatic function, it has been known to form a conductive film having a surface resistance of about 10 ² to 10 ¹⁰ Ω / □. It is also known that electromagnetic waves are emitted from a display device such as a cathode ray tube. Therefore, apart from the above-described antistatic function, these electromagnetic waves and an electromagnetic field formed with the emission of the electromagnetic waves are also known. It has been known to form a conductive film for shielding electromagnetic waves having a low surface resistance of, particularly, 10 ² to 10 ⁴ Ω / □ on the surface of a display panel such as a cathode ray tube in order to shield the electromagnetic wave.

As a method for forming a film having an antistatic function as described above, a method of forming a conductive metal oxide on a surface of a substrate using a conductive film forming coating liquid containing conductive metal oxide fine particles such as ITO is used. A method for forming a conductive film containing fine particles of an object is known. As a method for forming a low surface resistance conductive film for shielding electromagnetic waves, a coating liquid for forming a conductive film containing fine particles of metal such as Ag is used. A method for forming a metal fine particle-containing coating on the surface of a substrate has been known.

However, in the conductive film formed on the substrate surface as described above, the fine metal particles contained in the conductive film are oxidized, or the fine metal particles grow due to ionization of the metal, and Corrosion of the metal fine particles may occur, which causes a problem in that the conductivity and light transmittance of the coating film decrease, and the display device lacks reliability. In addition, since the conductive oxide particles and the metal fine particles contained in the conductive film have a large refractive index, there is a problem that the irradiated light is reflected.

For this reason, as described above, a transparent film having a lower refractive index than the conductive film is further provided on the conductive film to prevent reflection and protect the conductive film. However, with conventional transparent coatings,
When formed on the surface of a conductive film containing conductive metal oxide fine particles such as ITO, visible light (wavelength range: 400 nm to 70 nm)
0 nm), the reflectance (bottom reflectance) is about 1% in the vicinity of the central wavelength range of 500 to 600 nm. Wavelength 500n
It has been required to reduce the luminous reflectance (average reflectance over the entire visible light range) as well as the luminous reflectance (reflectance near m).

In the case of a conventional transparent coating containing a matrix such as silica, when a transparent coating is formed on the surface of the conductive coating, the density of the conductive coating is determined by the difference in shrinkage between the transparent coating and the conductive coating. May be non-uniform, and there may be a portion where there is no electrical contact between the conductive fine particles, so that sufficient conductivity may not be obtained as a whole film. In addition, the transparent coating does not densify sufficiently during the heat treatment,
It becomes porous and cracks and voids are generated, and there is a problem that such cracks and voids are apt to be penetrated by chemicals such as acids and alkalis together with moisture.

Further, the acid or alkali which has entered the transparent film reacts with the surface of the base material to lower the refractive index, and when a conductive film is formed, the metal or metal in the conductive film is This causes a problem that the chemical resistance of the coating film is reduced, and the antistatic function and the effect of shielding electromagnetic waves are reduced. In the case where a transparent film is formed on the surface of the conductive film containing metal fine particles, the bottom reflection is as low as about 0.2%, but the bottom reflection is 400 nm and 7 nm.
High reflectance near 00 nm and luminous reflectance of 0.5
Since the size is about 1%, reflection (reflection) felt by eyes may be felt strongly or it may be difficult to suppress coloring of the reflected color. Improvement was required.

Therefore, the present inventors have further studied a low refractive index film formed on the surface of the conductive film. As a result, the matrix is made of a fluorine-containing silicone-based material having a fluoroalkyl group and has an outer shell layer. The transparent coating containing inorganic compound particles having a porous or hollow inside has an extremely low refractive index, and also has low shrinkage and hydrophobicity. It has been found that the adhesiveness to the conductive layer is high and the film strength, particularly the scratch strength, is excellent. And the substrate with the transparent coating on which such a transparent coating is formed is excellent in durability, water resistance, chemical resistance, antireflection performance, and antistatic when the transparent coating is formed on the conductive coating surface. It is found that it is possible to form a display device having excellent display performance, excellent electromagnetic wave shielding properties, low luminous reflectance, low reflection, coloration of reflection color, and excellent display performance. The present invention has been completed.

[0013]

SUMMARY OF THE INVENTION The present invention has a low refractive index, low shrinkage and hydrophobicity due to containing specific inorganic compound particles and a specific fluorine-containing silicone-based substance, and a transparent conductive layer (transparent conductive layer). Coating) or adhesion to substrate, film strength,
It is an object of the present invention to provide a substrate with a transparent coating on which a transparent coating excellent in water resistance, chemical resistance and the like is formed. The present invention also provides a coating liquid for forming a film which is preferably used for forming such a transparent film, and a display device having the transparent film-coated substrate and having excellent antistatic properties and electromagnetic shielding properties. It is an object.

[0014]

The substrate with a transparent coating according to the present invention comprises a substrate and a transparent coating provided on the surface of the substrate, wherein the transparent coating comprises (i) a fluorine-substituted alkyl group-containing silicone component. A matrix containing, (ii) having an outer shell layer, including inorganic compound particles having a porous or hollow interior,
Further, it is characterized in that the porous film or the cavity is maintained in the transparent film.

The substrate with a transparent film according to the present invention comprises a substrate, a conductive layer provided on the surface of the substrate, and a transparent film provided on the surface of the conductive layer. , (I)
A matrix containing a fluorine-substituted alkyl group-containing silicone component, and (ii) having an outer shell layer, containing inorganic compound particles having a porous or hollow interior, and in the transparent coating, a porous or hollow Is maintained.

A display device according to the present invention is characterized in that the display device includes a front plate made of the substrate with a transparent film, and a transparent film is formed on an outer surface of the front plate. The cathode ray tube according to the present invention is characterized in that it has a front plate composed of the base material with a transparent coating, and a transparent coating is formed on the outer surface of the front plate.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. The substrate with a transparent coating according to the present invention is a substrate, a transparent coating or a substrate provided on the surface of the substrate, a transparent conductive layer provided on the surface of the substrate, and provided on the surface of the transparent conductive layer. And a transparent coating.

[Substrate] Examples of the substrate used in the present invention include a flat plate, a film, a sheet or other molded body made of glass, plastic, metal, ceramic or the like, for example, a substrate such as a glass bottle, a PET bottle, or a sheet glass. Can be In the present invention, the following conductive layer may be provided on such a substrate surface.

[Conductive layer] As the conductive layer, 10 ¹² Ω / □
There is no particular limitation as long as it has the following surface resistance, and a known conductive material can be used. The thickness of the conductive layer is 5 to 200 nm, preferably 10 to 200 nm.
The thickness is preferably in the range of from 150 nm to 150 nm. With a thickness in this range, a substrate having excellent electromagnetic shielding effect and antistatic effect can be obtained.

The conductive layer having an antistatic function has a surface resistance of about 10 ⁴ to 10 ¹² Ω / □, and the conductive layer for electromagnetic shielding has a low surface resistance of 10 ² to 10 ⁴ Ω / □. One having a surface resistance is formed. Even if a transparent coating is provided on the surface of the conductive layer as in the present invention, the surface resistance of the conductive layer does not substantially fluctuate. Two or more conductive layers may be formed.

Examples of the transparent conductive material include metals, conductive inorganic oxides, inorganic conductive materials such as conductive carbon, polyacetylene, polypyrrole, polythiophene, polyaniline, polyisothianaphthene, polyazulene, polyphenylene, poly-p-phenylene, Poly-p-phenylenevinylene, poly-2,5-thienylenevinylene, polyacetylene,
Conductive polymers such as polyacene and polyperinaphthalene are used.

The conductive polymer may be doped with a dopant ion, if necessary.
Among these, as the conductive material, an inorganic conductive material such as a metal, a conductive inorganic oxide, and conductive carbon is preferable. Usually, when a conductive layer is formed from these conductive materials, fine metal particles (that is, fine metal particles) or fine conductive inorganic oxides (conductive inorganic oxide fine particles) are used (in the present specification). These may be simply referred to as conductive fine particles).

As the “metal fine particles” used in the present invention, conventionally known metal fine particles can be used. The metal fine particles may be metal fine particles composed of a single component, or two or more metal components may be used. The composite metal fine particles may be included. 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 decrease in conductivity and light transmittance is small. It has excellent reliability.

Such metal fine particles include Au, Ag,
Pd, Pt, Rh, Ru, Cu, Fe, Ni, Co, Sn, Ti, In, Al, T
Fine particles of a metal selected from the group consisting of a and Sb. Further, as the composite metal fine particles, Au, Ag, Pd, Pt,
Composite metal fine particles of two or more metals selected from the group consisting of 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-Pd, Au-Rh, Pt-P
d, Pt-Rh, Fe-Ni, Ni-Pd, Fe-Co, Cu-Co, Ru-Ag,
Au-Cu-Ag, Ag-Cu-Pt, Ag-Cu-Pd, Ag-Au-Pd, A
u-Rh-Pd, Ag-Pt-Pd, Ag-Pt-Rh, Fe-Ni-Pd, Fe-
Co-Pd, Cu-Co-Pd and the like.

Also, Au, Ag, Pd, Pt, Rh, Cu, Co, Sn,
When metal particles selected from the group consisting of In and Ta are used, some of the particles may be in an oxidized state or may contain an oxide of the metal. Further, P and B atoms may be contained in combination. Such metal fine particles can be obtained by, for example, the following known method (Japanese Patent Laid-Open No. 10-1886).
No. 81).

(I) For example, there is a method of reducing one kind of metal salt or two or more kinds of metal salts simultaneously or separately in a mixed solvent of alcohol and water. In this method, a reducing agent may be added as necessary. As a reducing agent, ferrous sulfate, trisodium citrate, tartaric acid,
Examples include sodium borohydride and sodium hypophosphite. Moreover, you may heat-process in a pressure vessel at the temperature of about 100 degreeC or more. (ii) In addition, in the dispersion of the single-component metal fine particles or alloy fine particles, metal fine particles or ions having a standard hydrogen electrode potential higher than that of the metal fine particles or alloy fine particles are made to exist on the metal fine particles or / and alloy fine particles. A method of depositing a metal having a high standard hydrogen electrode potential can also be employed. In this method, a metal having a higher standard hydrogen electrode potential may be deposited on the obtained composite metal fine particles. Further, it is preferable that such a metal having the highest standard hydrogen electrode potential is 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 is present in a large amount in the surface layer of the composite metal fine particles, oxidation and ionization of the composite metal fine particles can be suppressed, and particle growth due to ion migration or the like can be suppressed. further,
Since such composite metal fine particles have high corrosion resistance, a decrease in conductivity and light transmittance can be suppressed.

The average particle diameter of the metal fine particles used is 1 to
It is desirably in the range of 200 nm, preferably 2 to 70 nm. When the particle size falls within such a range, the formed conductive layer becomes transparent. The average particle diameter of the metal fine particles is 20
If it exceeds 0 nm, the absorption of light by the metal increases, the light transmittance of the particle layer decreases, and the haze increases. For this reason, if 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.

As the conductive inorganic 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. .

The average particle size of these conductive inorganic fine particles is as follows:
It is preferably in the range of 1 to 200 nm, preferably 2 to 150 nm. Such a conductive layer can be prepared using a coating liquid for forming a conductive film. The coating liquid for forming a conductive film contains the conductive fine particles and a polar solvent.

The polar solvent used in the coating solution for forming the conductive film is 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 and diethylene glycol monoethyl ether; acetone;
Ketones such as methyl ethyl ketone, acetylacetone, and acetoacetate are exemplified. These may be used alone or as a mixture of two or more.

When a coating solution containing fine metal particles is used, it is possible to form a transparent conductive layer having a surface resistance of about 10 ² to 10 ⁴ Ω / □ in which an electromagnetic wave shielding effect is exhibited. When the conductive layer for electromagnetic shielding is formed using metal fine particles, the metal fine particles have a concentration of 0.05 to 5% by weight, preferably 0.5 to 5% by weight in the coating liquid for forming a conductive film.
Desirably, it is contained in an amount of 1 to 2% by weight.

When the amount of the fine metal particles in the coating solution for forming a conductive film is less than 0.05% by weight, the film thickness of the obtained film becomes thin, so that sufficient conductivity may not be obtained. is there. On the other hand, if 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. The electroconductive film-forming coating liquid, together with the fine metal particles, may be contained the above-conductive inorganic fine particles, 10 ² electromagnetic wave shielding effect is obtained
When a transparent conductive layer having a surface resistance of about 10 ⁴ Ω / □ is to be obtained,
The conductive inorganic fine particles described above may be contained in an amount of 4 parts by weight or less. When the amount of the conductive inorganic fine particles exceeds 4 parts by weight, the conductivity is lowered and the electromagnetic wave shielding effect may be lowered, which is not preferable.

When the conductive inorganic fine particles are contained together with such metal fine particles, a transparent conductive fine particle layer having more excellent transparency can be obtained as compared with the case where the transparent conductive fine particle layer is formed only with metal fine particles. Can be formed. Further, by containing the conductive inorganic fine particles, the transparent conductive layer can be formed at low cost. Further, in the case where the conductive layer has a surface resistance of about 10 ⁴ to 10 ¹² Ω / □ having an antistatic function, usually, only the conductive inorganic fine particles are contained in the coating liquid for forming a conductive film. Good. In the coating liquid for forming a conductive film, the conductive inorganic fine particles are contained in an amount of 0.1%.
It is desirable that it be contained in an amount of 1 to 10% by weight, preferably 0.5 to 5% by weight. When the amount of the conductive inorganic fine particles in the coating liquid for forming a conductive film is less than 0.1% by weight, the film thickness of the obtained film is small, so that sufficient antistatic performance may not be obtained. On the other hand, when the amount of the conductive fine particles in the coating liquid for forming a conductive film exceeds 10% by weight, the film thickness is increased, the light transmittance is reduced, the transparency is deteriorated, and the appearance is also deteriorated.

Further, dyes, pigments and the like may be added to these coating liquids for forming a conductive film so that the visible light transmittance is constant in a wide wavelength range of visible light. The solid content concentration (total amount of metal fine particles and / or conductive fine particles other than metal fine particles and additives such as dyes and pigments added as necessary) in the coating liquid for forming a conductive film used in the present invention is as follows. It is preferably 15% by weight or less, and more preferably 0.15 to 5% by weight, from the viewpoint of fluidity of the liquid and dispersibility of particulate components such as metal fine particles in the coating liquid.

The coating liquid for forming a conductive film used in the present invention may contain a metal component after forming the film and a matrix component acting as a binder for the conductive fine particles other than the metal fine particles. As such a matrix component, conventionally known ones can be used. In the present invention, silica, a silica-based composite oxide, zirconia, and a precursor of one or more oxides selected from the group consisting of antimony oxide are used. In particular, a hydrolyzed polycondensate of an organosilicon compound such as alkoxysilane or a silicic acid obtained by dealkalizing an aqueous solution of an alkali metal silicate is preferably used. In addition, a resin for paint or the like can be used.

Such a matrix component is used 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.
It may be contained in parts by weight. Further, in order to improve the dispersibility of the conductive fine particles, an organic stabilizer may be contained in the coating liquid for forming a conductive film. 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. And its salts, sulfonates, organic sulfonates, phosphates, organic phosphates, heterocyclic compounds, and mixtures thereof.

Such an organic stabilizer differs depending on the type of the organic stabilizer, the particle size of the conductive fine particles, and the like.
The amount may be 0.005 to 0.5 part by weight, preferably 0.01 to 0.2 part by weight, per 1 part by weight of the fine particles. 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.

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

When the above-mentioned matrix forming component is contained in the coating liquid for forming a conductive film, a heat treatment may be performed to cure the matrix component. In the heat treatment, the dried coating film is heated to cure the matrix component. The heat treatment temperature at this time is 1
It is desirable that the temperature is not lower than 00 ° C, preferably 150 to 300 ° C. If the temperature is lower than 100 ° C., the matrix component may not be cured sufficiently. The upper limit of the heat treatment temperature varies depending on the type of the base material, but may be lower than the temperature at which the base material does not decompose, dissolve or burn.

Further, as the treatment for curing the matrix component, in addition to the heat treatment, a curing treatment by electromagnetic wave irradiation, a treatment in a gas atmosphere in which curing is promoted, and the like can be performed. [Transparent film] In the present invention, a transparent film is formed on the surface of the substrate or the surface of the conductive layer. The transparent coating contains the following inorganic compound particles and a matrix.

Inorganic Compound Particles The inorganic compound particles used in the present invention have an outer shell layer,
The particles are porous or hollow inside. The porosity or cavity inside the inorganic compound particles is maintained in the transparent coating.

FIGS. 1 (a) to 1 (d) show schematic sectional views of such inorganic compound particles. 1 (a) to 1 (d), the subscript 1 is an outer shell layer, the subscript 2 is porous (substance), and the subscript 3 is a cavity. The inorganic compound particles used in the present invention are shown in FIG.
As shown in FIG. 1 (a), even if the inside of the outer shell layer is porous, as shown in FIG. However, Fig. 1 (c)
As in (d), the outer shell layer may include a porous substance and a cavity.

The cavity 3 is filled with contents such as a solvent (to be described later) and a gas used when preparing the inorganic compound particles. The average particle diameter of such inorganic compound particles is 5 to 3
It is desirably in the range of 00 nm, preferably 10 to 200 nm. The average particle diameter of the inorganic compound particles to be used is appropriately selected according to the thickness of the formed transparent film.

The thickness of the outer shell layer is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. When the thickness of the outer shell layer is less than 1 nm, the particles may not be completely covered, and a fluorine-containing matrix precursor such as a fluorine-containing silicone compound monomer or oligomer used for forming a matrix described later may be used. In some cases, the body easily enters the inside of the inorganic compound particles, the porosity inside decreases, and the effect of a low refractive index may not be sufficiently obtained.
Further, when the thickness of the outer shell layer exceeds 20 nm, fluorine-containing matrix precursors such as fluorine-containing silicone compound monomers and oligomers do not enter the inside,
Since the ratio of the outer shell layer is increased, the ratio of the porous substance inside the particles is reduced, and the effect of the low refractive index may not be sufficiently obtained.

Further, particles having a hollow inside (FIG. 1 (b))
When the thickness of the outer shell layer is less than 1 nm, the particle shape may not be maintained. However, the effect of the low refractive index may not be sufficiently obtained. The porosity of the inorganic compound particles used in the present invention is 10
Desirably, it is at least volume%. In the case of particles in which the inside of the outer shell layer is porous, the porosity is 10% by volume to 20%.
It is in the range of less than volume%. In the case of particles having a hollow inside the outer shell layer, the porosity is 20% by volume or more.

The outer shell layer of the inorganic compound particles contains silica.
It is preferable to use it as a main component. In addition, outside the inorganic compound particles
The shell layer may contain components other than silica,
Typically, Al_TwoO_Three, B_TwoO_Three, TiO_Two, ZrO_Two, SnO_Two,
CeO_Two, P_TwoO_Five, Sb_TwoO_Three, Sb_TwoO_Five, MoO_Three, ZnO,
WO_ThreeAn oxide selected from the group consisting of Outside
Compounds that constitute the porosity inside the shell layer (hereinafter referred to as porous materials
) Is composed of silica, silica and silica
Consisting of inorganic compounds other than mosquito, CaF_Two, NaF,
NaAlF₆, MgF and the like. this
Especially, complex oxidation of silica and inorganic compounds other than silica
Those consisting of objects are preferred. Inorganic compounds other than silica
As Al_TwoO_Three, B_TwoO_Three, TiO_Two, ZrO_Two, Sn
O_Two, CeO _Two, P_TwoO_Five, Sb_TwoO_Three, Sb_TwoO_Five, MoO_Three, Zn
O, WO_ThreeAt least one selected from the group consisting of
Can be. Compounds that constitute such a porous material (porous material)
Material), silica is converted to SiO 2_TwoExpressed with nothing other than silica
Compounds with oxides (MO_x), The molar ratio MO_x
/ SiO_TwoBut 0.0001 to 1.0, preferably 0.00
It is desirable to be in the range of 01 to 0.3. Porous material
Molar ratio of_x/ SiO_TwoIs less than 0.0001
Is difficult, and even if obtained, the refractive index is even lower.
You don't get anything. Also, the molar ratio of the porous material M
O_x/ SiO_Two However, if it exceeds 1.0, the ratio of silica is small.
Particles with low pore volume and low refractive index
You may not get a child.

When the outer shell layer contains silica as a main component, the inorganic compound particles used in the present invention preferably have a refractive index of less than 1.41. When the inside of the outer shell layer of such inorganic compound particles is porous containing silica as a main component, the refractive index is in the range of 1.41 to 1.37,
The porosity at this time is in the range of 10% by volume or more and less than 20% by volume. Further, when the inside of the outer shell layer is hollow (including the case where the outer shell layer is made of a porous material and a hollow), the refractive index is less than 1.37, preferably less than 1.36, and the porosity is 20% by volume or more. Preferably, it is at least 22% by volume. The use of such low-refractive-index particles makes it possible to obtain a coated substrate having particularly excellent reflection performance.

As for the refractive index, the weight ratio (matrix (SiO ₂ ): inorganic compound particles (MO _x + SiO ₂ )) of the SiO ₂ matrix forming component liquid (M) and the inorganic compound particles was calculated as follows. 100: 0, 90:10, 80:20, 60:40, 50:50, 25:75 to prepare a mixed coating solution for refractive index measurement, each coating solution, the surface at 50 ℃ 3 on the kept silicon wafer
After applying each by the spinner method at 00 rpm and heating at 160 ° C. for 30 minutes, the refractive index of the refractive index measuring film formed by the ellipsometer was measured. : (MO _x + SiO ₂ ) / [particles:
(MO _x + SiO ₂ ) + matrix: SiO ₂ ) was plotted, and the refractive index when the particles were 100% was obtained by extrapolation, which was defined as the refractive index of the inorganic compound particles.

The porosity is calculated from the difference from the refractive index (1.45) of pure SiO ₂ using the refractive index obtained by the above method to calculate the porosity contained in air. I asked. The cavity in the outer shell layer is filled with contents such as a solvent, a gas, and a part of a porous substance used in preparing the particles. Further, the solvent may contain an unreacted product of the particle precursor used in preparing the particles, the used catalyst, and the like. These contents may be composed of a single component, or may be a mixture of a plurality of components. Inorganic compounds inorganic compound other than silica and silica in the particles: the molar ratio MO _x / SiO ₂ of (MO _X in terms of oxide) 0.0001 to 1.0, preferably 0.0001 to 0.
It is desirably in the range of 3.

The porosity or cavity inside the outer shell layer of such inorganic compound particles is maintained in the transparent film as described above. FIG. 2 shows a cross-sectional TEM photograph of the inorganic compound particles having a hollow inside the outer shell layer. The outer shell layer is made of silica (thickness: 15 nm, particle size: 96 nm), and has a refractive index of 1.31 and a porosity of 31%. When the ratio of the cavities is calculated with the inside as air, the ratio of the cavities is 32%, and it is clear that the cavities are formed inside the outer shell layer.

FIG. 3 shows a cross-sectional TEM image of the inorganic compound particles having a hollow inside the outer shell layer when a transparent film is formed together with a matrix described later.
A photograph is shown. As is clear from FIG. 3, the matrix component does not enter the cavity, and the cavity is maintained even in the transparent coating. Preparation of Inorganic Compound Particles As a method for producing such inorganic compound particles, for example, a method for preparing composite oxide colloid particles disclosed in JP-A-7-133105 is suitably employed.

Specifically, the inorganic compound particles are composed of silica and
When composed of an inorganic compound other than silica, the following first to first
It is manufactured by the third step. First step: Preparation of porous substance precursor particles In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared,
Alternatively, a mixed aqueous solution of a silica raw material and an inorganic compound raw material other than silica is prepared, and this aqueous solution is gradually added to an alkaline aqueous solution having a pH of 10 or more with stirring according to the composite ratio of the target composite oxide. Thus, precursor particles of a porous substance (hereinafter referred to as porous substance precursor particles) are prepared.

As the silica raw material, a silicate of an alkali metal, ammonium or an organic base is used. As the alkali metal silicate, sodium silicate (water glass) or potassium silicate is used. As an organic base,
Examples include quaternary ammonium salts such as tetraethylammonium salts and amines such as monoethanolamine, diethanolamine and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound, or the like to a silicic acid solution.

As a raw material of the inorganic compound other than silica, an alkali-soluble inorganic compound is used. Specifically, Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo,
Examples include oxo acids of elements selected from Zn, W, and the like, and alkali metal salts or alkaline earth metal salts, ammonium salts, and quaternary ammonium salts of the oxo acids.
More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

The pH value of the mixed aqueous solution changes at the same time as mixing the aqueous solutions of the raw materials as described above, but there is no particular operation for controlling the pH value to a predetermined range. The aqueous solution finally has a pH value determined by the type of inorganic oxide and its mixing ratio. At this time, the addition rate of the aqueous solution is not particularly limited. When the porous substance inside the inorganic compound particles is a composite oxide, a dispersion of seed particles can be used as a starting material when producing the porous substance precursor particles. The seed particles are not particularly limited, but fine particles of an inorganic oxide such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or a composite oxide of these are used. Can be. Further, the porous substance precursor particle dispersion obtained by the above-described production method may be used as a seed particle dispersion. When a seed particle dispersion is used, after adjusting the pH of the seed particle dispersion to 10 or more, an aqueous solution of the compound is added to the seed particle dispersion while being stirred into the above-described alkaline aqueous solution. Also in this case, it is not always necessary to control the pH of the dispersion. In this way, when the seed particles are used, the particle size of the prepared porous substance precursor particles can be easily controlled, and particles having a uniform particle size can be obtained.

The above silica raw materials and inorganic compound raw materials have high solubility on the alkali side. However, if the two are mixed in this pH range where the solubility is large, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these compounds precipitate and grow into fine particles, or seed particles grow. Precipitates on top and particle growth occurs. Therefore, it is not always necessary to control the pH as in the conventional method when depositing and growing particles.

In the first step, the composite ratio of silica and the inorganic compound other than silica is determined by converting the inorganic compound to an oxide (MO _x ).
And the molar ratio of MO _x / SiO ₂ is 0.05 to 2.
0, preferably in the range of 0.2 to 2.0. Within this range, the smaller the proportion of silica, the greater the pore volume of the porous material. In addition, MO _x /
Even if the molar ratio of SiO ₂ exceeds 2.0, the pore volume of the porous material hardly increases. On the other hand, when the molar ratio of MO _x / SiO ₂ is less than 0.05, the pore volume becomes small. When a cavity is formed in the outer shell layer of an inorganic compound, MO
the molar ratio of _x / SiO ₂ is preferably in the range of 0.25 to 2.0. If the molar ratio of MO _x / SiO ₂ is less than 0.25, it may not be possible to form a cavity in the next second step.

Second step: Particle formation from the porous material precursor particles
In the second step of removing inorganic compounds other than silica, at least a portion of the inorganic compound other than silica (elements other than silicon and oxygen) is selectively removed from the porous substance precursor particles obtained in the first step. I do. As a specific removal method, the inorganic compound in the porous substance precursor particles is dissolved and removed using a mineral acid or an organic acid, or is ion-exchanged and removed by contact with a cation exchange resin.

The porous substance precursor particles obtained in the first step are particles having a network structure in which silicon and an inorganic compound constituent element are bonded via oxygen. Inorganic compounds (elements other than silicon and oxygen) from such porous substance precursor particles
By removing, porous particles having a larger volume and a larger pore volume are obtained, and the porous particles constitute the porosity inside the outer shell layer.

If the amount of the inorganic compound other than silica removed from the porous material precursor particles is increased, particles having a hollow inside the outer shell layer can be prepared. Further, prior to removing the inorganic compound other than silica from the porous substance precursor particles, the porous substance precursor particle dispersion obtained in the first step is treated with a silica obtained by dealkalizing an alkali metal salt of silica. It is preferable to add an acid solution or a hydrolyzable organosilicon compound to form a silica protective film on the surface of the porous substance precursor particles. The thickness of the silica protective film may be 0.5 to 15 nm. Even if a silica protective film is formed, since the silica protective film formed in this step is porous and thin, it is necessary to remove the above-mentioned inorganic compound other than silica from the porous substance precursor particles. Is possible.

By forming the silica protective film in this manner, the above-mentioned inorganic compound other than silica can be removed from the porous substance precursor particles while maintaining the particle shape. Further, by forming a silica protective film, when forming a silica shell layer described later, the pores of the porous particles are formed of a hydrolyzable organosilicon compound or a silicic acid solution which is a silica shell layer forming component. Therefore, the silica outer shell layer described later can be formed without lowering the pore volume.

When the amount of the inorganic compound to be removed from the porous substance precursor particles is small, it is not always necessary to form a protective film because the particles are not broken. When particles having a hollow inside of the outer shell layer are prepared, it is particularly desirable to form this silica protective film. When preparing particles having a hollow inside of the outer shell layer, by removing the inorganic compound, a silica protective film and a solvent in the silica protective film, a part of the porous material remaining undissolved and remaining. When a silica outer shell layer described below was formed on the particle precursor, the formed silica protective film and silica outer shell layer became an outer shell layer, and a cavity was formed inside. Inorganic compound particles are obtained.

The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, so that it may be difficult to remove inorganic compounds other than silica from the porous substance precursor particles. The hydrolyzable organosilicon compound used for forming the silica protective film includes a compound represented by the general formula R _n Si (OR ′) _4-n
An alkoxysilane represented by [R, R ': a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group, an acryl group, and n = 0, 1, 2, or 3] can be used. In particular,
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

As a method of addition, a solution obtained by adding a small amount of an alkali or an acid as a catalyst to a mixed solution of these alkoxysilane, pure water and alcohol is added to the dispersion of the porous substance precursor particles, The silicic acid polymer produced by hydrolyzing the silane is deposited on the surface of the porous substance precursor particles. At this time, the alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, hydroxides of alkali metals and amines can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

When the dispersion medium of the porous substance precursor particles is water alone or when the ratio of water to the organic solvent is high,
It is also possible to form a silica protective film using a silicic acid solution. When using a silicic acid solution, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time, an alkali is added to deposit the silicic acid solution on the surface of the porous substance precursor particles. In addition, you may produce a silica protective film using a silicic acid liquid and the said alkoxysilane together.

As described above, by removing the inorganic compound other than silica from the porous substance precursor particles, the dispersion liquid of the porous particles or the precursor dispersion liquid of the particles having a hollow inside of the outer shell layer is obtained. Prepared. Third Step: Formation of Silica Shell Layer In the third step, a hydrolyzable organosilicon compound is added to the porous particle dispersion prepared in the second step (including the precursor dispersion of particles for forming cavities). Alternatively, the surface of the porous particles (particle precursors for forming cavities) is coated with a hydrolyzable organosilicon compound or a polymer such as a silicic acid solution by adding a silicic acid solution or the like to form a silica outer shell layer. Form.
It is desirable to use the hydrolyzable organosilicon compound alone. When a silicic acid solution is used, it is desirable to use it together with a hydrolyzable organic silicon compound, and it is desirable that the amount of silicic acid is less than 30% by weight.

Examples of the hydrolyzable organosilicon compound used for forming the silica outer layer include the above-mentioned general formula R _n Si (OR ′) _4-n [R, R ′: alkyl group, aryl group , Vinyl group, hydrocarbon group such as acrylic group, n = 0,
1, 2 or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

A solution obtained by adding a small amount of an alkali or an acid as a catalyst to a mixed solution of these alkoxysilanes, pure water and alcohol was added to the porous particle dispersion, and the mixture was produced by hydrolyzing the alkoxysilanes. A silicic acid polymer is deposited on the surface of the porous particles to form an outer shell layer. At this time, alkoxysilane, alcohol,
The catalyst may be added to the dispersion at the same time. As the alkali catalyst, ammonia, hydroxides of alkali metals and amines can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

In the case where the dispersion medium of the porous particles (particle precursor in the case of forming cavities) is water alone or a mixed solvent with an organic solvent and a mixed solvent having a high ratio of water to the organic solvent, The outer shell layer may be formed using a silicic acid solution. The silicic acid liquid is an aqueous solution of a low-polymerized silicic acid obtained by subjecting an aqueous solution of an alkali metal silicate such as water glass to an ion exchange treatment and dealkalizing.

When a silicic acid solution is used, the silicic acid solution is added to a dispersion of porous particles (in the case of forming cavities, a precursor of the particles) and an alkali is added at the same time to add a low-silicic acid polymer to the porous particles. An outer shell layer is formed by depositing on the surface. The silicic acid solution may be used together with the above-mentioned alkoxysilane for forming the outer shell layer. The amount of the organosilicon compound or the silicic acid solution used for forming the outer shell layer may be such that the surface of the porous particles can be sufficiently coated. ~ 20n
m in the porous particle dispersion. When the silica protective film is formed, the organosilicon compound or the silicic acid solution is added in such an amount that the total thickness of the silica protective film and the silica outer layer is in the range of 1 to 20 nm.

Next, if necessary, the dispersion liquid of the particles having the outer shell layer formed thereon is subjected to a heat treatment. The heat treatment densifies the formed silica shell layer. The heating temperature at this time is not particularly limited as long as the pores of the silica outer layer can be closed, and is preferably in the range of 80 to 300 ° C.
When the heating temperature is higher than the boiling point of the solvent, a pressure vessel such as an autoclave may be used. If the heat treatment temperature is lower than 80 ° C., the fine pores of the silica shell layer may be closed and densification may not be achieved, and a long processing time may be required. When the heat treatment temperature exceeds 300 ° C. for a long time, if the inside of the outer shell layer is porous,
The compound (porous substance) constituting the porous material may be densified, and the effect of a low refractive index may not be obtained.

The inorganic compound particles thus obtained have a low refractive index of 1.41 or less. Therefore, such an inorganic compound particle has a low refractive index because the porosity of the porous substance is retained inside or the inside is hollow. The matrix transparent coating contains a fluorine-substituted alkyl group-containing silicone component as a matrix. As the fluorine-substituted alkyl group-containing silicone component, the following formulas (1) to (1)
Those having the structural unit represented by (3) are preferable.

[0073]

Embedded image

In the formula, R ¹ represents a fluoroalkyl group having ¹ to 16 carbon atoms or a perfluoroalkyl group, and R ² represents an alkyl group having 1 to 16 carbon atoms, a halogenated alkyl group,
An aryl group, an alkylaryl group, an arylalkyl group, an alkenyl group, or an alkoxy group, a hydrogen atom or a halogen atom. X is _{- (C a H b F c} ) - indicates, a is an integer from 1 to 12, b + c is 2a, b is 0
An integer of from 24 to 24, and c represents an integer of from 0 to 24. As such X, a group having a fluoroalkylene group and an alkylene group is preferable.

The matrix forming such a structural unit is usually derived from a fluorine-containing silicone compound having a fluoroalkyl group represented by the following formula (4) or (5).

[0076]

Embedded image

In the formula, R ¹ represents a fluoroalkyl group having ^{1 to} 16, preferably 3 to 12 carbon atoms or a perfluoroalkyl group, and R ^{2 to} R ⁷ represent 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms. Alkyl group, carbon number 1-6, preferably 1-4
A halogenated alkyl group; an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms;
An alkylaryl group, an arylalkyl group, an alkenyl group having 2 to 8, preferably 2 to 6 carbon atoms, or an alkoxy group having 1 to 6, preferably 1 to 3 carbon atoms, a hydrogen atom or a halogen atom.

X represents-(C _{a Hb} F _c )-, and a represents 1 to 1
An integer of 2, b + c is 2a, b is an integer of 0 to 24,
c shows the integer of 0-24. As such X, a group having a fluoroalkylene group and an alkylene group is preferable. Specifically, examples of such a fluorine-containing silicone compound include heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecyltrichlorosilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, and tridecafluorooctyl. Trimethoxysilane, and the chemical formula (Me
O) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (MeO) ₃ methoxydisilane compound and the like.

When the matrix contains a silicone component containing a fluorine-substituted alkyl group, the formed transparent film itself has hydrophobicity, so that the transparent film is not sufficiently densified and porous. In addition, even when cracks or voids are present, penetration of the transparent coating by chemicals such as moisture, acid, and alkali is suppressed. Further, there is no reaction between fine particles such as metals contained in the surface of the substrate and the lower conductive layer and chemicals such as moisture and acids and alkalis. For this reason, such a transparent coating has excellent chemical resistance.

When the matrix contains a fluorine-substituted alkyl group-containing silicone component, not only such a hydrophobic property but also a good sliding property (low contact resistance) and therefore a transparent coating excellent in scratch strength are obtained. Can be obtained. Further, when the matrix contains a fluorine-substituted alkyl group-containing silicone component having such a structural unit, when a conductive layer is formed as a lower layer, the contraction rate of the matrix is equal to or close to that of the conductive layer. Therefore, a transparent film having excellent adhesion to the conductive layer can be formed. Further, when the transparent film is subjected to the heat treatment, the conductive layer does not peel off due to the difference in the shrinkage ratio, and there is no portion where the transparent conductive layer has no electrical contact. Therefore, sufficient conductivity can be maintained for the entire film.

The transparent film containing the fluorine-substituted alkyl group-containing silicone component and the inorganic compound particles has high scratch strength, high film strength evaluated by eraser strength or nail strength, and high pencil hardness. An excellent transparent film can be formed on the film. In the present invention,
Such a matrix may contain components other than the above-mentioned fluorine-substituted alkyl group-containing silicone component.

Other components include silica, zirconia,
Examples include inorganic oxides such as titania, and composite oxides such as silica-zirconia, silica-titania, and titania-zirconia. Of these, silica is particularly desirable. The amount of the fluorine-substituted alkyl group-containing silicone component having the structural units represented by the above formulas (1) to (3) in the matrix is 0.1 to 70% by weight in terms of SiO ₂ in the matrix. Is preferably in the ratio of More preferably, it is in the range of 1 to 30% by weight.

When the amount of the fluorine-substituted alkyl group-containing silicone component having the structural units represented by the above formulas (1) to (3) in the matrix is less than 0.1% by weight, the fluorine-substituted alkyl group-containing silicone component , The slipperiness of the surface of the formed transparent film is not sufficiently exhibited, and a transparent film having excellent scratch strength may not be obtained. Other components (such as inorganic oxide precursors) have a higher shrinkage ratio than the fluorine-substituted alkyl group-containing silicone component. Therefore, when the amount of other components increases, the shrinkage ratio of the transparent coating itself increases, When performing heat treatment (curing treatment)
If the transparent film curves the substrate or, for example, a conductive layer is formed underneath, a difference in the shrinkage ratio between the transparent film and the conductive film occurs, and the conductive layer peels off or an electrical In some cases, no contact occurs, and sufficient conductivity may not be obtained for the entire substrate. Further, since the shrinkage is large, the film becomes too dense, and the porosity cannot be obtained, so that the effect of lowering the refractive index of the transparent film may be insufficient.
Furthermore, since the content of the fluorine compound having a low electron density is small, the lowering of the refractive index of the transparent film tends to be insufficient. Furthermore, since the amount of the fluorine-substituted alkyl group-containing silicone component is small, the hydrophobicity of the transparent film becomes insufficient, and sufficient chemical resistance may not be obtained.

When the amount of the fluorine-substituted alkyl group-containing silicone component having the structural units represented by the above formulas (1) to (3) in the matrix exceeds 70% by weight in terms of SiO ₂ , the transparent film is formed. The strength of the transparent film is reduced due to being too porous, or the film strength such as the transparent film eraser strength or the scratch strength is reduced, and further, the adhesion to the base material or the conductive layer may be insufficient. is there.

The matrix used in the present invention preferably has a refractive index of 1.6 or less. When other components are contained in the matrix together with the fluorine-substituted alkyl group-containing silicone component, the mixture preferably has a refractive index of 1.6 or less. In the present invention, the weight ratio of the matrix and the inorganic compound particles in the transparent coating (matrix / inorganic compound particles, both in terms of oxide) is in the range of 0.1 to 10, preferably 0.2 to 5. Desirably.

Transparent Film Forming Coating Solution The transparent film is formed using, for example, a transparent film forming coating solution containing a matrix precursor and the inorganic compound particles. Matrix precursor As the matrix precursor, the fluorine-containing silicone compound represented by the above formula (4) or (5), a hydrolyzate of the fluorine-containing silicone compound, a polycondensate of the hydrolyzate ( Hereinafter, a fluorine-substituted alkyl group-containing silicone component precursor is used.

Such a fluorine-substituted alkyl group-containing silicone component precursor preferably has a molecular weight in the range of 500 to 10,000 as a number average molecular weight in terms of polystyrene, and particularly preferably 700 to 2500. The matrix precursor may contain the inorganic oxide precursor and / or the precursor of the inorganic composite oxide as necessary.

As a precursor of an inorganic oxide and / or a precursor of a composite oxide which may be contained as required, a silica precursor is preferable, and in particular, a partial hydrolyzate of a hydrolyzable organosilicon compound, A hydrolyzed polycondensate or a silicic acid solution obtained by dealkalizing an aqueous alkali metal silicate solution, particularly a silica precursor which is a hydrolyzed polycondensate of an alkoxysilane represented by the following general formula [A], is preferable. .

R _a Si (OR ′) _4-a [A] (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 1 to 3. Examples of such alkoxylans include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraoctylsilane,
Examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltriisopropoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and the like.

Further, the silica precursor preferably has a molecular weight in the range of 500 to 10,000 in terms of polystyrene equivalent number average molecular weight. If the silica precursor has a molecular weight of less than 500 in terms of polystyrene, an unhydrolyzed product may be present in the coating solution, and the coating solution for forming a transparent film may not be uniformly applied to the conductive layer. Even if it can be applied, the adhesion between the conductive layer and the transparent film may be poor. If the molecular weight in terms of polystyrene of the silica precursor exceeds 10,000, the strength of the coating tends to decrease.

In the above, the mixing ratio of the fluorine-substituted alkyl group-containing silicone component precursor to the inorganic oxide precursor and / or the inorganic composite oxide precursor is such that the fluorine-substituted alkyl group-containing silicone component precursor is mixed with the inorganic oxide precursor. When the precursor of and / or the precursor of the inorganic composite oxide are converted to oxides, the fluorine-substituted alkyl group-containing silicone component precursor is preferably in the range of 0.1 to 70% by weight, more preferably Desirably, it is in the range of 1 to 30% by weight.

When the amount of the fluorine-substituted alkyl group-containing silicone component precursor (in terms of oxide) is less than 0.1% by weight,
Since the amount of the fluorine-substituted alkyl group-containing silicone component precursor is small, the shrinkage rate of the transparent film itself formed by other components (such as an inorganic oxide precursor) added as necessary increases, and the heating of the transparent film increases. When performing the treatment (curing treatment), the difference in the shrinkage rate between the transparent film and the conductive layer is caused when the transparent film shrinks and the base material is curved or when the conductive layer is provided in the lower layer. As a result, the conductive layer may be peeled off, or there may be a portion where there is no electrical contact between the conductive fine particles, and sufficient conductivity may not be obtained for the entire substrate. In addition, since the shrinkage of the transparent film is large, the film becomes too dense, the porosity cannot be obtained, and the effect of lowering the refractive index of the transparent film may be insufficient. Furthermore, when the amount of the fluorine-substituted alkyl group-containing silicone component precursor is small, the formed transparent film may have insufficient hydrophobicity and may not have sufficient chemical resistance.

If the amount of the fluorine-substituted alkyl group-containing silicone component precursor exceeds 70% by weight, the transparent film becomes too porous, resulting in a decrease in the strength of the transparent film or poor adhesion to the lower conductive layer. May be sufficient. Further, as in the present invention, when a transparent film is formed on the conductive layer surface using a transparent film forming coating solution containing a fluorine-substituted alkyl group-containing silicone component precursor as a matrix precursor, the hydrophobic fluorine-substituted film is obtained. Part of the alkyl group covers the metal fine particles on the surface of the conductive layer, and a protective layer composed of a hydrophobic fluorine-substituted alkyl group-containing silicone component is formed at the boundary between the conductive layer and the transparent film. Chemical properties are also improved.

Further, the fluorine-substituted alkyl group-containing silicone component precursor tends to have a two-dimensional chain structure,
Such a fluorine-substituted alkyl group-containing silicone component precursor having a two-dimensional chain structure is more easily adsorbed or bonded to inorganic compound particles as compared with, for example, an inorganic oxide precursor such as a silica matrix precursor. Therefore, the aggregation of the inorganic compound particles in the coating liquid for forming a transparent film is suppressed by the fluorine-substituted alkyl group-containing silicone component precursor having a two-dimensional chain structure, and the inorganic compound particles are contained in the coating liquid for forming a transparent film. Disperse evenly. In the transparent film obtained by applying the coating liquid for forming a transparent film, a state in which the inorganic compound particles are uniformly dispersed is maintained even in the film, and a transparent film in which the inorganic compound particles are uniformly dispersed is obtained. Therefore,
When such a coating liquid for forming a transparent film is used, even for a larger substrate, the inorganic compound particles are uniformly dispersed,
In addition, a transparent film having an excellent appearance can be formed. Further, the method for forming a transparent film using the coating liquid for forming a transparent film is excellent in industrial manufacturing reliability (yield).

When the coating liquid for forming a transparent film containing the fluorine-substituted alkyl group-containing silicone component precursor and the inorganic compound particles is applied and dried, the solvent is evaporated and the inorganic compound is formed on the upper layer of the transparent film. A large amount of particles and a fluorine-substituted alkyl group-containing silicone component precursor are present. The two-dimensional chain-like fluorine-containing silicone compound in the transparent film has a small shrinkage and low porosity, so that the refractive index is low, and the inorganic compound particles themselves have a low refractive index. The refractive index is small. Further, as described above, in the transparent coating surface layer, since the fluorine-substituted alkyl group-containing silicone component precursor is selectively present, the transparency of the transparent coating surface layer is good, so that a transparent coating having high scratch strength can be obtained. . Further, in the lower layer of the transparent film, a large number of inorganic oxide precursors such as a silica matrix precursor other than the fluorine-substituted alkyl group-containing silicone component precursor are present. It has a higher refractive index than the component precursors and the inorganic compound particles. For this reason, a gradient refractive index film in which the refractive index decreases from the lower layer portion to the upper layer portion of the transparent film is obtained, and a transparent film having excellent reflectance, particularly excellent luminous reflectance, is obtained.

A transparent film formed from a coating solution containing these matrix precursors has a small refractive index, and the resulting substrate with a transparent film has excellent antireflection properties. Preparation of Transparent Film Forming Coating Solution The inorganic compound particles are mixed with a dispersion in which the matrix precursor is dispersed to prepare a transparent film forming coating solution.

The matrix precursor dispersion is prepared by dissolving or dispersing a fluorine-substituted alkyl group-containing silicone component precursor and, if necessary, an oxide precursor such as silica in a water-alcohol mixed solvent. You.
The matrix precursor dispersion is obtained by dissolving or dispersing a fluorine-based silicone compound and, if necessary, an oxide precursor such as silica in a water-alcohol mixed solvent, for example, in the presence of an acid catalyst. It may be prepared by hydrolysis.

The concentration of the inorganic compound particles contained in the coating solution for forming a transparent film is preferably in the range of 0.05 to 3% by weight in terms of oxide. Particularly preferably 0.2.
２2% by weight. When the concentration of the inorganic compound particles contained in the coating liquid for forming a transparent film is less than 0.05% by weight, the amount of the inorganic compound particles is too small, and the resulting transparent film may have poor antireflection performance. If the concentration of the compound particles exceeds 3% by weight, cracks may occur in the resulting film or the strength of the film may be reduced.

The concentration of the matrix precursor contained in the coating solution is 0.05 when converted to oxide.
It is preferably in the range of 10 to 10% by weight. Particularly preferably, it is in the range of 0.1 to 5.0% by weight. The concentration of the matrix precursor contained in the coating solution is 0.0
When the amount is less than 5% by weight, the resulting film is so thin that the water resistance and the antireflection performance may be poor, and a film having a sufficient film thickness may not be obtained by one coating. When coating is repeated, a film having a uniform thickness may not be obtained.

If the concentration of the matrix precursor exceeds 10% by weight in terms of oxide, cracks may occur in the obtained film or the strength of the film may be reduced. Further, the film may be too thick and the antireflection performance may be insufficient. The weight ratio of the matrix precursor to the inorganic compound particles in the coating liquid for forming a transparent film (matrix precursor / inorganic compound particles, both in terms of oxide) is 0.1 to 10, preferably 0.2 to 10. It is desirably in the range of 5.

Further, the coating liquid for forming a transparent film includes:
Fine particles composed of a low refractive index material such as magnesium fluoride, a small amount of conductive fine particles and / or additives such as dyes or pigments may be contained so as not to impair the transparency and antireflection performance of the transparent film. . Forming the transparent film The method for forming the transparent film is not particularly limited, and the above-described coating solution is dipped according to the material such as the base material,
A wet thin film forming method in which the composition is applied by a spinner method, a spray method, a roll coater method, a flexographic printing method, or the like, and then dried, can be adopted.

The thickness of the transparent film to be formed is 50 to 50.
300 nm, preferably in the range of 80 to 200 nm, preferably exhibiting excellent water resistance and a low bottom reflectance and luminous reflectance when the film thickness is in such a range, excellent antireflection performance. Demonstrate. When the thickness of the transparent coating is less than 50 nm, the strength, water resistance, antireflection performance and the like of the coating may be inferior.

When the thickness of the transparent film exceeds 300 nm,
Cracks may occur in the film or the strength of the film may be reduced, and the film may be too thick to have an insufficient antireflection performance. In the present invention, a coating formed by applying such a coating liquid for forming a transparent coating, at the time of drying, or after drying,
Heating at 100 ° C. or higher, or irradiating an uncured 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 it to an active gas atmosphere such as ammonia Good. By doing so, the curing of the film-forming component is promoted, and the hardness of the obtained transparent film is increased.

Further, when the coating liquid for forming a transparent coating is applied to form a coating, the coating liquid for forming a transparent coating is applied by a spray method while maintaining the substrate at about 40 to 90 ° C. Is formed, ring-shaped irregularities are formed on the surface of the transparent film, and an anti-glare substrate with a transparent film having less glare can be obtained. The transparent film may be formed by laminating two or more kinds of films having different refractive indices. For example, if a transparent film having a small refractive index is sequentially formed from the surface of the substrate, a substrate with a transparent film having extremely excellent antireflection properties can be obtained. Can be obtained. The transparent film formed on the lower layer may not contain the inorganic compound particles and the fluorine-substituted alkyl group-containing silicone component.

When forming a transparent film on the surface of the conductive layer,
Usually, the difference in the refractive index between the conductive layer and the transparent film is preferably at least 0.3. If the difference in refractive index is less than 0.3, the antireflection performance may be insufficient. [Display Device] The display device according to the present invention includes a front plate made of the base material with a transparent film, and a transparent film is formed on an outer surface of the front plate.

Among the substrates with a transparent coating according to the present invention, especially those having a conductive layer having a surface resistance of 10 ¹² Ω / □ or less are formed on the surface of the conductive layer in the visible light region and near infrared region. It has excellent antireflection performance in the region, and is suitably used as a front panel of a display device (for example, a panel glass for a cathode ray tube). The display device according to the present invention is a device that displays an image electrically, such as a cathode ray tube (CRT), a fluorescent display tube (FIP), a plasma display (PDP), a liquid crystal display (LCD), and the like. A front plate made of a transparent base material with a transparent coating. The front plate at this time may be a front plate in which a conductive layer and a transparent coating are formed on the surface of the display face panel, and before the conductive layer and the transparent coating are formed on a substrate different from the display face panel. It may be a face plate.

When a display device having a conventional front panel is operated, dust or the like may adhere to the front panel, or an electromagnetic wave may be emitted from the front panel at the same time that an image is displayed on the front panel. In the case where a conductive layer having a surface resistance of 10 ¹² Ω / □ or less is formed on the front plate, dust and the like are unlikely to adhere,
When a conductive layer having a surface resistance of 10 ² to 10 ⁴ Ω / □ is formed on the front plate, such an electromagnetic wave and an electromagnetic field generated by emission of the electromagnetic wave can be effectively shielded.

When reflected light is generated on the front plate of the display device, the reflected light makes it difficult to see a displayed image. However, in the display device according to the present invention, the front plate has a low refractive index transparent film formed thereon. Since both the bottom reflectance and the luminous reflectance are low, such reflected light can be effectively prevented over the visible light region and the near infrared region.

In such a display device, since a transparent film having high scratch strength is formed on the surface, scratches and the like are not formed, so that a clear image can be maintained for a long period of time. Further, when the front plate of the cathode ray tube is composed of the substrate with a transparent coating according to the present invention, and at least one of the transparent conductive layer and the transparent coating contains a small amount of dye or pigment, Alternatively, each of the pigments absorbs light having a unique wavelength, whereby the contrast of a display image projected from a cathode ray tube can be improved.

Further, since a transparent film containing the inorganic compound particles having a low refractive index according to the present invention is formed on the front plate of the cathode ray tube, the antireflection performance is excellent, and a clear display image without scattering of visible light is obtained. can get. Since this transparent film has excellent adhesion to the conductive layer, it also has a performance as a protective film, and can maintain excellent display performance for a long time. For this reason, the conductivity of the conductive layer can be maintained for a long time, so that the antistatic performance and the electromagnetic wave shielding performance do not decrease.

[0111]

The substrate with a transparent film according to the present invention has on its surface a transparent film containing low refractive index inorganic compound particles and a fluorine-substituted alkyl group-containing silicone component. Such a substrate with a transparent coating has high adhesion between the transparent coating and the substrate or the conductive layer, and the transparent coating itself has high film strength, particularly high scratch strength, and also has excellent water resistance and chemical resistance. . Further, such a substrate with a transparent film has low water resistance, low bottom reflectance and low luminous reflectance, and thus has excellent antireflection performance over a wide wavelength range of visible light.

The coating solution for forming a transparent film according to the present invention can be suitably used for forming the above-mentioned group having an excellent transparent film. ADVANTAGE OF THE INVENTION Since the display apparatus which concerns on this invention is excellent also in antireflection performance and water resistance, a clear display image is obtained without scattering of visible light, and excellent display performance can be maintained for a long period of time. Further, even if the conductive layer is formed, the conductive property can be maintained for a long time because of high chemical resistance, and thus the antistatic performance and the electromagnetic wave shielding performance do not decrease.

[0113]

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

[0114]

[Preparation Example 1] Preparation of inorganic compound particles (P-1) (in outer shell layer)
(Parts of which are porous) A reaction mother liquor was prepared by mixing 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by weight with 1900 g of pure water, and heated to 80 ° C. The pH of the reaction mother liquor was 10.5.
9000 g of a 1.5 wt% aqueous sodium silicate solution as SiO ₂ and 9000 g of a 0.5 wt% aqueous sodium aluminate solution as Al ₂ O ₃ were simultaneously added to the mother liquor. Meanwhile, the temperature of the reaction solution was maintained at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate, and hardly changed thereafter. After the addition was completed, the reaction solution was cooled to room temperature, washed with an ultrafiltration membrane, and washed with a solid concentration of 20% by weight.
Dispersion (A) of iO ₂ · Al ₂ O ₃ porous substance precursor particles
Was prepared. (First Step) To 500 g of the dispersion liquid (A) of the porous substance precursor particles, 1,700 g of pure water was added, and the mixture was heated to 98 ° C., and while maintaining this temperature, the aqueous solution of sodium silicate was subjected to cation exchange. 3,000 g of a silicic acid solution (SiO ₂ concentration 3.5% by weight) obtained by dealkalization with a resin was added to form a silica protective film on the surface of the porous substance precursor particles. The obtained dispersion of the porous substance precursor particles is washed with an ultrafiltration membrane to adjust the solid content concentration to 13% by weight. In addition, concentrated hydrochloric acid (35.5% by weight) was added dropwise to adjust the pH to 1.0, and a dealumination treatment was performed.

Next, while adding 10 L of a hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the dissolved aluminum salt was separated by an ultrafiltration membrane, and SiO _2.
A dispersion liquid (B) of Al ₂ O ₃ porous particles was prepared. (Second step) 1500 g of the dispersion (B) of the porous particles and 50 parts of pure water
After heating a mixture of 0 g, 1,750 g of ethanol and 626 g of 28% aqueous ammonia at 35 ° C., 104 g of ethyl silicate (28% by weight of SiO ₂ ) was added, and the surface of the porous particles was hydrolyzed with ethyl silicate. A silica outer shell layer of the polycondensate was formed. Next, after concentrating to a solid content concentration of 5% by weight with an evaporator, ammonia water having a concentration of 15% by weight was added to adjust the pH to 10, and the mixture was heated at 180 ° C. for 2 hours in an autoclave, and the solvent was changed to ethanol using an ultrafiltration membrane. A dispersion liquid of the substituted inorganic compound particles (P-1) having a solid content concentration of 20% by weight was prepared. (Third Step) Table 1 shows the average particle size of the particles (P-1), the whole particles (including the laminated outer shell layer), SiO ₂ / MO _x (molar ratio), and the refractive index. Here, the average particle size was measured by a dynamic light scattering method, and the refractive index was measured by the following method.

[0116]How to measure the refractive index of particles (1) The matrix forming component obtained in Preparation Example 9 described later
The weight ratio of the liquid separation (M) and the inorganic compound particles in terms of oxide
(Matrix (SiO_Two): Inorganic compound particles (MO_x+ SiO _Two))
But 100: 0, 90:10, 80:20, 60:40, 50:50, 25:
Prepare the mixed coating solution for refractive index measurement to be 75.
Was. (2) Apply each coating solution to a silicon wafer whose surface is kept at 50 ° C.
300 rpm, spinner method each on the coater, then
After heating at 160 ° C for 30 minutes, use an ellipsometer
The refractive index of the formed refractive index measuring film was measured. (3) Next, the obtained refractive index and particle mixing ratio (particle:
(MO_x+ SiO_Two) / [Particle: (MO_x+ SiO_Two) + Matri
Box: SiO_Two｝) Is plotted.
Find the refractive index at 00%. (4) The porosity is determined by using the obtained refractive index to obtain pure SiO.
_TwoFrom the refractive index (1.45) of the
The calculated gap was determined.

[0117]

[Preparation Example 2] Preparation of inorganic compound particles (P-2) (in outer shell layer)
Particles having a porous part) Dispersion (A) 1 of porous material precursor particles obtained above
1,00 g of pure water was added to 00 g, and the mixture was heated to 95 ° C. While maintaining this temperature, an aqueous solution of sodium silicate (Si
27,000 g of an aqueous sodium aluminate solution (0.5% by weight as Al ₂ O ₃ ) and 27,000 g of an aqueous sodium aluminate solution (1.5% by weight as O ₂ ) were gradually added at the same time, and a dispersion liquid (A The particles were grown using the particles of ()) as seed particles. After completion of the addition, the mixture was cooled to room temperature, washed with an ultrafiltration membrane, and concentrated to obtain a solid having a solid concentration of 20% by weight.
Dispersion (C) of iO ₂ · Al ₂ O ₃ porous substance precursor particles
I got (First Step) After taking 500 g of the dispersion liquid (C) of the porous substance precursor particles and forming the silica protective film of the second step by the same method as in Preparation Example 1, the aluminum removal treatment was performed. In the third step, a process of forming a silica outer layer with a hydrolyzate of ethyl silicate was performed, and a dispersion of inorganic compound particles (P-2) shown in Table 1 was prepared.

[0118]

[Preparation Example 3] Preparation of inorganic compound particles (P-3) (in outer shell layer)
Part of the particles are porous) 1,900 g of pure water is added to 100 g of the dispersion liquid (C) of the SiO ₂ · Al ₂ O ₃ porous substance precursor particles obtained above, and the mixture is heated to 95 ° C. While maintaining this temperature, an aqueous solution of sodium silicate (1.5 g wt% as SiO ₂ )
00 g and 7,000 g of an aqueous solution of sodium aluminate (0.5% by weight as Al ₂ O ₃ ) were gradually added at the same time to allow the particles to grow. After completion of the addition, the mixture was cooled to room temperature, washed with an ultrafiltration membrane and concentrated to obtain a dispersion liquid (D) of SiO ₂ .Al ₂ O ₃ porous substance precursor particles having a solid content of 13% by weight. .

This porous material precursor particle dispersion (D) 5
Then, 1,125 g of pure water was added thereto, and concentrated hydrochloric acid (35.5%) was added dropwise to adjust the pH to 1.0, followed by a dealumination treatment. Next, while adding 10 liters of a hydrochloric acid aqueous solution having a pH of 3 and 5 liters of pure water, the dissolved aluminum salt was separated by an ultrafiltration membrane, and a dispersion liquid of SiO ₂ · Al ₂ O ₃ porous particles from which a part of aluminum was removed was added. (E) was prepared.

1500 g of dispersion (E) of the above porous particles
And a mixture of 500 g of pure water, 1,750 g of ethanol and 626 g of ammonia water having a concentration of 28% by weight were heated to 35 ° C.
After heating, 210 g of ethyl silicate (SiO ₂ 28% by weight) was added, and the surface of the porous particles was coated with a hydrolyzed polycondensate of ethyl silicate to form a silica shell layer. Next, the solid content concentration was 5% by weight using an evaporator.
After concentration, the pH was adjusted to 10 by adding aqueous ammonia having a concentration of 15% by weight, and the mixture was heated in an autoclave at 180 ° C. for 2 hours. A dispersion (solid content concentration: 20% by weight) of (P-3) was prepared.

[0121]

[Preparation Example 4] Preparation of inorganic compound particles (P-4) (in outer shell layer)
Particles having a hollow portion) 10 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by weight and 190 g of pure water are mixed to prepare a reaction mother liquor;
Warmed to 95 ° C. The pH of the reaction mother liquor was 10.5, and 24,900 g of a 1.5 wt% sodium silicate aqueous solution as SiO ₂ and 0.5 as Al ₂ O ₃ were added to the mother liquor.
36,800 g of an aqueous solution of sodium aluminate by weight were added simultaneously. Meanwhile, the temperature of the reaction solution was kept at 95 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate, and hardly changed thereafter. After the addition was completed, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a dispersion (F) of SiO ₂ .Al ₂ O ₃ porous substance precursor particles having a solid content of 20% by weight. (First Step) Next, a dispersion liquid (F) 50 of the porous substance precursor particles is prepared.
0 g was collected, 1,700 g of pure water was added, the mixture was heated to 98 ° C., and while maintaining this temperature, a sodium silicate aqueous solution was dealkalized with a cation exchange resin (SiO ₂ solution). (A concentration of 3.5% by weight) was added to form a silica protective film on the surface of the porous substance precursor particles.
The obtained dispersion liquid of the porous substance precursor particles was washed with an ultrafiltration membrane to adjust the solid content concentration to 13% by weight, and then 500 g of the dispersion liquid of the porous substance precursor particles was added to 1,125 g of pure water.
, And concentrated hydrochloric acid (35.5%) is added dropwise to adjust pH.
1.0, and after dealumination, pH 3
Was dissolved in an ultrafiltration membrane while adding 10 L of aqueous hydrochloric acid and 5 L of pure water to prepare a particle precursor dispersion. (Second Step) 1500 g of the particle precursor dispersion, 500 g of pure water, 1,750 g of ethanol and 626 of 28% ammonia water
After heating the mixture with 35 g to 35 ° C., 104 g of ethyl silicate (28% by weight of SiO ₂ ) is added, and a silica outer layer is formed on the particle precursor surface with a hydrolytic polycondensate of ethyl silicate. Thus, particles having a cavity inside the outer shell layer were produced. Then, after concentrating to a solid content concentration of 5% by weight with an evaporator, aqueous ammonia having a concentration of 15% by weight was added to adjust the pH to 10, and the content was adjusted to 180 with an autoclave.
A heat treatment was performed at 2 ° C. for 2 hours, and a dispersion of inorganic compound particles (P-4) having a solid content of 20% by weight in which the solvent was replaced with ethanol was prepared using an ultrafiltration membrane. (Third Step) The cross section of the obtained particles was observed with a transmission electron microscope (TEM). As a result, particles having cavities formed inside the outer shell layer as shown in FIG. 2 were obtained.

[0122]

[Preparation Example 5] Preparation of inorganic compound particles (P-5) (in outer shell layer)
Part of the particles are porous) Instead of sodium aluminate in preparing the inorganic compound particles (P-1), 9,000 g of a 0.5% by weight aqueous solution of potassium stannate was used as SnO ₂ . Except for the above, in the same manner as the inorganic compound particles (P-1), a SiO ₂ .SnO ₂ porous substance precursor particle having a solid content of 20% by weight was obtained, and further the same as the inorganic compound particles (P-1). After the formation of the silica protective film by the method, the Sn removal treatment (the same treatment as the dealumination treatment in Preparation Example 1) and the formation of the silica outer layer were performed, and the dispersion of the inorganic compound particles (P-5) shown in Table 1 was performed. A liquid was prepared.

[0123]

[Preparation Example 6] Preparation of inorganic compound particles (P-6) (Comparative Example:
100 g of silica sol having an average particle size of 5 nm and a SiO ₂ concentration of 20% by weight in the same manner as in the preparation of the inorganic compound particles (P-1) without forming an outer shell layer.
And 1900 g of pure water were heated to 80 ° C. The pH of this reaction solution was 10.5, and 9000 g of a 1.5% by weight aqueous sodium silicate solution as SiO ₂ and 9000 g of a 0.5% by weight aqueous sodium aluminate solution as Al ₂ O ₃ were simultaneously added to the reaction solution. Was added. Meanwhile, the temperature of the reaction solution was maintained at 80 ° C. Immediately after the addition of the reaction solution,
Rose to 12.5 and then changed little.
After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane.
A dispersion liquid (solid content concentration: 20% by weight) of O ₂ · Al ₂ O ₃ porous particles (P-6) was prepared.

[0124]

Preparation Example 7 Preparation of Inorganic Compound Particles (P-7) (Comparative Example:
To a mixture of 100 g of methyl silicate (SiO ₂ : 39% by weight) and 530 g of methanol was added 79 g of 28% by weight aqueous ammonia, and the mixture was stirred at 35 ° C. for 24 hours. After washing using a filtration membrane, the solvent was replaced with ethanol to prepare a dispersion (solid content concentration: 20% by weight) of the porous silica particles (P-7) shown in Table 1.

[0125]

[Table 1]

[0126]

Preparation Example 8 Preparation of Dispersion of Conductive Fine Particles Dispersions (S-1, S-2) of composite metal fine particles (Q-1, Q-2) 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 the composite metal fine particles to which trisodium citrate was obtained. An aqueous solution of silver nitrate and palladium nitrate was added so that the seeds had the weight ratios shown in Table 2, and an aqueous solution of ferrous sulfate having the same mole number as the total mole number of silver nitrate and palladium nitrate in the solution was added. The mixture was stirred for 1 hour to obtain a dispersion of composite metal fine particles having the composition shown in Table 2. The resulting dispersion was washed with water using a centrifugal separator to remove impurities, and then dispersed in water. Then, the solvent (1-ethoxy-2) shown in Table 3 was used.
After mixing with (propanol), water was removed with a rotary evaporator and the mixture was concentrated to prepare metal fine particle dispersions (S-1 and S-2) having a solid content concentration shown in Table 2.

A dispersion (S-3) of tin-doped indium oxide particles (Q-3) was prepared as follows. A solution obtained by dissolving 79.9 g of indium nitrate in 686 g of water and a solution obtained by dissolving 12.7 g of potassium stannate in a potassium hydroxide solution having a concentration of 10% by weight were prepared. To 1000 g of pure water maintained at 50 ° C.
Added over time. During this time, the pH in the system was maintained at 11. The tin-doped indium oxide hydrate dispersion was filtered and washed from the tin-doped indium oxide hydrate dispersion, dried, then calcined in air at 350 ° C. for 3 hours, and further heated in air at 600 ° C. By firing at a temperature for 2 hours, tin-doped indium oxide fine particles (Q-3) were obtained. This was dispersed in pure water to a concentration of 30% by weight, and the pH was adjusted to 3.5 with an aqueous nitric acid solution.
The sol was prepared by pulverizing for a while. Next, the sol was treated with an ion-exchange resin to remove nitrate ions, and pure water was added to the sol to add tin-doped indium oxide (IT).
O) A dispersion of fine particles (S-3) was prepared.

Antimony-doped tin oxide fine particles (Q-4)
(S-4) was prepared as follows. 57.7 g of tin chloride and 7.0 g of antimony chloride were added to methanol 1
00 g was dissolved to prepare a solution. The resulting solution was added to 1000 g of pure water with stirring at 90 ° C. for 4 hours to conduct hydrolysis, and the resulting precipitate was separated by filtration, washed, and calcined at 500 ° C. for 2 hours in dry air. Antimony-doped tin oxide fine powder was obtained. 30 g of this powder was added to 70 g of an aqueous potassium hydroxide solution (3.0 g as KOH), and the mixture was pulverized with a sand mill for 3 hours while maintaining the mixture at 30 ° C. to prepare a sol. Next, the sol was treated with an ion exchange resin, dealkalized, and pure water was added thereto to add tin oxide (ATO) fine particles (Q-
A dispersion liquid (S-4) of 4) was prepared.

[0129]

Preparation Example 9 c) Preparation of Matrix Forming Component Solution Preparation of Matrix Forming Component Solution (M-1) Ethyl orthosilicate (TEOS) (SiO ₂ : 28% by weight) 5
0 g, 9.52 g of heptadecafluorodecyltrimethoxysilane, 194.6 g of ethanol, 1.4 g of concentrated nitric acid and 34 g of pure water were stirred at room temperature for 5 hours.
A liquid (M-1) containing a matrix-forming component having a concentration of 5% by weight in terms of O ₂ was prepared.

Preparation of Matrix Forming Component Solution (M-2) Ethyl orthosilicate (TEOS) (SiO ₂ : 28% by weight) 5
0 g, heptadecafluorodecyltrimethoxysilane 4
7.5 g, ethanol 194.6G, a mixed solution of concentrated nitric acid 1.4g and pure water 34g was stirred at room temperature for 5 hours, SiO ₂
A liquid (M-2) containing a matrix-forming component having a concentration of 5% by weight when converted to was prepared.

Preparation of Matrix Forming Component Solution (M-3) Ethyl orthosilicate (TEOS) (SiO ₂ : 28% by weight) 5
_{0g, (CH 3 O) 3} SiC 2 H 4 C 6 F 12 C 2 H 4 Si (CH 3
O) ₃ 6.57 g, ethanol 194.6 g, concentrated nitric acid 1.4
g and 34 g of pure water were stirred at room temperature for 5 hours,
A liquid (M-3) containing a matrix-forming component having a concentration of 5% by weight in terms of SiO ₂ was prepared.

Preparation of Matrix Forming Component Solution (M-4) Ethyl orthosilicate (TEOS) (SiO ₂ : 28% by weight) 5
0 g, heptadecafluorodecyltrimethoxysilane 1
A mixed solution of 2.14 g, 194.6 g of ethanol, 1.4 g of concentrated nitric acid and 34 g of pure water was stirred at room temperature for 5 hours.
A liquid (M-4) containing a matrix-forming component having a concentration of 5% by weight in terms of O ₂ was prepared.

Preparation of Matrix Forming Component Solution (M-5) Ethyl orthosilicate (TEOS) (SiO ₂ : 28% by weight) 5
0 g, heptadecafluorodecyltrimethoxysilane 2
A mixed solution of 0.65 g, 194.6 g of ethanol, 1.4 g of concentrated nitric acid and 34 g of pure water was stirred at room temperature for 5 hours.
A liquid (M-5) containing a matrix-forming component having a concentration of 5% by weight in terms of O ₂ was prepared.

Preparation of Matrix Forming Component Solution (M-6) Ethyl orthosilicate (TEOS) (SiO ₂ : 28% by weight) 5
A mixed solution of 0 g, 194.6 g of ethanol, 1.4 g of concentrated nitric acid and 34 g of pure water was stirred at room temperature for 5 hours to prepare a liquid (M-6) containing a matrix-forming component having a SiO ₂ concentration of 5% by weight. Table 3 shows the composition of the prepared matrix forming component liquid.

[0135]

Preparation Example 10 d) Preparation of Coating Liquid for Forming Conductive Film The dispersion liquids (S-1) to (S-3) as described above, a matrix forming component liquid (M-6), ethanol, The coating liquids (CS-1) to (CS-3) for forming a conductive film were prepared by mixing ethoxy-2-propanol so as to have the composition shown in Table 4.

[0136]

[Table 2]

[0137]

[Table 3]

[0138]

[Table 4]

[0139]

Example 1 Preparation of Coating Solution (B-1) for Forming Transparent Film The solution ( M-1) containing the above-mentioned matrix-forming component was added to ethanol / butanol / diacetone alcohol / isopropyl alcohol (2: 1: 1: 5). (Mixing ratio by weight), the dispersion of the inorganic compound particles (P-1) prepared above was added, and the concentration as a solid content of the inorganic compound particles and the SiO _{2 of the} matrix forming component were converted. Having a concentration shown in Table 5, respectively.
1) was prepared.

Production of Glass with Transparent Coating While maintaining the surface of the glass substrate at 40 ° C., the coating solution for forming a transparent coating (B-
1) was applied so that the thickness of the transparent film was 100 nm, dried, and baked at 160 ° C. for 30 minutes to produce a glass with a transparent film (G-1).

The haze of the substrate with a transparent coating obtained as described above was measured with a haze computer (3000 N, manufactured by Nippon Denshoku Co., Ltd.). The reflectance is measured using a reflectance meter (MCPD-2000, manufactured by Otsuka Electronics Co., Ltd.) according to JIS Z8727, and the wavelength is 400.
The reflectance at the wavelength having the lowest reflectance in the range of ~ 700 nm is defined as the bottom reflectance, and the wavelength is defined as 400-700 nm.
The average reflectance in the range of nm was displayed as luminous reflectance. For the particle diameter of the fine particles, a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.) was used.

Further, the film strength was evaluated by the eraser strength and the scratch strength as described below. Eraser strength Further , an eraser (manufactured by Lion Corporation: 1K) was set on the transparent coating of the substrate with a transparent coating obtained above, and 1 ± 0.1
A load of Kg was applied and reciprocated 25 times with a stroke of about 25 mm. The shavings generated at this time were removed with high-pressure air each time.

After the eraser was reciprocated 25 times, the surface was visually observed at a distance of 45 cm from the surface of the transparent film under illumination of 1000 lux. Criteria A: No scratch is observed. B: The reflected color changes under a fluorescent lamp (from purple to red). C: Scratches are observed without reflection under a fluorescent lamp.

D: Underlayer (silicon wafer) is visible. Scratch strength Standard test needle (made by Rockwell Co., Ltd.) on a transparent film: hardness
HRC-60, φ0.5 mm) was set, a load of 1 ± 0.3 kg was applied, and sweeping was performed with a stroke of 30 to 40 mm. After sweeping, 45 lux from the coating surface under 1000 lux illumination
The surface was visually observed at a distance of cm.

Judgment Criteria A: No scratch is observed. B: The reflected color changes under a fluorescent lamp (from purple to red). C: Scratches are observed without reflection under a fluorescent lamp. D: The underlayer (silicon wafer) is visible. Table 6 shows the results.

[0146]

Examples 2 to 6 Preparation of coating liquids (B-2 to B-6) for forming a transparent film
(M-1) solution containing the matrix-forming component manufactured by (M-4) solution,
A mixed solvent of ethanol / butanol / diacetone alcohol / isopropyl alcohol (2: 1: 1: 5 weight ratio) and the inorganic compound particles prepared above (P-2, P-3, P-
5) Alternatively, a dispersion of the hollow particles (P-4) is mixed, and the concentration of each particle and the concentration of the matrix forming component as a solid content are as shown in Table 5, respectively. B-6)
Was prepared.

Production of Glass with Transparent Coating While maintaining the surface of the glass substrate at 40 ° C., the coating solution for forming a transparent coating (B-
2) to (B-6) are applied so that the film thickness of the transparent film is 100 nm, then dried and baked at 160 ° C. for 30 minutes to form a glass with a transparent film (G-2) to (G-6). Was prepared.

The obtained glass with a transparent coating was evaluated in the same manner as in Example 1. Table 6 shows the results.

[0149]

Comparative Examples 1 to 5 of coating liquids for forming a transparent film (B-7 to B-11)
Preparation (M-1) solution containing the matrix forming component, (M-5) solution, (M
-6) A mixed solvent of liquid, ethanol / butanol / diacetone alcohol / isopropyl alcohol (2: 1: 1: 5 weight ratio), and inorganic compound particles (P-6, P-7, P The dispersions of -1) were mixed to prepare coating liquids (B-7 to B-11) for forming transparent films having the concentrations shown in Table 5 for the concentrations of the respective particles and the solid components of the matrix forming components. .

Production of Glass with Transparent Coating While maintaining the surface of the glass substrate at 40 ° C., the coating solution for forming a transparent coating (B-
7) to (B-11) are applied so that the film thickness of the transparent film is 100 nm, then dried and baked at 160 ° C. for 30 minutes to obtain a glass with a transparent film (G-7) to (G-11). Was prepared.

The obtained glass with a transparent coating was evaluated in the same manner as in Example 1. Table 6 shows the results.

[0152]

[Table 5]

[0153]

[Table 6]

[0154]

Example 7 Production of Panel Glass with Transparent Coating While holding the surface of CRT panel glass (14 ″) at 40 ° C., the above-mentioned coating solution for forming a conductive coating (CS) was spinnered at 100 rpm for 90 seconds. -1) when the thickness of the conductive layer is 2
It was applied to a thickness of 0 nm and dried.

Next, on the conductive layer thus formed, the coating solution (B-1) for forming a transparent film was similarly applied at 100 rpm for 90 seconds by the spinner method, so that the thickness of the transparent film was 100 nm. Apply and dry so that it becomes
After baking for minutes, a substrate with a transparent coating was obtained. The haze of the substrate with a transparent coating obtained above is replaced with a haze computer (Nippon Denshoku
(3000A). The reflectivity is measured using a reflectometer (MCPD-2000, manufactured by Otsuka Electronics Co., Ltd.) in accordance with JIS Z8727. As the reflectance,
The average reflectance in the wavelength range of 400 to 700 nm was displayed as luminous reflectance.

The surface resistance of each substrate with a transparent coating was determined by connecting two solder electrodes parallel to each other and 5 cm apart from each other on the substrate on which the transparent coating was formed by using an ultrasonic soldering apparatus (Asahi Glass Co., Ltd.).
Manufactured by SUNBONDER USM-III type, solder: wire diameter 1.6Φ, melting temperature 224 ° C) (at this time, the solder electrode penetrates the transparent coating on the surface and conducts with the conductive layer),
Cut off the outside of the electrode and tester (HIOKI Electric Co., Ltd.) in a desiccator in an atmosphere of 23 ± 5 ° C. and humidity of 40% or less.
Manufactured by High Tester 3244) to evaluate the resistance value between the electrodes.

The adhesiveness was determined by making 11 scratches on the surface of the transparent film with a knife at intervals of 1 mm each in the vertical and horizontal directions to form 100 squares, attaching an adhesive tape to the squares, and then peeling the adhesive tape. The number of squares in which the film remained without peeling was evaluated in the following two stages. 95 or more of the remaining squares: ○ 94 or less of the remaining squares: × Also, using the base material with a transparent coating obtained above, assemble a display device, and display the image at a distance of 5 m from the image and the image surface as the display performance. The degree of reflection (reflection) and the degree of coloring of a certain fluorescent lamp were observed and evaluated according to the following criteria.

Reflection (reflection) and coloring are weak, and the image is clear: ◎ Reflection (reflection) is weak but coloring is recognized, but the image is clear: ○ Reflection (reflection) and coloring Strong, part of the image is unclear: △ Strong reflection (reflection) and coloring, and reflection is clearer than the image: × In addition, the following water resistance of the substrate with a transparent coating obtained above Was evaluated.

Further, the film strength was evaluated by the eraser strength and the scratch strength as described below. Eraser strength Further , an eraser (manufactured by Lion Corporation: 1K) was set on the transparent coating of the substrate with a transparent coating obtained above, and 1 ± 0.1
A load of Kg was applied and reciprocated 25 times with a stroke of about 25 mm. The shavings generated at this time were removed with high-pressure air each time.

After the eraser was reciprocated 25 times, the surface was visually observed at a distance of 45 cm from the surface of the transparent film under illumination of 1000 lux. Criteria A: No scratch is observed. B: The reflected color changes under a fluorescent lamp (from purple to red). C: Scratches are observed without reflection under a fluorescent lamp.

D: Underlayer (silicon wafer) is visible. Scratch strength Standard test needle (made by Rockwell Co., Ltd.) on a transparent film: hardness
HRC-60, # 0.5 mm) was set, a load of 1 ± 0.3 kg was applied, and sweep was performed with a stroke of 30 to 40 mm. After sweeping, 45 lux from the coating surface under 1000 lux illumination
The surface was visually observed at a distance of cm.

Criteria A: No scratch is observed. B: The reflected color changes under a fluorescent lamp (from purple to red). C: Scratches are observed without reflection under a fluorescent lamp. D: The underlayer (silicon wafer) is visible. Further, the film strength was evaluated by the eraser strength and the scratch strength by the method described above.

Further, water resistance and chemical resistance were evaluated as follows. Evaluation of Water Resistance After immersing the substrate with a transparent film in boiling distilled water at 100 ° C. for 30 minutes, the surface resistance, reflectance and haze were measured in the same manner as described above. Evaluation of Chemical Resistance (1) The substrate with a transparent coating was immersed in a 5% by weight aqueous hydrochloric acid solution for 10 hours, and the surface resistance, reflectance and haze were measured in the same manner as described above.

Evaluation of Chemical Resistance (2) A substrate with a transparent coating was placed in a 5% by weight aqueous hydrochloric acid solution for 200 hours.
After immersion for a time, the surface resistance, reflectance, and haze were measured in the same manner as described above. Table 7 shows the results.

[0165]

Examples 8 to 14 Production of Panel Glass with Transparent Coating In the same manner as in Example 7 except that the coating liquids for forming a conductive coating (CS-1 to CS-4) shown in Table 7 were used. After forming the conductive layer so as to have the thickness shown, the coating solution for forming the transparent film
Using (B-2 to B-6), a substrate with a transparent coating was obtained in the same manner as in Example 7.

The surface resistance, haze, reflectance, adhesion, film strength and display performance of the obtained substrate with a transparent coating were evaluated.
Table 7 shows the results. Further, water resistance, chemical resistance (1) and chemical resistance (2) were evaluated in the same manner as in Example 7. In addition, about Example 12, evaluation of chemical resistance (2) was not implemented. Table 7 shows the results. FIG. 4 shows a reflectance curve of the substrate with a transparent coating of Example 13 at a wavelength of 400 to 700 nm.

[0167]

Comparative Examples 6 to 12 Production of Panel Glass with Transparent Coating A transparent conductive layer (thickness: 20 nm) was formed in the same manner as in Example 7 using a coating liquid for forming a conductive coating (CS-1). A substrate with a transparent coating was obtained in the same manner as in Example 7 except that the coating liquid for forming a transparent coating (B-7 to B-11) was used (Comparative Examples 6 to 9,
12).

In the same manner as in Example 12, the transparent conductive layer (film thickness: 100
nm), and a substrate with a transparent coating was obtained in the same manner as in Example 6 except that the coating liquid for forming a transparent coating (B-9) was used (Comparative Example 10). In the same manner as in Example 13, the transparent conductive layer (film thickness 2
0 nm), and a substrate with a transparent coating was obtained in the same manner as in Example 13 except that the coating liquid for forming a transparent coating (B-9) was used (Comparative Example 11).

The surface resistance, haze, reflectance, adhesion and display performance of the obtained substrate with a transparent coating were evaluated. The results are shown in Table 7. Further, water resistance, chemical resistance (1) and chemical resistance (2) were evaluated in the same manner as in Example 7. In addition, about the comparative example 9, evaluation of chemical resistance (2) was not implemented. Table 7 shows the results.

[0170]

[Table 7]

[Brief description of the drawings]

FIG. 1 shows a schematic cross-sectional view of inorganic compound particles and hollow particles.

FIG. 2 shows a TEM photograph of a cross section of an inorganic compound particle (particle having a cavity in an outer shell layer).

FIG. 3 shows a TEM photograph of a cross section of a transparent coating containing inorganic compound particles (particles having a cavity in an outer shell layer).

FIG. 4 shows a substrate with a transparent coating of Example 13 from 400 to 70.
4 shows a reflection curve in a wavelength range of 0 nm.

[Explanation of symbols]

 1. Porous material 2. Shell layer 3. Cavity

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takeo Ito 1-9-2 Harara-cho, Fukaya-shi, Saitama Prefecture Inside the Toshiba Fukaya Plant (72) Inventor Shuzo Matsuda 1 Harara-cho, Fukaya-shi, Saitama No. 9-2, Toshiba Fukaya Plant Co., Ltd. (72) Inventor Yoshimi Otani 1-10-1, Kitahonmachi, Funabashi-shi, Chiba Asahi Glass Co., Ltd. (72) Inventor Kazuhiko Aoi Funabashi, Chiba Prefecture Asahi Glass Co., Ltd., 1-10-1, Kitahoncho, Toshiharu (72) Inventor Toshiharu Hirai 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Hiroyasu Nishida 13-2 Kitaminato-machi, Wakamatsu-ku, Kitakyushu-city, Fukuoka Prefecture Inside the Wakamatsu Plant of Catalyst Chemicals Co., Ltd. (72) Inventor Toshiro Komatsu 13-2 Kitaminato-machi, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Young Corporation Factory in the F-term (reference) 4F100 AA17B AA17H AA20B AA20H AG00 AK52B AL06B AT00A BA02 CA13B CA13H DE04B DE04H GB41 JB07 JK12 JN01 JN01B YY00B 4J038 DL071 HA446 KA20 MA04 NA01 5C032 AA02 EE02 EF01 EF05

Claims (9)

[Claims] 1. A substrate comprising: a substrate; and a transparent film provided on the surface of the substrate, wherein the transparent film comprises: (i) a matrix containing a fluorine-substituted alkyl group-containing silicone component; and (ii) an outer shell layer. And a porous or hollow inorganic compound particle, and the porous or hollow substrate is maintained in the transparent film. 2. A base material, a conductive layer provided on the surface of the base material, and a transparent film provided on the surface of the conductive layer, wherein the transparent film comprises (i) a fluorine-substituted alkyl group-containing silicone component. And (ii) an inorganic compound particle having an outer shell layer and having a porous or hollow inside, and that the porous or hollow is maintained in the transparent coating. Characteristic substrate with transparent coating. 3. The inorganic compound particles having an average particle size of 5 to 3
The substrate with a transparent coating according to claim 1 or 2, wherein the thickness is in the range of 00 nm. 4. The inorganic compound particle according to claim 1, wherein the outer shell layer has a thickness of 1 to 3.
The substrate with a transparent coating according to any one of claims 1 to 3, which is in a range of 20 nm. 5. The substrate with a transparent coating according to claim 1, wherein the outer shell layer of said inorganic compound particles contains silica as a main component. 6. The inorganic compound particles are composed of silica and an inorganic compound other than silica, the silica being represented by SiO ₂ and the inorganic compound other than silica being represented by an oxide (MO _x ) molar ratio MO _x. / SiO ₂ is, with a transparent film substrate according to any one of claims 1 to 5, characterized in that in the range of 0.0001 to 1.0. 7. A matrix precursor and inorganic compound particles, (i) the matrix precursor comprises a silicone compound having a fluorine-containing alkyl group and / or a hydrolyzate thereof, and (ii) an inorganic compound particle. Are particles having an outer shell layer and having a porous or hollow interior. 8. A display comprising a front plate made of the substrate with a transparent coating according to claim 1, wherein a transparent coating is formed on an outer surface of the front plate. apparatus. 9. A cathode ray comprising a front plate made of the substrate with a transparent coating according to claim 1, wherein a transparent coating is formed on an outer surface of the front plate. tube.