WO2008149470A1

WO2008149470A1 - Monolayer fluor fine particle film, fluor fine particle film-layered body, and manufacturing method thereof and display device and photoreceptor and sensor, which are made by using them

Info

Publication number: WO2008149470A1
Application number: PCT/JP2007/061946
Authority: WO
Inventors: Kazufumi Ogawa
Original assignee: Kazufumi Ogawa
Priority date: 2007-06-07
Filing date: 2007-06-07
Publication date: 2008-12-11

Abstract

Micrometer size or nanometer size fluor fine particles have been developed and manufactured. An effective use of the inherent functions of these fluor fine particles requires making fluor fine particles in a covering film with an even thickness. However, no idea of manufacturing a covering film with the even thickness on a particle size level by using those fluor fine particles. A monolayer fluor fine particle film, having a covalent bond of a film of a monolayer of a fluor fine particle, which is formed on a surface of a base material, to a first organic film formed on the surface of the base material, through a second organic film formed on the surface of the fluor fine particle. The first organic covering film formed on the surface of the base material differs from the second organic film formed on the surface of the fluor fine particle.

Description

DESCRIPTION

MONOLAYER FLUOR FINE PARTICLE FILM, FLUOR FINE PARTICLE FILM-LAYERED

BODY, AND MANUFACTURING METHOD THEREOF AND DISPLAY DEVICE AND PHOTORECEPTOR AND SENSOR, WHICH ARE MADE BY USING THEM

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to a monolayer fluor fine particle film having even film thickness, a fluor fine particle film-layered body made by layering the monolayer fluor fine particle film, and a display device, photoreceptor, and sensor using them.

According to the present invention, "fluor fine particle" includes mainly an alkali halide, rare earth ion fluor, manganese fluor, and sulfide fluor. In addition, the fluor fine particle mentioned herewith includes so-called EL material.

Description of Related Art

Conventionally, there is a known method called Langmuir-Blodgett (LB) method for layering a monomolecular film on a surface of a substrate by arranging molecules on a water surface by using amphipathic organic molecules. On the other hand, there is a known method called chemical adsorption (CA) for layering the monomolecular film in a solution, in which a surfactant has been solved, by using the chemical adsorption method.

A reference patent document includes, for example, Japanese Published Patent Application No. 2001-279471.

SUMMARY OF THE INVENTION

However, a covering film (hereafter, monolayer fluor fine particle film,) which is made by arranging only a monolayer of fluor fine particles on an arbitrary base material surface, having even thickness in a molecular size level, the covering film

(fluor fine particle film-layered body) made by layering a plurality of layers of the film, which is made by arranging fluor fine particles as only a monolayer, in a shape, and the manufacturing method thereof have not been yet developed and provided.

Conventionally, micrometer-sized or nanometer-sized fluor fine particles have been abundantly developed and manufactured. However, applying effectively inherent functions of these fluor fine particles requires making fluor fine particles in a covering film having an even thickness. However, there was no idea of manufacturing the covering film having an even thickness on a particle size level by using these fluor fine particles.

Using fluor fine particle and without a loss of a function inherent in a variety of fluor fine particles, the present invention aims to provide, the covering film (monolayer fluor fine particle film,) which is made by arranging only a single layer of fluor fine particles on the arbitrary base material surface in the form, having even thickness in the molecular size level, the covering film (fluor fine particle film-layered body) made by layering the plurality of layers of the film, which is made by arranging fluor fine particles only as the monolayer, and the manufacturing method thereof. A first invention provided as a means for solving the problem is a monolayer fluor fine particle film having a covalent bond of a film of a monolayer of a fluor fine particle formed on a surface of a base material to a first organic film formed on the surface of the base material, through a second organic film formed on the surface of the fluor fine particle. A second invention according to the first invention is the monolayer fluor fine particle film, wherein the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle are different from each other.

A third invention according to the first invention is the monolayer fluor fine particle film, wherein the covalent bond is a -N-C- bond formed by a reaction of an epoxy group and an imino group.

A fourth invention according to the second invention is the monolayer fluor fine particle film, wherein the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle are constituted of a monomolecular film.

A fifth invention according to the first to the fourth inventions is a display device, using the fluor fine particle film. A sixth invention according to the first to the fourth inventions is a photoreceptor, using the fluor fine particle film.

A seventh invention according to the first to the fourth invention is a sensor, using the fluor fine particle film. An eighth invention is a manufacturing method for the monolayer fluor fine particle film, comprising: a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material; a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; a step of contacting, for a reaction, the fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; and washing out the fluor fine particle covered with an excessive second reactive organic film.

A ninth invention according to eighth invention is the manufacturing method for the monolayer fluor fine particle film, comprising: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material and a step of forming the second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle, followed by washing each of the base material and the surface of the fluor fine particle with an organic solvent to form a first and second reactive monomolecular films having the covalent bond to the base material and the surface of the fluor fine particle.

A tenth invention according to eighth invention is the manufacturing method for the monolayer fluor fine particle film, wherein the first reactive organic film contains an epoxy group and the second reactive organic film contains an imino group or the first reactive organic film contains the imino group and the second reactive organic film contains the epoxy group.

An eleventh invention according to ninth invention is the manufacturing method for the monolayer fluor fine particle film, wherein the first reactive monomolecular film contains an epoxy group and the second reactive monomolecular film contains an imino group or the first reactive monomolecular film contains the imino group and the second reactive monomolecular film contains the epoxy group.

A twelfth invention is a fluor fine particle film-layered body wherein the fluor fine particle layered as stratification on the surface of the base material has the covalent bond between layers through an organic covering film formed on the surface of the fluor fine particle.

A thirteenth invention according to twelfth invention is the fluor fine particle film-layered body, wherein there are 2 kinds of organic covering films formed on the surface of the fluor fine particle, the fluor fine particle, on which the first organic film is formed, and the fluor fine particle, on which the second organic film is formed, are layered alternately.

A fourteenth invention according to thirteenth invention is the fluor fine particle film-layered body, wherein the first organic film reacts to the second organic film to form the covalent bond.

A fifteenth invention according to twelfth invention is the fluor fine particle film-layered body, wherein the covalent bond is the -N-C- bond formed by the reaction of the epoxy group to the imino group.

A sixteenth invention is the display device, using the fluor fine particle film-layered body according to the twelfth to the fifthteenth inventions.

A seventeenth invention is a photoreceptor, using the fluor fine particle film-layered body according to twelfth to fifthteenth inventions.

An eighteenth invention is a sensor, using the fluor fine particle film-layered body according to twelfth to fifthteenth inventions.

A nineteenth invention is a manufacturing method for the fluor fine particle film-layered body using: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting, for the reaction, the first fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; the step of washing out the first fluor fine particle covered with the excessive second reactive organic film to form the first monolayer fluor fine particle film; the step of forming the third reactive organic film on the surface of the second fluor fine particle by dispersing the second fluor fine particle in the chemical adsorption solution prepared by blending at least the third alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the second fluor fine particle; the step of contacting and reacting the second fluor fine particle covered with the third reactive organic film to the surface of the base material having the first monolayer fluor fine particle film covered with the second reactive organic film; and the step of washing out the second fluor fine particle covered with the excessive third reactive organic film to form the second monolayer fluor fine particle film. A twentieth invention according to nineteenth invention is the manufacturing method for the fluor fine particle film-layered body, wherein the first reactive organic film is identical to the third reactive organic film.

A twenty first invention according to nineteenth invention is the manufacturing method for the fluor fine particle film-layered body of a multilayer structure, wherein, following the step of forming the second monolayer fluor fine particle film, similarly, the step of forming the first monolayer fluor fine particle film and the step of forming the second monolayer fluor fine particle film are repeated.

A twenty second invention according to nineteenth invention is the manufacturing method for the fluor fine particle film-layered body, wherein, following the step of forming the first to third reactive organic films, for each of their steps, surfaces of the base material or the fluor fine particle are washed with the organic solvent to form the first to third reactive monomolecular films having the covalent bond to the surface of the base material and the fluor fine particle. A twenty third invention according to nineteenth invention is the manufacturing method for the fluor fine particle film-layered body, wherein the first and third reactive organic films contain the epoxy group and the second reactive organic film contains the imino group or the first and third reactive organic films contain the imino group and the second reactive organic film contains the epoxy group.

A twenty fourth invention according to the fifth and the nineteenth inventions is the manufacturing method for the monolayer fluor fine particle film and the fluor fine particle film-layered body, wherein, replacing to the silanol condensation catalyst, a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound are used.

A twenty fifth invention according to fifth and nineteenth inventions is the manufacturing method for the fluor fine particle film-layered body, wherein the silanol condensation catalyst is blended with ketimine compound or at least 1 selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound for use as a promoter.

The summary of the present invention will be described below.

The present invention aims to provide the monolayer fluor fine particle film, wherein the monolayer film of the fluor fine particle, which is formed on the surface of the base material, has the mutual covalent bond to the first organic film, which is formed on the surface of the base material, through the second organic film formed on the surface of the fluor fine particle, by: a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material; a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; a step of contacting, for a reaction, the fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; and washing out the fluor fine particle covered with an excessive second reactive organic film. Where, it is preferable for making control of the film thickness of the monolayer fluor fine particle film easy that, following a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material and a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle, washing each of the surface of the base material and the surface of the fluor fine particle with an organic solvent to form a first and second reactive monomolecular films having the covalent bond to the surface of the base material and the surface of the fluor fine particle.

Containing the epoxy group in the first reactive organic film and containing the imino group in the second reactive organic film or containing the imino group in the first reactive organic film and containing the epoxy group in the second reactive organic film is preferable for preparing the monomolecular fluor fine particle film having the covalent bond on the surface of the base material.

Containing an epoxy group in the first reactive monomolecular film and containing an imino group in the second reactive monomolecular film or containing the imino group in the first reactive monomolecular film and containing the epoxy group in the second reactive monomolecular film is preferable for preparing the monomolecular fluor fine particle film having the covalent bond on the surface of the base material.

Moreover, using the ketimine compound or the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound as a replacement of the silanol condensation catalyst is preferable for shortening the time for fabricating the film.

Using the ketimine compound or at least 1 selected from the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound as the promoter for blending with the silanol condensation catalyst is preferable for shortening further the time for fabricating the film.

Making different the first organic film, which is formed on the surface of the fluor fine particle, from the second organic film formed on the surface of the base material, is preferable for binding a single layer of the monolayer fluor fine particle film on the surface of the base material.

Using the -N-C- bond, which is formed by the reaction of the epoxy group to the imino group, as the covalent bond is preferable for providing the monolayer fluor fine particle film excellent in adhesion strength against the base material.

Composing the first organic covering film, which is formed on the surface of the fluor fine particle, and the second organic film formed on the surface of the base material, with the monomolecular film is preferable for improving evenness of the film thickness. The present invention provides the fluor fine particle film-layered body having the covalent bond of fluor fine particles, which is made by layering on the surface of the base material in stratification, between each other layer through the organic film, which is formed on the surface of the fluor fine particle, by: the step of forming the first reactive organic film on the surface of the base material by contacting at least the surface of the base material with the chemical adsorption solution prepared by blending the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting, for the reaction, the first fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; the step of washing out the first fluor fine particle covered with the excessive second reactive organic film to form the first monolayer fluor fine particle film; the step of forming the third reactive organic film on the surface of the second fluor fine particle by dispersing the second fluor fine particle in the chemical adsorption solution prepared by blending at least the third alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting and reacting the second fluor fine particle covered with the third reactive organic film to the surface of the base material having the first monolayer fluor fine particle film covered with the second reactive organic film; and the step of washing out the second fluor fine particle covered with the excessive third reactive organic film to form the second monolayer fluor fine particle film. Using the same materials for the first reactive organic film and the third reactive organic film is preferable for simplifying the method for manufacturing the fluor fine particle film-layered body. Following the step of forming the second monolayer fluor fine particle film, similarly, when the step of forming the first monolayer fluor fine particle film and the step of forming the second monolayer fluor fine particle film are repeated, the fluor fine particle film-layered body having the multilayer structure can be readily manufactured.

Following the step of forming the first to third reactive organic films, for each of their steps, washing the surface of the base material or the fluor fine particle with the organic solvent to form the first to third reactive monomolecular films having the covalent bond to the surfaces of the base material and the fluor fine particle is preferable for making the film thickness of the fluor fine particle film-layered body even.

Containing the epoxy group in the first and third reactive organic films and containing the imino group in the second reactive organic film or containing the imino group in the first and third reactive organic films and containing the epoxy group in the second reactive organic film are preferable for manufacturing the fluor fine particle film-layered body the covalent bond between layers by the reaction of the epoxy group to the imino group.

Replacing to the silanol condensation catalyst, using the ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound is preferable for shorten the time for making the film.

Using by blending the silanol condensation catalyst with ketimine compound or at least 1 selected from the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound as the promoter is preferable for further shorten the time for making the film.

Using two kinds of the organic films formed on the surface of the fluor fine particle, layering alternately the fluor fine particle, on which the first organic film is formed, and the fluor fine particle, on which the second organic film is formed, is preferable for manufacturing the fluor fine particle film-layered body having the multilayer structure in a simple process.

The covalent bond made by reaction of the first organic film and the second organic film is preferable for providing the fluor fine particle film-layered body excellent in adhesion strength. In addition, using the -N-C- bond, which is formed by the reaction of the epoxy group to the imino group, as the covalent bond is preferable for providing the fluor fine particle film-layered body excellent in strength.

As described above, according to the present invention, using the fluor fine particle, without loss of the inherent function of a variety of fluor fine particles, the following peculiar effects can be provided: the covering film (monolayer fluor fine particle film) made by the arrangement of only 1 layer of the fluor fine particles on the surface of the arbitrary base material and having the even thickness in the particle size level; the covering film (fluor fine particle film-layered body) made by layering the plurality of films made by arranging only 1 layer of the fluor fine particles; and manufacturing methods for them at a low cost.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same becomes better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein like reference numerals refer to like parts throughout the various views unless otherwise specified:

FIG. 1 is a conceptual rendering obtained by molecular level enlargement of the reaction of the surface of the fluor fine particle in the first example according to the present invention, FIG. 1A is a figure of the surface of the zinc sulfate fluor fine particle before the reaction, FIG. 1 B is the figure after the monomolecular film containing the epoxy group was formed, and FIG. 1 C is the figure after the monomolecular film containing the amino group was formed.

FIG. 2 is the conceptual rendering obtained by molecular level enlargement of the reaction of the surface of the glass base material in the second example according to the present invention, FIG. 2A is the figure of the surface before the reaction, FIG. 2B is the figure after the monomolecular film containing the epoxy group was formed, FIG. 2C is the figure after the monomolecular film containing the amino group was formed.

FIG. 3 is the conceptual rendering made by molecular level enlargement of the reaction of the surface of the glass base material in the third and fourth examples according to the present invention, FIG. 3A shows the figure of the surface of the base material, on which the monolayer zinc sulfate fluor fine particle film is formed, FIG. 3B shows the figure of the surface of the base material, on which two layers of the monolayer zinc sulfate fluor fine particle film were formed.

DETAILED DESCRIPTION

The present invention provides a display device, photoreceptor, and sensor using the fluor fine particle film-layered body having the covalent bond of fluor fine particles, which is made by layering on the surface of the base material in stratification, between each other layer through the organic film, which is formed on the surface of the fluor fine particle, by: the step of forming the first reactive organic film on the surface of the base material by contacting at least the surface of the base material with the chemical adsorption solution prepared by blending the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting, for the reaction, the first fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; the step of washing out the first fluor fine particle covered with the excessive second reactive organic film to form the first monolayer fluor fine particle film; the step of forming the third reactive organic film on the surface of the second fluor fine particle by dispersing the second fluor fine particle in the chemical adsorption solution prepared by blending at least the third alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting and reacting the second fluor fine particle covered with the third reactive organic film to the surface of the base material having the first monolayer fluor fine particle film covered with the second reactive organic film; and the step of washing out the second fluor fine particle covered with the excessive third reactive organic film to form the second monolayer fluor fine particle film.

Consequently, by using two kinds of the fluor fine particle covered with two kinds of covering films, without loss of the inherent function of a variety of fluor fine particles, the present invention has the effect of providing a product by using the covering film (monolayer fluor fine particle film) made by the arrangement of only 1 layer of the fluor fine particles on the surface of the arbitrary base material and having the even thickness in the particle size level and the covering film (fluor fine particle film-layered body) made by layering the plurality of films made by arranging only 1 layer of the fluor fine particles, and a manufacturing method for them conveniently at a low cost.

Details of the present invention will be described as follows with reference to examples. However, the present invention is not restricted by these examples.

The fluor fine particle of the monolayer fluor fine particle film and the fluor fine particle film-layered body according to the present invention includes mainly an alkali halide, rare earth ion fluor, manganese fluor, and sulfide fluor. A zinc sulfate fine particle fluor will be described below as the typical example. [Example 1]

First, an anhydrous zinc sulfate fine particle 1 having a size of about 100 nm was prepared and dried well. Subsequently, the reactive functional group such as the epoxy group or the imino group as the chemical adsorbent in the functional site and the drug containing the alkoxy silyl group, which is exemplified by the drug shown by the following formula (chemical formula C1 ) or (chemical formula C2,) in the other terminal were weighed to make 99 weight percent each, and, dibutyltin diacetylacetonate or acetic acid being an organic acid, for example, as a silanol condensation catalyst is weighed to make about 1 weight percent. All these drugs were dissolved in a mixture solvent made of a silicone solvent, for example, hexamethyl disiloxane and dimethyl formamide (50: 50) to make about 1 weight percent concentration (preferable concentration of the chemical adsorbent ranges from about 0.5 to 3%) to prepare a chemical adsorbent solution. [C1]

O OCH₃

CH₂-CHCH₂O(CH₂)SSi -OCH₃

OCH₃ [C2J

OCH₃

H₂N(CH₂)₃Si —OCH₃ OCH₃

Anhydrous zinc sulfate fluor fine particle 1 was mixed with this adsorbent solution, stirred, and reacted in normal air (relative humidity 45%) for about 2 hours. At this time, a dangling bond of the surface of the anhydrous zinc sulfate fluor fine particle contains many hydroxyl groups 2 (FIG. 1A) and, thus, -Si- (OCH₃) group of the chemical adsorbent makes dealcohol (in this case, deCH₃OH) reaction to the hydroxyl groups in the presence of the silanol condensation catalyst or the acetic acid as the organic acid to make the bond shown in the following formula (chemical formula C3) or (chemical formula C4) resulting in formation of the chemical adsorption monomolecular film 3, which contains the epoxy group chemically bonded to the surface across all the surface of the fluor fine particle, or the chemical adsorption film 4, which contains the amino group, in the film thickness of about 1 nanometer (FIG. 1B, 1C.) When the adsorbent containing the amino group was used, the tin-based catalyst causes a precipitation and, therefore, the organic acid such as the acetic acid should be used. On the other hand, the amino group contains the imino group. Substances, except the amino group, containing the imino group include a pyrrole derivative and imidazol derivative. Moreover, using a ketimine derivative allows introducing easily the amino group by hydrolysis following formation of the covering film. Thereafter, stirring and washing after adding the chlorine-based solvent (in this example, trichloroethylene,) chloroform, allowed preparing each of zinc sulfate fluor fine particle 5 covered with the chemical adsorption monomolecular film having the reactive functional group such as the epoxy group on the surface, or, zinc sulfate fluor fine particle 6 covered with the chemical adsorption monomolecular film having the amino group. [C3]

O O—

CH₂-CHCH₂O(CH₂)SSi -O-

[C4]

O—

H₂N(CH₂)₃Si — O — O—

This covering film has the film thickness very thin on the nanometer level and, therefore, showed no loss of the particle size.

On the other hand, exposing to air without washing caused almost no change of reactivity and evaporation of the solvent. As the result, the chemical adsorbent left on the surface of the particle reacted to water in air on the surface to gave the fluor fine particle, on which the very thin polymer film, which is slightly thicker in comparison with the monomolecular film and composed of the chemical adsorbent, was formed on the surface.

Features of this method using the dealcohol reaction is that the fluor fine particle of an organic material can be used to enable to apply to a wide range of application fields.

[Example 2]

First, similar to Example 1 , glass base material 11 was prepared and dried well. Next, the reactive functional group such as the epoxy group or the imino group as the chemical adsorbent in the functional site and the drug containing the alkoxy silyl group, which is exemplified by the drug shown by the formula (chemical formula C1 ) or (chemical formula C2,) as described above in the other terminal were weighed to make 99 weight percent each, and, dibutyltin diacetylacetonate, for example, as the silanol condensation catalyst is weighed to make about 1 weight percent. All these drugs were dissolved in the silicon solvent, for example, the hexamethyl disiloxane solvent to make about 1 weight percent concentration (preferable concentration of the chemical adsorbent ranges from about 0.5 to 3%) to prepare the chemical adsorbent solution.

Next, glass base material 11 was soaked in this adsorbent solution for reaction in normal air (relative humidity 45%) for about 2 hours. At this time, the surface of glass base material 11 contains many hydroxyl groups 12 (FIG. 2A) and, thus, -Si- (OCH₃) group of the chemical adsorbent causes dealcohol (in this case, deCHaOH) reaction to the hydroxyl groups in the presence of the silanol condensation catalyst to make the bond shown in the formula (chemical formula C3) or (chemical formula C4) resulting in the formation of the chemical adsorption monomolecular film 13 (FIG. 2B₁) which contains the epoxy group chemically bonded to the surface across all the surface of glass base material 11 , (or the chemical adsorption film 14 containing the amino group (FIG. 2C) in the film thickness of about 1 nanometer.

Then, washing with chloroform as the chlorine-based solvent (in this example, trichloroethylene) allowed preparing glass base material 15 covered with the chemical adsorption monomolecular film having the reactive functional group such as the epoxy group on the surface, or, glass base material 16 covered with the chemical adsorption monomolecular film having the amino group (FIG. 2B and 2C.)

This covering film has the film thickness very thin on the nanometer level and, therefore, showed no loss of the clarity of the glass base material.

On the other hand, exposing to air without washing caused almost no change of reactivity and evaporation of the solvent. As the result, the chemical adsorbent left on the surface of the glass base material reacted to water in air on the surface to gave the glass base material, on which the very thin polymer film, which is composed of the chemical adsorbent, was formed on the surface.

[Example 3]

Next, on the surface of glass base material 15 covered with the chemical adsorption monomolecular film having the epoxy group, zinc sulfate fluor fine particle

6 covered with the chemical adsorption monomolecular film having the amino group

(replacement is a combination of the zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the epoxy group and the surface of the glass base material covered with the chemical adsorption monomolecular film having the amino group) was dispersed on alcohol to be applied and heated (in this example, 100 deg C.) As the result, the amino group on the surface of the zinc sulfate fluor fine particle contacting to the epoxy group on the surface of the glass base material was added by the reaction shown by the following formula (Chemical formula C5) to bind the fluor fine particle to the glass base material through the two monomolecular films resulting in the final hardening. At this time, evaporating alcohol irradiating an ultrasonic wave enabled to improve the evenness of the film thickness of the covering film.

[C5]

O -(CH₂)CH -CH₂ + H₂NCH₂ -

► - (CH₂)CHCH₂ -NHCH₂ -

OH

Then, washing again the surface of the base material with alcohol to wash out the zinc sulfate fluor fine particle, which is covered with the chemical adsorption monomolecular film having an excess of an unreacted amino group, enables to form the monolayer fluor fine particle film 17 in a state of single layer arrangement of the zinc sulfate fluor fine particles, which was covered with the chemical adsorption monomolecular film having the amino group having the covalent bond to the surface of glass base material 15, having the even thickness in the particle size level (FIG. 3A.)

On the other hand, when the covering film of the zinc sulfate fluor fine particle, which is covered with the chemical adsorption monomolecular film having the epoxy group, is formed on the surface of the glass base material, which is covered with the chemical adsorption monomolecular film having the amino group, the monolayer fluor fine particle film was formed in the state of only single layer arrangement of the zinc sulfate fluor fine particles covered with the chemical adsorption monomolecular film having the epoxy group with the covalent bond to the surface of glass base material, having the even thickness in the particle size level. The thickness of the monolayer fluor fine particle film of the zinc sulfate fluor fine particles was about 100 nm with very even thickness and, hence, interference colors were never observed. [Example 4] Meanwhile, when thickening the film thickness of the fluor fine particle film is desired, following Example 3, zinc sulfate fluor fine particle 5 covered with the chemical adsorption monomolecular film having the epoxy group was dispersed in alcohol, applied to the surface of glass base material 15, on which the monolayer fluor fine particle film 17 was formed in the state of only single layer arrangement of the zinc sulfate fluor fine particles covered with the chemical adsorption monomolecular film having the amino group with the covalent bond, having the even thickness on the particle size, and heated (in the present example, to 100 deg C.) Then, the epoxy group on the surface of the zinc sulfate fluor fine particle contacting to the amino group on the surface of the glass base material, on which the monolayer fluor fine particle film of the zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the amino group was formed, was added by the reaction shown by the formula (Chemical formula C5) to bind the zinc sulfate fluor fine particle, which is covered with the chemical adsorption monomolecular film having the epoxy group, to the fluor fine particle, which is covered with the chemical adsorption monomolecular film having the amino group, on the glass base material through the two monomolecular films resulting in the final hardening.

Then, washing again the surface of the base material with alcohol to wash out the zinc sulfate fluor fine particle, which is covered with the chemical adsorption monomolecular film having an excess of the unreacted epoxy group, enables to form a double layer fluor fine particle film 18 having a double layer structure in the state of only single layer arrangement of the zinc sulfate fluor fine particles of a second layer, which has the covalent bond to the surface of glass base material 15, having the even thickness in the particle size level (FIG. 3B.) Following these steps, similarly, layering alternately the zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the amino group and the zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the epoxy group allowed fabricating the layered covering films of the fluor fine particle having the arbitrary thickness and the multilayer structure.

In Examples 1 and 2 as described above, the material shown in the formula (Chemical formula C1) or (Chemical formula C2) was used as the chemical adsorbent containing the reactive group. Other materials, which are shown in the following (1) to (16,) than those as described above were usable.

(1 ) (CH₂OCH) CH₂O (CHa)₇ Si(OCH₃)₃

(2) (CH₂OCH) CH₂O (CH₂)H Si(OCH₃)₃

(3) (CH₂CHOCH (CH₂)₂) CH(CH₂)₂ Si(OCH₃)₃

(4) (CH₂CHOCH (CH₂)₂) CH(CH₂)₄ Si(OCH₃)₃ (5) (CH₂CHOCH (CH₂)₂) CH(CH₂)₆ Si(OCH₃)₃

(6) (CH₂OCH) CH₂O (CH₂)₇ Si(OC₂Hs)₃

(7) (CH₂OCH) CH₂O (CH₂)H Si(OC₂Hs)₃

(8) (CH₂CHOCH (CHz)₂)CH (CH₂)₂ Si(OC₂Hs)₃

(9) (CH₂CHOCH (CH₂)₂)CH (CH₂)₄ Si(OC₂Hs)₃ (10) (CH₂CHOCH (CH₂)₂)CH (CH₂)₆ Si(OC₂Hs)₃

(11 ) H₂N (CH₂) ₅Si (OCH₃)₃

(12) H₂N (CHz) ₇Si (OCH₃)s

(13) H₂N (CHz) ₉Si (OCHs)₃

(14) H₂N (CH₂) 5Si (OC₂Hs)₃ (15) H₂N (CH₂) ₇Si (OC₂Hs)₃

(16) H₂N (CH₂) 9Si (OC₂Hs)₃

Here, (CH₂OCH)- group represents the functional group expressed by the following formula (Chemical formula C7) and (CH₂CHOCH (CH₂)₂) CH- group represents the functional group expressed by the following formula (Chemical formula C8.) [C6] O CH₂-CH

[C7]

D _CH__CH2

\ / \

CH CH

\ /

CH₂ - CH₂

In Examples 1 and 2, usable silanol condensation catalysts include a metal salt of a carboxylic acid, the metal salt of a carboxylic acid ester, polymer of the metal salt of the carboxylic acid, a chelate of the metal salt of the carboxylic acid, titanic acid ester, and chelates of the titanic acid ester. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, tin dioctanoate, lead naphtenate, cobalt naphtenate, iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate ester salt, dioctyltin maleate ester salt, dibutyltin maleate salt polymer, dimetyltin mercaptopropionate salt polymer, dibutyltin bisacetyl acetate, dioctyltin bisacetyl laurate, tetrabutyl titanate, tetranonyl titanate, and bis (acetyl acetonyl) dipropyl titanate were usable.

Usable solvents for a film formation solution were an organic chlorine-based solvent containing no water, hydrocarbon-based solvent, or carbon fluoride-based solvent, and silicone-based solvent, or a mixture thereof. In the case of attempting to increase a particle concentration by evaporating the solvent without washing, a boiling point of the solvent ranges preferably from about 50 to 250 deg C. In addition, in the case where the adsorbent is assumed as an alkoxysilane-based and the organic covering film is formed by evaporating the solvent, in addition to the solvents as described above, alcohol-based solvents such as methanol, ethanol, and propanol or the mixture thereof could be used.

Specifically usable solvents include a chlorosilane-based nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzene, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosine, dimethyl silicone, phenyl silicone, alkyl denatured silicone, polyether silicone, and dimethyl formamide. Carbon fluoride-based solvents include freon-based solvent, Frorinate (made by Sumitomo 3M Limited,) and Aflude (Asahi Glass Co. made.) These may be singly used as the monolayer and, if they are blended well, may be used in a combination of two kinds. In addition, the organic chlorine-based solvent such as chloroform may be added. On the other hand, when silanol condensation catalysts as described above were replaced for use by the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound, a process time could be shorten to make a half to 2/ 3 of the time necessary for the same concentration. Moreover, using the silanol condensation catalyst by mixing (a range from 1 :

9 to 9: 1 can be applied, but normally around 1 : 1 is preferable) with the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound can make the process time fast several-fold (up to about 30 minutes) resulting in shortening of the time for making the film up to several-fold decrease.

For example, dibutyltin oxide being the silanol catalyst was replaced by Japan Epoxy Resin Co. made H3 being the ketimine compound under the same condition. Almost same result was obtained except that the reaction time became short to about 1 hour. In addition, the silanol catalyst was replaced by the mixture (mixture ratio was

1 : 1 ) of Japan Epoxy Resin Co. made H3 being the ketimine compound and dibutyltin bisacetyl acetonate being the silanol catalyst and other conditions were set identical. Almost same result was obtained except that the reaction time became short to about 30 minutes. Consequently, from the results as described above, it found that the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound has a higher activity than that of the silanol condensation catalyst.

Furthermore, it was observed that using 1 of the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound by mixing with the silanol condensation catalyst shows further higher activity.

Where, usable ketimine compounds are not specially restricted, but include, for example, 2,5,8-triaza-1 ,8-nonadiene,

3, 11 -dimethyl-4,7, 10-triaza-3, 10-tridecadiene, 2,10 dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4, 12, 14-tetramethyl-5,8, 11 -triaza-4, 11 -pentadecadiene, 2,4, 15,17- tetramethyl-5,8, 11 , 14-tetraaza-4, 14-octadecadiene, 2,4,20,22- tetramethyl-5, 12,19-triaza-4, 19-trieicosadiene.

Usable organic acids are not specially restricted, but include, for example, formic acid, or acetic acid, propionic acid, butyric acid, and malonic acid and showed the almost same effect.

Using the monolayer fluor fine particle film and the fluor fine particle film-layered body enables to manufacture the display device excellent in evenness of brightness, photoreceptor excellent in evenness of display quality, and sensor excellent in evenness of sensitivity. In Examples 1 to 4 as described above, the description is made for the zinc sulfate fluor fine particle and the glass base material as examples of the fluor. The present invention can be applied to the alkali halide, rare earth ion fluor, manganese fluor, and sulfide fluor, and also applied to an organic fluor of which surface has an active hydrogen such as the hydroxyl group and the imino group. Furthermore, application of the present invention includes a display, fluorescent lighting, indication board, photographic plate, for example, for an X-ray, optical recording medium, electronic photographic image bar, and gas concentration sensor.

Claims

1. A monolayer fluor fine particle film having a covalent bond of a film of a monolayer of a fluor fine particle formed on a surface of a base material to a first organic film formed on the surface of the base material, through a second organic film formed on the surface of the fluor fine particle.

2. The monolayer fluor fine particle film according to claim 1 , wherein the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle are different from each other.

3. The monolayer fluor fine particle film according to claim 1 , wherein the covalent bond is a -N-C- bond formed by a reaction of an epoxy group and an imino group.

4. The monolayer fluor fine particle film according to claim 1 or claim 2, wherein the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle are constituted from a monomolecular film.

5. A display device, using the fluor fine particle film according to one of claim 1 to claim 4.

6. A photoreceptor, using the fluor fine particle film according to one of claim 1 to claim 4.

7. A sensor, using the fluor fine particle film according to one of claim 1 to claim 4.

8. A manufacturing method for the monolayer fluor fine particle film, comprising: a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material; a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; a step of contacting, for a reaction, the fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; and washing out the fluor fine particle covered with an excessive second reactive organic film.

9. The manufacturing method for the monolayer fluor fine particle film according to claim 8, comprising: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material and a step of forming the second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle, followed by washing each of the base material and the surface of the fluor fine particle with an organic solvent to form a first and second reactive monomolecular films having the covalent bond to the base material and the surface of the fluor fine particle.

10. The manufacturing method for the monolayer fluor fine particle film according to claim 8, wherein the first reactive organic film contains an epoxy group and the second reactive organic film contains an imino group or the first reactive organic film contains the imino group and the second reactive organic film contains the epoxy group.

11. The manufacturing method for the monolayer fluor fine particle film according to claim 9, wherein the first reactive monomolecular film contains an epoxy group and the second reactive monomolecular film contains an imino group or the first reactive monomolecular film contains the imino group and the second reactive monomolecular film contains the epoxy group.

12. A fluor fine particle film-layered body layered as stratification on the surface of the base material, wherein the fluor fine particle has the covalent bond between layers through an organic covering film formed on the surface of the fluor fine particle.

13. The fluor fine particle film-layered body according to claim 12, wherein there are 2 kinds of organic covering films formed on the surface of the fluor fine particle, the fluor fine particle, on which the first organic film is formed, and the fluor fine particle, on which the second organic film is formed, are layered alternately.

14. The fluor fine particle film-layered body according to claim 13, wherein the first organic film reacts to the second organic film to form the covalent bond.

15. The fluor fine particle film-layered body according to claim 12, wherein the covalent bond is the -N-C- bond formed by the reaction of the epoxy group to the imino group.

16. The display device, using the fluor fine particle film-layered body according to one of claims from 12 to 15.

17. The photoreceptor, using the fluor fine particle film-layered body according to one of claims from 12 to 15.

18. The sensor, using the fluor fine particle film-layered body according to one of claims from 12 to 15.

19. A manufacturing method for the fluor fine particle film-layered body comprising: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting, for the reaction, the first fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; the step of washing out the first fluor fine particle covered with the excessive second reactive organic film to form the first monolayer fluor fine particle film; the step of forming the third reactive organic film on the surface of the second fluor fine particle by dispersing the second fluor fine particle in the chemical adsorption solution prepared by blending at least the third alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the second fluor fine particle; the step of contacting and reacting the second fluor fine particle covered with the third reactive organic film to the surface of the base material having the first monolayer fluor fine particle film covered with the second reactive organic film; and the step of washing out the second fluor fine particle covered with the excessive third reactive organic film to form the second monolayer fluor fine particle film.

20. The manufacturing method for the fluor fine particle film-layered body according to claim 19, wherein the first reactive organic film is identical to the third reactive organic film.

21. The manufacturing method for the fluor fine particle film-layered body of a multilayer structure according to claim 19, wherein, following the step of forming the second monolayer fluor fine particle film, similarly, the step of forming the first monolayer fluor fine particle film and the step of forming the second monolayer fluor fine particle film are repeated.

22. The manufacturing method for the fluor fine particle film-layered body according to claim 19, wherein, following the step of forming the first to third reactive organic films, for each of their steps, surfaces of the base material or the fluor fine particle are washed with the organic solvent to form the first to third reactive monomolecular films having the covalent bond to the surface of the base material and the fluor fine particle.

23. The manufacturing method for the fluor fine particle film-layered body according to claim 19, wherein the first and third reactive organic films contain the epoxy group and the second reactive organic film contains the imino group or the first and third reactive organic films contain the imino group and the second reactive organic film contains the epoxy group.

24. The manufacturing method for the monolayer fluor fine particle film and the fluor fine particle film-layered body according to claim 5 or claim 19, wherein, replacing to the silanol condensation catalyst, a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound are used.

25. The manufacturing method for the monolayer fluor fine particle film and the fluor fine particle film-layered body according to claim 5 or claim 19, wherein the silanol condensation catalyst is blended with ketimine compound or at least 1 selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound for use as a promoter.