WO2008136129A1

WO2008136129A1 - Pattern-like fine particle film and manufacturing method

Info

Publication number: WO2008136129A1
Application number: PCT/JP2007/059286
Authority: WO
Inventors: Kazufumi Ogawa
Original assignee: Kazufumi Ogawa
Priority date: 2007-04-23
Filing date: 2007-04-23
Publication date: 2008-11-13

Abstract

By a step of forming a first organic film on a surface of a base material by contacting with a chemical adsorption solution prepared by blending an alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react to an alkoxysilane compound to a surface of a base material; a step of processing the first organic film to make a predetermined pattern; a step of forming a second organic film on a surface by dispersing in a chemical adsorption solution prepared by blending a second alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; a step of contacting a fine particle covered with the second organic film to a surface of the first base material to make selectively a reaction; and a step of washing and removing excessive fine particles covered with the second organic film, a pattern-like monolayer fine particle film having a mutual covalent bond is provided through a first organic film and a second organic film.

Description

DESCRIPTION

PATTERN-LIKE FINE PARTICLE FILM AND MANUFACTURING METHOD

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to a pattern-like monolayer fine particle film, a pattern-like layered fine particle film, and a manufacturing method. More specifically, the present invention relates to the pattern-like monolayer fine particle film, the pattern-like layered fine particle film made from fine particles, of which the surface is given heat-reactivity or photoreactivity or radical reactivity or ion reactivity, and a manufacturing method.

According to the present invention, "inorganic fine particle" includes a conductive base material fine particle, semiconductor fine particle, insulant fine particle, magnetic fine particle, fluorescent base material fine particle, light absorption fine particle, light transmission fine particle, and pigment fine particle. "Organic fine particle" includes an organic fluorescent base material fine particle, organic light absorption fine particle, organic light transmission fine particle, organic pigment fine particle, and drug fine particle. Organic- inorganic hybrid fine particle" includes a drug fine particle used for DDS (Drug Delivery System,) fine particle used for cosmetics, and organic-inorganic hybrid pigment fine particle.

Description of Related Art Conventionally, there is a known method called the Langmuir-Blodgett (LB) method for layering a monomolecular film on a surface of a substrate by arranging molecules on a water surface by using amphipatic 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. However, a covering film (pattern-like monolayer fine particle film) with even thickness in a molecular size, which is made by arranging only a monolayer of fine particles on an arbitrary base material surface, the covering film (pattern-like layered fine particle films) made by layering a plurality of layers of the film, which is made by arranging fine particles as only a monolayer, in a pattern-like shape, and the manufacturing method have not been developed and provided.

Conventionally, micron sizes and nano sizes of fine particles having a variety of functions, such as electric functions, magnetic functions, and optical functions have been developed and manufactured. Applying effectively inherent functions of these fine particles requires making fine particles in a covering film with an even thickness. However, there was no idea of manufacturing the covering film with an even thickness on a particle size level by using these fine particles.

SUMMARY OF THE INVENTION

The present invention aims to provide the covering film (pattern-like monolayer fine particle film) with even thickness in a molecular size, which is made by arranging only the monolayer of fine particles on the arbitrary base material surface in the pattern-like shape, the covering film (pattern-like layered fine particle films) made by layering a plurality of layers of film, which is made by arranging fine particles only as a monolayer, and the manufacturing method.

A first invention provided as a means for solving the problem is A pattern-like monolayer fine particle film having a covalent bond of a film of a monolayer of a fine particle formed selectively on a surface of a base material to a first organic film formed selectively on a surface of a base material, through a second organic film formed on a surface of a fine particle.

A second invention according to the first invention is a pattern-like monolayer fine particle film, wherein a first organic covering film formed on a surface of a base material and a second organic film formed on a surface of a fine particle are different from each other.

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

A fourth invention according to the first and the second invention is a pattern-like monolayer fine particle film, wherein each of the first organic covering film formed on a surface of a base material and a second organic film formed on a surface of a fine particle are constituted from a monomolecular film. A fifth invention is a manufacturing method for a pattern-like monolayer fine particle film, comprising: a step of forming a first reactive organic film on a surface of a base material by contacting a surface of a 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 a surface of a base material; a step of processing the first reactive organic film to make a predetermined pattern; a step of forming a second reactive organic film on a surface of the fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least a second alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; a step of contacting, for a selective reaction, a fine particle covered with the second reactive organic film to a surface of a base material having the first reactive organic film formed thereon; and washing and removing a fine particle covered with an excessive second reactive organic film.

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

A seventh invention according to the fifth invention is the manufacturing method for a pattern-like monolayer fine particle film, wherein the first reactive organic film contains an epoxy group and the second reactive organic film contains an imino group.

An eighth invention according to the sixth invention is the manufacturing method for a pattern-like monolayer fine particle film, wherein the first reactive monomolecular film contains an epoxy group and the second reactive monomolecular film contains an imino group.

A ninth invention is a pattern-like layered fine particle film layered as stratification selectively on a surface of a base material having a fine particle having the covalent bond between layers through an organic covering film formed on a surface of a fine particle. A tenth invention according to the ninth invention is a pattern-like layered fine particle film, wherein there are two kinds of an organic covering film formed on a surface of a fine particle, the particle having the first organic film and the particle having the second organic film are layered alternately.

An eleventh invention according to the tenth invention is a pattern-like layered fine particle film, wherein the first organic film reacts to the second organic film to form the covalent bond.

A twelfth invention according to the ninth invention is A pattern-like layered fine particle film, wherein the covalent bond is an -N-C- bond formed by a reaction of an epoxy group to an imino group. A thirteenth invention is a manufacturing method for a pattern-like layered fine particle film comprising: the step of forming the first reactive organic film on a surface of a base material by contacting a surface of a base material with a chemical adsorption solution prepared by blending at least the first alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a base material; the step of processing the first reactive organic film to make a predetermined pattern; the step of forming the second reactive organic film on a surface of a fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least the second alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; the step of contacting, for the selective reaction, a fine particle covered with the second reactive organic film to a surface of a base material having the first reactive organic film formed thereon; the step of washing and removing the first fine particle covered with the excessive second reactive organic film to form selectively the first pattern-like monolayer fine particle film; the step of forming the third reactive organic film on a surface of the second fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least the third alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; the step of contacting and reacting the second fine particle covered with the third reactive organic film to a surface of a base material having the first pattern-like monolayer fine particle film covered with the second reactive organic film; and the step of washing and removing the second fine particle covered with the excessive third reactive organic film to form selectively the second pattern-like monolayer fine particle film.

A fourteenth invention according to the thirteenth invention is the manufacturing method for a pattern-like layered fine particle film, wherein the first reactive organic film is identical to the third reactive organic film.

A fifteenth invention according to the thirteenth invention is a manufacturing method for a pattern-like layered fine particle film of a multilayer structure, wherein, following the step of forming the second pattern-like monolayer fine particle film, similarly, the step of forming and the step of forming the first pattern-like monolayer fine particle film and the second pattern-like monolayer fine particle film are repeated. A sixteenth invention according to the thirteenth invention is a manufacturing method for a pattern-like layered fine particle film, wherein, following the step of forming the first to third reactive organic films, each, a surface of a base material or a fine particle is washed with the organic solvent to form the first to third reactive monomolecular films having the covalent bond to a surface of a base material and a fine particle. A seventeenth invention is a manufacturing method for a pattern-like layered fine particle film having the first and third reactive organic films containing the epoxy group and the second reactive organic film contains the imino group.

A eighteenth invention according to the fifth invention and thirteenth invention is the manufacturing method for a pattern-like monolayer fine particle film and a pattern-like layered fine particle film, wherein, replacing to a silanol condensation catalyst, a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound are used.

A nineteenth invention according to the fifth invention and thirteenth invention is a manufacturing method for a pattern-like monolayer fine particle film and a pattern-like layered fine particle film, wherein a silanol condensation catalyst is blended with ketimine compound or at least one selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound for use as a promoter. Further descriptions are given as follows in detail.

The present invention aims to provide a pattern-like monolayer fine particle film, wherein the film of the monolayer of a fine particle, which is formed selectively on a surface of a base material, has a covalent bond to the first organic film, which is formed selectively on a surface of a base material, through the second organic film formed on a surface of a fine particle, by a step of forming a first reactive organic film on a surface of a base material by contacting a surface of a 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 a surface of a base material, a step of processing the first reactive organic film to make a predetermined pattern, a step of forming a second reactive organic film on a surface of a fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least a second alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle, a step of contacting, for a selective reaction, a fine particle covered with the second reactive organic film to a surface of a base material having the first reactive organic film formed thereon, and washing and removing a fine particle covered with an excessive second reactive organic film.

Where, it is preferable that, following a step of forming a first reactive organic film on a surface of a base material by contacting a surface of a 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 a surface of a base material and a step of forming a second reactive organic film on a surface of a fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least a second alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle, washing each of a surface of a base material and a surface of a fine particle with an organic solvent to form a first and second reactive monomolecular films having a covalent bond to a surface of a base material and a surface of a fine particle enables easily to control the thickness of a pattern-like monolayer fine particle film.

Furthermore, containing an epoxy group in the first reactive organic film and containing an imino group in the second reactive organic film are preferable for preparing a pattern-like monolayer fine particle film having a covalent bond to a surface of a base material.

On the other hand, containing an epoxy group in the first reactive monomolecular film and containing an imino group in the second reactive monomolecular film are preferable for preparing a pattern-like monolayer fine particle film having a covalent bond to a surface of a base material. In addition, using, replacing to a silanol condensation catalyst, a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound is preferable for shortening a time for preparing the film.

Moreover, using a silanol condensation catalyst by blending 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 is preferable for shortening further the time for preparing the film.

Where, making the first organic covering film formed on a surface of a fine particle and the second organic film formed on a surface of a base material different from each other is preferable for bonding only one layer of a pattern-like monolayer fine particle film to a surface of a base material. In addition, using an -N-C- bond as a covalent bond formed by a reaction of an epoxy group to an imino group is preferable for providing a pattern-like monolayer fine particle film excellent in strength of a contact to a base material.

On the other hand, constituting the first organic covering film formed on a surface of a fine particle and the second organic film formed on a surface of a base material from the monomolecular film is preferable for improving the evenness of a film thickness.

Further, the present invention aims to provide a pattern-like layered fine particle film, which is made by layering selectively on a surface of a base material in stratification, having a covalent bond of fine particles between each other layer through the organic covering film formed on a surface of a fine particle by: the step of forming the first reactive organic film on a surface of a base material by contacting a surface of a base material with a chemical adsorption solution prepared by blending at least the first alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a base material; the step of processing the first reactive organic film to make a predetermined pattern; the step of forming the second reactive organic film on a surface of a fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least the second alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; the step of contacting, for the selective reaction, a fine particle covered with the second reactive organic film to a surface of a base material having the first reactive organic film formed thereon; the step of washing and removing the first fine particle covered with the excessive second reactive organic film to form selectively the first pattern-like monolayer fine particle film; the step of forming the third reactive organic film on a surface of the second fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least the third alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; the step of contacting and reacting the second fine particle covered with the third reactive organic film to a surface of a base material having the first pattern-like monolayer fine particle film covered with the second reactive organic film; and the step of washing and removing the second fine particle covered with the excessive third reactive organic film to form selectively the second pattern-like monolayer fine particle film.

Where, using the first reactive organic film and the third reactive organic film, when they are identical to each other, is preferable for simplify the manufacturing method for a pattern-like layered fine particle film. In addition, following the step of forming the second pattern-like monolayer fine particle film, similarly, repeating the step of forming and the step of forming the first pattern-like monolayer fine particle film and the second pattern-like monolayer fine particle film enables easy manufacture of a pattern-like layered fine particle film of the multilayer structure. Furthermore, following the step of forming the first to third reactive organic films, each, washing a surface of a base material or a fine particle with the organic solvent to form the first to third reactive monomolecular films having a covalent bond to a surface of a base material and a fine particle is preferable for making the film thickness of a pattern-like layered fine particle film even. Still further, containing the epoxy group in the first and third reactive organic films and containing the imino group the second reactive organic film are preferable for manufacturing a pattern-like layered fine particle film having a covalent bond between layers by a reaction of an epoxy group to an imino group.

Moreover, using, replacing to a silanol condensation catalyst, the ketimine compound or the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound is preferable for shortening the time for manufacturing the film.

Using the ketimine compound or at least one selected from the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound as the promoter for blending with a silanol condensation catalyst is preferable for shortening further the time for manufacturing the film. Additionally, here, using two kinds of organic covering films formed on a surface of a fine particle to layer alternately the particle having the first organic film and the particle having the second organic film is preferable for manufacturing the multilayer pattern-like layered fine particle film in a simple process.

Further, forming a covalent bond by reaction of the first organic film to the second organic film is preferable for providing a pattern-like layered fine particle film excellent in strength of contact. On the other hand, using the -N-C- bond formed by a reaction of an epoxy group to an imino group as a covalent bond is preferable for providing a pattern-like layered fine particle film excellent in strength.

As described above, according to the present invention, using a fine particle, without loss of the inherent function of a variety of fine particles, the following prominent effects can be provided at a low cost: diffraction grating using a pattern-like monolayer fine particle film made by arranging only one layer of fine particles on an arbitrary surface of a base material and having an even thickness in a particle size level and the diffraction grating using a pattern-like layered fine particle film made by layering a plurality of films made by arranging only one layer of fine particles and manufacturing methods hereof.

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 schematic view of a reaction mechanism on a surface of glass base material enlarged to a molecular level in a first Embodiment according to the present invention, while Fig. 1 A is a view of the surface before a reaction, Fig. 1 B is a view after the monomolecular film containing the epoxy group was formed, Fig. 1 C is a view after the monomolecular film containing the amino group was formed.

Fig. 2 is a schematic view of a reaction mechanism on a surface of the nickel fine particle enlarged to a molecular level in a second Embodiment according to the present invention, while Fig. 2A is a view of the surface of the nickel fine particle before the reaction, Fig. 2B is a view after the monomolecular film containing the epoxy group was formed, Fig. 1 C is a view after the monomolecular film containing the amino group was formed.

Fig. 3 is a schematic view of a reaction mechanism on a surface of glass base material enlarged to a molecular level in a third and fourth Embodiments according to the present invention, while Fig. 3A is a view of the surface of a base material formed as a pattern-like monolayer nickel fine particle film diffraction grating, Fig. 3B is a view of a surface of a base material, on which two layers of a pattern-like monolayer nickel fine particle film were formed as the diffraction grating.

DETAILED DESCRIPTION

Embodiments of the present invention are described herein. In the following description, numerous specific details are set forth to provide a thorough understanding of embodiments of the invention. One skilled in the relevant art will recognize, however, that the invention can be practiced without one or more of the specific details, or with other methods, components, materials, etc. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.

The present invention provides a pattern-like layered fine particle film, which is made by layering on a surface of a base material in stratification, having a covalent bond of fine particles between each other layer through the organic covering film formed on a surface of a fine particle by: the step of forming the first reactive organic film on a surface of a base material by contacting a surface of a base material with a chemical adsorption solution prepared by blending at least the first alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a base material; the step of processing the first reactive organic film to make a predetermined pattern; the step of forming the second reactive organic film on a surface of a fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least the second alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; the step of contacting, for the selective reaction, a fine particle covered with the second reactive organic film to a surface of a base material having the first reactive organic film formed thereon; the step of washing and removing the first fine particle covered with the excessive second reactive organic film to form the first pattern-like monolayer fine particle film; the step of forming the third reactive organic film on a surface of the second fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least the third alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; the step of contacting and reacting the second fine particle covered with the third reactive organic film to a surface of a base material having the first pattern-like monolayer fine particle film covered with the second reactive organic film; and the step of washing and removing the second fine particle covered with the excessive third reactive organic film to form the second pattern-like monolayer fine particle film.

Therefore, using the two kinds of fine particles covered with two kinds of covering films, without loss of the inherent function of a variety of fine particles, the present invention can provide the following actions and manufacture conveniently them at a low cost: the diffraction grating using the covering film (a pattern-like monolayer fine particle film) made by selectively arranging only one layer of fine particles on an arbitrary surface of a base material and having an even thickness in a particle size level; and the diffraction grating using the covering film (a pattern-like layered fine particle film) made by selectively layering a plurality of films made by arranging only one layer of fine particles.

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

Usable "inorganic fine particle" preparation of a pattern-like monolayer fine particle film and a pattern-like layered fine particle film according to the present invention includes a conductive fine particle, semiconductor fine particle, insulant fine particle, magnetic fine particle, fluorescent fine particle, light absorption fine particle, light transmission fine particle, and pigment fine particle. Usable "organic fine particle" includes an organic fluorescent fine particle, organic light absorption fine particle, organic light transmission fine particle, organic pigment fine particle, and drug fine particle. Furthermore, usable "organic- inorganic hybrid fine particle" includes a drug fine particle used for DDS (Drug Delivery System,) fine particle used for cosmetics, and organic- inorganic hybrid pigment fine particle. A nickel fine particle will be described below as a typical example. [Embodiment 1]

First, a glass base material was prepared and dried well. Subsequently, as the chemical adsorbent, a functional group such as the epoxy group having reactivity in a functional site and a drug containing an alkoxy silyl group, which is exemplified by the drug shown by the following formula (C1 ), in the other terminal are weighed to make 99 weight percent each, and, as a silanol condensation catalyst, dibutyltin acetylacetonate, for example, is weighed to make about 1 weight percent. All these drugs were dissolved in a silicon solvent, for example, hexamethyl disiloxane solvent to make 1 weight percent concentration (preferable concentration of the chemical adsorbent solution ranges from about 0.5% to 3%) to prepare a chemical adsorbent solution. [C1] O OCH₃

CH₂-CHCH₂O(CH₂)SSi -OCH₃

OCH₃

Next, glass base material 1 was soaked in this adsorbent solution to react in normal air (relative humidity 45%) for about 2 hours. At this time, a surface of the glass base material 1 contains many hydroxyl group 2 (Fig. 1A) and, thus, -Si- (OCH₃) of the chemical adsorbent makes dealcohol reaction (in this case, deCH₃OH) to the hydroxyl group in the presence of a silanol condensation catalyst to make a bond shown in the following formula (C2) resulting in formation of a chemical adsorption monomolecular film 3, which contains the epoxy group chemically bonded to a surface across all a surface of glass base material 1 , in the film thickness of about 1 nanometer.

[C2]

O O—

CH₂-CHCH₂O(CH₂J₃Si -O-

O—

Following this step, washing with a chlorine-based solvent such as trichloroethylene allowed preparing each of glass base material 4 covered with the chemical adsorption monomolecular film having the reactive functional group such as the epoxy group on a surface. (Fig. 1 B)

This covering film is very thin in the thickness of a nanometer order and, hence, did not cause a loss of transparency of the glass base material. On the other hand, exposing in air without washing showed no change of transparency and reactivity, but caused evaporation of the solvent. As the result, the chemical adsorbent left on a surface of the glass base material reacted to water in the air on a surface to give the glass base material, on which a very thin, reactive, polymer film composed of the chemical adsorbent was formed on a surface. Next, in case of manufacturing the diffraction grating, an excimer laser and a mask were used for irradiating selectively (for example, line and space was 1 micrometer) an unnecessary part of a surface of a base material to remove the reactive monomolecular film by ablation (Fig. 1 C) or to open the epoxy group for inactivation (Fig. 1 D). In conclusion, a base material 6, 6^J, of which surface has the epoxy group, covered selectively with a pattern-like covering films 5, 5' can be prepared.

As another method, a cation-based polymerization initiator such as IRGACURE 250 made by Ciba Specialty Chemicals was applied to a surface of the epoxy covering film by diluting with methylethyl ketone to open selectively the epoxy group as shown in Fig. 1 D for polymerization by exposing selectively to an infrared ray resulting in pattern-like inactivation. [Embodiment 2]

Similar to Embodiment 1 , first, anhydrous nickel fine particle 11 with an about 10 nm size was prepared and dried well. Subsequently, as the chemical adsorbent, a functional group such as the epoxy group or imino group, which has reactivity in a functional site, and a drug containing an alkoxy silyl group, which is exemplified by the drug shown by the formula (C1 ) or the following formula (C3) in the other terminal are weighed to make 99 weight percent each, and, as a silanol condensation catalyst, acetic acid as the organic acid, for example, is weighed to make 1 weight percent. All these drugs were dissolved in a silicon solvent, for example, hexamethyl disiloxane and dimethyl formamide (50: 50) mixture solvent to make 1 weight percent concentration (preferable concentration of the chemical adsorbent solution ranges from about 0.5 to 3%) to prepare a chemical adsorbent solution. [C3]

OCH₃ H₂N(CH₂)SSi -OCH₃

OCH₃

Anhydrous nickel fine particle 11 was mixed with this adsorbent solution, stirred, and exposed to normal air (relative humidity 45%) for about 2 hours. At this time, a surface of the anhydrous nickel fine particle contains many hydroxyl groups 12 (Fig. 2A) and, thus, -Si (OCH₃) group of the chemical adsorbent makes dealcohol (in this case, de CH3OH) reaction to the hydroxyl groups in the presence of the acetic acid as the organic acid to make the bond shown in the formula (C2) and the following formula (C4) resulting in formation of the chemical adsorption monomolecular film 13, which contains the epoxy group chemically bonded to a surface across all a surface of nickel fine particle, or the chemical adsorption film 14, which contains the amino group, in the film thickness of about 1 nanometer (Fig. 2B₁ 2C). [C4]

Here, in case of using the chemical adsorbent containing the amino group, a tin-based catalyst causes precipitation and, hence, it was better to use the organic acid such as the acetic acid. In addition, the amino group contains the imino group and other substances containing the imino group other than the amino group includes a pyrrole derivative and imidazol derivative. Moreover, using a ketimine derivative allows easily introducing the amino group by hydrolysis following formation of the covering film.

Thereafter, stirring and washing by adding the chlorine-based solvent such as trichloroethylene allowed preparing each of nickel fine particle 15 covered with the chemical adsorption monomolecular film having the reactive functional group such as the epoxy group on a surface, or, nickel fine particle 16 covered with the chemical adsorption monomolecular film having the amino group.

This covering film having the film thickness on the nanometer order is very thin and, therefore, showed no loss of particle size.

On the other hand, exposing to air without washing caused almost no change in reactivity and evaporation of the solvent. As the result, the chemical adsorbent left on a surface of the particle reacted to water in air on a surface to give the nickel fine particle, on which the very thin (in comparison with the monomolecular film, slightly thicker,) reactive, polymer film composed of the chemical adsorbent was formed on a surface. Features of this method using the dealcohol reaction is that a fine particle of an organic material or a metal oxide can be used to enable to apply to a wide range of application fields.

On the other hand, in the case where a material of a fine particle was Au, using the drug, of which terminal Si (OCH₃)₃ was substituted by -SH or a triazine thiol group, enabled to prepare a gold fine particle, on which the monomolecular film containing the amino group via S was formed. On the other hand, using the drug such as HS(CH2)3Si(OCH₃)3 having -SH and methoxysilyl group on both the terminals allowed preparing the gold fine particle, on which the monomolecular film containing the methoxysilyl group via S was formed on a surface. [Embodiment 3]

Next, nickel fine particle 23, which was covered with the chemical adsorption monomolecular film having the amino group, was applied to a surface of glass base material 22, which was covered selectively with chemical adsorption monomolecular film 21 having the epoxy group, by dispersing in alcohol and heated at 100 degrees Celsius. As the result, the amino group on a surface of the nickel fine particle contacting to the epoxy group on a surface of the glass base material was added by the reaction shown in the following formula (C5) to selectively make the bond of the nickel fine particle to the glass base material via two monomolecular films. At this time, evaporating alcohol by irradiating an ultrasonic wave allowed improving the evenness of film thickness of the covering film. [C5]

O

/ \

-(CH₂)CH-CH₂ + H₂NCH₂ —

► - (CH₂)CHCH₂-NHCH₂ -

OH

Then, a surface of a base material was again washed with alcohol and the nickel fine particle covered with the chemical adsorption monomolecular film having excessive amino groups, which had not reacted to a surface of a base material, was washed and removed. As the result, with the state of arranging selectively only one layer of the nickel fine particle covered with the chemical adsorption monomolecular film having amino groups, which had a covalent bond to a surface of glass base material 22, a pattern-like monolayer nickel fine particle film can be formed having even thickness in the particle size level (Fig. 3A). Here, the thickness of pattern-like monolayer nickel fine particle film is about

10 nm and showed very good evenness. [Embodiment 4]

In addition, in case of desiring to make the thickness of the nickel fine particle film thicker to improve a lightproof property, following Embodiment 3, in the state of arranging pattern-likely only one layer of the nickel fine particle covered with the chemical adsorption monomolecular film having amino groups having a covalent bond, and, nickel fine particle 25, which was covered with the chemical adsorption monomolecular film having the epoxy group, was applied to a surface of glass base material, on which a pattern-like monolayer nickel fine particle film 24 was formed having even thickness in the particle size level, by dispersing in alcohol and heated at 100 degrees Celsius. As the result, the epoxy group on a surface of the nickel fine particle contacting to the amino group of the part, which was formed in a pattern-like monolayer of the nickel fine particle covered with the chemical adsorption monomolecular film having the amino group, was added by the reaction shown in the formula (C5). Finally, the nickel fine particle covered with the chemical adsorption monomolecular film having the amino group was bonded to the nickel fine particle covered with the chemical adsorption monomolecular film having the epoxy group via monomolecular films on glass base material resulting in hardening. Then, a surface of a base material was again washed with alcohol to wash out for removing the nickel fine particle covered with the chemical adsorption monomolecular film having excessive and unreacted epoxy groups. As the result, in the state of arranging only one layer of the nickel fine particle of the second layer having a covalent bond via the nickel fine particle covered with the chemical adsorption monomolecular film having epoxy groups, a pattern-like layered nickel fine particle film 26 of a double layer stricture was formed having even thickness in the particle size level (Fig. 3B). Similarly, layering alternately the nickel fine particle covered with the chemical adsorption monomolecular film having the amino group and the nickel fine particle covered with the chemical adsorption monomolecular film having the epoxy group allowed preparing the diffraction gratings composed of the layered covering films of the nickel fine particle having the multilayer structure having the absolute lightproof property in the line part.

In Embodiments 1 and 2 as described above, substances shown in formula (C1) or (C3) were used as the chemical adsorbent containing the reactive group. Other substances, which were shown in the following (1 ) to (16), other than those as described above were usable.

(1 ) (CH₂OCH)CH₂O(CH2)7Si(OCH3)3

(2) (CH₂OCH)CH₂O(CH2)iiSi(OCH3)3 (3) (CH₂CHOCH(CH₂)₂)CH(CH₂)2Si(OCH3)3 (4) (CH₂CHOCH(CH2)2)CH(CH₂)₄Si(OCH3)3 (5) (CH₂CHOCH(CH₂)₂)CH(CH₂)6Si(OCH₃)3

(6) (CH₂OCH)CH₂O(CH2)7Si(OC₂H5)3

(7) (CH₂OCH)CH₂O(CH₂)IiSi(OC₂Hs)₃ (8) (CH₂CHOCH(CH₂)2)CH(CH₂)₂Si(OC₂H5)3 (9) (CH₂CHOCH(CH₂)₂)CH(CH₂)₄Si(OC₂H5)3 (10) (CH₂CHOCH(CH2)₂)CH(CH₂)₆Si(OC₂H5)3

(11 ) H₂N(CH₂)5Si(OCH₃)3

(12) H₂N(CH₂)₇Si(OCH₃)₃

(13) H₂N(CH₂)9Si(OCH₃)3

(14) H₂N(CH₂)SSi(OC₂Hs)₃ (15) H₂N(CH₂)TSi(OC₂Hs)₃

(16) H₂N(CHz)₉Si(OC₂Hs)₃

In these formulas, the (CH₂OCH) - group represents a functional group shown by the formula (C6) below, and the (CH₂CHOCH (CH₂)₂) CH - group represents a functional group shown by the formula (C7) below: [C6] O CH₂-CH -

[C7]

In Embodiments 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 the chelate 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, dibutyltin mercaptopropionate salt polymer, dibutyltin bisacetyl acetate, dioctyltin bisacetyl laurate, tetrabutyl titanate, tetranonyl titanate, and bis (acetyl acetonyl) dipropyl titanate.

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 no washing and evaporating the solvent, a boiling point of the solvent ranges preferably from about 50 to 250 ⁰C. 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.

More specifically, 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, etc., can be selected as an applicable solvent. 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 a pattern-like 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 a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkyl alkoxysilane compound is used instead of the above-mentioned silanol condensation catalyst, it was found that processing time can be reduced to a half to two thirds, even with the same concentration. When a silanol condensation catalyst mixed with a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkyl alkoxysilane compound (mixing ratio at 1 :9 to 9:1 is possible, but around 1 :1 is preferable) is used, processing speed can be increased several times (around 30 minutes as processing time) and film forming time can be reduced to a fraction of the original time.

For example, when dibutyltin oxide, one of the silanol catalysts, was replaced with H3 manufactured by Japan Epoxy Resin Co., one of the ketimine compounds without changing other conditions, it was found that reaction time can be reduced to around one hour while keeping the other results without change. Further, when the silanol catalyst was replaced with mixture of H3 manufactured by Japan Epoxy Resin Co., one of the ketimine compounds, and dibutyltin bisaetylacetonate, one of the silanol catalysts (mixing ratio at 1 :1 ), without changing other conditions, it was found that reaction time can be reduced to around 30 minutes while keeping the other results without change. Therefore, the above results clarified that a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxysilane compound have higher activity than a silanol condensation catalyst. Further, it was found that use mixtures of one substance selected from a ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxysilane compound, and a silanol condensation catalyst makes activity higher. Here applicable ketimine compounds, for example, include:

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-tetramethy 1-5,8, 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, etc. without limited to these.

Applicable organic acids, for example, include: formic acid, or acetic acid, propionic acid, butyric acid, and malonic acid, etc. without limited to these. They showed similar effect.

In the above Embodiments 1 through 4, the glass base material and the nickel fine particle were described. The present invention can be applied to any electronic devices such as a semiconductor device and a printed substrate, on which an electronic circuit has been formed.

Claims

1. A pattern-like monolayer fine particle film having a covalent bond of a film of a monolayer of a fine particle formed selectively on a surface of a base material to a first organic film formed selectively on a surface of a base material, through a second organic film formed on a surface of a fine particle.

2. A pattern-like monolayer fine particle film according to claim 1 , wherein the first organic covering film formed on a surface of a base material and the second organic film formed on a surface of a fine particle are different from each other.

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

4. A pattern-like monolayer fine particle film according to claim 1 or claim 2, wherein each of the first organic covering film formed on a surface of a base material and the second organic film formed on a surface of a fine particle are constituted from a monomolecular film.

5. A manufacturing method for a pattern-like monolayer fine particle film, comprising: a step of forming a first reactive organic film on a surface of a base material by contacting a surface of a 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 a surface of a base material; a step of processing the first reactive organic film to make a predetermined pattern; a step of forming a second reactive organic film on a surface of a fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least a second alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; a step of contacting, for a selective reaction, a fine particle covered with the second reactive organic film to a surface of a base material having the first reactive organic film formed thereon; and washing and removing a fine particle covered with an excessive second reactive organic film.

6. The manufacturing method for a pattern-like monolayer fine particle film according to claim 5, comprising: the step of forming the first reactive organic film on a surface of a base material by contacting a surface of a base material with a chemical adsorption solution prepared by blending at least the first alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a base material and a step of forming the second reactive organic film on a surface of a fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least the second alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle, followed by washing each of a surface of a base material and a surface of a fine particle with an organic solvent to form a first and second reactive monomolecular films having a covalent bond to a surface of a base material and a surface of a fine particle.

7. The manufacturing method for a pattern-like monolayer fine particle film according to claim 5, wherein the first reactive organic film contains an epoxy group and the second reactive organic film contains an imino group.

8. The manufacturing method for a pattern-like monolayer fine particle film according to claim 6, wherein the first reactive monomolecular film contains an epoxy group and the second reactive monomolecular film contains an imino group.

9. A pattern-like layered fine particle film layered as stratification selectively on a surface of a base material, wherein a fine particle has a covalent bond between layers through an organic covering film formed on a surface of a fine particle.

10. A pattern-like layered fine particle film according to claim 9, wherein a surface of a fine particle has two kinds of the organic covering film, the particle having the first organic film, and the particle having the second organic film are layered alternately.

11. A pattern-like layered fine particle film according to claim 10, wherein the first organic film reacts to the second organic film to form a covalent bond.

12. A pattern-like layered fine particle film according to claim 9, wherein a covalent bond is an -N-C- bond formed by a reaction of an epoxy group to an imino group.

13. A manufacturing method for a pattern-like layered fine particle film comprising: the step of forming the first reactive organic film on a surface of a base material by contacting a surface of a base material with a chemical adsorption solution prepared by blending at least the first alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a base material; the step of processing the first reactive organic film to make a predetermined pattern; the step of forming the second reactive organic film on a surface of a fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least the second alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; the step of contacting, for the selective reaction, a fine particle covered with the second reactive organic film to a surface of a base material having the first reactive organic film formed thereon; the step of washing and removing the first fine particle covered with the excessive second reactive organic film to form selectively the first pattern-like monolayer fine particle film; the step of forming the third reactive organic film on a surface of the second fine particle by dispersing a fine particle in a chemical adsorption solution prepared by blending at least the third alkoxysilane compound and a silanol condensation catalyst and a non-aqueous organic solvent to react an alkoxysilane compound to a surface of a fine particle; the step of contacting and reacting the second fine particle covered with the third reactive organic film to a surface of a base material having the first pattern-like monolayer fine particle film covered with the second reactive organic film; and the step of washing and removing the second fine particle covered with the excessive third reactive organic film to form selectively the second pattern-like monolayer fine particle film.

14. The manufacturing method for a pattern-like layered fine particle film according to claim 13, wherein the first reactive organic film is identical to the third reactive organic film.

15. The manufacturing method for a pattern-like layered fine particle film of a multilayer structure according to claim 13, wherein, following the step of forming the second pattern-like monolayer fine particle film, similarly, the step of forming and the step of forming the first pattern-like monolayer fine particle film and the second pattern-like monolayer fine particle film are repeated.

16. The manufacturing method for a pattern-like layered fine particle film according to claim 13, wherein, following the step of forming the first to third reactive organic films, for each of their steps, a surface of a base material or a fine particle is washed with the organic solvent to form the first to third reactive monomolecular films having a covalent bond to a surface of a base material and a fine particle.

17. The manufacturing method for a pattern-like layered fine particle film according to claim 13, wherein the first and third reactive organic films contain the epoxy group and the second reactive organic film contains the imino group.

18. The manufacturing method for a pattern-like monolayer fine particle film and a pattern-like layered fine particle film according to claim 5 or claim 13, wherein, replacing to a silanol condensation catalyst, a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound are used.

19. The manufacturing method for a pattern-like monolayer fine particle film and a pattern-like layered fine particle film according to claim 5 or claim 13, wherein a 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.