JP2007118276A - Single-layer fine particle film, cumulated fine particle film and manufacturing method of them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a single-layer fine particle film having a uniform thickness in a particle size level. <P>SOLUTION: The manufacturing method of the single-layer fine particle film has a process for bringing the surface of a base material into contact with a chemical adsorbing liquid, which is prepared by mixing a first alkoxysilane compound, a silanol condensing catalyst and a non-aqueous organic solvent, and reacting the alkoxysilane compound with the surface of the base material to form a first reactive organic film on the surface of the base material, a process for dispersing fine particles in the chemical adsorbing liquid, which is prepared by mixing a second alkoxysilane compound, the silanol condensing catalyst and the non-aqueous organic solvent, and reacting the alkoxysilane compound with the surfaces of the fine particles to form a second reactive organic film on the surfaces of the fine particles and a process for bringing the fine particles coated with the second reactive organic film into contact with the surface of the base material on which the first reactive organic film is formed to react them. By this manufacturing method, the single-layer fine particle film 17 wherein the fine particles of one film layer formed on the surface of the base material are mutually bonded by a covalent bond through the first organic film formed on the surfaces of the fine particles and the second organic film formed on the surface of the base material is obtained. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a laminated film of fine particles. In more detail, inorganic fine particles made of metal or metal oxide, thermal fine or photoreactive, or radical or ionic reactivity on the surface, organic fine particles made of polymer or polymer micelle, or organic-inorganic The present invention relates to a laminated film of hybrid fine particles.

  In the present invention, “inorganic fine particles” include conductor fine particles, semiconductor fine particles, insulator fine particles, magnetic fine particles, phosphor fine particles, light absorbing fine particles, light transmitting fine particles, and pigment fine particles. “Organic fine particles” include organic phosphor fine particles, organic light absorbing fine particles, organic light transmitting fine particles, organic pigment fine particles, and drug fine particles. The “organic-inorganic hybrid fine particles” include drug fine particles for DDS (Drug Delivery System), fine particles for cosmetics, and organic-inorganic hybrid pigment fine particles.

  Conventionally, a Langmuir-Bloget (LB) method is known in which amphiphilic organic molecules are used, molecules are arranged on the water surface, and a monomolecular film is accumulated on the substrate surface. Further, a chemical adsorption (CA) method is known in which a monomolecular film is accumulated using a chemical adsorption method in a solution in which a surfactant is dissolved.

  However, a film having a uniform thickness (hereinafter referred to as a single-layer fine particle film) at a particle size level in which only one layer of fine particles is arranged on an arbitrary substrate surface, or a film in which a plurality of films in which only one layer of fine particles is arranged (hereinafter referred to as a single layer). And the manufacturing method thereof have not yet been developed or provided.

  Conventionally, many micron-sized or nano-sized fine particles having various functions such as an electric function, a magnetic function, and an optical function have been developed and manufactured. In order to effectively use the original functions of these fine particles, it is necessary to make the fine particles into a uniform film thickness, but there is no idea of using these fine particles to produce a uniform thickness film at the particle size level. It was.

  The present invention uses fine particles, and does not impair the original functions of various fine particles, and a single layer of fine particles (single-layer fine particle film) or fine particles with a particle size level in which only one layer of fine particles is arranged on the surface of an arbitrary substrate. An object of the present invention is to provide a film (cumulative fine particle film) obtained by accumulating a plurality of layers in which only the films are arranged, and a method for producing them.

A first invention provided as a means for solving the above-described problems is that a fine particle film formed on one surface of a base material is formed on a first organic film formed on the base material surface and the surface of the fine particles. A single-layer fine particle film characterized by being covalently bonded to each other via a second organic film.

A second invention is a single-layer fine particle film according to the first invention, wherein the first organic film formed on the substrate surface and the second organic film formed on the fine particle surface are different from each other. .

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

According to a fourth invention, in the first invention and the second invention, the first organic film formed on the surface of the substrate and the second organic film formed on the surface of the fine particles are formed of a monomolecular film. This is a single-layer fine particle film.

In the fifth invention, the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to react the alkoxysilane compound with the substrate surface. And forming a first reactive organic film on the surface of the base material, and a chemical adsorption solution prepared by mixing fine particles with at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of dispersing and reacting the alkoxysilane compound with the surface of the fine particles to form a second reactive organic film on the surface of the fine particles; and a second reaction on the surface of the substrate on which the first reactive organic film is formed. A method of producing a single-layer fine particle film, comprising: a step of contacting and reacting fine particles coated with a reactive organic film; and a step of cleaning and removing the excessive fine particles coated with a second reactive organic film Ah .

In a sixth aspect of the invention, the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, whereby the alkoxysilane compound and the substrate surface are brought into contact with each other. A step of forming a first reactive organic film on the surface of the substrate by reacting, and a chemical adsorption solution prepared by mixing fine particles with at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent After the step of dispersing the alkoxysilane compound and the surface of the fine particles to form a second reactive organic film on the fine particle surface, the substrate and the fine particle surface are washed with an organic solvent, respectively. 6. The method for producing a single-layer fine particle film according to claim 5, wherein the first and second reactive monomolecular films covalently bonded to each other are formed.

According to a seventh invention, in the fifth invention, 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 is an imino A method for producing a single-layer fine particle film, wherein the second reactive organic film containing a group contains an epoxy group.

According to an eighth invention, in the sixth invention, 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 A method for producing a single-layer fine particle film, wherein the film contains an imino group and the second reactive monomolecular film contains an epoxy group.

According to a ninth aspect of the present invention, there is provided a cumulative fine particle film characterized in that the fine particles are accumulated in layers on the surface of the substrate and are covalently bonded to each other through an organic film formed on the fine particle surface.

According to a tenth aspect, in the ninth aspect, there are two types of organic coatings formed on the surface of the fine particles, and the fine particles on which the first organic film is formed and the fine particles on which the second organic film is formed alternately It is a cumulative fine particle film characterized by being laminated.

An eleventh invention is the cumulative fine particle film according to the tenth invention, wherein the first organic film and the second organic film react to form a covalent bond.
A twelfth invention is the cumulative fine particle film according to the ninth invention, wherein the covalent bond is a —N—C— bond formed by a reaction between an epoxy group and an imino group.

In the thirteenth invention, at least the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to react the alkoxysilane compound with the substrate surface. Forming a first reactive organic film on the surface of the base material, and chemical adsorption formed by mixing the first fine particles with at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent A step of dispersing the alkoxysilane compound and the surface of the fine particles to form a second reactive organic film on the surface of the first fine particles, and a substrate on which the first reactive organic film is formed; A step of bringing the first fine particles coated with the second reactive organic film into contact with the surface for reaction; and washing and removing the first fine particles coated with the extra second reactive organic film First single layer particulate film A step of forming, and dispersing the second fine particles in a chemical adsorption solution prepared by mixing at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and reacting the surface of the alkoxysilane compound with the fine particles. Forming a third reactive organic film on the surface of the second fine particles, and forming a third reactive organic film on the surface of the substrate on which the first single-layer fine particle film coated with the second reactive organic film is formed. A step of bringing the second fine particles coated with the reactive organic film into contact with each other and reacting, and the second fine particles coated with the extra third reactive organic film are removed by washing. And a step of forming a layer fine particle film.

A fourteenth aspect of the invention is a method for producing a cumulative fine particle film according to the thirteenth aspect of the invention, wherein the first reactive organic film and the third reactive organic film are the same.

According to a fifteenth aspect, in the thirteenth aspect, after the step of forming the single-layer fine particle film, a step of similarly forming the first single-layer fine particle film and a step of forming the second single-layer fine particle film Is a method for producing a cumulative fine particle film having a multilayer structure.

According to a sixteenth aspect, in the thirteenth aspect, after the step of forming the first to third reactive organic films, the substrate or the surface of the fine particles is washed with an organic solvent, respectively, to form the surface of the substrate or the fine particles. A method for producing a cumulative fine particle film, comprising forming a covalently bonded first to third reactive monomolecular film.

According to a seventeenth aspect, in the thirteenth aspect, the first and third reactive organic films contain an epoxy group and the second reactive organic film contains an imino group, or the first and third reactions The method for producing a cumulative fine particle film is characterized in that the conductive organic film contains an imino group and the second reactive organic film contains an epoxy group.

The eighteenth invention uses a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound in place of the silanol condensation catalyst in the fifth invention and the thirteenth invention. A method for producing a single-layer fine particle film and a cumulative fine particle film.

The nineteenth invention is selected from the ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound as a co-catalyst for the silanol condensation catalyst in the fifth invention and the thirteenth invention. A method for producing a single-layer fine particle film and a cumulative fine particle film, wherein at least one of them is used in combination.

Hereinafter, the gist of the present invention will be described.
In the present invention, the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the substrate surface are reacted. A step of forming a first reactive organic film on the surface of the substrate, and dispersing the fine particles in a chemical adsorption solution prepared by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of reacting the alkoxysilane compound with the surface of the fine particles to form a second reactive organic film on the surface of the fine particles, and a second reactive property on the surface of the substrate on which the first reactive organic film is formed. The fine particles formed on the surface of the base material by the step of bringing the fine particles coated with the organic film into contact with each other and the step of washing and removing the fine particles coated with the extra second reactive organic film There is summarized as providing a first organic layer and second organic film monolayer particulate film is covalently bonded to each other through the formed microparticle surface formed on the substrate surface.

  At this time, the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the substrate surface are reacted to form a group. A step of forming a first reactive organic film on the surface of the material, and dispersing fine particles in a chemical adsorption solution prepared by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. After the step of reacting the alkoxysilane compound with the fine particle surface to form a second reactive organic film on the fine particle surface, the substrate and the fine particle surface were washed with an organic solvent, respectively, and covalently bonded to the base material and the fine particle surface. It is convenient to form the first and second reactive monomolecular films because the thickness of the single-layer fine particle film can be easily controlled.

Further, an epoxy group is included in the first reactive organic film and an imino group is included in the second reactive organic film, or an imino group is included in the first reactive organic film. Including an epoxy group in the organic film is convenient for producing a single-layer fine particle film covalently bonded to the substrate surface.
In addition, the first reactive monomolecular film includes an epoxy group and the second reactive monomolecular film includes an imino group, or the first reactive monomolecular film includes an imino group and the second reactive monomolecular film includes an imino group. When the reactive monomolecular film includes an epoxy group, it is convenient to produce a single-layer fine particle film covalently bonded to the substrate surface.

Furthermore, it is convenient to use a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound in place of the silanol condensation catalyst for shortening the film formation time.
In addition, the use of a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound as a co-catalyst as a co-catalyst for the silanol condensation catalyst can further reduce the film formation time. convenient.

Here, if the first organic film formed on the fine particle surface and the second organic film formed on the substrate surface are different from each other, only one layer of the single-layer fine particle film is bonded to the substrate surface. Convenient above.
Furthermore, the use of —N—C— bond formed by the reaction of an epoxy group and an imino group as a covalent bond is advantageous in providing a single-layer fine particle film having excellent adhesion strength to a substrate.
In addition, it is convenient to improve the film thickness uniformity when the first organic film formed on the surface of the fine particles and the second organic film formed on the surface of the substrate are formed of a monomolecular film.

  Furthermore, the present invention is such that at least the surface of the substrate is brought into contact with a chemical adsorption solution prepared by mixing a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to react the alkoxysilane compound with the substrate surface. Forming a first reactive organic film on the surface of the substrate, and a chemical adsorption solution prepared by mixing the first fine particles with at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent A step of forming a second reactive organic film on the surface of the first fine particle by dispersing the alkoxysilane compound and the surface of the fine particle, and a surface of the substrate on which the first reactive organic film is formed The first fine particles coated with the second reactive organic film are brought into contact with each other and reacted, and the first fine particles coated with the extra second reactive organic film are removed by washing. 1 single particle And the second fine particles are dispersed in a chemical adsorption solution prepared by mixing at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to react the alkoxysilane compound with the surface of the fine particles. A step of forming a third reactive organic film on the surface of the second fine particles, and a surface of the substrate on which the first single-layer fine particle film coated with the second reactive organic film is formed. A step of bringing the second fine particles coated with the third reactive organic film into contact with each other, and a second step of removing the second fine particles coated with the extra third reactive organic film by washing and removing the second fine particles. The object of the present invention is to provide a cumulative fine particle film in which a single layer fine particle film is formed in a layer form on a substrate surface and the fine particles are covalently bonded to each other through an organic film formed on the fine particle surface. To do.

At this time, it is convenient to purify the accumulated fine particle film as a single layer by using the same one for the first reactive organic film and the third reactive organic film.
Further, after the step of forming the second single-layer fine particle film, if the step of forming the first single-layer fine particle film and the step of forming the second single-layer fine particle film are repeated, the multilayer structure is accumulated. A fine particle film can be easily manufactured.

  Further, after the steps of forming the first to third reactive organic films, the first to third reactive units each having a substrate or fine particle surface washed with an organic solvent and covalently bonded to the substrate or fine particle surface, respectively. Formation of a molecular film is convenient for making the film thickness of the accumulated fine particle film uniform.

Furthermore, the first and third reactive organic films contain an epoxy group and the second reactive organic film contains an imino group, or the first and third reactive organic films contain an imino group and the second reactive organic film contains an imino group. When the reactive organic film contains an epoxy group, it is convenient to produce a cumulative fine particle film covalently bonded between the layers by the reaction of the epoxy group and the imino group.

Furthermore, it is convenient to use a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound in place of the silanol condensation catalyst for shortening the film formation time.
In addition, the use of a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound as a co-catalyst as a co-catalyst for the silanol condensation catalyst can further reduce the film formation time. convenient.
Also, here, two kinds of organic coatings formed on the surface of the fine particles are used, and when the fine particles formed with the first organic film and the fine particles formed with the second organic film are alternately laminated, a multilayer cumulative fine particle film is formed. It is convenient for manufacturing by a single layer pure process.

  Furthermore, when the first organic film and the second organic film react to form a covalent bond, it is convenient to provide a cumulative fine particle film having excellent adhesion strength. In addition, when a —NC— bond formed by a reaction between an epoxy group and an imino group is used as a covalent bond, it is convenient to provide a cumulative fine particle film excellent in strength.

  As described above, according to the present invention, a coating having a uniform thickness (single-layer fine particles) using fine particles and having a single particle size arranged on the surface of an arbitrary substrate without impairing the original functions of various fine particles. Film) and a film (cumulative fine particle film) obtained by accumulating a plurality of layers in which only one layer of fine particles are arranged and a manufacturing method thereof can be provided at a low cost.

In the present invention, at least the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the substrate surface are reacted. A step of forming a first reactive organic film on the surface of the substrate; and a chemical adsorption solution prepared by mixing the first fine particles with at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent And a step of reacting the alkoxysilane compound with the surface of the fine particles to form a second reactive organic film on the surface of the first fine particles, and a surface of the substrate on which the first reactive organic film is formed. The step of bringing the first fine particles coated with the second reactive organic film into contact with each other and reacting, and the first fine particles coated with the extra second reactive organic film are removed by washing. Shaped single layer fine particle film And dispersing the second fine particles in a chemical adsorption solution prepared by mixing at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and reacting the alkoxysilane compound with the surface of the fine particles. A step of forming a third reactive organic film on the surface of the second fine particle, and a third surface of the base material on which the first single-layer fine particle film coated with the second reactive organic film is formed. A step of contacting and reacting the second fine particles coated with the reactive organic film; and a second single layer by washing and removing the excess second fine particles coated with the third reactive organic film. The step of forming the fine particle film provides a cumulative fine particle film in which the fine particles are accumulated in layers on the surface of the substrate and the fine particles are covalently bonded to each other through an organic film formed on the fine particle surface.

  Accordingly, in the present invention, by using two kinds of fine particles covered with two kinds of coatings, a particle size level in which only one layer of fine particles is arranged on the surface of an arbitrary substrate without impairing the original functions of various fine particles. Can provide a film with a uniform thickness (single-layer fine particle film) and a film (cumulative fine particle film) obtained by accumulating a plurality of layers in which only one layer of fine particles is arranged, and a method for producing them easily and at low cost. There is.

  Hereinafter, although the detail of this invention is demonstrated using an Example, this invention is not limited at all by these Examples.

  Further, the fine particles of the single-layer fine particle film and the cumulative fine particle film according to the present invention include conductive particles, semiconductor particles, insulator particles, magnetic particles, phosphor particles containing hydrophilic oxide or hydroxide on the surface, There are light-absorbing particles, light-transmitting particles, pigment particles, medicinal particles, cosmetic particles, abrasive particles, wear-resistant material particles, and the like. First, silica fine particles will be described as light-transmitting particles as representative examples.

First, anhydrous silica fine particles 1 having a size of about 100 nm were prepared and dried well. Next, as a chemical adsorbent, a functional group having a reactive functional group at the functional site, for example, an epoxy group or imino group and an alkoxysilyl group at the other end, for example, the following formula (Chemical Formula 1) or (Chemical Formula 2) For example, 99% by weight of the drug and 1% by weight of dibutyltin diacetylacetonate or acetic acid which is an organic acid as a silanol condensation catalyst were weighed to a silicone solvent such as hexamethyldisiloxane and dimethylformamide (50 50) A chemical adsorption solution was prepared by dissolving in a mixed solvent so as to have a concentration of about 1 wt% (preferably the concentration of the chemical adsorbent is about 0.5 to 3%).

Anhydrous silica fine particles 1 were mixed in the adsorbed liquid and stirred, and reacted in ordinary air (relative humidity 45%) for about 2 hours. At this time, since the surface of the anhydrous silica fine particles contains a large number of hydroxyl groups 2 (FIG. 1 (a)), the -Si (OCH ₃ ) group of the chemical adsorbent and the hydroxyl group are composed of a silanol condensation catalyst or acetic acid. In the presence, dealcoholization (in this case, de-CH ₃ OH) was reacted to form a bond as shown in the following formula (Chemical Formula 3) or (Chemical Formula 4) and chemically bonded to the surface over the entire surface of the fine particles. A chemisorption monomolecular film 3 containing an epoxy group or a chemisorption film 4 containing an amino group was formed with a film thickness of about 1 nanometer (FIGS. 1B and 1C).
Here, when an adsorbent containing an amino group is used, since a precipitate is generated with a tin-based catalyst, it is better to use an organic acid such as acetic acid. The amino group contains an imino group, but substances containing an imino group in addition to the amino group include pyrrole derivatives and imidazole derivatives. Furthermore, when a ketimine derivative was used, an amino group could be easily introduced by hydrolysis after film formation.

Thereafter, when a chlorine-based solvent such as trichlene is added and washed with stirring, the silica fine particles 5 covered with a chemical adsorption monomolecular film having a reactive functional group, for example, an epoxy group on the surface, or a chemical adsorption single molecule having an amino group. The silica fine particles 6 covered with the molecular film could be produced respectively.

Note that this film was extremely thin with a nanometer-level film thickness, so the particle diameter was not impaired.
On the other hand, when taken out into the air without washing, the reactivity does not change substantially, but the chemical adsorbent remaining on the particle surface reacts with the moisture in the air by evaporation of the solvent, and the chemical adsorbent on the surface. Fine particles on which an extremely thin polymer film was formed were obtained.

Since this method is characterized by a dealcoholization reaction, it can be used even if the fine particles are organic or inorganic and has a wide range of applications.
When the fine particle material is Au, the terminal Si (OCH ₃ ) ₃ is replaced with —SH or a triazine thiol group, for example, H ₂ N (CH ₂ ) ₁₁ —SH, or H ₂ N By using (CH ₂ ) ₂ —SH or the like, it was possible to produce gold fine particles in which a monomolecular film containing an amino group was formed via S. Meanwhile, agents with -SH and methoxy silyl groups at both terminals, for example, _{HS (CH 2) 3 Si (} OCH 3) 3 to be used, the monomolecular film containing trimethoxysilyl group to the surface via the S is formed Gold fine particles could be produced. Further, since the gold fine particles have methoxysilyl oxide on the surface, a single-layer gold fine particle film could be directly formed on the substrate surface in the same manner as the monomolecular film formation in this example.

As in Example 1, first, a glass substrate 11 was prepared and thoroughly dried. Next, as a chemical adsorbent, a functional group reactive at the functional site, for example, an epoxy group or imino group and an agent containing an alkoxysilyl group at the other end, for example, the above formula (Formula 1) or (Formula 2) For example, 99% by weight of the drug and 1% by weight of dibutyltin diacetylacetonate or acetic acid as the silanol condensation catalyst are weighed, and the concentration is about 1% by weight in a silicone solvent such as hexamethyldisiloxane solvent ( A chemical adsorbent was prepared by dissolving so that a preferable concentration of the chemical adsorbent was about 0.5 to 3%.

Next, the glass substrate 11 was immersed in this adsorbing solution and reacted in ordinary air (relative humidity 45%) for about 2 hours. At this time, since the surface of the glass substrate 11 contains a large number of hydroxyl groups 12 (FIG. 2 (a)), the -Si (OCH ₃ ) group of the chemical adsorbent and the hydroxyl group are composed of a silanol condensation catalyst or acetic acid. In the presence, dealcoholization (in this case, de-CH ₃ OH) is reacted to form bonds as shown in the above formula (Chemical Formula 3) or (Chemical Formula 4), and the surface of the glass substrate 11 is entirely covered with the surface. A chemically adsorbed monomolecular film 13 containing chemically bonded epoxy groups (FIG. 2B) or a chemically adsorbed film 14 containing amino groups (FIG. 2C) is formed with a thickness of about 1 nanometer.

Thereafter, when the substrate is washed with a chlorinated solvent such as trichlene, the glass substrate 15 covered with a chemisorption monomolecular film having a reactive functional group such as an epoxy group on the surface, or a chemisorption monolayer having an amino group is used. Glass substrates 16 covered with molecular films could be produced respectively. (Fig. 2 (b), 2 (c))

In addition, since this film was extremely thin with a film thickness of nanometer level, the transparency of the glass substrate was not impaired.
On the other hand, if it is taken out into the air without washing with a chlorinated solvent, the reactivity will not change substantially, but the chemical adsorbent that has evaporated on the surface of the glass substrate reacts with the moisture in the air. Thus, a glass substrate having an extremely thin polymer film formed of the chemical adsorbent on the surface was obtained although the film thickness was slightly thicker than that of the monomolecular film.

Next, on the surface of the glass substrate 15 covered with the chemisorption monomolecular film having an epoxy group, silica fine particles 6 covered with the chemisorption monomolecular film having an amino group (the chemisorption monomolecule having the amino group). The glass substrate surface covered with a film may be a combination of silica fine particles covered with a chemisorption monomolecular film having an epoxy group.) Dispersed in alcohol and heated to about 100 ° C. The amino group on the surface of the silica fine particle in contact with the epoxy group on the surface of the material was added by the reaction shown in the following formula (Chemical Formula 5), and the fine particle and the glass substrate were bonded and solidified through two monomolecular films. . At this time, when the alcohol was evaporated while applying ultrasonic waves, the film thickness uniformity of the coating could be improved.

そこで、再びアルコールで基材表面を洗浄し、余分で未反応のアミノ基を有する化学吸着単分子膜で被われたシリカ微粒子を洗浄除去すると、ガラス基材表面１５に共有結合したアミノ基を有する化学吸着単分子膜で被われたシリカ微粒子が１層のみ並べた状態で、且つ粒子サイズレベルで均一厚みの単層微粒子膜１７が形成できた。（図３（ａ））

Then, the surface of the base material is again washed with alcohol, and the silica fine particles covered with the extraneous unreacted amino group chemically adsorbed monomolecular film are washed and removed to have the amino group covalently bonded to the glass base material surface 15. A single-layer fine particle film 17 having a uniform thickness at the particle size level could be formed in a state where only one layer of silica fine particles covered with the chemisorption monomolecular film was arranged. (Fig. 3 (a))

On the other hand, when a coating of silica fine particles covered with a chemisorption monomolecular film having an epoxy group is formed on the surface of a glass substrate covered with a chemisorption monomolecular film having an amino group, A single-layer fine particle film having a uniform thickness at the particle size level could be formed with only one layer of silica fine particles covered with a chemically adsorbed monomolecular film having a covalently bonded epoxy group.
Here, when the light transmittance of the glass substrate on which the single-layer fine particle film of silica fine particles is formed is measured, the light transmittance is improved by about 2% compared to the glass substrate on which the single-layer fine particle film of silica fine particles is not formed. It was. That is, this coating functioned as an antireflection film.
Further, the thickness of the single layer fine particle film of silica fine particles was about 100 nm, and the uniformity was very good, so no interference color was seen at all.

Further, when it is desired to increase the film thickness of the fine particle film, the silica fine particles covered with the chemically adsorbed monomolecular film having a covalently bonded amino group are arranged in a state where only one layer is arranged, and at the particle size level. When silica fine particles 5 covered with a chemically adsorbed monomolecular film having an epoxy group are dispersed and applied to a glass substrate surface 15 on which a single-layer fine particle film 17 having a uniform thickness is formed and heated to about 100 ° C. The epoxy group on the surface of the silica fine particle in contact with the amino group on the surface of the glass substrate on which the single layer fine particle film of the silica fine particle covered with the chemically adsorbed monomolecular film having an amino group is formed is represented by the above formula (Formula 5). The fine particles covered with the chemically adsorbed monomolecular film having amino groups and the fine silica particles covered with the chemically adsorbed monomolecular film having epoxy groups on the surface of the glass substrate are added by the reaction shown in FIG. One of bound solidified through the monomolecular film.

Therefore, again washing the substrate surface with chloroform, extra, when the silica fine particles covered by the chemical adsorption monomolecular film having unreacted epoxy groups washed off, chemisorption single having an amino group on the surface of the glass base material 15 A single-layer fine particle film 18 having a two-layer structure with a uniform thickness at the particle size level was formed with only one layer of the second layer silica fine particles covalently bonded via the fine particles covered with the molecular film. (Fig. 3 (b))
Similarly, when the silica fine particles covered with the chemisorption monomolecular film having amino groups and the silica fine particles covered with the chemisorption monomolecular film having epoxy groups are alternately laminated, the coating of the fine particles having a multilayer structure is also cumulatively produced. did it.

In Examples 1 and 2, the substances shown in the formula (Chemical Formula 1) or (Chemical Formula 2) were used as chemical adsorbents containing reactive groups. In addition to the above, the following (1) The substances shown in (16) were available.
(1) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(2) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) ₃
(3) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₂ Si (OCH ₃ ) _{3
(4) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
_{(5) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OCH 3) 3
_{(6) (CH2OCH) CH 2} O (CH 2) 7 Si (OC 2 H 5) 3
(7) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OC ₂ H ₅ ) _{3
(8) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OC 2 H 5) 3
_{(9) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
(10) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₆ Si (OC ₂ H ₅ ) ₃
(11) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(12) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(13) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(14) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(15) H ₂ N (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(16) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

Here, the (CH ₂ OCH) — group represents a functional group represented by the following formula (Formula 6), and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group is represented by the following formula (Formula 7). Represents a functional group.

In Examples 1 and 2, silanol condensation catalysts include carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates. Is available. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyl Laurate, tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) dipropyl titanate could be used.

Further, as a solvent for the film-forming solution, it is possible to use an organic chlorine-based solvent, a hydrocarbon-based solvent, a fluorinated carbon-based solvent, a silicone-based solvent, or a mixture thereof that does not contain water. In addition, when it is going to raise particle concentration by evaporating a solvent, without wash | cleaning, the boiling point of a solvent is good at about 50-250 degreeC. Further, when the adsorbent is an alkoxysilane type and the organic film is formed by evaporating the solvent, an alcohol type solvent such as methanol, ethanol, propanol, or a mixture thereof can be used in addition to the solvent.

Specifically usable are chlorosilane-based non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl modified Examples thereof include silicone, polyether silicone, and dimethylformamide.

Fluorocarbon solvents include fluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). These may be used alone or in combination of two or more if mixed well. Further, an organic chlorine solvent such as chloroform may be added.

On the other hand, when a ketimine compound or organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound is used instead of the above-mentioned silanol condensation catalyst, the treatment time is reduced to about half to 2/3 even at the same concentration. did it.

Furthermore, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound can be used in a range of 1: 9 to 9: 1. )), The processing time can be increased several times faster (up to about 30 minutes), and the film forming time can be reduced to a fraction of a minute.

For example, dibutyltin oxide, which is a silanol catalyst, was replaced with H3 from Japan Epoxy Resin, which is a ketimine compound, and the other conditions were the same, but the reaction time was reduced to about 1 hour. Results were obtained.

Furthermore, the silanol catalyst was replaced with a mixture of ketimine compound Japan Epoxy Resin H3 and silanol catalyst dibutyltin bisacetylacetonate (mixing ratio is 1: 1), and other conditions were the same. The same results were obtained except that the reaction time could be shortened to about 30 minutes.

Therefore, the above results revealed that ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are more active than silanol condensation catalysts.

Furthermore, it was confirmed that the activity is further increased when one of a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound is mixed with a silanol condensation catalyst.

Here, the ketimine compound that can be used is not particularly limited. 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-pentadeca Diene, 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 and the like.

Further, the organic acid that can be used is not particularly limited, but there are, for example, formic acid, acetic acid, propionic acid, lactic acid, malonic acid, and the like, which have almost the same effects.

In the above Examples 1 to 4, the silica fine particles and the glass substrate have been described as examples. However, the present invention may be fine particles containing active hydrogen on the surface, that is, hydrogen of a hydroxyl group, hydrogen of an amino group or imino group. For example, it can be applied to any fine particle or substrate.

Specifically, as “inorganic fine particles”, conductive fine particles, semiconductor fine particles, insulator fine particles, magnetic fine particles, fluorescent fine particles, light absorbing fine particles, light transmitting fine particles, pigment fine particles, “organic fine particles”, organic fluorescent fine particles, Organic light-absorbing fine particles, organic light-transmitting fine particles, organic pigment fine particles, drug fine particles, and “organic-inorganic hybrid fine particles” such as drug fine particles for DDS (Drug Delivery System), cosmetic fine particles, organic-inorganic hybrid pigment fine particles, etc. In addition, the “substrate” can be applied to a resin plate, a metal plate, a ceramic plate, and the like.

FIG. 2 is a conceptual diagram in which the reaction on the surface of the fine particles in the first embodiment of the present invention is expanded to the molecular level, (a) is a view of the surface of the fine particles before the reaction, and (b) is a monomolecular film containing an epoxy group. (C) shows a view after a monomolecular film containing an amino group is formed. It is the conceptual diagram which expanded reaction of the glass substrate surface in the 2nd Example of this invention to the molecular level, (a) is the figure of the surface before reaction, (b) is a monomolecular film containing an epoxy group. The figure after formation, (c) shows the figure after the monomolecular film containing an amino group is formed. It is the conceptual diagram which expanded the reaction of the glass substrate surface in the 3rd and 4th Example of this invention to a molecular level, (a) is a figure of the substrate surface in which the single layer fine particle film was formed, (b) These show the figure of the base-material surface in which two single-layer fine particle films | membranes were formed.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Silica fine particle 2 Hydroxyl group 3 Monomolecular film containing an epoxy group 4 Monomolecular film containing an amino group
Silica fine particles covered with monomolecular film containing 5 epoxy groups
Silica fine particles covered with monomolecular film containing 6 amino group 11 Glass substrate 12 Hydroxyl group
13 Monomolecular film containing an epoxy group 14 Monomolecular film containing an amino group
Glass substrate covered with a monomolecular film containing 15 epoxy groups
Glass substrate covered with monomolecular film containing 16 amino groups
17 single layer fine particle film
18 Single-layer fine particle film of two-layer structure

Claims (19)

A film of fine particles formed on one surface of a substrate is covalently bonded to each other via a first organic film formed on the surface of the substrate and a second organic film formed on the surface of the particles. Single layer fine particle film. The single-layer fine particle film according to claim 1, wherein the first organic film formed on the surface of the substrate and the second organic film formed on the surface of the fine particle are different from each other. The single-layer fine particle film according to claim 1, wherein the covalent bond is a —N—C— bond formed by a reaction between an epoxy group and an imino group. The single-layer fine particle film according to claim 1 or 2, wherein the first organic film formed on the substrate surface and the second organic film formed on the fine particle surface are formed of a monomolecular film. The substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to cause the alkoxysilane compound and the substrate surface to react with each other. A step of forming a first reactive organic film; and an alkoxysilane compound by dispersing fine particles in a chemical adsorption liquid prepared by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. Forming a second reactive organic film on the surface of the fine particle by reacting the surface of the fine particle with the second reactive organic film on the surface of the substrate on which the first reactive organic film is formed A method for producing a single-layer fine particle film, comprising the step of bringing the fine particles into contact with each other and reacting, and removing the fine particles coated with an extra second reactive organic film. The substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to cause the alkoxysilane compound and the substrate surface to react with each other. A step of forming a first reactive organic film; and an alkoxysilane compound by dispersing fine particles in a chemical adsorption solution prepared by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. After the step of reacting the surface of the fine particles with the surface of the fine particles to form the second reactive organic film on the surface of the fine particles, the first and 6. The method for producing a single-layer fine particle film according to claim 5, wherein a second reactive monomolecular film is formed. 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 an imino group and the second reactive organic film is 6. The method for producing a single-layer fine particle film according to claim 5, comprising an epoxy group. The first reactive monolayer contains an epoxy group and the second reactive monolayer contains an imino group, or the first reactive monolayer contains an imino group and the second reactive monolayer The method for producing a monolayer fine particle film according to claim 6, wherein the monomolecular film contains an epoxy group. A cumulative fine particle film characterized in that the fine particles are accumulated in layers on the surface of a base material and are covalently bonded to each other through an organic film formed on the fine particle surface. 10. There are two types of organic coatings formed on the surface of the fine particles, and the fine particles on which the first organic film is formed and the fine particles on which the second organic film is formed are alternately laminated. The cumulative particulate film described. The cumulative fine particle film according to claim 10, wherein the first organic film and the second organic film react to form a covalent bond. The cumulative fine particle film according to claim 9, wherein the covalent bond is a —N—C— bond formed by a reaction between an epoxy group and an imino group. At least the base material surface is brought into contact with a chemical adsorption solution prepared by mixing a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to cause the alkoxysilane compound and the base material surface to react with each other. A step of forming a reactive organic film, and a first fine particle dispersed in a chemical adsorption solution prepared by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to obtain an alkoxy A step of forming a second reactive organic film on the surface of the first fine particle by reacting the silane compound with the surface of the fine particle; and a second reactivity on the surface of the substrate on which the first reactive organic film is formed. A step of bringing the first fine particles coated with the organic film into contact with each other, and a first single layer fine particle film by washing and removing the first fine particles coated with the extra second reactive organic film Forming the step and The second fine particles are dispersed in a chemical adsorption solution prepared by mixing at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the surface of the fine particles are reacted to produce the second fine particles. A step of forming a third reactive organic film on the surface, and a third reactive organic film on the surface of the substrate on which the first single-layer fine particle film coated with the second reactive organic film is formed. A step of contacting and reacting the second fine particles coated with the film, and a second single-layer fine particle film formed by washing and removing the second fine particles coated with the extra third reactive organic film And a process for producing the cumulative fine particle film. 14. The method according to claim 13, wherein the first reactive organic film and the third reactive organic film are the same. 14. The step of forming the first single-layer fine particle film and the step of forming the second single-layer fine particle film are similarly performed after the step of forming the second single-layer fine particle film. A method for producing a cumulative fine particle film having a multilayer structure as described. After the steps of forming the first to third reactive organic films, the first to third reactive monomolecular films in which the substrate or the surface of the fine particles are washed with an organic solvent and covalently bonded to the surface of the substrate or the fine particles, respectively. The method of manufacturing a cumulative fine particle film according to claim 13, wherein: The first and third reactive organic films contain an epoxy group and the second reactive organic film contains an imino group, or the first and third reactive organic films contain an imino group and the second reactivity The method according to claim 13, wherein the organic film contains an epoxy group. 14. The single-layer fine particle film and cumulative fine particles according to claim 5, wherein a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of the silanol condensation catalyst. A method for producing a membrane. 14. The method according to claim 5, wherein at least one selected from a ketimine compound or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound is used as a co-catalyst for the silanol condensation catalyst. The manufacturing method of the single-layer fine particle film and cumulative fine particle film of description.

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