JP5200244B2 - Fine particle film and manufacturing method thereof - Google Patents

Description

The present invention relates to a fine particle film and a manufacturing method thereof. More specifically, the present invention relates to a fine particle film obtained by curing a coating film containing fine particles by a crosslinking reaction between a reactive group introduced on the surface of the fine particles and a crosslinking agent, and a method for producing the same.

Fine particle films containing fine particles arranged on the surface of a substrate are used in a wide range of applications such as surface protective films, antireflection films, magnetic recording media compatible with high-density magnetic recording and reproduction, and are manufactured by various methods. Yes. As a known method for producing a fine particle film, a method utilizing an autonomous accumulation force of fine particles such as advection accumulation method, Langmuir-Blodgett method (LB method), a suspension of metal oxide fine particles as a base material A method of sintering after coating, a method of dispersing and coating fine particles in a binder resin, curing the binder resin, and agglomeration of fine particles on the surface of a binder layer formed by attaching amphiphilic molecules to the surface of a solid substrate Examples include a method of forming and fixing a film (see, for example, Patent Document 1).

JP-A-8-229474

However, the following problems exist in the manufacturing method of these fine particle films.
In the method using the autonomous accumulation force of fine particles, there is a problem in the stability of the fine particle film because the method for immobilizing the fine particles is not incorporated.
In the method in which the suspension of the metal oxide fine particles is applied to the base material and then sintered, a sintering process is required, so that the production process of the fine particle film is complicated and cannot be used for forming organic fine particles.
The method of dispersing and applying fine particles in a binder resin and curing the binder resin has a major problem that the original physical properties and functions of the fine particles are largely impaired.
In the method of forming and fixing the fine particle aggregated film on the surface of the binder layer formed by adhering amphiphilic molecules to the surface of the solid substrate, a process for forming the fine particle film is complicated because a process for forming the binder layer is required.

In view of the above problems, an object of the present invention is to provide a fine particle film which does not contain a binder resin at all and can be produced by a simple method and has high stability, and a production method thereof.

The fine particle film according to the first invention provided as means for solving the above-mentioned problems is the formation of the first film compound having the first reactive group which is either an amino group , an imino group or an epoxy group. A fine particle whose surface is covered with a coating film, and an epoxy group when the first reactive group is an amino group or an imino group, an amino group when the first reactive group is an epoxy group, or N—CH ₂ formed by applying a mixture containing a cross-linking agent having a plurality of cross-linking reactive groups that are imino groups to the surface of the substrate, and performing a cross-linking reaction between the first reactive group and the cross-linking reactive group. Cured by CH (OH) bond .
The fine particle film according to the second reaction includes fine particles whose surface is covered with a film formed by the first film compound having the first reactive group which is an amino group or an imino group, and a plurality of crosslinks which are isocyanate groups. A mixture containing a crosslinking agent having a reactive group is applied to the surface of the substrate, and cured by N—CH ₂ CH (OH) bonds formed by a crosslinking reaction between the first reactive group and the crosslinking reactive group. doing.

In the fine particle film according to the first or second invention, the film formed by the first film compound is preferably a monomolecular film.

In the fine particle film according to the first aspect of the invention, the bond formed by the cross-linking reaction between the first reactive group and the cross-linking reactive group is formed by the reaction of an amino group or imino group with an epoxy group. CH ₂ CH (OH) is a bond.

In the fine particle film according to the second invention, NH— formed by a reaction between an amino group or imino group and an isocyanate group is formed by a cross-linking reaction between the first reactive group and the cross-linking reactive group. CONH is a bond.

In the fine particle film according to the first or second invention, the surface of the substrate is a film formed by a second film compound having a second reactive group that reacts with the crosslinking reactive group to form a bond. It is preferably covered and fixed to the surface of the base material via a bond formed by a crosslinking reaction between the second reactive group and the crosslinking reaction group.

In the fine particle film according to the first or second invention, the first and second film compounds may be the same compound.

In the fine particle film according to the first or second invention, the film formed by the second film compound is preferably a monomolecular film.

The method for producing a fine particle film according to the third invention includes a first film compound having a first reactive group and a first bonding group, which are either an amino group , an imino group or an epoxy group, at both ends of the molecule. Contacting the fine particles, forming a bond between the first binding group and the surface of the fine particles, and producing reactive fine particles whose surface is covered with a coating formed by the first film compound; A plurality of the reactive fine particles, an epoxy group when the first reactive group is an amino group or an imino group, and an amino group or an imino group when the first reactive group is an epoxy group. A step of producing a paste-like film precursor by mixing a crosslinking agent having a crosslinking reactive group and a solvent, a step of forming a coating film of the film precursor on the surface of the substrate, and the first Cross-linking reaction between a reactive group and the cross-linking reactive group And a step of curing the coating film by _N-CH 2 CH (OH) bonds formed by.
According to a fourth aspect of the present invention, there is provided a method for producing a fine particle film, comprising bringing a first film compound having an amino group or an imino group and a first bonding group at both ends of the molecule into contact with the fine particles, Forming a bond between the first binding group and the surface of the fine particle to produce a reactive fine particle whose surface is covered with a coating formed by the first film compound, the reactive fine particle, A step of producing a paste-like film precursor by mixing a crosslinking agent having a plurality of cross-linking reactive groups which are isocyanate groups, and a solvent; and a step of forming a coating film of the film precursor on the surface of the substrate; And a step of curing the coating film by an N—CH ₂ CH (OH) bond formed by a crosslinking reaction between the first reactive group and the crosslinking reaction group .

In the method for producing a fine particle film according to the third or fourth invention, the coating film formed by the first film compound is preferably a monomolecular film.

In the method of manufacturing the fine particle film according to the third invention, the bond formed by the cross-linking reaction between the first reactive group and the cross-linking reactive group is formed by a reaction between an amino group or imino group and an epoxy group. and a _N-CH 2 CH (OH) bond.

In the method for manufacturing a fine particle film according to the fourth invention, the bond formed by the crosslinking reaction between the first reactive group and the crosslinking reactive group is formed by the reaction of an amino group or imino group with an isocyanate group. It was a NH-CONH bonds.

In the method of manufacturing a fine particle film according to the third invention, the first reactive group may be a functional group having an epoxy group, and the crosslinking agent may be an imidazole derivative.

In the method for producing a fine particle film according to a fourth aspect of the invention, the first reactive group is a functional group containing one of an amino group and an imino group, and the crosslinking agent has 2 or 3 or more isocyanate groups. It may be either a compound or a compound having 2 or 3 or more epoxy groups.

In the method for producing a fine particle film according to the third or fourth invention, before the film precursor is applied to the base material, the base material reacts with the second binding group and the cross-linking reactive group to bond to the base material. Contacting a second membrane compound having a second reactive group at each end of the molecule to form a bond between the second binding group and the surface of the substrate; It is preferable to further include a step of producing a reactive substrate whose surface is covered with a membrane compound.

In the method of manufacturing a fine particle film according to the third or fourth invention, the first and second film compounds may be the same compound.

In the method for producing a fine particle film according to the third or fourth invention, the coating film formed by the second film compound may be a monomolecular film.

The fine particle film according to any one of claims 1 to 6 , and the fine particle film production method according to any one of claims 7 to 14 , wherein the fine particle whose surface is covered with a first film compound having a first reactive group, A mixture containing a cross-linking agent having a plurality of cross-linking reactive groups that react with a reactive group to form a bond is applied to the surface of the substrate, and a coating film is formed by a cross-linking reaction between the first reactive group and the cross-linking reactive group. Therefore, it is possible to provide a highly stable fine particle film that does not require a binder resin for curing and a method for producing the same.

In particular, in the fine particle film according to claim 3 , since the coating film formed by the first film compound is a monomolecular film, the original physical properties and functions of the fine particles can be maintained.

In the fine particle film of claim 1, wherein coupling is formed by the crosslinking reaction between the crosslinking reactive group and the first reactive group, N-CH ₂ which is formed by reaction of the amino or imino group and an epoxy group Since it is a CH (OH) bond, a strong bond can be formed by heating.

3. The fine particle film according to claim 2 , wherein the bond formed by the crosslinking reaction between the first reactive group and the crosslinking reactive group is an NH—CONH bond formed by a reaction between an amino group or an imino group and an isocyanate group. Therefore, a strong bond can be formed by heating.

5. The fine particle film according to claim 4 , wherein the surface of the base material is covered with a second film compound having a second reactive group that forms a bond by reacting with a cross-linking reactive group. Since it fixes to the surface of a base material through the coupling | bonding formed by the crosslinking reaction of a sex group and a crosslinking reaction group, peel strength can be improved.

In the fine particle film according to claim 5 , since the first and second film compounds are the same compound, the manufacturing cost can be reduced.

In the fine particle film according to the sixth aspect , since the coating film formed by the second film compound is a monomolecular film, the peel strength of the fine particle film can be further improved.

In the method for producing a fine particle film according to any one of claims 7 to 14 , first, reactive fine particles whose surface is covered with a first film compound are prepared, and a cross-linking agent and a solvent are mixed with the fine particles, and a paste-like film precursor is prepared. Manufacturing. Next, this is applied to the surface of the base material to form a coating film of the film precursor, and the coating film is cured by a crosslinking reaction between the first reactive group and the crosslinking reactive group in the crosslinking agent to produce a fine particle film. Therefore, the binder resin is unnecessary, and the fine particle film can be easily produced without performing steps such as forming a binder layer on the substrate surface and sintering.

In the method of manufacturing the fine particle film according to the ninth aspect, since the film formed by the first film compound is a monomolecular film, the original physical properties and functions of the fine particles can be maintained.

In the method of manufacturing the fine particle film according to claim 7, since the bond formed by the crosslinking reaction is an N—CH ₂ CH (OH) bond formed by a reaction between an amino group or an imino group and an epoxy group, A strong bond can be formed by heating.

9. The method for producing a fine particle film according to claim 8, wherein the bond formed by the cross-linking reaction between the first reactive group and the cross-linking reactive group is NH formed by a reaction between an amino group or an imino group and an isocyanate group. Since it is a -CONH bond, a strong bond can be formed by heating.

In the method for producing a fine particle film according to claim 10 , since the first reactive group of the first reactive group and the crosslinking reactive group is a functional group having an epoxy group, and the crosslinking agent is an imidazole derivative, A strong N—CH ₂ CH (OH) bond is formed by heating, and the strength of the resulting fine particle film can be improved.

12. The method for producing a fine particle film according to claim 11 , wherein the first reactive group is a functional group containing any one of an amino group and an imino group, and the crosslinking agent has two or more isocyanate groups. Since it is one of compounds having two or more epoxy groups, either strong N—CH ₂ CH (OH) bond or NH—CONH bond is formed by heating, and the strength of the resulting fine particle film Can be improved.

13. The method for producing a fine particle film according to claim 12, wherein the surface of the substrate is coated with a second film compound having a second reactive group that reacts with a cross-linking reactive group to form a bond on the substrate before the film precursor is applied. Since the method further includes the step of manufacturing the reactive base material covered with, the peel strength of the obtained fine particle film can be improved.

In the method of manufacturing the fine particle film according to claim 13 , since the first and second film compounds are the same compound, the manufacturing cost can be reduced.

In the method of manufacturing a fine particle film according to claim 14 , since the film formed by the second film compound is a monomolecular film, the peel strength of the fine particle film can be further improved.

Hereinafter, a fine particle film according to an embodiment of the present invention will be described with reference to the drawings.
As shown in FIG. 1, a fine particle film 10 according to an embodiment of the present invention includes a film compound (first film) in which the surface of silica fine particles (an example of fine particles) 21 has an epoxy group (an example of a first reactive group). Epoxidized silica fine particles (an example of reactive fine particles) 11 coated with a monomolecular film 23 of (1 film compound), an imino group and an amino group (an example of a crosslinking reactive group) that react with an epoxy group to form a bond. A film precursor composed of a mixture containing 2-methylimidazole 12 which is an example of a cross-linking agent having an epoxy group (an example of a second reactive group) and a single molecule of a film compound (second film compound) A coating film 14 (see FIG. 3) of the obtained film precursor was applied to the surface of an epoxidized plate glass (an example of a reactive substrate) 13 which is a plate glass (an example of a substrate) 31 covered with a film 33. , Cross-linking reaction between epoxy group and cross-linking reactive group Obtained by further curing.

As shown in FIGS. 2 (a) and 2 (b), the method of manufacturing the fine particle film 10 includes a step A for manufacturing a epoxidized silica fine particle 11 by bringing a film compound having an epoxy group into contact with the silica fine particle 21, and a plate glass 31. A film compound having an epoxy group is brought into contact with step B to produce the epoxidized plate glass 13, and the epoxidized silica fine particles 11, 2-methylimidazole 12, and a solvent are mixed to produce a paste-like film precursor. Step C, coating the film precursor on the surface of the epoxidized plate glass 13, forming the coating film 14 as shown in FIG. 3, and curing the coating film 14 by the crosslinking reaction of the epoxy group and the crosslinking reaction group And a step E of manufacturing the fine particle film 10.

Hereinafter, the processes A to E will be described in more detail.
In step A, a film compound having an epoxy group is brought into contact with the silica fine particles 21 to produce epoxidized silica fine particles 11 whose surface is covered with a monomolecular film of the film compound having an epoxy group.

Although there is no restriction | limiting in particular in the particle size of the silica fine particle 21 which can be used, It is preferable to exist in the range of 10 nm-0.1 mm. When the particle diameter of the silica fine particles 21 is less than 10 nm, the influence of the molecular size of the film compound cannot be ignored. When the particle diameter exceeds 0.1 mm, the ratio of the mass to the surface area of the silica fine particles 21 is large. Therefore, the mass cannot be supported by the crosslinking reaction.

As the film compound having an epoxy group, any compound that can be adsorbed or bonded to the surface of the silica fine particles 21 and can form a monomolecular film by self-assembly can be used. Each having a functional group containing an epoxy group (oxirane ring) at the terminal and an alkoxysilyl group (an example of the first bonding group) at the other terminal, and represented by the following general formula (Formula 1) Compounds are preferred.

In the above formula, E represents a functional group having an epoxy group, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms.
Specific examples of the film compound having an epoxy group that can be used include alkoxysilane compounds shown in the following (1) to (12).

(1) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) _{3
(2) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OCH 3) 3
(3) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) _{3
(4) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OCH 3) 3
_{(5) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
(6) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₆ Si (OCH ₃ ) _{3
(7) (CH 2 OCH)} CH 2 O (CH 2) 3 Si (OC 2 H 5) 3
_{(8) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OC 2 H 5) 3
(9) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OC ₂ H ₅ ) ₃
(10) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₂ Si (OC ₂ H ₅ ) _{3
(11) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
_{(12) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OC 2 H 5) 3

Here, the (CH ₂ OCH) CH ₂ O— group represents a functional group (glycidoxy group) represented by Chemical Formula ₂ , and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group is represented by Chemical Formula 3. Functional group (3,4-epoxycyclohexyl group).

The production of the epoxidized silica fine particles 11 includes an alkoxysilane compound containing an epoxy group, a condensation catalyst for promoting the condensation reaction between the alkoxysilyl group and the hydroxyl group 22 on the surface of the silica fine particles 21, and a non-aqueous organic solvent. This is carried out by dispersing the silica fine particles 21 in the mixed reaction liquid and reacting in air at room temperature.

As the condensation catalyst, metal salts such as 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 can be used.
The addition amount of the condensation catalyst is preferably 0.2 to 5% by mass of the alkoxysilane compound, and more preferably 0.5 to 1% by mass.

Specific examples of carboxylic acid metal salts include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, naphthenic acid Lead, cobalt naphthenate, and iron 2-ethylhexenoate.

Specific examples of the carboxylic acid ester metal salt include dioctyltin bisoctylthioglycolate ester salt and dioctyltin maleate ester salt.
Specific examples of the carboxylic acid metal salt polymer include dibutyltin maleate polymer and dimethyltin mercaptopropionate polymer.
Specific examples of the carboxylic acid metal salt chelate include dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate.

Specific examples of the titanate ester include tetrabutyl titanate and tetranonyl titanate.
Specific examples of titanate chelates include bis (acetylacetonyl) dipropyl titanate.

The alkoxysilyl group and the hydroxyl group 22 on the surface of the silica fine particle 21 undergo a condensation reaction to produce a monomolecular film 23 of a film compound having an epoxy group having a structure represented by the following chemical formula 4. The three single bonds extending from the oxygen atom are bonded to the surface of the silica fine particle 21 or the silicon (Si) atom of the adjacent silane compound, and at least one of them is bonded to the silicon atom on the surface of the silica fine particle 21. doing.

Since the alkoxysilyl group decomposes in the presence of moisture, the reaction is preferably performed in air with a relative humidity of 45% or less. The condensation reaction is hindered by oils and fats and moisture adhering to the surface of the silica fine particles 21. Therefore, it is preferable to remove these impurities in advance by thoroughly washing and drying the silica fine particles 21.
When any of the above metal salts is used as the condensation catalyst, the time required for completion of the condensation reaction is about 2 hours.

When one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are used as the condensation catalyst instead of the above metal salts, Time can be shortened to about 1/2 to 2/3.

Alternatively, when these compounds are used as a co-catalyst and mixed with the above-described metal salt (mass ratio 1: 9 to 9: 1 can be used, preferably around 1: 1), the reaction time is further shortened. it can.

For example, when H3 from Japan Epoxy Resin Co., Ltd., which is a ketimine compound, is used as the condensation catalyst instead of dibutyltin oxide and the other conditions are the same, the quality of the epoxidized silica particles 11 is improved. The reaction time can be reduced to about 1 hour without loss.

Furthermore, when a mixture of H3 and dibutyltin bisacetylacetonate from Japan Epoxy Resin Co., Ltd. (mixing ratio is 1: 1) is used as the condensation catalyst, and the other conditions are the same, the epoxidized silica fine particles 11 are produced. The reaction time can be shortened to about 20 minutes.

The ketimine compound that can be used here is not particularly limited, and examples thereof 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-tetramethyl-5,8,11-triaza-4,11-penta Decadiene, 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.

Moreover, although it does not specifically limit as an organic acid which can be used, For example, a formic acid, an acetic acid, propionic acid, a butyric acid, malonic acid etc. are mentioned.

For the production of the reaction solution, an organic chlorine solvent, a hydrocarbon solvent, a fluorocarbon solvent, a silicone solvent, and a mixed solvent thereof can be used. In order to prevent hydrolysis of the alkoxysilane compound, it is preferable to remove water from the desiccant or the solvent used by distillation. Moreover, it is preferable that the boiling point of a solvent is 50-250 degreeC.

Specific usable solvents include non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, and alkyl-modified silicone. , Polyether silicone, dimethylformamide and the like.
Furthermore, alcohol solvents such as methanol, ethanol, propanol, or a mixture thereof can also be used.

Fluorocarbon solvents that can be used include fluorocarbon solvents, Fluorinert (manufactured by 3M, USA), Afludo (manufactured by Asahi Glass Co., Ltd.), and the like. In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Furthermore, an organic chlorine solvent such as dichloromethane or chloroform may be added.

The preferable density | concentration of the alkoxysilane compound in a reaction liquid is 0.5-3 mass%.

After the reaction, washing with a solvent to remove excess alkoxysilane compound and condensation catalyst remaining on the surface as unreacted substances, the epoxidized silica fine particles 11 whose surface is covered with a monomolecular film 23 of a film compound having an epoxy group Is obtained. A schematic view of the cross-sectional structure of the epoxidized silica fine particles 11 produced in this way is shown in FIG.

As the cleaning solvent, any solvent that can dissolve the alkoxysilane compound can be used, but dichloromethane, chloroform, N-methylpyrrolidone, etc. that are inexpensive, have high solubility, and can be easily removed by air drying are preferable. .

After the reaction, when the produced epoxidized silica fine particles 11 are left in the air without being washed with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air, and the produced silanol group becomes an alkoxy. Causes a condensation reaction with a silyl group. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the epoxidized silica fine particles 11. Although this polymer film is not fixed to the surface of the epoxidized silica fine particle 11 by a covalent bond, it contains an epoxy group. Therefore, the polymer film has a monomolecular film 23 of a film compound having an epoxy group with respect to the epoxidized silica fine particle 11. Similar reactivity. Therefore, even if cleaning is not performed, the manufacturing process after the process C is not particularly hindered.

In the present embodiment, an alkoxysilane compound having an epoxy group is used. However, the linear alkylene group has an amino group at one end and an alkoxysilyl group at the other end. An alkoxysilane compound represented by the formula (Formula 5) may be used.

In the above formula, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms.
Specific examples of the film compound having an amino group that can be used include alkoxysilane compounds shown in the following (21) to (28).

(21) H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃
(22) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(23) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(24) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(25) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(26) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(27) H ₂ N (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(28) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

Among the condensation catalysts that can be used in the reaction solution, compounds containing tin (Sn) salts react with amino groups to form precipitates, so they should be used as condensation catalysts for alkoxysilane compounds having amino groups. I can't.
Therefore, when using an alkoxysilane compound having an amino group, excluding carboxylic acid tin salt, carboxylic acid ester tin salt, carboxylic acid tin salt polymer, carboxylic acid tin salt chelate, and an alkoxysilane compound having an epoxy group Similar compounds can be used alone or in combination of two or more as a condensation catalyst.
The types of cocatalysts that can be used and combinations thereof, the types of solvents, the concentration of alkoxysilane compounds, condensation catalysts, and cocatalysts, reaction conditions, and reaction times are the same as in the case of alkoxysilane compounds having an epoxy group. Therefore, explanation is omitted.

In the present embodiment, silica fine particles are used as the fine particles, but other inorganic fine particles, organic fine particles, and organic-inorganic hybrid fine particles can also be used.
Specific examples of the 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.
Specific examples of the 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.
Specific examples of 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.

Even in the case of fine particles other than silica fine particles, an alkoxysilane compound can be used as the film compound when the surface has active hydrogen groups such as hydroxyl groups and amino groups. Specific examples of such fine particles include fine particles of metal oxides such as alumina and lead oxide, and fine metal particles.

In this embodiment, a silane compound that undergoes a condensation reaction with active hydrogen groups on the surface of the fine particles is used as the film compound. For example, in the case of gold fine particles or fine particles having a gold plating layer, the film compound is strong with gold atoms. Thiol compounds that form bonds can be used.
(End of process A)

In step B, a film compound having an epoxy group similar to that used in step A is brought into contact with plate glass 31 to produce epoxidized plate glass 13 whose surface is covered with monomolecular film 33 of the film compound having an epoxy group. .
The size of the plate glass 31 is not particularly limited.

The production of the epoxidized plate glass 13 is performed by a condensation for promoting a condensation reaction between an alkoxysilane compound containing an epoxy group and an alkoxysilyl group (an example of a second bonding group) and an alkoxysilyl group and a hydroxyl group on the surface of the plate glass 31. The reaction is performed by applying a reaction liquid obtained by mixing a catalyst and a non-aqueous organic solvent to the surface of the plate glass 31 and reacting in air at room temperature. The coating can be performed by any method such as a doctor blade method, a dip coating method, a spin coating method, a spray method, or a screen printing method.

Types of alkoxysilane compounds having an epoxy group that can be used in Step B, types of condensation catalysts, types of promoters and combinations thereof, types of solvents, concentrations of alkoxysilane compounds, condensation catalysts, and promoters, reaction conditions and reactions Since the time is the same as in step A, the description is omitted.

After the reaction, it is washed with a solvent to remove excess alkoxysilane compound and condensation catalyst remaining on the surface as unreacted substances, whereby an epoxidized plate glass 13 whose surface is covered with a monomolecular film 33 of a film compound having an epoxy group is obtained. can get.

As the washing solvent, the same washing solvent as in step A can be used.
After the reaction, when the produced epoxidized plate glass 13 is left in the air without being washed with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air, and the produced silanol group is converted to alkoxysilyl. Causes a condensation reaction with the group. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the epoxidized plate glass 13. Although this polymer film is not fixed to the surface of the epoxidized plate glass 13 by a covalent bond, since it contains an epoxy group, it is the same as the monomolecular film 33 of the film compound having an epoxy group with respect to the epoxidized plate glass 13. Has reactivity. Therefore, even if cleaning is not performed, the manufacturing process after the process C is not particularly hindered.

In this embodiment, an alkoxysilane compound having an epoxy group is used. However, as in Step A, an alkoxy group having an amino group at one end of a linear alkylene group and an alkoxysilyl group at the other end is used. Silane compounds may be used.
In the present embodiment, the same alkoxysilane compound as in step A is used, but a different alkoxysilane compound may be used. However, it must have a reactive group that reacts with the crosslinking reactive group of the crosslinking agent used in Step C to form a bond.

In the present embodiment, plate glass is used as a base material. However, when the surface has an active hydrogen group such as a hydroxyl group or an amino group, an alkoxysilane compound can be used as a film compound. Specific examples of such a substrate include ceramic plates, enamels, stone plates, steel plates, aluminum plates, metal plates such as silicon wafers, and the like.

In the present embodiment, a silane compound that undergoes a condensation reaction with active hydrogen groups on the surface of the substrate is used as the film compound. However, as in Step A, for example, in the case of a substrate having a gold plating layer, A thiol compound that forms a strong bond with a gold atom can be used.
(End of process B)

In Step C, epoxidized silica fine particles 11, 2-methylimidazole 12, and a solvent are mixed to produce a paste-like film precursor.
2-Methylimidazole has an amino group and an imino group that react with an epoxy group at the 1-position and 3-position, respectively, and forms a bond by a crosslinking reaction as shown in Chemical Formula 6 below.

The addition amount of 2-methylimidazole 12 is preferably 5 to 15% by weight of the epoxidized silica fine particles 11. When the addition amount of 2-methylimidazole 12 is less than 5% by weight of the epoxidized silica fine particles 11, the strength of the fine particle film 10 to be produced is low, and when it exceeds 15% by weight, the film precursor is likely to be gelled. The handling becomes worse. For the production of the film precursor, any solvent in which 2-methylimidazole 12 is soluble can be used. However, considering the price, volatility at room temperature, toxicity, etc., lower alcohols such as isopropyl alcohol and ethanol System solvents are preferred.

The amount of the solvent used for the production of the film precursor is appropriately determined depending on the particle size of the epoxidized silica fine particles 11, the film thickness of the fine particle film 10 to be produced, and the like. The amount is preferably such that the viscosity of the precursor is 5 to 20 Pa · s, and more specifically 10 to 50% by weight of the epoxidized silica fine particles 11 and 2-methylimidazole 12. Specifically, an amount necessary for coating the surface of the epoxidized silica fine particles 11 with a monomolecular film of 2-methylimidazole 12 may be set.
Mixing of the epoxidized silica fine particles 11, the 2-methylimidazole 12, and the solvent can be performed by any means such as a stirring spring and a hand mixer.

In the present embodiment, 2-methylimidazole is used as a crosslinking agent, but any imidazole derivative represented by the following chemical formula 7 can be used. Alternatively, an imidazole-metal complex may be used.

Specific examples of the imidazole derivative represented by Chemical Formula 7 include those shown in the following (31) to (38).
(31) 2-Methylimidazole (R ₂ = Me, R ₄ = R ₅ = H)
(32) 2-Undecylimidazole (R ₂ = C ₁₁ H ₂₃ , R ₄ = R ₅ = H)
(33) 2-Pentadecylimidazole (R ₂ = C ₁₅ H ₃₁ , R ₄ = R ₅ = H)
(34) 2-methyl-4-ethylimidazole _{(R 2 = Me, R 4} = Et, R 5 = H)
(35) 2-Phenylimidazole (R ₂ = Ph, R ₄ = R ₅ = H)
(36) 2-phenyl-4-ethylimidazole _{(R 2 = Ph, R 4} = Et, R 5 = H)
(37) 2-phenyl-4-methyl-5-hydroxymethylimidazole _{(R 2 = Ph, R 4} = Me, R 5 = CH 2 OH)
(38) 2-Phenyl-4,5-bis (hydroxymethyl) imidazole (R ₂ = Ph, R ₄ = R ₅ = CH ₂ OH)
Me, Et, and Ph represent a methyl group, an ethyl group, and a phenyl group, respectively.

In addition, compounds such as acid anhydrides such as phthalic anhydride and maleic anhydride, and phenol derivatives such as dicyandiamide and novolak, which are used as curing agents for epoxy resins, may be used as a crosslinking agent. In this case, an imidazole derivative may be used as a catalyst in order to accelerate the crosslinking reaction.

In this embodiment, the case where a film compound having an epoxy group as a reactive group is used is described. However, when a film compound having an amino group or an imino group as a reactive group is used, a crosslinking reaction is performed. A crosslinking agent having 2 or 3 or more epoxy groups or 2 or 3 or more isocyanate groups as a group is used. Specific examples of the compound having an isocyanate group include hexamethylene-1,6-diisocyanate, toluene-2,6-diisocyanate, and toluene-2,4-diisocyanate.
The addition amount of these diisocyanate compounds is preferably 5 to 15% by weight of the epoxidized silica fine particles as in the case of 2-methylimidazole. In this case, examples of the solvent that can be used for the production of the film precursor include aromatic organic solvents such as xylene.
Moreover, as a crosslinking agent, the compound which has 2 or 3 or more epoxy groups, such as ethylene glycol diglycidyl ether, can also be used.
(End of process C)

In step D, a film precursor is applied to the surface of the epoxidized plate glass 13 to form a coating film 14 as shown in FIG.
The film precursor can be applied by any method such as a doctor blade method, a spin coating method, or a spray method.
(End of process D)

In step E, the coating film 14 is heated, and the coating film 14 is cured by a crosslinking reaction between the epoxy groups on the epoxidized silica fine particles 11 and the epoxidized plate glass 13 and 2-methylimidazole 12, thereby producing the fine particle film 10.
The heating temperature is preferably 100 to 200 ° C. If the heating temperature is less than 100 ° C., it takes a long time for the crosslinking reaction to proceed. If the heating temperature exceeds 200 ° C., the crosslinking reaction proceeds rapidly on the surface of the coating film 14 so that the confined solvent is less likely to volatilize. A uniform fine particle film 10 cannot be obtained.

In addition, although the epoxidized plate glass was used in this Embodiment, the process B may be abbreviate | omitted and a normal plate glass may be used as a base material.

In step E, the bond formed by the crosslinking reaction may be any of a covalent bond, an ionic bond, a coordinate bond, and a bond due to intermolecular force, but the strength of the fine particle film 10 to be formed and the film precursor In view of the ease of forming the coating film 14 and the like, a covalent bond formed by heating or irradiation of energy rays such as light after the coating film 14 is formed is preferable.
Specific examples of the covalent bond formed by heating include an N—CH ₂ CH (OH) bond formed by a reaction between an epoxy group and an amino group or an imino group (see Chemical Formula 8), an isocyanate group and an amino group. NH-CONH bonds formed by the reaction (see Chemical Formula 9) and the like can be mentioned.

Specific examples of the covalent bond formed by light irradiation include a covalent bond formed by a photodimerization reaction of a cinnamoyl group (see Chemical Formula 10) or a chalconyl group (Chemical Formula 11).

（以上工程Ｅ）

(End of process E)

Examples carried out for confirming the effects of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
(1) Production of Epoxidized Silica Fine Particles Silica fine particles (average particle size 100 nm) were prepared, washed thoroughly and dried.
0.99 parts by weight of 3-glycidoxypropyltrimethoxysilane (Chemical Formula 12, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.01 parts by weight of dibutyltin bisacetylacetonate (condensation catalyst) were weighed, and this was 100 parts by weight. Was dissolved in a hexamethyldisiloxane solvent to prepare a reaction solution.

Silica fine particles were mixed in the reaction solution thus obtained and reacted in air (relative humidity 45%) for about 2 hours while stirring.
Thereafter, the mixture was washed with chloroform to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate.

(2) Production of film precursor, formation of coating film, and formation of fine particle film 100 parts by weight of the epoxidized silica fine particles produced in (1) and 7 parts by weight of 2-methylimidazole are mixed, and isopropyl alcohol 40 is mixed therewith. Part by weight was added. The obtained mixture was sufficiently mixed to obtain a pasty film precursor.
Thus, the obtained film | membrane precursor was apply | coated on soda glass, and the coating film with a film thickness of 1 micrometer was formed.
After evaporating isopropyl alcohol at room temperature, the soda-lime glass and the coating film formed thereon were heated at 170 ° C. for 30 minutes to form a fine particle film.

(Example 2)
(1) Production of Epoxidized Silica Fine Particles Silica fine particles (average particle size 1 μm) were prepared, washed thoroughly and dried.
0.99 parts by weight of 3-glycidoxypropyltrimethoxysilane (Chemical Formula 12) and 0.01 parts by weight of dibutyltin bisacetylacetonate (condensation catalyst) were weighed and added to 100 parts by weight of hexamethyldisiloxane solvent. It melt | dissolved and the reaction liquid was prepared.

Silica fine particles were mixed in the reaction solution thus obtained and reacted in air (relative humidity 45%) for about 2 hours while stirring.
Thereafter, the mixture was washed with chloroform to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate.

(2) Production of Epoxidized Plate Glass Blue plate glass was prepared, washed thoroughly and dried.
0.99 parts by weight of 3-glycidoxypropyltrimethoxysilane (Chemical Formula 11) and 0.01 parts by weight of dibutyltin bisacetylacetonate (condensation catalyst) were weighed and added to 100 parts by weight of hexamethyldisiloxane solvent. It melt | dissolved and the reaction liquid was prepared.

The reaction solution was applied to the surface of the blue plate glass plate and reacted in air (relative humidity 45%) for about 2 hours.
Thereafter, the mixture was washed with chloroform to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate.

(3) Production of film precursor, formation of coating film, and formation of fine particle film 100 parts by weight of epoxidized silica fine particles produced in (1) and 7 parts by weight of 2-methylimidazole are mixed, and isopropyl alcohol 40 is mixed therewith. Part by weight was added. The obtained mixture was sufficiently mixed to obtain a pasty film precursor.
The film precursor was applied on the epoxidized plate glass produced in (2) to form a coating film having a thickness of 10 μm.
After evaporating isopropyl alcohol at room temperature, the epoxidized plate glass and the coating film were heated at 170 ° C. for 30 minutes to form a fine particle film.

Since the obtained fine particle film was fixed to the surface of the epoxidized plate glass via a bond formed by a crosslinking reaction between an epoxy group and 2-methylimidazole, it was excellent in peel strength and durability.

(Example 3)
(1) Production of aminated silica fine particles Silica fine particles (average particle size 300 nm) were prepared, washed well and dried.
0.99 parts by weight of 3-aminopropyltrimethoxysilane (Chemical 13 manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.01 part by weight of acetic acid (condensation catalyst) were weighed, and 100 parts by weight of hexamethyldisiloxane- A reaction solution was prepared by dissolving in a dimethylformamide mixed solvent (1: 1 v / v).

Silica fine particles were mixed in the reaction solution thus obtained and reacted in air (relative humidity 45%) for about 2 hours while stirring.
Then, it wash | cleaned with chloroform and the excess alkoxysilane compound and acetic acid were removed.

(2) Production of aminated plate glass Blue plate glass was prepared, washed thoroughly and dried.
0.99 parts by weight of 3-aminopropyltrimethoxysilane (Chemical Formula 13) and 0.01 part by weight of acetic acid (condensation catalyst) were weighed and mixed with 100 parts by weight of a mixed solvent of hexamethyldisiloxane-dimethylformamide (1: 1 v / v) to prepare a reaction solution.

The reaction solution was applied to the surface of the blue plate glass plate and reacted in air (relative humidity 45%) for about 2 hours.
Then, it wash | cleaned with chloroform and the excess alkoxysilane compound and acetic acid were removed.

(3) Production of film precursor, formation of coating film, and formation of fine particle film 100 parts by weight of aminated silica fine particles produced in (1) and 9 parts by weight of hexamethylene-1,6-diisocyanate were mixed. 40 parts by weight of xylene was added. The obtained mixture was sufficiently mixed to obtain a pasty film precursor.
The film precursor was applied on the aminated plate glass produced in (2) to form a coating film having a thickness of 3 μm.
After evaporating xylene at room temperature, the aminated plate glass and the coating film were heated at 170 ° C. for 30 minutes to form a fine particle film.

Example 4
A lead oxide fine particle film was formed on the surface of the galvanized steel plate in the same manner as in Example 2 using fine particles of lead oxide as fine particles and a galvanized steel plate as the base material.

It is explanatory drawing which represented typically the cross-sectional structure of the fine particle film which concerns on one embodiment of this invention. In the manufacturing method of the fine particle film, in order to explain the process of producing epoxidized silica fine particles, it is a conceptual diagram expanded to the molecular level, (a) is a cross-sectional structure of silica fine particles before reaction, (b) is an epoxy group Each represents a cross-sectional structure of a silica fine particle in which a monomolecular film of a film compound having s is formed. It is the conceptual diagram expanded to the molecular level in order to demonstrate the process of forming the coating film of a film | membrane precursor in the manufacturing method of the fine particle film.

Explanation of symbols

10: fine particle film, 11: epoxidized silica fine particle, 12: 2-methylimidazole, 13: epoxidized plate glass, 14: coating film, 21: silica fine particle, 22: hydroxyl group, 23: single molecule of film compound having epoxy group Film, 31: plate glass, 33: monomolecular film of film compound having epoxy group

Claims (14)

Fine particles whose surface is covered with a film formed by a first film compound having a first reactive group which is either an amino group, an imino group or an epoxy group, and the first reactive group is an amino group or When the imino group is an epoxy group, and when the first reactive group is an epoxy group, a mixture containing a cross-linking agent having a plurality of cross-linking reactive groups which is an amino group or an imino group is used. A fine particle film, which is applied to and cured by an N—CH ₂ CH (OH) bond formed by a crosslinking reaction between the first reactive group and the crosslinking reactive group. A mixture comprising fine particles whose surface is covered with a film formed by a first film compound having a first reactive group which is an amino group or an imino group, and a crosslinking agent having a plurality of crosslinking reactive groups which are isocyanate groups N-CH formed by a crosslinking reaction between the first reactive group and the crosslinking reactive group ₂ A fine particle film cured by CH (OH) bonding. 3. The fine particle film according to claim 1, wherein the film formed by the first film compound is a monomolecular film. The fine particle film according to any one of claims 1 to 3 , wherein the surface of the base material is a second film compound having a second reactive group that reacts with the cross-linking reactive group to form a bond. A fine particle film which is covered with a film to be formed and is fixed to the surface of the base material through a bond formed by a crosslinking reaction between the second reactive group and the crosslinking reactive group . 5. The fine particle film according to claim 4 , wherein the first and second film compounds are the same compound. 6. The fine particle film according to claim 4 , wherein the coating film formed by the second film compound is a monomolecular film. A first film compound having a first reactive group and a first binding group, which are either an amino group, an imino group or an epoxy group, at both ends of the molecule is brought into contact with the fine particles, and the first binding group and Forming a bond with the surface of the fine particle to produce a reactive fine particle whose surface is covered with a coating formed by the first film compound; the reactive fine particle; and the first reactive group A crosslinking agent having a plurality of crosslinking reactive groups which are an amino group or an imino group when the first reactive group is an epoxy group , and a solvent. a step of producing a paste film precursor admixture, and forming a coating film of the film precursor on the surface of the substrate, the crosslinking reaction between the crosslinking reactive group and the first reactive group the formed _N-CH 2 CH (O ) A method of manufacturing a fine particle film; and a step of curing the coating film by the binding. A first film compound having a first reactive group which is an amino group or an imino group and a first binding group at each end of the molecule is brought into contact with the fine particles, and the first binding group and the surface of the fine particles are brought into contact with each other. A step of producing reactive fine particles whose surface is covered with a film formed by the first film compound, and a crosslinking agent having a plurality of cross-linking reactive groups that are the reactive fine particles and isocyanate groups And a step of producing a paste-like film precursor by mixing a solvent, a step of forming a coating film of the film precursor on the surface of the substrate, the first reactive group and the cross-linking reactive group N-CH formed by crosslinking reaction with ₂ And a step of curing the coating film by CH (OH) bonding. 9. The method for producing a fine particle film according to claim 7 , wherein the coating film formed by the first film compound is a monomolecular film. 8. The method for producing a fine particle film according to claim 7 , wherein the first reactive group is a functional group having an epoxy group, and the crosslinking agent is an imidazole derivative. 9. The method for producing a fine particle film according to claim 8 , wherein the first reactive group is a functional group including any one of an amino group and an imino group, and the cross-linking agent has two or three or more isocyanate groups. A method for producing a fine particle film, which is one of a compound and a compound having two or more epoxy groups. The method of manufacturing a fine particle film according to any one of claims 7 to 11, prior to applying the film precursor to the substrate, to the substrate, and a second coupling group and the crosslinking group Contacting a second membrane compound having a second reactive group that reacts to form a bond at each end of the molecule to form a bond between the second binding group and the surface of the substrate; The method for producing a fine particle film, further comprising the step of producing a reactive substrate whose surface is covered with the second film compound. 13. The method for producing a fine particle film according to claim 12 , wherein the first and second film compounds are the same compound. 14. The method for producing a fine particle film according to claim 12 , wherein the coating film formed by the second film compound is a monomolecular film.

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